EP1701912A2 - Procede de fabrication de nanotubes a paroi unique - Google Patents

Procede de fabrication de nanotubes a paroi unique

Info

Publication number
EP1701912A2
EP1701912A2 EP05700681A EP05700681A EP1701912A2 EP 1701912 A2 EP1701912 A2 EP 1701912A2 EP 05700681 A EP05700681 A EP 05700681A EP 05700681 A EP05700681 A EP 05700681A EP 1701912 A2 EP1701912 A2 EP 1701912A2
Authority
EP
European Patent Office
Prior art keywords
process according
reactor
target
explosively
electron beams
Prior art date
Legal status (The legal status 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 status listed.)
Withdrawn
Application number
EP05700681A
Other languages
German (de)
English (en)
Inventor
Valentin Dediu
Riccardo Lotti
Francesco Cino Matacotta
Carlo Taliani
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Individual
Original Assignee
Individual
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
Application filed by Individual filed Critical Individual
Publication of EP1701912A2 publication Critical patent/EP1701912A2/fr
Withdrawn legal-status Critical Current

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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
    • 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
    • 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
    • C01B2202/00—Structure or properties of carbon nanotubes
    • C01B2202/02—Single-walled nanotubes
    • 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
    • C01B2202/06—Multi-walled nanotubes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J2237/00—Discharge tubes exposing object to beam, e.g. for analysis treatment, etching, imaging
    • H01J2237/30—Electron or ion beam tubes for processing objects
    • H01J2237/31—Processing objects on a macro-scale
    • H01J2237/3142—Ion plating
    • H01J2237/3146—Ion beam bombardment sputtering

Definitions

  • the present invention relates to a process for manufacturing single- wall carbon nanotubes. More specifically, the present invention relates to the preparation of nanoparticles (clusters) of carbon formed by nanotubes or nanofibers and particularly to the preparation of single- wall-nanotubes or SWNT.
  • Carbon nanotubes can be classified into two large categories: multiwall nanotubes and single-wall nanotubes. These two categories of nanotubes form two very different kinds of material in terms of structure and synthesis.
  • Multiwall carbon nanotubes comprise a plurality of single-wall carbon nanotubes arranged concentrically. Nanotube physics is an interesting overlap of molecular physics along the transverse cross-section and of solid-state physics along the axis.
  • the nanotubes can be arranged in bundles of nanotubes (or nanotube strings).
  • high-quality nanotubes is understood to reference nanotubes that have no chemical and structural defects or impurities or amorphous phases over a significant length along the axis of tube.
  • the processes currently used to prepare single-wall carbon nanotubes are based mainly on two techniques: laser ablation, which is a low-yield process that produces mainly single-wall nanotubes (the multiwall nanotube fraction can be a minority), and the Arc- Jet, which is a high-yield process that produces a mixture of nanotubes, mainly multiwall nanotubes, from which it is possible to extract single-wall nanotubes. Growth from the vapor phase instead is used to grow exclusively multiwall carbon nanotubes.
  • the yield depends on the quantity and type of catalysts, on the power and wavelength of the laser, on the temperature, on the pressure and type of inert gas, and on the geometry of the fluid stream in the vicinity of the carbon target.
  • this technique has an important disadvantage, i.e., it allows only to produce fractions of a gram per hour.
  • the material that is collected contains up to 80% by weight of nanotubes, more than half of which is constituted by single- wall nanotubes. The difference is constituted by metallic particles, amorphous carbon and graphite.
  • the Arc- Jet technique which is the most commonly used synthesis process for manufacturing carbon nanotubes, is based on the use of a plasma arc between graphite electrodes.
  • the apparatus used in this technique is constituted schematically by a sealed container in which inert gas is made to flow and in which an electric arc is created between two graphite electrodes that contain suitable catalyst particles. The arc causes the evaporation of the graphite, which cools rapidly by making contact with the inert gas.
  • a large amount of soot is thus produced which is constituted by nano- and microscopic particles of carbon, which are to a large extent amorphous.
  • part of the formed material is constituted by carbon nanotubes, mostly of the multiwall type.
  • the catalysts that are commonly used are particles of iron, nickel, cobalt, yttrium and alloys thereof. This technique produces relatively large quantities of low-purity material.
  • CVD chemical vapor deposition
  • Various forms of carbon fiber, filaments and multiwall nanotubes have been synthesized by CVD.
  • the technique of ablation by pulsed electron beams also known as Channel Spark Ablation (CSA), disclosed in US-5,576,593, has been used successfully to deposit various materials (mainly complex oxides) in the form of thin layers of extremely high purity.
  • CSA Channel Spark Ablation
  • the CSA system is based on generating, inside a hollow cathode, pulsed electron beams from the "glow-discharge" plasma environment.
  • the electron pulse source is supplied by a bank of capacitors, charged by a 5-30 kV HT power supply. By switching an air gap switch or by means of another system capable of ionizing the gas at the base of the apparatus, the electron pulse is activated.
  • the plasma in the hollow cathode generates an electron stream on the order of kA.
  • the resulting electron beam is accelerated by the electrical field and exits, with a duration of 40-200 nanoseconds, through a dielectric channel in the anode deposition chamber.
  • the main applications of the CSA technique are high- temperature superconductor deposition and colossal magnetoresistance manganite deposition.
  • the CSA technique provides a higher deposition rate, a better film quality and also a lower density of defects with respect to the expensive pulsed laser ablation technique.
  • the CSA technique has been used to transfer directly the material of the target onto a substrate in the form of a thin film.
  • the formation of single-wall carbon nanotubes has never been described by means of the CSA technique.
  • Disclosure of the Invention The aim of the present invention is to provide a process for producing single-wall and multiwall carbon nanotubes that also meets the set of requirements mentioned above.
  • a particular object of the present invention is to provide a process that allows to obtain carbon nanotubes in which the content of single-wall nanotubes is higher than the content of multiwall nanotubes.
  • Another object of the present invention is also to provide a process that is more simple and effective and has a lower energy consumption. This aim and these and other objects are achieved, according to the present invention, by a process for preparing single-wall and multiwall carbon nanotubes by ablation, with pulsed electron beams, of a graphite target containing metallic catalysts.
  • a graphite target containing metallic catalysts arranged within a reactor, is subjected to pulsed electron beams, in a stream of inert or hydrogen-containing and oxygen-free preheated gas, in order to produce the explosive evaporation of surface material of the target, said explosively evaporated material being conveyed by said gas stream through the reactor and optionally heated further.
  • the deposition technique uses a tubular deposition reactor made of quartz or of another inert and refractory material, which is in communication with a system for generating pulsed discharges (channel- spark system) (provided as disclosed in US-5,576,793).
  • An inert gas or a gas containing hydrogen in order to eliminate any traces of oxygen in the reaction area, preheated to 700-1200°, is made to flow in the reactor.
  • a graphite target is provided that contains suitable catalyst metals according to the background art related to the two techniques mentioned earlier.
  • Said target is struck by pulsed beams of electrons that arrive from the channel-spark system.
  • each electron pulse causes the explosive vaporization of the material arranged on the surface of the target.
  • Said material constituted by a mixture of ions, neutral atoms and clusters of variously ionized atoms, constitutes a so-called plasma plume at extremely high temperature (much higher than 1200°), which thermalizes with the gas stream kept at 700-1200° and is conveyed toward the area of the reactor where it is heated further.
  • This additional heating can be performed: a) either by means of a heater with a tubular resistor arranged outside the reactor b) or by means of a microwave pulse, optionally in phase relationship with respect to the electron pulse of the channel spark, released by means of an antenna that is arranged collectively with respect to the reactor or by means of a waveguide arranged outside the reactor.
  • a metallic surface is provided downstream of the heating area that is cooled appropriately to a temperature from 500° to 0° C (condenser) and on which the particles produced by the synthesis condense and can be collected.
  • An important aspect of the present invention is the system for adjusting the pressure inside the reactor and inside the channel-spark system, since these two parts of the system necessarily are in communication in order to allow the electron beam to exit from the discharge generator and strike the target arranged in the reactor.
  • the gas pressure required to obtain carbon nanotubes in the reactor is much higher than the maximum pressure at which a correct electron pulse can form in the channel-spark system and accelerate against the target, it is necessary to apply a particular differential pumping system that is capable of maintaining a pressure differential of at least two orders of magnitude between the hollow cathode kept at 10 "2 mbar and the volume that contains the target, which is kept at a pressure between 1 and 10 mbar.
  • the present invention it is possible to operate with electron pulses at a relatively low energy level (lower than 10 kW). However, it is possible to perform heating of the material that derives from the plasma of the plume very rapidly, to a temperature that cannot be determined but is higher than that of the inert carrier gas, (with the possibility to perform synchronization with respect to the electron pulse on the order of tens of nanoseconds and with a pulse duration ranging from tens of nanoseconds to tens of seconds) and very selectively (by utilizing the different absorption of microwaves by the molecular aggregates of carbon and metals that constitute the catalyst with respect to the carrier gas) by means of microwave pulses that are optionally synchronized with the electron pulses of the channel spark, where the term "synchronized" is used in the sense of having the same frequency and a preset phase relationship with respect to them.
  • the process according to the present invention allows to obtain single-wall carbon nanotubes that have identical characteristics as regards purity, homogeneity and intrinsic characteristics with respect to those that can be obtained with laser ablation techniques.
  • the obtainable yields are several orders of magnitude higher, because: a) the yield (in terms of ablated material) per pulse (for an equal energy carried by a single pulse) is higher because of the higher efficiency of the energy release process on the part of the electrons with respect to the photons of the laser; b) the pulse repeat frequency can be increased up to hundreds of hertz, against the tens of hertz that are typical of pulsed lasers that can be used for laser ablation; c) the lower cost of the channel-spark system with respect to laser ablation systems, the lower energy consumption and the greater simplicity of the system allow, for an equal cost, the simultaneous use of at least three devices.
  • Example Figure 1 illustrates the experimental layout used: the central part of a quartz tubular reactor 1 is heated by two electric high-temperature heaters 2, which maintain the temperature in the reactor at 1050 °C.
  • a microwave antenna 11 At the center of the reactor, in a downward region, an opening 3 allows the entry of the pulsed electron beams that arrive from a channel-spark source 4 (shown schematically), which is provided as disclosed in US-5,576,793.
  • a target 9, constituted by a graphite disk containing 0.5 at% of Ni and 0.5 at% of Co is kept at an angle of 45°, at a height of 11-12 mm from the electron passage opening by a quartz support.
  • a sooty material is collected on the nanotube collector 10 (which is associated with a heat exchanger 12), which is constituted by a copper block inserted at the right end of the reactor by means of a sealed coupling and cooled in its part located outside the reactor by an air stream generated by a fan coil (temperature of the internal end of the collector ⁇ 300 °C); said sooty material is constituted, in addition to amorphous carbon and graphite for a total fraction by weight of 15%, by carbon nanotubes, 65% of which is of the single-wall type.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Nanotechnology (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Manufacturing & Machinery (AREA)
  • Composite Materials (AREA)
  • Carbon And Carbon Compounds (AREA)
  • Catalysts (AREA)

Abstract

L'invention concerne un procédé de fabrication de nanotubes à paroi unique et à parois multiples, lequel comprend l'étape consistant à enlever au moyen de faisceaux électroniques pulsés une cible de graphite contenant des catalyseurs métalliques.
EP05700681A 2004-01-08 2005-01-04 Procede de fabrication de nanotubes a paroi unique Withdrawn EP1701912A2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
IT000008A ITMI20040008A1 (it) 2004-01-08 2004-01-08 Processo per la produzione di nanotubi di carbonio a singola parete
PCT/EP2005/000016 WO2005069700A2 (fr) 2004-01-08 2005-01-04 Procede de fabrication de nanotubes a paroi unique

Publications (1)

Publication Number Publication Date
EP1701912A2 true EP1701912A2 (fr) 2006-09-20

Family

ID=34779431

Family Applications (1)

Application Number Title Priority Date Filing Date
EP05700681A Withdrawn EP1701912A2 (fr) 2004-01-08 2005-01-04 Procede de fabrication de nanotubes a paroi unique

Country Status (4)

Country Link
US (1) US20090246116A1 (fr)
EP (1) EP1701912A2 (fr)
IT (1) ITMI20040008A1 (fr)
WO (1) WO2005069700A2 (fr)

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Publication number Priority date Publication date Assignee Title
JP5246765B2 (ja) * 2008-10-29 2013-07-24 国立大学法人 東京大学 カーボンナノチューブ形成方法
IT1395701B1 (it) * 2009-03-23 2012-10-19 Organic Spintronics S R L Dispositivo per la generazione di plasma e per dirigere un flusso di elettroni verso un bersaglio
JP5436348B2 (ja) * 2009-08-07 2014-03-05 ニコライ ククサーノフ カーボンナノ構造体の製造方法および製造装置
JP5523290B2 (ja) * 2010-11-30 2014-06-18 洋 清水 カーボンナノホーンの製造方法および製造装置
RU2614966C2 (ru) * 2015-09-17 2017-03-31 Федеральное государственное унитарное предприятие "Центральный научно-исследовательский институт машиностроения" (ФГУП ЦНИИмаш) Способ получения углеродных нанотрубок в сверхзвуковом потоке и устройство для его осуществления

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Publication number Priority date Publication date Assignee Title
DE4208764C2 (de) * 1992-03-19 1994-02-24 Kernforschungsz Karlsruhe Gasgefüllter Teilchenbeschleuniger
JP3434926B2 (ja) * 1995-02-09 2003-08-11 科学技術振興事業団 巨大フラーレンの製造方法
US7112315B2 (en) * 1999-04-14 2006-09-26 The Regents Of The University Of California Molecular nanowires from single walled carbon nanotubes
DE10207835C1 (de) * 2002-02-25 2003-06-12 Karlsruhe Forschzent Kanalfunkenquelle zur Erzeugung eines stabil gebündelten Elektronenstrahls

Non-Patent Citations (1)

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Title
See references of WO2005069700A2 *

Also Published As

Publication number Publication date
US20090246116A1 (en) 2009-10-01
WO2005069700A3 (fr) 2005-11-24
ITMI20040008A1 (it) 2004-04-08
WO2005069700A2 (fr) 2005-07-28

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