VAPOUR PHASE GROWN CARBON FIBRE

Carbon nanofiber with high crystallinity synthesized with the vapor phase
method. Superior in thermal conductivity, electrical conductivity, strength
property and slidability (lubricity). Due to its fiber diameter larger than that of
carbon nanotube, it can be easily handled (dispersion, etc.) and used for wider
purposes
.
Characteristics
With an extremely small average fiber diameter (150nm), functions as excellent
filler with thermal conductivity, electrical conductivity, strength, and slidability.
 Chemically stable, with small specific surface area and with minute amount of
absorption moisture.
 With almost 10 years of mass production performance, quality is stable.
Representative characteristics
Unit Graphitized product
Fiber diameter nm 150
Fiber length µm 10 - 20
Aspect ratio － 10 - 500
True density g/cm 3 2.0
Apparent density VGCF(R) (standard type) g/cm 0.04
VGCF(R) -H (high apparent-density type) 0.08
Specific surface area m 2 /g 13
Crystal Co Å 6.78
Lc Å 400
Electrical conductivity Powder resistivity Ωcm 0.012
Single fiber specific resistance Ωcm 1 x 10 - 4
Ash ％ 0.1
Main application
 For batteries (Li ion secondary batteries, capacitors, fuel cells, etc.)
 Addition of thermal conductivity, electric al conductivity, sliding ability
(lubricity), and strength to resin
 Addition of electrical conductivity and strength to ceramics
 Improvement of thermal conductivity of metal
 INTRODUCTION Vapor-grown carbon nanofibers (VGCNF’s) are one kind of pyrolytic
products made by pyrolyzing hydrocarbon compounds in the presence of a transition metal
catalyst in a hydrogen atmosphere. Because of their distinctive properties, such as high
strength and electric conductivity and special functional properties, scientists have shown a
great deal of attention to the mass production of these materials. Tibbetts et al.1 anticipated,
after studying physical properties of vaporgrown carbon fibers, that vapor-grown carbon
fibers with smaller diameters should be stronger than those with larger diameters, and
experimental results proved this anticipation.2 Furthermore, it was reported that the diameter
of the nanofibers is governed by the size of the catalyst particles,3 and for the mass
production of VGCNF’s the key process is the seeding of the catalyst particles. Tibbetts and
Gorkiewicz4 produced VGCNF’s with diameters of 50–100 nm successfully using a mixture
of ferrocene and liquid hydrocarbon in a vertical furnace. The results show that this method
provides the possibility of mass production. However, because of the difficulty of efficiently
dispersing small Fe particles in spraying catalyst solution, undefined mixtures of fibers and
soot were always obtained. Rodriguez5 produced carbon nanofibers with diameters of 50–80
nm from catalytic decomposition of hydrocarbon gas with catalyst metal powder using the
support catalyst method. Although the support catalyst method can produce high quality
fibers, the preparation and defined dispersion of ultrafine catalyst particles are very difficult,
and the yield of this method is too inefficient to be commercialized. In order to solve the
above problems advantages of the floating catalyst-method and support catalyst method to
produce carbon nanofibers with diameters of 50–100 nm. In this study, pure VGCNF’s with
diameters of 10–200 nm were prepared under different reaction factors by an improved
floating catalyst method. The morphology and microstructure and crystallinity of carbon
nanofibers obtained were investigated.


II. EXPERIMENTAL In the experiment, the floating catalyst method was applied in a
horizontal reactor to gain half-continuous growth of VGCNF’s. The horizontal reactor, one
part of the experiment apparatus, was a quartz glass tube 30 mm in diameter and 1000 mm in
length and was heated by a silicon carbide heating element 500 mm long. In the experiment,
benzene was used as carbon source, hydrogen as carrying gas, and ferrocene as catalyst
precursor. It is known that ferrocene begins to vaporize at about 458 K and decompose at
above 673 K. During the reaction procedure, ultrafine catalyst particles that were vaporized
from ferrocene were carried into the reaction tube by a mixture of benzene vapor and
hydrogen gas to accumulate into appropriate catalyst to grow carbon nanofibers. The reaction
temperature was maintained at 1423–1473 K, and the grown fibers stayed in the reacting
zone and fully blocked the tube rather than flying out with the reacted gas. In this experiment,
because the VGCNF’s obtained were blocked in the reaction tube for a long time, high-
quality VGCNF’s can be obtained, and this aspect makes use of the advantage of the support
catalyst method. In addition, because the catalyst precursor ferrocene successively flowed
into the reaction region, the yield of VGCNF’scan be very high, which makes use of the
advantage of floating catalyst methods. When the reactor was cool enough under argon gas
protection, the product was taken out. The morphology and structure of VGCNF’s were
observed in the as-prepared state and after separation by ultrasound in alcohol using scanning
electron microscopy (SEM), transmission electron microscopy(TEM), and high resolution
transmission electron microscopy (HRTEM). Moreover, the graphitic crystallinity of
VGCNF’s was analyzed using selected area diffraction (SAD), convergent beam electron
diffraction, and x-ray diffraction method.