[ 539 1

The Growth of Fission Gas Bubbles in Irradiated

Uranium Dioxide

By R. M. CORNELL
Central Electricity Generating Board, Berkeley Nuclear Laboratories,
Berkeley, Gloucestershire

[Received 2 February 1968 and in final form 28 October 19681

ABSTRACT
The growth of fission gas bubbles from supersaturated solution in irradiated
uranium dioxide has been studied by electron microscopy under isothermal
annealing conditions between 1300" and 1500"~. Measurements of the
kinetics of bubble growth have enabled the diffusion coefficients of atomic
xenon and krypton in irradiated uranium dioxide to be determined. The
diffusion coefficients obtained may be expressed by the equation:

0 = ( 2 . 1 + l.l)lO-'exp
[
-91 000; 14000

The results obtained from the current experiments are believed to be more
precise than most of those obtained using the Booth model for gas released
from solid samples of irradiated uranium dioxide during a post-irradiation
anneal.

5 1.
INTRODUCTION
WHEN uranium dioxide is irradiated a t temperatures >900°c it is
probable that the fission product gases will precipitate t o form gas bubbles
due to their extreme insolubility. It is believed that the release of these
gases from uranium dioxide fuel irradiated above this temperature is in
part controlled by the growth and migration of these bubbles. It is
valuable therefore to establish the diffusion coefficients for xenon and
krypton atoms in irradiated uranium dioxide since if gas bubbles are
formed then their growth in the early stages will be controlled by the
migration of these gases to existing nuclei. However, if gas bubbles
are not formed in any quantity due to irradiation-induced re-solution, then
the accumulation of gas in bubbles at the grain boundaries will still be
controlled by the atomic d8usion of xenon and krypton through the lattice.
Attempts have been made by many workers to determine the diffusion
coefficients for atomic xenon and krypton over the temperature range
1000"-1700"c (Booth and Rymer 1958, Susko 1968, Belle 1959, Lindner
and Matzke 1959, Auskern 1960, Belle, Auskern, Bostrom and Susko 1961,
Stevens, MacEwan and Ross 1961, Davies and Long 1963) using the
Booth model (Booth 1957) for gas released from a lightly irradiated sample
540 R. M. Cornell on the
during a post-irradiation anneal. Values obtained a t 1200'c ranged from
4.7 x 10-14 to 5.6 x lO-l9cm2/sec.
Due to the very wide range of values obtained for the diffusion constants
by these workers it appears opportune to evaluate the diffusion constants
for gas atom migration in irradiated uranium dioxide by an alternative
method.
The diffusion constants for xenon and krypton atoms in uranium dioxide
irradiated a t 8 0 0 " have
N ~ been determined from the rates of growth of
the gas bubbles on isothermal annealing between 1300" and 1500"~.

$ 2 . PREVIOUS WORK
I n a recent review (Childs 1963) 17 measurements of the diffusion
coefficients of krypton and xenon in irradiated uranium dioxide are
listed. The activation energies for the diffusion are found t o vary from
24-128 kcals/mole. Such a variation cannot be explained solely by
experimental error and it seems likely that in many instances incorrect
characterization of the fuel, excessive burn -up and non-stoichiometry
effect are sources of possible variations. The method employed is to
measure the release of xenon or krypton into the swept or evacuated
space surrounding a sample during a post -irradiation anneal. Diffusion
constants are deduced from such experiments using the appropriate
solution of the diffusion equation for small gas releases from a series of
uniform spheres.
However, it is known that gas atoms become trapped in the material
during the annealing treatment even if the irradiation dose is very low
(MacEwan and Morel 1965). The analysis used in the Booth model
ignores the presence of traps and therefore will not be expected to give
consistent or accurate values for the diffusion coefficients.
However, a theory for the diffusion of fission gas from a sphere taking
into account trapping and return from the traps has been evolved.
(Hurst 1962). Experiments carried out on the release of xenon and
krypton from an irradiated uranium dioxide sample during a post-
irradiation anneal have been analysed utilizing this theory (MacEwan
and Stevens 1964, MacEwan and Morel 1965) and gave activation energies
of 87 kcals/mole for gas atom diffusion and diffusion coefficients approxi-
mately 30 times those obtained in the current experiments a t the same
temperature.
$ 3 . KINETICSOF BUBBLE GROWTH
If uranium dioxide is irradiated below about 9OO"c the gas atoms do
not agglomerate into observable gas bubbles. When thin foils of such
material are isothermally annealed between 1300' and 1 6 0 0 " ~fission
gas bubbles are observed t o nucleate and grow from the supersaturated
solution. Measurements taken from individual bubbles throughout
a series of isothermal anneals of known duration enable the mean rate
 Growth of Fission Gas Bubbles in Irradiated Uranium Dioxide 541
of growth of the bubbles to be determined. Effects due to coalescence
of bubbles are not included in the results since enlargement of the bubbles
produced this way does not involve the precipitation of further gas atoms
as required in the growth formulae. I n all cases it is assumed that the
forces derived from the gas pressure and surface tension are in equilibrium.
The theory of bubble growth from supersaturated solution has been
formulated (Speight 1968) and will not be reproduced here in detail.
The instantaneous rate of change of gas concentration in the lattice is
given by (Ham 1958) :
dc - -3RDc
-_-
at a3 ’
. . . . . . . . (1)

where D is the gas atom diffusion coefficient, R is the bubble radius, c is

the instantaneous gas atom concentration in the lattice and 2a is the
bubble nucleation spacing. If the average concentration of gas in the
lattice drops from an initial value co atoms/cm3to a level c, then on average
a bubble collects $na3(c,-c) gas atoms. Hence, assuming perfect gas
behaviour then it can be shown (Speight 1968) that

where y is the surface energy of uranium dioxide.

The solution of eqns. ( 1 ) and (2) gives the following bubble growth
equation :
-
In [ R ,+R] -
--3DRA
Rt-R a3
where R , is the final bubble radius after complete precipitation of the
gas and t is the annealing time. However, since the gas bubbles are
very small the perfect gas equation is not strictly applicable and Van der
Waals’ equation should be used instead. The exact solution of eqn. (1)
and a modified eqn. ( 2 ) ) assuming Van der Waals’ behaviour, is rather
complex but an approximate solution is given by :

and

where b is the Van der Waals) gas constant, R , is the radius the gas bubble
would have if it were filled with ‘ perfect ’ gas and t, is the time taken
for it to attain this size. R is the actual radius of the Van der Waals’
gas bubble holding the same number of gas atoms collected in a shorter
time t .
542 R. M. Cornell on the
Replacing R, and t, in eqn. (3) leads us to the modified growth equation :
R I
1 d(1+ 2yb/kTR,) + d(1+ 2yblkTR)
2/1+ 2yb/kTR In R * (6)
d(1+ 2yb/kTR,) - .\/(1+2yblkTR) 1
The left-hand side of this equation plotted against the time of the
anneal enables the dBusion coefficient for atomic xenon and krypton
to be obtained from a knowledge of the final bubble radius, the mean
bubble spacing, the Van der Waals' gas constant b and the surface energy
of uranium dioxide y.

3 4. EXPERIMENTAL
WORK
The uranium dioxide used in this experiment was taken from a Mark 2

-
fuel pin irradiated in the Windscale A.G.R. to a total burn-up of
4270 MWD/Te (U) ( 0.55 atomic yo burn-up heavy atoms) a t a mean
rating of 14.3 MW/Te (U). The maximum temperature of the fuel during
irradiation was not greater than 800"c.
Slices of the fuel 1.0cm diameter and approximately 0-9mm thick
were cut from the pin using a remotely operated diamond saw and discs
of 3mm diameter were obtained from the uncracked outer regions of
the slices using a centreless diamond drill. The discs were reduced in
thickness using standard metallographic techniques to approximately
0.01mm and then electropolished to form thin foils using the standard
technique (Whapham and Sheldon 1963).
Discs were mounted in a standard Philips EM200 electron-microscope
sample holder and examined before annealing to confirm the absence
of bubbles. Samples were repeatedly annealed in a furnace for intervals
varying from 5 min a t 1600"c t o two hours a t 1300"~. In each case
the temperature was maintained constant to -I 3"c using an Ether stepless
temperature controller. I n all cases the furnace atmosphere consisted
of hydrogen containing 1% by volume of water-vapour t o preserve the
stoichiometry of the sample (Roberts, Brock, Findley, Frost, Russell,
Sayers and Wait, 1965). After each annealing treatment samples were
replaced in the sample holder in exactly the same position as before and
photographed a t the same magnification and tilt position.
The photographic plates were printed on sheet film at a linear
magnification of approximately 3 x lo5 and the growth of a series of
bubbles followed to completion in a particular area by measurement
of the diameters of individual bubbles. I n all cases the changes in diameter
of about 30 bubbles, whose radii varied by not more than a factor of 2 ,
were measured throughout the annealing treatments and the average
increase of radius calculated. Bubbles which disappeared from the
foils or coalesced during the annealing treatments were not included
in any of the results.
 Growth of Fission Gas Bubbles in Irradiated Uranium Dioxide 543
The number of gas bubbles observed in a given area of foil was measured
after each annealing treatment and plotted against the time of the anneal.
The thicknesses of several foils were calculated from the number of Bragg
fringes observed occasionally a t wedge -shaped edges and were found
to be approximately 15008. This value was adopted as representative
of the thickness of all foils for the purpose of establishing bubble densities.

$ 5 . RESULTS
The change in bubble radius with annealing time a t each temperature
in the range 1300"-16OO"c is plotted in fig. 1 whilst the data are summarized
in table 1. Figure 2 shows a series of photographs of an area in a thin
foil of irradiated uranium dioxide after repeatedly annealing a t 1300"~.

Fig. 1
l o , , , , , , . . . . . , , , , . , I ,

The increase in gas bubble radius with annealing time for the four annealing
temperatures 1300", 1400", 1600" and 1600"~.

The effect of increasing the temperature of the annealing treatment

is to raise the average size of the gas bubbles and to reduce the time needed
for total precipitation. I n each case a rise in annealing temperature
of 1OO"c reduces the time taken for the growth to appear to be completed
by a factor of 3.
The density of gas bubbles observed in any foil falls, as the annealing
proceeds, due to coalescence and loss of bubbles from the foil. The
rate of reduction is greatest a t 1600"~. Due to this density decrease
 Table. 1

1300% 1400'~ 1500"~ 1600"~

~
I I
Left-hand Left-hand Left-hand Left-hand
Annealing Bubble side of Annealing Bubble side of Annealing Bubble side of Annealing Bubble side of
time radius time radius time radius time radius growth
1(' equation (mk) 1(' equation (min) (A) equation (min) (4 equation

30 12.9 0-105 30 0-230 25.1 0-228 5 44.1 0.768

120 16.5 0.171 45 :::: 0-309 1 1; 30.8 0.348 0.839

240 19-8 0.252 75 33.1 0.430 30 35.7 0.499 lo

15 I f:: 0.904

360 21.5 I 0.304 I 135 1 37.8 I 0.630 I 60 I 40.6 I 0-760 20 46.4 0-992

480 23-8 0.394 195 40.1 0.812 75 42-4 0.968 25 47-0 1.089

1- 25-9 0-510 255 41.8 1.087 90 43.4 1-196 30 47.5 1.214

720 27.2 I 0.614 375 42.5 1.401t 120 43.9 146t 35 47.9 1.3677
1I II 11 I1 11 II
Iterative Iterative Iterative
840 28-0 0.703 co 42.8 final m 44.2 final co 48.5 final
radius radius radius

960 28.6 0.805

~~

1080
Iterative
m 29.8 final
radius

t At this point growth appears to be completed.

 Growth of Fission Gas Bubbles in Irradiated Uranium Dioxide 545

Fig. 2

(c) (4
Photomicrographs of the same area of a thin foil of irradiated uranium dioxide
annealed for (a)2 hours, (6) 8 hours, (c) 14 hours and ( d ) 18 hours at
1300"~.
two values are taken for the mean density representing the probable
spread likely to be relevant during the growth of the bubbles. The
first value considered is the initial value a t very short annealing times
( 5 min) and the second value is the value when R=O.QR, during the
annealing treatment. Figure 3 shows the number of bubbles/cm3
plotted against reciprocal temperature for the two cases above, This
shows that the bubble density is inversely proportional to the absolute
temperature between 1300" and 1 6 0 0 " ~ .
546

5.0 5.5 60 6.5

10.000 (OK)
1
The variation of gas bubble concentration with annealing temperature.

Fig. 4

ANNEALING TIME bsl

The plot of the growth equation versus annealing time for the four annealing
temperatures.
 Growth of Fission Gas Bubbles in Irradiated Uranium Dioxide 547

The left-hand side of the growth equation (eqn. (6)) is plotted against
annealing time for the temperatures 1300°, 1400" and 15OO0c, in fig. 4.
(The value of R, used in eqn. (5) is discussed later.) The results indicate
that eqn. (6) corrects reasonably well for the bubbles being small. The
remaining curvature in the lines is probably caused by the non-equilibrium
between the gas pressure inside the bubbles and surface tension. No
way of correcting for this variation has been attempted. Least-squares
lines are fitted t o the four sets of results and make small non-coincidental
intercepts on the y axis. The failure of these lines to pass through the
origin is probably due to the error mentioned above and to the impreciseness
of the growth equation a t very small bubble radius rather than to the
presence of pre-existing bubble nuclei in the as-irradiated material.

The variation of the gas atom diffusion coefficient with annealing temperature.
548 R. M. Cornell on the
The slopes of the lines for each annealing temperature are measured
from fig. 4 and from a knowledge of the final bubble radius and the bubble
spacing (obtained from fig. 3), the coefficients for rare gas diffusion are
obtained for each temperature since D = 2*3a3(slope)/3R,.
An Arrhenius plot of the logarithm of the diffusion coefficient D versus
the reciprocal of the absolute temperature is shown in fig. 5 . The
activation energy for the diffusion process derived from the slope is
91 f 14kcals/mole and a value of (2.1 & 1.1) 10-4cm2/sec for Do.

Q 6. DISCUSSION
During the annealing of irradiated uranium dioxide over the temperature
range 1300"-16OO"c it may be assumed that a stable cluster which can
grow further is formed when an associated pair of gas atoms meet another
gas atom (Whapham and Sheldon 1965). It is further assumed that
vacancies will always be available in sufficient numbers t o be non-rate-
controlling. The binding energy between gas atoms as well as the
nucleation of gas bubbles is discussed in greater detail elsewhere (Speight
and Cornell 1968).
Thin foils examined carefully in the early stages of annealing failed
to show any increase in the number of bubbles observed with increasing
annealing time. As far as can be seen no incubation period for bubble
nucleation exists and therefore bubble nuclei must be formed extremely
early in the annealing treatment, certainly in less than 5min above
1500"~.
Changes in individual bubble radii were measured throughout the
growth process between 1300" and 1600"~. I n these experiments the
measurement error was probably & loyo, but since all the bubbles
measured a t any one annealing temperature were not of the same size
(their diameters did not vary by more than a factor of 2), the total error
on any individual measurement has t o include a factor allowing for its
variation from the mean size of all the bubbles. I n order to improve
the accuracy of the measurements, results were taken from a series of
growing bubbles and the rate of increase of the average bubble radius
obtained. Only bubbles which could be positively identified throughout
the growth processes were used. Typical results from the anneal a t
1 3 0 0 " ~are shown in table 2.
The variation on the mean bubble radius is 0 1 2 ~ ~ 1 2where
, n is the number
of measurements and u is the standard deviation of the values measured ;
from all the values of the bubble radii measured this is determined t o be a
maximum of +3.8yo. When the mean bubble radius equals 0-9Rf
it can further be shown that the error in the left-hand side of the growth
equation is approximately rt 10% (corresponding t o i-3.8% standard
error on the mean radius). Thus, if in the left-hand side of the growth
equation the criterion is adopted that i- 10% error is acceptable, results
on the growth of bubbles can be used with R < 0*9Rf.
 Table 2. The growth of fission gas bubbles at 1300"~. (Bubble radii in millimetres)
~~

Bubble 0.5 hr 2 hrs 4 hrs 6 hrs 8 hrs 10 hrs 12 hrs 14 hrs 16 hrs 18 hrs
No.
1 0.60 0.68 0.95 1.20 1-45 1.45 1-65 1.70 1-75 1.75
2 1.05 1-30 1.40 1.53 1.65 1.68 1.73 1-75 1.83 1-85
3 0-85 1.03 1.10 1-13 1-20 1.40 1-55 1-60 1.75 1-75
4 0.70 1.10 1.35 1-40 1.45 1-55 1-55 1.60 1.68 1.70
5 0.70 0.80 0.95 1-23 1.45 1-50 1-50 1.55 1-60 1.60
6 1-35 1.55 1.60 1.60 1-60 1.65 1.68 1-73 1.80 1.80
7 1.35 1.70 1.90 2.00 2-00 2.00 2.05 2-05 2.00 2.00
8 0.80 1.00 1.10 1.15 1.25 1.45 1.45 1.50 1-58 1-60
9 0.75 0.85 1-03 1.35 1.48 1.65 1.75 1-88 1-88 1-88
10 0.70 0.85 0-95 1.15 1-30 1.55 1.60 1-70 1-70 1.70
11 0.80 0.90 1.10 1.25 1.40 1-65 1-85 1.95 1.95 1.95
12 0.65 0-85 1-05 1-20 1.40 1-50 1-55 1-63 1.65 1.65
13 0.70 0.75 1.05 1.15 1.20 1.38 1-48 1-60 1-70 1.70
14 0.70 0.85 1.05 1-15 1-25 1.45 1-50 1-60 1-68 1.70
15 0.65 0.85 1-15 1-15 1.25 1-45 1.45 1.48 1.58 1.60
16 0.70 0.95 1.30 1.50 1-75 1-80 1-85 1.90 2.00 2.00
17 0-60 0.83 1.20 1.30 1.45 1-70 1-80 1.90 1.90 1.90
18 0.83 1.10 1.35 1.45 1-55 1.75 1.75 1-85 1.90 1.88
19 0-55 0.75 1-05 1-15 1.30 1.60 1.68 1.70 1.75 1.75
20 0.80 0.95 1.25 1.30 1-55 1.75 1.85 1.90 1.90 1.93
21 0.85 1-15 1.30 1-33 1-48 1-60 1.65 1.68 1-68 1.68
22 0.65 0.78 0.98 1.15 1.25 1.30 1-38 1-43 1.43 1-43
23 0.65 0.95 1.15 1.25 1-25 1.45 1-50 1.50 1.55 1-55
24 0.63 0.88 1-05 1.10 1.30 1.30 1.45 1.55 1-55 1.50
25 0-63 0.85 1.10 1.15 1.20 1-20 1-30 1.30 1.35 1-38
26 1.15 1.30 1.40 1.40 1-45 1.45 1.50 1-50 1-50 1.50
27 0.55 0.75 1-00 1-08 1.23 1.45 1.60 1-65 1-65 1.65
28 0.58 0-95 1.20 1.20 1.38 1.48 1.53 1.55 1-60 1.58
29 0.55 0.90 1.05 1.10 1-35 1.48 1-70 1-75 1.73 1.75
N 30 0-65 0.83 1.00 1.15 1.35 1-43 1.53 1-58 1.60 1-60
0 31 0.80 1.05 1.10 1.15 1.35 1.50 1-50 1.50 1-53 1.53
32 0.68 1.02 1.25 1-35 1*45 1.45 1.53 1-53 1-55 1.55
33 0.55 0.83 1-03 1.15 1-30 1-35 1.45 1.45 1.45 1.45
34 1.05 1.10 1.10 1.15 1.30 1.43 1-50 1.60 1.65 1.65
35 0.65 1.00 1-13 1.25 1.43 1.45 1.48 1-50 1.55 1.55
550 R. M. Cornell on the
Examination of the results in table 1 shows that only the first six values
a t 13OO0c, and the first four values at 1400" and 1 5 0 0 " ~can be utilized
before the error in the growth equation exceeds & 10%. The values
a t 1600"c all unfortunately lie outside the range of 0.9R,and are therefore
inadmissible. However, it is interesting to note that if all the 1600"c
experimental values are accepted and a diffusion coefficient obtained
in the usual manner then the value obtained, 4-2 x 10-15 cm2/sec lies
extremely close to that obtained by extrapolation of the results in fig. 5.
During the experiments growing gas bubbles were very occasionally
observed to coalesce and also to disappear from the foils. However,
the former process normally took place only after long annealing times,
when R approached R,. Both effects lead to a small increase in the
bubble spacing and for this reason the bubble spacing parameter contains
an error of & 3 yo,since for the purposes of calculation all diffusion coefficients
were obtained from the average of the two values for a obtained from
fig. 3. The foil thicknesses were taken as 15008 but the actual thicknesses
were probably 1500 f 250 6 which introduced another f 5% error into
the bubble spacing. Since the diffusion coefficient obtained is proportional
to u3 (the volume surrounding each growing nucleus) their values vary
by f 25% due t o these two effects.
Whilst the gas bubbles were growing it was observed that a slight
random bubble movement took place. Under these circumstances some
sweeping up of gas atoms by the growing bubbles could take place.
Since the growth of the gas bubbles by this mechanism is not taken into
account in the theoretical analysis, errors will be introduced into the
diffusion coefficients depending upon the amounts of gas swept up by the
growing bubbles.
However, the magnitudes of the random bubble migration distances
were small relative to the mean bubble spacings and the results obtained
a t 1 4 0 0 " ~illustrate this fact. Utilizing the data of Gulden (1967),
obtained on identical material to that used in these experiments and
annealed in a similar manner, a t 1400"c the root -mean-square migration
distance for a 3 0 6 radius 'mean gas bubble' is - 4 5 8 after 64 hours

-
annealing. The total volume explored in a series of random jumps

-
by this ' mean gas bubble ' can be shown to be 5 x 10-19 om3, compared
with a value of 1-5x 1O-l' cm3 for a3, and therefore the migrating
' mean gas bubble ' only absorbs 3% of its total gas content due to
N

sweeping. This will represent an upper limit since the diffusion

coefficients determined here are all obtained from bubbles growing to
0.9R,. Thus, the sweeping up of gas atoms by the growing gas bubbles
will introduce only a small error into the diffusion coefficients determined
here.
On the very few occasions that coalescence was observed, the bubbles
involved were seen to lie very close together so that the distance migrated
by the bubbles for this to occur was considerably less than the bubble
spacing. I n any case this effect was most marked a t 1600"c and as these
 Growth of Fission Gas Bubbles in Irradiated Uranium Dioxide 551
values are not being used in the determination of the diffusion parameters
this effect can be ignored. Another source of uncertainty lies in the
accuracy of bubble size measurement ; the electron microscope magnifica-
tion error is approximately +_ 1% here. A series of photographs were
taken under a variety of reflection conditions of an area containing gas
bubbles in a foil annealed for several hours at 1500"~. A range of
reflections was used and the sign and magnitude of the excitation error ' S '
changed in each case. Examination of the diffraction patterns showed
that in all cases low-order reflections predominated, with either (11l ) ,
(200) or (220) appearing. The excitation error was found to be positive and
variable throughout. High-order reflections were extremely uncommon.
It is well known that low-order reflections do not produce appreciable
visible strain contrast (Brown and Mazey 1964) and the apparent diameter
of the bubbles appeared to be the same on all the negatives in which
the bubbles could be reasonably viewed. Hence no apparent changes
in gas bubble diameter were brought about by slight changes in the
reflection conditions during the experiment.
I n the as-irradiated condition samples contain 3.3 x loL9gas atoms/cm3
N

since ~ 1 4 . 2 %of the fission products are xenon and krypton. If the
regions of the sample used in these experiments are considered to be
of plate-type geometry, then theory predicts that between 8 and 40%
of the gas generated within the sample would be released by atomic
diffusion during the growth process at 1300" to 1500"c respectively if
no traps were present in the sample, no bubbles formed and assuming
the diffusion coefficients determined here. Using the Van der Waals'
gas equation to determine the number of gas atoms in a small bubble
and assuming a value of 103ergs/cm2for the surface energy of uranium
dioxide, 88 +. 12, 95 +_ 5 and 76 f 9% of the gas generated within the
samples are found in the gas bubbles after growth is completed at 1300",
1400" and 1600"c respectively. The limits on the gas concentrations
are determined from the variations in the bubble concentrations, bubble
radii and the foil thickness. Thus, within the accuracy of the experiment
a very large proportion of the fission product gases can be accounted
for within the bubbles at the end of the growth process.
Since the number of fission gas atoms which escape from the samples
without being trapped in the bubbles appears to be quite small, then
eqn. (1) will quite accurately describe the rate of change of the gas
concentration in the lattice with time. Realising that the loss of gas
atoms from the sample causes a lower diffusion coefficient to be measured
than actually exists it can be shown that a 10% loss of gas from the sample
during the annealing treatment brings about an approximately 74 %
error in the diffusion coefficient.
Throughout these experiments the value of the surface energy of
uranium dioxide was taken as 1000ergs/cm2. If a f50% variation
is made in this parameter, the values obtained for the diffusion coefficients
will all alter by approximately f 12+%. However, the activation energy
2 0 2
552 R. M. Cornell on the
value determined here is unlikely t o be affected since the variation in
the diffusion coefficient brought about by a change in the surface energy
is almost independent of temperature.
It can be seen from table 1 that at some stage in the growth process
no further increase in the bubble diameters could be detected and a
final bubble radius was assigned to the results a t each annealing
temperature. However, it is likely that growth was still taking place
but a t such a slow rate that other physical processes such as coalescence
and loss of bubbles from the foil predominated and made establishment
of the true final bubble radius impossible. Since this value could not
be determined with absolute certainty an iterative final bubble radius
was determined for each annealing temperature such that all the experi-
mental values could be plotted in fig. 4 with the least deviation from a
straight line. The values established for the iterative final bubble radii
are shown in table 1, and compare very favourably with the measured
values. The error introduced into the activation energy by ignoring
this correction is approximately 1 kcal/mole.
The diffusion coefficient a t 1 4 0 0 " ~obtained from these experiments
is approximately 3 x 10-ls cm2/sec, whilst the commonly accepted value
for this temperature is approximately 5 x 10-15 cm2/sec (Davies and
Long 1963). The latter authors' results are obtained using the Booth
model for gas released from small irradiated uranium dioxide spheroids
during a post-irradiation anneal. A probable explanation for the
discrepancy between the present results and those of Davies and Long lies
in the fact that their diffusion coefficients are very sensitive to the value
taken for the equivalent sphere radius a. The apparent diffusion coefficient
D'=Da-2, where D is the real diffusion coefficient and D is normally
evaluated via the product D'a2. Examination of Davies and Long's
experimental results showed that a considerable variation existed in
their equivalent sphere radius values for apparently identical batches
of material. This fact coupled with the rather low quality of some of
their batches of material suggested that the accuracy of their results
may not be high.
Further, since all the spheroids tested were polycrystalline it seems
likely that the diffusion path for the gas atoms could be shorter than
the assumed equivalent sphere radius (29-125 p in this case) and lie closer
to t,he grain size which must have been 15-30 p say. Once a gas atom has
reached a grain boundary it is likely t o diffuse along i t until it reaches an
open surface from which it can escape. Under these circumstances the
diffusion coefficients measured will all be lower by up to an order of
magnitude, which would bring the two sets of results into closer agreement.
It is interesting to note that Davies and Long also included in their
experimental results some values of the diffusion coefficients for fused and
annealed spheroids of N 1 5 p grain size and 6 0 p diameter. Here, their
results were quite different and lie very close to those of the present
experiments. The smaller physical size of these sphercids relative to
 Growth of Fission Gas Bubbles in Irradiated Uranium Dioxide 553

the grain size could be further evidence of the true diffusion path being
smaller than the equivalent sphere radius as invoked above.
Some observations of the growth of gas bubbles in annealed irradiated
uranium dioxide have been published (Whapham and Sheldon 1965).
The results suggested to these workers that the growth of gas bubbles
in such material is much more rapid than would be expected from the
diffusion coefficients measured by Davies and Long at 11OO"c and 1300"c
and in agreement with their value a t 1 5 0 0 " ~ . These results, however,
are not in agreement with those of the present experiments which are
more in line with currently accepted values.
The values obtained for the diffusion coefficients in this experiment
are for both fission product gases and not for xenon or krypton separately. 1

However, none of the reported data indicates any significant difference

between the values for the diffusion coefficients of xenon or krypton and
therefore comparison between the results of this work and those of others
involving mainly xenon is reasonable.
Trapping of gas in lightly irradiated samples has been shown (MacEwan
and Morel 1965) to be confined to pre-existing porosity. For these
samples a value for the activation energy of the migration of gas atoms
of 87kcals/mole was obtained which agrees very well with the results
of the present work. Unfortunately the ' true diffusion coefficients '
from which this value is derived are approximately twenty five times
larger than the values obtained in the present work a t the same temperature.
It has recently been shown (Matzke 1965) that inert gas atoms do not
migrate by vacancies on the uranium sub-lattice and it is inferred from
further evidence (Lichtenberger 1965, Long, Stanaway and Davies 1964)
that they do not migrate by vacancies on the oxygen sub-lattice either.
Thus it is most likely that the inert gas atoms migrate interstitially or as
a complex since vacancies are also required by the growing bubbles and it
is possible that gas atoms migrate associated with either uranium or
oxygen ion vacancies or both.
The agreement of the experimental results with the theoretical model
is better than was expected a t the outset of the work and gives confidence
in the results obtained. This confidence is only diminished by the failure
of the lines to pass through the origin in fig. 4 ; the reason for this
discrepancy is not fully understood.

9 7. CONCLUSIONS
Measurements of the growth of gas bubbles from supersaturated solution
on annealing irradiated uranium dioxide has been used t o obtain the
diffusion coefficients of migration of atoms of xenon and krypton in the
temperature range 1300"c-1500"c in this material. The diffusion
coefficients may be expressed by the equation:

D = ( 2 . 1 f 1.1)10-4exp
(- 91 000 & 14000)
RT
554 On the. Growth of Pission Gas Bubbles in Irradiated Uranium Dioxide
It is suggested that the results of the present experiments are more
precise than the majority of those obtained using the Booth model for
gas released from solid samples during a post-irradiation anneal since
the true gas atom diffusion path is likely to be considerably different from
the equivalent sphere radius established for the material. Trapping
of gas atoms upon internal porosity will also introduce further errors
into the experimental results obtained using this model.

ACKNOWLEDGMENTS
This paper is published by permission of the Central Electricity
Generating Board.
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