Graphite & Carbon Fiber

Reference:
Hugh O. Pierson, “Handbook of Carbon, Graphite, Diamond
and Fullerenes,” Noyes Publications, Park Ridge, NJ, 1994
Chapters 3,4 and selected paragraphs from chapters 5-10.
 Natural Graphite

http://mineral.galleries.com/scripts/item.exe?LIST+Minerals+Elements+Graphite
 World Mine Production (Natural Graphite)

• Although natural graphite was not produced in the United States, approximately 200 U.S.
firms used it for a wide variety of applications.
• The major uses of natural graphite in 2003 were refractory applications, 25%; brake
linings, 13%; foundry operations, 9%; lubricants, 8%; and other uses (including steel
making), 45%.
• Despite graphite is know to us and seems to be common, it is a high tech material with
amazing possibilities.
Graphite Crystals
Three-dimensional Structure of Graphite
-Stacked Graphene-

• Space Group:
C6/mmc C-centered hexagonal
• Lattice parameters
• a = 2.4612 Å
• c = 6.7079 Å
• Atoms/unit cell 4
• Cell volume: 35.189*10-24 cm3
• X-ray density: 2.2670 gcm3
 Graphene
Why is graphene planar?
Why is it important to
distinguish between
graphene and graphite?
Edges of a Graphene Sheet
Arches of Graphene Sheets
Single-layer arches Double-layer arches
Structure of Hexagonal Graphite Crystal

Stacking sequence: -ABABAB- B

Structure of Hexagonal Graphite Crystal
Structure of Rhombohedral Graphite Crystal

Rhombohedral graphite is thermodynamically unstable, and can be

considered as an extended stacking fault of hexagonal graphite.
 Electronic Structure of Graphite

Brillouin zone
Unit cell (k-space,
(real space) where k is the
wavevector of
the electron)

Dispersion of the graphite π band near

Fermi energy EF
Graphite is zero-gap semiconductor
Fermi point is K
Surface of a Graphite Crystal
High Resolution TEM image of Graphite
High Resolution TEM of Graphite
Structure of Turbostratic Graphite

No registry between the graphene sheets

Anisotropy of Graphite Crystal

Young’s modulus of
graphite crystal as a
function of angle (Θ)
with c axis.
Anisotropy of Graphite Crystal

Coefficient of Thermal
Expansion (CTE) of
pyrolytic graphite as a
function of temperature
Strength of Graphite

Specific strength as a
function of temperature
of graphite and other
High-temperature materials.
 Molded Graphite

Graphite electrode.
(Photograph courtesy of
Carbon/Graphite
Group Inc., St. Marys, PA.)
 Graphite electrode

http://www.sglgroup.com/cms/international/industries/iron-and-steel-industry
 Applications of Molded Graphite

The specialty graphites listed in

the table include the molded
graphites produced for
Chassis: Molded graphite
semiconductor, electrical,
Backboard: composite integrated chemical, nuclear, biomedical,
Molded Graphite mechanical, and aerospace
industries.
Czochralski Apparatus for Crystal Growth of
Silicon
 Nuclear Application of Molded Graphite
• High neutron-moderating
efficiency
• Low neutron-absorption
cross section
• Good mechanical strength
• Chemical resistance
• Ease of machinability
• Relatively low cost

Dimensional changes as a result of

nuclear radiation
 Nuclear Application of Molded Graphite
• High neutron-moderating
efficiency
• Low neutron-absorption
cross section
• Good mechanical strength
• Chemical resistance
• Ease of machinability
• Relatively low cost

http://www.euronuclear.org/info/
encyclopedia/p/pebble.htm
 Pyrolytic Graphite – CVD & CVI
A unique form of graphite manufactured by decomposition of a hydrocarbon
gas at very high temperature in a vacuum furnace

PERFORMANCE FEATURES APPLICATIONS

• Chemically Inert • Sputtering Targets
• High Purity • Ion Beam Grids
• Stable to 3000°C • Ion Implant Hardware
• Impermeable • Liquid Phase Epitaxy Hardware
• Directional Electrical & Thermal • Thermal Insulators
Characteristics • Rocket Nozzles
• Self-Lubricating • Heater Elements
• Nondusting
• Low Etch Rate
Chemical Vapor Deposition / CVD
Chemical Vapor Deposition / CVD
Experimental Apparatus for the Production of
Pyrolytic Graphite
Schematic of a Cold-wall Reactor for the
Production of Pyrolytic Graphite
Schematic of a
Fluidized-bed CVD
Reactor for the
Deposition of
Pyrolytic Graphite.

What are the

advantages/
disadvantages of the
different reactor
types?
Cutting and Machining Graphite

http://www.graphite-eng.com/
 HOPG - Highly Oriented Pyrolytic Graphite
A Substrate Material for Scanning Tunneling Microscopy and Atomic Force Microscopy

• HOPG, is a relatively new form of

high purity carbon, provides
surface
microscopists with a renewable and
smooth surface.
• Unlike mica, HOPG is completely
non-polar and it provides a
background with only carbon in the
elemental signature.
• The extreme smoothness of HOPG
makes results in a featureless
background, except of course, at
atomic levels of resolution.
 Carbon Fibers
Most of carbon fibers are derived from one of two precursor materials

• Pitch
• PAN (Polyacrylonitrile) fibers
Schematic of Spinning Processes of PAN fibers
 Polyacrylonitrile (PAN), a precursor for carbon fiber
Mw ~ 150,000 g/mol
 Stabilization and Oxidation

 Heat treatment in air at

200°C, 1 hr at ~2°C/min.
(under tension)
 Formation of C=C bonds and
the incorporation of Hydroxyl
(-OH) and carbonyl (-CO)
groups in the structure.
 Promotes cross-linking and
thermal stabilization of the
fiber.

Pierson, H. O. Handbook of Carbon, Graphite, Diamond

and Fullerenes, 1993, Noyes Publication.
 Hitco process for PAN fibers

Fitzer E., et al.: Fibers in Ullmann's encyclopedia of

industrial chemistry, 7. ed. , Wiley-VCH; Berlin; 2004.
Pitch-based Carbon Fibers
Schematic of the Production Steps in the
Manufacture of Pitch-based Carbon Fibers
Strength and Modulus
of Carbon and
Other Fibers
 Carbon - Carbon Composites
A material with high strength carbon fiber and carbon matrix.
This composite having excellent mechanical properties is suitable for use in a variety
of high temperature applications.

Features
• High Strength to Weight Ratio
• Excellent Heat and Thermal
Shock Resistance
• Excellent Chemical Resistance
• Low Coefficient of Thermal
Expansion
• Low Thermal Conductivity
• High Purity
Applications
• Components for Crystal
Pullers
• Furnace Structural Parts
• Heaters, etc.
 Carbon - SiC Composites

Jet nozzle ARIANE

Cone shaped tips of emergency space
shuttles

Fiber:gauze of C-fibers
Matrix: C/SiC
SiC as oxidation protection layer

CFC C-fiber reinforced carbon

Siliconized (C/SiC)
 Fiber Bridging Across Matrix Cracks

SEM micrograph of crack After B. Lawn, Fracture of Brittle Solids,

propagation through a C/C composite 1993
R.J. Zaldavar, et al., J. Am. Ceram. Soc., 78 [3] (1995).
 Carbon Fiber Composites in Cars
- Actually carbon fiber composites attract the interest of automobile
manufacturer to safe fuel with light weight constructions.
- Mass production is only possible when going away from hand crafted
solutions to mass production.
- The use of short fibers and 3D spinning machines are possibilities towards mass
production.
Effect of Diameter on Fiber Strength

How to make stronger fibers ?

 Electrospinning Process
 1934 – first patent on electrospinning process was issued to
A. Formhals1, Germany.
What is Electrospinning?
• The use of electrostatic
charge to produce ultra-fine fibers
from a polymer solution.
Controlling parameters:
• Solution viscosity
• Molecular weight
• Polymer concentration
• Solution temperature
• Applied voltage
• Spinning distance
• Spinning environment

Formhals, A., Patent No. 1,975,504, 1934

Nanofiber Yarn Production system
 Effect of Polymer Concentration on Fiber
Diameter (Pure PAN)

H. Lam, Drexel University

Microstructures of Carbonized Nanofibers