WO2011097441A1 - Fibres/filaments de nanotubes de carbone formulés à partir d'un catalyseur de nanoparticule en métal et d'une source de carbone - Google Patents

Fibres/filaments de nanotubes de carbone formulés à partir d'un catalyseur de nanoparticule en métal et d'une source de carbone Download PDF

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WO2011097441A1
WO2011097441A1 PCT/US2011/023692 US2011023692W WO2011097441A1 WO 2011097441 A1 WO2011097441 A1 WO 2011097441A1 US 2011023692 W US2011023692 W US 2011023692W WO 2011097441 A1 WO2011097441 A1 WO 2011097441A1
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fiber
fibers
mixture
polymer
carbon
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PCT/US2011/023692
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Teddy M. Keller
Matthew Laskoski
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The Government Of The United States Of America, As Represented By The Secretary Of The Navy
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Priority claimed from US12/911,117 external-priority patent/US9085720B2/en
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Publication of WO2011097441A1 publication Critical patent/WO2011097441A1/fr

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    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
    • D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
    • D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
    • D01F9/14—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments
    • D01F9/145—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from pitch or distillation residues
    • 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
    • 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
    • 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
    • C01B32/16—Preparation
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
    • D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
    • D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
    • D01F9/14—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments
    • D01F9/20—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products
    • D01F9/21—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F9/22—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyacrylonitriles
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
    • D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
    • D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
    • D01F9/14—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments
    • D01F9/20—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products
    • D01F9/24—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds

Definitions

  • the present disclosure is generally related to fibers containing carbon nanotubes.
  • High-performance synthetic fibers have been under development for the past half century, motivated in particular by the high strength and stiffness of the covalent carbon-carbon bond and by the ability to achieve alignment with the fiber axis where they are in the form of polymer molecules or graphene sheets.
  • An advantage of pure carbon fibers is that the mechanical properties are derived from the in-plane stiffness and strength of graphene sheets, without the adulterating effect of additional atoms to satisfy available carbon bonds.
  • the route to carbon fibers involves the alignment of precursor structures, which are then covalently bonded to each other to create the final structure.
  • Carbon fibers are thus comparatively brittle, especially when they are heat treated above 1500°C to maximize stiffness.
  • the very high axial strength and stiffness of individual carbon nanotubes opens up the possibility of processing them directly into continuous fibers.
  • the benefits of high-performance polymeric fibers, especially directness of processing and fiber toughness can be combined with the advantages of nano fibers consisting of carbon atoms.
  • the processing routes developed so far to incorporate CNTs into polymeric fibers borrow concepts from polymer fiber processing technologies.
  • PAN Polyacrylonitrile
  • petroleum pitch and cellulosic fibers are typically used as carbon fiber precursors.
  • Other high temperature polymers have also been used.
  • PAN is the precursor of choice.
  • thermo- oxidative stabilization typically in the 200-300°C range is a key step.
  • the PAN fibers are fed through a series of specialized ovens during the time-consuming oxidative stage. The process combines oxygen molecules from the air with the PAN fibers in the warp and causes the polymer chains to start crosslinking.
  • the crosslinked fibers then have a definite shaped (will not soften) and are then carbonized under inert conditions typically between 700 and ends in a high temperature furnace at 1200°C to 1500°C. While dwell times are sometimes proprietary, oxidative dwell time is measured in hours, while carbonization is an order of magnitude shorter, measured in minutes. As the fiber is carbonized, it loses weight and volume, contracts by 5 to 10 percent in length and shrinks in diameter.
  • the CNTs can be dispersed in solvents such as dimethylformamide (DMF) and dimethylacetamide (DM AC). Carbonized and activated PAN/CNT films are very promising for supercapacitor electrode applications. Solution spun PAN/CNT fibers containing 10 wt-% nanotubes exhibit a 100 percent increase in tensile modulus at room temperature, a significant reduction in thermal shrinkage, and a 40°C increase in the glass transition temperature. These observations provide evidence of the interaction between PAN and the CNTs.
  • solvents such as dimethylformamide (DMF) and dimethylacetamide (DM AC).
  • One parameter in making high-strength fibers from carbon nanotubes is the availability of nanotubes which are as long and as structurally perfect as possible. Another parameter is to align all nanotubes as perfectly as possible with the fiber axis, so as to maximize the translation of their axial properties to those of the fiber.
  • the bonding between adjacent nanotubes is weak in shear (graphite is a lubricant) and thus as great a contact length as possible is necessary to transfer the load into any given nanotube.
  • Another advantage of thin walled nanotubes (single or double) is that they tend to facet or flatten so to maximize their contact area. Alignment is typically achieved through mechanical forces whether applied to a partly linked array of fibers or through fluid-flow forces on a lyotropic suspension.
  • a method comprising: providing a mixture of a polymer or a resin and a transition metal compound, producing a fiber from the mixture, and heating the fiber under conditions effective to form a carbon nanotube-containing fiber.
  • the polymer or resin is an aromatic polymer or a precursor thereof and the mixture is a neat mixture or is combined with a solvent.
  • Also disclosed herein is a fiber or nano fiber sheet comprising at least 15 wt.% carbon nanotubes.
  • a fiber or nano fiber sheet comprising a mixture of: a polymer or a resin, as described above, and a transition metal compound.
  • fiber or nano fiber sheet comprising: an aromatic polymer and metal nanoparticles.
  • Fig. shows photographs of large CNT-containing fibers and rods formulated from PAN and phthalonitrile, respectively.
  • Figs. 2 and 3 show SEM images showing the crude fibers and the CNTs appearing somewhat aligned within the fibers.
  • Fig. 4 shows a synthetic scheme for an embodiment of the method.
  • a high-yield method has been developed for the production of carbon nanotubes (CNTs) and carbon nanotube-magnetic metal nanoparticle compositions in a bulk carbonaceous solid.
  • the yield of CNT formation can be controlled as a function of the carbonization temperature and exposure time at elevated temperatures.
  • CNTs are formed in a bulk carbonaceous solid from thermal decomposition of various amounts of an organometallic compound and/or metal salts in the presence of an excess amount of a carbon source such as selected highly aromatic compounds. Only a small amount of the organometallic compound or metal salt is needed to achieve the formation of CNTs in high yield, but larger quantities of the metal source can also be incorporated, if desired.
  • the disclosed process is concerned with the formation of neat aligned CNT fibers from precursor compositions formulated from (1) a carbon source such as polyacrylonitrile (PAN) or copolymers thereof, pitch-based compounds, high temperature compounds or resins that char and (2) a metal salt(s) and/or organometallic compound(s).
  • a carbon source such as polyacrylonitrile (PAN) or copolymers thereof, pitch-based compounds, high temperature compounds or resins that char and (2) a metal salt(s) and/or organometallic compound(s).
  • PAN polyacrylonitrile
  • copolymers thereof pitch-based compounds
  • high temperature compounds or resins that char
  • a metal salt(s) and/or organometallic compound(s) a metal salt(s) and/or organometallic compound(s).
  • the spinning of fibers occurs from the precursor compositions either melted or dissolved or dispersed in a dipolar aprotic solvent, and thermal treatment of the precursor composition resulting in the de
  • nanoparticle/carbon nanotube fibers during a carbonization process.
  • the carbonization process to form the carbon nanotube fibers occurs in temperature steps from, for example, about 600°C to 1500°C.
  • the property of the carbon nanotube fibers will depend on the heat treatment.
  • the process may result in the high-yield formation of multi-walled carbon nanotubes (MWNTs) in the solid carbonaceous domain upon heat treatment to elevated temperatures under ambient pressure.
  • the method permits the large-scale inexpensive production of MWNTs in a shaped, solid configuration.
  • the MWNTs are formed under atmospheric pressure during the carbonization process above 500°C in the carbonaceous solid.
  • the catalytic metal atoms, nanoclusters, and/or nanoparticles formed from the decomposition of the organometallic compound or metal salt are the key to the formation of the carbon nanotubes in the developing carbonaceous nanomaterial by reacting with the developing polycondensed aromatic ring system.
  • the average size as determined by X-ray diffraction studies are 5-30 nm.
  • Small metal nanoparticles (1-3 nm) could produce single-walled carbon nanotubes.
  • the composition can be tailored to have mainly CNTs or varying amounts of CNTs and magnetic metal nanoparticles, as formed. Shaped solid forms, films, and fibers/rods can be readily formulated from the precursor mixtures. If desired, CNT-containing powders can be obtained by milling of the carbonaceous solid.
  • the CNT content of the bulk solid can be controlled by the final pyro lysis temperature. For example, a final pyrolysis temperature of 800°C and 1300°C may afford a CNT content of approximately 20 and 70 wt. %, respectively.
  • a suitable range of pyrolysis temperatures includes, but is not limited to, 600-2700°C.
  • the initial fiber form of the initial materials may be made by a variety of methods that are known in the art including, but not limited to, spinning with a spinneret, electrospinning, solvent precipitation, and physically pulling a fiber from a mixture of the materials. A variety of such methods are described in US Provisional Application No. 61/301,279.
  • the materials may be mixed neat in the melt or liquid state, or mixed or dissolved in a solvent. When the precursor composition is completely dissolved in a solvent, it can help to ensure that metal salt(s) and/organometallic compounds are deposited within the spun polymeric fibers.
  • the fiber is a threadlike material and may have the same dimensions as is typical for other carbon fibers.
  • Suitable carbon sources include aromatic polymers and precursors thereof.
  • the polymer may be a crosslinked or thermoset polymer, with the crosslinking occuring during or after formation of the fiber.
  • the aromatic polymer may be an aromatic phthalonitrile polymer or oligomer, or a thermoset thereof, such as a phthalonitrile oligomer made from bisphenol A and benzophenone.
  • a precursor is a compound or material that can be converted to an aromatic polymer or material by heating before forming the CNTs. Such heating may be in oxygen, including atmospheric air. The heating may be, for example, from 200-300°C. When heated in this way, PAN converts to an aromatic polymer as the side groups form rings.
  • Pitch resins such as coal pitch (coal tar pitch), petroleum pitch, or synthetic pitches also form aromatic materials.
  • Other suitable carbon sources include any aromatic material, or material that converts to an aromatic, that forms a char when heated in an inert atmosphere. Such materials and their products are disclosed in US Patent Nos. 6,673,953; 6,770,583; 6,846,345; 6,884,861; and 7,819,938.
  • the transition metal compound may be, for example, a metal salt or an organometallic compound. Such compounds can decompose at elevated temperatures to form metal
  • Such suitable compounds include, but are not limited to, octacarbonyldicobalt, 1 -(ferrocenylethynyl)-3-(phenylethynyl)benzene, diironnonacarbonyl, and
  • the small metal nanoparticles formed by thermal degradation/decomposition of the metal salt(s) and/or organometallic compounds, are responsible for the formation of the CNTs within the carbonized fiber upon heat treatment to elevated temperatures.
  • the precursor polymeric fibers carbon source and metal salt
  • the precursor compositions such as polyacrylonitrile, phthalonitriles, petroleum pitches, etc. and metal salts and/or organometallic compound are mixed and heated to cause the decomposition of the metal component into metal atoms, clusters, and/or metal nanoparticles (controlling the metal particle size to less than 25 nm).
  • the small metal nanoparticles are responsible for and catalyze the formation of the CNTs.
  • Large metal nanoparticles larger than 40 nm in size may afford graphite; thus it may be important to keep the metal catalyst at much smaller sizes. Stretching may help to align the molecules within the small diameter sized fibers and provides the basis for the formation of the tightly bonded carbon crystals after carbonization and the means for aligning the CNTs within the fibers.
  • Carbon nanotube fibers may be fabricated by injecting a solution of a precursor composition formulated from a carbon source-metal salt and/organometallic compound into a protic solvent such as water, by drawing from the melt of a B-staged thermoset resin at elevated temperatures or by conventional spinning techniques of a carbon precursor followed by carbonization of the polymeric fibers formed by the listed methods of preparation.
  • a protic solvent such as water
  • experiments have been conducted whereby fibers were drawn from the melt of a Fe2(CO)9/phthalonitrile precursor composition and by the deposition of a fiber into water from a solution of Fe2(CO)9/polyacrylonitrile (PAN) and a dipolar aprotic solvent.
  • the polymeric fibers were used in the direct formation of the carbon nanotube (MWNT) fibers by slowly heating to 1000°C under inert conditions.
  • MWNT carbon nanotube
  • any CNT precursor composition formulation from a carbon source and a metal salt(s) and/or organometallic compound that can be spun or drawn into a fiber and carbonized by the method can be converted into carbon nanotube fibers.
  • precursor materials such as PAN and petroleum pitches that are currently used to form carbon and graphitic fibers.
  • large diameter fibers and rods were formed from a phthalonitrile oligomer and PAN and converted into CNT large fibers and rods (see Fig. 1).
  • CNTs can occur directly from a mixture of a metal salt such as Fe2(CO)9, Co2(CO)8, and nickel(cyclooctadiene) and carbon sources such as PAN or phthalonitriles in a shaped composition including large diameter fibers and rods
  • these precursor compositions are suitable candidates to spin polymeric fibers that can be directly converted into MWNT-fibers during the carbonization process.
  • the fibers may also contain various quantities of magnetic metal nanoparticles depending upon the initial concentration of the metal salt(s) or organometallic compound(s) in the precursor composition.
  • the photographs show carbon nanotube fibers obtained from PAN (top) and phthalonitrile (bottom).
  • XRD x-ray diffraction
  • TEM transmission electron microscopy
  • the formation and heat treatment of the fibers may be similar to method known in the art for that of the same materials in the absence of the transition metal compound. A variety of such methods are described in US Provisional Application No. 61/301,279.
  • the resulting fiber may have at least 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70,
  • the CNTs may be generally aligned parallel with each other and the length of the fiber.
  • the fiber may also contain metal nanoparticles. However, if heated to a high enough temperature the metal nanoparticles may be removed. These properties also apply to nanofiber sheets.
  • CNT fibers Potential payoffs and impact areas of the CNT fibers include structural, motor/generator, energy (fuel cell electrodes, Li-batteries, hydrogen storage, and electricity carrier - electrically conductive carbon nanotubes), membrane for water purification, air filtration (toxin removal), and various catalytic applications.
  • energy fuel cell electrodes, Li-batteries, hydrogen storage, and electricity carrier - electrically conductive carbon nanotubes
  • membrane for water purification membrane for water purification
  • air filtration toxin removal
  • Metal nanoparticles also present in the fibers could be of importance for many of these applications.
  • Co 2 (CO) 8 50 mg, 0.146 mmol
  • PAN polyacrylonitrile
  • 10 mL of methylene chloride were added to a 50 mL round bottomed flask.
  • the Co 2 (CO)g readily dissolved in the methylene chloride.
  • the PAN did not dissolve.
  • the slurry was allowed to stir for 5 min before the solvent was removed under reduced pressure. The mixture was vacuum dried and isolated as an off-white solid.
  • Example 1 (22.8 mg) was heated in a TGA chamber under nitrogen at 10°C/min to 1000°C resulting in a shaped composition and a char yield of 36%.
  • the DTA curve showed an exotherm at 308°C.
  • X-ray studies confirmed the presence of carbon nanotubes-cobalt nanoparticles in the carbon composition.
  • the x-ray diffraction study showed the four characteristic reflection values [(002), (100), (004), and (110)] for carbon nanotubes and the pattern for fcc-cobalt nanoparticles.
  • the x-ray (002) reflection for carbon nanotubes was readily apparent.
  • Example 1 (21.5mg) was heated in a TGA chamber under nitrogen at 10°C/min to 1500°C resulting in a shaped composition and a char yield of 32%.
  • the DTA curve showed an exotherm at 310°C.
  • X-ray studies confirmed the presence of carbon nanotubes-cobalt nanoparticles in the carbon composition.
  • the x-ray diffraction study showed the four characteristic reflection values [(002), (100), (004), and (110)] for carbon nanotubes and the pattern for fcc-cobalt nanoparticles.
  • the x-ray (002) reflection for carbon nanotubes was readily apparent.
  • the x-ray diffraction study showed the four characteristic reflection values [(002), (100), (004), and (110)] for carbon nanotubes and the pattern for fcc-cobalt nanoparticles.
  • the x- ray (002) reflection for carbon nanotubes was readily apparent.
  • the x-ray diffraction studies showed the four characteristic reflection values [(002), (100), (004), and (110)] for carbon nanotubes and the pattern for fcc-cobalt nanoparticles.
  • the x-ray (002) reflection for carbon nanotubes was readily apparent.
  • compositions The x-ray diffraction studies showed the four characteristic reflection values [(002), (100), (004), and (110)] for carbon nanotubes and the pattern for bcc-iron nanoparticles. The x-ray (002) reflection for carbon nanotubes was readily apparent.
  • the x-ray diffraction studies showed the four characteristic reflection values [(002), (100), (004), and (110)] for carbon nanotubes and the pattern for fcc-cobalt nanoparticles.
  • the x-ray (002) reflection for carbon nanotubes was readily apparent.
  • the drawn fibers were cured or solidified by heating at 280°C for 12 hr, 300°C for 2 hr, 350°C for 3 hr, and 375°C to form a thermoset fiber, which was carbonized by heating at 2°C/min in a flow of nitrogen. Drawing the fibers at 325°C permitted the retention of shape during the curing process.
  • the x-ray diffraction and transmission electron microscopy (TEM) studies showed the presence of carbon nanotubes within the fibers.
  • the shaped composition was cooled and a sample (84.65 mg) was heated under nitrogen at 10°C/min to 1000°C resulting in a char yield of 67%.
  • the DTA curve showed exotherms at 530 and 751°C.
  • X-ray studies confirmed the presence of carbon nanotubes-cobalt nanoparticles in the carbon composition.
  • the x-ray diffraction studies showed the four characteristic reflection values [(002), (100), (004), and (110)] for carbon nanotubes and the pattern for fcc-cobalt nanoparticles.
  • the x-ray (002) reflection for carbon nanotubes was readily apparent.
  • the shaped composition was cooled and a sample (65.24 mg) was heated under nitrogen at 10°C/min to 1000°C resulting in a char yield of 67%.
  • the DTA curve showed exotherms at 530 and 751°C.
  • X-ray studies confirmed the presence of carbon nanotubes-cobalt nanoparticles in the carbon composition.
  • the x-ray diffraction studies showed the four characteristic reflection values [(002), (100), (004), and (110)] for carbon nanotubes and the pattern for fcc-cobalt nanoparticles.
  • the x-ray (002) reflection for carbon nanotubes was readily apparent.
  • the drawn fibers were cured or solidified by heating at 280°C for 12 hr, 300°C for 2 hr, 350°C for 3 hr, and 375°C for 4 hr to form a thermoset fiber, which was carbonized by heating at 2°C/min in a flow of nitrogen. Drawing the fibers at 325°C permitted the retention of shape during the curing process, which was initiated at a lower temperature (270 °C) so that the fiber would retain its solid shape while curing to a thermoset fiber.
  • TEM transmission electron microscopy
  • X-ray studies confirmed the presence of carbon nanotubes-cobalt nanoparticles in the carbonized fibers/rods.
  • the x-ray diffraction studies showed the four characteristic reflection values [(002), (100), (004), and (110)] for carbon nanotubes and the pattern for fcc-cobalt nanoparticles.
  • the x-ray (002) reflection for carbon nanotubes was readily apparent.
  • the phthalonitrile (1.00 g, 1.12 mmol) was dissolved in 25 mL of methylene chloride in a 50 mL round bottomed flask.
  • Ni[COD] 2 (27.5 mg, 0.100 mmol) dissolved in 2 mL of methylene chloride was added dropwise and a brown precipitate formed. The solvent was removed under reduced pressure, the mixture vacuum was dried, and the mixture was isolated as a dark brown solid.
  • Example 31 Samples of the mixture from Example 29 (45.92 mg and 35.43 mg) were heated at 10°C/min to 1100°C and to 1400°C in a TGA chamber under nitrogen resulting in shaped components to afford char yields of 30%> and 27%, respectively.
  • X-ray studies confirmed the presence of carbon nanotubes-cobalt nanoparticles in the carbon compositions.
  • the x-ray diffraction studies showed the four characteristic reflection values [(002), (100), (004), and (110)] for carbon nanotubes and the pattern for fcc-cobalt and cobalt oxide nanoparticles.
  • the x-ray (002) reflection for carbon nanotubes was readily apparent.
  • the polymeric fibers were heat treated at 200°C for 2 hr, 250°C for 12 hr in air and 300°C for 4 hr, 350°C for 2 hr and 375°C for 4 hr under argon.
  • Different fibers were then carbonized by heating under nitrogen to 1000°C and to 1500°C at 0.3°C/min and holding for 1 hour to produce CNT-containing fibers. Higher yield of CNTs were obtained for the higher temperature treated fibers. It was important that the fibers be initially heated at a temperature below the temperature of the melt so as to convert to a solid thermoset before heat treatment to higher temperatures.
  • Different polymeric fibers were then carbonized by heating under nitrogen to 1000°C and to 1500°C, respectively at 0.3°C/min, and holding for 1 hour to produce in situ CNT-containing fibers. Higher yield of CNTs were obtained for the higher temperature treated fibers.
  • the polymeric nanofiber sheets of Example 43 were oxidatively stabilized by heating at 1.5°C/min to 260°C and holding at this temperature for 3-5 hr in a flow of air followed by rapid heating (5°C/min) to 300°C followed by cooling.
  • the color of the sheets changed from off white to a dark tan color.
  • Oxidative stabilization of sample (film) formulated from 1/20 by weight
  • the polymeric nanofiber sheets of Example 50 are oxidatively stabilized by heating at 1.5°C/min to 230-260°C and holding at the temperature for 3- 5 hr in a flow of air followed by rapid heating (5°C/min) to 300°C followed by cooling.
  • the color of the sheets is expected to change from off white to a dark color.
  • Samples of the carbon nanotube-nano fiber carbon sheets of Example 52 are further heated at 5°C/min to 1500°C and held at this temperature for 2 hr under a flow of nitrogen.
  • X-ray diffraction studies are expected to show a large 002 peak at about 25.83 and the peak attributed to the amorphous carbon is expected to be greatly diminished. This study is expected to show that the amount of carbon nanotubes within the nanofibers can be controlled as a function of the heat treatment temperature.
  • the fibers/tows were heated from room temperature to 250°C at l°C/min in a flow of air; dwell time at 250°C was for 5 hr followed by heating at l°C/min to 300°C and then cooling back to room temperature. During the heat treatment, the fibers changed in color from light yellow- brown to amber to dark brown to black.
  • Carbonization of the oxidatively stabilized Fe-Pan fibers at 1300°C - Oxidatively stabilized fibers of Example 56 were mounted onto a graphite rack system and carbonized in a graphitic furnace in inert gas (helium).
  • the stabilized fibers were heated under a constant tension from room temperature to 1300°C at 10°C/min and allowed to dwell at 1300°C for 1 hr followed by cooling back to room temperature at 50°C/min.
  • the fibers had weight retention of 49.39%. Scanning electron microscopy studies of the black fibers showed the presence of carbon nanotubes within the fibers that had been formed in situ within the fibers during the
  • Graphitization of the oxidatively stabilized Fe-Pan fibers at 2700°C - Oxidatively stabilized fibers of Example 56 were mounted onto a graphite rack system and graphitized in a graphitic furnace in inert gas (helium).
  • the stabilized fibers were heated under a constant tension from room temperature to 1300°C at 10°C/min and allowed to dwell at 1300°C for 1 hr followed by heating at 50°C/min to 2700°C and dwelling at 2700°C for 1 hr and cooling back to room temperature at 50°C/min.
  • the fibers had weight retention of 47.77%.
  • Scanning electron microscopy studies of the black fibers showed the presence of carbon nanotube within the fibers that had been formed in situ within the fibers during the carbonization and graphitization processes; the carbon nanotubes were mostly aligned along the direction of the fibers.
  • Formulation of wt.% solutions in DMAC from 1/20 by weight Co 2 (CO) 8 /PAN mixture - Varying wt.% polymeric solutions in DMAC were prepared using the Co 2 (CO)g/PAN mixture of Example 42 and thoroughly mixed by heating at 120°C for 1 hr.
  • the fibers/tows are heated from room temperature to 250°C at l°C/min in a flow of air; dwell time at 250°C is for 5 hr followed by heating at l°C/min to 300°C and then cooling back to room temperature. During the heat treatment, the fibers/tows are expected to change in color from off-white to amber to dark brown to black.
  • Carbonization of the oxidatively stabilized Co-Pan fibers at 1300°C - Oxidatively stabilized fibers/tows of Example 61 are mounted onto a graphite rack system and carbonized in a graphitic furnace in inert gas (helium).
  • the stabilized fibers/tows are heated under a constant tension from room temperature to 1300°C at 10°C/min and allowed to dwell at 1300°C for 1 hr followed by cooling back to room temperature at 50°C/min.
  • Scanning electron microscopy studies of the black fibers are expected to show the presence of carbon nanotube within the fibers formed in situ within the fibers during the carbonization process with the carbon nanotubes mostly aligned along the direction of the fibers based on the results of Example 49. Transmission electron microscopy studies should show the presence of carbon nanotubes and Co nanoparticles within the fibers as in Example 57.
  • Graphitization of the oxidatively stabilized Co-Pan fibers at 2700°C - Oxidatively stabilized fibers of Example 61 are mounted onto a graphite rack system and graphitized in a graphitic furnace in inert gas (helium).
  • the stabilized fibers are heated under a constant tension from room temperature to 1300°C at 10°C/min and allowed to dwell at 1300°C for 1 hr followed by heating at 50°C/min to 2700°C and dwelling at 2700°C for 1 hr and cooling back to room temperature at 50°C/min.
  • metal salt/naphthalene-derived mesophase pitch (AR pitch resin by Mitsubishi) mixture -
  • Various concentrations of metal salts and/or organometallic compounds/resins such as octacarbonyldicobalt, diironnonacarbonyl, and ferrocene-based materials are mixed with AR pitch resin.
  • the metal salt-AR pitch resin composition are thoroughly mixed in powdered form and heated at an elevated temperature above where the AR pitch resin flows with stirring by mechanical means under inert condition to homogeneously mix. These samples are then cooled to room temperature.
  • Spinning of fibers from 1/20 by weight Co 2 (COVAR pitch resin mixture - A sample of 1/20 by weight Co 2 (CO)g/AR pitch resin mixture of Examples 33 and 64 is used to spin fiber at 300-370°C through a spinneret. The fibers/filament passes through a nitrogen atmosphere as they leave the spinneret and before being taken up by a reel.
  • Carbonization of the mesophase AR pitch fibers derived from Co 2 (COVAR pitch resin mixture - AR pitch thermosetting fibers produced by Example 66 are carbonized by heating up to 2000°C in an inert (helium) atmosphere and holding from 5-30 min. Carbon nanotubes are expected to grow in situ within the fibers along with other carbonaceous materials. As carbon nanotubes were observed in Examples 34 and 35 on solid sample and fibers pulled from the melt and carbonized under similar conditions, fibers formed by this procedure using a spinneret (Example 65) should contain carbon nanotubes with the yield dependent on the carbonization temperature. X-ray diffraction, scanning electron microscopy, and transmission electron microscopy studies are used to analyze the fibers for the carbon nanotubes.
  • a sample of 1/20 by weight Fe 2 (CO) 9 /AR pitch resin mixture of Example 64 is used to spin fibers at 300-370°C through a spinneret.
  • the fibers/filaments pass through a nitrogen atmosphere as they leave the spinneret and before being taken up by a reel.
  • Fe 2 (CO)9/AR pitch resin mixture - AR pitch fibers produced by Example 68 are stabilized to a thermoset by heating between 250-350°C in an air atmosphere for 5-60 min.
  • the fibers are oxidatively heated so that they will not soften when heated to carbonization and the fibers should be totally infusible so they will not sag during carbonization.
  • Carbonization of the mesophase AR pitch fibers derived from Fe 2 (CO)9/AR pitch resin mixture - AR pitch thermosetting fibers produced by Example 69 are carbonized by heating up to 2000°C in an inert (helium) atmosphere and holding from 5-30 min. Carbon nanotubes are expected to grow in situ within the fibers along with other carbonaceous materials. As carbon nanotubes were observed in Examples 34 and 35 on solid sample and fibers pulled from melt and carbonized under similar conditions, small diameter fiber formed by this procedure should also have carbon nanotubes with the yield dependent on the carbonization temperature. X-ray diffraction, scanning electron microscopy, and transmission electron microscopy studies are used to analyze the fibers for the carbon nanotubes.

Abstract

L'invention concerne un procédé consistant : à fournir un mélange d'un polymère ou d'une résine et d'un composé de métal de transition, à produire une fibre à partir du mélange, et à chauffer la fibre dans des conditions efficaces pour former une fibre carbonée contenant des nanotubes de carbone. Le polymère ou la résine est un polymère aromatique ou un précurseur correspondant et le mélange est un mélange pur ou est combiné avec un solvant. L'invention concerne également une fibre carbonée ou une feuille de nanofibre carbonée ayant au moins 15 % en poids de nanotubes de carbone, une fibre ou feuille de nanofibre ayant le polymère ou la résine et le composé de métal de transition, et une fibre ou feuille de nanofibre ayant un polymère aromatique et des nanoparticules de métal.
PCT/US2011/023692 2010-02-04 2011-02-04 Fibres/filaments de nanotubes de carbone formulés à partir d'un catalyseur de nanoparticule en métal et d'une source de carbone WO2011097441A1 (fr)

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US12/911,117 US9085720B2 (en) 2004-12-22 2010-10-25 Highly aromatic compounds and polymers as precursors to carbon nanotube and metal nano particle compositions shaped solids

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CN111589463A (zh) * 2020-03-10 2020-08-28 上海电力大学 一种碳化铁复合一氧化钛的纳米颗粒光热催化剂及其制备

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