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sp2 - Graphite
sp3 - Diamond
CRYSTALLINE FORMS
GRAPHITE DIAMOND
Graphite has shorter bond length in the plane Graphite has stronger in-plane bonding Hexagonal Rhombohedral
CRYSTALLINE GRAPHITE
HIGHEST AND LOWEST BOND ENERGIES - in 'a' and 'c' directions GREATEST ANISOTROPY IN PROPERTIES
YOUNG MODULUS: - a axis = 1050GPa (c11); c axis = 36GPa (c33) SHEAR MODULUS: ~ 4GPa EXPANSION COEFFICIENT: 'a' ~ -1 10-6; 'c' ~ 30 10-6 THERMAL CONDUCTIVITY: 'a' > 2000 Wm-1K-1 ELECTRICAL RESISTIVITY 0.4 - 0.8 ohm.m
1 = s ( 1- 2 ) 2 + s 4 + ( 2 s + s ) 2 (1 2 ) 11 33 13 44 E ( where = 1 cos )
C-axis elastic constant (c33) Inter-layer shear (c44) DOMINATE AT ALL BUT NARROWEST ANGLES Therefore generally low moduli except for highly a axis aligned structures, e.g. fibres
c axis () misalignment
THERMAL EXPANSION
c-AXIS EXPANSION COEFFICIENT, VERY HIGH a-AXIS EXPANSION COEFFICIENT, NEGATIVE TO SLIGHTLY POSITIVE ABOVE ABOUT 300oC SYNTHETIC CARBONS/GRAPHITES HAVE VERY DIFFERENT COEFFICIENTS
SPECIFIC HEAT
From Burchell
THERMAL CONDUCTIVITY
For given solid specific heats and phonon velocities are same Therefore conductivity is directly proportional phonon mean free path
=1 3 C l
where C is specific heat
Graphite Oxidation
Basal plane is unreactive Reaction occurs at exposed atoms edge
Even within the plane the oxidation rate is anisotropic Etch pits bordered by zig-zag or armchair planes Relative reactivity can change with temperature Catalyst particles may act on the exposed edges
SUMMARY - GRAPHITE
Most anisotropic crystal Strongest bonding in-plane, weakest in c-direction High in-plane elastic modulus High in-plane thermal conductivity Low in-plane expansion coefficient Semi-metallic conductor Basal plane is low energy surface non-wetting to polar species Oxidation is anisotropic reaction from edge sites Poor shear properties
MICROSTRUCTURE Crystallinity Domains of oriented structure Pores Size distribution & orientation (pore shape)
Schematic of 2 piles of layers: L2 is the real layer extent, L, the defect-free part, N the number of layers coherently stacked, la the coherent length in-plane and lc the coherent length along the stacking direction (dashed: coherent domain).
Graphitising Carbons
Lc
As the ordering increases, properties along the basal axis improve; Thermal / electrical conductivity Elastic modulus
La
LMO Local molecular ordering of the BSUs (Basic Structural Units) VERY IMPORTANT FOR GRAPHITISATION.
2730oC
2000oC
Lc =
k bcos
N.B. Coherence lengths are still in the nano-scale, even after graphitisation!
NON-GRAPHITISING CARBONS
e.g. from Phenolic Resin
Some carbons do not develop the graphitic structure even when heated to 3000oC. No stacking sequence
There is some peak narrowing, but no extensive increase in coherence lengths in either direction.
Kipling et al
Graphitisation Parameters
Franklin d = 3.440 -0.086(1-p) 0.064p(1-p) p = proportion of misaligned layers p < 0.25 Bacon d = 3.440 - 0.086 (1-p2)
Turbostratic
Raman Spectroscopy -1
Raman Spectroscopy - 2
1580 cm-1 peak narrows with graphitisation
Raman Spectroscopy - 3
Relative intensity of two peaks changes on graphitisation. Can be used empirically to estimate the a direction coherence length, La
The peak occurs when the mean free path due to Umklapp scattering becomes larger than the grain size and grain boundary scattering begins to dominate
(Taylor et al 1968)
As the crystallite size increases the thermal conductivity peak occurs both at a lower temperature and has a numerically larger value (Kelly & Gilchrist 1969)
Temperature
Increasing HTT
-1
-1
400
600
1000
1200
1400
Green Coke
Heat 1200-1400C
Pitch binder
Calcined Coke
Grinding & classification
Mixing at T~ 150C
Re-impregnated block
Carbonised block
Graphitised >2750C
Graphitised block
High temperature halogenation
Pitch Factors
Graphitisability Carbon yield Rheology Different for binder and impregnant Optimum binder content
Too high, porosity due to volumetric shrinkage during carbonisation and bubble like pores.
Binder content %
Coke textures
Mesophase deformation during flow gives needle coke characteristics and elongated, anisotropic particles
b d Figure 4.1.1. Optical micrographs of (a) PGA (reflected light) and (b) PGA (polarised light) showing large filler grains. Note the orientation of the individual grains revealed by interference colours and texture within these grains; (c) Gilsocarbon (reflected light) and (d) Gilsocarbon (polarised light) showing large spherical filler grains. Note the resin-filled pores between grains (NC = needle-coke grain; SG=spherical grain; LC=lenticular crack; B=binder; P=pore; GP=globular pore; R=resin)
50 m
After Mochida et al
undeformed
sheared
Coke textures
Mesophase deformation during flow gives needle coke characteristics and elongated, anisotropic particles
Disclinations in mesophase are retained in the coke/carbon and carried through to the graphite
N.B. Note the dimensions of the oriented domains, tens to hundreds of microns X-ray coherence lengths are up to 100nm
Coke texture and disclinations have a strong influence on crack development and propagation
Shrinkage cracks during carbonisation and on cooling may follow lamelliform texture.
THERMAL EXPANSION
Expansion coefficients very different from crystal values Partly because of lower macroscopic anisotropy or for nuclear graphite, ideally isotropic behaviour Also c axis expansion is partly accommodated in the lamellar fissures, Mrozowski cracks resulting from anisotropic shrinkage during cooling or carbonisation
Examples are extruded graphites with preferred orientation of needle-like coke grains
The term Grain in this context refers to the coke filler particles not the crystallites themselves
120 3-point bending 100 Load, P (N) 0.1 0.2 0.3 Displacement, u (mm) 80 60 40 20 0 0.0
IG110 Gilsocarbon Ucar (parallel) Ucar (perpendicular)
Non-catastrophic fracture behaviour Residual strength after maximum stress Relatively large work of fracture Results from crack deflection and weak interfaces
0.4
0.5
Crack propagation is mostly around grains, where there is relatively weak bonding
Typical tortuous crack pattern in graphite
Filler grains protrude from fracture surface Propagation through needle grain
4m
20m 500m
Anisotropic contraction on cooling opens cracks parallel to layer planes, which affect modulus and strength. Expansion into cracks on reheating closes them, increasing the modulus and strength.
Conclusions
Graphite is intrinsically anisotropic in its crystal structure and its properties Synthetic graphite, in bulk form, is a composite produced from coke-pitch mixtures. The two phases both graphitise but the degree of graphitisation may differ. The dimensions of oriented domains differ significantly for the two phases. The final heat treatment is greatly important to the degre of graphitisation. The bodies produced are porous and contain lamellar microcracks oriented wrt the graphene layers. These cracks are of great significance leading to reduced coefficient of expansion and mechanical properties increasing with measurement temperature. As will be seen they are also critically important in the irradiation behaviour.