U.S. patent number RE44,069 [Application Number 13/369,269] was granted by the patent office on 2013-03-12 for method of producing carbon nanostructure.
This patent grant is currently assigned to Sumitomo Electric Industries, Ltd.. The grantee listed for this patent is Takeshi Hikata. Invention is credited to Takeshi Hikata.
United States Patent |
RE44,069 |
Hikata |
March 12, 2013 |
Method of producing carbon nanostructure
Abstract
A method of producing a carbon nanostructure is provided which
can increase evenness of a shape and a purity of the carbon
nanostructure and can reduce a production cost. In a method of
producing a carbon nanostructure, a carbon crystal is grown by
vapor phase epitaxy from a crystal growth surface of a catalyst
base including a catalyst material, and the catalyst base is formed
by diameter-reduction processing. The catalyst base is preferably
formed as an aggregate including an arrangement of a plurality of
catalyst structures each formed with a non-catalyst material, a
material not having a substantial catalytic function for growth of
the carbon crystal, formed on at least a portion of a side surface
of the catalyst material of a columnar shape having the crystal
growth surface as a top surface. In addition, a non-catalyst
material is preferably formed on at least a portion of a side
surface of the aggregate, and the catalyst structures preferably
have variations of at most CV 10% in surface areas of the catalyst
material on the crystal growth surface.
Inventors: |
Hikata; Takeshi (Osaka,
JP) |
Applicant: |
Name |
City |
State |
Country |
Type |
Hikata; Takeshi |
Osaka |
N/A |
JP |
|
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Assignee: |
Sumitomo Electric Industries,
Ltd. (Osaka, JP)
|
Family
ID: |
35502972 |
Appl.
No.: |
13/369,269 |
Filed: |
May 19, 2005 |
PCT
Filed: |
May 19, 2005 |
PCT No.: |
PCT/JP2005/009154 |
371(c)(1),(2),(4) Date: |
September 06, 2006 |
PCT
Pub. No.: |
WO2005/121023 |
PCT
Pub. Date: |
December 22, 2005 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
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Reissue of: |
10591740 |
Sep 6, 2006 |
7658971 |
Feb 9, 2010 |
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Foreign Application Priority Data
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Jun 8, 2004 [JP] |
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2004-170016 |
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Current U.S.
Class: |
427/249.1 |
Current CPC
Class: |
B21C
1/003 (20130101); B01J 23/892 (20130101); C01B
32/162 (20170801); B01J 23/8906 (20130101); B82Y
30/00 (20130101); B01J 23/89 (20130101); B01J
23/8913 (20130101); B01J 37/0009 (20130101); B21C
37/047 (20130101); B01J 23/686 (20130101); B82Y
40/00 (20130101) |
Current International
Class: |
C23C
16/00 (20060101) |
Field of
Search: |
;427/249.1 |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
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60-054998 |
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Mar 1985 |
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JP |
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64-036703 |
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Feb 1989 |
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JP |
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10-088256 |
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Apr 1998 |
|
JP |
|
2001-020071 |
|
Jan 2001 |
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JP |
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2001-020071 |
|
Jan 2001 |
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JP |
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2002-526354 |
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Aug 2002 |
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JP |
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2002-526354 |
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Aug 2002 |
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JP |
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2002-255519 |
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Sep 2002 |
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JP |
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2002-255519 |
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Sep 2002 |
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JP |
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2003-277033 |
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Oct 2003 |
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JP |
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2003-292315 |
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Oct 2003 |
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JP |
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2003-292315 |
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Oct 2003 |
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JP |
|
Other References
English Translation of Taiwanese Office Action, dated Mar. 9, 2011
for Application No. 094118298. cited by applicant .
English counterpart publication WO 00/19494, published Apr. 6,
2000. cited by applicant .
Japanese Office Action dated Jul. 14, 2009, issued in related
Japanese application 2004-170016. cited by applicant.
|
Primary Examiner: Culbert; Roberts
Attorney, Agent or Firm: Foley & Lardner LLP
Claims
The invention claimed is:
1. A method of producing a carbon nanostructure wherein a carbon
crystal is grown by vapor phase epitaxy from a crystal growth
surface of a catalyst base including a catalyst material, the
method comprising: forming said catalyst base as a columnar body
having said crystal growth surface at a first end surface of the
columnar body and a non-crystal growth surface at a second end
surface of the columnar body opposite the first end surface.[.,
including performing diameter-reduction processing by at least one
of drawing, extrusion, rolling, and forging.].; forming said
catalyst material to extend from said crystal growth surface to
said non-crystal .[.grown.]. .Iadd.growth .Iaddend.surface; and
disposing a non-catalyst material on said crystal growth surface
and on at least a portion of a side surface of said catalyst
material; wherein said non-catalyst material does not have a
substantial catalytic function for growth of said carbon
crystal.
2. The method of producing a carbon nanostructure according to
claim 1, wherein forming said catalyst base comprises forming an
aggregate including an arrangement of a plurality of catalyst
structures, said catalyst structures include the non-catalyst
material on said crystal growth surface and on at least a portion
of a side surface of said catalyst material, said non-catalyst
material is formed on at least a portion of a side surface of said
aggregate, and said catalyst structures have variations of at most
CV 10% in surface areas of said catalyst material on said crystal
growth surface.
3. The method of producing a carbon nanostructure according to
claim 1, wherein said catalyst material is formed with at least one
of a member selected from the group consisting of Fe, Go, Mo, and
Ni, and said non-catalyst material is formed with Ag and/or an
Ag-containing alloy.
4. The method of producing a carbon nanostructure according to
claim 1, wherein surface processing is performed by at least one of
oxidation, nitriding and carbonization to define an interface
between said catalyst material and said non-catalyst material on
said crystal growth surface.
5. The method of producing a carbon nanostructure according to
claim 1, wherein said catalyst base having a multilayer structure
is formed by alternately stacking said catalyst material and said
non-catalyst material by a vapor phase method.
.[.6. The method of producing a carbon nanostructure according to
claim 1, wherein said diameter-reduction processing is performed
such that, an outside diameter of a solid or hollow catalyst
material after the diameter-reduction processing becomes at least
1.times.10.sup.-6% and at most 1% of that before the
diameter-reduction processing..].
7. The method of producing a carbon nanostructure according to
claim 1, wherein said catalyst material has a multilayer structure
on the crystal growth surface.
8. The method of producing a carbon nanostructure according to
claim 1, wherein said catalyst base is formed such that, said
catalyst material has at least any of a round shape, a ring-like
shape, a polygonal shape, a spiral shape, a waved shape, and a
branching shape on the crystal growth surface.
9. The method of producing a carbon nanostructure according to
claim 1, wherein mechanical polishing and/or sputtering is
performed as surface processing for said crystal growth
surface.
10. The method of producing a carbon nanostructure according to
claim 9, wherein an ion is entered into said catalyst material
before and/or after said surface processing.
11. The method of producing a carbon nanostructure according to
claim 1, comprising the steps of: supplying carbon from a
non-crystal growth surface of said catalyst base to set at least a
portion of carbon in said catalyst material to a saturated state;
and growing a carbon crystal from said crystal growth surface.
12. The method of producing a carbon nanostructure according to
claim 1, wherein a reducing gas is brought into contact with at
least the crystal growth surface of said catalyst material before
or during growth of the carbon crystal.
13. The method of producing a carbon nanostructure according to
claim 1, wherein a material gas and/or carbon is ionized and
brought into contact with said catalyst base.
.Iadd.14. The method of producing a carbon nanostructure according
to claim 13, wherein said forming said catalyst base includes
performing diameter-reduction processing is performed by at least
any of drawing, extrusion, rolling, and forging..Iaddend.
.Iadd.15. The method of producing a carbon nanostructure according
to claim 14, wherein said diameter-reduction processing is
performed such that, an outside diameter of a solid or hollow
catalyst material after the diameter-reduction processing becomes
at least 1.times.10.sup.-6% and at most 1% of that before the
diameter-reduction processing..Iaddend.
Description
TECHNICAL FIELD
The present invention relates to a method of producing a carbon
nanostructure which enables a carbon nanostructure having a more
even shape to be produced stably and at a high purity, and which
can also reduce a production cost.
BACKGROUND ART
A carbon nanotube, which is formed with carbon atoms arranged in a
tubular shape having a diameter of a nanometer level, has been
receiving considerable attention in recent years as a carbon-based
highly functional material having advantages such as high
conductivity and mechanical strength. As one method of generating
the carbon nanotube, a thermal decomposition method has been
devised, in which thermal decomposition of a material gas such as
an alcohol-based or hydrocarbon-based gas is performed in a heating
furnace using a catalyst particle having a diameter of a nanometer
level to grow a carbon crystal on the catalyst particle to form the
carbon nanotube. The thermal decomposition method includes a method
in which a base material is made to carry the catalyst particle by
application or the like, or a method in which a catalyst is
suspended in a vapor phase.
Japanese Patent Laying-Open No. 60-054998 (Patent Document 1), for
example, proposes a method of generating a vapor phase epitaxy
carbon fiber in a suspended state by heating a mixed gas including
a gas of an organotransition metal compound, a carrier gas and a
gas of an organic compound to 800-1300.degree. C.
Japanese Patent Laying-Open No. 2001-020071 (Patent Document 2)
proposes a method of synthesizing a carbon nanotube including a
step of forming a catalyst metal film on a substrate, a step of
etching the catalyst metal film to form an isolated nano-sized
catalyst metal particle, and a step of supplying a carbon source
gas into a thermochemical vapor phase deposition device to grow a
carbon nanotube on each of the isolated nano-sized catalyst metal
particle by a thermochemical vapor phase deposition method to form
a plurality of carbon nanotubes aligned vertically on the
substrate, in which the step of forming the isolated nano-sized
catalyst metal particle is performed by a gas etching method using
at least one eching gas selected from the group consisting of an
ammonia gas, a hydrogen gas and a hydride gas after thermal
decomposition.
Japanese Patent Laying-Open No. 2002-255519 (Patent Document 3)
proposes a method in which a hydrocarbon gas and a carrier gas are
sent onto a base including a heat resistant porous carrier carrying
dispersed fine catalyst particles to vapor-phase synthesize a
monolayer carbon nanotube utilizing thermal decomposition of the
hydrocarbon gas.
Japanese Patent Laying-Open No. 2003-292315 (Patent Document 4)
proposes a method of producing a carbon nanotube on a surface of a
metal by a chemical vapor phase epitaxy method with flowing a gas
as a carbon source onto a heated metal, which is characterized in
that a microcrystal of an oxide is generated beforehand on the
surface of the metal to form minute projections and depressions on
the surface of the metal.
In a conventional method as described in each of Patent Documents
1-4, however, a carbon substance such as amorphous carbon or
graphite as an impurity is generated concurrently with an intended
carbon nanotube during production of the carbon nanotube. In
addition, generated carbon nanotubes have large variations in
diameters, and it is difficult to stably produce even carbon
nanotubes.
One of causes of the variations in diameters of carbon nanotubes is
variations in sizes of catalyst particles. Since it is difficult to
control a shape of a catalyst particle when the catalyst particle
is formed by a chemical method such as heat decomposition,
variations in shapes of catalyst particles themselves are
generated. Aggregation of catalyst particles also causes variations
in shapes. Shapes of carbon nanotubes may also vary due to
variations in growth speeds of carbon crystals on the catalyst
particles.
In addition, a carbon nanotube having a large fiber length cannot
be easily generated using the catalyst particle.
Patent Document 1: Japanese Patent Laying-Open No. 60-054998
Patent Document 2: Japanese Patent Laying-Open No. 2001-020071
Patent Document 3: Japanese Patent Laying-Open No. 2002-255519
Patent Document 4: Japanese Patent Laying-Open No. 2003-292315
DISCLOSURE OF THE INVENTION
Problems to be Solved by the Invention
An object of the present invention is to provide a method of
producing a carbon nanostructure which solves the above-described
problems, can increase evenness of a shape and a purity of the
carbon nanostructure, and can reduce a production cost.
Means for Solving the Problems
The present invention relates to a method of producing a carbon
nanostructure wherein a carbon crystal is grown by vapor phase
epitaxy from a crystal growth surface of a catalyst base including
a catalyst material, and the catalyst base is formed by
diameter-reduction processing.
The catalyst base is preferably formed as an aggregate including an
arrangement of a plurality of catalyst structures each formed with
a non-catalyst material, a material not having a substantial
catalytic function for growth of the carbon crystal, formed on at
least a portion of a side surface of the catalyst material of a
columnar shape having the crystal growth surface as a top
surface.
In addition, a non-catalyst material is preferably formed on at
least a portion of a side surface of the aggregate. Furthermore,
the catalyst structures preferably have variations of at most CV
10% in surface areas of the catalyst material on the crystal growth
surface of the catalyst base formed as an aggregate.
The catalyst material is preferably formed with at least one of a
member selected from the group consisting of Fe, Co, Mo, and Ni,
and the non-catalyst material is preferably formed with Ag and/or
an Ag-containing alloy.
Surface processing is preferably performed by at least one of
oxidation, nitriding and carbonization to define an interface
between the catalyst material and the non-catalyst material on the
crystal growth surface.
A method of alternately stacking the catalyst material and the
non-catalyst material by a vapor phase method to form a catalyst
base having a multilayer structure is also preferably used. With
this, a catalyst base can be made which has the catalyst material
in a spiral shape on the crystal growth surface.
The diameter-reduction processing of the present invention is
preferably performed by at least any of drawing, extrusion,
rolling, and forging.
The diameter-reduction processing is preferably performed such
that, an outside diameter of a solid or hollow catalyst material
after the diameter-reduction processing becomes at least
1.times.10.sup.-6% and at most 1% of that before the
diameter-reduction processing.
In the catalyst base used in the present invention, the catalyst
material preferably has a multilayer structure on the crystal
growth surface. Alternatively, the catalyst material preferably has
at least any of a round shape, a ring-like shape, a polygonal
shape, a spiral shape, a waved shape, and a branching shape on the
crystal growth surface.
In the present invention, surface processing is preferably
performed for the catalyst material of the catalyst base used. In
particular, mechanical polishing and/or sputtering is preferably
performed.
Processing for entering an ion in the crystal growth surface is
preferably performed before and/or after the surface processing for
the catalyst material of the catalyst base to prevent surface
disorder of the crystal growth surface due to the mechanical
polishing and/or sputtering.
The method of producing according to the present invention
preferably includes the steps of supplying carbon from a
non-crystal growth surface of the catalyst base to set at least a
portion of carbon in the catalyst material to a saturated state,
and growing a carbon crystal from the crystal growth surface.
In the present invention, a reducing gas is preferably brought into
contact with at least the crystal growth surface of the catalyst
material before or during growth of the carbon crystal.
In addition, an ionized material gas and/or carbon is preferably
brought into contact with the catalyst base.
EFFECTS OF THE INVENTION
Since a catalyst base including a catalyst material is formed by
diameter-reduction processing in the present invention, a crystal
growth surface having a desired shape and an even size can be
efficiently formed. With this, a carbon nanostructure having a
shape reflecting a shape of the crystal growth surface can be
produced stably and at a high purity. In addition, the catalyst
base used in the present invention can be formed as a colunmar body
exposing the catalyst material on the crystal growth surface and a
non-crystal growth surface. In this situation, carbon of a higher
concentration can be absorbed from the non-crystal growth surface
into the catalyst material, which increases production efficiency
of the carbon nanostructure and can effectively suppress generation
of an impurity.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 shows an example of a method of making a catalyst base used
in the present invention.
FIG. 2 shows an example of a method of making a catalyst base
having a multilayer structure which is used in the present
invention.
FIG. 3 is a cross-sectional view of a crystal growth surface of a
catalyst base having a multilayer ring structure which is used in
the present invention.
FIG. 4 is a cross-sectional view of a crystal growth surface of a
catalyst base having a waved structure which is used in the present
invention.
FIG. 5 shows an example of a production device of a carbon
nanostructure.
FIG. 6 shows an example of a construction of a catalyst base used
in the present invention.
FIG. 7 shows an example of a production device of a carbon
nanostructure which includes a plasma cementation device.
DESCRIPTION OF THE REFERENCE SIGNS
11, 204, 31, 41, 52, 62, 72: catalyst material, 12, 15, 201, 205,
207, 210, 32, 42, 53, 63, 73: non-catalyst material, 13, 16, 206,
208, 211: composite material, 14, 209: drawing dice, 17, 212, 54,
64, 74: catalyst base, 202, 203: deposition source, 51, 61, 71:
heat and pressure-resistant heating furnace tube, 55, 66: seal
material, 56: diaphragm, 57: crystal growth surface, 58, 67, 76:
carbon nanostructure, 65: porous body, 75: anode.
BEST MODES FOR CARRYING OUT THE INVENTION
The present invention is characterized in that, a catalyst base
including a catalyst material is formed by diameter-reduction
processing, and a carbon crystal is generated by vapor phase
epitaxy from a crystal growth surface formed with the catalyst
material on the catalyst base to produce a carbon nanostructure
having a desired shape. In the present invention,
diameter-reduction processing is performed for preferably at least
two times for a catalyst material or a composite material of a
catalyst material and a non-catalyst material which is prepared
beforehand to decrease a diameter thereof by plastic deformation of
the catalyst material and the non-catalyst material, which enables
making of a catalyst base having a very small crystal growth
surface of a nanometer size with high accuracy. With this, a shape
of the crystal growth surface can be arbitrarily set according to a
desired shape of a carbon nanostructure such as a carbon nanotube
or a carbon nanofiber.
A solid or hollow, thin line-shaped or rod-shaped catalyst
material, for example, is preferably adopted to efficiently perform
diameter-reduction processing with high accuracy. In this
situation, it is preferable to repeatedly perform the
diameter-reduction processing to form a catalyst material having a
diameter of a nanometer level, which is then cut to a desired
length to form a solid or hollow columnar body having an intended
height, and an end surface of the columnar body, that is, at least
one cut surface thereof is preferably made to be a crystal growth
surface. The shape of the crystal growth surface can be arbitrarily
controlled by changing a cross-sectional shape of the catalyst
material provided to diameter-reduction processing, and carbon
nanostructures having various cross-sectional shapes can be
produced. In the present invention, the diameter-reduction
processing can be performed such that, an outside diameter of the
catalyst material after the diameter-reduction processing becomes,
for example, at most 1% of that before the diameter-reduction
processing, especially within a range of 1.times.10.sup.-6-1%. In
this situation, the outside diameter of the catalyst material
before the diameter-reduction processing is relatively large and a
cross-sectional shape is easily designed. In addition, the catalyst
material having the outside diameter of a nanometer level can be
readily made by the diameter-reduction processing.
Though the catalyst base used in the present invention may be
formed only with the catalyst material, a non-catalyst material
which does not have a substantial catalytic function for growth of
a carbon crystal is preferably formed on at least a portion of a
side surface of the catalyst material which is formed as a columnar
body having a crystal growth surface as an end surface. In this
situation, spreading of the carbon crystal in a direction of the
crystal growth surface is prevented by presence of the non-catalyst
material, and a growth direction of the carbon crystal is
controlled to enable production of a carbon nanostructure having a
more even shape.
A material generally used as a catalyst in production of a carbon
nanostructure can be used as the catalyst material. More
specifically, a metal or an alloy including at least one member
selected from Fe, Co, Mo, Ni, In, and Sn can be used. These
materials can be used singly or in combination of at least two
kinds. Among these, Fe, Co and Fe--Co alloy materials are suitable
because they substantially do not form alloy or the like with Ag
which is preferably used as the non-catalyst material as described
below, and because they are catalysts which are not easily
deteriorated.
The non-catalyst material may be any material which does not have a
substantial catalytic function for growth of a carbon crystal. More
specifically, a metal or an alloy including at least one member
selected from Ag, Au, Ru, Rh, Pd, Os, Ir, and Pt is preferably
used. Among these, Ag and an Ag-containing alloy are suitable
because they are relatively inexpensive, can be processed easily,
and are chemically stable. As the Ag-containing alloy, alloys such
as Ag--Pd, Ag--Pt and Ag--Au alloys can be preferably used.
When a catalyst base formed with a composite body of the catalyst
material and the non-catalyst material is used, the catalyst
material and the non-catalyst material which substantially do not
generate an alloy or cause a reaction when they contact each other
and which have a low possibility of degrading a shape of the
crystal growth surface are preferably used in combination. Such
combination includes, for example, a combination of an oxide as the
catalyst material and Ag or an Ag-containing alloy as the
non-catalyst material, and a combination of a nitride as the
catalyst material and Ag or an Ag-containing alloy as the
non-catalyst material. In addition, a combination of the catalyst
material formed with at least one member selected from Fe, Co, Mo,
Ni, In, and Sn and the non-catalyst material formed with Ag and/or
an Ag-containing alloy is also preferred.
The non-catalyst material preferably has a melting point higher
than a generation temperature of the carbon nanostructure. In this
situation, deformation of the non-catalyst material does not easily
occur during crystal growth and a carbon nanostructure having an
even shape can be generated.
In the present invention, a columnar catalyst base formed by
arranging a plurality of columnar catalyst structures each formed
with the catalyst material and the non-catalyst material, for
example, can be preferably used to efficiently generate the carbon
nanostructure. Production efficiency of the carbon nanostructure
can be increased by using the catalyst base formed with a plurality
of catalyst structures.
When the catalyst base is formed as a columnar aggregate including
an arrangement of the plurality of catalyst structures each formed
with the catalyst material and the non-catalyst material, it is
preferable to further form the non-catalyst material on at least a
portion of a side surface of the aggregate. In this situation,
unevenness of a shape of the carbon nanostructure due to a
generated carbon crystal spreading in a direction of the crystal
growth surface is further suppressed by a contribution of the
non-catalyst material formed on the side surface of the aggregate,
in addition to a contribution of the non-catalyst material in each
of the catalyst structures.
When the catalyst base is formed by arranging the plurality of
catalyst structures each formed with the catalyst material and the
non-catalyst material, the catalyst structures preferably have
variations of at most CV 10% in surface areas of the catalyst
material on the crystal growth surface. In this situation, evenness
of a cross-sectional shape of the carbon nanostructure can be
ensured with a sufficiently even shape of the crystal growth
surface. A surface area of the catalyst material can be calculated
by, for example, an image analysis based on a figure observation
with an STM (scanning tunneling microscope).
A reinforcing material for suppressing deformation of the catalyst
base may be formed in at least a portion of the catalyst base
formed with the catalyst material and the non-catalyst material,
preferably in at least a portion of a periphery of the catalyst
base. In this situation, generation of a gap between the catalyst
material and the non-catalyst material is suppressed by the
reinforcing material and generation of carbon as an impurity from
an interface between the catalyst material and the non-catalyst
material is avoided, which can further increase evenness of the
carbon nanostructure. As the reinforcing material, a material
having a Young's modulus larger than that of the catalyst base
formed with the catalyst material and the non-catalyst material in
a condition of production of the carbon nanostructure is preferably
used. In particular, a material having heat resistance higher than
that of the non-catalyst material is preferably used. More
specifically, a heat-resistant high-strength metal such as tungsten
carbide, ceramics or Inconel, for example, is used.
A method which enables reduction of a diameter by plastic
deformation of the catalyst material or the composite material of
the catalyst material and the non-catalyst material can be adopted
as a method of diameter-reduction processing in the present
invention. More specifically, at least one processing selected from
drawing, extrusion, rolling, and forging is preferred. When two or
more of the processings are performed in combination, a method of
thinning a material formed in a rod-like shape to a degree by
rolling and then further reducing a diameter thereof by drawing or
extrusion, or a method of embossing to apply a stress in a
direction of a radius of a rod-shaped material by forging for
thinning to a degree and then further reducing a diameter thereof
by drawing or extrusion, for example, can be adopted. When the
diameter-reduction processing is performed, it is preferable to
select a processing condition as appropriate not to cause rapid
plastic deformation in order to prevent deterioration of physical
properties of the material.
A method of making the catalyst base used in the present invention
will now be described referring to the drawing. FIG. 1 shows an
example of a method of making the catalyst base used in the present
invention. First, as shown in FIG. 1(A), a pipe-shaped non-catalyst
material 12 is filled with a rod-shaped catalyst material 11 to
obtain a composite material 13. Then, as shown in FIG. 1(B),
composite material 13 is passed through a drawing dice 14 for
drawing to cause diameter-reduction with plastic deformation of
composite material 13, and is further used to fill a pipe-shaped
non-catalyst material 15 to obtain a composite material 16, as
shown in FIG. 1(C). As shown in FIG. 1(D), composite material 16
obtained is passed through drawing dice 14 again for
diameter-reduction with plastic deformation. By repeating filling
and diameter-reduction operations as described above, a columnar
aggregate including an arrangement of a plurality of catalyst
materials 11 each having a diameter of at most 10 nm, for example,
is obtained. The aggregate is cut to a prescribed length and a cut
surface thereof is polished to finally obtain a catalyst base 17 as
shown in FIGS. 1(E) and 1(F) which is a columnar body formed with
the plurality of catalyst materials 11, which columnar body has one
end surface as a crystal growth surface and the other end surface
as a non-crystal growth surface (herein, portions enclosed with
dotted lines in FIGS. 1(E) and 1(F) indicate an identical region).
On each of the crystal growth surface and the non-crystal growth
surface of catalyst base 17 shown in FIG. 1(E), catalyst material
11 has a round shape. A catalyst material layer may be provided,
for example, on the non-crystal growth surface of catalyst base 17.
When the catalyst base having a construction as such is used and a
material gas is brought into contact with the non-crystal growth
surface, carbon of a high concentration dissolves in catalyst
material 11 with a contribution of the catalyst material layer
having a large surface area, and since carbon of the high
concentration is supplied to the crystal growth surface, a speed of
generation of the carbon nanostructure can be increased.
In the catalyst base used in the present invention, the catalyst
material preferably has at least any of a round shape, a ring-like
shape, a spiral shape, a polygonal shape, a waved shape, and a
branching shape on the crystal growth surface. It is also
preferable to form the catalyst material to have a multilayer
structure on the crystal growth surface. In this situation, a shape
of the crystal growth surface is reflected to a cross section of
the carbon nanostructure generated, and a carbon nanostructure
having a monolayer or multilayer spiral shape or ring-like shape,
for example, can be arbitrarily generated. As a method of forming a
multilayer structure or a ring structure on the crystal growth
surface, a method of interposing the non-catalyst material between
monolayer or multilayer catalyst materials by a method of
alternately stacking the catalyst material and the non-catalyst
material by a vapor phase method, or by a method of performing,
once or at least two times, a step of filling the catalyst material
or the non-catalyst material prepared to have a pipe-like shape
with the catalyst material or the non-catalyst material prepared to
have a rod-like shape, for example, can be preferably adopted. In
the catalyst base shown in FIG. 1, though catalyst material 11 on
the crystal growth surface has a round shape because rod-shaped
catalyst material 11 is used, when the non-catalyst material is
used in place of catalyst material 11 and the catalyst material is
used in place of non-catalyst material 12, for example, a catalyst
base having a ring-shaped crystal growth surface can be made.
FIG. 2 shows an example of a method of making a catalyst base
having a multilayer structure which is used in the present
invention. As shown in FIG. 2(A), a non-catalyst material 201 is
rotated in a direction of an arrow, and a non-catalyst material and
a catalyst material are concurrently deposited on non-catalyst
material 201 from a deposition source 202 for depositing the
non-catalyst material and a deposition source 203 for depositing
the catalyst material. With this, as shown in FIG. 2(B), a
composite material 206 having a multilayer structure including a
catalyst material 204 and a non-catalyst material 205 formed in a
spiral shape on a periphery of non-catalyst material 201 is
obtained. Then, as shown in FIG. 2(C), a pipe-shaped non-catalyst
material 207 is filled with composite material 206 to obtain a
composite material 208. As shown in FIG. 2(D), composite material
208 is passed through a drawing dice 209 to cause
diameter-reduction with plastic deformation and, furthermore, a
non-catalyst material 210 is filled with composite material 208 to
obtain a composite material 211, as shown in FIG. 2(E). As shown in
FIG. 2(F), composite material 211 is passed through drawing dice
209 to cause diameter-reduction with plastic deformation and,
finally, a catalyst base 212 as shown in FIGS. 2(G) and 2(H) which
is a columnar body formed with a plurality of composite materials
206 each having the catalyst material formed in a spiral shape can
be made, which columnar body has one end surface as a crystal
growth surface (herein, portions enclosed with dotted lines in
FIGS. 2(G) and 2(H) indicate an identical region).
A number or thicknesses of layers of the multilayer structure can
be readily controlled by controlling an amount of deposition of the
catalyst material and/or the non-catalyst material, a rotation
speed of non-catalyst material 201 or the like in a step shown in
FIG. 2(A). In addition, a layered structure may be arbitrarily
controlled by adjusting a deposition start time and/or a deposition
end time of the catalyst material or the non-catalyst material from
deposition sources 202 and 203. It is to be noted that, the
catalyst material may be used in place of non-catalyst material 201
according to a desired structure of a carbon nanostructure. In this
situation, the catalyst material on the crystal growth surface has
a shape having a filled center portion.
FIG. 3 is a cross-sectional view of a crystal growth surface of a
catalyst base having a multilayer ring structure which is used in
the present invention. In the catalyst base shown in FIG. 3, a
catalyst material 31 and a non-catalyst material 32 are formed to
have a layered structure and catalyst material 31 has a crystal
growth surface of a multilayer ring-like shape. FIG. 4 is a
cross-sectional view of a crystal growth surface of a catalyst base
having a waved structure which is used in the present invention. In
the catalyst base shown in FIG. 4, a catalyst material 41 is formed
on a periphery of a non-catalyst material 42 and catalyst material
41 has a crystal growth surface of a waved ring-like shape.
When a rod-shaped and/or pipe-shaped catalyst material or composite
material of the catalyst material and the non-catalyst material is
used, it is preferable to cut the catalyst material or the
composite material subjected to diameter-reduction processing to a
desired length, and polish cut surfaces (end surfaces) thereof by,
for example, ion milling or laser beam processing to obtain a
columnar catalyst base having one of the end surfaces as a crystal
growth surface and the other as a non-crystal growth surface.
When the catalyst base is formed as a columnar body, a thickness of
the catalyst base, that is, a height of the columnar body is
preferably set to, for example, about 1-1000 .mu.m. The catalyst
base is readily prepared when the thickness of the catalyst base is
at least 1 .mu.m, and carbon is stably supplied to the crystal
growth surface even if a material gas is brought into contact with
only the non-crystal growth surface when the thickness is at most
1000 .mu.m. When the thickness of the catalyst base is relatively
small, however, deformation of the catalyst base may occur
depending on a production condition such as a condition of supply
of an atmospheric gas. In this situation, it is preferable to affix
a porous body formed with a non-catalyst material to the
non-crystal growth surface of the catalyst base, supply a material
gas from a side of the porous body, and grow a carbon crystal from
the crystal growth surface. With this, deformation of the catalyst
base can be prevented without decreasing an amount of supply of
carbon into the catalyst material. Furthermore, it is preferable to
reinforce the catalyst material by, for example, forming a film on
the non-crystal growth surface, as shown in FIG. 5.
In the present invention, surface processing by mechanical
polishing and/or sputtering is preferably performed beforehand for
the crystal growth surface in order to increase evenness of a shape
of a generated carbon nanostructure by cleaning and smoothing of
the crystal growth surface. At least one kind selected from a
plasma, an ion beam and a laser beam is preferably used in the
sputtering since the crystal growth surface can be processed to be
more smooth with high processing efficiency. Furthermore, a cluster
ion beam and an ultrashort pulse laser are preferably used as the
ion beam and the laser beam, respectively.
Furthermore, it is preferable to enter an ion in the crystal growth
surface before and/or after the surface processing to resolve
surface disorder of the crystal growth surface due to the
mechanical polishing and/or sputtering. As a method of entering the
ion, a method such as a cementation method or a plasma method, for
example, can be adopted.
In addition, in order to further resolve the surface disorder of
the crystal growth surface and define an interface between the
catalyst material and the non-catalyst material, at least one
processing selected from oxidation, nitriding and carbonization is
preferably performed for the crystal growth surface. With this,
generation of an impurity other than a desired carbon nanostructure
can be suppressed and production efficiency of the carbon
nanostructure can be increased. Oxidation, for example, can be
performed by heat treatment in an oxygen atmosphere or the
like.
Reactivation processing is preferably performed for the crystal
growth surface after generation of the carbon nanostructure using
at least one processing selected from, for example, chemical
polishing, physical polishing and sputtering. The catalyst base can
be reused by reactivation of the crystal growth surface, and a
production cost can be reduced.
In the present invention, a gas generally used for producing a
carbon nanostructure including a hydrocarbon-based gas such as a
propane gas, an ethylene gas or an acetylene gas, an alcohol-based
gas such as a methyl alcohol gas or an ethyl alcohol gas, or carbon
monoxide can be used as a material gas for growing the carbon
nanostructure. When a material having a relatively low deformation
temperature is used as a material forming the catalyst base, for
example, the alcohol-based gas is preferably used which enables
generation of the carbon nanostructure at a lower temperature.
Since the carbon nanostructure generated may be degraded by a
hydrogen gas or the like, a gas which does not substantially
deteriorate the carbon crystal generated is preferably supplied as
a carrier gas to a portion near the crystal growth surface. A
preferable carrier gas includes, for example, an inert gas such as
argon or nitrogen.
Though a condition of supply of a gas brought into contact with the
catalyst base may be the same for the portion near the crystal
growth surface and a portion near the non-crystal growth surface,
the condition is preferably made different for each portion so that
dissolving of carbon into the catalyst material and precipitation
of the carbon crystal are controlled to occur in separate regions
of a surface of the catalyst base. When a material gas is brought
into contact with the portion near the non-crystal growth surface
and a carrier gas not including a carbon source is brought into
contact with the portion near the crystal growth surface, for
example, only carbon which is supplied from the non-crystal growth
surface, moves inside the catalyst base and reaches the crystal
growth surface is supplied to the crystal growth surface.
Therefore, generation of an impurity, which is readily generated
when carbon exists in an atmospheric gas near the crystal growth
surface, can be suppressed and the carbon nanostructure with a
higher purity can be generated. Besides, high production efficiency
can be attained because carbon of a high concentration is always
supplied to the crystal growth surface. In this situation, since
the material gas is not supplied to the portion near the crystal
growth surface and a pressure due to entering of carbon is not
applied to the crystal growth surface from a surface toward an
internal portion of the catalyst material, carbon is supersaturated
in the portion near the crystal growth surface and can precipitate
as a carbon crystal.
Though only one kind of material gas or a combination of two kinds
of gases, that is, a material gas and a carrier gas, for example,
can be adopted as a gas used in the present invention, gases of at
least three kinds may be combined and used. More specifically, a
combination for bringing a material gas into contact with the
catalyst material in a region other than that near the crystal
growth surface, supplying a first carrier gas for accelerating
growth of the carbon nanostructure to the portion near the crystal
growth surface, and further supplying a second carrier gas for
moving the carbon nanostructure generated, or a combination of a
gas for suppressing precipitation of carbon from a material gas
itself or from a contact region between the catalyst base and the
material gas and the material gas, for example, can be adopted.
In addition, when at least two kinds of atmospheric gases are
supplied, the atmospheric gases can be supplied to contact the
catalyst base with different pressures. In this situation, a growth
speed of the carbon nanostructure or a structure such as a number
of layers in the generated carbon nanostructure can be controlled
with a difference in pressures of the atmospheric gases.
Particularly, setting of a pressure of an atmospheric gas in a
contact region between the catalyst base and the material gas to be
higher than a pressure of an atmospheric gas near the crystal
growth surface is preferable because carbon generated by thermal
decomposition of the material gas is absorbed into the catalyst
material more efficiently.
In addition, at least one kind of the atmospheric gases is
preferably supplied to contact the catalyst base with a pressure of
at least an atmospheric pressure. When the material gas contacts
the catalyst base with the pressure of at least the atmospheric
pressure, carbon is absorbed into the catalyst material more
efficiently. In addition, deformation of the catalyst base can be
suppressed by setting a pressure of the atmospheric gas near the
crystal growth surface to be equal to a pressure of the atmospheric
gas on a side of supply of the material gas.
It is also preferable to set a surface area of the catalyst
material contacting the material gas on a surface of the catalyst
base to be larger than a surface area of the crystal growth
surface. In this situation, production efficiency of the carbon
nanostructure is increased because carbon of a higher concentration
which is generated by thermal decomposition of the material gas is
supplied to the crystal growth surface.
In the present invention, a reducing gas is preferably brought into
contact with at least the crystal growth surface of the catalyst
material before or during growth of the carbon crystal. The crystal
growth surface of the catalyst material may be oxidized during the
steps of making the catalyst base, surface-processing the crystal
growth surface, and the like. With contacting the reducing gas, a
metal oxide layer on the crystal growth surface can be removed and
the carbon nanostructure can be generated in a more even shape. As
a method of contacting the reducing gas, for example, a method of
supplying an atmospheric gas including a hydrogen gas or the like
to bring the atmospheric gas into contact with the crystal growth
surface can be adopted.
Though a temperature for generating the carbon nanostructure in the
present invention is not specifically limited and can be selected
as required according to properties of an applied catalyst base, a
kind of a material gas or the like, the temperature can be set to,
for example, about 500-960.degree. C. Depending on a production
condition, however, the catalyst material may be deformed or may be
deteriorated by an impurity attached to a surface of the catalyst
material, which forms an alloy or a compound of the catalyst
material and decreases a catalyst activity. Since reliable growth
of the carbon nanostructure having a desired shape becomes
difficult when the crystal growth surface of the catalyst material
is deformed or deteriorated, the temperature for generating the
carbon nanostructure is preferably set to at most a temperature
which does not cause deformation or deterioration of the catalyst
base. When the catalyst material including Fe is used, for example,
the temperature for generating the carbon nanostructure is
preferably set to at least an A.sub.1 transformation temperature of
Fe (iron) (for example, 723.degree. C. which is an A.sub.1
transformation temperature of pure iron), especially to at least
850.degree. C.
A method of producing a carbon nanostructure according to the
present invention preferably includes the steps of supplying carbon
from a side of the non-crystal growth surface of the catalyst base
to set at least a portion of carbon in the catalyst material to a
saturated state, and growing a carbon crystal from the crystal
growth surface. In this situation, since the carbon crystal is
grown with carbon of a high concentration supplied to the crystal
growth surface, evenness of a shape of the carbon nanostructure
obtained and production efficiency can be increased. More
specifically, a method including a step of setting a temperature
near the crystal growth surface to be higher than a temperature for
generating the carbon crystal while bringing a material gas into
contact with the non-crystal growth surface to supply carbon into
the catalyst base to set carbon in the catalyst material to a
saturated state, and a subsequent step of decreasing the
temperature near the crystal growth surface to be at most the
temperature for generating the carbon crystal to grow the carbon
crystal from the crystal growth surface, for example, can be
preferably adopted. The temperature near the crystal growth surface
can be controlled by, for example, providing a heat source near the
crystal growth surface.
The method of producing a carbon nanostructure in the present
invention will now be described. FIG. 5 shows an example of a
production device of a carbon nanostructure. In a heat and
pressure-resistant heating furnace tube 51 including an electric
furnace as a heating device, a gas introduction and exhaust system,
a growth temperature control system, a vacuum control system, a gas
flowmeter, and the like, a catalyst base 54 formed with a catalyst
material 52 and a non-catalyst material 53 is inserted, and
catalyst base 54 is fixed to heat and pressure-resistant heating
furnace tube 51 with a seal material 55 filling a gap therebetween.
Heat and pressure-resistant heating furnace tube 51 is separated
into a space of a crystal growth surface side and a space of a
non-crystal growth surface side with catalyst base 54 and seal
material 55. In the space of the non-crystal growth surface side, a
diaphragm 56, for example, is provided to supply a material gas so
as to flow in a direction of an arrow. A carrier gas is supplied to
the space of the crystal growth surface side. Carbon generated by
thermal decomposition of the material gas supplied to the space of
the non-crystal growth surface side moves inside catalyst material
52 in catalyst base 54, reaches a crystal growth surface 57 and
precipitates from crystal growth surface 57 as a carbon crystal to
grow a carbon nanostructure 58.
FIG. 6 shows an example of a construction of a catalyst base used
in the present invention. In a heat and pressure-resistant heating
furnace tube 61 including an electric furnace as a heating device,
a gas introduction and exhaust system, a growth temperature control
system, a vacuum control system, a gas flowmeter, and the like, a
catalyst base 64 formed with a catalyst material 62 and a
non-catalyst material 63 is inserted. A porous body 65 formed with
a non-catalyst material is formed to contact a non-crystal growth
surface side of catalyst base 64, and catalyst base 64 is fixed to
heat and pressure-resistant heating furnace tube 61 with a seal
material 66. Heat and pressure-resistant heating furnace tube 61 is
separated into a space of a crystal growth surface side and a space
of the non-crystal growth surface side with catalyst base 64 and
seal material 66 filling a gap. A material gas is supplied to the
space of the non-crystal growth surface side in a flow in a
direction of an arrow, and carbon generated by thermal
decomposition of the material gas passes through a pore portion of
porous body 65, moves inside catalyst material 62 in catalyst base
64, reaches a crystal growth surface and precipitates as a carbon
crystal to grow a carbon nanostructure 67.
In the present invention, it is also preferable to ionize a
material gas containing carbon and bring it into contact with the
catalyst material in order to generate the carbon nanostructure
more efficiently. By ionizing the material gas and accelerating
ionized carbon with an electric field to allow collision thereof
with the catalyst material, solubility of carbon to the catalyst
material can be increased and carbon can penetrate to a deeper
region of the catalyst material from a contact surface between the
material gas and the catalyst material. With this, carbon of a high
concentration is supplied to the crystal growth surface and
production efficiency of the carbon nanostructure can be increased.
Plasma cementation, for example, can be adopted as a method of
ionizing the material gas and bringing it into contact with the
catalyst material. For the plasma cementation, for example, a
method of applying a voltage between a furnace tube supplied with a
material gas formed with a gas such as a mixed gas of a gas
containing a carbon source and a carrier gas and the catalyst base
to cause glow discharge and generating plasma of the material gas
to ionize the material gas can be adopted.
FIG. 7 shows an example of a production device of a carbon
nanostructure which includes a plasma cementation device. In the
production device formed with a heat and pressure-resistant heating
furnace tube 71 including an electric furnace as a heating device,
a gas introduction and exhaust system, a growth temperature control
system, a vacuum control system, a gas flowmeter, and the like, a
catalyst base 74 formed with a catalyst material 72 and a
non-catalyst material 73 is inserted, and a space formed with heat
and pressure-resistant heating furnace tube 71 is separated into a
space of a crystal growth surface side and a space of a non-crystal
growth surface side with catalyst base 74. An anode 75 is arranged
on the non-crystal growth surface side. As an example, a mixed gas
including a propane gas, a methane gas, an ethylene gas, a hydrogen
gas, an argon gas, or the like is supplied as a material gas to the
space of the non-crystal growth surface side, catalyst base 74 is
used as a cathode to apply a voltage between anode 75 and catalyst
base 74 to generate plasma with glow discharge, and carbon
generated by decomposition of the material gas is supplied in an
ionized state to the non-crystal growth surface.
The production device of a carbon nanostructure used in the present
invention may have a construction provided with, for example, a
supply mechanism for a purified gas to enable purification of a
material gas containing a decomposed gas or the like after
generation of the carbon nanostructure. In addition, it is
preferable to electrify the carbon nanostructure generated in the
present invention and collect it with force of static electricity
or the like.
The carbon nanostructure produced with the method of the present
invention has an even shape and is highly pure, which can be
suitably applied to various uses such as an electronic circuit, a
high-strength composite material, an electric wire material, and a
cushion material.
EXAMPLES
Though the present invention will be described in more detail with
examples, the present invention is not limited thereto.
Example 1
(1) Making of Catalyst Base
In this example, a catalyst base was made by a method indicated in
FIG. 1. Composite material 13 (FIG. 1(A)), which was obtained by
inserting an Fe (iron) rod as catalyst material 11 having an
outside diameter of 40 mm into an Ag (silver) pipe as non-catalyst
material 12 having an outside diameter of 60 mm and an inside
diameter of 40 mm, was subjected to wiredrawing with drawing dice
14 until an outside diameter thereof became 1.2 mm to obtain a wire
1 (FIG. 1(B)). Wire 1 was cut at every length of 1 m and bundled
together to fill an Ag pipe as non-catalyst material 15 having an
outside diameter of 60 mm and an inside diameter of 40 mm, while
spacers of Ag were used to fill gaps to avoid generation of a
cavity, to form composite material 16 (FIG. 1(C)). Composite
material 16 was passed through drawing dice 14 for wiredrawing
until a diameter thereof became 1.2 mm to obtain a wire 2 (FIG.
1(D)). The step of obtaining wire 2 from wire 1 was repeated and,
finally, an aggregate having a diameter of 30 mm was obtained which
was formed with a bundle of a plurality of catalyst structures each
formed with the catalyst material and the non-catalyst material, in
which an outside diameter of Fe was set to 3 nm. The aggregate was
cut to have a length of 1 mm, and cut surfaces of both ends (both
end surfaces) were polished by buffing.
Lateral sputtering of the both end surfaces was performed using a
cluster ion beam so that a structure of an Fe portion as the
catalyst material was exposed on the both end surfaces in a round
shape to make catalyst base 17 having a large number of Fe portions
as catalyst materials 11 arranged in Ag portions as non-catalyst
materials 12 (FIG. 1(E)).
A crystal growth surface within a range of 0.1 .mu.m square
randomly selected from the catalyst base formed was observed with a
scanning electron microscope to calculate a cross-sectional area of
the catalyst material in each catalyst structure, and variations in
cross-sectional areas in the catalyst structures were obtained with
the following expression. CV(%)=standard deviation of all measured
values/average value of all measured values.times.100
As a result, the variations in the cross-sectional areas of the
catalyst materials on the crystal growth surface was at most 5% in
CV (%).
(2) Production of Carbon Nanostructure
A carbon nanotube as a carbon nanostructure was produced using the
catalyst base obtained as above. The catalyst base formed with the
catalyst material and the non-catalyst material was inserted into a
heat and pressure-resistant heating furnace tube including an
electric furnace as a heating device, a gas introduction and
exhaust system, a growth temperature control system, a vacuum
control system, a gas flowmeter, and the like. While flowing an
argon gas in the heat and pressure-resistant heating furnace tube,
a temperature inside the heat and pressure-resistant heating
furnace tube was set to 850.degree. C. After leaving for 1 hour
with flowing an ethanol gas, the temperature was further gradually
decreased to 500.degree. C., and then supply of the ethanol gas was
stopped, which was followed by cooling to a room temperature.
As a result, generation of fibrous carbon from the crystal growth
surface was recognized. When the catalyst base and the generated
fibrous carbon were observed with the scanning electron microscope,
it was ensured that the fibrous carbon was growing from the crystal
growth surface of the catalyst material. When the fibrous carbon
was further observed with a transmission electron microscope, it
was ensured that the fibrous carbon was a carbon nanotube and an
impurity such as amorphous carbon, graphite or the catalyst
material was hardly included.
After observation with the electron microscope, the catalyst base
was entered into the heat and pressure-resistant heating furnace
tube and an attempt was made to generate the carbon nanotube again
in a condition similar to that described above, but the carbon
nanotube was not generated due to contamination of a surface of the
catalyst base and the like. Therefore, sputtering of the crystal
growth surface with an excimer laser was performed and, thereafter,
an attempt was made to generate the carbon nanotube again in the
condition similar to that described above. As a result, the carbon
nanotube could be generated.
Example 2
(1) Making of Catalyst Base
In an Ag (silver) pipe having an outside diameter of 60 mm and an
inside diameter of 50 mm, an Fe (iron) pipe having an outside
diameter of 50 mm and an inside diameter of 45 mm was inserted, ard
an Ag rod having an outside diameter of 45 mm was further inserted
therein. A composite metal material obtained was subjected to
wiredrawing with a drawing dice until an outside diameter thereof
became 1.2 mm to obtain wire 1. Wire 1 was cut at every length of 1
m and bundled together to fill an Ag pipe having an outside
diameter of 60 mm and an inside diameter of 40 mm, while spacers of
Ag were used to fill gaps to avoid generation of a cavity, and the
Ag pipe was subjected to wiredrawing with the drawing dice until a
diameter thereof became 1.2 mm to obtain wire 2. The step of
obtaining wire 2 from wire 1 was repeated and, finally, an
aggregate having a diameter of 30 mm was obtained which was formed
with a bundle of a plurality of catalyst structures in which an
outside diameter of Fe was set to 7 nm. The aggregate was cut to
have a length of 0.2 mm, and cut surfaces of both ends (both end
surfaces) were mechanically polished by buffing or the like.
Thereafter, a carbon ion is injected into a polished surface using
an ion implantation device. Planarization of the both end surfaces
was performed using an excimer laser and a cluster ion beam so that
a structure of an Fe portion as the catalyst material was exposed
on the both end surfaces in a ring-like shape. Then, an Fe film
having a thickness of 1 .mu.m was formed on one end surface of the
aggregate to make a catalyst base having the end surface on a side
having the Fe film formed as a non-crystal growth surface and the
end surface on a side not having the Fe film formed as a crystal
growth surface.
(2) Production of Carbon Nanostructure
A carbon nanotube as a carbon nanostructure was produced with the
production device shown in FIG. 5 using the catalyst base obtained
as above. Heat and pressure-resistant heating furnace tube 51
including the electric furnace as the heating device, the gas
introduction and exhaust system, the growth temperature control
system, the vacuum control system, the gas flowmeter, and the like
was separated into a space of a crystal growth surface side and a
space of a non-crystal growth surface side with catalyst base 54
inserted and seal material 55. While flowing a mixed atmospheric
gas containing an acetylene gas and an argon gas in a ratio of 1:4
at 1.5 atm in the space of the non-crystal growth surface side, a
temperature inside heat and pressure-resistant heating furnace tube
51 was set to 960.degree. C. On the other hand, an argon gas as a
carrier gas was supplied to the crystal growth surface side.
Thereafter, a ratio of supply of an acetylene gas was gradually
decreased to zero while keeping a pressure of the atmospheric
gas.
As a result, generation of fibrous carbon from the crystal growth
surface was recognized. When catalyst base 54 and the generated
fibrous carbon were observed with the scanning electron microscope,
it was ensured that the fibrous carbon was growing from the crystal
growth surface of the catalyst material. When the fibrous carbon
was further observed with the transmission electron microscope, it
was ensured that the fibrous carbon was a carbon nanotube and an
impurity such as amorphous carbon, graphite or the catalyst
material was hardly included.
After observation with the electron microscope, the catalyst base
was entered into heat and pressure-resistant heating furnace tube
51 and an attempt was made to generate the carbon nanotube again in
a condition similar to that described above, but the carbon
nanotube was not generated due to contamination of a surface of the
catalyst base and the like. Therefore, sputtering of the crystal
growth surface with a cluster ion beam was performed and,
thereafter, an attempt was made to generate the carbon nanotube
again in the condition similar to that described above. As a
result, the carbon nanotube could be generated.
Example 3
(1) Making of Catalyst Base
In this example, a catalyst base was made by a method shown in FIG.
2. That is, while rotating an Ag rod as non-catalyst material 201
having an outside diameter of 40 mm, Fe and Ag were concurrently
deposited on a periphery of the Ag rod from deposition sources 202
and 203 (FIG. 2(A)) to form composite material 206 in a spiral
shape having respective 10 layers of Fe as catalyst materials 204
each having a thickness of 1 .mu.m and Ag layers as non-catalyst
materials 205 each having a thickness of 5 .mu.m (FIG. 2(B)). An Ag
layer as non-catalyst material 207 was further formed to make an
outside diameter of a periphery of a resulting composite material
208 become 60 mm (FIG. 2(C)).
Composite material 208 obtained was passed through drawing dice 209
for wiredrawing until an outside diameter thereof became 1.2 mm to
obtain wire 1 (FIG. 2(D)). Wire 1 was cut at every length of 1 m
and bundled together to fill an Ag pipe as non-catalyst material
210 having an outside diameter of 60 mm and an inside diameter of
40 mm, while spacers of Ag were used to fill gaps to avoid
generation of a cavity, to form composite material 211 (FIG. 2(E)).
Composite material 211 obtained was passed through drawing dice 209
for wiredrawing until a diameter thereof became 1.2 mm to obtain
wire 2 (FIG. 2(F)). The step of obtaining wire 2 from wire 1 was
repeated and, finally, an aggregate having a diameter of 10 mm was
obtained which was formed with a bundle of a plurality of catalyst
structures in which a thickness of each of Fe layers was set to 2
nm. The aggregate was cut to have a length of 0.5 mm, and cut
surfaces of both ends (both end surfaces) were mechanically
polished by buffing or the like.
Planarization of the both end surfaces was performed using a
cluster ion beam so that a structure of an Fe portion as the
catalyst material was exposed on the both end surfaces in a spiral
shape to make catalyst base 212 having a large number of composite
materials 206 each having the catalyst material included in
non-catalyst material 207 (FIG. 2(G)).
(2) Production of Carbon Nanostructure
A carbon nanotube as a carbon nanostructure was produced with the
production device shown in FIG. 5 using the catalyst base obtained
as above. Heat and pressure-resistant heating furnace tube 51
including the electric furnace as the heating device, the gas
introduction and exhaust system, the growth temperature control
system, the vacuum control system, the gas flowmeter, and the like
was separated into a space of a crystal growth surface side and a
space of a non-crystal growth surface side with catalyst base 54
inserted and seal material 55. While supplying an acetylene gas
together with an argon gas to the space of the non-crystal growth
surface side, a temperature inside heat and pressure-resistant
heating furnace tube 51 was set to 840.degree. C. On the other
hand, an argon gas as a carrier gas was supplied to the space of
the crystal growth surface side.
As a result, generation of fibrous carbon from the crystal growth
surface was recognized. When catalyst base 54 and the generated
fibrous carbon were observed with the scanning electron microscope,
it was ensured that the fibrous carbon was growing from the crystal
growth surface of the catalyst material. When the fibrous carbon
was further observed with the transmission electron microscope, it
was ensured that the fibrous carbon was a carbon nanotube and an
impurity such as amorphous carbon, graphite or the catalyst
material was hardly included.
After observation with the electron microscope, catalyst base 54
was entered into heat and pressure-resistant heating furnace tube
51 and an attempt was made to generate the carbon nanotube again in
a condition similar to that described above, but the carbon
nanotube was not generated due to contamination of a surface of the
catalyst base and the like. Therefore, sputtering of the surface of
the catalyst base with a cluster ion beam was performed and,
thereafter, an attempt was made to generate the carbon nanotube
again in the condition similar to that described above. As a
result, the carbon nanotube could be generated.
Example 4
(1) Making of Catalyst Base
In an Ag--Au (silver-gold) alloy pipe having an outside diameter of
60 mm and an inside diameter of 50 mm, an Fe (iron) pipe having an
outside diameter of 50 mm and an inside diameter of 45 mm was
inserted, and an Ag--Au alloy rod having an outside diameter of 45
mm was further inserted therein. A composite material obtained was
subjected to wire-drawing with a drawing dice until an outside
diameter thereof became 1.2 mm to obtain wire 1. Wire 1 was cut at
every length of 1 m and bundled together to fill an Ag--Au pipe
having an outside diameter of 60 mm and an inside diameter of 40
mm, while spacers of an Ag--Au alloy were used to fill gaps to
avoid generation of a cavity, and the Ag--Au pipe was subjected to
wiredrawing with the drawing dice until a diameter thereof became
1.2 mm to obtain wire 2. The step of obtaining wire 2 from wire 1
was repeated and, finally, an aggregate having a diameter of 5 mm
was obtained which was formed with a bundle of a plurality of
catalyst structures in which an outside diameter of Fe was set to
20 nm. The aggregate was cut to have a length of 2 mm, and cut
surfaces of both ends (both end surfaces) were mechanically
polished by buffing or the like.
Planarization of the both end surfaces was performed using a
cluster ion beam or the like so that an Fe portion as the catalyst
material was exposed on the both end surfaces in a ring-like shape.
Then, an Fe film having a thickness of 2 .mu.m was formed on one
end surface to make a catalyst base having the end surface on a
side having the Fe film formed as a non-crystal growth surface and
the end surface on a side not having the Fe film formed as a
crystal growth surface.
(2) Production of Carbon Nanostructure
A carbon nanotube as a carbon nanostructure was produced with the
production device shown in FIG. 5 using the catalyst base obtained
as above. Heat and pressure-resistant heating furnace tube 51
including the electric firnace as the heating device, the gas
introduction and exhaust system, the growth temperature control
system, the vacuum control system, the gas flowmeter, and the like
was separated into a space of a crystal growth surface side and a
space of a non-crystal growth surface side with catalyst base 54
inserted and seal material 55. While flowing a mixed atmospheric
gas containing a propane gas and an argon gas in a ratio of 1:4 at
1.5 atm in the space of the non-crystal growth surface side, a
temperature inside heat and pressure-resistant heating furnace tube
51 was set to 960.degree. C. On the other hand, an argon gas as a
carrier gas was supplied to the crystal growth surface side.
Thereafter, a ratio of supply of an acetylene gas was gradually
decreased to zero while keeping a pressure of the atmospheric
gas.
As a result, generation of fibrous carbon from the crystal growth
surface was recognized. When catalyst base 54 and the generated
fibrous carbon were observed with the scanning electron microscope,
it was ensured that the fibrous carbon was growing from the crystal
growth surface of the catalyst material. When the fibrous carbon
was further observed with the transmission electron microscope, it
was ensured that the fibrous carbon was a carbon nanotube and an
impurity such as amorphous carbon, graphite or the catalyst
material was hardly included.
After observation with the electron microscope, catalyst base 54
was entered into heat and pressure-resistant heating furnace tube
51 and an attempt was made to generate the carbon nanotube again in
a condition similar to that described above, but the carbon
nanotube was not generated due to contamination of a surface of the
catalyst base and the like. Therefore, sputtering of the surface of
the catalyst base with a cluster ion beam was performed and,
thereafter, an attempt was made to generate the carbon nanotube
again in the condition similar to that described above. As a
result, the carbon nanotube could be generated.
Example 5
(1) Making of Catalyst Base
In an Ag (silver) pipe having an outside diameter of 60 mm and an
inside diameter of 50 mm, an Fe (iron) pipe having an outside
diameter of 50 mm and an inside diameter of 45 mm was inserted, and
an Ag rod having an outside diameter of 45 mm was further inserted
therein. A composite metal material obtained was subjected to
wiredrawing with a drawing dice until an outside diameter thereof
became 1.2 mm to obtain wire 1. Wire 1 was cut at every length of 1
m and bundled together to fill an Ag pipe having an outside
diameter of 60 mm and an inside diameter of 40 mm, while spacers of
Ag were used to fill gaps to avoid generation of a cavity, and the
Ag pipe was subjected to wiredrawing with the drawing dice until a
diameter thereof became 1.2 mm to obtain wire 2. The step of
obtaining wire 2 from wire 1 was repeated and, finally, an
aggregate having a diameter of 5 mm was obtained which was formed
with a bundle of a plurality of catalyst structures in which an
outside diameter of Fe was set to 12 nm. The aggregate was cut, and
cut surfaces of both ends (both end surfaces) were mechanically
polished by buffing or the like to obtain a thickness of 1 mm.
Planarization of the both end surfaces was performed using a
cluster ion beam or the like so that a structure of an Fe portion
as the catalyst material was exposed on the both end surfaces in a
ring-like shape. Thereafter, a porous body made of Ag having a
thickness of 3 mm and including a large number of pores of about 80
.mu.m.phi. was subjected to pressure welding to one end surface of
a catalyst base to be a non-crystal growth surface, and was joined
by heating or the like. Furthermore, irradiation with an ion beam
or the like was performed for the other end surface to be a crystal
growth surface, and the catalyst base was made to be a thin film
until a length between the both end surfaces, that is, a thickness
of the catalyst base became 80 .mu.m. Finally, planarization of the
crystal growth surface with a cluster ion beam was performed to
remove surface roughness on the crystal growth surface of the
catalyst material, and making of the catalyst base was
completed.
(2) Production of Carbon Nanostructure
A carbon nanotube as a carbon nanostructure was produced using the
production device shown in FIG. 5 and the catalyst base obtained as
above. Heat and pressure-resistant heating furnace tube 51
including the electric furnace as the heating device, the gas
introduction and exhaust system, the growth temperature control
system, the vacuum control system, the gas flowmeter, a plasma
cementation device, and the like was separated into a space of a
crystal growth surface side and a space of a non-crystal growth
surface side with catalyst base 54 inserted and seal material 55. A
material gas including an ethylene gas and a hydrogen gas mixed in
a ratio of 1:2 was introduced into the space of the non-crystal
growth surface side to be about 3 Torr (about 399 Pa) at
880.degree. C. Heat and pressure-resistant heating furnace tube 51
was used as an anode and the catalyst base was used as a cathode to
apply a DC voltage between both electrodes to cause glow discharge
and generate plasma, and thereby carbon penetrated from the
non-crystal growth surface into the catalyst material. On the other
hand, a mixed gas of an argon gas and an H.sub.2 gas was introduced
to the crystal growth surface side and, thereafter, supply of only
the H.sub.2 gas was stopped.
As a result, generation of fibrous carbon from the crystal growth
surface was recognized. When catalyst base 54 and the generated
fibrous carbon were observed with the scanning electron microscope,
it was ensured that the fibrous carbon was growing from the crystal
growth surface of the catalyst material. When the fibrous carbon
was further observed with the transmission electron microscope, it
was ensured that the fibrous carbon was a carbon nanotube and an
impurity such as amorphous carbon, graphite or the catalyst
material was hardly included.
Example 6
(1) Making of Catalyst Base
In this example, a catalyst base having the construction shown in
FIG. 6 was used. In an Ag (silver) pipe having an outside diameter
of 36 mm and an inside diameter of 9 mm, an Fe (iron) pipe (an Fe
purity: about 4 N (99.99%)) having an outside diameter of 9 mm and
an inside diameter of 7 mm was inserted, and an Ag rod having an
outside diameter of 7 mm was further inserted therein. A composite
material obtained was subjected to wiredrawing with a drawing dice
until an outside diameter thereof became 2 mm to obtain wire 1.
Wire 1 was cut at every length of 1 m and bundled together to fill
an Ag pipe having an outside diameter of 36 mm and an inside
diameter of 9 mm, while spacers of Ag were used to fill gaps to
avoid generation of a cavity, and the Ag pipe was subjected to
wiredrawing with the drawing dice until a diameter thereof became
about 1.2 mm to obtain wire 2. The step of obtaining wire 2 from
wire 1 was repeated to finally obtain an aggregate formed with a
composite material having Fe penetrating through an Ag base
material having a diameter of 20 mm which was formed with a bundle
of a plurality of catalyst structures in which an outside diameter
of Fe was set to 8 nm. The aggregate was cut, and cut surfaces of
both ends (both end surfaces) were polished by buffing or the like
to have a thickness of 50 .mu.m.
Planarization of one end surface was performed using a cluster ion
beam or the like so as to expose a structure of an Fe portion as
the catalyst material to form a non-crystal growth surface exposing
the catalyst material in a ring-like shape. Thereafter, porous body
65 made of Ag having a thickness of 3 mm, which included holes of
about 200 .mu.m.phi. to form a lotus root-like shape, was subjected
to pressure welding to the non-crystal growth surface of catalyst
base 64, joined by heating or the like, and further reinforced with
a base material made of WC (tungsten carbide). Finally,
planarization of a crystal growth surface was performed using a
cluster ion beam so as to expose the catalyst material in a
ring-like shape to make catalyst base 64 having porous body 65
formed thereon.
(2) Production of Carbon Nanostructure
A carbon nanotube as a carbon nanostructure was produced using the
production device shown in FIG. 6 and the catalyst base obtained as
above. Heat and pressure-resistant heating furnace tube 61
including the heating device, the gas introduction and exhaust
system, the growth temperature control system, the vacuum control
system, the gas flowmeter, a plasma cementation device, and the
like was separated into a space of a non-crystal growth surface
side and a space of a crystal growth surface side with catalyst
base 64 inserted and seal material 66.
A material gas including a hydrogen gas, a methane gas and an argon
gas mixed in a ratio of 2:1:2 was used to fill the space of the
non-crystal growth surface side to attain about 4 Torr (about 532
Pa) at 860.degree. C. The heat and pressure-resistant heating
furnace tube was used as an anode and the catalyst base was used as
a cathode to apply a DC voltage between both electrodes to cause
glow discharge and generate plasma, and thereby carbon penetrated
from the non-crystal growth surface side into catalyst material 62
via porous body 65. A carrier gas including a hydrogen gas and an
argon gas was used to fill the space of the crystal growth surface
side and, after the carbon nanotube as carbon nanostructure 67 was
generated, supply of the hydrogen gas was stopped to supply only
the argon gas to the space of the crystal growth surface side.
As a result, generation of fibrous carbon from the crystal growth
surface was recognized. When the catalyst base and the generated
fibrous carbon were observed with the scanning electron microscope,
it was ensured that the fibrous carbon was growing from the crystal
growth surface of the catalyst material. When the fibrous carbon
was further observed with the transmission electron microscope, it
was ensured that the fibrous carbon was a carbon nanotube and an
impurity such as amorphous carbon, graphite or the catalyst
material was hardly included.
In this example, during generation of the carbon nanotube, the
hydrogen gas was supplied to the non-crystal growth surface and the
crystal growth surface to reduce an iron oxide layer on an exposed
surface of the catalyst material to accelerate penetration of
carbon into the catalyst material and precipitation of a carbon
crystal from the crystal growth surface.
Example 7
(1) Making of Catalyst Base
In an Ag (silver) pipe having an outside diameter of 36 mm and an
inside diameter of 18 mm, an Fe (iron) pipe (an Fe purity: at least
about 5 N (99.999%)) having an outside diameter of 18 mm and an
inside diameter of 14 mm was inserted, and an Ag rod having an
outside diameter of 14 mm was further inserted therein. A composite
material obtained was subjected to wiredrawing with a drawing dice
until an outside diameter thereof became 2 mm to obtain wire 1.
Wire 1 was cut at every length of 1 m and bundled together to fill
an Ag pipe having an outside diameter of 36 mm and an inside
diameter of 18 mm, while spacers of Ag were used to fill gaps to
avoid generation of a cavity, and the Ag pipe was subjected to
wiredrawing with the drawing dice until a diameter thereof became 2
mm to obtain wire 2. The step of obtaining wire 2 from wire 1 was
repeated to finally obtain an aggregate formed with a composite
material having Fe penetrating through an Ag base material having a
diameter of 20 mm which was formed with a bundle of a plurality of
catalyst structures in which an outside diameter of Fe was set to
about 8 nm.
The aggregate was cut, and cut surfaces of both ends (both end
surfaces) were polished by buffing or the like to have a thickness
of about 40 .mu.m. Thereafter, a cluster ion beam or the like was
used to perform planarization of a non-crystal growth surface so as
to expose the catalyst material in a ring-like shape, and an Fe
film having a thickness of about 5 .mu.m was further formed on the
non-crystal growth surface. The end surface to be a crystal grow
surface was polished with the cluster ion beam, sputtering was
performed to obtain a thickness of a catalyst base of about 10
.mu.m, and planarization of the crystal grow surface was performed
to expose the catalyst material in a ring-like shape. The catalyst
base was made as above.
(2) Production of Carbon Nanostructure
A carbon nanotube as a carbon nanostructure was produced using the
production device shown in FIG. 7 and the catalyst base obtained as
above. The production device formed with heat and
pressure-resistant heating furnace tube 71 including the electric
furnace as the heating device, the gas introduction and exhaust
system, the growth temperature control system, the vacuum control
system, the gas flowmeter, a plasma cementation device, and the
like was separated into a space of a non-crystal growth surface
side and a space of a crystal growth surface side with catalyst
base 74 inserted. Anode 75 was provided in the space of the
non-crystal growth surface side. Catalyst material 72 was exposed
on the non-crystal growth surface side and the crystal growth
surface side. A temperature inside the production device was set to
850.degree. C., a DC voltage was applied between anode 75 and
catalyst base 74 set as a cathode, and a material gas including a
methane gas, a propane gas, a hydrogen gas, and an argon gas mixed
in a ratio of 1:1:1:1 was supplied at about 6-8.times.10.sup.2 Pa
(about 5-6 Torr) so as to set a current density of glow discharge
to about 0.2 mA/cm.sup.2 to generate plasma with glow discharge to
supply ionized carbon to a surface of the catalyst base having the
Fe film formed thereon, that is, to the non-crystal growth
surface.
On the other hand, a carrier gas including a hydrogen gas and an
argon gas was used to fill the crystal growth surface side and,
after an iron oxide layer on the crystal growth surface was
reduced, supply of the hydrogen gas was stopped to fill the space
only with the argon gas to generate carbon nanostructure 76. A gas
pressure in the space of the crystal growth surface side was set to
be substantially equal to a gas pressure in the space of the
non-crystal growth surface side in order to suppress deformation of
the catalyst base.
As a result, generation of fibrous carbon from the crystal growth
surface was recognized. Since catalyst base 74 was charged due to
voltage application during the glow discharge, the fibrous carbon
was also charged, and therefore the fibrous carbon was collected by
attraction and taking-up by a take-up roll utilizing this
charge.
When the catalyst base and the generated fibrous carbon were
observed with the scanning electron microscope, it was ensured that
the fibrous carbon was growing from the crystal growth surface of
the catalyst material. When the fibrous carbon was further observed
with the transmission electron microscope, it was ensured that the
fibrous carbon was a carbon nanotube and an impurity such as
amorphous carbon, graphite or the catalyst material was hardly
included.
Comparative Example
Heating was performed by a method similar to that in example 1
except that a catalyst base, which included an alumina base
material carrying Fe particles having an average particle diameter
of about 10 nm which were generated by thermal decomposition of
ferrocene, was inserted into the heat and pressure-resistant
heating furnace tube. As a result, a carbon nanotube having a
ring-like cross-sectional shape could be generated. When the carbon
nanotube obtained was observed with the transmission electron
microscope, however, presence of impurities such as Fe particles,
amorphous carbon and graphite was recognized. Furthermore, since a
shape of the catalyst cannot be arbitrarily changed in the method
of this comparative example, a carbon nanotube having a spiral or
waved cross-sectional shape cannot be grown.
Results of the examples and the comparative example show that an
even and highly pure carbon nanostructure having a desired shape
can be obtained using the method of the present invention.
It should be understood that the embodiments and examples disclosed
herein are illustrative and non-restrictive in every respect. The
scope of the present invention is defined by the terms of the
claims, rather than the description above, and is intended to
include any modifications within the meaning and scope equivalent
to the terms of the claims.
INDUSTRIAL APPLICABILITY
According to the present invention, a catalyst base having a
crystal growth surface in a desired shape can be efficiently formed
with relatively easy operations by adopting diameter-reduction
processing. Therefore, a carbon nanostructure having an even shape
can be produced with a high purity and a production cost can be
reduced.
* * * * *