GB2399092A - Nanotube and/or nanofibre synthesis - Google Patents

Nanotube and/or nanofibre synthesis Download PDF

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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
composite material
nanotubes
catalyst
matrix
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GB2399092B (en
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Bojan Boskovic
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Morgan Crucible Co PLC
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Morgan Crucible Co PLC
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    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/63Preparing 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
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00Nanotechnology for materials or surface science, e.g. nanocomposites
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00Manufacture or treatment of nanostructures
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00Carbon; Compounds thereof
    • C01B32/15Nano-sized carbon materials
    • C01B32/158Carbon nanotubes
    • C01B32/16Preparation
    • C01B32/162Preparation characterised by catalysts
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/71Ceramic products containing macroscopic reinforcing agents
    • C04B35/78Ceramic products containing macroscopic reinforcing agents containing non-metallic materials
    • C04B35/80Fibres, filaments, whiskers, platelets, or the like
    • C04B35/83Carbon fibres in a carbon matrix
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01FCHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F9/00Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
    • D01F9/08Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
    • D01F9/12Carbon filaments; Apparatus specially adapted for the manufacture thereof
    • D01F9/127Carbon 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
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F41WEAPONS
    • F41HARMOUR; ARMOURED TURRETS; ARMOURED OR ARMED VEHICLES; MEANS OF ATTACK OR DEFENCE, e.g. CAMOUFLAGE, IN GENERAL
    • F41H5/00Armour; Armour plates
    • F41H5/02Plate construction
    • F41H5/04Plate construction composed of more than one layer
    • F41H5/0471Layered armour containing fibre- or fabric-reinforced layers
    • F41H5/0485Layered armour containing fibre- or fabric-reinforced layers all the layers being only fibre- or fabric-reinforced layers
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74Iron group metals
    • B01J23/745Iron
    • B01J35/58
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/34Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
    • B01J37/341Irradiation 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
    • B01J37/343Irradiation 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
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30Constituents and secondary phases not being of a fibrous nature
    • C04B2235/40Metallic constituents or additives not added as binding phase
    • C04B2235/405Iron group metals
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    • C04B2235/00Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/50Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
    • C04B2235/52Constituents or additives characterised by their shapes
    • C04B2235/5208Fibers
    • C04B2235/526Fibers characterised by the length of the fibers
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/50Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
    • C04B2235/52Constituents or additives characterised by their shapes
    • C04B2235/5208Fibers
    • C04B2235/5264Fibers characterised by the diameter of the fibers
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/50Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
    • C04B2235/52Constituents or additives characterised by their shapes
    • C04B2235/5284Hollow fibers, e.g. nanotubes
    • C04B2235/5288Carbon 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.
References [1] S. Iijima, Nature, 354 (1991) 56.
[2] T.W. Ebbesen, and P.M. Ajayan, Nature, 358 (1992) 220.
[3] P.M. Ajayan, and S. Iijima, Nature, 361 (1993) 33.
[4] A. Thess, R. Lee, P. l\likolaev, H. Dai, P.Petit, J. Robert, C. Xu, Y. H. Lee, S.G.
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.
[11] N. M. Rodrigue%, J. Mate Res. (1993) 3233.
[12] L.C. Qin, D. Zhou, A.R. Krauss, and D.M. Gruen, Appl. Pays. Lett., 72 (1998) 3437.
Agent's Ref BP-09-0312 [13] S.H. Tsai, C.W. Chao, C.L. Lee, and H.C. Shih, Pulpal. Phys. I est., 74 (1999) 3462.
[14] Y.C. Choi, ct al., Ippl. Phys. Lett., 76 (2000) 2367.
[15] C. Bower, W. Zhu, S. Jin, O. Zhou, Appl. Phys. Lest., 77 (2000) 830.
[16] M. Okai, T. Muncyoshi, T. Yaguchi, and S. Sasaki, Appl. Phys. I est., 77 (2000) 3468.
[17] F. Hoshi, K. Tsugawa, A. Goto, T. Ishikura, S. Yamashita, M. Yumura, T. Hirao, K. Oura, Y. Koga, Diamond and Rel. Mat. 10 (2001) 254.
[18] B. O. Boskovic, V. Stolojan, R. U. A. Khan, S. Haq, and S. R. P. Silva, Nature Materials 1 (2002) 165-168.
[19] A.K.M. Fazle Kibria, i'. H. Mo, K. S. Nahim, M. J. Kim, Carbon 40 (2002) 1241-1241 [20] J-F. Colomer, P. Piedigross, l. Willems, C. Journet, P. Bernier, G. Van Tendelo, A. Fonseca and J. B. Nagy Chem. Soc., Faraday Trans., 94 (1998) 3753-3758 [21] P. G. Collins, K. Bradley, M. Ishigami, A. Zettl, Science, 287 (2000) 1801 1 1

Claims (22)

Agent's Rcf BP-09-03 12 CLAIMS
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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Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998039251A1 (en) * 1997-03-07 1998-09-11 President And Fellows Of Harvard College Preparation of carbide nanorods
WO1999025652A1 (en) * 1997-11-18 1999-05-27 Martin Moskovits Controlled synthesis and metal-filling of aligned carbon nanotubes
US6232706B1 (en) * 1998-11-12 2001-05-15 The Board Of Trustees Of The Leland Stanford Junior University Self-oriented bundles of carbon nanotubes and method of making same
WO2001049599A2 (en) * 2000-01-07 2001-07-12 Duke University High yield vapor phase deposition method for large scale single walled carbon nanotube preparation
WO2001062665A1 (en) * 2000-02-25 2001-08-30 Sharp Kabushiki Kaisha Carbon nanotube and method for producing the same, electron source and method for producing the same, and display
WO2001085612A2 (en) * 2000-05-11 2001-11-15 Her Majesty The Queen In Right Of Canada, As Represented By The Minister Of National Defence Process for preparing carbon nanotubes
WO2002092506A1 (en) * 2001-05-15 2002-11-21 Cambridge University Technical Services Limited Synthesis of nanoscaled carbon materials
WO2003002456A2 (en) * 2001-06-28 2003-01-09 Institut National Polytechnique De Toulouse Method for the selective production of ordered carbon nanotubes in a fluidised bed
WO2003004410A1 (en) * 2001-07-03 2003-01-16 Facultes Universitaires Notre-Dame De La Paix Catalyst supports and carbon nanotubes produced thereon
WO2003018474A1 (en) * 2001-08-22 2003-03-06 Johnson Matthey Public Limited Company Nanostructure synthesis

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6835366B1 (en) * 1998-09-18 2004-12-28 William Marsh Rice University Chemical derivatization of single-wall carbon nanotubes to facilitate solvation thereof, and use of derivatized nanotubes
EP1129990A1 (en) * 2000-02-25 2001-09-05 Lucent Technologies Inc. Process for controlled growth of carbon nanotubes
US8715790B2 (en) * 2001-07-27 2014-05-06 University Of Surrey Production of carbon nanotubes

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998039251A1 (en) * 1997-03-07 1998-09-11 President And Fellows Of Harvard College Preparation of carbide nanorods
WO1999025652A1 (en) * 1997-11-18 1999-05-27 Martin Moskovits Controlled synthesis and metal-filling of aligned carbon nanotubes
US6232706B1 (en) * 1998-11-12 2001-05-15 The Board Of Trustees Of The Leland Stanford Junior University Self-oriented bundles of carbon nanotubes and method of making same
WO2001049599A2 (en) * 2000-01-07 2001-07-12 Duke University High yield vapor phase deposition method for large scale single walled carbon nanotube preparation
WO2001062665A1 (en) * 2000-02-25 2001-08-30 Sharp Kabushiki Kaisha Carbon nanotube and method for producing the same, electron source and method for producing the same, and display
WO2001085612A2 (en) * 2000-05-11 2001-11-15 Her Majesty The Queen In Right Of Canada, As Represented By The Minister Of National Defence Process for preparing carbon nanotubes
WO2002092506A1 (en) * 2001-05-15 2002-11-21 Cambridge University Technical Services Limited Synthesis of nanoscaled carbon materials
WO2003002456A2 (en) * 2001-06-28 2003-01-09 Institut National Polytechnique De Toulouse Method for the selective production of ordered carbon nanotubes in a fluidised bed
WO2003004410A1 (en) * 2001-07-03 2003-01-16 Facultes Universitaires Notre-Dame De La Paix Catalyst supports and carbon nanotubes produced thereon
WO2003018474A1 (en) * 2001-08-22 2003-03-06 Johnson Matthey Public Limited Company Nanostructure synthesis

Cited By (30)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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EP1637828A2 (en) * 2004-09-20 2006-03-22 Lockheed Martin Corporation Ballistic fabrics with improved antiballistic properties
US8080487B2 (en) 2004-09-20 2011-12-20 Lockheed Martin Corporation Ballistic fabrics with improved antiballistic properties
EP1652573A1 (en) 2004-11-02 2006-05-03 Korea Institute of Energy Research Method and device for manufacturing nanofilter media
US8038887B2 (en) 2005-08-24 2011-10-18 Lawrence Livermore National Security, Llc Membranes for nanometer-scale mass fast transport
WO2007025104A2 (en) * 2005-08-24 2007-03-01 The Regents Of The University Of California Membranes for nanometer-scale mass fast transport
WO2007025104A3 (en) * 2005-08-24 2007-08-23 Univ California Membranes for nanometer-scale mass fast transport
EP1995213A1 (en) * 2006-03-13 2008-11-26 Nikon Corporation Process for production of carbon nanotube aggregates, carbon nanotube aggregates, catalyst particle dispersion membrane, electron emitters, and field emission displays
EP1995213A4 (en) * 2006-03-13 2010-03-24 Nikon Corp Process for production of carbon nanotube aggregates, carbon nanotube aggregates, catalyst particle dispersion membrane, electron emitters, and field emission displays
US20100192851A1 (en) * 2007-01-03 2010-08-05 Lockheed Martin Corporation Cnt-infused glass fiber materials and process therefor
US20110168083A1 (en) * 2007-01-03 2011-07-14 Lockheed Martin Corporation Cnt-infused ceramic fiber materials and process therefor
US9574300B2 (en) 2007-01-03 2017-02-21 Applied Nanostructured Solutions, Llc CNT-infused carbon fiber materials and process therefor
US9573812B2 (en) 2007-01-03 2017-02-21 Applied Nanostructured Solutions, Llc CNT-infused metal fiber materials and process therefor
US9005755B2 (en) 2007-01-03 2015-04-14 Applied Nanostructured Solutions, Llc CNS-infused carbon nanomaterials and process therefor
US8951632B2 (en) 2007-01-03 2015-02-10 Applied Nanostructured Solutions, Llc CNT-infused carbon fiber materials and process therefor
US8951631B2 (en) 2007-01-03 2015-02-10 Applied Nanostructured Solutions, Llc CNT-infused metal fiber materials and process therefor
WO2009004346A1 (en) * 2007-07-03 2009-01-08 Meggitt Aerospace Limited Carbon-carbon composite
US8940173B2 (en) 2008-05-29 2015-01-27 Lawrence Livermore National Security, Llc Membranes with functionalized carbon nanotube pores for selective transport
US8580342B2 (en) 2009-02-27 2013-11-12 Applied Nanostructured Solutions, Llc Low temperature CNT growth using gas-preheat method
US10138128B2 (en) 2009-03-03 2018-11-27 Applied Nanostructured Solutions, Llc System and method for surface treatment and barrier coating of fibers for in situ CNT growth
US8969225B2 (en) 2009-08-03 2015-03-03 Applied Nano Structured Soultions, LLC Incorporation of nanoparticles in composite fibers
US9722255B2 (en) 2009-12-17 2017-08-01 Johnson Matthey Fuel Cells Limited Catalyst layer assembly
US9876234B2 (en) 2009-12-17 2018-01-23 Johnson Matthey Fuel Cells Limited Catalyst layer assembly
US8784937B2 (en) 2010-09-14 2014-07-22 Applied Nanostructured Solutions, Llc Glass substrates having carbon nanotubes grown thereon and methods for production thereof
US8815341B2 (en) 2010-09-22 2014-08-26 Applied Nanostructured Solutions, Llc Carbon fiber substrates having carbon nanotubes grown thereon and processes for production thereof
WO2012131321A1 (en) 2011-03-25 2012-10-04 The Morgan Crucible Company Plc Lithium ion batteries and electrodes therefor
WO2013039453A1 (en) * 2011-09-12 2013-03-21 National University Of Singapore A ceramic membrane containing carbon nanotubes
EP2719660A1 (en) * 2012-10-09 2014-04-16 Korea Institute of Energy Research Method for synthesizing carbon nanowires at high density on surface of pores or gaps in structure, and hierarchical structure synthesized by the method
US9028916B2 (en) 2012-10-09 2015-05-12 Korea Institute Of Energy Research Method for synthesizing carbon nanowires on surface of pores or gaps in structure
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