Curbon 1969, Vol. 7, pp. 683-688. Pergamon Press.

Printed in Great Britain

KINETICS OF GRAPHITIZATION - II.

PRE-EXPONENTIAL FACTORS
H. N. MURTY, D. L. BIEDERMAN and E. A. HEINTZ
Airco Speer Research Laboratory, Packard Road and 47th Street,
Niagara Falls, N.Y. 14302, U.S.A.

(Received 2’7January 1969)

Abstract- In the preceding article on kinetics of graphitization it has been demonstrated

that for three typical cokes used industrially, the activation energy for graphitization is
the same and is equal to 230 f 15 kcals/mol. However, in contrast to work done elsewhere,
it is shown that systematic differences in respective rates of graphitization of various
cokes, do become manifest and can be interpreted by focussing the attention on the
‘structural envoronments’ of calcined cokes themselves. It is shown that differences in the
rate of graphitization of various cokes are due to differences in pre-exponential factor.
The ‘anisotropy’ of calcined cokes which can be determined by X-ray methods is qualita-
tively correlated to the rate or ease of graphitization (pre-exponential factor); the rate of
graphitization increasing with the ‘anisotropy’ of the calcined coke.

1. INTRODUCTION apparent layer size (~5,). For equal apparent

One of the most perplexing and least layer sizes the apparent stack height is greater
understood aspects of the gt-aphitization of for a graphitizing than a non-graphitizing
various graphitic carbons are their widely carbon; in other words, the layer stacking is
differing rates of graphitization. It is of im- more perfect in graphitizing than in non-
portance to understand why various graphitic graphitizing carbons with a comparable layer
carbons have different ‘graphitizabilities’ and structure. This difference is observed[4]
what structural property of coke controls well below the range of temperatures where
the rate of graphitization. measurable graphitization can occur. How-
In the preceding article[l], it has been ever, such major structural differences ob-
demonstrated that, for three diverse indus- served through the measured L, and L,
trial Cokes A, B and C, the activation energy exists only between non-graphitizing and
for graphitization is the same. Then it is graphitizing carbons and the parameters L,
pertinent to compare the respective rates of and L, cannot be conveniently used to
graphitization of these cokes and consider differentiate the structural differences, for
how different rates of graphitization ori- example in different graphitizing carbons
ginate and whether the respective rates can exhibiting different rates of graphitization.
be correlated to a characteristic property of Fischbach[3], from his studies on petro-
the coke itself. leum coke, pitch coke, and pitch-coke
Franklin[2], through her studies on composite concluded that the three carbons
graphitizing and non-graphitizing carbons, have an identical activation energy- a con-
has shown that the two types of carbons have clusion which is in agreement with the pre-
basically different structures. The differen- sent work[l]. However, he found that the
ces in structure are apparent from the ear- rate of graphitization is much the same for
liest stages of carbonization. The most the three cokes despite the fact that the cokes
striking difference appears in a comparison are different.
of the apparent stack height (L,) and the Thus, there exists in the literature a diver-
683

CARVol. 7. NoG-D
684 H. N. MURTY, D. L. BIEDERMAN and E. A. HEINTZ

sity of opinion concerning the origin of log (rate) = logRa-EJRT. (6)

different ~aphitizabilities and whether or
not a characteristic structural property of the The temperature-dependent and tempera-
calcined coke can be correlated to its graphi- ture-independent parts on the right-hand
tizability. The following work is undertaken side of equations (5) and (6) can be compared
to elucidate some of these aspects of graphi- from which we get the pre-exponential
tization. factor given by,

4. THEORY log Ri, = log no- logtoo+ (I+ l/n) loggo (7)
In the present work, the degree of graphi-
tization, go, defined by the equation logR, = log ($gol+l/D). (8)

(1)
Further, when go = 1 (ct = co)
will be employed as the kinetic parameter.
Here co and c, are the lattice constants of Ro = (&i,) . c-9
misoriented and oriented regions respec-
tively while cd is the lattice constant of coke To obtain log Ro, the rate, (dgo/dt) is calcula-
heat-treated at temperature T for time t . ted from equation (4) at constant go and log
The isothermal kinetic changes in go are (rate) is plotted against l/T. Figures 1 and 2
represented by an empirical equation [l]

go= (,?i)i (2)

where t is the residence time, n is a constant

characteristic of each coke and it was shown
[l] that n #f(T) and to is a characteristic
parameter which depends on temperature
according to the relation,

IITxlO-’
to= tooe'E, lRr. (3)
Fig. 1. Arrhenius plot for constant go values for
Cokes A, B and C.
From (2) and (3)

rate = 9 = ~(;;“t”“, =L_n&-’ go'+l/n*

(4)
0

The negative sign on the right hand side of

equation (4) merely indicates that the changes
in time and go are in opposite directions.
Combining (3) and (4) we have

log (rate) = log n -log toi)+ ( 1+ l/n) log go

- E,IRT. (5)
Fig. 2. Arrhenius plot for constant go values for
From the Arrhenius equation, Cokes A, B and C.
 KINETICS OF GRAPHITIZATION - II 685

show plots of log (rate) vs. l/T, for constant it is this physical property which can be used
values of go for the three cokes, A, B and C. to differentiate various cokes. In general, two
From the set of parallel lines in Fig. 1 and 2, methods have been employed to date, to
it is seen that the activation energy is the same determine the anisotropy of the starting
for all three cokes but the ‘rate of graphi- materials.
tization’ is different for each coke. Further-
1. X-ray determination of preferred
more, it can also be seen from Figs. 1 and 2,
orientation [4]
that the differences in the rates of graphi-
2. anisotropy determination via polarized
tization between the cokes increases as the
light microscopy [5].
process proceeds. This can also be noted from
equation (7), since n is different for each Only the first method is used in the present
coke, for two cokes of given values of n, the work, although the second can be used with
differences in rate increases with decreasing equal facility.
R@
Thus it is shown above that the activation 3. X-RAY METHOD
energy is the same for the three cokes and yet A measure of the anisotropy of the starting
the rate of graphitization is different for materials can be obtained fror the ratio of
each coke for a constant go value. Hence, the the intensity of (001) diffraction line in
difference in rates of graphitization should be reflection to that in transmission[6]. For an
due to different pre-exponential factors, isotropic material this ratio is unity and the
with each coke having a characteristic value. farther this ratio deviates from unity the
Since the pre-exponential factor reflects the more anisotropic is the material. Other
‘structural configurations’ of the starting workable forms of the test, for reasons of
material, the differences in the respective simplicity, employ relative changes in inten-
rates of graphitization should be due to sity of the (002) diffraction line in reflection
differences in the structure of the starting I 002 R9 the P.O.R.” uoo2)Rl~(lo)R) [71,
material-the coke itself. This leads one to (1oo2R,/&,,2R)[B], etc., where the superscript R
the possibility that the pre-exponential refers to the diffraction line in reflection and
factor of the three Cokes, A, B and C, can be p is the full-width at half-maximum intensity.
related to some property of the starting Although the magnitude of each of these
material which is characteristic of its ‘struc- parameters is different, the relative changes
tural configuration’. Normally changes in in each of these parameters reflect the aniso-
X-ray lattice constants (a and c) and/or tropy of the starting material and a close
changes in crystallite dimensions (L, and L,) correspondence between various parameters
of carbons are used to study the individual was found to exist [7]. It has also been
structural differences. For example, Franklin demonstrated that each of these parameters
[2] has shown that in cokes having compar- can qualitatively describe the relative ease of
able crystallite diameter L,, graphitizing graphitization of carbons. In the present case
cokes have a larger L, compared to non- the parameters
graphitizing cokes. Although such relations
1 1002 R zoo2R 1o02R
are quite valid, these are useful only when 002R, - -
-.p
002
R

major exist.
IIOR ’ P 002R’ IIOR
structural differences For
example, L, under the above conditions can- were determined for each coke calcined to
not be used to differentiate various gra- 1300°C. The experimental details of sample
phitizable cokes. Nevertheless, even in gra- preparation etc. were described in detail
phitizable cokes there exists a wide variation
in the isotropy of the starting materials and *Preferred Orientation Ratio.
686 H. N. MURTY, D. L. BIEDERMAN and E. A. HEINTZ

elsewhere[4]. It is found that for the three
cokes PaozRis nearly equal and hence ZWR or
Z~Rl~~R would yield identical results in
regards to the relative magnitude of the
anisotropy of each coke. Table 1 gives the
anisotropy factor (ZWzR,etc.) has a larger R0
and hence is more readily ‘graphitizable’.
This is of profound significance for a proper-
ty of the starting material can be related to
its relative rate of ease of graphitization.

Table 1.

Coke A Coke 3 Coke C

z(002)
R
(in arb. units) 560 450 165
ZIOR band
(in arb. units) 7‘5 9.0 11.5
Preferred orientation
ratio P = ZtoozjR/Z~
10jR 75 50 14.4
P(oo2,R
(corrected full width at
half-maximum intensity) 2-12” 2*10” 2.10”
P*&30ZP 159-o 105.0 30.2
Pre-exponential factor
R. in units min-’ 1.7 x lOI9 1*5x 10’9 0.4 x 10’9

values of the various ‘anisotropy parameters’
of the three cokes along with the pre-
exponential factor R. of each coke deter-
mined from equation (9). It can be seen that
a coke having a larger ‘anisotropy parameter’
(ZWzR,etc.} also has a larger pre-exponential
factor and hence larger rate of ~aphitization.
Figure 3 shows such a relation and it can be
seen that qualitatively a coke having a higher
0 20 40 60 80
However, a quantitative and accurate cor-
relation between the anisotropy factor and
pre-exponential factor is not considered
feasible for the following reasons.
From equation (6),
log (rate) = log R,, - EJRT
it is shown that E, the activation energy is
about 230 + 15 kcal/mol. The probable error
in determining E, is about 5-10 per cent and
the errors in the determination of E, reflect
in the accuracy of determining Ro. In the
temperature range of T - 25OO”K, for a
given rate, an error in determination of E, of
about 5 per cent, results in error in R. of the
order of lo*-103.
Because the differences in Re for the cokes
studied here, though real, are only of the
order of, or less than the possible error, a
quantitative correlation between the pre-
exponential factor and anisotropy parameter
of a calcined coke is not considered feasible.

4. DISCUSSION
Fig. 3. Schematic plot of pre-exponential factor vs.
P.O.R. (ZMzR). It has been demonstrated earlier that for
 KINETICS OF GRAPHITIZATION - II 687

three typical industrially used cokes, A, B From this correlation (cf: Fig. 3) it can be
and C, the activation energy for graphitiza- seen that a coke in which the crystallites are
tion is the same[l]. Since the rates of graphi- more favorably oriented (i.e. more aniso-
tization of these cokes are different, this tropic) have a higher pre-exponential factor
difference should manifest in different pre- and hence a higher rate or ease of graphi-
exponential factors with each coke having tization. This conclusion is in agreement with
its characteristic value. Fischbach [3] from his the crystallite growth studies of Franklin[2]
studies on petroleum coke, coal-tar pitch as well as Akamatu and Kuroda[9].
and pitch-coke composite concluded that the
activation energy for these carbons is the 5. CONCLUSIONS
same: a conclusion which is in agreement A new approach has been developed to
with the present work. However, possibly study the transformation of carbon to gra-
because of the choice of three cokes that do phite. By comparing the instantaneous rate
not differ drastically in the respective gra- of graphitization at constant extents of
phitization rates, or possibly because his transformation, it is demonstrated that for
method of ‘shifting or scaling the curves’ all the carbons studied the activation energy
does no permit one to follow graphitization is the same and yet the rates of graphi-
as a continuous function of the extent of tization were different. The differences in the
transformation, Fischbach reached the con- corresponding ‘rates’ originate due to differ-
clusion that the three carbons he studied in ences in the pre-exponential factors. The pre-
addition to having identical activation ener- exponential factor of each coke was correlated
gies have much the same rate of graphitiza- to the corresponding ‘anisotropy para-
tion. meter(s)’ which is a measure of the relative
In contrast, using the present method of orientation of crystallites in the calcined
following the rate of graphitization as a con- coke itself. From this correlation (cf:
tinuous function of the extent of transfor- Fig. 3) it is seen that a coke in which
mation it has been clearly demonstrated here the crystallites are more favorably
that systematic changes in the respective oriented have a higher pre-exponential
graphization rates of cokes do become mani- factor and hence a higher rate or ease
fest and can be interpreted by focussing the of graphitization. This is of profound
attention on the ‘structural configurations’ of significance for a characteristic property of
the calcined cokes themselves. Clearly, the the starting material itself is correlated to its
different ct values observed for the cokes for relative ease of graphitization.
given heat-treatment conditions is not what
is expected if the activation energies as well Acknowledgments-The authors are indebted to
as the pre-exponential factors are the same Drs. W. E. Parker, F. M. Collins and M. L. Pearce
of this Laboratory for critical reviews and con-
for all the cokes. Quite the contrary, the
structive suggestions. All experimental work was
family of parallel lines seen in Figs. 1 and 2 performed by E. G. Haley and A. M. Puglisi of
suggests identical activation energies but this Laboratory.
different graphitization rates and hence
different pre-exponential factors for various
cokes. Thus the pre-exponential factors REFERENCES
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which are some measure of the relative orien- III, pp. 22-23. Carbon Sot. of Japan, Tokyo
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