Carbon nanofiber

Regular carbon nanofibers.

Stacked-cup carbon nanofiber: electron micrograph
(left) and model (right).[1]

Carbon nanofibers (CNFs), vapor grown

carbon fibers (VGCFs), or vapor grown
carbon nanofibers (VGCNFs) are cylindric
nanostructures with graphene layers
arranged as stacked cones, cups or plates.
Carbon nanofibers with graphene layers
wrapped into perfect cylinders are called
carbon nanotubes.
Introduction
Carbon has a high level of chemical
bonding flexibility, which lends itself to the
formation of a number of stable Organic
and Inorganic Molecules. Elemental
carbon has a number of
allotropes(variants) including diamond,
graphite, and fullerenes.[2] Though they all
consist of elemental carbon, their
properties vary widely. This underscores
the versatility of CNFs, which are notable
for their thermal, electrical,
electromagnetic shielding, and mechanical
property enhancements.[3] As carbon is
readily available at low cost, CNFs are
popular additives to composite
materials.[4] CNFs are very small, existing
at the nanometer scale. An atom is
between .1-.5nm, thus specialized
microscopic techniques such as Scanning
Tunneling Microscopy and Atomic Force
Microscopy are required to examine the
properties of CNFs.

Synthesis
Catalytic chemical vapor deposition
(CCVD) or simply CVD with variants like
thermal and plasma-assisted is the
dominant commercial technique for the
fabrication of VGCF and VGCNF. Here, gas-
phase molecules are decomposed at high
temperatures and carbon is deposited in
the presence of a transition metal catalyst
on a substrate where subsequent growth
of the fiber around the catalyst particles is
realized. In general, this process involves
separate stages such as gas
decomposition, carbon deposition, fiber
growth, fiber thickening, graphitization, and
purification and results in hollow fibers.
The nanofiber diameter depends on the
catalyst size. The CVD process for the
fabrication of VGCF generally falls into two
categories:[5] 1) fixed-catalyst process
(batch), and 2) floating-catalyst process
(continuous).
In the batch process developed by
Tibbetts,[6] a mixture of
hydrocarbon/hydrogen/helium was
passed over a mullite (crystalline
aluminum silicate) with fine iron catalyst
particle deposits maintained at 1000 °C.
The hydrocarbon used was methane in the
concentration of 15% by volume. Fiber
growth in several centimeters was
achieved in just 10 minutes with a gas
residence time of 20 seconds. In general,
fiber length can be controlled by the gas
residence time in the reactor. Gravity and
direction of the gas flow typically affects
the direction of the fiber growth.[5]
The continuous or floating-catalyst
process was patented earlier by Koyama
and Endo[7] and was later modified by
Hatano and coworkers.[8] This process
typically yields VGCF with sub-micrometre
diameters and lengths of a few to 100 µm,
which accords with the definition of
carbon nanofibers. They utilized
organometallic compounds dissolved in a
volatile solvent like benzene that would
yield a mixture of ultrafine catalyst
particles (5–25 nm in diameter) in
hydrocarbon gas as the temperature rose
to 1100 °C. In the furnace, the fiber growth
initiates on the surface of the catalyst
particles and continues until catalyst
poisoning occurs by impurities in the
system. In the fiber growth mechanism
described by Baker and coworkers,[9] only
the part of catalyst particle exposed to the
gas mixture contributes to the fiber growth
and the growth stops as soon as the
exposed part is covered, i.e. the catalyst is
poisoned. The catalyst particle remains
buried in the growth tip of the fiber at a
final concentration of about a few parts
per million. At this stage, fiber thickening
takes place.

The most commonly used catalyst is iron,

often treated with sulfur, hydrogen sulfide,
etc. to lower the melting point and
facilitate its penetration into the pores of
carbon and hence, to produce more
growth sites.[2] Fe/Ni, Ni, Co, Mn, Cu, V, Cr,
Mo, Pd, MgO, and Al2O3 are also used as
catalyst.[10][11] Acetylene, ethylene,
methane, natural gas, and benzene are the
most commonly used carbonaceous
gases. Often carbon monoxide (CO) is
introduced in the gas flow to increase the
carbon yield through reduction of possible
iron oxides in the system.

Safety
The Occupational Safety and Health Act
(United States) (1970) was a driving force
behind many of the changes made
regarding safety in the workplace over the
last few decades. One small group of the
numerous substances to be regulated by
this act is carbon nanofibers (CNF). While
still an active area of research, there have
been studies conducted that indicate
health risks associated with carbon
nanotubes (CNT) and CNF that pose
greater hazards than their bulk
counterparts. One of the primary hazards
of concern associated with CNT and CNF
is respiratory damage such as pulmonary
inflammation, granuloma, and fibrosis. It is
important to note, however, that these
findings were observed in mice, and that it
is currently unknown whether the same
effects would be observed in humans.
Nonetheless these studies have given
cause for an attempt to minimize
exposure to these nanoparticles.[12]

A separate study conducted prior to the

2013 annual Society of Toxicology
meeting aimed to identify potential
carcinogenic effects associated with
multi-walled carbon nanotubes (MWCNT).
The findings indicated that, in the
presence of an initiator chemical, the
MWCNTs caused a much greater
incidence of tumors in mice. There was no
indication of increased presence of
tumors in the absence of the initiator
chemical, however. Further studies are
needed for this scenario.[12]

One of the major hurdles in identifying

hazards associated with CNF is the
diversity of fibers that exist. Some of the
contributing factors to this diversity
include shape, size, and chemical
composition. One exposure standard
(2015) states that the acceptable limit for
CNT and CNF exposure is 1 μg/m3 of
respirable size fraction elemental carbon
(8-hour time-weighted average). This
standard was based on information
gathered from 14 sites whose samples
were analyzed by transmission electron
microscopy (TEM).[13]

A recent safety data sheet (SDS) for CNF

(revised in 2016) lists the nanofibers as an
eye irritant, and states that they have
single exposure respiratory system organ
toxicity. Smaller CNF possess a greater
potential for forming dust clouds when
handling. As such, great care must be
taken when handling CNF. The
recommended personal protective
equipment (PPE) for handling CNF
includes nitrile gloves, particle respirators,
and nanomaterial-impervious clothing
(dependent on workplace conditions). In
addition to exposure controls while
working with the CNF, safe storage
conditions are also important in
minimizing the risk associated with CNF.
Safe CNF storage entails storing the fibers
away from oxidizing agents and open
flames. Under fire conditions, CNF form
hazardous decomposition products
though the exact nature of these
decomposition products is not currently
known. Apart from carcinogenicity and
organ toxicity, toxicological data for CNF is
currently rather limited.[14]

Applications
Researchers are using nanofibers to
delivery therapeutic drugs. They have
developed an elastic material that is
embedded with needle like carbon
nanofibers. The material is intended to
be used as balloons which are inserted
next diseased tissue, and then inflated.
When the balloon is inflated the carbon,
nanofibers penetrate diseased cells and
delivery therapeutic drugs. Researchers
at MIT have used carbon nanofibers to
make lithium ion battery electrodes that
show four times the storage capacity of
current lithium ion batteries.
Researchers are using nanofibers to
make sensors that change color as they
absorb chemical vapors. They plan to
use these sensors to show when the
absorbing material in a gas mask
becomes saturated.[15]
The unique structure of these porous
carbon nanofibers resulted in good
electrochemical performance such as
high reversible capacity and good cycle
stability when they were used as anodes
for rechargeable lithium-ion batteries.[16]
Further market development will depend
on material availability at reasonable
prices. We have achieved bulk
production capacities of high purity
carbon nanofibers (CNFs) at low cost by
a catalytic chemical vapor deposition
(CCVD) process.[4]
Unlike catalytic synthesis,
electrospinning polyacrylonitrile (PAN)
followed by stabilization and
carbonization has become a
straightforward and convenient route to
make continuous carbon nanofibers.[17]
Field electron emission sources
Field electron emission (also known
as field emission (FE) and electron
field emission) is emission of
electrons induced by an
electrostatic field. The most
common context is field emission
 from a solid surface into vacuum.
However, field emission can take
place from solid or liquid surfaces,
into vacuum, air, a fluid, or any non-
conducting or weakly conducting
dielectric. The field-induced
promotion of electrons from the
valence to conduction band of
semiconductors (the Zener effect)
can also be regarded as a form of
field emission.[18]
Composite materials
Scanning probe microscopy tips
Scanning probe microscopy (SPM)
is a branch of microscopy that
 forms images of surfaces using a
physical probe that scans the
specimen.[19]
Carrier material for various catalysts in
petrochemistry
In vertically-aligned arrays, a platform
for gene delivery. (See Impalefection)
Impalefection is a method of gene
delivery using nanomaterials, such
as carbon nanofibers, carbon
nanotubes, nanowires. Needle-like
nanostructures are synthesized
perpendicular to the surface of a
substrate. Plasmid DNA containing
the gene, intended for intracellular
 delivery, is attached to the
nanostructure surface. A chip with
arrays of these needles is then
pressed against cells or tissue.
Cells that are impaled by
nanostructures can express the
delivered gene(s).[20]
For electrode materials[21]
Oil spill remediation[22]
Oil spill remediation: The process
for the manufacture of a carbon-
carbon-composite material
comprises the steps of treating a
carbonaceous carrier material with
a metal-containing catalyst
material. The metal is capable of
forming nanosize carbon
structures, and growing nanosize
carbon structures by means of a
chemical vapor deposition method
on the treated carrier in a gas
atmosphere comprising a carbon-
containing gas, followed by an
optional surface modification step.
This process allows optimizing
porosity, hydrodynamical properties
and surface chemistry
independently from each other,
which is particularly beneficial in
respect of the use of the composite
for water purification. Carbon black-
 based composites are particularly
useful for filler applications.[23]

History
One of the first technical records
concerning carbon nanofibers is probably
a patent dated 1889 on synthesis of
filamentous carbon by Hughes and
Chambers.[24] They utilized a
methane/hydrogen gaseous mixture and
grew carbon filaments through gas
pyrolysis and subsequent carbon
deposition and filament growth. The true
appreciation of these fibers, however,
came much later when their structure
could be analyzed by electron
microscopy.[2] The first electron
microscopy observations of carbon
nanofibers were performed in the early
1950s by the Soviet scientists
Radushkevich and Lukyanovich, who
published a paper in the Soviet Journal of
Physical Chemistry showing hollow
graphitic carbon fibers that are 50
nanometers in diameter.[25] Early in the
1970s, Japanese researchers Morinobu
Endo, now the director of the Institute of
Carbon Science and Technology at
Shinshu University, reported the discovery
of carbon nanofibers, including that some
were shaped as hollow tubes.[26] He also
succeeded in the manufacturing of VGCF
with a diameter of 1 µm and length of
above 1 mm.[27] Later, in the early 1980s,
Tibbetts[6] in the USA and Benissad[28] in
France continued to perfect the VGCF
fabrication process. In the USA, the deeper
studies focusing on synthesis and
properties of these materials for advanced
applications were led by R. Terry K.
Baker.[29] They were motivated by the need
to inhibit the growth of carbon nanofibers
because of the persistent problems
caused by accumulation of the material in
a variety of commercial processes,
especially in the particular field of
petroleum processing. In 1991, Japanese
researchers Sumio Iijima, while working at
NEC, synthesized hollow carbon
molecules and determined their crystal
structure. The following year, these
molecules were called "carbon nanotubes"
for the first time.[30] VGCNF is produced
through essentially the same
manufacturing process as VGCF, only the
diameter is typically less than 200 nm.
Several companies around the globe are
actively involved in the commercial scale
production of carbon nanofibers and new
engineering applications are being
developed for these materials intensively,
the latest being a carbon nanofiber
bearing porous composite for oil spill
remediation.[31]
See also
Allotropes of carbon
Carbon nanotubes
Carbon black
Carbon nanocone
Carbon fiber
Impalefection, a method of cell
transfection using carbon nanofibers

References
1. Guadagno, Liberata; Raimondo,
Marialuigia; Vittoria, Vittoria; Vertuccio,
Luigi; Lafdi, Khalid; De Vivo, Biagio;
Lamberti, Patrizia; Spinelli, Giovanni; Tucci,
Vincenzo (2013). "The role of carbon
nanofiber defects on the electrical and
mechanical properties of CNF-based
resins". Nanotechnology. 24 (30): 305704.
Bibcode:2013Nanot..24D5704G .
doi:10.1088/0957-4484/24/30/305704 .
PMID 23843601 .
2. Morgan, P. (2005) Carbon Fibers and
Their Composites, Taylor & Francis Group,
CRC Press, Boca Raton, FL.
3. Tibbetts, G; Lake, M; Strong, K; Rice, B
(2007). "A review of the fabrication and
properties of vapor-grown carbon
nanofiber/polymer composites".
Composites Science and Technology. 67
(7–8): 1709–18.
doi:10.1016/j.compscitech.2006.06.015 .
4. Hammel, E; Tang, X; Trampert, M;
Schmitt, T; Mauthner, K; Eder, A; Pötschke, P
(2004). "Carbon nanofibers for composite
applications". Carbon. 42 (5–6): 1153–8.
doi:10.1016/j.carbon.2003.12.043 .
5. Burchell, T.D. (1999) Carbon Materials for
Advanced Technologies, Pergamon
(Elsevier Science Ltd.), Oxford, UK.
6. Tibbetts, Gary G (1985). "Lengths of
carbon fibers grown from iron catalyst
particles in natural gas". Journal of Crystal
Growth. 73 (3): 431–8.
Bibcode:1985JCrGr..73..431T .
doi:10.1016/0022-0248(85)90005-3 .
7. Koyama, T. and Endo, M.T. (1983)
"Method for Manufacturing Carbon Fibers
by a Vapor Phase Process," Japanese
Patent 1982-58, 966.
8. Hatano, M.; Ohsaki, T.; Arakawa, K.
(1985). "Graphite Whiskers by New Process
and Their Composites" . Science of
Advanced Materials and Processes,
National SAMPE Symposium, 30: 1467–76.
9. Baker, R (1972). "Nucleation and growth
of carbon deposits from the nickel
catalyzed decomposition of acetylene".
Journal of Catalysis. 26: 51–62.
doi:10.1016/0021-9517(72)90032-2 .
10. De Jong, Krijn P; Geus, John W (2007).
"Carbon Nanofibers: Catalytic Synthesis and
Applications". Catalysis Reviews. 42 (4):
481–510. doi:10.1081/CR-100101954 .
11. Dadvar, Saeed; Tavanai, Hossein;
Morshed, Mohammad (2012). "Effect of
embedding MgO and Al2O3 nanoparticles in
the precursor on the pore characteristics of
PAN based activated carbon nanofibers".
Journal of Analytical and Applied Pyrolysis.
98: 98–105.
doi:10.1016/j.jaap.2012.08.001 .
12. Occupational Exposure to Carbon
Nanotubes and Nanofibers . Current
Intelligence Bulletin 65. National Institute
for Occupational Safety and Health.
13. Dahm, Matthew M; Schubauer-Berigan,
Mary K; Evans, Douglas E; Birch, M. Eileen;
Fernback, Joseph E; Deddens, James A
(2015). "Carbon Nanotube and Nanofiber
Exposure Assessments: An Analysis of 14
Site Visits" . Annals of Occupational
Hygiene. 59 (6): 705–23.
doi:10.1093/annhyg/mev020 .
PMC 4507369  . PMID 25851309 .
14.
http://www.pyrografproducts.com/Merchan
t5/pdf/SDS_v9_PS.pdf
15. Nanofibers: Uses and Applications of
Nanofibers
http://www.understandingnano.com/nanofi
ber-applications.html (accessed Nov 27,
2017).
16. Ji, Liwen; Zhang, Xiangwu (2009).
"Fabrication of porous carbon nanofibers
and their application as anode materials for
rechargeable lithium-ion batteries".
Nanotechnology. 20 (15): 155705.
Bibcode:2009Nanot..20o5705J .
doi:10.1088/0957-4484/20/15/155705 .
PMID 19420557 .
17. Iwasaki, Tomohiro; Makino, Yuri;
Fukukawa, Makoto; Nakamura, Hideya;
Watano, Satoru (2016). "Low-temperature
growth of nitrogen-doped carbon nanofibers
by acetonitrile catalytic CVD using Ni-based
catalysts". Applied Nanoscience. 6 (8):
1211–8. Bibcode:2016ApNan...6.1211I .
doi:10.1007/s13204-016-0535-x .
18. Fowler, R. H; Nordheim, L (1928).
"Electron Emission in Intense Electric
Fields". Proceedings of the Royal Society A:
Mathematical, Physical and Engineering
Sciences. 119 (781): 173–81.
Bibcode:1928RSPSA.119..173F .
doi:10.1098/rspa.1928.0091 .
JSTOR 95023 .
19. Salapaka, Srinivasa; Salapaka, Murti
(2008). "Scanning Probe Microscopy". IEEE
Control Systems Magazine. 28 (2): 65–83.
doi:10.1109/MCS.2007.914688 .
20. McKnight, Timothy E; Melechko, Anatoli
V; Hensley, Dale K; Mann, David G. J; Griffin,
Guy D; Simpson, Michael L (2004).
"Tracking Gene Expression after DNA
Delivery Using Spatially Indexed Nanofiber
Arrays". Nano Letters. 4 (7): 1213–9.
Bibcode:2004NanoL...4.1213M .
doi:10.1021/nl049504b .
21. Rassaei, Liza; Sillanpää, Mika; Bonné,
Michael J; Marken, Frank (2007). "Carbon
Nanofiber–Polystyrene Composite
Electrodes for Electroanalytical Processes".
Electroanalysis. 19 (14): 1461–6.
doi:10.1002/elan.200703887 .
22. Parris, Alton (May 2010)Carbon
Nanotubes and Carbon Nanofibers For Oil
Spill Remediation Developed by Sud-
Chemie .
nanopatentsandinnovations.blogspot.com
23.
https://www.google.ch/patents/EP1871709
A1?hl=de&cl=en
24. Hughes, T. V. and Chambers, C. R.
(1889) "Manufacture of Carbon Filaments",
U.S. Patent 405,480 .
25. Радушкевич, Л. В. (1952). "О
Структуре Углерода, Образующегося При
Термическом Разложении Окиси
Углерода На Железном Контакте" [About
the Structure of Carbon Formed by the
Thermal Decomposition of Carbon Oxide on
the Iron Contact] (PDF). Журнал
Физической Химии (in Russian). 26: 88–
95.
26. Oberlin, A; Endo, M; Koyama, T (1976).
"Filamentous growth of carbon through
benzene decomposition". Journal of Crystal
Growth. 32 (3): 335–49.
Bibcode:1976JCrGr..32..335O .
doi:10.1016/0022-0248(76)90115-9 .
27. Koyama, Tsuneo; Endo, Morinobu
(1973). "Structure and Growth Process of
Vapor-Grown Carbon Fibers". Oyo Buturi. 42
(7): 690–6.
doi:10.11470/oubutsu1932.42.690 .
28. Benissad, Farida; Gadelle, Patrice;
Coulon, Michel; Bonnetain, Lucien (1988).
"Formation de fibres de carbone a partir du
methane: I Croissance catalytique et
epaississement pyrolytique" [Formation of
carbon fibers from methane: I Catalytic
growth and pyrolytic thickening]. Carbon (in
French). 26 (1): 61–9. doi:10.1016/0008-
6223(88)90010-3 .
29. Baker, R. Terry K. Synthesis, Properties
And Applications Of Graphite Nanofibers .
wtec.org
30. Iijima, Sumio (1991). "Helical
microtubules of graphitic carbon". Nature.
354 (6348): 56–8.
Bibcode:1991Natur.354...56I .
doi:10.1038/354056a0 .
31. Schlogl, Robert et al. (2009)
"Nanocarbon-activated carbon composite"
U.S. Patent 20,090,220,767

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