Carhn
1968,
Vol. 6, pp. 55-63.
Pergamon Press. Printedin GreatBritain
THE INFLUENCE OF CRYSTALLITE SIZE ON THE DIMENSIONAL CHANGES INDUCED IN CARBONACEOUS MATERIALS BY HIGH-TEMPERATURE IRRADIATION” J. C. BOKROS,
G. L. GUTHRIEt
and A. S. SCHWARTZ
Gulf General Atomic Incorporated, John Jay Hopkins Laboratory Science, San Diego, California
for Pure and Applied
(Received 11 August 1967)
Abstract-Measurement have been made of the dimensional changes induced by fast neutrons in natural graphite, annealed pyrolytic carbon, catalytically graphitised carbon, and turbostratic carbon, for irradiation temperatures below 1300°C. Plots of the rate of change of the crystallite dimensions vs. temperature show the existence of a minimum rate for all but the natural crystals. This minimum rate occurs at a temperature which increases with increasing crystallite size. For the largest crystallite sizes (natural crystals), the rate decreases monotonically with temperature up to the highest investigated ( 1300°C). For large crystallites (> 200 A) and low irradiation temperatures (- 2OO”C), the rate of dimensional change is insensitive to crystallite size. The rate becomes increasingly dependent on crystallite size as the irradiation temperature is increased. At temperatures near 12OO”C, the rate varies by over two orders of magr’ntude for the various crystallite sizes used in the present study. The functional dependencies noted from the data are qualitatively consistent with the ideas of REYNOLDS and THROWER that involve the temperature-dependent heterogeneous nucleation of widely spaced interstitial clusters.
1. INTRODUCTION WHEN
graphite
energetic
knock-on
by collisions the
graphite
atoms
is irradiated carbon
carbon
to form loops,
that are produced
or become
annihilated
tural defects such as crystallite causing
dimensional
tion temperatures, nucleation
low temperature
changes.@) the spacing
dimensional dent
by
of
the
which
average
observed clusters
in
Consequently,
produce are nearly
crystallite temperatures,
shown that the dimensional
thus
crystallite than
of heterogeneous carbons,
spacings
nucleated
irradiations
change
At high irradiation
at struc-
At low irradia-
sites, even in turbostratic
the
rates
of
indepen-
size
in
the
sample.(4)
nucleate
boundaries,
with
homogeneously
large single crystals of graphite.c3)
atoms are generated
atoms recombine,
compared
between
of neutrons with carbon atoms in carbon lattice. (1) The displaced
and the vacancies
the recoiling
large
with fast neutrons,
is
it has been depend
on
size (LE) when the L, values are larger
N 100 A. NETTLEY
compared
and MARTIN(~)
the dimensional
as-deposited in graphitised
*Work supported by U.S. Atomic Energy Commission, Contract AT(O4-3)-167, Project Agreement 12. t Present address: Battelle Northwest, P.O. Box 999, Richland, Washington 99352.
changes
changes
have
induced
in
(L, < 200 A) and pyrolytic carbon (L, = - 1000 A)
pyrolytic
carbon
after irradiations at 600” and 700°C. They found that at 6OO”C, the rate of dimensional change for the as-deposited carbon was twice as high as that 55
for the graphitised
specimens,
and
at
56
J. C. BOKROS, G. L. GUTHRIE
7OO"C, the rate for the less crystalline was
about
six
times
PRICE(~* 7) irradiated carbons
higher.
a variety
and reported
little
carbons
(L, =
temperatures,
stratic
carbons
Large
between
the rates
N 1000
A)
however,
at
for the
strain
rates
stallite
arise for materials
sizes at high
because these materials nucleation To
a unified
picture
crystallite
size
of carbonaceous
temperatures
mens of four uniformly materials
were
crystalline
included
in
capsules that were irradiated at
exposures demonstrate on
high
dimensional
changes
direction
measured
basal
tion
irradiation The
These
and
high
changes
size
irradiation
slightly carbon
material
density available. than
by annealing
in the range
3000” to
this treatment,
the
orienta-
size of N 1600 A. This in the form
parallelepipeds.
were measured
The
of small
dimensional
with a machinist
micro-
scope using 0.3 mm holes as fiducial
marks.(@)
In most of the experiments,
were cut
could
the changes be
pyrolytic
provide A
(g/ml)
(A)
R,
Annealed massive pyrolytic carbon
2.25
1600
3.35
0.13
Natural graphite crystals
2.26
co
3.35
0
Catalytically graphitised carbon Turbostratic carbon
2.33
800
3.35
0.44
2.10
170
3.40
0.48
Supplementary
on the direct
were made to
measurements
of
changes.
uniformly
CARBONACEOUS
directly.
of density changes
a check
dimensional
specimens
in the a- and c-directions
measured
measurements
OF THE
accurate
less crystalline
After
a crystallite
included
PARAMETERS
in the
crystals were chosen as repre-
crystals were obtained
rectangular
the
from
accompanying
was irradiated
Layer spacing
Density
changes
of the
samples
and
Crystallite size L, (A)
Material
plane
calculated
of the most graphitic
material
results
of crystallite
annealed
1. STRUCTURAL
were
had a high degree of preferred
carbon, catalytically graphitised pyrolytic carbon, and a high density turbostratic carbon TABLE
using
material
selected for irradiation crystals,
microscope
carbonaceous
2. EXPERIMENTAL graphite
dimensional
plane were meas-
for 70 min.
so that
natural
The
as fiducial marks. The changes
massive pyrolytic
temperatures.
The materials
argon.
3300°C
eight
at
in
to the basal
a machinist
the natural
to various neutron
effect
with
Carbon
for
Essex
first for 4 hr at
5OO”C, speci-
temperature.
the strong
2400°C parallel
sentative
and the
materials
above
at
the c-axis
of the relation changes
(from
by heating
changes.(E)
of vacancies.
crystals
and then for an additional
determinations
offer more heterogeneous
the neutron-induced
irradiation
cry-
at
were purified and stabilised
in vacuum
twin markings
temperatures
sites for the elimination
obtain
between
with small
irradiation
irradiated
1900°C
ured
NOLDSet al.@)have suggested that high crystallite
were
graphite
New York)
changes
REY-
materials
in the range 500” to 1300°C.
prior to irradiation 4 hr
turbo-
higher.
The
natural
County,
of high density
were dramatically
1).
temperatures
100 to 200 A) and
polycrystalline graphites (L, = changed dimension at N 500°C; higher
(Table
and
of turbostratic
difference
the rate at which the crystallites turbostratic
material
BOKROS
and A. S. SCHWARTZ
crystalline
MATERIALS
Anisotropy
material
with
a
IRRADUTED
Remarks
RII 0.93 Annealed at 3000 to 3300°C for 70 min 1 Obtained from Essex County, New York 0.78 Deposited at 2100°C from 3% CH, in He; contains 2.7 atom-% Ti 0.76 Deposited at 2200°C from 12% CH, in He
THE crystallite
INFLUENCE
at 2100°C
carbon
and
in a fluidising
material
contained
particles
about
been
a titanium
furnace.
discrete
titanium
Details
and the structure
reported
This
deposition
material
was
described.(8*
in helium
lo* 11) turbostratic
carbon
furnace
and
size of 170 A. A high density
carbon
plication
was selected
to avoid
of irradiation-induced
which has been reported turbostratic
carbons
had
a
turbo-
the com-
densification,
when poorly crystalline
with a substantial
defect are irradiated Specimens
was
from 12 per cent methane
in a fluidising
crystallite stratic
density
at 2200°C
density
with fast neutrons.(ep 7* lo+r2)
of this material
were also irradiated
as strips or disks. The
degree
annealed by
of preferred
massive pyrolytic
X-ray
diffraction
nique.(13)
A modified
the
specimens
beds.04) each
using
R,
BACON tech-
of this technique
the preferred in
of preferred
was characterised
and
RI,, which
pole figure
formulated
the
deposited
degree
material
meters, (002)
The
of the
carbon was measured
version
was used to measure of
orientation
orientation the
according
fluidised
orientation
of
by two para-
are derived
from a
to the procedures
by BACON:
s” s
where the integrals
The
dimensional
pendicular
angle
4.““)
R, by RI,=
The
Table
1 -
RJ2.
structural parameters material irradiated. The
irradiations
RI,is
Table that
graphically
changes
parallel
principle
u-axis
and
per-
direction,
2, together
with
the irradiation
condi-
Specimens carbon diated again
of
the
catalytically
and the turbostratic
graphitised
carbons
were irra-
twice, first at 520” and 670°C at 840” and 900°C
and then
(see Table
2). Virgin
samples were also irradiated
at 840” and 900°C.
The data for the turbostratic
carbons
show that
at 840” and 900°C
the specimens
previously
temperature identical
(specimens
in Table
2
the behavior
irradiated
of
at a lower
a”, b”, c”, and d”) was
to that of the virgin specimens
(speci-
mens a’, b’, c’, and d’). The previous irradiation at a lower
temperature
turbostratic
carbons.
more crystalline mens
that
been
changed
no effect
the other
catalytically
had
temperature
had
On
on the
hand,
graphitised
irradiated dimension
at
a
at 840”
the
specilower and
:
2ln
related
characterise
(1+$+!)+ln(l+$?) +
In
vs. the
1 summarises
were conducted
tion capsules instrumented
the
tions.*
relation
plane normal)
parameter
to
for catalytically graphitised Al II! iI and AIJl, carbon and turbostratic carbon are listed in
from a plot of I(+) (the number of (002) poles per unit solid angle that are inclined at the angle + to the deposition
Test
3. RESULTS
oXiaI(4) sin 4 d$ can be obtained
All of the irradia-
in the Engineering
*For cases in which the changes AIJ, were derived from the changes in 111 and p, the exact
n/2I(+) sin3 4 d$
R,=
of these capsules have
previously.os)
the analysis of nickel and iron flux wires.
previously
high
57
have
either as strips or as disks of the type
The
The design and operation
CHANGES
Reactor (ETR). The integrated total fast flux for each cell of each capsule was obtained from
irradiated
deposited
DIMENSIONAL
tions were conducted
carbide
of this material
ON THE
been reported
throughout
of the
previously.@)
by
catalyst
The resulting
1 CLin dia. dispersed
microstructure.
process
SIZE
size of 800 to 900 A was obtained
co-depositing
the
OF CRYSTALLITE
to the
was used when approximate
the changes relation :
exceeded
each
in irradia-
with thermocouples.
was used when the changes
were smaller.
-
4%.
The
J. C. BOKROS, G. L. GUTHRIE
58
900°C (specimens e”, f”, g”, and h”) at a faster rate than the virgin specimens (specimens e’, f’, g’, and h’) during the irradiation at 840” and 900°C. This may be evidence for a seeding effect in the more crystalline material.(r7) The concentration of potential heterogeneous nucleaTABLE 2. DIMENSIONAL CHANGESINDUCED BY
and A. S. SCHWARTZ
tion sites in the turbostratic material was probably too high to be altered significantly by the previous irradiation at a lower temperature. The rates of crystallite dimensional changes, ln(1 + AXc/Xc> and ln(1 + AX./X.) per 1021 nvt, were used to compare the relative stability CARBON AND
INTURBOSTRATIC
IRRADIATION
AT
VARIOUS
CATALYTICALLY
Total change
Turbostratic
Catalytically graphitised carbon
carbon Neutron dose, nvt x 102r (E > 0.18 MeV)
Irradiation temperature
0.94 0.94 1.0 1.0
520 520 670 670 530 530 920 920 505 505 915 915 848 840 900 900 840 840 900 900 900 900 940 940 1225 1275
2.8 2.8 2.8 2.7 3.8 3.8 5.6 5.6 3.2 3.2 3.7 3.7 3.2 3.2 3.7 3.7 2.5 2.5 1.8 1.8 1.8 2.1
(“C)
3, x 100 111 -0.47(a) -0.48(b)
y
*
-0.55 (c) -0.52(d) 1 -1.65 -1.74 -7.40 -7.05 -4.19 -4.53 -16.7 -15.3 -10.9(a”) - 11.3(b”) - 15.5(c”) - 15.3(d”) * - 11.4 (a’) -11.2(b’) -15.3 (c’) - 15.6 (d’) -10.3 -10.5
GRAPI-IITISED CARBON
TEMPERATURES
I
x 100
+0.13 +0.20 0.00 -0.06 f1.4 +1.5 $16 +15 +7.0 +7.8 +54 +49 $26 +28 +48 +47
+28 +29 +46 +46 +21 +21
3’
x 100
F
4l
-0.11 (e) -0.12(f) -0.083 (g) -0.095(h)
-0.56 -0.63 -0.90 -0.75 -
-0.67 -0.68 -0.42 -0.47 -2.74 -2.78
t
I
x 100
+0.52 +0.70 +0.43 +0.19 +0.87 +0.97 +1.9 +1.7 +2.9 +2.2 +4.2 +4.6 +3.4 +3.3 +1.7 +1.9 +0.78 +1.1 +0.45 +0.72 +4.5 +4.9
*Specimens a”, b”, C” and d” were previously irradiated at 520” and 670°C (specimens a, b, c and d); the neutron doses and length changes listed for the specimens irradiated at 840” and 900°C are those accumulated at 840” and 9OO’C and are in addition to those due to the irradiation at 520” and 670°C. Specimens a’, b’, c’ and d’ are virgin specimens irradiated at 840” and 900°C. tSpecimens e”, f”, g” and h” were previously irradiated at 520” and 670°C (specimens e, f, g and h); the neutron doses and length changes listed for the specimens irradiated at 840” and 900°C are those accumulated at 840’ and 900°C and are in addition to those due to the irradiation at 520’ and 670°C. Specimens e’, f’, g’ and h’ are virgin specimens irradiated at 840” and 900°C.
THE of the
INFLUENCE
materials
graphite
irradiated.
crystals,
For
these quantities
by direct measurement; it was necessary
OF CRYSTALLITE the
SIZE ON THE DIMENSIONAL
natural
were obtained
for the other materials,
to derive the crystallite
changes
carbon
are
function
plotted
in Figs.
of the irradiation
59
CHANGES la
and
1 b as a
temperature.
Similar
plots with a reduced abscissa for the catalytically graphitised
and
turbostratic
carbons
are
pre-
from the bulk changes by plotting ln( 1 + Al II/I1,) and ln(1 + Al,/ll) as a function of the corre-
sented in Figs. 2a and 2b. To facilitate
sponding parameters, Iill and R,, and extrapolating to R = 0 and R = 1. This procedure
Fig.
of the curves from Fig. 2a are plotted on Fig. la.
is based on the BACON formulation:
Near
son, the curves from Fig. 2 without
the data
of one another,
1 are also drawn points,
6OO”C, the rates
for the four materials
comparion
and a portion
of dimensional
change
are within a factor of four
but at 12OO”C, the strain rates
of the most and the least crystalline materials differ by over two orders of magnitude.
.
I
which
has been shown to be appropriate for materials.‘B* ‘9 12) The quantities pyrolytic
and In( 1 + A&/X,) are the ln(l + AX/-K) crystallite changes and are given by the ordinate intercepts
R =
at
the
were normalised (E >
abscissa
1, respectively. 0.18
graphite
values
R = 0 and
comparison,
all data
linearly to a unit dose of 1OZ1nvt
MeV). crystals
For The
and
data the
for
annealed
the
natural pyrolytic
FIG. 1b. Average crystallite growth rates, ln( 1 + AX,l Xc) per lOa nvt (E > 0.18 MeV), for natural graphite crystals and annealed pyrolytic carbon. 4. DISCUSSION The data in Figs. I and 2 provide picture
of the influence
on irradiation-induced carbonaceous
dimensional
materials.
These
perfection changes
data
in
together
with those reported
earlier(g= 7, 12f show that the
crystallite
growth
rates,
10Z1 nvt,
for dense
sizes less than FIG. la, Average crystallite shrinkage rates, ln(l + AX,Ix,) per lOa nvt (E > 0.18 MeV), for natural graphite crystals and annealed pyrolytic carbon.
a unif$ng
of crystalline
temperatures
ln( 1 +
materials
A-X,/X$.) per
with
crystallite
N 200 A saturate for irradiation above 1000°C at a value of N 0.4
Using the damage function calculated by THOMPSON and WRIGHT”*) and the fact that for large
interstitial
clusters,
the fractional
c-axis
J. C. BOKROS,
60
G. L. GUTHRIE
and A. S. SCHWARTZ
is smaller, heterogeneous the damage rate.oo-24) The dimensional line
behavior
carbonaceous
poorly
nucleation
phases
pret.oo-*a* 24) This dense crystallites,
difficulty
submicroscopic due
arises,
not
density
to
phases
defect
by irradiation,(8* the
densification
only
in small that
(present
inter- and intra-crystalline
sity) are densified strains
contain to inter-
nucleation
but also because
a substantial
that
is difficult
because of the heterogeneous contain
of the polycrystal-
conglomerates
crystalline
increases
as
poro-
‘* 10. 12) and provide
an
I .o
FIG. ?a. Average crystallite shrinkage rates, ln(l + A&/X,) per 10’1 nvt (E > 0.18 MeV), for catalytically graphitised carbon and turbostratic carbon. approximately
growth
atoms present
equals
found that a large fraction that
are
interstitial
the
in the interstitial
displaced
(-
sites. The
fraction
must
natural
of
clusters,(r@) it is
of the carbon
0.4)
c
atoms
end
graphite
up
at
crystals,
on the other hand, retain little damage at 1200°C and the crystallite
c-axis growth
orders of magnitude measured the
rates
are two
less. The values of AX,/X,
for these crystals are compatible
size
and
distribution
of interstitial
with loops
observed by REYNOLDS and THROWER in natural crystals
after irradiation
For irradiation the
high
produce may
be
vacancies
temperatures
survival c-axis due
at 1200”C.(8)
growth in
part
by diffusion
at lower temperatures for turbostratic
above N lOOO”C,
of interstitials
carbons
in sites
in turbostratic to
the
that
carbons
elimination
to crystal
defects,@)
the higher
growth
of but rates
with L, = 40 A (data
point
on Fig. 2 of ref. 6 and also the result of NETTLEY and MARTIN(~)) must be attributed to the heterogeneous
nucleation
of interstitials
FIG. 2b. Average crystallite growth rates, In( 1 + A&/ Xc) per lO*r nvt (E > 0.18 MeV), for catalytically graphitixd carbon and turbostratic carbon.
at
pre-existing crystal defects. At still lower temperatures near 2OO”C, the crystal growth rates appear to be controlled by homogeneous nucleation for materials with crystallite sizes greater than N 200 A; (4) however, when the crystallite
additional
unannealable
superimposed crystallite that the poorly
upon
shrinkage which is irradiation-induced
the
shape change.o*) irradiation-induced
crystalline
It should be noted densification of
phases is quite different
from
the densification of bulk carbonaceous conglomerates that occurs by the closure of large intra-crystalline cracks by irradiation-induced c-axis growth. (u) Because of these complexities, the purported that
verifications
use some selected
or rejections
ofmodels
set of “standard
single
crystal data” and are supposed to represent the behavior of some carbonaceous conglomerate
THE under
INFLUENCE
irradiation
are
and controversy When
not
always
SIZE
dimensional
ON THE
at about
convincing,
benefit
in this area abounds.
crystallite
calculated crystalline
OF CRYSTALLITE
changes
are
from dimensional changes of polyconglomerates after irradiation at
The
DIMENSIONAL
650°C
that more crystalline
temperatures.
quacies of the available portion
of phases
appears
present
effort
characterise
merates
if their
irradiation
to increase
carbonaceous
treatment
the raw materials in poorly case
in refs. 28 through
size by
may offer
the stability
of some
especially
when
histories
crystalline
conglomerates
of certain
isotropic
used such
graphites.
carbon,
graphite
above
sensitively
for natural
stability
under
hanced
when
carbon
irradiation the
during
at 2 lOO”C, the
is substantially
irradiation
during
cial graphite containing that
the
graphitisation
can be realised
additives most
en-
temperature
above about 700°C. PARKER et a1.(27) have reported densification
the
is
that increased of commermetal-
are used. They conjectured stable
graphites
rates become
would be those which densified
lite
increased
To test their supposition, treated
irradiated
with various
heat
additives
(together
bodies
prepared
with controls)
size
materials
with
temperature,
than
increasingly the
with
the
rate occurs
size increases.
These
results show that the change
dimension
to crystallite
is near 200°C
until
to The were
size when
and the crystallite
200 A. However, dependent
irradiation
these
on crystal-
temperature
at temperatures
near
is
12OO”C,
the rates vary by over two orders of magnitude with crystallite size. The dependence of the rate at which
the crystallites
for high density carbonaceous *For nuclear applications where the conservation of neutrons is important, it may be desirable to use a metal catalyst of low cross section, e.g. zirconium, or to remove the catalyst by purification after the graphitisation process.
1300°C. that
insensitive
as
size. The dimension
at first and then increase
with earlier
sizes are greater
irradiation
continuously
of about
as the crystallite
the irradiation
processing
a higher final density.
decreases
at which the minimum
are relatively
the most during they
change
rate at which the crystallites
under irradiation
and as a result had
5OO”C, the changes
irradiation
data together
if certain
dimensionally
increasing
and
about
for all of the other
temperature
at
on the crystallite
crystals
increasing
carbon,
that
temperatures
studied decrease
titanium*
pyrolytic
show
rate at which the crystallites irradiation
changes
annealed
graphitised
carbon
temperatures depend
dimensional
crystals,
catalytically
turbostratic
rates
of pyrolytic
are found
33.
The irradiation-induced
of
deposition
data on the
5. SUMMARY
under
the crystallite
with catalysts
cent
Further
a
for each
conglo-
is to be fully
and processing
atom-per
is needed
of catalysts on graphitisation
The data in Fig. 2 show that with the addition 2.7
is formed when a
in ref. 9 show that
condition.
aggregate.
It
data
of catalyst
influence
behavior
conglomerates,
The
amount
in natural
of improving
as in the
heat
graphite
must be made
temperature
means of graphitisation a method
critical
that
results from the fact
is used and further show that a real is realised only at higher irradiation
in the crystal-
carbonaceous
dimensional
at high
understood. The ability
result
in the
that a concerted
better
in Fig.
models, but a substantial
must be due to variations
linity to
material
may arise from inade-
little
the use of the additives.
with catalysts
the
graphitized
from
data in Fig. 2 show that the stability
is obtained catalyst benefit
catalytically
and found that relatively
accrued
temperatures above about 6OO”C, the data scatter in the areas on either side of the curve for 2.(26) Part of this scatter
61
CHANGES
change
dimension
materials
on their
crystallite size and the irradiation temperature is illustrated in Fig. 3. These dependences are qualitatively
consistent
with ideas due to REY-
NOLDS and THROWER which,
at a given irradia-
tion
the
temperature,
involve
heterogeneous
62
J. C. BOKROS, G. L. GUTHRIE
and A. S. SCHWARTZ
3. REYNOLDS W. N. and THROWERP. A., Phil. Mag. 12, 573 (1965). 4. KELLY B. T., MARTIN W. H. and NETTLEY P. T., Phil. Trans. Roy. Sot. London, Ser. A260,37 (1966).
5. NETTLEY P. T. and MARTIN W. H., Paper presented at the AIME Nuclear Metallurgy Symposium on High-Temperature Nuclear Fuels, Delevan, Wisconsin, October 1966. To be published. J. C. and PRICER. J., Carbon 4,441 (1966). 6. BOKROS J. C. and PRICER. J., Carbon 5,301 (1967). 7. BOKROS 8. REYNOLDSW. N., THROWERP. A. and SIMMONS J. H. W., Second Conference on Industrial Carbon and Graphite, p. 493. Society of Chemical Industry, London ( 1966). 9. SCHWARTZA. S. and BOKROSJ. C., Carbon 5,
CRYsrALLlTE DIMENSIONAL CHANQE
325 (1967).
10. BOKROSJ. C. and SCHWARTZA. S., Trans. AIME 239, 7 (1967). IRRADIATION
TEMPERATURE
FIG. 3. Schematic diagram showing the dependence on irradiation temperatu?e of the neutron-induced crystallite dimensional change rates for carbons with various crystallite sizes. nucleation spacing
of
interstitial
of heterogeneous
clusters nucleating
when
the
centers is
11. BOKROSJ. C., Carbon 3, 17 (1965). 12. BOKROSJ. C. and SCHWARTZA. S., General Atomic Report GA-7700, March 1967 (to be published). 13. BACONG. E., J. Ap~l. Chem. 6,477 (1956). 14. BOKROS.J. C., Carbon 3, 167 (1965). 15. PRICE R. J. and BOKR~SJ. C., J.‘Appl. Phys. 36, 1897 (1965’). 16. CARPENTERF. D. et al., In International Symposium on Developments in Irradiation Capsule Technology, Pleasanton, California, May 1966 p, 421 (D. R. HOFFMAN, ed.), USAEC Report CONF-6605 11
above a critical value.o* 3, s* a4) authors thank F. C. CARPENTER, B. B. SPILLANEand R. J. GRENDAfor incorporating the carbon specimens in the irradiation capsule; W. H. ELLIS and F. J. GAGNONfor performing a large portion of the experimental measurements; and G. W. HINMANfor the natural graphite crystals. The irradiations were conducted under USAEC Contracts AT(O4-3)-633 and AT(04-3)-167 (Project Agreement No. 12). The preparation of some of the carbon specimens was supported by the High Temperature Reactor Development Associates (HTRDA) Fuel and Fuel Cycle Development Program. The HTRDA group consists of 23 investor-owned electric utility companies located in the United States. Acknowledgments-The
REFERENCES
(1967). 17. REYNOLDSW. N. and THROWERP. A., Carbon 1, 185 (1964). 18. THOMPSONM. W. and WRIGHT S. B., J. Nucl. Mater. 16, 146 (1965). 19. KELLY B. T., Second Conference on Industrial Carbon and Graphite, p. 483. Society of Chemical Industry, London ( 1966). 20. DE HALAS D. R. and YOSHIKAWA H. H., Proceedings of the Fifth Conference on Carbon, University Park, Pennsylvania, 1961. Vol. 1, p. 249. Pergamon Press, Oxford (1962). 21. YOSHIKAWA H. H. et al., In Radiation Damage in Reactor Materials, Vol. IV, p. 581. IAEA, Vienna (1963). 22. YOSHIKAWAH. H., Carbon 1,201 (1964). 31 NIGHTINGALE R. E., COLLINS C. G. and __. MCGURTY 1. A., Proceedings Third Geneva Conference, United Nations, New York, Vol. 9, p. 35 1
1. SIMMONSJ. H. W., Radiation Damage in Graphite. Pergamon Press, Oxford ( 1965). 2. REYNOLDS W. N., In Chemistry and Physics of Carbon, Vol. 2, pp. 136-153 (P. L. WALKER, JR.
ed.), Marcel Dekker, New York (1966).
(P/254) (1965). 24.
KELLY B. T. et al., Second Conference on Industrial Carbon and Graphite, p. 499. Society of Chemical
Industry, London ( 1966).
THE
INFLUENCE
OF CRYSTALLITE
SIZE ON THE DIMENSIONAL
CHANGES
63
25. THROWER P. A. and REYNOLDSW. N., J. AJucl. Muter. 8, 22 1 ( 1963). 26. ENGLE G. B., General Atomic. Unpublished
30. KARU A. E. and BEER M., J. Appl. Phys. 37,2 179 (1966). 31. U.S. Pat. 3,260,614, July 12, 1966.
data. 27. PARKER W. E., MAREK R. W. and WOODRUFF E. M., Carbon 2, 395 (1965). 28. BANERJEEB. C., HIRT T. J. and WALKER P. L., Nature 192, 450 (1961). 29. BANERJEEB. C. and WALKER P. L., J. Ap~l. Phys.
32. YOKOKAWA C., HOSOKAWAK. and TAKEGAMIY., Carbon 4, 459 (1966). 33. YOSHIZAWA S. and ISHIKAWAT., In Symposium on Carbon, July 20-23, 1964, Nippon Toshi Center, III-PO. Carbon Society of Japan, Tokyo (1964). 34. LIDIARDA. B. and PERRINR., Phil. Mag. 14,433
33,229
(1962).
(1966).