WO2008119138A1 - Production de forêts de nanotubes - Google Patents

Production de forêts de nanotubes Download PDF

Info

Publication number
WO2008119138A1
WO2008119138A1 PCT/AU2008/000480 AU2008000480W WO2008119138A1 WO 2008119138 A1 WO2008119138 A1 WO 2008119138A1 AU 2008000480 W AU2008000480 W AU 2008000480W WO 2008119138 A1 WO2008119138 A1 WO 2008119138A1
Authority
WO
WIPO (PCT)
Prior art keywords
forest
nanotube
substrate
nanotubes
forests
Prior art date
Application number
PCT/AU2008/000480
Other languages
English (en)
Inventor
Stephen Charles Hawkins
Chi Phuong Huynh
Original Assignee
Commonwealth Scientific And Industrial Research Organisation
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from AU2007901768A external-priority patent/AU2007901768A0/en
Application filed by Commonwealth Scientific And Industrial Research Organisation filed Critical Commonwealth Scientific And Industrial Research Organisation
Publication of WO2008119138A1 publication Critical patent/WO2008119138A1/fr

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/158—Carbon nanotubes
    • C01B32/16—Preparation
    • C01B32/162—Preparation characterised by catalysts
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2202/00—Structure or properties of carbon nanotubes
    • C01B2202/08—Aligned nanotubes

Definitions

  • a carbon nanotube is comprised of one or more concentric cylinders of' graphene, that is sheets of planar sp2 bonded carbon that are one atom thick and rolled into a cylinder with the edges joined. If only one cylinder is present, the CNT is classed as a single walled nanotube (SWNT), if two concentric cylinders, then as a double wall nanotube (DWNT) and if more then as a multi-wall nanotube (MWNT).
  • SWNT single walled nanotube
  • DWNT double wall nanotube
  • MWNT multi-wall nanotube
  • SWNTs are typically about 1 nm
  • MWNTs which may comprise many tens of concentric tubes
  • Lengths are commonly in the order tens of microns for SWNTs up to several millimetres for MWNTs.
  • CNTs are also termed 'Buckytubes' or 'Fullerenes'.
  • Carbon nanotubes particularly of the single-walled variety, have a range of spectacular properties such as high elastic modulus ( ⁇ 1 TPa) and high mechanical strength ( ⁇ 30 GPa) that are of great technological interest.
  • a low volumetric density ⁇ 1330 kg/m 3 ) means that the specific properties are even more exceptional when compared with most other materials commonly available, e.g., the modulus and strength of SWNTs are ⁇ 20 and ⁇ 50 times that of high tensile steel.
  • SWNTs also display excellent properties such as high electrical conductivity (10-30 kS/cm) and high thermal conductivity (-2000 W nV 1 K '1 ).
  • Carbon nanotubes are synthesised as randomly oriented tangles or bundles, or as highly aligned arrays in which the CNTs are substantially of the same length and diameter, and stand closely packed and in parallel on a substrate as trees in a forest.
  • it is necessary to disperse them in and combine them with other materials such as polymers to create composite structures, or, following dispersion, to remove the polymer or other dispersion medium such as a solvent to create pure CNT structures.
  • This dispersion operation is termed 'wet processing'.
  • the CNTs can be randomly oriented or can be aligned in one, two or (pseudo) three dimensions.
  • Two dimensional alignment, wherein the CNTs are arranged in parallel within a plane, and pseudo-three dimensional alignment, wherein the CNTs are aligned in a yarn, are most desirable as these alignments enable the properties of CNTs to be most effectively realised.
  • CNT composites have the advantage that the CNTs are dispersed and handled with relatively little difficulty.
  • the CNTs are either randomly oriented, or can be aligned by drawing the composites into films and fibres.
  • One disadvantage of composites is that the maximum loading of CNTs to polymer that can be achieved is rarely above 10% and often less than 5% as the CNTs greatly influence the melt or solution properties of the composite, such as by increasing viscosity.
  • the composite exhibits mainly the properties of the polymer rather than the nanotubes.
  • impressive mechanical benefits have been obtained for polymer-solution-spun SWNTs, which in large part can be attributed to the mechanical properties of the nanotubes.
  • An alternative to composite formation is to disperse the CNTs in a continuous medium such as a solvent or polymer, which is then partially or substantially removed during or after the process of structure formation to leave a mat or paper of CNTs.
  • a method that avoids the problems of wet processing utilises forests of close packed parallel aligned nanotubes on a solid substrate to fabricate nanotube yarn.
  • this method entails the capturing by forceps and drawing away from the face of a forest of a bundle of nanotubes, whereby nanotubes behind the bundle are sufficiently attached to also be drawn out, and whereby contiguously attached nanotubes are also drawn out.
  • the result is that a continuous chain of nanotubes in the nature of a yarn is drawn away from the forest.
  • the yarn so produced is of very poor strength and deficient in other physical properties.
  • This method utilises MWNTs grown in forests with the important property that they are "drawable” laterally of the nanotube orientation as a longitudinal nanotube assembly. If the forest is drawable, when the row of nanotubes of an outer face of the forest is withdrawn generally laterally of the nanotube orientation, the nanotubes in the next row are sufficiently connected to the first row to then be pulled out after it, followed by each successive row or rank. This process continues indefinitely through the ranks of nanotubes in the forest, ultimately creating a longitudual nanotube assembly in the form of a continuous yarn, ribbon, sheet or web of nanotubes.
  • the individual nanotubes are largely aligned in two dimensions in that they are parallel and within a plane, having been rotated into the plane of the yarn or web by the action of drawing.
  • This web of nanotubes has sufficient integrity to be used by itself or to be twisted into a yarn.
  • drawing “laterally” in this context is meant at an angle to the nanotube orientation. The angle may be, and indeed is preferably, about 90 °.
  • the webs and yarns have excellent mechanical strength and electrical conductivity and can be used in many applications. As no dispersion or wet processing is required, this operation is termed 'dry processing' or 'dry spinning' or 'dry drawing' of CNTs, and the CNT forests from which they are drawn are termed 'drawable' or 'spinnable' nanotube forests.
  • drawable nanotube forests A difficulty for the methods that rely on the use of drawable nanotube forests is that existing processes for forming such nanotube forests are very sensitive to conditions of reaction and hence are susceptible to failure. Known such processes include those described by Jiang et al in US patent application 2004053053 "Carbon nanotube array and method for forming same".
  • the various process parameters need to be carefully controlled within specific ranges of values.
  • the forest is grown from an iron catalyst layer vapour-deposited on a silicon wafer as substrate placed in a reactor having an inert gas atmosphere to which acetylene is admitted as a reactive gas.
  • the critical parameters include the purity and method of deposition and subsequent treatment of the catalyst layer, the choice and handling of the silicon substrate, the quality of the inert and reactive gas supplies, and the exact flow rates, temperature profiles and gas compositions and running times for the reaction, etc.
  • the concept of the present invention is essentially to grow nanotube forests on substrates in such a fashion that the outer tips of the nanotubes bear upon a closure that, in certain embodiments, may be a further substrate or an oppositely growing forest of similar nanotubes.
  • the substrates upon which the nanotubes are grown may be silicon dioxide or quartz or any other compatible refractory material and are preferably coated with a simple single layer of catalyst that does not require pretreatment with hydrogen, and the closure may be of an identical material to the substrate, whether or not coated with catalyst, or may be any other compatible refractory material.
  • the forest thereby exhibits base growth as the seed catalyst nano particles remain at the substrate surface(s). It is preferred, at least in some aspects of the invention, that there is no additional layer of catalyst or catalyst sandwich material such as titanium nitride of aluminium or aluminium oxide or silicon nitride, nor an air gap or sacrificial layer.
  • apparatus for producing a nanotube forest including:
  • [18.1] means for defining a first substrate having a coating of a material that is a catalyst for growth of a nanotube forest thereon, the substrate and coating being configured so that the nanotube forest exhibits base growth;
  • [18.3] means for maintaining across the tips of the nanotubes of the forest as the forest grows, a closure that restricts access to the substrate to traversal of the forest by the reactive carbon gas(es) which pass laterally through the forest among the nanotubes thereof;
  • closure is dimensioned and reaction parameters set whereby the mean nanotube height across the forest is substantially uniform.
  • the closure is a second substrate for a further nanotube forest on its obverse face, arranged so that the reverse face of the second substrate contacts said tips of the nanotubes of the first mentioned forest.
  • the aforesaid closure is an assembly of a second substrate and a further nanotube forest growing thereon, arranged so that the respective nanotube forests grow by base growth towards each other.
  • the nanotube forest is a forest that is drawable laterally of the nanotube orientation as a longitudinal nanotube assembly.
  • laterally in this specification is meant at an angle to the nanotube orientation. The angle may be about 90° and indeed is preferably about 90°.
  • the invention provides a method of producing a nanotube forest, including:
  • the second substrate may have an obverse face coated for growing a further nanotube forest thereon, such forest being itself covered by a third substrate, and a reverse face that contacts the tips of the nanotubes of the first substrate.
  • the second substrate may be coated on both its obverse and reverse sides and grow nanotube forests on both sides, being in contact respectively with the first and third substrates.
  • the first and second substrates are arranged so that the respective nanotube forests that grow thereon grow towards each other.
  • the nanotube forest is a forest that is drawable laterally of the nanotube orientation as a longitudinal nanotube assembly that grow thereon grow towards each other.
  • the invention provides a carbon nanotube structure or stack comprising multiple carbon nanotube forests interspersed with substantially parallel substrates supporting the forests. There may be a single nanotube forest layer between adjacent substrates, or alternatively there may be pairs of forests between adjacent substrates in which the tips of the respective forests are substantially coplanar or overlapping.
  • the invention also provides a carbon nanotube structure comprising a pair of carbon nanotube forests projecting towards each other from respective substrates supporting the forests, the respective forests being distinct and separate and their carbon nanotubes substantially not bonded at their adjacent tips.
  • each forest is preferably drawable laterally of the nanotube orientation as a longitudinal nanotube assembly
  • the atmosphere about the substrate(s) is preferably primarily an inert gas or mix of such gases.
  • the reactive carbon gas(es) preferably include(s) acetylene.
  • the catalyst is preferably iron, cobalt, nickel or combinations or alloys thereof. The catalyst is conveniently vapour-deposited on the substrate.
  • these gaseous impurities may typically include phosphine, arsine, acetone, hydrogen sulphide and water, benzene, styrene and other thermal degradation products of acetylene, and also hydrogen as a by-product of the reaction of acetylene with the catalyst.
  • phosphine arsine
  • acetone hydrogen sulphide
  • water hydrogen sulphide
  • benzene styrene and other thermal degradation products of acetylene
  • hydrogen as a by-product of the reaction of acetylene with the catalyst Other mechanisms of action are possible.
  • the invention therefore also provides, in a fourth aspect, a method of producing a nanotube forest, including causing a nanotube forest to grow, in an atmosphere that includes one or more suitable reactive carbon gases, on and outwardly from a first substrate having a coating of a material that is a catalyst for growth of the forest, the substrate and coating being configured so that the nanotube forest exhibits base growth and, as the forest grows, causing the reactive carbon gas(es) to flow into the forest primarily by flowing through the forest among the nanotubes thereof, rather than into the forest past the tips of the nanotubes, thereby resulting in enhanced conditioning of the reactive carbon gas(es) by the nanotubes of the forest, wherein the closure is dimensioned and reaction parameters set whereby the mean nanotube height across the forest is substantially uniform.
  • Such conditioning of the reactive carbon gas(es) may include absorption or adsorption of gaseous impurities and by-products entrained with the reactive carbon gas.
  • the forest is preferably a forest that is drawable laterally of the nanotube orientation as a longitudinal nanotube assembly.
  • the invention also provides apparatus for producing a nanotube forest, including:
  • [31.1] means for defining a first substrate having a coating of a material that is a catalyst for growth of a nanotube forest thereon, the substrate and coating being configured so that the nanotube forest exhibits base growth;
  • [31.2] means for defining a chamber about said substrate for an atmosphere that includes one or more suitable reactive carbon gases, whereby a nanotube forest can be caused to grow on and outwardly from said coated first substrate;
  • [31.3] means for restricting access to the coated substrate to traversal of the growing forest by said reactive carbon gas(es) which therefore must pass laterally through the forest among the nanotubes thereof and thereby be filtered, conditioned or otherwise beneficiated, rather than being able to enter at the tips of the nanotube forest and pass down between the nanotubes to their base at the substrate;
  • the invention provides a method of improving any gas comprising passing that gas among the nanotubes of a nanotube forest whereby the gas is filtered, conditioned or otherwise beneficiated by the nanotubes of the forest, for example, by absorption or adsorption of gaseous impurities and by-products entrained with the gas.
  • the catalyst-coated substrate(s) may conveniently be a regenerated substrate obtained by heating and thereby oxidising and regenerating a catalyst-coated substrate on which a nanotube forest has previously been grown.
  • Figure 1 is a diagrammatic representation of the side elevation of a starting pair of substrates catalyst-coated with a single simple layer of catalyst on both of the opposed sides that are in substantial contact to be treated in accordance with a first embodiment of the invention
  • FIG. 36 is a similar diagram of the same pair of catalyst-coated substrates, after nanotube forests have been grown on the substrates;
  • Figure 2a is a diagram of the pair of substrates, as depicted in Figure 2, in a reactor in which the nanotube forests have grown;
  • Figures 3 and 4 are isometric views of alternate suitable substrates for carrying out embodiments of the invention.
  • Figures 5 and 6 are views corresponding to Figures 1 and 2 for a second embodiment of the invention, in which a single forest is grown between two substrates;
  • Figures 7 and 8 are views corresponding to Figures 1 and 2 for a third embodiment of the invention, in which there is a small stack of alternate substrates and forests;
  • Figures 9 and 10 are views corresponding to Figures 1 and 2 for a fourth embodiment of the invention, in which the substrates are of different dimensions;
  • Figure 11 is a photograph showing a nanotube ribbon being drawn from a drawable forest grown on a catalyst-coated quartz substrate that was overlain by a catalyst-coated silicon dioxide substrate, illustrating that substrates need not be the same size or material;
  • Figures 12 and 13 are views similar to Figures 1 and 2 for a fifth embodiment of the invention, in which the structure of Figures 1 and 2 is repeated in a stack;
  • Figure 14a is a photograph showing a stack of 26 pairs of substrates about to be loaded into a reactor.
  • Figure 14b is a photograph of stacks of 30 pairs of substrates before (right) and after (left) growth of nanotube forests, illustrating the increase in stack height due to the accumulated length of 60 nanotube forests.
  • Figure 15 depicts a sixth embodiment of the invention comprising a stack containing substrates coated with catalyst on both sides;
  • Figure 16 is a diagram of a structure for conditioning a gas or liquid stream.
  • drawable nanotube forests are grown on each of a pair of facing substrates 101 , 104 each coated with a catalyst 102, 105.
  • the substrate can be silicon dioxide of any thickness commensurate with structural and mechanical integrity. It is to be understood that this invention is applicable to any substrates that are or can be made suitable for the base growth of preferably drawable carbon nanotube forests.
  • the following description will use the term 'substrate' for convenience but it is understood that this term implies substrates in the form of silicon dioxide, silicon dioxide coated wafers, quartz slides, and all other substrates of the suitable materials in any shape or size.
  • Each substrate 101 , 104 should have at least one surface that is smooth by virtue of having been polished, fused, crystallised, planed, coated, or by any other natural or artificial means, and may be of any size or thickness that may be conveniently handled.
  • the substrate is silicon dioxide of 100 nm thickness supported by a P type silicon wafer of 550 ⁇ m thickness and 100 mm diameter, and in another embodiment, substrates are quartz glass slides 126 mm square and 2 mm thick.
  • each substrate 101 , 104 is coated with catalyst 102, 105 by any means including electron beam, plasma, sputter, thermal filament or boat, or chemical vapour deposition, or solution deposition.
  • the catalyst may be of the metals iron, cobalt or nickel or combinations or alloys thereof, with iron being the preferred metal at a thickness of from 1 to 10 nm but preferably 5 nm.
  • the catalyst is applied directly to the substrate surface. This ensures the aforementioned preferred base growth of the nanotubes rather than tip growth.
  • catalyst or catalyst sandwich material such as titanium nitride of aluminium or aluminium oxide or silicon nitride, nor an air gap or sacrificial layer. It is also preferred that the catalyst not be pretreated with hydrogen prior to nanotube growth.
  • Substrate 101 , 104 with their catalyst layer 102, 105 are paired and matched for material, size and shape, and arranged such that the coated sides are placed face to face and such that they are aligned and substantially in contact with one another, having substantially no space or gap between them.
  • the pair of substrates is placed in a reactor being, in one embodiment ( Figure 2a), a horizontal quartz glass tube 200 of 45 mm internal diameter and of 1000 mm in length with a surrounding furnace 205 for heating that section holding the substrates, and a means of supplying inert and reactive carbon and other gases at one end 202.
  • the pair of substrates 101 ,104 may be placed at any angle within the reactor but most conveniently horizontally, and be supported at its edges by the wall of the tube or be placed on or in a support 210 of inert material.
  • the reactor is closed and flushed thoroughly with an inert gas of high purity such as nitrogen or a noble gas, but preferably helium.
  • the substrates are heated in the reactor within the atmosphere of the inert gas to a temperature in the range 500 0 C to 1200 0 C but preferably around 680 0 C.
  • the inert gas is adjusted to a flow rate of from 100 to 2000 seem, preferably 700 seem, and a reactive gas that is a source of carbon is added to the inert gas flow in the amount of up to 100% but preferably 5% by volume.
  • the reactive gas may be, for example, methane or a higher alkane, ethylene or a higher alkene, acetylene or a higher alkyne, benzene or its derivatives, or any derivatives and combinations of these, but is preferably acetylene.
  • the reactive gas flow may optionally include additional gases such as hydrogen and ammonia.
  • a controlled flow of inert and reactive gases, and a controlled temperature is maintained for 1 to 60 minutes, preferably 20 minutes, after which the reactive gas is stopped.
  • inert and reactive gas or gases diffuse or flow or insinuate between the substrates and there interact with the catalyst coating or grow carbon nanotubes in respective forests 103, 106 on substrates 101 , 104.
  • heating is continued for a short further time with the inert gas flowing to remove residual reactive material before the reactor and contents are cooled and unloaded.
  • Nanotube 103, 106 is represented by a repeating pattern of lines. It will be understood that this is not intended to indicate the appearance of the nanotubes: it is simply a drawing device to deal with objects that cannot practically be illustrated at their real size or in their precise geometry. Nanotubes in fact are often not vertically straight, often have wavy- style forms, and regularly touch each other at locations remote from their base. There may be of the order of 10 10 to 10 12 nanotubes per cm 2 of substrate.
  • 103,106 forests exhibit base growth in that the seed catalyst nano particles remain at the substrate surface: the result is separate and distinct forests growing from the respective substrates. : The nanofibre tips of the forests, being the points farthest from their respective substrates, impinge and do not substantially interpenetrate. The adjacent tips of the opposing forests substantially do not bond together: the forests remain distinct and separable. As a result, the nanotubes push each other and the respective substrates apart as the growth proceeds.
  • the size of the substrates 101 , 104 is thought to influence the structure of the. forest grown, with distance from the edge being the key variable.
  • the preferred maximum distance of any point on a substrate 101 to an edge in particular to ensure the aforesaid feature of substantially uniform mean nanotube height, can be from 0.1 mm up to 150 mm or more with the optimum distance dependent upon the reactor conditions.
  • the desired distance for example 10 mm, is achieved either by cutting the substrate into pieces of suitable dimension, such as 20 mm wide and of greater length than 20 mm as illustrated, or by taking a large substrate 101 ( Figure 4) and perforating it 115 such that no point is greater than the required distance from a perforation or edge 108.
  • one substrate 704 is smooth and coated with catalyst 702, 705 on both sides, and each coated side is placed substantially in contact with respective other substrates 701 , 707 that may or may not themselves be coated (the latter is illustrated). Growth of nanotubes on such an assembly ( Figure 8) results in the coated substrate 704 growing nanotube forests 703, 706 on the respective coatings 702, 705 on both sides and thereby pushing the uncoated substrates 701 , 707 apart.
  • Figure 11 shows nanotube ribbon being drawn from a drawable forest grown on a quartz slide - the second substrate in this case was of smaller dimensions than the slide, and the substrates were also of different materials.
  • pairs of substrates of like material such as silicon dioxide
  • pairs of substrates of unlike material may also be used.
  • Such combinations are not limited to silicon dioxide and quartz or quartz and magnesia but encompass any dissimilar materials that are compatible with the growth of CNTs, where the word 'substrate' is understood to stand for any material of the types described in any size or shape, and that the word 'pair' is understood to stand for any two pieces of material whether or not substantially similar in size, shape or substance.
  • the preferred embodiment describes the use of one pair of substrates, it is also to be understood that pairs of substrates may be stacked one upon another ( Figure 12), in which each substrate 1201 has a catalyst coating 1202.
  • Stacks can be placed side by side or in line to the maximum extent of the reactor capacity or to an extent limited by the capacity to maintain the appropriate reactor environment with respect to reactant and waste gases, gas flows, temperatures etc.
  • Treatment of the stacks results (Figure 13) in each catalyst layer eg 1202 generating a base-growth nanotube forest eg 1203 and thereby pushing the substrates eg 1201 apart; a portion of such a stack is illustrated.
  • Figure 14a is a photograph of a stack of 26 pairs of substrates, being loaded into a reactor and (Fig 14 b), stacks of 30 pairs before (right) and after (left) treatment, illustrating the increase in stack height due to the accumulated length of 60 drawable nanotube forests produced during a single reaction cycle.
  • other compatible materials that may or may not grow nanotubes can be placed on or under or around the pairs or stacks of substrates to support or constrain them or to direct the flow of gases.
  • stacks can be formed by placing multiple single substrates eg 1501 rather than pairs one atop another, such that the back of one substrate is substantially in contact with the front of the next and wherein either one or both of each pair of surfaces that are in substantial contact is coated with catalyst and hence can grow a drawable forest. This is illustrated for a portion of a stack wherein both sides of each substrate eg 1501 are coated 1502, 1505 and grow nanotube forests 1503, 1506, thereby mutually pushing the substrates apart.
  • substrates that were previously coated with iron and used to grow drawable forests can be oxidised in air at 400 0 C to 1000 0 C, preferably 700 0 C for 10 minutes to 12 hours preferably one hour, with or without the careful prior removal of the drawable forest.
  • substrates when placed in the reactor face to face with another substrate, whether or not coated, and processed as described, again grow drawable forests (not illustrated). This process can be repeated at least 10 times with no diminution in quality.
  • the iron which, following heating in air is present as the oxide, is directly reduced to the catalytic form by the reactive carbon gas rather than requiring an alternative reductant such as hydrogen or ammonia.
  • an alternative reductant such as hydrogen or ammonia.
  • substrates that in their first exposure failed to grow drawable forests, and are oxidised and treated as described will not grow drawable forests in subsequent exposures, whereas substrates that succeeded on the first cycle will succeed on subsequent cycles, indicating that the first cycle permanently templates the iron structure.
  • the reactor size, geometry and operation are able to be widely varied and still achieve the objective of CNT synthesis.
  • the reactor may be horizontal or vertical or any angle, the diameter and length may be varied as may be the gas flows, temperatures, catalysts, running times, and substrate treatments.
  • the substrates eg 1601 can be of a size and number and constrained within a framework eg 1600 that obliges gases (arrows 1620) to enter at one location, being the upstream face of a stack for example, and having passed over the catalyst coatings eg 1602 and through the forests eg 1605 and been filtered, purified, modified or conditioned, to leave at another location, being the downstream face of the stack. It is also recognised that the gases so processed (arrows 1625) and the conditions used can be other than those required to grow the forest once the forest structure has been generated.

Abstract

L'invention porte sur un procédé de production d'une forêt de nanotubes qui est de préférence étirable. Ce procédé consiste à faire croître une forêt de nanotubes, dans une atmosphère qui comprend un ou plusieurs gaz de carbone réactifs appropriés, sur et à l'extérieur d'un premier substrat ayant un revêtement d'une matière qui est un catalyseur pour la croissance de la forêt. Le substrat et le revêtement sont conçus de telle sorte que la forêt de nanotubes présente une croissance de base. A mesure que la forêt grandit, une fermeture est maintenue à travers les extrémités des nanotubes de la forêt, restreint l'accès au substrat revêtu, empêchant le(s) gaz de carbone réactif(s) de traverser la forêt en croissance, lesquels gaz doivent donc passer latéralement à travers la forêt parmi les nanotubes de celle-ci, plutôt que de pouvoir entrer aux extrémités de la forêt de nanotubes et descendre entre les nanotubes jusqu'à leur base au niveau du substrat. La fermeture est dimensionnée et les paramètres de réaction réglés, grâce à quoi la hauteur moyenne des nanotubes à travers la forêt est sensiblement uniforme. L'invention porte également sur un appareil et une structure de nanotubes de carbone.
PCT/AU2008/000480 2007-04-03 2008-04-03 Production de forêts de nanotubes WO2008119138A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
AU2007901768A AU2007901768A0 (en) 2007-04-03 Production of nanotube forests
AU2007901768 2007-04-03

Publications (1)

Publication Number Publication Date
WO2008119138A1 true WO2008119138A1 (fr) 2008-10-09

Family

ID=39807735

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/AU2008/000480 WO2008119138A1 (fr) 2007-04-03 2008-04-03 Production de forêts de nanotubes

Country Status (1)

Country Link
WO (1) WO2008119138A1 (fr)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013007645A3 (fr) * 2011-07-08 2013-03-07 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Système de couches comprenant une couche de nanotubes de carbone parallèles et une couche de recouvrement électriquement conductrice, procédé de fabrication de ce système de couches et son utilisation dans les microsystèmes
US8515557B2 (en) 2007-11-19 2013-08-20 Cochlear Limited Electrode array for a cochlear implant
CN103837583A (zh) * 2013-11-13 2014-06-04 电子科技大学 一种双向生长型碳纳米管阵列传感器及其制备方法
US9159918B2 (en) 2013-01-08 2015-10-13 National Tsing Hua University Resistive random access memory
US9502675B2 (en) 2009-10-23 2016-11-22 Nantero Inc. Methods for passivating a carbonic nanolayer
US9589580B2 (en) 2011-03-14 2017-03-07 Cochlear Limited Sound processing based on a confidence measure
RU2714350C2 (ru) * 2017-12-26 2020-02-14 Федеральное государственное бюджетное учреждение науки Институт физической химии и электрохимии им. А.Н. Фрумкина РАН (ИФХЭ РАН) Способ получения упорядоченного массива углеродных нанотрубок при использовании молекул-координаторов, развития в полученных супрамолекулярных структурах вторичной пористости и материал, полученный этим способом

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000063115A1 (fr) * 1999-04-16 2000-10-26 Commonwealth Scientific And Industrial Research Organisation Films de nanotubes de carbone a multiples couches
US20040053780A1 (en) * 2002-09-16 2004-03-18 Jiang Kaili Method for fabricating carbon nanotube yarn
WO2005102922A1 (fr) * 2004-04-20 2005-11-03 Koninklijke Philips Electronics N.V. Nanostructures et leur procede de production
WO2007015710A2 (fr) * 2004-11-09 2007-02-08 Board Of Regents, The University Of Texas System Fabrication et applications de rubans, feuilles et fils retors ou non de nanofibres
US20070090489A1 (en) * 2005-10-25 2007-04-26 Hart Anastasios J Shape controlled growth of nanostructured films and objects
US20070284631A1 (en) * 2006-06-09 2007-12-13 Hsu David S Y Integrally gated carbon nanotube field ionizer device and method of manufacture therefor

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000063115A1 (fr) * 1999-04-16 2000-10-26 Commonwealth Scientific And Industrial Research Organisation Films de nanotubes de carbone a multiples couches
US20040053780A1 (en) * 2002-09-16 2004-03-18 Jiang Kaili Method for fabricating carbon nanotube yarn
WO2005102922A1 (fr) * 2004-04-20 2005-11-03 Koninklijke Philips Electronics N.V. Nanostructures et leur procede de production
WO2007015710A2 (fr) * 2004-11-09 2007-02-08 Board Of Regents, The University Of Texas System Fabrication et applications de rubans, feuilles et fils retors ou non de nanofibres
US20070090489A1 (en) * 2005-10-25 2007-04-26 Hart Anastasios J Shape controlled growth of nanostructured films and objects
US20070284631A1 (en) * 2006-06-09 2007-12-13 Hsu David S Y Integrally gated carbon nanotube field ionizer device and method of manufacture therefor

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
CHEN Z. ET AL.: "Fabrication and characterization of carbon nanotube arrays using sandwich catalyst stacks", CARBON, vol. 44, 2006, pages 225 - 230, XP005136846 *

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8515557B2 (en) 2007-11-19 2013-08-20 Cochlear Limited Electrode array for a cochlear implant
US9502675B2 (en) 2009-10-23 2016-11-22 Nantero Inc. Methods for passivating a carbonic nanolayer
US10084138B2 (en) 2009-10-23 2018-09-25 Nantero, Inc. Methods for forming nanotube fabric layers with increased density
US9589580B2 (en) 2011-03-14 2017-03-07 Cochlear Limited Sound processing based on a confidence measure
US10249324B2 (en) 2011-03-14 2019-04-02 Cochlear Limited Sound processing based on a confidence measure
WO2013007645A3 (fr) * 2011-07-08 2013-03-07 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Système de couches comprenant une couche de nanotubes de carbone parallèles et une couche de recouvrement électriquement conductrice, procédé de fabrication de ce système de couches et son utilisation dans les microsystèmes
US9159918B2 (en) 2013-01-08 2015-10-13 National Tsing Hua University Resistive random access memory
TWI513074B (zh) * 2013-01-08 2015-12-11 Nat Univ Tsing Hua 電阻式記憶體
CN103837583A (zh) * 2013-11-13 2014-06-04 电子科技大学 一种双向生长型碳纳米管阵列传感器及其制备方法
CN103837583B (zh) * 2013-11-13 2017-03-08 电子科技大学 一种双向生长型碳纳米管阵列传感器及其制备方法
RU2714350C2 (ru) * 2017-12-26 2020-02-14 Федеральное государственное бюджетное учреждение науки Институт физической химии и электрохимии им. А.Н. Фрумкина РАН (ИФХЭ РАН) Способ получения упорядоченного массива углеродных нанотрубок при использовании молекул-координаторов, развития в полученных супрамолекулярных структурах вторичной пористости и материал, полученный этим способом

Similar Documents

Publication Publication Date Title
Aljerf et al. Developed greener method based on MW implementation in manufacturing CNFs
Merchan-Merchan et al. Combustion synthesis of carbon nanotubes and related nanostructures
Kumar et al. Chemical vapor deposition of carbon nanotubes: a review on growth mechanism and mass production
Qin et al. Growing carbon nanotubes by microwave plasma-enhanced chemical vapor deposition
Martin-Gullon et al. Differences between carbon nanofibers produced using Fe and Ni catalysts in a floating catalyst reactor
Harris Carbon nanotube science: synthesis, properties and applications
WO2008119138A1 (fr) Production de forêts de nanotubes
US8246927B2 (en) Process and apparatus for producing carbon nanotube, carbon nanotube fiber, and the like
US7736616B2 (en) Membrane separation of feed and growth environments in carbon nanostructure growth
US20110024697A1 (en) Methods of Producing Carbon Nanotubes and Applications of Same
KR20130105634A (ko) 그 위에 성장된 카본 나노튜브를 갖는 금속 기재 및 이의 제조 방법
Sonoyama et al. Synthesis of carbon nanotubes on carbon fibers by means of two-step thermochemical vapor deposition
WO2008029927A1 (fr) Procédé destiné à produire un nanotube de carbone
Mittal et al. Carbon nanotubes synthesis using diffusion and premixed flame methods: a review
Shukrullah et al. Mass production of carbon nanotubes using fluidized bed reactor: A short review
Iyuke et al. Synthesis of carbon nanomaterials in a swirled floating catalytic chemical vapour deposition reactor for continuous and large scale production
López et al. A study of carbon nanotube formation by C2H2 decomposition on an iron based catalyst using a pulsed method
Hussein et al. Synthesis of carbon nanotubes by chemical vapor deposition
JP5036564B2 (ja) プレートレット型スリット気相法炭素繊維の製造方法
Maruyama Carbon nanotube growth mechanisms
Khavrus et al. Chemical catalytic vapor deposition (CCVD) synthesis of carbon nanotubes by decomposition of ethylene on metal (Ni, Co, Fe) nanoparticles
Boye et al. Carbon nanotubes: the building blocks of nanotechnology development
Böttcher et al. Growth of novel carbon phases by methane infiltration of free-standing single-walled carbon nanotube films
Srikanth et al. History of Carbon Nanotubes
Karwa et al. Carbon nanofiber synthesis within 3-Dimensional sintered nickel microfibrous matrices: optimization of synthesis conditions

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 08733314

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 08733314

Country of ref document: EP

Kind code of ref document: A1