WO2012019819A1 - Procédé de croissance de nanotubes de carbone sur des fibres - Google Patents

Procédé de croissance de nanotubes de carbone sur des fibres Download PDF

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Publication number
WO2012019819A1
WO2012019819A1 PCT/EP2011/060611 EP2011060611W WO2012019819A1 WO 2012019819 A1 WO2012019819 A1 WO 2012019819A1 EP 2011060611 W EP2011060611 W EP 2011060611W WO 2012019819 A1 WO2012019819 A1 WO 2012019819A1
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Prior art keywords
carbon
fibers
fabrics
carbon nanotubes
process according
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PCT/EP2011/060611
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English (en)
Inventor
Michel Calame
Matthias Graeber
Mickael Lucien Perrin
Christian Schoenenberger
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Huntsman Advanced Materials (Switzerland) Gmbh
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Publication of WO2012019819A1 publication Critical patent/WO2012019819A1/fr

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    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
    • D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
    • D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
    • D01F9/127—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
    • D01F9/1273—Alkenes, alkynes
    • 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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/18—Carbon
    • B01J21/185—Carbon nanotubes
    • 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
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
    • B01J35/58—Fabrics or filaments
    • 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
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0234—Impregnation and coating simultaneously
    • 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
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/10—Particle morphology extending in one dimension, e.g. needle-like
    • C01P2004/13—Nanotubes

Definitions

  • the present invention relates to a process to grow carbon nanotubes onto fibers, in particular carbon fibers, and to a method to produce composite materials with such fibers.
  • the first option is to act on the resin. This
  • CNT carbon nanotubes
  • CNT's Another remarkable property of CNT's is their tensile strength. Values up to 150 GPa have been reported, which exceed by far the 2.8 GPa of diamond. Carbon nanotubes also exhibit an amazing behavior under compression. They are able to form kink-like ridges that can relax elastically when the compressive stress is released. Reversible deformations up to 50% of their length have been reported. And last but not least, CNT's have a density which has been measured to be around 1 .3-1.4 g/cm 3 . Combining this property with their amazing strength, one obtains a specific strength (strength to density ratio) up to 1 15 000 kN m / kg . This makes CNT the best of all known materials as far as mechanical properties are concerned.
  • the second option to improve composites is by acting on the fiber part. This can be
  • CNT may be good candidates due to their exceptional properties and enormous surface area to volume ratio.
  • Fiber- reinforced polymer composites are typically materials made from a resin matrix such as an epoxy resin and reinforcing material such as carbon or glass fiber woven mats, comprising individual cylindrical fiber filaments with diameters of the order few-tens of micrometers, typically from 5 to 100 micrometers.
  • a resin matrix such as an epoxy resin
  • reinforcing material such as carbon or glass fiber woven mats
  • One of the distinct advantages of fiber-reinforced polymer composites compared to other materials is the combination of low weight and high strength. Fiber reinforced polymer composites are therefore commonly used in aerospace, automotive, or sports applications.
  • Carbon nanotubes with diameters in the nanometer range and lengths up to millimetres, typically from 20 to 200 micrometers, are an ideal candidate for the surface modification of fiber filaments, as they offer a large aspect ratio and, in addition, a very high stiffness.
  • the international application WO2008/054541 shows the catalytic growth of Carbon nanotubes forests on graphite fiber. However, the growth is not isotropic with respect to the fiber surface, in particular, only a part of the fiber filament surface is covered by carbon nanotubes.
  • the object of the present invention is to find a process to grow carbon nanotubes (CNT) onto fibers which does not exhibit the disadvantages of the conventional fabrication processes.
  • An object of the present invention is, in particular, to find a process to grow carbon nanotubes (CNT) onto fibers, particularly carbon fibers, which is simple, not expensive and feasible on an industrial scale, which facilitates an homogeneous growth of dense arrays of vertical long carbon nanotubes on the whole surface of the fibers.
  • Another object of the present invention is to produce composite materials by infiltrating fibers onto which carbon nanotubes have been grown, whereby the produced composite materials exhibit outstanding mechanical properties, in particular a high interlaminar shear strength.
  • a process to grow carbon nanotubes onto carbon, glass or metal fibers comprises the following steps:
  • ALD Atomic Layer Deposition
  • Chemical vapor deposition could be also used.
  • An alternative deposition process of Al could be dipping the fibers in a solution containing the Al-catalyst. The homogeneous Fe-coverage of the filaments is reached, for example, through the dipping process of the fibers in a solution containing the Fe-catalyst.
  • step a) is carried out by providing carbon fibers or graphite fibers, 0.005-0.080 mm in diameter, whereby several carbon fibers are twisted together to form a yarn, which is woven into a carbon fabric.
  • Steps b) to d) are carried out on such a carbon fabric or even on a stack of carbon fabrics placed one over another.
  • step a) comprises the step of placing carbon fabrics one over the other, so as to create a stack of fabrics comprising at least two fabrics, and the fabrics are sandwiched between two plates fixed at a fixed distance, so that no vertical expansion of the fabrics is possible during the growth of the carbon nanotubes.
  • Steps b) to d) are carried out on such a "confined" carbon fabric or "confined” stack of carbon fabrics placed one over another.
  • step b) is carried out with the process of Atomic Layer Deposition (ALD) or chemical vapour deposition (CVD) and the produced aluminum oxide layer exhibits over the whole surface of the fibers a homogeneous und uniform thickness up to 100 nm, for example between 1 and 50 nm.
  • ALD Atomic Layer Deposition
  • CVD chemical vapour deposition
  • step b) comprises the step of depositing homogeneous single atomic layers of Al 2 0 3 up to a thickness of 50 nm.
  • the thickness of such a layer is for example between 1 and 50 nm, preferably between 1 and 20 nm.
  • step c) is carried out by dipping the fibers or fabrics in an iron containing solution, for example an iron nitrate Fe(N0 3 ) 3 solution.
  • step d) comprises the steps of:
  • the carbon feedstock gas is selected from the group consisting of acetylene, ethylene, methane, butane and propane.
  • the deposited carbon nanotubes are perpendicular to the axis of the fibers onto which they have been deposited, without any preferential growth direction, and exhibit a growth length of at least 5 ⁇ , preferably at least 20 ⁇ , most preferably between 40 or 50 ⁇ and 2 mm.
  • Fibers or carbon fibers with carbon nanotubes grown onto their surfaces are produced preferably with the process according to the invention.
  • a process to produce composite materials comprises the following steps:
  • Curing by heat is a preferred process on the industrial scale.
  • a process to produce composite materials comprises the following steps:
  • the composite materials can be produced in this way:
  • Composite material produced with a process according to the invention are easy and inexpensive to produce on an industrial scale and exhibit outstanding mechanical properties, in particular a high interlaminar shear strength.
  • FIG. 1 shows micrographs obtained with a Philipps XL-30 scanning electron microscope (SEM) of a carbon fiber cloth before and after carrying out the inventive process. After the inventive process highly aligned arrays of carbon nanotubes are attached to the fiber filament surface.
  • SEM scanning electron microscope
  • FIG. 2 shows on a SEM micrograph the controlled, homogeneous and nearly cylinder-symmetrical growth of carbon nanotube arrays (forests) at a carbon filament surface obtained thanks to the inventive process.
  • the growth of carbon nanotubes is not homogeneous on the filament surface and vertical arrays are not formed.
  • FIG. 4 shows the CNT length in micrometer obtained with the inventive process as a function of the Al 2 0 3 layer thickness measured in number of cycles of ALD (step b).
  • the arrows in the legend point out which axis must be considered to read the correct scale.
  • Pronounced maxima of the obtained nanotube array height exist. The maxima are at 50 cycles ALD for an lron(lll)Nitrate
  • FIG. 5 shows the CNT length in micrometer obtained with the inventive process as a function of the temperature of CVD (step d) for 15 and 30 minutes.
  • the arrows in the legend point out which axis must be considered to read the correct scale. A pronounced maximum occurs at 725°C.
  • FIG. 6 b) and c) show two scanning electron micrographs of carbon fiber cloths consisting of individual filaments with carbon nanotubes obtained with the inventive process.
  • the viewing direction is parallel to the fiber direction, in Figure 6 c) it is perpendicular. Stripes of parallel carbon nanotubes form inter-links between the carbon fiber filaments.
  • Figure 6 a) shows untreated carbon fiber filaments before the inventive process as reference. DETAILED DESCRIPTION OF EMBODIMENTS
  • HexForcer HexPrimeTMG0926 D 1304 TCT carbon fiber cloths available by Hexcel have been provided.
  • Such carbon fibers (CF) contained 6k carbon fibers per yarn with a width of 2.17 mm per yarn.
  • the carbon fiber cloths were introduced in the deposition chamber of an Atomic Layer Deposition (ALD) apparatus (Savannah 100, by Cambridge NanoTech Inc.).
  • ALD Atomic Layer Deposition
  • the carbon fiber (CF) cloth is introduced in the ALD apparatus so that a thin layer of aluminum oxide (AIO_x) is deposited on the fiber surface.
  • ALD was then used to depose aluminum oxide on the CF with Trimethylaluminium (TMA) as precursor and water (H 2 0).
  • TMA Trimethylaluminium
  • the thickness of the aluminum oxide layer can be controlled by the number of ALD cycles that are run. Each cycle deposits a fraction of a monolayer onto the fiber cloth. Typically a growth rate of 0.1 nm of deposited aluminum oxide per cycle is achieved and a number of cycles ranging from 10 to 200 have been run, corresponding to obtained thicknesses of the AI2O3 layers ranging from 1 nm to 20 nm.
  • Such a film is thin, homogeneous and covering the whole surface of the fibers.
  • a particular advantage of this technique is the homogeneity of the deposited layer in terms of low surface roughness and spatial coverage of the substrate.
  • there are no shadowi ng effects on the fi ber filaments due to neighboring filaments as wo u l d be the case for conventional deposition techniques such as thermal evaporation or sputtering.
  • An homogeneous AI2O3 layer covering the whole surface of the fibers can be produced not only by ALD, but also with other methods. It could also be possible to deposit the aluminum oxide layer from a solution containing Al, by dipping the fibers in such a solution. Similar surface coverage and the absence of shadowing effects are expected as well.
  • Another alternative process to produce the Al layer would be chemical vapor deposition (CVD). The same furnace used for the following growth of CNT could be used in this case, with evident cost advantages for the industrial production scale.
  • the fiber cloth is then dipped in Ferric nitrate (Fe(N0 3 ) 3 ) / 2-propanol solution (Iron(lll) nitrate deposition). By dipping, a thin layer of Iron is deposited on top of the aluminum oxide. Such a film is homogeneous and covering the whole surface of the fibers.
  • the Fe catalyst application on the aluminum oxide -coated fiber cloth is performed as follows: Ferric nitrate (Fe(N0 3 ) 3 ) is dissolved in 2-propanol with concentrations ranging from 10 to 60 mMol/l and sonicated for about 10 minutes to ensure a well-suspended solution.
  • the carbon fiber yarns are cut into 3 cm long samples and submerged n times for t minutes in the catalytic solution (with 1 ⁇ n ⁇ 25 and 1/6 ⁇ t ⁇ 50 min). Between the dips the samples were dried at room temperature.
  • the samples were then ready for CNT growth and put on a quartz boat and loaded in the chemical carbon vapor deposition (CVD) furnace.
  • the fiber cloth is introduced into a CVD chamber with feedstock gas flow and Carbon nanotubes grow at the surface of the fiber.
  • the furnace used for CVD (MTF 12/38/250 tube furnace from Carbolite) consists of a quartz tube with length of 1 m, an inner diameter of 30 mm and an outer diameter of 35 mm. Samples are loaded at room temperature and heated up under a protective flow of argon with a flow rate of 1000 seem (standard cubic centimeters per minute). Once the desired synthesis temperature has been reached, the Hydrogen flow (flow rate 500 seem) and Ethylene flow (flow rate 85 seem) are turned on and the argon flow is stopped. The synthesis temperature could be varied between 650 and 850 °C. The growth time in the furnace could be varied between 1 and 120 minutes. After growth completion the ethylene flow is turned off and the samples are cooled down under a protective flow of
  • Carbon nanotubes have been grown on carbon fibers with the specific process parameters reported in Table 1 .
  • FIG. 1 shows micrographs obtained with a Philipps XL-30 scanning electron microscope (SEM) of a carbon fiber cloth before and after the inventive process carried out with the process parameters according to Table 1. After the inventive process, highly aligned arrays of carbon nanotubes are attached to the fiber filament surface.
  • SEM scanning electron microscope
  • FIG. 2 shows on a SEM micrograph the controlled, homogeneous and nearly cylinder-symmetrical growth of carbon nanotube arrays (forests) at a carbon filament surface after the inventive process has been carried out with the process parameters according to Table 1. Thanks to the inventive process, dense arrays of long carbon nanotubes essentially perpendicular to the carbon fiber axis have been grown, which cover homogeneously the whole surface of the fiber and exhibit a length of approximately 10 micrometer.
  • FIG. 6 b) and c) show two scanning electron micrographs of carbon fiber cloths consisting of individual filaments with carbon nanotubes after the inventive process has been carried out with the process parameters according to table 1 .
  • Figure 6 a) shows untreated carbon fiber filaments before the inventive process as reference.
  • Increasing the fiber interface through the growth of carbon nanotubes can improve the mechanical properties of a composite material obtained, for example, by infiltrating with epoxy resins such fibers.
  • the mechanical properties of such a composite can, however, be also improved by the crosslinking and interlinking between the fibers.
  • Fig. 6 shows that the fibers produced according to the invention could be certainly advantageously used for the production of composite material exhibiting outstanding mechanical properties.
  • the CNT's will lead to an increase of the fiber/epoxy interface surface area.
  • the fiber/epoxy interface is considered to be the interface between the reinforcement (fibers + CNT's) and the matrix (epoxy resin for example). Since CNT's have a enormous surface to volume ratio, growing CNT's on the
  • the CNT's may lead to a major improvement of the interface area and interfiber links may be formed. By using long CNT's, interply links may occur.
  • the FVF fiber volume fraction
  • the FVF mainly determines the mechanical properties of a composite.
  • the ideal FVF is 60%.
  • Carbon nanotubes have been grown on carbon fibers with the specific process parameters reported in Table 2.
  • the growth of carbon nanotubes is not homogeneous on the filament surface and vertical CNT arrays are not formed.
  • Carbon nanotubes have been grown on carbon fibers with all the combinations of specific process parameters reported in Table 3.
  • a control of the carbon nanotube length can be achieved by controlling the Aluminum oxide layer thickness.
  • the catalytic efficiency of the combination of the Aluminum and the Iron catalyst depends sensitively on the thickness of the aluminum oxide coating and the concentration of Iron(lll) Nitrate in the dipping solution.
  • FIG. 4 shows the CNT length in micrometer obtained with the inventive process carried out with all the combinations of the specific process parameters reported in Table 3.
  • Fig. 4 shows that pronounced maxima of the obtained nanotube array height exist.
  • the maxima are at 50 cycles of aluminum oxide deposition for an lron(lll)Nitrate concentration of 50 mMol/L and at 100 cycles for an lron(lll)Nitrate concentration of 15 and 30 mMol/L, respectively.
  • No vertical nanotube arrays have been observed below 50 cycles run in the aluminum oxide deposition, which corresponds to an estimated obtained aluminum oxide thickness of about 5 nm.
  • carbon nanotubes lengths between 10 and 50 micrometers have been measured.
  • Carbon nanotubes have been grown on carbon fibers with all the combinations of specific process parameters reported in Table 4.
  • FIG. 5 shows the CNT length in micrometer obtained with the inventive process carried out with all the combinations of specific process parameters reported in Table 4.
  • a Control of carbon nanotube length can be achieved by controlling the growth temperature of the CVD process.
  • test samples In order to test the mechanical properties of composites produced with carbon fibers with carbon nanotubes, test samples needed to be made.
  • Carbon fibers mats HexForcer HexPrimeTMG0926 D 1304 TCT were provided by Hexcel and cut into pieces of approximately 10cm x 10cm.
  • CNT growth on carbon fibers has been realized using two different strategies: ' free growth' and ' confined growth'.
  • the selected epoxy system was Araldite LY 8615 (resin) with the Aradur 8615 (hardener), obtainable in the market by Huntsman Advanced Material.
  • the first one is called "vacuum bagging".
  • the fiber mats are placed on a rigid Teflon plate.
  • sealant tape and transparent nylon foil a vacuum bag is made and an inlet and outlet tube are added.
  • the outlet tube is used to connect a vacuum pump.
  • the purpose of the inlet tube is to guide the epoxy system into the bag. Both tubes are reinforced to prevent collapse caused by vacuum.
  • the epoxy system is prepared. 2:1 mass fraction of the resin and the hardener. The two components are mixed by stirring for at least 2 minutes to ensure a homogeneous mixture. This mixture is then placed in a vacuum chamber to degas the air bubbles, which might be present in the epoxy. The vacuum pump is then switched on and the inlet closed to create vacuum inside the bag.
  • the inlet is then slowly opened to allow the epoxy system to enter the bag and infuse the fabrics.
  • the inlet When a sufficient amount of resin has entered the bag the inlet is closed while letting the outlet open. This causes the epoxy system to be sucked through the sample and the air bubbles trapped inside the sample to be evacuated. When the epoxy system has infused the entire stack of fabrics and the air bubbles have left the bag, the composite sample is ready for curing.
  • the setup is similar as the one for "vacuum bagging", but instead of applying pressure by vacuum pumping, pressure was now applied by applying a weight on top of the fabrics. The weight was distributed over the sample using a Teflon plate. The pressure on the samples is estimated to be around 0.4 bar. This is less than for vacuum bagging, but allowed to infuse more than 10 composite samples simultaneously. This is not possible using vacuum bagging, since the pump is not powerful enough to infuse several composite samples at the same time.
  • composite materials with satisfactory mechanical properties can be surprisingly obtained using less plies of carbon fiber fabrics, less fiber volume fraction (FVF) and less carbon fibers.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Nanotechnology (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • General Chemical & Material Sciences (AREA)
  • Textile Engineering (AREA)
  • General Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Composite Materials (AREA)
  • Carbon And Carbon Compounds (AREA)
  • Reinforced Plastic Materials (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)

Abstract

La présente invention concerne un procédé de croissance de nanotubes de carbone sur des fibres de carbone, de verre ou de métal comprenant les étapes suivantes : a) fourniture de fibres de carbone, de verre ou de métal ; b) dépôt sur les fibres de carbone, de verre ou de métal d'une couche d'oxyde d'aluminium ayant une épaisseur inférieure à 150 nm ; c) dépôt sur les fibres de carbone, de verre ou de métal d'une couche comprenant un catalyseur de fer ; d) croissance de nanotubes de carbone sur la fibre de carbone, de verre ou de métal, de préférence par dépôt chimique en phase gazeuse (CVD).
PCT/EP2011/060611 2010-08-13 2011-06-24 Procédé de croissance de nanotubes de carbone sur des fibres WO2012019819A1 (fr)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016092267A1 (fr) * 2014-12-09 2016-06-16 University Of Surrey Nanotubes de carbone
WO2016210249A1 (fr) * 2015-06-25 2016-12-29 Vladimir Mancevski Appareil et procédés pour l'obtention d'un volume élevé de graphène et de nanotubes de carbone sur des feuilles minces de grandes dimensions
US10046539B2 (en) 2014-07-22 2018-08-14 United Technologies Corporation Secondary reinforcement at interface of laminate structure
JP2018197186A (ja) * 2014-03-31 2018-12-13 日本製紙株式会社 繊維複合体およびその製造方法
CN112900075A (zh) * 2021-01-13 2021-06-04 郑州大学 一种SWNTs/MWNTs同轴纤维及其制备方法和应用

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103088648B (zh) * 2013-01-25 2015-01-07 中国科学院新疆生态与地理研究所 一种复合纳米结构碳纤维材料的制备方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050170089A1 (en) * 2004-01-15 2005-08-04 David Lashmore Systems and methods for synthesis of extended length nanostructures
WO2007136613A2 (fr) 2006-05-17 2007-11-29 University Of Dayton Procédé de croissance de nanomatériaux de carbone sur divers substrats
WO2008054541A2 (fr) 2006-05-19 2008-05-08 Massachusetts Institute Of Technology Articles composites renforcés par des nanostructures et procédés
WO2008054409A2 (fr) 2005-11-28 2008-05-08 University Of Hawaii Nanocomposites multifonctionnels renforcés de façon tridimensionnelle
US20100178825A1 (en) * 2007-01-03 2010-07-15 Lockheed Martin Corporation Cnt-infused carbon fiber materials and process therefor

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050170089A1 (en) * 2004-01-15 2005-08-04 David Lashmore Systems and methods for synthesis of extended length nanostructures
WO2008054409A2 (fr) 2005-11-28 2008-05-08 University Of Hawaii Nanocomposites multifonctionnels renforcés de façon tridimensionnelle
WO2007136613A2 (fr) 2006-05-17 2007-11-29 University Of Dayton Procédé de croissance de nanomatériaux de carbone sur divers substrats
WO2008054541A2 (fr) 2006-05-19 2008-05-08 Massachusetts Institute Of Technology Articles composites renforcés par des nanostructures et procédés
US20100178825A1 (en) * 2007-01-03 2010-07-15 Lockheed Martin Corporation Cnt-infused carbon fiber materials and process therefor

Non-Patent Citations (5)

* Cited by examiner, † Cited by third party
Title
A. RAHTU B., S. LIM, R.G. GORDON: "Atomic layer deposition of transition metals", NATURE, vol. 2, 2003, pages 749 - 754, XP002997436
GARCIA ET AL., COMPOSITES SCIENCE AND TECHNOLOGY, vol. 68, 2008, pages 2034 - 41
JOURNAL OF APPLIED PHYSICS, vol. 91, no. 9, 2002, pages 6034 - 6037
QU L ET AL: "Carbon microfibers sheathed with aligned carbon nanotubes: towards multidimensional, multicomponent, and multifunctional nanomaterials", SMALL WILEY-VCH GERMANY, vol. 2, no. 8-9, August 2006 (2006-08-01), pages 1052 - 1059, XP002609255, ISSN: 1613-6810 *
YAMAMOTO N ET AL: "High-yield growth and morphology control of aligned carbon nanotubes on ceramic fibers for multifunctional enhancement of structural composites", CARBON, ELSEVIER, OXFORD, GB LNKD- DOI:10.1016/J.CARBON.2008.10.030, vol. 47, no. 3, 1 March 2009 (2009-03-01), pages 551 - 560, XP025898503, ISSN: 0008-6223, [retrieved on 20081105] *

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* Cited by examiner, † Cited by third party
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JP2018197186A (ja) * 2014-03-31 2018-12-13 日本製紙株式会社 繊維複合体およびその製造方法
US10046539B2 (en) 2014-07-22 2018-08-14 United Technologies Corporation Secondary reinforcement at interface of laminate structure
WO2016092267A1 (fr) * 2014-12-09 2016-06-16 University Of Surrey Nanotubes de carbone
WO2016210249A1 (fr) * 2015-06-25 2016-12-29 Vladimir Mancevski Appareil et procédés pour l'obtention d'un volume élevé de graphène et de nanotubes de carbone sur des feuilles minces de grandes dimensions
CN112900075A (zh) * 2021-01-13 2021-06-04 郑州大学 一种SWNTs/MWNTs同轴纤维及其制备方法和应用

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