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Determination of the Single Interstitial Migration Energy

From Stored Energy and Thermal Resistivity Changes
____________________ in Irradiated Graphite*________________
Eg;
-3
Donald G. Schweitzer
Brookhaven National Laboratory
Upton, New York NASIL
Abstract

The model used to evaluate the single interstitial migration energy

from property changes due to interstitials is extended to account for vacancy

contributions. The annealing function obtained can be used to determine the

relative contributions of the defects and is sufficiently sensitive to distin­

guish vacancy effects that are an order of magnitude less than interstitial

effects.

Application of the model to stored energy and thermal resistivity data

yields the same values of the activation energy and temperature independent

terra obtained from c-axis and macroscopic length expansion rates. The

results indicate that the stored energy associated with the di-interstitial is

at least ten times greater than the stored energy associated with the vacancy.

•This work was performed under the auspices of the U. S. Atomic Energy
C ommission.
LEGAL NOTICE
ne me emmms * Qmeeme =mm
, e m3 = •e

e==-m = “ mem •e

e smem e •e Cne

• me we l ——
 * - • em • —m • e = *

The minor role of vacancies in phonon scattering is discussed.

Analysis of the annealing function obtained from electrical resistivity

changes in irradiated graphite indicates that the ratios of charge-carriers

to scattering centers varies with irradiation temperature below 55°C. Above

this temperature the changes are attributed to equal contributions from

vacancies and interstitials.

) -2-
 introduction

In other work‘1) the migration energy of the single interstitial and the

absolute rate of displacing atoms by neutrons were determined from c-axis

and macroscopic length expansion rates by assuming that these changes were

proportional to the rate of formation of di-interstitials.

In this paper the model is extended to account for rates of property

changes with irradiation (dPg/dnvt) which can be described by

dP dP, dP
i v
ar —— 4 ...... (for integrated flux t C nvt) (1)
dt dt dt

The contribution to the rate of change from the di-interstitial is

dPi 2 (2)
dt= a dt
and from the vacancy is

dPv (dv
dt-bd (3)

where a and b denote temperature independent proportionality constants.

The models are applied to stored energy, thermal resistivity, and

electrical resistivity changes in order to determine the relative contributions

of vacancies and interstitials to these properties.

-3 -
►
 Sensitivity of the Annealirg Function to Vacancy Effects

The rate of di - inter st ft ial production through the reactions

o(fast neutron) ♦ C°(graphite) - C,+v(vacancy) K (4)

(5)
C1 * C1 - C 2

C1 + trap - CjT (6)

was shown to be(1)

I2-K.k e -(E/2RT)
dt 4 (7)

where the rate of annealing (R ) is given by the right term of equation (7).

Since the single interstitials anneal to traps. the rate of vacancy

production is temperature independent and is given by

dv = (8)
dt = K
For property changes described by reaction (1), substitution from

equations (2), (3), (7), and (8). gives

dP
__ s
= a[K - RJ + bK = K(a*b) - aR (9)
dt

where the temperature independent term is now"•

dP
K(a-b) = (dP/A)^ > at’ (10)

-4 -
 The term K(a-b) can also be evaluated from experiment’ 1) by ex-

pressing it as the product of a constant (x) and the observed rate of change

of the property at 30°C.

K(a+b) - x(dPs/dt)300c • x[(dP/dt)300c + (dP,/dt)] (11)

Equating (10) and (11)

x(dP,/dt)30°c + x(dPv/dt) = (dP,/dtooK + (dPv/dt) (12)

where (dP,/dt),og (from c-axis expansions") is given by

(13)
(dP,/dtoPK - 2.5(dP,/dt)30Pc
Equation (12) expressed in terms of vacancy and interstitial rates is now

(2.5-x)a(dCa/dt)30°c = (x-1)b(dv/dt) (14)

The rate terms can be eliminated from (14) by the relations

(dC„/dt).g = Kdv/dt) (15)

(dc,/dt)300c = 2e(dc,/dt)ok = E(dv/at),"• (16)

to yield

b _ 2.5-x
a 5(x-l) (17)
1

-5 -
 Thus, if the property measured reflects both vacancy and interstitial

effects, the annealing function

aR a = x(dP s /dt),o (18)

30°C - (dP/dt),
s T

can be used to obtain their relative contributions through equation (17). For

changes due only to interstitials, Ps = Ps and x =2.5.

The sensitivity of the annealing function to vacancy effects can be

demonstrated by using values of x lower than 2.5 and noting the variation in
activation energy from the assumed standard of 0.037 ev.‘1 This method gives

the error in activation energy when a property dependent on interstitials is

incorrectly assumed to reflect both vacancy and interstitial contributions.

Table 1 gives representative data that yield an activation energy of

0.0370 ev when the annealing equation is plotted for x = 2.5. Figure 1 shows

an Arrhenius plot of this function along with one obtained from the same values

of dP/dt for x = 2.0. It is seen that a 35% increase in activation energy occurs

when the assumed vacancy contribution is only 1/10 of the interstitial contribu­

tion. For lower values of x the plot shows curvature at the higher tempera­

tures. When vacancies and di-interstitials actually change a property to the

same extent (b/a = 1), a value of x equal to 1.25 should give a linear plot with

an activation energy of 0.0370 ev.

I - 6-
 Table 1
Annealing Function [aR = 2.5(dP/dt) 0 -(dP/dt, ] for E =0.0370 ev.
3l 3 C I

aR
dP/dt 1/T, OK a
1.000 0.0033 1.500
0.934 0.0032 1.566
0.865 0.0031 1.635
0.794 0.0030 1.706
0.720 0.0029 1.780
0.641 0.0028 1.859
0.559 0.0027 1.941
0.464 0.0026 2.036
0.385 0.0025 2.115
0.293 0.0024 2.207
0.195 0.0023 2.305
0.094 0.0022 2.406
0.000 0.0021 2.500

- 7-
 Application to Stored Energy Data

Figure 2 shows an Arrhenius plot of the annealing function calculated

from stored energy accumulation rates (R ) obtained by various investigations,

s
(2)
The data of Rappeneau and Quetier * did not include measurements at

an irradiation temperature of 30pC and were normalized with the data of Bridge
(3)
et al. by matching stored energy releases for irradiations at 100°C. (The

rate of accumulation of stored energy at an irradiation temperature of 100°C

20
is 30 cal/g/10 nvt in reference (3). The value of the exposure at 100°C cor­

responding to a release of 30 cal/g was taken from the data of Rappeneau and

Quetier and the releases after this exposure at other irradiation temperatures

were used to calculate the rates.)

(4)
The data of Davidson for exposures cf 193 Mwd/AT were replotted

directly. The experiments of Rappeneau and Quetier represent stored energy

released at 400°C while the other measurements were obtained from tot.l

stored energy accumulations.

It can be seen that all the data yield the same activation energy when

the temperature independent term is 2.5 times the rate observed at 30°C.

The value of the activation energy (0.037 ev) is the value obtained from macro­

scopic and c-axis expansion rates.

-8 -
 Vacancy and Interstitial Effects on Thermal Resistivity
and Electrical Resistivity Changes_ Y
a
Electrical resistivity") changes and thermal resistivity^6' changes

at 30°C have been reported for graphites irradiated at various temperatures.

Comparison of the annealing functions of these data with other property

changes indicates that the electrical resistivity changes are not proportional

to the number of vacancies or interstitials generated by irradiation whereas

the thermal resistivity changes reflect properties of interstitials.

The annealing equations are plotted in Figure 3 where the electrical

resistivity and thermal resistivity data are compared with a typical curve ob-

tained from either macrosccpic length expansion rates, c-axis expansion rates,

or stored energy accumulation rates. The initial fractional rates of increase

of thermal resistivity with irradiation were calculated from the data points
(6)
at ~200 Mwd/AT. The fractional rates of increase of electrical resistivity
18 2(5)
where taken from the slopes from 0 to ~10 n/cm . It can be seen that

the thermal resistivity data fulfill the criteria for successful application of

the first model but the electrical resistivity data do not satisfy either model

at temperatures below 55°C.

Graphite is a material in which the thermal conductivity at low tem-

(6 7)
peratures is determined by the specific heat/ ‘ At higher temperatures,

1
 heat conduction is determined by the mean free path for phonon scattering (A),

which Debye has shown to be proportional to reciprocal absolute temperature.

The intrinsic parameters of graphite are such that the value of A at about 200°K

(7)
is of the order of the crystallite size in synthetic graphites. At higher tern-

peratures, A decreases because of thermal scattering and the thermal resistivity

should become insensitive to crystallite size above some minimum value. The

effect is supported by the observation that the room temperature thermal con­

ductivity of polycrystalline nuclear graphites is about the same as that of single

crystal natural graphite.

Boron doping of graphite, causing large changes in the charge-carrier

(8)
population, only slightly effects the thermal conductivity. Since electronic
(6)
contributions to the thermal conductivity do not play a significant role in graphite,

(9)
possible charge trapping properties of the vacancy can be neglected. The

vacancy effect on scattering is probably limited to the plane in which it is formed

and can be assumed to be similar to the scattering effect of grain boundaries.

On the other hand, the interstitial will perturb at least two planes over a volume

that may be considerably greater than the effective scattering area of a vacancy.

Correlations al high temperatures, of dimensional annealing with the

annealing of radiation induced thermal resistivity changes, are not necessarily

useful in supporting or contradicting the assumption that the thermal resisitivity

changes

-10-
 reflect properties of di-interstitials. Annealing presumably involves cluster-
(6)
ing of di-interstitials and the relative scattering effects of different clusters

may vary in an independent manner from the relative changes in dimensional

parameters. Comparisons at the first stages of annealing (~-200°C) after 30°C

irradiations (where the di-interstitials are the predominant species) are per­

haps more valid. In this temperature region, the thermal resistivity data and

the dimensional data show the same reverse annealing/ 10

Electrical resistivity changes are expected to depend on the number of

charge-carriers and the number of scattering centers."5,9,11 Interpretation

(12)
of older work to show that the electron trapping rate caused by neutron

(13)
damage is constant, is not supported by recent work which shows that the

trapping efficiency of irradiation defects at low temperatures changes with

measuring temperature. The shape of the resistivity function in Figure 3 may

be due to changes in the ratio of charge-carriers to scattering centers with

irradiation temperature. The linear increases in fractional electrical resistivity

(at low doses) then are not sufficient evidence to conclude that the resistivity changes

are proportional only to the concentration of defects. The slope of the electrical

resistivity curve at low temperatures is seen to be greater than the slope of the

linear annealing functions, while at high temperatures it is less. It was shown

that corrections accounting for differences in relative contributions of vacancies

and interstitials will not

- 11 -
2 yield a curve with such a shape. (If, during irradiation, interstitials anneal
to vacancies and sinks simultaneously" 14 neither the rate of change of inter-

stitials nor vacancies can be described by the annealing function plotted in

Figure 1 . No property would then be expected to yield a linear plot.) It is

worth noting that the resistivity curve is Linear above 55°C, the curvature below
this temperature extending to -75°c.65 H it is assumed that the data above

55°C can be treated by the model described in this work (i.e-, the ratio of

carriers to scattering centers only varies below 55°C), then equation (18) can

be modified by the relation

2.5(dP/dt)300 = 2.9(dP/dt)550 (see Table 1). (19)

The relative vacancy and interstitial parameters are now given by

b 2.9-x (30)
a = 5.8(x-1) *

The data above 55°C then yield an activation energy of 0.037 ev for b/a ~ l.

-12-
 Conclusions

The model used to account for interstitial property changes during the

first irradiation can be modified to account for vacancy contributions. Appli­

cation of the models to stored energy and thermal resistivity changes shows

that both of these properties depend mainly on interstitials. This interpreta­

tion is supported by the observation that stored energy releases at 400°C fit

the same annealing function for total stored energy releases. Equivalence

would be expected if the number of interstitials that anneal at a given tem­

per atu re is a fixed fraction of the total interstitial concentration. The same

assumption applied to vacancy annealing would not be reasonable because of

(15)
the large value of the migration energy for this defect.

The small value of the stored energy associated with a vacancy suggests

that the theoretical estimates for the relaxation at the vacancy are probably
. (16) n . , g .. _th.
too low. If a high relaxation energy for the vacancy Signifies that the

disturbed region adjusts to minimize the energy between the perturbed and

unperturbed lattice, the minor role of the vacancy in phonon scattering is not

surprising. The effect might also account for the small changes in Lattice
(6)
parameter in the "a" direction relative to the large* changes in the C-axis.

Electrical resistivity changes at all irradiation temperatures can not

be accounted for by either of the models considered. The shape of the annealing

-13-
function for these data below 55°C are attributed to variations with tempera­

ture in the number of charge-carriers per scattering center. The resistivity

changes above 55°C then result from equal vacancy and interstitial contribu­

tions.

- 14 -
 References

1. D. G. Schweitzer, Phys. Rev. 128, No. 2, 556 (1962).

2. J. Rappeneau and M. Quetier, "Proc, of the Fifth Conference on Carbon"

(Pergamon Press, New York, 1962), p. 322.

3. H. Bridge, B. T. Kelly, and B. S. Gray, ibid., p. 296.

4. J. M. Davidson, US/UK Graphite Conference, TEO-7565 (Pt. 1), p. 18 (1959).

5. G. H. Kinchin, Proc, of the Conf, on Peaceful Uses of Atomic Energy (United

Nationa, New York), Vol. 7, p. 472 (1955).

6. R. E. Nightingale, “Nuclear Graphite” (Academic Press, New York, 1962).

7. J. G. Castle, Jr., "Proc. of the First Conf, on Carbon” (Waverly Press,

Baltimore, Md.), p. 13 (1956).

8. J. C. Bowman, J. A. Krumhansi, and J. T. Meers, Paper presented at the

Society of Chemical Industry Conference on Industrail Carbon and Graphite

(London) (1957).

9. G. R. Hennig and J. E. Hove, Proc, of Conf, on Peaceful Uses of Atomic

Energy (United Nations, New York, 1956), Vol. 7, p. 666.

10. W. K. Woods, L. P. Bupp, and J. F. Fletcher, ibid., p. 455.

11. J. E. Hove, Proc, of the First and Second Conf. on Carbon (Waverly Press,

Baltimore, Md.), p. 125 (1956).

- 15 -
12. G. R. Hennig, J. Chern. Phys. 20, 1443, 1448 (1952).

13. G. L. Montet, Nuclear Sci. and Eng. 15, 69 (1963).

14. G. J. Dienes and A. C. Damask, "Kinetics of Vacancy-Interstitial An-

hihilation: III. Interstitial Migration to Sinks.” Accepted for publica-

tion in Phys. Rev.

15. G. J. Dienes and G. H. Vineyeard, "Radiation Effects in Solids” (Inter-

science Publishers, Inc., New York, 1957).

16. C. Baker and A. Kelly, Nature 193, 235 (1962).

- 16 -
 3

Figure Captions
1
Figure 1 Annealing function vs. reciprocal temperature.

Figure 2 Annealing function from stored energy data.

Figure 3 Annealing (unction from thermal resistivity and electrical

resistivity data.

- 17 -
 4

o
ANNEALING FUNCTION vs RECIPROCAL TEMPERATURE
4 T T T T T T

H
CL
0
a
—
«0-- 2
P
d:
x =2.5
■o
--
Mt E=.0370 eV
M
•
(X
x = 2.0

♦
E =.0505 eV

1 — 1 1 _ _ i 1__ —I
2.0 2.2 24 2.6 2.8 3.0 3.2
IOOO/T (°K)

FIGURE 1
/
#

IO
T T T T T
9
RATE OF ANNEALING SINGLE INTERSTITIALS
8
FROM STORED ENERGY DATA
7

5 ■ DAVIDSON STORED ENERGY

DATA
• BRIDGE et al, STORED ENERGY
4 DATA
o RAPPENEAU 8 QUETIER
STORED ENERGY DATA
C
△ SCHWEITZER, C-AXIS DATA
3
O
r
E =0.037 eV
C
m
CM
M

1 — I |
2.2 2.4 2.6 2.8 3JO 3.2
IOOO/T CK )

FIGURE 2
 RATE OF ANNEALING FUNCTION vs IRRADIATION
TEMPERATURE
IO T T T T T T

9 -

8 —

6 -

Z 5 -
D

Q TYPICAL CURVE FOR C-AXIS. MACROSCOPIC

LENGTH AND STORED ENERGY DATA
tr 4 -
CD
or
«

— 3 -
THERMAL
C
। RESISTIVITY
9 DATA

M
C
o 2 — ELECTRICAL
CM
H
RESISTIVITY
Po DATA

1 1 1__ 1__ 1__ —1

1 —
2.0 2.2 24 2.6 2.8 3.0 3.2
IOOO/T CK)

FIGURE 3