U.S. patent application number 10/864602 was filed with the patent office on 2004-11-11 for carbon nanostructures and methods of preparation.
Invention is credited to Chang, Robert P.H..
Application Number | 20040221813 10/864602 |
Document ID | / |
Family ID | 22689548 |
Filed Date | 2004-11-11 |
United States Patent
Application |
20040221813 |
Kind Code |
A1 |
Chang, Robert P.H. |
November 11, 2004 |
Carbon nanostructures and methods of preparation
Abstract
Methods and apparatus for the preparation of tubular carbon
nanostructures by manipulating the heat treatment and pressure of
various carbon precursors. Methods and apparatus for the
preparation of tubular carbon nanostructures by bombarding
graphitizable carbon precursors with the electron charged
particles.
Inventors: |
Chang, Robert P.H.;
(Glenview, IL) |
Correspondence
Address: |
WINSTON & STRAWN
PATENT DEPARTMENT
1400 L STREET, N.W.
WASHINGTON
DC
20005-3502
US
|
Family ID: |
22689548 |
Appl. No.: |
10/864602 |
Filed: |
June 10, 2004 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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10864602 |
Jun 10, 2004 |
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10231925 |
Aug 29, 2002 |
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6765949 |
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10231925 |
Aug 29, 2002 |
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PCT/US01/07237 |
Mar 7, 2001 |
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60187579 |
Mar 7, 2000 |
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Current U.S.
Class: |
118/723E ;
423/447.1 |
Current CPC
Class: |
B01J 2219/0809 20130101;
B01J 19/088 20130101; B01J 2219/0894 20130101; B82Y 30/00 20130101;
B82Y 40/00 20130101; C01B 32/16 20170801; Y10S 977/743 20130101;
Y10S 977/742 20130101; C01B 32/162 20170801; C01B 32/164 20170801;
B01J 2219/0886 20130101; Y10S 977/90 20130101; C01B 32/154
20170801; C01B 2202/06 20130101; Y10S 977/842 20130101; B01J
2219/0871 20130101; B01J 2219/083 20130101 |
Class at
Publication: |
118/723.00E ;
423/447.1 |
International
Class: |
D01F 009/12 |
Goverment Interests
[0002] The United States government has rights in this invention
pursuant to Grant Nos. DMR9703669 and DMR9632472 from the National
Science Foundation, to Northwestern University.
Claims
What is claimed is:
1. A method for forming tubular carbon nanostructures which
comprises heating a non-graphitizable carbon precursor in the
presence of a gas at a temperature and a pressure sufficient to
form the tubular carbon nanostructures from the carbon precursor,
wherein the temperature and pressure are maintained such that
sublimation of the non-graphitizable carbon precursor is
minimized.
2. The method of claim 1, which further comprises including a
dopant in the non-graphitizable carbon precursor in an amount
sufficient to form increased length tubular carbon nanostructures
than if the dopant is not present.
3. The method of claim 2, wherein the dopant is amorphous boron
which is present in an amount sufficient to increase the length of
the tubular carbon nanostructures to greater than 0.5 microns.
4. The method of claim 1, wherein the non-graphitizable carbon
precursor is carbon black or sucrose carbon.
5. The method of claim 1, wherein the transformation of the
precursor is conducted in the absence of any detectable quantities
carbon vapor.
6. The method of claim 1, wherein the temperature is about
1500.degree. C. to about 3500.degree. C.
7. The method of claim 1, wherein the pressure is from about 50
Torr to atmospheric.
8. The method of claim 1, wherein the temperature is about
1500.degree. C. to about 3500.degree. C. and the pressure is from
about 50 Torr to atmospheric.
9. An apparatus for forming tubular carbon nanostructures which
comprises a furnace including a source of non-graphitizable carbon
precursor, a gas source for adjusting pressure, a heat source
sufficient for formation of tubular carbon nanostructures at a
desired pressure, and a conveyor belt operably connected to the
furnace, the conveyor belt for retaining the source of carbon
precursor in the furnace for a period of time sufficient to form
tubular carbon nanostructures.
10. The apparatus of claim 9, wherein the temperature and pressure
are maintained such that the sublimation of the non-graphitizable
carbon precursor is minimized.
11. The apparatus of claim 10, wherein the furnace is a resistance
furnace.
12. The apparatus of claim 10, wherein the source of
non-graphitizable carbon supplies a dopant so that doped
non-graphitizable carbon is supplied.
13. The apparatus of claim 12, wherein the non-graphitizable carbon
is doped with amorphous boron in an amount sufficient to increase
the length of the tubular carbon nanostructures to greater than 0.5
microns.
14. The apparatus of claim 12, wherein the source of
non-graphitizable carbon precursor supplies carbon black or sucrose
carbon.
15. The apparatus of claim 12, wherein the heat source provides a
temperature of about 1500.degree. C. to about 3500.degree. C.
16. The apparatus of claim 12, wherein the pressure is maintained
at from about 50 Torr to atmospheric.
17. The apparatus of claim 12, wherein the heat source provides a
temperature of about 1500.degree. C. to about 3500.degree. C. and
the pressure is maintained at from about 50 Torr to
atmospheric.
18. An apparatus for forming tubular carbon nanostructures which
comprises a resistance furnace including a source of
non-graphitizable carbon precursor, a gas source for adjusting
pressure, and a heat source sufficient for formation of tubular
carbon nanostructures at a desired pressure.
19. The apparatus of claim 18, which further comprises a conveyor
belt operably connected to the resistance furnace, the conveyor
belt for retaining the source of carbon precursor in the resistance
furnace for a period of time sufficient to form tubular carbon
nanostructures.
20. The apparatus of claim 18, wherein the temperature and pressure
are maintained such that the sublimation of the non-graphitizable
carbon precursor is minimized.
21. The apparatus of claim 20, wherein the source of
non-graphitizable carbon supplies a dopant so that doped
non-graphitizable carbon is supplied.
22. The apparatus of claim 21, wherein the non-graphitizable carbon
is doped with amorphous boron in an amount sufficient to increase
the length of the tubular carbon nanostructures to greater than 0.5
microns.
23. The apparatus of claim 20, wherein the source of
non-graphitizable carbon precursor supplies carbon black or sucrose
carbon.
24. The apparatus of claim 20, wherein the heat source provides a
temperature is about 1500.degree. C. to about 3500.degree. C.
25. The apparatus of claim 20, wherein the pressure is maintained
at from about 50 Torr to atmospheric.
26. The apparatus of claim 20, wherein the heat source provides a
temperature of about 1500.degree. C. to about 3500.degree. C. and
the pressure is maintained at from about 50 Torr to atmospheric.
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application is a division of U.S. application Ser. No.
10/231,925, filed Aug. 29, 2002, which is a continuation of the
U.S. National Stage designation of International Application
PCT/US01/07237, filed Mar. 7, 2001, which claims the benefit of
U.S. Provisional Application No. 60/187,579, filed Mar. 7, 2000.
The contents of each of these applications is expressly
incorporated herein by reference thereto.
BACKGROUND OF THE INVENTION
[0003] Since the discovery of carbon nanotubes (S. Iijima, Nature
354, 56 (1991); T. W. Ebbesen and P. M. Ajayan, Nature 358, 220
(1992)) there have been many applications for such materials. Their
size and high aspect ratios leads to possible use as electron
emitters for flat panel displays (Q. H. Wang, A. A. Setlur, J. M.
Lauerhaas, J. Y. Dai, E. W. Seelig, and R. P. H. Chang, Appl. Phys.
Lett. 72, 2912 (1998)) and AFM/STM probes. (H. Dai, J. H. Hafner,
A. G. Rinzler, D. T. Colbert, and R. E. Smalley, Nature 384, 147
(1996).) In addition, the reduced number of defects in nanotubes
could make them the ultimate carbon fiber in terms of strength and
stiffness. (M. M. J. Treacy, J. M. Gibson, and T. W. Ebbesen,
Nature 381, 678 (1996); E. W. Wong, P. E. Sheehan, and C. M.
Lieber, Science 277, 1971 (1997).)
Carbon Nanotubes
[0004] Carbon tubules and related nanostructures are typically
prepared using standard arc-discharge techniques. Generally, the
discharge is in a reaction vessel through which an inert gas flows
at a controlled pressure. The potential, either direct or
alternating current, is applied between two graphite electrodes in
the vessel. As the electrodes are brought closer together, a
discharge appears resulting in plasma formation. As the anode is
consumed, a carbonaceous deposit forms on the cathode, a deposit
that under the proper conditions contains the desired carbon
nanotubules.
[0005] However, conventional methods of making multi-walled
nanotubes via arc discharge do not easily lend themselves to large
scale production. (D. T. Colbert, J. Zhang, S. M. McClure, P.
Nikolaev, Z. Chen, J. H. Hafner, D. W. Owens, P. G. Kotula, C. B.
Carter, J. H. Weaver, A. G. Rinzler, and R. E. Smalley, Science
266, 1218 (1994).)
[0006] A variation of this general synthetic procedure is reflected
in U.S. Pat. No. 5,482,601, wherein carbon nanotubes are produced
by successively repositioning an axially extending a graphite anode
relative to a cathode surface, while impressing a direct current
voltage therebetween, so that an arc discharge occurs with the
simultaneous formation of carbon nanotubes as part of carbonaceous
deposits on the various portions of the cathode surface. The
deposits are then scraped to collect the nanotubes. The anode must
be repositioned respective to the cathode, repeatedly, to provide
larger quantities of the desired nanotube product.
[0007] Related technology is described in U.S. Pat. No. 5,877,110
whereby carbon fibrils are prepared by contacting a metal catalyst
with a carbon-containing gas. The fibrils can be prepared
continuously by bringing the reactor to reaction temperature,
adding metal catalyst particles, then continuously contacting the
catalyst with a carbon-containing gas. Various complexities
relating to feed rates, competing side reactions and product
purity, among others, tend to detract from the wide-spread
applicability and acceptance of this approach.
[0008] At low temperatures, namely below 1500.degree. C. processes
currently used in chemical vapor deposition syntheses of carbon
nanotubes require metal catalysts such as iron, nickel or cobalt.
This approach necessitates an additional chemical-processing step
to remove the metal particle catalysts. In so doing, defects are
generated in the carbon nanotubes.
[0009] It is possible to make spherical or polyhedral graphitic
nanoparticles like those made in the carbon arc by the heat
treatment of various carbon materials. (A. Oberlin, Carbon 22, 521
(1984); P. J. F. Harris and S. C. Tsang, Phil. Mag. A 76, 667
(1997); W. A. de Heer and D. Ugarte, Chem. Phys. Lett. 207, 480
(1993); P. J. F. Harris, S. C. Tsang, J. B. Claridge. M. L. H.
Green, J. Chem. Soc. Faraday Trans. 90, 2799 (1994).) However, only
short (<100 nm) nanotubes have been made by annealing fullerene
soot. (W. A. de Heer and D. Ugarte, Chem. Phys. Lett. 207, 480
(1993); P. J. F. Harris, S. C. Tsang, J. B. Claridge. M. L. H.
Green, J. Chem. Soc. Faraday Trans. 90, 2799 (1994).). While it is
possible to scale up heat treatment methods, significant
improvements need to be made in order to produce high quality
nanotubes like those produced by the arc method.
Graphitization of Carbon
[0010] Understanding the growth mechanisms for carbon
nanostructures is important as a first step towards developing new
apparatus and methods for preparation. It is instructive to
consider several concepts underlying graphitization in the
preparation of carbon nanotubes. Graphitization begins with carbon
self-diffusion, leading to order in the ab planes of graphite. (L.
E. Jones and P. A. Thrower, Carbon 29, 251 (1991).) Once ordering
begins to occur, graphitic regions assemble into a layered
structure. In this process, defects are progressively removed from
aromatic layers at higher temperatures. (L. E. Jones and P. A.
Thrower, Carbon 29, 251 (1991); E. Fitzer, K. Mueller, and W.
Schaefer, in Chemistry and Physics of Carbon (Marcel Dekker, Inc.,
New York, 1971), Vol. 7, p. 237; D. B. Fischbach, in Chemistry and
Physics of Carbon (Marcel Dekker, Inc., New York, 1971), Vol. 7, p.
1; A. Oberlin, Carbon 22, 521 (1984); R. E. Franklin, Proc. Roy.
Soc. A 209, 196 (1951); P. J. F. Harris and S. C. Tsang, Phil. Mag.
A 76, 667 (1997).)
[0011] When many of the defects initially present in
non-graphitizable carbons cannot be removed, extensive formation of
three dimensional graphite is prevented. Consequently,
graphitization of a carbon material is controlled by the initial
structure of the carbon material as well as the processing
conditions. (E. Fitzer, K. Mueller, and W. Schaefer, in Chemistry
and Physics of Carbon (Marcel Dekker, Inc., New York, 1971), Vol.
7, p. 237; D. B. Fischbach, in Chemistry and Physics of Carbon
(Marcel Dekker, Inc., New York, 1971), Vol. 7, p. 1; A. Oberlin,
Carbon 22, 521 (1984); R. E. Franklin, Proc. Roy. Soc. A 209, 196
(1951); P. J. F. Harris and S. C. Tsang, Phil. Mag. A 76, 667
(1997).)
[0012] To date, there is a general consensus in the art that carbon
vapor in the form of atoms, ions, or small molecules is necessary
for multiwalled nanotube growth without metal catalysts. (E. G.
Gamaly and T. W. Ebbesen, Phys. Rev. B 52, 2083 (1995); T. Guo, P.
Nikolaev, A. G. Rinzler, D. Tomanek, D. T. Colbert, and R. E.
Smalley, J. Phys. Chem. 99, 10694 (1995); J. C. Charlier, A. De
Vita, X. Blase, and R. Car, Science 275, 646 (1997); Y. K. Kwon, Y.
H. Lee, S. G. Kim, P. Jund, D. Tomanek, and R. E. Smalley, Phys.
Rev. Lett. 79, 2065 (1997); M. Buongiomo Nardelli, C. Roland, J.
Bernholc, Chem. Phys. Lett. 296, 471 (1998).) It has also been
proposed that ordered, graphitic precursors are essential for
nanotube growth. (J. M. Lauerhaas, J. Y. Dai, A. A. Setlur, and R.
P. H. Chang, J. Mater. Res. 12, 1536 (1997).) The complexity of the
arc process makes it very difficult to study the formation of these
materials or draw any conclusions regarding conditions necessary to
maximize optimal growth and/or yield.
[0013] Accordingly, there is still a need in the art of
manufacturing tubular carbon nanostructures, such as carbon
nanotubes, for processes and apparatus therefor, which can provide
carbon nanotubes essentially free of carbon overcoat, free of any
metal catalysts, and generally free of defects caused by removal of
catalytic materials usually present in carbon nanotubes prepared by
chemical vapor deposition processes.
[0014] There are a considerable number of problems and deficiencies
associated with carbon nanostructures of the prior art, with most
such shortcomings resulting from the current methods of
preparation. There is a demonstrated need for innovative methods of
preparation so as to provide such compositions in high yield, at
large scale and with the desired mechanical, structural and
performance properties.
OBJECTS OF THE INVENTION
[0015] Accordingly, it is an object of the present invention to
provide various methods and/or apparatus, which can be used in the
preparation of carbon nanostructures, thereby overcoming the
problems, deficiencies and shortcomings of the prior art, including
those outlined above. It will be understood by those skilled in
that the art that one or more aspects of this invention can meet
certain objectives, while one or more other aspects can meet
certain other objectives. Each objective may not apply equally, in
all instances, to every aspect of this invention. As such, the
following objects can be viewed in the alternative with respect to
any one aspect of the present invention.
[0016] It can also be an object of the present invention to provide
a method of using solid disordered carbon materials in the
preparation of multi-walled carbon tubes and/or hollow, tube-like
structures of nanometer dimension.
[0017] It can also be an object of the present invention to provide
a method of using a disordered carbon material, and/or by utilizing
techniques and processes analogous to graphitization.
[0018] It can also be an object of the present invention to provide
a disordered carbon material as a source of pentagonal carbon
and/or polyhedral structure enroute to the preparation of various
tubular carbon nanostructures.
[0019] It can also be an object of the present invention to provide
a method of preparing carbon nanotubes under conditions not
conducive to carbon sublimation and/or substantially without the
use of carbon vapor.
[0020] It can also be an object of the present invention to provide
a method for preparation of carbon nanostructures of the type
described herein, having enhanced and/or superior structural or
mechanical properties, including but not limited to overall length
and strength.
[0021] It can also be an object of one present invention to prepare
carbon nanostructures of lengths exceeding those now available
through the prior art, including lengths up to and greater than 0.5
.mu.m, through choice of carbon precursor and/or process
conditions, none of which would be evident, suggested or taught by
the prior art.
[0022] It can also be object of the present invention to provide a
method of using temperature, heating rate and/or related process
kinetics to control the growth, development and/or structure of
carbon nanotubes and/or tubular structures.
[0023] It can also be an object of the present invention to provide
a method of promoting open-ended growth of carbon nanocompositions,
so as to enhance various mechanical or performance properties of
the resulting structures.
[0024] It can also be an object of the present invention to provide
an apparatus to effect one or more of the objects presented herein,
as well as to increase the yield and/or production rate of carbon
nanotubes.
[0025] It can also be an object of the present invention to provide
a method and/or apparatus for the batch, continuous or
semi-continuous production of carbon nanostructures, of the type
described herein, and/or to optimize process conditions enroute to
tubules and tube-like structures having enhanced structural,
mechanical and/or performance properties.
[0026] Other objects, features, benefits and advantages of the
present invention will be apparent in this summary, together with
the following descriptions and examples, and will be readily
apparent to those skilled in the art having knowledge of various
synthetic methods, preparation of such carbon compositions and/or
apparatus which can be used therewith. Such objects, features,
benefits and advantages will be apparent from the above as taken in
conjunction with the accompanying examples, figures, data and all
reasonable inferences to be drawn therefrom.
SUMMARY OF THE INVENTION
[0027] The present invention, which addresses the needs of the
prior art, provides a method of forming tubular carbon
nanostructures by heating a disordered carbon precursor in the
presence of a gas at a temperature and pressure sufficient to form
the tubular carbon nanostructures. The tubular carbon
nanostructures made by the methods of the present invention include
multiwalled carbon nanotubes having an outside diameter of
typically 5 to 40 nm and a length in the range of 50 to 150
micrometers. The method is enhanced by further adding charged
particles provided by an electrical discharge between a cathode and
an anode. The formation of tubular carbon nanostructures is also
enhanced by including a dopant in the disordered carbon precursor.
The temperature and pressure at which the methods for forming
tubular carbon nanostructures are conducted must be adjusted such
that they are below that which would cause sublimation of the
disordered carbon precursor. The dopant is preferably amorphous
boron which is added in an amount sufficient to increase the length
of the tubular carbon nanostructures to greater than 0.5 microns.
The disordered precursor useful in the present invention is
fullerene soot, ball milled graphite, carbon black or sucrose
carbon. The methods provided by the present invention are
preferably conducted in the absence of any significant sources of
carbon vapor. The methods of the invention further include
controlling the arc-furnace temperature and the heating rate of the
precursor to form multiwalled carbon nanotubes.
[0028] The methods of the present invention also include forming
tubular carbon nanostructures by discharging a direct current arc
between an anode and cathode, the anode, including a conducting
electrode containing a carbon precursor, the discharging occurring
in the presence of a gas, at a temperature and pressure such that
the carbon precursor is maintained in solid phase and for a period
of time sufficient to form tubular carbon nanostructures. When
forming the tubular carbon nanostructure is accomplished primarily
by heating, the carbon precursor is preferably non-graphitizable
carbon. On the other hand, when the method includes heating the
carbon precursor with electron charged particles then the preferred
carbon precursor can include graphitizable carbon. A
non-graphitizable carbon includes fullerene soot, carbon black or
sucrose carbon. Graphitizable carbon includes PVC. The methods of
the present invention can be conducted at the pressure from 50 torr
to atmospheric and at a temperature range from about 1500.degree.
C. to about 3500.degree. C.
[0029] The present invention also provides an apparatus for forming
tubular carbon nanostructures which is preferably an arc-furnace.
The apparatus comprises a cathode, an anode opposite the cathode, a
source of voltage and current in an amount sufficient to create
charged particles and to produce an arc between the anode and
cathode, a source of gas to surround the arc, and the source of
carbon precursor positioned adjacent the anode and within the arc,
such that the arc has a sufficiently high temperature and is
maintained at a pressure for a time sufficient to heat the carbon
precursor to form carbon nanotubes upon the anode.
[0030] The anode may have different geometries. The anode
preferably has a recess positioned in the anode to receive the
charged particles from the arc. In the recess of the anode the
carbon precursor is received. The methods of the invention are
conducted in a gaseous environment, wherein the gas is a inert gas
or nitrogen. The anode may also be a platform positioned within the
arc and optionally including a surface which envelopes the platform
to retain the precursor therein. The platform may be further
movable through the enveloping structure of the anode. The anode
may also be circular platform having radial ribs, and spaces
between the ribs for receiving the carbon precursor and also a
recess for collecting the carbon nanotubes. The anode can also
include a circular platform rotatably attached to the anode such
that the platform includes a location for the carbon precursor and
a recess for collecting the carbon nanotubes.
[0031] The present invention also provides an apparatus for forming
tubular carbon nanostructures which includes a resistance furnace
having at least one opening adapted to receive a conveyor belt. The
furnace further includes a source of carbon precursor, a gas source
for adjusting the pressure, a heat source sufficient for the
formation of tubular carbon nanostructures at the desired pressure.
The conveyor belt is operably connected to the resistance furnace
and is utilized to retain the source carbon precursor in the
resistance furnace for a period of time sufficient to form the
tubular carbon structures. Once they have been formed the conveyor
belt takes the carbon nanotubes out of the resistance furnace for
delivery to a user.
BRIEF DESCRIPTION OF THE DRAWINGS
[0032] FIG. 1 shows micrographs of products made when annealing
activated fullerene soot with amorphous boron at 2200.degree. C.:
1A, Scanning electron microscopy (SEM) micrograph showing nanotubes
and nanotube bundles; 1B, Transmission electron microscopy (TEM)
micrograph of a nanotube tip showing incomplete closing of the
nanotube tip; 1C, TEM micrograph of a nanotube with its inner
shells closed off; 1D, TEM micrograph of polyhedral graphitic
particles.
[0033] FIG. 2 shows TEM micrographs of the products made when
annealing other carbon materials with boron to 2200.degree. C.: 2A,
twisted and tangled graphitic layers made when annealing carbon
black with boron; and 2B, large closed carbon particles made when
annealing ball milled carbon and boron.
[0034] FIG. 3 shows, graphically, products made when annealing a
sucrose carbon with boron to 2200.degree. C.: 3A, TEM micrograph of
an open ended nanotube; and 3B, TEM micrograph of a one nanotube
possibly attached to a larger graphitic particle and another
nanotube with numerous inner compartments.
[0035] FIG. 4 shows micrographs of products made by annealing
carbon materials with an arc furnace: 4A, SEM micrograph of
nanotubes and nanotube bundles made using activated fullerene soot;
4B, High resolution TEM micrograph of a multiwalled nanotube made
using activated fullerene soot; 4C, SEM micrograph of nanotubes and
nanotube bundles made using carbon black; and 4D, SEM micrograph of
annealed graphite powder.
[0036] FIGS. 5A and 5B provide schematic representations of
apparatus and/or equipment of the type useful with the methods of
this invention.
[0037] FIG. 6A shows micrographs of nanostructured product, in
accordance with this invention, and more particularly as provided
through the apparatus Example 7: 6A-L show, by increasing
magnification, product formed in the anode recess and as lifted
therein to show the various structural features and morphologies;
FIGS. 6I-6L, in particular, show the resulting carbon nanotubes in
good detail.
[0038] FIG. 7 is a schematic representation of a system, as further
discussed in Example 8, which can be used with the continuous or
semi-continuous production of carbon nanotubes and/or related
structures, as otherwise described herein and in accordance with
this invention.
[0039] FIG. 8A is a schematic representation of an arc-furnace
known in the art.
[0040] FIG. 8B is a schematic representation of an arc-furnace of
the type useful with the methods of the present invention.
[0041] FIGS. 9A and 9B are schematic representations of an
arc-furnace where the anode electrode is made of radial ribs in
FIG. 9A and the anode electrode is made of spiraling-shaped ribs in
FIG. 9B.
[0042] FIG. 10 shows a micrograph of a carbon nanotube layer
obtained by using an arc-furnace having tungsten electrodes.
[0043] FIGS. 11A and 11B show micrographs of carbon nanotubes
formed in an arc-furnace under atmospheric pressure of helium
gas.
[0044] FIG. 12 is an arc-furnace wherein the anode electrode has
two holes.
[0045] FIG. 13 is a micrograph of carbon nanotubes formed from PVC
as carbon precursor.
[0046] FIG. 14 shows micrographs of carbon nanotubes formed from a
mixture of 50% carbon black and 50% graphite powder and 100% carbon
black when subjected to the methods of the invention.
[0047] FIG. 15 is a high resolution micrograph of a section of a
typical carbon nanotube made from carbon black precursor at 100
torr of helium gas and in the arc-furnace of the invention.
[0048] FIG. 16 is a schematic representation of a system as
described in Example 12 for an alternate feed configuration.
DETAILED DESCRIPTION OF THE INVENTION
[0049] As would be well known to those skilled in the art and made
aware by this invention, the tubular, carbon compositions can have
structures similar to those described in the prior art--sheets
arranged about a longitudinal axis to provide multi-walled
configurations. Examples of such structures, and of the type
available through use of the present invention, are shown in the
figures described herein. In particular, however, it has been shown
that a scrolled arrangement is a preferred structure, one providing
a variety of enhanced mechanical properties. Through the present
invention, process conditions can be optimized to increase yield of
the structures having the desired mechanical, structural and
performance properties.
[0050] According to the present invention, the process of carbon
nanotube formation can be accelerated by increasing the synthesis
temperature between 1500.degree. C. to 3500.degree. C., doping the
carbon precursors with boron to enhance diffusion, and interacting
the carbon precursors with a large flux of low (in the tens of
volts) energy electrons. High energy electrons help to break and
reconfigure the carbon bonds in the precursors used in the
synthesis process. Doping of the carbon precursors with boron
enhances the synthesis of nanotubes at 2200.degree. C.
[0051] In another embodiment, an alternate method was developed in
which the furnace temperature was increased to about 3500.degree.
C. and low energy electrons were also added to enhance the
process.
[0052] In the methods of Iijima, the arc electrodes are made of two
graphite rods as shown in FIG. 8-a. During the operation, the anode
materials are evaporated and nanotube deposits are formed on the
cathode. The deposits are then scrapped off for analysis.
[0053] In the present invention an arc furnace as shown in FIG.
8-b, the anode electrode had a hole drilled to receive the carbon
precursors. The rim of the anode electrode served to conduct most
of the current of the arc. By operating at the right pressure range
the evaporation of the carbon precursor was minimized. In addition,
the arc plasma electrons were also attracted to the precursor in
the "crucible" or recess of the anode. The energy of these
electrons was typically a few tens electron volts, so they could
help the process of making carbon nanotubes. With this electron
bombardment, it was possible to use graphitizable carbon as a
precursor for the formation of carbon nanotubes, as also described
in Example 4 hereinbelow.
[0054] While this present invention teaches the formation of carbon
nanotubes using solid state sources, it should also apply to liquid
or fluidic state of the precursors. In fact, when polymeric
precursors are used, with the increase of temperature the material
goes through a phase transition to a glassy state. Thus, all glassy
(fluidic) and solid state precursors with the presence of
non-hexagonal and hexagonal structures will be useful for the
purposes of the present invention.
[0055] As discussed more thoroughly in the following examples, an
apparatus usable with the present invention can include an anode,
graphitic or of other construction, with a recess of appropriate
surface and/or volume dimension. An arc discharge between a
suitable cathode structure and the anode anneals a solid
carbonaceous material positioned within the recess. Larger
quantities of carbon nanostructures can be prepared by increasing
the recess dimension, corresponding surface area and/or the amount
of carbon starting material positioned therein.
[0056] Properties of the carbon nanotubes obtained in the
arc-furnace of the present invention have an outside diameter of
typically 5 to 40 nm and a length in the range of 50 to 150
micrometer, and an aspect ratio in the range of ten thousand. The
quality of the carbon nanotubes is similar to that produced by the
classical arc method-very low defects, very low wall coating of
carbonaceous materials as can be seen in FIG. 15. In fact, by using
the methods of the invention with the addition of hydrogen gas
10-20% the carbon nanotubes are free of surface and internal carbon
debris. See, for example, U.S. Pat. No. 5,916,642 to R. P. H.
Chang.
[0057] The prior art has been concerned with finite geometries for
plasma generation; i.e., standard electrode configurations. The
present invention, however, also provides alternate geometries for
apparatus to effect the methods described herein. For example, a
suitable carbon precursor can be placed or contained on a surface
or platform. Another surface can envelop or cup the precursor
platform, whereby application of a potential between the two
surfaces provides a discharge, resulting plasma and a current drawn
through the precursor. Preferred embodiments for such an apparatus
can include a precursor platform moveable through or within the
aforementioned biased cup or enveloping structure. Sequential
application of potential provides for the continuous or
semi-continuous production of the desired carbon
nanostructures.
[0058] For instance, through a straightforward adaptation of the
apparatus described herein, various anode geometries and/or carbon
precursor supports can be arranged in conjunction with a moving
surface, and biased at a potential difference relative to a
proximate a cathode or other such conducting geometry. Such a
support might be arranged as part of a conveyor or belt, or similar
such structure as would be understood by those skilled in the art.
Alternatively, the cathode or equivalent structure might be
positioned sequentially relative to a corresponding array of carbon
starting materials. Regardless, kilogram quantities of the desired
carbon nanostructures can be prepared, as described in or could be
understood through the following examples.
[0059] In another embodiment, the arc furnace was again made of two
electrodes, each having a 10 inch diameter or larger as shown in
FIG. 9-a. The anode electrode was made of radial ribs with sections
in between for the radial feed of precursors. The hole in the
center of the anode is the location from where the processed carbon
nanotubes are extracted. In another related embodiment the anode
was rotating the radial feed at one location only. In this case the
anode electrode was made of spiraling shaped ribs as shown in FIG.
9-b. Again, the processed carbon nanotubes were extracted from the
center recess or hole.
[0060] An arc furnace having electrodes of 3/8" diameter to 1"
diameter were used to synthesize carbon nanotubes. It was found
that the rate of deposition or carbon nanotubes was typically 2.5
mg/minute for 1" diameter rod. By extrapolating this rate to a
ten-inch diameter electrode in a continuous feed process as
described above, 360 grams/day can be obtained. However, 30%
efficiency, 100 grams/day, can be produced. Thus, ten processing
units can produce 1 Kg/day.
[0061] In another aspect of the present invention, another method
of synthesizing carbon nanotubes in a continuous way is provided by
using the arc-furnace shown in FIG. 16. Carbon precursors are fed
into a tubing which they are transported into the arc-furnace
zone(s) for processing. There can be a series of arc-furnaces in
tandem to improve the processing efficiency. The arc-furnace was
the same as that described in Example 7 except that the electrodes
are tubular and constructed of metal, for example tungsten. The
arc-furnace is again powered by a direct current supply. After
going through the heating zone(s), the carbon nanotubes are
extracted from the opposite end. The feeding of the precursors can
be by a mechanical pusher or pressurized gas.
[0062] As described elsewhere, herein, use of a dopant such as
boron can alter the operative kinetics and lower the effective
reaction temperature relative to heat treatment techniques. An
alternate approach, also described as part of the present
invention, is the interaction of charged particles with a suitable
carbon precursor. As mentioned above, in the context of the prior
art, an arc discharge effectively generates a high current and the
requisite charged species. The resulting plasma can be used alone
or in combination with a heat source to effect the desired
transformation. The requisite power input that is sufficient or
appropriate for the methods described herein, and as would be
well-known to those skilled in the art and familiar with this
invention and standard energy relationships. However, typical arc
energy content and corresponding power inputs can approach 2
kilowatts/cm.sup.2 and can reach or exceed 5 kilowatts/cm.sup.2 as
necessary or to effect the sort of transformations described
herein.
[0063] The plasma conditions can be utilized alone or in
combination with a heat source--ranging from radiant thermal energy
to any radiation within the electromagnetic spectrum, as would be
well known to those skilled in the art. The temperatures employed
are generally up to about 2000.degree. C., or as otherwise dictated
by the heat resistance and functional limitations of the apparatus
components. As new materials and components are devised, the
operative temperature range can expand with improvements in
structural integrity.
[0064] Even so, increasing temperature is a concern with respect to
the source of carbon precursor. High temperatures under given
pressure conditions can vaporize the precursor before reaction. Use
of carbon sources, as described herein, is therefore incumbent upon
consideration of competing sublimation reactions. As would be
understood by those skilled in the art, a straightforward
consideration of the interaction between pressure and temperature,
the proper combination of reaction parameters can be chosen to
effect the desired transformation--such conditions not inducing
sublimation of either the carbon precursor or the resulting
nanostructures.
EXAMPLES OF THE INVENTION
[0065] The following non-limiting examples and data illustrate
various aspects and features relating to the compositions,
apparatus and methods of this invention, including the surprising
and unexpected results obtained using solid disordered carbon
precursors in the preparation of structures of nanometer dimension.
Comparable advantage, benefit and/or utility can be realized using
various other carbon sources or other embodiments of the inventive
methods and/or apparatus.
Example 1
[0066] Fullerene soot was made by the arc evaporation of graphite
at 450 Torr of He, then activated in a flowing CO.sub.2 atmosphere
at 850.degree. C., which increased its surface area. The soot was
then mixed with varying amounts (0-20 wt %) of amorphous boron and
annealed under flowing He in a graphite resistance furnace to
2200-2400.degree. C. Boron was added to accelerate the assembly of
fullerene soot by acting as a fast diffuser in the basal planes of
graphite. Annealing fullerene soot without boron provided
polyhedral carbon particles as in previous experiments. In
comparison, analysis of the annealed fullerene soot mixed with
boron showed nanotubes with length much longer than 0.5 .mu.m (FIG.
1A).
Example 2
[0067] High resolution micrographs (FIGS. 1B and 1C) show that the
tubes of example 1 made using boron were similar to multiwalled
nanotubes made using an arc discharge, with occasional kinks in the
nanotube (FIG. 1C). However, some nanotube ends were not completely
closed and had disordered carbon around the tip (FIG. 1B). The
disordered carbon at the tip indicates that growth was frozen
either when the furnace was cooling or when the local carbon supply
was exhausted. The inner shells of nanotubes were occasionally
closed off, as in some nanotubes produced in an arc discharge (FIG.
1C). Polyhedral graphitic nanoparticles were the majority of the
products (FIG. 1A).
Example 3
[0068] The applicability of this invention was extended to other
disordered carbon materials: for example, ball milled graphite and
sucrose carbon. While heat treatment of ball milled graphite with
boron (FIG. 2) did not produce any nanotubes (only bent and tangled
graphitic sheets and closed particles are found), annealing sucrose
carbon with boron does produced multiwalled carbon nanotubes (FIG.
3). Open nanotubes were also seen in these experiments (FIG. 3A).
The overall yield of nanotubes when annealing sucrose carbon was
low. These experiments show that it is possible to make nanotubes
by controlling the heat treatment of common and inexpensive organic
materials. Also, some nanotubes might be attached to graphitic
particles as shown in FIG. 3B. These larger graphitic particles
might act as nucleation sites for nanotubes. However, if this were
the case, every heat treatment sample should have nanotubes because
after heat treatment all samples had similar graphitic particles.
Consequently, it is believed that the presence of larger graphitic
particles does not influence the nucleation of these nanotubes.
[0069] There were no significant sources of carbon vapor in these
experiments, because the annealing temperature was kept well below
the sublimation point for carbon (>3000 K). Consequently, it is
unlikely that single carbon atoms, ions, or molecules directly lead
to multiwalled nanotube growth, which is in direct contrast to many
mechanisms known in the art for carbon nanotube growth.
[0070] One possibility is that boron or another such dopant could
catalyze nanotube growth through a carbon dissolution and
precipitation process through boron carbide nanoparticles. This is
a common mechanism for the acceleration of graphitization in the
presence of impurities and would be similar to catalytic processes
to make nanotubes. However, if nanotubes were made by this process
the starting structure of the carbon should not affect the yield of
nanotubes.
[0071] Boron carbide (B.sub.4C) was formed by the reaction of
elemental boron with disordered carbon when T>1600.degree. C.,
and it begins to decompose at T>2000.degree. C. However, this
mechanism should not be dependent upon the initial carbon material,
only the dissolution and precipitation of carbon. As shown herein,
the initial carbon material and its structure determine whether or
not nanotubes are made.
[0072] In addition, it appears that the nanotubes prepared herein
grow by an open-ended mechanism (FIGS. 1B and 3A), in contrast to
nanotubes grown by catalytic and carbide decomposition methods. It
is, therefore, believed that nanotubes were not made by a
dissolution/precipitation process in these experiments, but rather
that the structure of the starting carbon determined nanotube
formation in a manner analogous to a graphitization process.
[0073] Even with the proper carbon source or precursor, processing
conditions controlled or contributed to nanotube formation. If the
role of boron or another dopant was to lower the temperature and/or
accelerate the kinetics of the heat treatment, in light of one
present invention it would be possible to otherwise manipulate the
heat treatment of the present carbon materials to prepare nanotubes
in good yield, usable quantities and without impurities.
Presumably, the kinetics of this process would be quickened (in
comparison to a typical furnace experiment) if the heating rate and
ultimate heat treatment temperature were as high as possible.
Example 4
[0074] Other interactions can help keep the nanotubes open during
growth. For example, there was some interaction found between the
walls of some of the open nanotubes as shown in FIG. 3A. This could
be interpreted as experimental evidence of the "lip-lip"
interaction between the walls of a growing nanotube.
[0075] A key structural parameter in the disordered carbons that
determined nanotube growth in these experiments was the presence of
pentagons. Amorphous carbon produced by arc evaporation has been
described as small hexagonal regions separated by pentagons and
heptagons and the presence of pentagons in fullerene soot has been
inferred through its chemical reactivity. It also has been proposed
that pentagons may be present in non-graphitizable carbons, such as
sucrose carbon and carbon black and that they are a defect that
determines whether or not a carbon is graphitizable. Pentagons in a
graphite sheet would allow it to curl up and form a nucleus for
nanotube or nanoparticle growth. Upon formation of a nucleus, the
process of agglomeration and ordering of hexagons and pentagons in
non-graphitizable carbons led to formation of carbon nanotubes and
polyhedral particles. The importance of pentagons explains the
rarity of nanotubes in experiments with graphitizable carbons.
There are variations in the nanotube yields for different
non-graphitizable carbons. Presumably, this is due to changes in
the structure (pentagon/hexagon/heptagon ratio) of the
non-graphitizable carbon.
[0076] In processing these materials, extremely high temperatures
or fast diffusers were necessary in order to facilitate carbon
nanotube growth. This would lead to more diffusion and a wider and
thicker nanotube/nanoparticle nucleus structure, which would tend
to keep the nanotube open for growth. The incomplete formation of
the tip as shown in FIGS. 1B and 3A indicated that these nanotubes
were probably formed via an open-ended growth process. The tendency
to form additional graphitic layers when the kinetics was enhanced
was also seen in the polyhedral particles formed in experiments
according to the present invention as shown in FIG. 1D. In general,
the carbon nanotubes obtained by methods of the present invention
were larger with thicker walls than those found when annealing pure
fullerene soot at about 2400.degree. C.
Example 5
[0077] In this example, an arc discharge was used to fuel a furnace
for annealing carbon materials at high temperature and ramp rates.
Reference is made to FIGS. 5A-B. Cathode (18) was a water cooled Cu
rod, and the graphite anode (16) was 1.0 cm in diameter had a 0.5
cm hole bored 0.5 cm deep into it with an appropriate carbon
material (12) packed therein. An arc was struck (17-18 V, 100 A,
and 4 minutes duration) under 100 Torr of He, which is quite
different from the optimal pressure for nanotube deposit growth on
the cathode. The resulting plasma can be used alone or in
combination with a heat source (15) to effect the desired
transformation. The center of the anode top was then analyzed by
SEM and TEM.
Example 6
[0078] When fullerene soot, without any added boron was treated
using the furnace of the preceding example, the products were
multiwalled carbon nanotubes and nanoparticles as shown in FIGS. 4A
and B. This method of making carbon nanotubes was also extended to
other non-graphitizable carbons such as carbon black as illustrated
in FIG. 4C. In contrast, when annealing graphitizable carbons such
as polyvinyl chloride carbon or graphite powder, carbon nanotubes
were generally not found in the center of the anode as shown in
FIG. 4D. Again, the dependence upon the starting carbon material
suggests the formation of nanotubes is analogous to a
graphitization process.
Example 7
[0079] Using apparatus (10) of the type illustrated in FIG. 5B, a
suitable amount of carbon black (12) was positioned in the recess
(14) of a graphite anode (16). After several minutes, under
appropriate conditions (.about.20 V, 100 A, 1-760 Torr of He),
several milligrams of nanostructured material were produced, as
characterized elsewhere herein, and as shown micrographically in
FIGS. 6A-6L. A fold of the resulting material was lifted as shown
in FIGS. 6A-6D to reveal various structural features. Increasing
magnification in FIG. 6 shows the fine, tubular morphology.
Example 8
[0080] With reference to apparatus (10) illustrated in FIG. 7, the
production of carbon nanotubes could be scaled up to provide
kilogram quantities, given 1 gram production using a 1-inch
diameter surface, over a 24-hour period. An array of such
anode/carbon starting material configurations (20) can be
sequentially positioned relative to a suitably-dimensioned cathode
structure (i.e., 18 or 22). Repetitious arc discharges can provide
the energy required for the desired production. Various other
electrode or equipment configurations can be employed, consistent
with this invention and the methods described herein, so as to
provide the energy necessary for the synthetic transformation. Such
quantities can be used to further investigate the structure,
properties and uses of these materials.
Example 9
[0081] In this experiment, the arc furnace had a pair of electrodes
made from tungsten, which has a melting temperature of 3410.degree.
C. The cathode side was made from a cylinder having 1 inch in
diameter. The anode side was made from a similar cylinder, having 1
inch diameter with a hole of {fraction (3/4)} inch in diameters
drilled to a depth of {fraction (3/4)} inch. This hole was then
completely filled with carbon black for the process. FIG. 10 shows
the carbon nanotubes formed from the carbon black in the anode cup
after 1 minute of processing. The parameters used in this
experiment were: He gas at 100 Torr, temperature about 3000.degree.
C., arc-furnace with a 100 A current and 19 V, process time was 1
minute.
Example 10
[0082] In this experiment, the same experimental conditions as
those of Example 9 were followed, except that the helium gas was
kept at atmospheric pressure. Carbon nanotubes formed as shown in
FIG. 11. This experiment indicates that the apparatus of the
present invention can be utilized in the absence of a vacuum
pump.
Example 11
Comparison Example
[0083] This experiment was conducted under the same experimental
conditions as in Example 9 except that the anode had two holes each
being approximately {fraction (1/4)} inch in diameter in diameter
as shown in FIG. 12. One hole was filled with carbon black and the
other with another carbon percursor, either graphitizable or
non-graphitizable. Thus, experiments were conducted in which one
hole of the anode was completely filled with carbon black and the
other was filled with PVC in one run, pure graphite in a second
run, and a mixture of 50% graphite and 50% carbon black in a third
run. When PVC was used, carbon nanotubes were formed as shown in
FIG. 13. When the experiment was conducted with graphite, no carbon
nanotubes had been observed. When the experiment was conducted with
the mixture of graphite and carbon black some carbon nanotubes were
formed as shown in FIG. 14.
Example 12
[0084] In this experiment, the same experimental conditions as
those of Example 10 were followed except that carbon black was used
as the precursor with the pressure kept at atmospheric level by
using helium or nitrogen gas. When the experiment was conducted in
helium gas, a good concentration of carbon nanotubes was obtained
as shown in FIG. 11. When the experiment was conducted using
nitrogen gas, the yield of carbon nanotubes was somewhat lower.
These results indicate that the methods of the present invention
can be conducted by using an inexpensive gas such as nitrogen in
the absence of a vacuum pump.
[0085] The preceding examples show the utility of preparing
multiwalled nanotubes through control of the heat treatment and
pressure of carbon materials. By using dopants and/or hitting with
charged electrons, the kinetics for the formation of carbon
nanotubes from solid carbon precursors were considerably increased.
This presents new possibilities to understand and control nanotube
growth. These methods give insight into a range of possible growth
mechanisms and precursors for multiwalled carbon nanotube
syntheses, and the mass production of carbon nanotubes.
[0086] While the principles of this invention have been described
in connection with specific embodiments, it should be understood
clearly that these descriptions, along with the chosen figures and
data, are made only by way of example and are not intended to limit
the scope of this invention, in any manner. Various other apparatus
and/or equipment configurations could be used to effect the
methodology described herein. Likewise, various other carbon
sources, consistent with this invention, can be used with
comparable benefit. Other advantages and features of this invention
will be apparent to those skilled in the art, having been made
aware of the information described herein, with the scope of the
invention as further determined by reasonable equivalents
thereto.
[0087] Thus, while we have described what are the preferred
embodiments of the present invention, further changes and
modifications can be made by those skilled in the art without
departing from the true spirit of the invention, and it is intended
to include all such changes and modifications as come within the
scope of the claims set forth below.
* * * * *