Patent Grant
6890505
1. Field of the Invention
The present invention relates to carbon materials including fullerenes as its components, especially fine carbon wires, and methods for producing the same.
2. Description of the Related Art
C60 is a typical fullerene. It is known that a needle-like substance containing C60 can be obtained from a solution of C60 in toluene (See S. Ogawa, H. Furusawa, T. Watanabe, and H. Yamamoto, “Observation of condensed structure of C60 assembled from solution” Journal of Physics and Chemistry of Solids, 61(2000) 1045-1050).
However, the reference only shows a technique in which C60 is deposited from a solution of C60 in toluene and thereby yields such a needle-like substance. According to this technique, the needle-like substance very slowly grows to about 20 mm in length over six months. The growth rate of the needle-like substance of C60 according to the technique is excessively low and it takes a much long time for the needle-like substance to grow.
According to such conventional techniques, a practically sufficient growth rate cannot be obtained in the production of one-dimensional substances including fullerenes as its components, especially wire-like carbon materials.
The conventional needle-like substance of C60 is obtained by depositing from a solution of C60 containing toluene alone as a solvent. The resulting needle-like substance is amorphous (see the aforementioned reference).
Japanese Unexamined Patent Application Publication No. 10-1306 discloses a cluster obtained by adding a poor solvent for fullerenes to a solution of a fullerene monomer.
Such a cluster, however, is made of the fullerene monomer associated by the van der Waals force and is not a crystal but a granule.
It is also known that the needle-like substance of C60 can also be obtained by evaporating a solution of C60 in a mixture of 95 wt % of hexane and 5 wt % of benzene or a solution having a similar composition at temperatures ranging from room temperature to 80° C. (Y. Yosida, Jpn. J. Appl. Phys. 1992; 31: L505, “Scanning electron microscope images of C60 whiskers”).
The needle-like crystal of the above-mentioned substance has a very rough surface and is apparently different from a needle-like fullerene crystal having a smooth surface. In addition, the scanning electron microscope images of the needle-like crystal in the reference show that this crystal is a polycrystal.
Electric drive mechanisms of microminiature devices such as micro-sensor assemblies and micromachines require fine conductive wires for supplying electricity. However, fine metal wires include grain boundaries formed by crystallization and inevitably cause increased electric resistance due to segregation of dopants into the grain boundaries, and rupture and increased surface roughness at the grain boundaries.
The tip shapes of such fine metal wires depend n the crystal habit of the metal crystals, and the fine metal wires can hardly have a nearly spherical tip having a curvature on the order of nanometers.
In addition, the metallic fine wires cannot significantly have a chemically modified structure by combining a specific functional group to the surface so as to constitute a higher order structure.
Accordingly, an object of the present invention is to provide a novel fine carbon wire including a fullerene as its component. Another object of the present invention is to produce a fine carbon wire including a fullerene as its component from a solution of the fullerene at high speed.
Specifically, the present invention provides, in a first aspect, a fine carbon wire including a fullerene in the form of a needle-like crystal having a smooth surface.
The present invention provides, in a second aspect, a fine carbon wire including a fullerene in the form of a branched needle-like crystal.
In a third aspect, the present invention provides a method for producing a fine carbon wire including a fullerene. This method includes the steps of (1) putting together a solution containing the fullerene dissolved in a first solvent with a second solvent having less solvency for the fullerene than the first solvent; (2) forming a liquid-liquid interface between the solution and the second solvent; and (3) depositing a fine carbon wire at the liquid-liquid interface.
In a fourth aspect, the present invention provides a method for producing a fine carbon wire including a fullerene. This method includes the steps of (1) putting together a solution containing the fullerene dissolved in a first solvent with a second solvent having less solvency for the fullerene than the first solvent; and (2) subjecting the solution and the second solvent to ultrasonic treatment to thereby deposit a fine carbon wire.
The present invention is based on the finding that, when a solvent is added to a solution of a fullerene dissolved in another solvent different from the former solvent, the resulting solution deposits a single wire-like crystal of the fullerene (a fullerene wire) having crystal habit.
After further investigations based on the above finding, the present inventors have found that a carbon material is obtained by putting together a solution containing a fullerene dissolved in a first solvent with a second solvent having less solvency for the fullerene than the first solvent, forming a liquid-liquid interface between the solution and the second solvent and depositing the carbon material from the solution, and that the resulting carbon material is a needle-like fullerene crystal having a smooth surface that has not been obtained in conventional equivalents. The present invention has been accomplished based on these findings.
The term “wire” as used herein means “fine wire” and the term “a fine carbon wire” means “a wire including carbon as its component”. Such fine carbon wires include needle-like crystals (inclusive of needle-like single crystals and needle-like polycrystals) each including a fullerene.
Fine carbon wires each including a fullerene in the form of a needle-like crystal are referred to as “fullerene wires” or “fullerene whiskers”. The term “fullerene wires” means and includes fine carbon wires mainly including wire-like single fullerene crystal having crystal habit. The term “fullerene whiskers” means and includes fine carbon wires including a wire-like single fullerene crystal, and needle-like single crystals and needle-like polycrystals of a fullerene.
The present invention in the first aspect relates to a fine carbon wire including a needle-like fullerene crystal having a smooth surface.
Fullerenes for use in the present invention include C60, C70 and other higher fullerenes. Needle-like crystals of such fullerenes include needle-like single crystals and needle-like polycrystals.
The smooth surface of the needle-like fullerene crystal according to the present invention is a kind of crystal habits of the needle-like fullerene crystal itself. In general, the term “crystal habit” means dimensional characteristics, i.e., the size and shape, of the crystal.
The needle-like fullerene crystal according to the present invention has a needle-like crystal form that varies depending on the degree of growth of crystallographically equivalent faces.
The term “needle” as used herein means a shape having an external diameter of 1 nm or more, a length of 1 μm or more and an aspect ratio (the ratio of the length to the external diameter) of 2 or more.
The needle-like fullerene crystal having a crystal habit of smooth surface has been first found by the present inventors.
The fine carbon wire including a fullerene according to the first aspect of the present invention is a needle-like fullerene crystal having a smooth surface, and can therefore avoid the problems in surface roughness of conventional fine metal wires and the like. Additionally, the fine carbon wire has a low friction coefficient and can therefore be applied to, for example, sliding parts of micromachines.
The present invention in the second aspect relates to a fine carbon wire including a branched needle-like fullerene crystal.
The branched needle-like fullerene crystal has been first found by the present inventors.
The fine carbon wire including a fullerene according to the second aspect of the present invention is a branched needle-like fullerene crystal and can therefore be applied to, for example, conductive circuits.
The present invention in the third aspect relates to a method of producing a fine carbon wire including a fullerene, and specifically to a method of producing a needle-like fullerene crystal having a smooth surface (this method may be hereinafter briefly referred to as “Method 1”).
In this method, a first solvent dissolves a material fullerene and thereby yields a solution. The first solvent includes a solvent system that can dissolve the fullerene.
In the above method, a second solvent is added to the solution of the fullerene. The second solvent includes a solvent system that is of a type different from the first solvent and has less solvency for the fullerene than the first solvent.
The second solvent serves to deposit a fine carbon wire including the fullerene from the fullerene solution.
According to Method 1, a fine carbon wire including a fullerene is produced by putting together the solution of the fullerene with the second solvent, forming a liquid-liquid interface between the fullerene solution and the second solvent and depositing a fine carbon wire from the fullerene solution.
The aforementioned fine carbon wire includes substances derived from the first and second solvents combined with the fullerene by at least one bond selected from the group consisting of an intermolecular bond due to intermolecular force, an ionic bond and a covalent bond.
Method 1 can easily yield a fine carbon wire including a fullerene at a high growth rate of about 10 to 400 μm/h by deposition at a liquid-liquid interface using a given first solvent and a second solvent different therefrom.
According to Method 1, the substances derived from the first and second solvents are combined with the fullerene by a given chemical bond and an intermolecular bond and, in addition, the molecules of the fullerene are combined with each other by an intermolecular bond. The resulting carbon materials, specifically fine carbon wires, have significantly higher strength than those including a pure fullerene alone.
The present invention in the fourth aspect relates to a method of producing a fine carbon wire including a fullerene, and specifically to a method of producing a branched needle-like fullerene crystal (this method may be hereinafter briefly referred to as “Method 2”).
Method 2 is similar to Method 1, except that the second step is different. In the second step of Method 2, the solution and the second solvent are subjected to ultrasonic treatment to thereby deposit a fine carbon wire.
Method 2 can easily yield a fine carbon wire including a fullerene, especially a branched needle-like crystal of the fullerene at a high growth rate as in Method 1.
The fine carbon wires of the present invention include fullerenes as needle-like fullerene crystals each having a smooth surface and are novel fine carbon wires. Accordingly, they can solve problems in surface roughness of conventional fine metal wires and can be applied to sliding parts of micromachines because of their low friction coefficients.
The methods of producing a fullerene according to the present invention can easily yield such fine carbon wires including fullerenes from a fullerene solution at a high growth rate of from 10 to 400 μm/h.
For a better understanding of the invention as well as other objects and features thereof, reference is made to the following detailed description to be read in conjunction with the accompanying drawings, wherein:
Carbon materials including fullerenes as components in the present invention include fine carbon wires [including fullerene wires and fullerene whiskers (hereinafter briefly referred to as “FWs”)], and materials prepared from such fine carbon wires by at least one means such as cutting or pulverization to a predetermined average length or average grain size.
(1) First Aspect
The present invention in the first aspect includes carbon materials having crystal habit, having a wire-like shape and including a single crystal of the fullerene.
(1-1) Fullerene Wires
Wire-like single fullerene crystals according to the present invention have crystal habit. The term “crystal habit” as used herein means the characteristics or features of the size and shape of the crystal in question.
The single fullerene crystal according to the present invention has a wire-like crystal form which varies depending on the degree of growth of crystallographically equivalent faces.
The term “needle” as used herein means and includes a shape having an external diameter of 3 nm or more, a length of 50 μm or more and an aspect ratio (the ratio of the length to the outer diameter) of 2 or more.
Such a wire-like single fullerene crystal having crystal habit is novel and has been first found by the present inventors.
The carbon material including a fullerene according to the present invention is a wire-like single fullerene crystal having crystal habit, has a higher strength than a powdered crystal of a fullerene alone, has anisotropy and can serve as an excellent insulator or conductor. In addition, the carbon material can exhibit excellent low-dimensional conductivity by applying a high voltage or by adding an electrically conductive substance thereto.
According to the present invention, such wire-like crystals can have an external diameter of from 3 nm to 1000 μm, a length of from 50 μm to 20 mm and an aspect ratio of from 2 to several hundreds. The needle-like crystals of the present invention can have an external diameter of from 1 nm to 1000 μm, a length of from 1 μm to 20 mm and an aspect ratio of from 2 to several thousands or more.
The minimum value of the aspect ratio of the crystal for use in the present invention can be set at 2, which is larger than the crystallographically acceptable minimum aspect ratio of 1.63 when the [0001] axis in a hexagonal crystal is defined as the growth axis. The maximum value of the aspect ratio is not specifically limited and can be set at 100, 200, 300, or several hundreds or more. These ranges are supposed to be preferred as a result of observation in wires having a length of 2 cm and a diameter of 0.2 mm.
Such thin and slender crystals are supposed to form by action of anisotropy in preferred orientation or in growth rate.
After investigations, the present inventors have found that these wire-like crystals each have fullerene face-centered cubic crystals as a basic unit cell and include strain or distortion portions of face-centered cubic crystals formed by insertion of a substance other than the fullerene into pores between fullerene molecules.
The strain portions of the face-centered cubic crystal constitute a rhombohedral or another crystal that has anisotropy in preferred orientation, and crystals of the fullerene grow on, for example, side faces of the rhombohedral crystal.
The wire-like fullerene crystals according to the present invention can have crystal habit. The crystal habit appears as various wire-like crystal forms depending on the degree of growth of crystallographically equivalent faces, in contrast to crystals (face-centered cubic crystals) of pure fullerenes.
This crystal habit can clearly be determined as a hexagon, for example, by the observation of cross sections of wire-like crystals.
When a powdered crystal of a fullerene is molded at high temperatures and high pressures within specific ranges, the fullerene may be polymerized to yield a rhombohedral crystal which can become a powder having a crystal habit plane. At temperatures and pressures equal to or more than the specific ranges, the powered fullerene crystal is supposed to form a glassy carbon or diamond having a crystal habit plane.
However, the investigations made by the present inventors show that this type of crystal habit has not been observed in a linear carbon material obtained from a fullerene by charging C60 into a silver tube and wire-drawing to thereby yield a wire.
The fine carbon wire according to the first aspect includes a wire-like single fullerene crystal having the crystal habit. The single crystal can have a wire-like shape owing to, for example, anisotropy in a molecular bond.
The wire-like single crystal can yield a carbon material that is excellent in strength and exhibits superior insulative or conductive anisotropy as compared with powdered carbon materials, amorphous carbon materials or bulk carbon materials.
The carbon materials of the present invention can be applied to a wide variety of fields such as appliance industry, automobile industry, mechanical industry and aerospace industry.
The carbon materials of the present invention can have high strength and can satisfactorily be used in the fields of lubricating materials, ferroelectric fillers, dispersion reinforcing materials and semiconductors.
They can be applied to products such as ferroelectric ceramics and polymers, piezoelectric elements, self-lubricating ceramics and polymers, insulating materials and semiconductor materials.
The carbon materials of the present invention can yield polymerized fullerene wires that are polymerized by high pressure hot-pressing or polymerized fullerene wire-ceramics complexes that are prepared by hot-pressing the carbon materials with ceramics at high pressures.
(1-2) Fullerene Whiskers
The term “fullerene whisker(s)” or “FW(s)” herein is used as a generic name of needle-like fullerene crystals including the aforementioned fullerene wires.
The fullerene whiskers according to the present invention can have a nearly spherical tip having a curvature on the order of nanometers.
The fullerene whiskers according to the present invention are frequently obtained as polycrystals each having a large external diameter. Such poly-crystalline fullerene whiskers may have a structure consisting of a bundle of several single-crystalline fullerene whiskers.
(1-3) Fullerene Nanowhiskers
Among the fullerene whiskers of the present invention, single-crystalline fine carbon wires each having a submicron or less external diameter are referred to as fullerene nanowhiskers (FNWs). The length of such fullerene nanowhiskers ranges from several folds of its external diameter to several tens of millimeters. The term “fullerene nanowhiskers” has been first used by the present inventors.
The fullerene nanowhiskers according to the present invention are needle-like crystals of fullerenes (e.g., C60 and C70) each having a submicron external diameter. All of the fullerene nanowhiskers according to the conventional studies consist of single crystals alone and have a growth axis in a closest packing direction of fullerene molecules.
In this connection, carbon fibers are obtained by heating organic polymeric fibers at high temperatures of 800° C. to 3000° C. or by spinning pitch and heating the spun pitch, and do not include fullerenes as a constitutional unit.
The fullerene whiskers and fullerene nanowhiskers according to the present invention are needle-like fullerene crystals and have a three-dimensional periodic structure whose symmetry is defined by the space group. In contrast, the polymers or clusters of fullerene (see Japanese Unexamined Patent Application Publication No. 10-1306) are not crystalline and can clearly crystallographically be distinguished from the fullerene whiskers and fullerene nanowhiskers.
Carbon nanotubes each have a structure of a cylindrically rounded graphite sheet and can apparently be distinguished from the fullerene whiskers and fullerene nanowhiskers consisting of fullerene molecules.
The fullerenes has low friction coefficient and the fullerene nanowhiskers have no grain boundary. Accordingly, the fullerene nanowhiskers can have very small surface roughness at an atomic level.
The fullerene nanowhiskers have a smooth surface having a low friction coefficient and can be used as light-weight conductive fine wires, thus solving the problems in weight and surface roughness of conventional fine metal wires. In addition, the fullerene nanowhiskers may possibly become superconductors by adding alkali metal elements thereto.
Since the fullerene nanowhiskers have a surface covered with fullerene molecules such as C60, the surface of the fullerene nanowhiskers can be modified with organic molecules that yield covalent bonds. This modification cannot be achieved in conventional fine metal wires.
The fullerene nanowhiskers according to the present invention can be applied to a wide variety of fields such as electronic industry, mechanical industry and aerospace industry. It can also be applied to chemical industry, since the fullerene nanowhiskers can form chemical bonds with organic materials and can be used as reagents.
These fullerene nanowhiskers are semiconductors and can be used as low-dimensional semiconductors or quantum wires in the semiconductor industry. By regularly arraying, the fullerene nanowhiskers can yield novel photonic crystals and can therefore be used in the optoelectronic device industry.
Since the fullerenes satisfactorily store hydrogen and the fullerene nanowhiskers can be used as materials for a hydrogen-storing unit, the fullerene nanowhiskers can be used in the energy industry.
The C60 molecule is known to be an excellent field emission material. Therefore the fullerene nanowhiskers of C60 (C60 NW) can be used as field-emitter devices such as plasma displays.
Since a tip of the fullerene nanowhiskers consisting of C60 has a spherical structure having a curvature radius on the order of nanometers, the tip has a very smooth shape. The fullerene nanowhiskers can therefore be used as probes in tracer surface profiling instruments. In addition, since the C60 NWs are conductive, they can be used as probes in scanning tunneling microscopes.
The C60 nanowhiskers can also be used as superconductive fine wires, since the constitutive C60 crystals can become superconductors by doping of alkali metals.
The use of these fullerene nanowhiskers as conductors in high-density printed wiring boards or integrated circuits can reduce the weight of the resulting equipment.
The fullerene nanowhiskers can chemically be modified, can therefore be compounded with organic molecules and can be used as reinforcing materials in, for example, photoresists.
In addition, the fullerene nanowhiskers are excellent in conductivity and linearity, exhibit low friction and can therefore be used as sliding members of micromachines.
The C60 nanowhiskers have introduced lattice dislocation, can plastically be deformed and can be deformed into optional shapes such as coils.
The C60 nanowhiskers are insulative when they have a large diameter. However, they have a decreasing resistivity with a decreasing diameter and therefore can be used as novel semiconductor materials.
(1-4) C70 Fullerene Whiskers
The fine carbon wires according to the first aspect of the present invention are preferably those including C70 in the form of needle-like crystals.
Such needle-like C70 crystals have high crystallinity and a low lattice defect density. In addition, they become a good conductor and, among them, needle-like single crystals are very satisfactory as fine carbon wires or field emission devices in transistors. The C70 whiskers have a multilayered lamina structure and therefore flexibly deform. They are expected to be high-temperature superconductors. They have a smooth surface, have a very low friction coefficient and are useful as sliding members in micromachines. The C70 whiskers are also expected to be doped with dopant elements in high concentration or to exhibit high catalytic activities since they have a high porosity.
(1-5) Cavity (Hollow Portions)
The needle-like fullerene crystals according to the present invention may have a cavity (hollow portion). The shape and the location of the cavity are not particularly limited. The needle-like fullerene crystals may each have the cavity at the core or at the tip, or both. Not only the needle-like polycrystals but also needle-like single crystals may have such a cavity. Unlike carbon nanotubes which have cylindrical structures made of graphite sheet, the needle-like fullerene crystals is a macromolecule in which fullerene molecules are linearly polymerized.
The cavity may be formed at the core of a bundle of needle-like fullerene crystals or may be formed at the core of a single fullerene crystal whisker. The investigations made by the present inventors show that the cavity may be formed by concentric shells of needle-like fullerene crystals, i.e., the cavity may have a “core-shell” structure. In the concentric shells, the cavity is formed by needle-like fullerene crystals concentrically surrounding therearound.
Such a hollow needle-like crystal having a cavity has a low spatial packing fraction and has a large surface area. The resulting fine carbon wire made of the hollow needle-like crystal is useful as a catalyst or a waveguide.
The hollow needle-like crystal has a higher specific strength and is useful as a fine carbon wire having flexibility. It can easily yield an electrode by introducing a liquid metal into the cavity and can therefore be used as a diode. In addition, it can yield high catalytic activity by introducing, for example, a catalytic element into the cavity.
(1-6) Multilayered Lamina
The needle-like fullerene crystal according to the present invention may have a multilayered lamina of the fullerene.
Such fullerene laminae are not specifically limited in thickness and other dimensions. For example, the multilayered lamina may have 1 to 100 piles of stacked slabs of the needle-like fullerene crystal each having a thickness of 1 to 50 nm or may have 1 to 100 pairs of one relatively thin lamina and one relatively thick lamina.
The resulting fine carbon wire comprising the multilayered lamina may be branched by partially delaminating the multilayered structure using physical or chemical means. Alternatively, a branched fine carbon wire can be produced by binding fine carbon wires with each other by means of physical or chemical procedures.
(1-7) Dopants
The needle-like fullerene crystal according to the present invention may further include dopants. Iodine, bromine and other halogen atoms, alkali metals, and methyl bromide may be recited by way of example.
The resulting doped needle-like fullerene crystal can have significantly improved physical properties. For example, doping of iodine yields a low-temperature ferromagnetic and doping of an alkali metal yields a superconductor, respectively, of the needle-like fullerene crystal.
The needle-like fullerene crystal can be doped with such dopants according to various techniques. For example, the fullerene crystal is doped with a dopant during its growth by adding the dopant into a solution in which the crystal is growing according to the method of the present invention.
Alternatively, the fullerene crystal can easily be doped with the dopant by preparing the crystal and subsequently exposing the resulting crystal to an atmosphere containing the dopant, such as a gas or solution.
(2) Second Aspect
The present invention in the second aspect relates to a fine carbon wire having a branched needle-like fullerene crystal.
The term “branched” as used herein means that the crystal has at least one branch. For example, it means that the needle-like fullerene crystal has a stem and a branch.
Such branched needle-like crystals include a needle-like crystal having a stem with some orientation from which two branches are branched off in two directions different from the orientation, and a needle-like crystal having a stem and one branch branched off the stem.
The fine carbon wire according to the second aspect consists of a branched needle-like fullerene crystal and can be designed into a circuit in accordance with the branch.
(3) Third Aspect (Method 1)
The method of the present invention according to the third aspect (Method 1) can yield crystalline fine carbon wires each having a thickness on the order of micrometers to nanometers from fullerenes.
According to Method 1 for the production of a fine carbon wire including a fullerene, a second solvent is added to a solution containing the fullerene dissolved in a first solvent to thereby deposit a carbon material from the solution.
Method 1 can yield a fine carbon wire including a fullerene in which the fine carbon wire is a fullerene single crystal and the fullerene single crystal is a needle-like fullerene crystal having a smooth surface and including a wire-like carbon material having crystal habit.
According to this method, the second solvent may be added to the solution of the fullerene dissolved in the first solvent to thereby deposit a carbon material comprising the fullerene from the fullerene solution.
Alternatively, the solution of the fullerene dissolved in the first solvent may be added to the second solvent to thereby deposit a carbon material comprising the fullerene from the fullerene solution.
(3-1) Materials
Fullerenes for use as the materials in the present invention include, for example, C60, C70, C80 and other fullerenes.
(3-2) First Solvents
First solvents for use herein have only to consist of a solvent system that can dissolve fullerenes. The solvent system may be made of one solvent alone or two or more types of solvents in combination.
Such first solvents may be good-solvent systems including, for example, good solvents for fullerenes. The good-solvent systems are solvent systems that can highly dissolve fullerenes.
Such good solvents for use in the present invention may include nonpolar solvents such as hydrocarbon solvents.
Preferred first solvents are hydrocarbon solvents including at least one hydrocarbon selected from the group consisting of toluene, xylene, benzene, hexane, heptane, and derivatives thereof (e.g., benzonitrile).
More preferably, the first solvent is a solvent consisting of at least one hydrocarbon selected from the group consisting of toluene, benzene and hexane. Such a solvent can highly dissolve fullerenes.
(3-3) Fullerene Solutions
Fullerene solutions for use in the present invention may be solutions each containing a fullerene dissolved therein. Such solutions may be either of saturated solutions and unsaturated solutions.
Preferred fullerene solutions are saturated fullerene solutions, since they can highly deposit the fullerene.
(3-4) Additives
The fullerene solution may further include additives that serve to improve the solvency for the fullerene, in addition to the first solvent. Additives that do not suppress the deposition of the target carbon material are preferred.
(3-5) Second Solvents
Second solvents for use herein may consist of solvent systems of different type from that of the first solvent dissolving the fullerene. Such solvent systems may include one solvent alone or two or more types of solvents in combination.
As the second solvent, poor-solvent systems consisting of poor solvents for fullerenes and other ingredients can be used. These poor-solvent systems are solvent systems having low solvency for fullerenes.
Such poor solvents may include, for example, polar solvents such as alcohol solvents.
Preferred second solvents are alcohol solvents including at least one alcohol selected from the group consisting of pentanol, butyl alcohol, isopropyl alcohol, n-propyl alcohol, methanol (methyl alcohol), ethanol (ethyl alcohol) and polyhydric alcohols such as ethylene glycol.
(3-6) Auxiliaries
The second solvent may further include, in addition to the second solvent, auxiliaries that accelerate the deposition of the target carbon material.
(3-7) Nucleation
According to the method of the present invention, a nucleus of a carbon material including a fullerene may be formed from the fullerene solution at the early stages of addition of the second solvent or during deposition of the carbon material. The nucleus may consist of the fullerene alone, the carbon material itself including the fullerene, substances derived from the first solvent and/or the second solvent, or other substances.
Such a nucleus may be added to the fullerene solution separately from the addition of the second solvent.
The nucleus grows by an appropriate procedure such as standing still of the solution mixed with the second solvent and thereby yields the carbon material including the fullerene.
(3-8) Nucleation Metals
Metals can be used to accelerate the nucleation. At least one metal selected from the group consisting of copper, aluminum, gold and stainless steel may be used as such a metal. The metal can be in the form of a wire, plate or mesh.
(3-9) Liquid-Liquid Interface
According to Method 1, the carbon material including the fullerene can be deposited from the fullerene solution by action of a liquid-liquid interface formed between the fullerene solution and the second solvent.
The liquid-liquid interface can be formed by using the first and second solvents including different types of solvent systems that are immiscible with each other.
To form the liquid-liquid interface, the first and second solvents may not always permanently be separated from each other and may be mixed during standing still.
For example, the use of toluene as the first solvent and isopropyl alcohol as the second solvent is typically preferred.
The liquid-liquid interface can be formed, for example, by gently adding the second solvent to the fullerene solution. This procedure is typically effective when the first and second solvents are solvent systems at least partly miscible with each other.
The liquid-liquid interface can be formed and maintained in at least one stage of the early stage of addition of the second solvent, during nucleation, during deposition and during growth, respectively, of the carbon material.
The first solvent dissolving the fullerene and the second solvent may preferably have different densities from each other. This configuration can more easily yield the liquid-liquid interface between the fullerene solution and the second solvent.
(3-10) Combinations of First and Second Solvents
Preferably, the first solvent including at least one substance selected from the group consisting of toluene, xylene, benzene, hexane, pentane and benzonitrile, and the second solvent used in combination comprises at least one alcohol selected from isopropyl alcohol, n-propyl alcohol, methanol, ethanol and ethylene glycol. For example, toluene (density: about 0.87 gcm−3) as the first solvent is used in combination with isopropyl alcohol (density: about 0.79 gcm−3) as the second solvent.
(3-11) Deposition Conditions
When deposition of the carbon material including the fullerene is performed, various conditions such as the type, purity and amount of the starting material fullerene, the types of the first and second solvents, the amount of first solvent, the type of the additives, the amount and adding procedure of the second solvent, the type of the auxiliaries, nucleation, addition of the nucleus, growth of the nucleus, formation and maintenance of the liquid-liquid interface, and temperatures can appropriately be set.
The fine carbon wire including the fullerene can be deposited at room temperature (around 21° C.). The deposition temperature is preferably from −20° C. to 75° C. and more preferably from 10° C. to 30° C.
By taking C60 as an example of the fullerene, 3 mL of isopropyl alcohol as the second solvent is preferably added to 3 mL of a saturated solution of the fullerene in toluene. Under this condition, the carbon material can grow at a rate on the order of 200 μm/h.
By appropriately setting the deposition conditions (parameters), the carbon material can grow at high speed, i.e., at a rate of 10 μm/h or more, according to the present invention. The growth rate can be set at preferably from 10 to 400 μm/h and more preferably from 200 to 400 μm/h.
(3-12) Deposition Containers
The carbon material of the present invention can be deposited in a variety of containers. Such containers are preferably transparent to see how the carbon material deposits. To avoid photochemical reactions of the fullerene, the container is preferably light-shielded, for example, by covering with aluminum foil except when the deposition is checked.
The container is not specifically limited in its size. Grooves formed on silicon substrates by lithography technique and having a size on the order of micrometers to nanometers can be used as the container. In general, bottles having a diameter of about 20 mm are preferably used, as they are easy to handle. To produce the carbon material in large quantity, beakers having a capacity of, for example, 100 mL can be used.
Lidded bottles such as vials can be used as the container to avoid evaporation of the solvents. The container is preferably made of glass for its inertness with various solvents, high stability and high durability.
(3-13) Deposited Carbon Materials
According to Method 1, substances derived from the first and second solvents are combined with the fullerene through at least one bond selected from the group consisting of intermolecular bond, ionic bond and covalent bond and thereby yield the carbon material including the fullerene.
A carbon material in which the fullerene molecules are combined with each other by intermolecular force is as hard as gold. A carbon material prepared by deposition of a fullerene from toluene alone as a solvent has an improved strength due to the intermolecular bond between toluene and the fullerene.
The carbon material of the present invention has a further improved strength, since the substances derived from two or more types of the solvents are combined with the fullerene through intermolecular bond or chemical bond in the carbon material. The improvement in strength is due to the intermolecular bond or chemical bond between the substances derived from the solvents and the fullerene, in addition to the intermolecular bond between the fullerene molecules with each other and the intermolecular bond between toluene and the fullerene.
By using substances that can form ionic bonds or substances having an alcoholic hydroxyl group as the first and/or second solvent, a carbon material including the fullerene that is combined with these substances or the substances derived from the solvents through an ionic bond or a covalent bond can be obtained.
The produced carbon material can be separated from the solution by an appropriate means such as filtration or centrifugal separation.
The carbon material can be pulverized to an appropriate size by an appropriate means such as a mill and thereby yields a carbon material having a uniform grain size, length and other dimensions.
The method of the present invention (Method 1) can yield the carbon material including the fullerene as a wire-like crystal (fullerene wire) having crystal habit. The wire-like crystal can be formed by allowing the fullerene to grow in the form of a wire in a predetermined direction. The crystal may be either a single crystal or polycrystal.
(4) Fourth Aspect (Method 2)
The present invention according to the fourth aspect relates to a method for producing a fine carbon wire including a fullerene by the use of ultrasonic treatment (Method 2).
Various conditions for the ultrasonic treatment such as intensity and time period may be employed. Preferably, the ultrasonic treatment is performed at room temperature for 1 to 30 minutes.
The investigations made by the present inventors suggest that ultrasonic treatment significantly increases the surface area of the interface between the droplets consisting of the first or second solvent and the second or first solvent to thereby accelerate crystal growth by action of the liquid-liquid interface. In addition, the ultrasonic treatment induces a local high pressure which may contribute to the nucleation and the growth of the crystal.
(4-1) Metallic Catalysts or Metal Oxide Catalysts
Metallic catalysts or metal oxide catalysts can be used in Method 2 to accelerate the crystal growth. Such catalysts can also be used in Method 1.
The metallic catalysts include, for example, copper, aluminum, iron, gold, other metals and combinations thereof.
The metal oxide catalysts include, but are not limited to, lead zirconate titanate, zirconium oxide, titanium oxide, lead oxide and combinations thereof.
(5) Advantages
The present invention can concurrently yield both needle-like crystals and single-crystal fibers (whiskers) of fullerenes at a liquid-liquid interface formed by a poor solvent for the fullerenes and a saturated solution of the fullerene dissolved in a good solvent.
The C60 fullerene whiskers are highly resistant semiconductors or insulators when they have an external diameter of 10 μm or more, but have a significantly reduced their resistivity and become conductive when they have an external diameter on the order of micrometers or less. Such conductivity can be explained by increased overlapping of the electron wave function due to a decreased distance between C60 molecules. The C60 fullerene whiskers may probably become superconductive fine wires by doping, for example, alkali metal elements.
The C60 nanowhiskers and C60 whiskers can undergo plastic working, can take various shapes and can therefore undergo heat treatment and processing according to similar procedures to those in metals. For example, they can be processed into coils and can be used as, for example, micro-antennas. The C60 whiskers have smooth surfaces all around, have a low friction coefficient and can therefore be applied to, for example, sliding parts of micromachines. The C60 nanowhiskers each have a spherical tip and can be applied to probes of tracer sensors.
The C60 whiskers can chemically be modified on their surfaces and can therefore be used as organic synthesis reagents. They can also yield a variety of novel functional substances as a result of combining or bonding with glass, polymers, ceramics or metals and can be used as excellent hydrogen-storing materials. They can yield materials that are optically, electrically or mechanically anisotropic by pressing them at high temperatures and high pressures to thereby three-dimensionally polymerize C60 molecules.
By geometrically arraying the C60 whiskers with the use of templates formed by lithography, they can yield, for example, novel photonic crystals, catalysts and field emission devices. The present invention can also be applied to C70 and other higher fullerenes. By using these fullerene whiskers as internal or external templates, substances can be synthesized or shaped. For example, coating of the fullerene whiskers with a ceramic colloidal solution and chemically or thermally treating the coated whiskers can yield composites of the fullerene whiskers and ceramics. In addition, chemical or thermal removal of the fullerene whiskers from the composites can yield porous ceramics or ceramic tubes. Compounding of the fullerene whiskers with metals, glass or polymers instead of ceramics can yield composites of the fullerene whiskers and porous metals, glass or polymers. Removal of the fullerene whiskers from these composites can yield metal tubes, polymer tubes or glass tubes using the fullerene whiskers as templates. The removed fullerene molecules can be reused.
As thus described above, the fullerene whiskers can significantly freely be applied.
The present invention will be illustrated in further detail with reference to several examples and attached drawings, which are not intended to limit the scope of the invention.
Isopropyl alcohol was gently added to a saturated C60 solution in toluene in a transparent container such as a glass vial (external diameter 20 mm), the vial was lidded and was allowed to stand still for about several hours to about nine hours.
Nuclei of needle-like crystals including C60 were formed and grew at the interface between toluene and isopropyl alcohol and thereby yielded fullerene wires.
As shown in
A line extending from the top to the bottom of each of
The fullerene wires were analyzed by scanning electron microscopy (SEM). As shown in a scanning electron micrograph of
The fullerene wires were subjected to energy-dispersive X-ray analysis (EDX) using SEM. The result is shown in
The production procedure of Example 1 was repeated, except that fullerene wires were produced in large quantity using a 100-mL beaker.
As a result, fullerene wires about 2 cm long could be produced in very large quantity in a short time. A precipitated dark brown floc was observed at the bottom of the beaker. The floc could easily be separated from the fullerene wires by washing with toluene.
Most of the products were fullerene wires as in Example 1. The floc was not clearly identified but was found to be stacked fibrous fullerene based on SEM observation. The true nature of the floc will be clarified in analysis later.
The fullerene wires were pulverized, and the resulting powdered fullerene was subjected to X-ray analysis. With reference to
Pure C60 has a lattice constant a of 1.412 nm in terms of a face-centered cubic crystal. The fullerene wires prepared in this example had a lattice constant a of 1.422±0.003 nm whereas it can be indexed by face-centered cubic crystal. The lattice constant of the fullerene wires was 0.01 nm larger than that of pure C60.
These results show that the fullerene wires consist of C60 molecules and that they have a crystal lattice as face-centered cubic crystal that is almost the same as in the original C60 molecules.
The results indicate that C60 molecules have large intermolecular interstices, and the solvent components and C70 and other higher fullerenes contained in the material C60 enter the interstices to thereby yield a substance indicated by C60+X, wherein X is, for example, the solvent molecule or higher fullerene. Support for these assumptions will be found in structural analysis such as thermal analysis or high-resolution transmittance electron microscopic observation later.
The grown fullerene wires were observed using a stereoscopic microscope. As shown in
The fullerene wires of the present invention can grow to a length on the order of several millimeters to centimeters and can grow at a rate on the order of about 200 μmh−1 surpassing the rate, 4 μmh−1, of conventional equivalents.
In this example, fullerene whiskers as shown in
A total of 50 mL of a saturated solution of C60 as the fullerene in toluene was placed in a 100-mL beaker at room temperature (about 21° C.), followed by gently pouring isopropyl alcohol to thereby form an interface between the saturated C60 toluene solution and isopropyl alcohol.
Immediately after addition of isopropyl alcohol, C60 whiskers and C60 nanowhiskers (C60 NWs) were formed.
As shown in the transmission electron micrograph (TEM) of
The C60 nanowhiskers had a growth axis of [110]c in terms of a cubic crystal. They had a C60 intermolecular distance along the [110]c growth axis 1% to 4% less than that of C60 molecular crystals of a face-centered cubic (FCC) structure, indicating that the C60 molecules yielded a chemical bond different from van der Waals bond and are polymerized in the growth axis direction. The scanning electron micrograph of
Combinations of solvents for use in the preparation of fullerene whiskers include any combinations, as long as they are combinations of good solvents for fullerenes such as toluene with poor solvents for fullerenes such as isopropyl alcohol and can form a liquid-liquid interface.
The relationship between the diameter and resistivity was determined on C60 needle-like crystals having different diameters. As shown in
As shown in the transmission electron micrograph of
The many stacking defects of the (002) plane show that the (002) plane becomes a low-energy interface. The fact that the surface of the C60 nanowhisker is covered with the (002) low-energy plane is not contradictory to the fact that the growth axis is the [110] axis.
The introduced lattice dislocation means that the C60 nanowhiskers can be plastically deformed and that they can undergo plastic working into various shapes such as coil shapes.
The C60 nanowhiskers do not decompose at temperatures lower than about 450° C. even in the air and can be plastically processed by elevating the temperature thereof to those at which the dislocation easily occurs. By subjecting the C60 nanowhiskers to plastic working at high temperatures, quenching the same and thereby fixing lattice defects such as dislocation, the hardness would be further increased.
As thus described, the C60 nanowhiskers are very promising fine carbon wires of conductive carbon polymer single crystals. In addition, all the C60 whiskers including such C60 nanowhiskers can undergo plastic working and each have a smooth surface.
With reference to
A whisker of C60 was prepared according to the liquid-liquid interface deposition process in which isopropyl alcohol was carefully placed onto a saturated C60 solution in toluene to thereby form an interface. The resulting whisker was bent on a grid of TEM and was then fixed.
As shown in
C60 and C70 nanowhiskers were synthesized in liquid phases, as shown in
They also have found that such C60 nanowhiskers can be prepared by a method using a liquid-liquid interface between a saturated C60 toluene solution and isopropyl alcohol (liquid-liquid deposition method) (K. Miyazawa et al., J. Mater. Res., 17[1] (2002) 83).
In this example, iodine was doped into C60 nanowhiskers, and C70 whiskers were prepared in the liquid-liquid interface deposition process.
Iodine was doped by adding a solution of iodine in isopropyl alcohol to a C60 solution in toluene. The C70 nanowhiskers were prepared by adding isopropyl alcohol to a C70 solution in toluene.
As a result, iodine-doped C60 nanowhiskers (I-C60 NWs) each having a diameter of 790 nm and a length of 100 μm or more were obtained as shown in FIG. 16.
As shown in the HRTEM image of
Preparation of C70 Whiskers from a Concentrated Solution
Powdered C70 was pulverized in a mortar, was dissolved in toluene by ultrasonic irradiation for 30 minutes and thereby yielded 0.001 molL−1 saturated C70 solution in toluene. A total of 5 mL of the prepared saturated solution was dispensed in a 10-mL glass bottle, and careful placement of 5 mL of isopropyl alcohol thereon yielded a liquid-liquid interface between the saturated C70 toluene solution and isopropyl alcohol. The glass bottle was allowed to stand at room temperature of about 21° C. for a day and thereby yielded a deposit.
The spacing (d220, 0.577 nm) of the (220) plane was near to the interplanar spacing (d220, 0.5294 nm) of a corresponding pure face-centered cubic (fcc) C70 crystal (lattice constant a=1.4974 nm). All the growth axes of the needle-like single C70 crystals were in parallel with the <110> orientation, the close-packed direction of the C70 molecules.
Preparation of C70 Whiskers from a Dilute Solution Powdered C70 was pulverized in a mortar, was dissolved in toluene by ultrasonic irradiation for 30 minutes and thereby yielded 0.001 molL−1 saturated solution of C70 in toluene. The prepared saturated solution was diluted two folds. A total of 5 mL of the diluted solution was dispensed in a 10-mL glass bottle, and careful placement of isopropyl alcohol thereon yielded a liquid-liquid interface between the C70 toluene solution and isopropyl alcohol. After the formation of the liquid-liquid interface, the glass bottle was allowed to stand at room temperature of about 21° C. for 7 days and thereby yielded needle-like C70 crystals.
As shown in
The transmission electron micrograph of
The scanning electron micrograph of the C70 nanowhiskers in
In this example, the structures of needle-like and wire-like C60 crystals formed in a PZT-C60 sol were investigated. In the preparation of a lead zirconate titanate (PZT) thin film according to a sol-gel process, it is known that a perovskite phase grows at low temperatures of 400° C. by the use of a PZT sol combined with a C60 toluene solution. After further investigations on such a C60-added PZT sol, the present inventors have found that needle-like and wire-like C60 crystals are formed as precipitates or deposits during this preparation procedure. In this example, the structures of these crystals were examined.
A total of 2 mL of a saturated C60 solution in toluene was added to 3 mL of an isopropyl alcohol solution (0.4 M PZT sol) containing lead acetate trihydrate, titanium tetraisopropoxide and zirconium tetra-n-propoxide, followed by stirring by ultrasonic application or the like.
The resulting brown precipitate was fixed to a TEM micro-grid and was observed by SEM and TEM (200 kV and 1250 kV, respectively).
As a result, needle-like C60 crystals each having clear crystal habit plane (
The effect of a metal wire in the liquid-liquid deposition process was determined. Ultrasonic blending of a sol of lead zirconate titanate (PZT) and a C60 toluene solution yielded nanowhiskers and needle-like crystals of C60.
The structures and other configurations of the nanowhiskers and needle-like crystals of C60 formed at the interface between the saturated C60 toluene solution and isopropyl alcohol (IP) were determined in this example.
Specifically, 3 mL of a saturated C60 toluene solution was placed in a 9-mL vial; next 3 mL of isopropyl alcohol was carefully placed therein to thereby form a liquid-liquid interface between the saturated C60 toluene solution and isopropyl alcohol. The vial was then allowed to stand to grow needle-like C60 crystals. In this procedure, a copper fine wire was placed in the vial to accelerate the nucleation.
Consequently, C60 crystals deposited in the vicinity of a point of intersection of the copper wire and the liquid-liquid interface. The C60 crystals included needle-like crystals having a diameter on the order of micrometers and a length of about 10 mm and needle-like crystals having a submicron diameter and a length of 100 μm or more.
The latter needle-like C60 crystals were found to be single crystals (C60 nanowhiskers) based on TEM observation. All the C60 nanowhiskers had a growth axis in the <110> axis, i.e., the closest packing direction of C60 crystals, without exception.
In this example, hollow needle-like fullerene crystals were examined. The liquid-liquid deposition process is a complicated process in which super-saturation is brought at an interface between two liquids to thereby deposit crystals. The deposition of the crystals according to this process depends on various factors such as the concentration of a solute, temperature and the volume ratio of the resulting solution. A variety of agravic experiments and simulations have been made on protein synthesis according to the liquid-liquid deposition process.
In this example, a liquid-liquid interface was formed using a saturated C60 toluene solution and isopropyl alcohol (IP) to thereby deposit two types of crystals, hollow needle-like C60 crystals and brown wire-like C60 crystals (C60 whiskers).
The fundamental characteristics of the resulting needle-like C60 crystals were determined herein.
Specifically, 30 mL of a saturated C60 toluene solution was placed in a 100-mL beaker; next, 30 mL of isopropyl alcohol (IP) was carefully placed thereon in such a manner that the two liquids were not mixed with each other to thereby form a liquid-liquid interface. The beaker was allowed to stand at room temperature, and the resulting needle-like C60 crystals were analyzed by SEM, powder X-ray diffractometry (powder XRD), thermogravimetry (TG), differential thermal analysis (DTA; rate of temperature rise: 10° C./min., in the air) and Fourier transform infrared spectrometry (FT-IR).
The needle-like C60 crystals were found to grow at high speed at the liquid-liquid interface between the saturated C60 toluene solution and isopropyl alcohol. As shown in
The powder X-ray diffraction pattern shows that the crystals are C60 cubic crystals. However, precise determination of lattice constants shows that these crystals have a lattice constant a of 1.4255±0.0033 nm, which is slightly larger than the lattice constant a of 1.4175±0.0014 nm of the original C60, indicating the former crystals expanded slightly.
As shown in
The crystals are found to be insulative. The crystals are damaged by irradiation of electron beams upon TEM observation.
In this example, hollow needle-like fullerene crystals are examined. Specifically, needle-like C60 crystals grew at high speed at a liquid-liquid interface between a saturated C60 toluene solution and isopropyl alcohol.
This is probably because supersaturation of C60 was brought at the interface between the two liquids.
The resulting needle-like crystals included two types of crystals. One was a black hollow crystal having a diameter of from several tens of micrometers to several hundreds of micrometers and a length of several millimeters to 1 cm. The other was a brown single crystal having a diameter of several hundreds of nanometers and a length of several tens of micrometers or more.
The needle-like C60 crystals each had a clear crystal habit plane, and some of them had a hexagonal cross section. The X-ray diffraction pattern of the hollow needle-like C60 crystal shows that it was a cubic crystal of C60.
A copper wire was then placed at the interface between the two liquids and was thereby plated with deposited C60 crystals. The resulting material will be applied as a fiber-reinforced composite material or a nano-material having various hopeful physical properties such as field emission or superconduction.
The structural characteristics of the needle-like C60 crystals were determined by transmission electron microscopy (TEM), X-ray diffractometry (XRD) and Fourier transform infrared spectrometry (FT-IR). Specifically, a solution of 3 wt % of powdered C60 (99.5%, available from MER Corp., Tucson, Ariz.) in toluene was prepared, was placed into a glass bottle (9 mL); next, isopropyl alcohol was carefully placed thereon to thereby form a liquid-liquid interface. An upper layer was isopropyl alcohol and a lower layer was the C60 toluene solution.
The bottle was lidded and was covered with aluminum foil, was allowed to stand still at room temperature (RT; about 21° C.) to thereby deposit needle-like crystals of grown C60. Separately, needle-like C60 crystals were prepared in large quantity using a 100-mL beaker.
The structures of the above obtained samples were analyzed by FT-IR, XRD, TEM and HRTEM (using JEM-1250 available from JEOL, Japan; 1250 kV). The samples were subjected to pretreatment according to a conventional procedure, and where necessary, an internal standard was used in analysis.
As shown in
The TEM images in
The C60 nanowhiskers are supposed to be formed by “2+2” cycloaddition, as schematically illustrated in
The C60 nanowhiskers may be prepared by polymerization according to the following mechanism. Specifically, the C60 molecules are confined within very small spaces at the interface between toluene and isopropyl alcohol to thereby bring supersaturation of C60 molecules and undergo a very high pressure. The pressure reaches on the order of gigapascals to thereby allow the C60 molecules to two-dimensionally polymerize by “2+2” cycloaddition.
Table 2 shows the interplanar spacing of the C60 nanowhisker determined by fast Fourier transform (FFT) image of a high-resolution transmission electron micrograph, that of a pure C60 crystal determined by X-ray diffractometry, and that of a needle-like C60 crystal determined by X-ray diffractometry.
The results show that the interplanar spacing of the (220)c plane of the C60 nanowhisker is less than that of the pure C60 crystal, indicating that the distance between the C60 molecules in the C60 nanowhisker is reduced as compared with that of the pure C60 crystal.
In contrast, the interplanar spacing of the (220)c plane of the needle-like C60 crystal having a diameter larger than the C60 nanowhisker is the same as that of the pure C60 crystal. These results suggest that the distance between C60 molecules decreases with a decreasing diameter of a needle-like C60 crystal, and the C60 molecules are combined with each other by action of a strong force in the growth axis direction.
Other embodiments and variations will be obvious to those skilled in the art, and this invention is not to be limited to the specific matters stated above.
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| Number | Date | Country | |
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| 20020192143 A1 | Dec 2002 | US |
