GB2399092A - Nanotube and/or nanofibre synthesis - Google Patents
Nanotube and/or nanofibre synthesis Download PDFInfo
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- GB2399092A GB2399092A GB0304826A GB0304826A GB2399092A GB 2399092 A GB2399092 A GB 2399092A GB 0304826 A GB0304826 A GB 0304826A GB 0304826 A GB0304826 A GB 0304826A GB 2399092 A GB2399092 A GB 2399092A
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- porous matrix
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- 239000002071 nanotube Substances 0.000 title claims abstract description 32
- 239000002121 nanofiber Substances 0.000 title description 8
- 230000015572 biosynthetic process Effects 0.000 title description 4
- 238000003786 synthesis reaction Methods 0.000 title description 3
- 239000011159 matrix material Substances 0.000 claims abstract description 61
- 239000003054 catalyst Substances 0.000 claims abstract description 33
- 238000000034 method Methods 0.000 claims abstract description 32
- 239000000463 material Substances 0.000 claims abstract description 14
- 239000000919 ceramic Substances 0.000 claims abstract description 10
- 238000009792 diffusion process Methods 0.000 claims abstract description 5
- 238000003421 catalytic decomposition reaction Methods 0.000 claims abstract description 4
- 239000000446 fuel Substances 0.000 claims abstract description 4
- 238000004806 packaging method and process Methods 0.000 claims abstract description 4
- 239000003575 carbonaceous material Substances 0.000 claims abstract 5
- 239000002131 composite material Substances 0.000 claims description 35
- 239000004744 fabric Substances 0.000 claims description 20
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- 239000000725 suspension Substances 0.000 claims description 8
- 238000000354 decomposition reaction Methods 0.000 claims description 3
- 239000012018 catalyst precursor Substances 0.000 claims 6
- -1 nanofibres Substances 0.000 claims 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 45
- 239000002041 carbon nanotube Substances 0.000 abstract description 21
- 229910021393 carbon nanotube Inorganic materials 0.000 abstract description 20
- 239000007789 gas Substances 0.000 abstract description 7
- 239000001257 hydrogen Substances 0.000 abstract description 3
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 abstract description 2
- 239000005977 Ethylene Substances 0.000 abstract description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 2
- 238000002844 melting Methods 0.000 abstract description 2
- 230000008018 melting Effects 0.000 abstract description 2
- 239000000376 reactant Substances 0.000 abstract 1
- 229910052799 carbon Inorganic materials 0.000 description 24
- 239000000758 substrate Substances 0.000 description 15
- 239000000835 fiber Substances 0.000 description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- 239000002245 particle Substances 0.000 description 8
- 238000001000 micrograph Methods 0.000 description 6
- 238000005334 plasma enhanced chemical vapour deposition Methods 0.000 description 5
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 description 5
- 239000011148 porous material Substances 0.000 description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 238000011068 loading method Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- 229910001111 Fine metal Inorganic materials 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000010891 electric arc Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical group 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000002923 metal particle Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 238000009834 vaporization Methods 0.000 description 2
- 230000008016 vaporization Effects 0.000 description 2
- 101100173048 Mus musculus Mcat gene Proteins 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 238000007233 catalytic pyrolysis Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004581 coalescence Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000004320 controlled atmosphere Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000004050 hot filament vapor deposition Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 229910052914 metal silicate Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000002230 thermal chemical vapour deposition Methods 0.000 description 1
Classifications
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- 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
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
-
- 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
- C01B32/162—Preparation characterised by catalysts
-
- 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
- C04B35/83—Carbon fibres in a carbon matrix
-
- 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
- D01F9/127—Carbon filaments; Apparatus specially adapted for the manufacture thereof by thermal decomposition of hydrocarbon gases or vapours or other carbon-containing compounds in the form of gas or vapour, e.g. carbon monoxide, alcohols
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F41—WEAPONS
- F41H—ARMOUR; ARMOURED TURRETS; ARMOURED OR ARMED VEHICLES; MEANS OF ATTACK OR DEFENCE, e.g. CAMOUFLAGE, IN GENERAL
- F41H5/00—Armour; Armour plates
- F41H5/02—Plate construction
- F41H5/04—Plate construction composed of more than one layer
- F41H5/0471—Layered armour containing fibre- or fabric-reinforced layers
- F41H5/0485—Layered armour containing fibre- or fabric-reinforced layers all the layers being only fibre- or fabric-reinforced layers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/745—Iron
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- B01J35/58—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/343—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of ultrasonic wave energy
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- 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
- 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
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/40—Metallic constituents or additives not added as binding phase
- C04B2235/405—Iron group metals
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- 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
- 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
- C04B2235/5208—Fibers
- C04B2235/526—Fibers characterised by the length of the fibers
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- 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
- 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
- C04B2235/5208—Fibers
- C04B2235/5264—Fibers characterised by the diameter of the fibers
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- 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
- 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
Abstract
A method of producing nanotubes and/or nanofibres by the catalytic decomposition of a gas feedstock on a catalyst is disclosed is characterised in that the catalyst is impregnated and dispersed within a porous matrix. The porous matrix may be fibrous, a carbon based material, a ceramic based material or polymeric. The nanotubes/nanofibres may be removed from the matrix by dissolving, reacting, melting or vaporisisng. The carbon nanotubes are grown using ethylene and hydrogen as reactants. The product formed finds use as a filter, a heat spreader, packaging, a gas diffusion layer for a fuel cell, and on electromagnetic shield.
Description
Agent's Ref BP-09-0312 2399092 NANOTUBE AND/OR NANOFIBRE SYNTHESIS This
invention relates to the production of nanotubes and/or nanofibres by the decomposition of gases on a substrate. The invention further relates to the nanotubes and/or nanofibres produced, and to novel composite materials comprising the nanotubes and/or nanofibres with the substrate.
The carbon nanotubes (CNTs), originally reported by lijima[] in 1991, were synthesized in a carbon arc-discharge. Since then, other authors have reported the growth of CNTs from an arc-discharge L2 33 and other methods have been developed to synthesize nanotubes. CNTs have also been produced by vaporization processes using lasers[4 5], electron beams[6] and solar energy [7]. Catalytic pyrolysis and chemical vapour deposition of hydrocarbons[8 9] are now widely used for carbon nanotube growth as simple and cl'l'icient methods. In addition to CNTs, similar methods have been used for the synthesis of carbon nanofibres (CNFs), also known as carbon filaments since the early 1950'sLi I. CNFs can be grown using catalytic decomposition of hydrocarbons over transition metal particles such as iron, cobalt, nickel, and their alloys at temperatures ranging from 500 to 1000 C Lad. A microwave plasma enhanced chemical vapour deposition (PECVD) process, used for the preparation of diamond and diamond-like carbon films, has been recently developed successfully for the growth of CNTs and CNFs['2-'7]. Recently the first evidence of carbon nanofibres growth at room temperature using radio frequency PECVD (r.f.
PECVD)[X] have been published. Nanotubes and nanofibres need not be of carbon alone and various other elements (e.g. boron) have been incorporated into nanotubes and nanofibres.
The most efficient of the known methods give growth of CNT and CNF using fine transition metal catalyst particles. Efficiency of the synthesis method is determined by the efficiency of the process of formation of small metal catalyst domains acting as nucleation seeds for CNT or CNF growth.
Agent's Ref BP-09-0312 It is known that the metal catalysts can be deposited on a substrate. For example, WO01/85612 is directed to a method in which the catalyst is deposited on a porous carbon substrate, which is then electrically heated while feedstoek gases are passed over the substrate. WOOI/85612 discloses a number of processes for depositing the catalyst onto a substrate including: 1) Producing a metal silicate gel, soaking carbon paper in the gel, and drying the paper to produce a carbon paper with a silicate containing iron catalyst particles deposited on the paper.
2) A suspension of fine metal particles is sprayed onto the carbon paper.
3) The fine catalyst particles are produced in a hollow cathode discharge apparatus 4) The method 3) used in conjunction with a plasma to prevent coalescence of the particles as they are discharged from the cathode.
All of these methods result in the catalyst particles being distributed on the surface of the carbon paper.
The inventor has found that when the catalyst is impregnated and dispersed within a fibrous matrix, rather than being left on the surface, a more efficient deposition of nanofibres and/or nanotubes results. Dispersion of the catalyst throughout the fibrous matrix appears to make the catalyst more active than when simply applied to the surface of a substrate. The inventors hypothesise, without wishing to be bound by this hypothesis, that dispersion within a fibrous matrix prevents agglomeration of the fine metal catalyst particles and so leads to a greater effective amount of catalyst being present. Alternatively, it may be that growth within a fibrous matrix present particularly good diffusion conditions for the feedstock gases.
The scope of the invention is as set out in the claims in the light of the following illustrative description with reference to the figures in whieh: Figs. I a and lb are micrographs of a carbon cloth substrate Fig. 2 is a micrograph of a ceramic paper substrate Fig. 3 is a micrograph showing nanofibre and nanotube growth within a carbon substrate Agent's Ref BP-09-0312 Figs. 4a and 4b are micrographs showing nanofibre and nanotube growth within the carbon cloth substrate of Figs. Ia and lb. Fig 5. is a micrograph showing nanofibre and nanotube growth within the carbon cloth substrate of Figs. 1 a and 1 b.
Figs. 6a and 6b. are micrographs showing nanofibre and/or nanotube growth inside the ceramic paper substrate of Fig. 2 In the following description reference is made throughout to carbon nanofibres and carbon nanotubes. The same principles can be applied to doped nanofibres and nanotubes (e.g. nanofibres or nanotubes containing boron).
Carbon and ceramic cloth and paper matrix were used to demonstrate the efficient CNT growth using a thermal CVD method.
Catalyst and substrate preparation Fine iron powder catalyst (6-8 rim in diameter) obtained from Goodfellow Ltd. Cambridge, UK was firstly dispersed in isopropanol (IPA) using an ultrasonic bath for 20-30 min. Then 2.5 mm thick VCL N carbon cloth, obtained from Morgan Speciality Graphite, Fostoria, OH, USA (Fig. 1) with pore size greater than approximately 50 x 50 m; or 3 mm thick ceramic paper with pore sizes greater then approximately 10 x 10 1lm, obtained from IsoDrax (Fig. 2) were soaked in the suspension and left in the ultrasonic bath for 30 min. The samples were then dried producing a fibrous matrix with an impregnated finely dispersed metal powder.
Nanofibre/nanotube production A tube furnace with controlled atmosphere was used.
Agent's Ref BP-09-0312 In order to evacuate the air Ar was introduced into the furnace with 300 scorn flow rate for 25 min. To reduce the impregnated metal powder catalyst hydrogen was next introduced into the furnace with 200 seem flow for 120 min at 450 "C. Carbon nanotubes and nanofibres were grown using ethylene (800 sccm) and hydrogen (200sccm) mixture at 650 C for 2 hours. After that the furnace was cooled down in Ar flow (200 sccm).
Synthesised carbon nanotubes and nanofibres have variation of diameters from approximately 10 rim to 150 nm and length of few microns (Fig. 3). According to the SEM examination it was observed that almost all iron powder was transformed into the seeds for carbon nanotubes and nanofibres growth. The nanotubes/nanofibres are produced in clumps originating from the surface of the catalyst particles. Catalyst particles were observed on the tip of CNF indicating the tip growth models'].
Examples of carbon nanotubes successfully grown inside carbon cloth are illustrated in Figs. 4 and 5, and inside ceramic paper in Fig. 6.
The amount of fibre produced could be controlled using variation of catalyst loading.
Very high density of CNT and CNF growth inside carbon cloth was illustrated in Fig. 4, which used O.Olg of Fe powder 6-8 microns in diameter in a 2 x 2cm sample of carbon cloth. (2.5mg/cm2).
When 0.1 g of fine iron powder was dispersed in 20 x 20 cm carbon cloth (0.25mg/cm2), 2.1 g of carbon nanotubes/nanofibres were produced (Fig.5) a yield of 2000%.
(Carbon nanotube yield was calculated using the formula CNT yield (%) =loox(mcNJ-mcAr)lmcAT where mCN is the mass of carbon nanotubes in the final product, and mCAT is the mass of the catalyst inside the fibre matrix after impregnation. Similar yield calculations are used in the literatures]).
Agent's Ref BP-09-0312 This corresponded to about 14% by weight nanotubcs/nanofibres in the cloth based upon the weight of cloth plus nanotoubes/nanofibre. The best yield the inventor has heard rumour of is 600%, although the best he is aware of in the written literature is 120% [9].
Efficient CNT growth was achieved, although density of CNT growth for a small catalyst loading (Fig. 5) was not very high comparing with the example illustrated in Fig. 4. Even with the smaller loading (Fig. 5) tensile strength of the cloth with CNT was increased by approximately 1() %, thermal conductivity by 18% and thermal diffusivity by 11%. It is expected that improvement of mechanical, electrical and thermal properties would be higher with higher CNT growth density.
Carbon nanotubes growth could however also be achieved inside any thermally sensitive fibre matrix (e.g polymer or organic fibre matrix) if r.f. PECVD method is used for CNF growth as described in ref. 18. Carbon nanotubes or nanofibres grown inside the fibre matrix could be extracted using high gas flow, or if the substrate fibre is suitable, by dissolution, reaction, melting, vaporization, or otherwise removal of the fibre matrix.
Composite materials with carbon nanotubcs and/or nanofibres grown inside a fibre matrix could be used as filter materials, where filter pore size is controlled by the density of the carbon nanotubes/nanofibres grown inside the fibre matrix. Very dense material, similar to that shown in Fig. 4a, could be used for big-hazard filters where small pore size is of extreme importance. Very dense materials with a lot of carbon nanotubes are expected to also have extremely good mechanical properties which can be used as a reinforcement and even bullet-proof materials.
The high thermal conductivity of these materials may be of use in automotive and aerospace applications and for heat distribution or hot spot control. The high electrical conductivity of these materials could be used for example in electronic components packaging, as gas diffusion layers in fuel cells, as electromagnetic shielding, as oxygen sensors (the rcsistivity of carbon nanotubes has been shown to vary with oxygen concentrations]). This method could be further developed for production of Agent's Rcf BP-09-03 12 carbon nanotube based sensing devices inside the fabric. This fabric can then be used as a layer inside smart' big- hazard and bullet-proof unifonns.
A composite cloth comprising a porous or fibrous matrix filled with nanofibres and/or nanotubes can be used in the production of rigid composite articles, e.g. by layering and impregnating with polymers to form a continuous polymeric phase filling the porosity of the porous material. Methods of donning such polymer-cloth composites are well known in relation to carbon fibrc and glass fibre composite materials.
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[2] T.W. Ebbesen, and P.M. Ajayan, Nature, 358 (1992) 220.
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Kim, D.T. Colbert, G. Scuseria, D. Tomanek, J.ES. Fisher, and R.E. Smalley, Science, 273 (1996) 483.
[5] A. M. Rao, E. Richer, S. Bandow, B. Chase, P.C. Eklund, K.A. Williams, S. Fang, K.R. Subbaswamy, M. Menon, A. Thess, R.E. Smalley, G. Dresselhaus, and M.S. Dresselhaus, Science, 275 (1997) I X7.
[6] L.A. Chernozitonskii, Z. Ja, Kosakovskaja, E.A. Federov, and V.l. Panov, Phys. Lett. A, 197 (1995) 40; Z. Ja. Kozavskaja, L.A. Chernozatonskii and E.A. Federov, Nature, 359 (1992) 670.
[7] D. Laplaze, P. Bernuer, W.R. Maser, G. Flament, and T. Guillard, Carbon, 36 (1998) 681.
[8] S. Amclinckx et ah, sciences 256 (1994) 678; M. Endo, et al., J. Phys. Chem. Solids, 54 (1993) 1841.
[9] M-J Yacaman, M. Miki-Yoshida, L. Rendon, and J.G. Santiesteban, Appl. Phys. Lett. 62 (1993) 657; A.M. Benito, Y Maiette, E. Munoz, and M.T. Matinez, Carbon, (1998) 681.
[10] Davis WR, Slawson RJ, Rigby GR,.Vature, 171 (1953) 756.
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Claims (22)
1. A method of producing nanotubes and/or nanofibres by the catalytic decomposition of a gas feedstock on a catalyst, in which the catalyst is impregnated and dispersed within a porous matrix.
2. A method, as claimed in Claim 1, in which the porous matrix is a fibrous matrix.
3. A method, as claimed in Claim I or Claim 2, in which the catalyst is fonned within the porous matrix by decomposition of a catalyst precursor.
4. A plethoras claimed in any one of Claims I to 3, in which: a) the catalyst or catalyst precursor is prepared as a suspension or solution b) the porous matrix is placed in the suspension or solution c) the porous matrix and suspension are agitated ultrasonically to impregnate and disperse the catalyst or catalyst precursor within the fibrous matrix.
5. A method, as claimed in any one of Claims I to 4, in which the porous matrix is a carbon based material.
6. A method, as claimed in any one of Claims I to 4, in which the porous matrix is a ceramic based material.
7. A method, as claimed in any one of Claims I to 4, in which the porous matrix is a polymeric material.
8. A method, as claimed in any one of Claims I to 7, in which the nanofibres and/or nanotubes are removed from the porous matrix.
9. A method, as claimed in Claim 8, in which the porous matrix is dissolved, reacted, melted, vaporised, or otherwise removed to leave the nanotubes or nanofibres. l
Agent's Ref BP-09-0312
I 0. A composite material comprising a porous matrix and nanotubes/nanofibres grown within the porosity of the porous matrix.
11. A composite material, as claimed in Claim 10, in which the porous matrix is a fibrous matrix
12. A composite material, as claimed in Claim 10 or Claim 1 1, comprising a porous matrix and >10% by weight nanofibres and/or nanotubes based on the weight of porous matrix, nanofibres, and nanotubes.
13. A composite material, as claimed in any one of Claims 10 to 12, in which the porous matrix is a fibrous matrix.
14. A composite material,asclaimedin any one ofClaims into 13,inwhichthe porous matrix is a carbon based material.
15. A composite material, as claimed in any one of Claims 10 to 13, in which the porous matrix is a ceramic based material.
16. A composite material, as claimed in any one of Claims 10 to 13, in which the porous matrix is a polymeric material.
17. A composite material, as claimed in any one of Claims 10 to 13, additionally comprising a continuous polymeric phase.
18. A cloth comprising the composite material of any of Claims 10 to 16.
19. A filter comprising the composite material of any of Claims 10 to 16.
20. A fabric reinforced with the composite material of any of Claims 10 to 16.
21. A gas diffusion layer for a fuel cell, comprising the composite material of any of Claims 9 to 14.
Agent's Ref BP-09-03 12 l3
22. An electromagnetic shield comprising the composite material of any of Claims 9to 15.
21. A heat spreader comprising the composite material of any of Claims 10 to 16.
Agenl's Rcf BP-09-03 12 22. Packaging for electrical components comprising the composite material of any of Claims lOto 16.
23. A gas diffusion layer for a fuel cell, comprising the composite material of any of Claims 10 to 16.
24. An electromagnetic shield comprising the composite material of any of Claims to 17.
Amendments to the claims have been filed as follows
AC !1
1. A method of producing nanotubes and/or nanofibres by the catalytic decomposition of a gas feedstock on a catalyst, in which the catalyst is impregnated and dispersed within a porous matrix which is a fibrous matrix.
2. A method, as claimed in Claim 1, in which the catalyst is Donned within the porous matrix by decomposition of a catalyst precursor.
3. A method, as claimed in Claim 1 or Claim 2, in which: a) the catalyst or catalyst precursor is prepared as a suspension or solution b) the porous matrix is placed in the suspension or solution c) the porous matrix and suspension are agitated ultrasonically to impregnate and disperse the catalyst or catalyst precursor within the fibrous matrix.
4. A method, as claimed in any one of Claims 1 to 3, in which the porous matrix is a carbon based material.
5. A method, as claimed in any one of Claims 1 to 3, in which the porous matrix is a ceramic based material.
6. A method, as claimed in any one of Claims 1 to 3, in which the porous matrix is a polymeric material.
7. A method, as claimed in any one of Claims 1 to 6, in which the nanofibres and/or nanotubes are removed from the porous matrix.
8. A method, as claimed in Claim 7, in which the porous matrix is dissolved, reacted, melted, vaporised, or otherwise removed to leave the nanotubes or nanofibres.
9. A composite material comprising a porous matrix which is a fibrous matrix and nanotubes/nanofibres grown within the porosity of the porous matrix.
Agent's Ref BP-09-0312 10. A composite material, as claimed in Claim 9, comprising a porous matrix and > 10% by weight nanofibres and/or nanotubes based on the weight of porous matrix, nanobbres, and nanotubes.
A composite material, as claimed in any one of Claims 9 to 10, in which the porous matrix is a fibrous matrix.
12. A composite material, as claimed in any one of Claims 9 to 11, in which the porous matrix is a carbon based material.
13. A composite material, as claimed in any one of Claims 9 to I 1, in which the porous matrix is a ceramic based matenal.
14. A composite material, as claimed in any one of Claims 9 to 11, in which the porous matrix is a polymeric material.
15. A composite material, as claimed in any one of Claims 9 to 1 1, additionally comprising a continuous polymeric phase.
16. A cloth comprising the composite material of any of Claims 9 to 14.
17. A filter comprising the composite material of any of Claims 9 to 14.
18. A fabric reinforced with the composite material of any of Claims 9 to 14.
19. A heat spreader comprising the composite material of any of Claims 9 to 14.
20. Packaging for electrical components comprising the composite material of any of Claims 9 to 14.
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GB0304826A GB2399092B (en) | 2003-03-03 | 2003-03-03 | Nanotube and/or nanofibre synthesis |
PCT/GB2004/000866 WO2004078649A1 (en) | 2003-03-03 | 2004-03-02 | Synthesis of carbon nanotubes and / or nanofibres on a porous fibrous matrix |
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GB0304826A GB2399092B (en) | 2003-03-03 | 2003-03-03 | Nanotube and/or nanofibre synthesis |
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GB2399092B GB2399092B (en) | 2005-02-16 |
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WO (1) | WO2004078649A1 (en) |
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WO2004078649A1 (en) | 2004-09-16 |
GB0304826D0 (en) | 2003-04-09 |
GB2399092B (en) | 2005-02-16 |
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