NAA-SR-3085

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ATOMICS IN IE ^NATIONAL
— A DIVISION OF NORTH AMERICAN AVIATION, INC.
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 NAA-SR-3085
METALLURGY AND CERAMICS
31 PAGES

GAS BUBBLE FORMATION

IN
IRRADIATED PLASTICS
AND
REACTOR FUELS

BY:
G. G. BENTLE

ATOMICS INTERNATIONAL
A DIVISION OF NORTH AMERICAN AVIATION, INC.
P.O. BOX 309 CANOGA PARK, CALIFORNIA

CONTRACT: AT (11-1)-GEN-8
ISSUED:
OCT i 1959
 t

DISTRIBUTION

This report has been distributed according to the category ’'Metallurgy and
Ceramics” as given in ’’Standard Distribution Lists for Unclassified Scientific
and Technical Reports” TID-4500 (14th Ed.), October 1, 1958. A total of 605
copies was printed.

ACKNOWLEDGMENT

The author wishes to thank W. W. Kenagy for much of the laboratory work
done in connection with this report.

/■
 TABLE OF CONTENTS
Page No.
Abstract................................................ v
I. Introduction............................................ 1
II. Material................................................... 2
III. Irradiation Methods And Effects . 3
IV. Results And Discussion.... 6
A. Bubble Nucleation .... 6
B. Gas Diffusion and Bubble Growth 10
C. External Stress Effects 16
D. Irradiations Above 42°C . 18
V. General Discussion............................... 22
VI. Conclusions.......................................... 24
References......................................... 25

iii
 LIST OF TABLES

Page No.

I. Activation Energy for Bubble Growth....................................................... 15

LIST OF FIGURES

1. Weight Loss of Unirradiated Plastic as a

Function of Isothermal Test Temperature................................................ 3
2. Gas Evolution from Irradiated Plastic....................................................... 4
3. Effect of Existing Bubbles on Bubble Formation
(00-4726)............................................................................................................. 7
4. Effect of Temperature on Bubble Formation (00-4720) .... 7
5. Effect of Nucleation Sites on Bubble Formation
(00-4724) (00-4727) ......................................................................................... 9
6. Activation Energy for the Diffusion of Gas into Air............................ 11
7. Bubble Growth at 130° C after 6-1/2 hr
Irradiation at 42° C......................................................................................... 12
8. Activation Energy for the Diffusion of Gas into
Bubbles.................................................................................................................... 13
9. Bubble Growth at Various Temperatures................................................ 14
10. Activation Energy for Bubble Growth....................................................... 14
11. Bubble Growth in Compression Specimens (00-4722)............................ 16
12. Bubble Growth in Tensile Specimens (00-4729).................................. 17
13. Bubble Growth During and After Irradiation (00-4718) .... 18
14. Effect of Temperature and Composition on Bubble
Appearance....................................................................................................... 20
15. Effect of Nucleation Sites on Bubble Formation
(7504-4705D) (7504-4705B)........................................................................... 21

iv
 ABSTRACT

A transparent plastic, in which gas was formed by gamma irradiation, was

used to investigate the mechanisms of gas bubble formation and growth. Bubble
formation and swelling were studied for several environments, both external
and internal to the plastic-gas systems. During irradiation at 100° C, larger
but fewer bubbles form in the plastic than on lower temperature irradiation fol­
lowed by 100° C annealing. Angular inclusions were found to increase bubble
formation, and internal surfaces to promote bubble growth. Calculations in­
dicate that volume diffusion of gas from the plastic into air is faster than into
bubbles.
An interpretation of these results, when applied to nuclear fuel swelling,
indicates that swelling may be decreased by increasing fission rate and by de­
creasing the available sites for bubble nucleation and growth.

v
 I. INTRODUCTION

Fuel instability during irradiation imposes severe limitations on nuclear

power reactors. Large volume increases occur in uranium metal fuels under
high temperature irradiation which are attributed to fission gas accumulation.
O
About 4. 4 cm of the gases xenon and krypton (measured at standard conditions)
are formed per cubic centimeter of fuel per atom percent burnup. The gases dif­
fuse at high temperature, ^ and accumulate in bubbles within the metal fuel,
2
causing the metal to swell due to the pressure within the bubble.
In the present experiments, swelling was studied in polymethyl methacry-
late which was irradiated with gamma rays from a CoDU 60 source, at various

temperatures, to produce internal gas. The plastic-gas systems were also

given postirradiation treatments to study the effect of specific environments on
their behavior. The substitution of plastic for uranium, with their obvious dis­
similarities, is made on the basis that gases produced by irradiation in both
materials obey diffusion laws and cause internal voids and swelling. The mech­
anics and kinetics of bubble growth and swelling are therefore emphasized, and
comparisons of gross behavior are limited.
3
Barnes studied the production of bubbles in polymethyl methacrylate by
thermal decomposition and pile irradiation. He concluded that nucleation oc­
curred on pre-existing sites during thermal decomposition; but that nucleation
occurred without pre-existing sites if the gas concentration was high, e. g.,
during a high flux irradiation. He suggests that internal gas would be distributed
as many small bubbles in uranium after a low temperature irradiation plus an­
nealing. The small bubbles would act as gas collection sites during further ir­
radiation.

1
 II. MATERIAL

The specimens used for this investigation were taken from a single sheet
4
of 1/4-in. polymethyl methacrylate. Physical characteristics of this material
include a room temperature elongation at fracture of 2 to 3%, a softening point
of 125° C, and a thermal decomposition temperature of 180° C. The chemical
composition is:

0
II

C - OCH3
1
-ch2 - c -
I
CH3

The plastic exhibits a diffuse X-ray diffraction pattern typical of amorphous

materials.

2
 III. IRRADIATION METHODS AND EFFECTS

Unirradiated samples were held in air, at various temperatures up to 150° C,

and the weight loss measured. The weight loss of unirradiated samples vs an-
anealing time is shown in Figure 1.

3 -n

ANNEALING TIME (hr)

Figure 1. Weight Loss of Unirradiated Plastic as a
Function of Isothermal Test Temperature

From Figure 1, the weight losses are negligible after 15 hr at 130 and 150°C.
It appears that all of the gas on the surface and inside the samples is released,
and that thermal decomposition is negligible at these temperatures. No internal
bubbles formed and no swelling occurred.
Plastic samples were irradiated in the center of a hollow, cylindrical, kil-
00 source at an absorption rate of 1 x 10°0 r/hr. Most irradiations
ocurie CoDU
were carried out at an ambient temperature of 42° C, but the sample holder con­
tained a resistance heater for higher temperature irradiations.
Two irradiation procedures were followed:
1) irradiation at 42° C followed by postirradiation heating at tempera­
tures up to 150°C

3
 m

2) irradiation at temperatures up to 150 °C

The plastic discolored on irradiation, but remained transparent. It in­
creased from a Barcol hardness of 35 to 40, after 20 hr exposure at 42° C, and
was too brittle to test after longer exposure. The hardness of specimens did
not change on irradiation above 100° C for exposures up to 20 hr.
Mass spectrographic and density determinations of the gas evolved by the
heating of irradiated and unirradiated samples indicate that most of the gas is
carbon monoxide and carbon dioxide, with a small amount of methane and a
trace of hydrogen.
Plastic samples, after irradiation at 42° C for various times up to 64 hr,
were heated in a mercury bath under vacuum for 1/2 hr at 150° C. The volumes
of off-gas are shown in Figure 2. There was no visible indication of a chemical
reaction between the plastic and mercury. The weight loss of the samples is
attributed to the evolved gas. A gas density of 2 gm/^ is calculated from the
weight loss and volume of off-gas.

o—

SAMPLES IRRADIATED AT 42°C

FOR VARIOUS PERIODS AND
HEATED AFTER IRRADIATION

10 20 30 40 50 60 70
IRRADIATION TIME (hr)

Figure 2. Gas Evolution from Irradiated Plastic

4
 The weight loss of samples under irradiation at 130 and 150° C was measured
hourly for 8 hr. The weight loss was equal to that of unirradiated samples
which were held at the same temperatures (see Figure 1). The additional gas
3 , 3
produced on irradiation is about 0. 063 cm* gas/cm sample-hr, from Figure 2,
and is equal to 0. 0001 gm gas/gm sample-hr, a quantity within the weighing
error. Internal bubble formation and swelling during irradiation at 130 and
150°C prevented longer exposure.
Electron microscopy indicates that a slight granulation occurred during
irradiation. No bubble formation was observed in the thin films used for elec­
tron microscopy.

5
 IV. RESULTS AND DISCUSSION

The characteristics of bubble nucleation and growth were studied in irradi­

ated plastic as a function of nucleation sites, temperature, gas supersaturation,
gas diffusion rates, and stress. The data are used to calculate activation ener­
gies for gas diffusion and bubble growth.
A. BUBBLE NUCLEATION
No bubbles were detected at 100X in the plastic after 42°C irradiation for
100 hr. Subsequent heating in an oil bath caused bubbles to appear and grow.
The minimum temperature for bubble appearance was 50°C, in samples with
100 hr irradiation, and 150°C, in samples with 4 hr irradiation, when they were
heated at a rate of 0. 5°C/min.
The rate of bubble appearance and the bubble spacing varied with irradiation
time. With postirradiation heating after 20 hr of irradiation, bubbles appeared
instantaneously with a uniform, close spacing. After shorter irradiations, they
appeared slowly in a nonuniform, widely spaced pattern. Figure 3 (a) illus­
trates the nonuniform spacing and Figure 3 (c) illustrates the uniform spacing.
The sample surfaces were generally bubble free for various depths up to
1/16 in. The depth of this surface, from which the gas had apparently diffused,
was dependent on irradiation time and heating rate.
Bubble nucleation was studied under controlled conditions. The samples
in Figure 4 were irradiated at 42° C for 24 hr. They show approximately equal
numbers of bubbles after postirradiation annealing for 90 min at 100° C or 10
min at 112° C. The heating rate for both samples was about 0. 5°C/min to the
respective test temperatures. Bubble nucleation probably occurs below the
lowest temperature used for the test (100° C); otherwise, fewer bubbles should
be present in the sample which was held at the higher temperature for the
shorter period.
In samples irradiated for 80 to 100 hr at 42° C, bubbles appeared instanta­
neously after heating to 50 or 60°C. The gas concentration (extrapolated from
3 3
the curve of Figure 2) is 4 cm gas/cm plastic; the gas diffusion constant (ex-
-11 2
trapolated from Figure 8) is < 10~ cm /sec, and the final bubble spacing is
about 30 p. Nucleation is probably homogeneous under these conditions.

6
 (a) 4X (b) 4X (c) 4X

Figure 3. Effect of Existing Bubbles on Bubble Formation

(a) Irradiated at 42° C for 10 hr, and held at 130°C for 15 min.
(b) Sample (a) reirradiated at 42° C for 40 hr, and held at 83°C for 25 min.
(c) Irradiated at 42° C for 50 hr, and held at 83° C for 25 min.

(a) 4X (b) 4X

Figure 4. Effect of Temperature on Bubble Formation

(a) Irradiated 24 hr at 42°C, and heated at 100°C for 90 min.
(b) Irradiated 24 hr at 42° C, and heated at 112° C for 10 min.
 The temperatures for bubble appearance were higher than the temperatures
for appreciable bubble growth. A sample irradiated at 42° C for 40 hr was held
at 9(F C for 4 hours with no visible bubble formation. The temperature was
raised to 95°C, where visible bubbles formed in 30 min. The temperature was
then lowered to 90°C, and bubble diameters increased atruO. 2%/min. Probably,
the nucleation process occurred below 90° C, but it was necessary to raise the
temperature to 95°C to lower the surface tension and increase the gas pressure
in bubbles so that invisible bubbles could grow. Surface tension restraint dis-
3
appears when they grow to visible size.
The formation of bubbles in the presence of existing bubbles is illustrated
in the middle of the sample in Figure 3(b). A sample with the bubbles shown in
Figure 3 (a) was irradiated at 42 °C. On postirradiation heating, few bubbles
formed in the middle section near existing bubbles, but the existing bubbles grew,
another indication that the growth of visible bubbles is easier than their forma­
tion.
Figures 5 (a), (b), and (c) show plastic sandwiches bonded with methylene
dichloride, which forms a strong bond but leaves a visible interface. The three
sandwiches, formed from the samples after their respective irradiations, were
heated together. The growth of bubbles is apparently preferential at the inter­
face.
The sandwich in Figure 5 (c) was split along the interface and cut into four
pieces. These pieces were repolished to make the sandwiches in Figures 5 (d)
and (e). The sandwich in 5 (d) was bonded as before, but the one in 5 (e) was
bonded with powdered alumina added at the interface. On reheating together
(this time at a lower temperature) the existing bubbles grew slightly in both
sandwiches. Many bubbles formed at the interface containing alumina, while
few formed at the interface without alumina. Some gas may come from the
alumina. However, the alumina had been heated above the test temperature,
prior to use, to minimize its gas content.
It appears that alumina particles provide collection sites for gas which are
more effective than internal surfaces, but approximately equivalent to small
bubbles (Figure 5 (e)). The alumina particles have irregular surfaces, compared
to a plane interface, which may make them more suitable as nucleation sites.
Once bubbles are formed, however, the internal surfaces are easy paths for gas

8
 (a) 3X (b) 3X (c) 3X

(These samples were made by bonding the top half to the bottom half with methylene dichloride)
(After bonding, they were heated together to 130° C for 25 min.)

Figure 5. The Effect of Nucleation Sites on Bubble Formation

(a) Top and bottom halves unirradiated.
(b) Top half irradiated. Bottom half unirradiated.
(c) Top and bottom halves irradiated.
(d) Bonded without alumina.
(e) Bonded with alumina.

CO
diffusion, since bubbles at these interfaces grow much faster than in the bulk ma­
terial. The flat interfaces also give rise to lens-shaped bubbles which, with
other factors equal, grow more easily than round bubbles. Contributions to bub­
ble growth from the methylene dichloride are small (Figure 5(a)).
The driving force for nucleation probably comes from the heat of solution
of the gas. If a slight decrease in entropy occurs as the first few atoms are fixed
at a given site, bubbles could form more easily, providing the nucleation site
decreases this entropy change. The size of nucleation sites in the case of the
alumina (>5p) would probably nucleate bubbles large enough to be unrestrained
by surface tension.
B. GAS DIFFUSION AND BUBBLE GROWTH
Constants for gas diffusion into air and into internal bubbles were calculated,
and activation energies for both processes were found. The constants for gas
diffusion into air were calculated from the data in Figure 1 and the following
assumptions:
1) the gas evolved from the plastic between 0 and 3 hr is mostly ad­
sorbed gas
2) the gas evolved at 130 and 150° C, during annealing between 3 and 28
hr, is the amount in equilibrium solid solution (0. 3 wt %of 1. 6 cm^ of gas/cm
plastic from a measured gas density of 2 gm/Ji).
A diffusion constant was calculated for each of the four curves with the
formula0 which was developed for brick-shaped samples from Fick’s Law:

C 512abc 77
exp -Dt + +
Co 2a

where
the fraction of gas in the sample after time t,

one-half a sample dimension (length, width, or thickness) (cm),

2
D the diffusion constant (cm /sec),
t time (sec).

10
 Only the first term of the trigonometric series was evaluated for each of the
three dimensions of a brick-shaped sample, and the product of the three series
was set equal to . Figure 6 shows the variation in diffusion constants, from

Q = 6100 cal /mole

160 140 120

TEMPERATURE (°C)

RECIPROCAL TEMPERATURE (I03/°K)

Figure 6. Activation Energy for the Diffusion of Gas into Air

-7 -6 2
10” to 10” cm /sec, for the temperature range of 40 to 150° C. The activation
energy (Q) from Figure 6, for the diffusion of gas into air is 6100 cal/mole, which
agrees with the activation energies for the diffusion of gases in plastics and rub­
bers. ^
The diffusion rate of gas into bubbles was calculated from bubble diameter
measurements during postirradiation heating. Bubble diameters were measured
in samples which had been irradiated at 42° C for 6 to 60 hr, and then held at a
constant temperature where bubbles would grow. Figure 7 illustrates the growth
of a typical bubble at 130° C in a sample with 6-1/2 hr irradiation. Diffusion con­
stants were calculated, for bubbles from 0. 04 to 0. 4 mm in diameter, from the

11
equation: 1
q 4 77 a C0 (ot +

where
q = gas lost into the bubble,
a = final radius of the bubble, which is assumed to be reached
at once,
CQ= gas concentration in the sample due to irradiation at the be­
ginning of the anneal,
D = diffusion constant,
t = total time for growth from nucleation.

-8
Diffusion constants of 10
-9 2
to 10“ cm /sec were calculated
from bubble growth data, over a
temperature range of 80 to 130° C.
These were plotted in Figure 8
and an activation energy (Q) of
30, 000 cal/mole was found.
An activation energy of 30, 000
cal/mole seems high for gas dif­
fusion or other processes in a
plastic which may control bubble
growth. Incorrect assumptions,
a restricted temperature range,
and other factors could make it
unreasonably high. However, the
activation energy for diffusion may
change when diffusion is opposed
by a gas pressure (or gas partial
—6 2
pressure). The absolute diffusion rates, at 130° C, of 2 x 10” cm /sec into air
-8 2
(from Figure 6) and 2 x 10“ cm /sec into bubbles (from Figure 8) indicate that the
gas in the plastic matrix diffuses into the air much faster than into bubbles.
The effect of bubble size on growth rate was studied. Volume vs time was plotted

12
 Q= 30,000 cal/mole

TEMPERATURE (°C)

3 2.6 2.7 2.8

RECIPROCAL TEMPERATURE (I03/°K)

Figure 8. Activation Energy for the Diffusion of

Gas into Bubbles

for bubbles of comparable initial size at various temperatures, as in Figure 9.

The slopes of these curves are plotted in Figure 10 to obtain activation energies.
These activation energies, tabulated in Table I, are arbitrary numbers which may
represent bubble growth tendencies. Their absolute values seem large for bubble
growth in a plastic; but the relative order indicates that, at each irradiation level,
the smaller bubbles grow with most difficulty. Probable reasons for this are:
1) there is more matrix material around the smaller bubbles to re­
strict them; and,
2) easier diffusion paths such as microcracks in the matrix, are opened
to the bubble as it grows.
The effect of surface tension on the growth rate of visible bubbles is probably
q
insignificant. The activation energy for gas diffusion into bubbles, 30, 000 cal/
mole, is the same magnitude as the activation energy for bubble growth in Table I.

13
 TEMP IRRADIATION INITIAL BUBBLE
(°C) SLOPE TIME (hr) DIAMETER (mm)
5 - A 98.5 0.0141 20 0.69
O 103.5 0.0185 20 0.64
O V 106.0 0.0273 20 0.66
□ 108.0 0.0300 20 0.61

10 20 30 40 50 60 70
TIME (min)
Figure 9. Bubble Growth at Various Temperatures

GROWTH
TEMPERATURE
(cmVmin) (I0 b )

0=28,000 cal/mole
(for 0.7 TO 1.10 mm
Bubbles)-------
GROWTH RATE

6 104 l<
TEMPERATURE (°C)

2.62 2.63 2.64 2.65 2.66 2.67

RECIPROCAL TEMPERATURE (I03/°K)

Figure 10. Activation Energy for Bubble Growth

 TADLE I

ACTIVATION ENERGY FOR BUBBLE GROWTH

Sample Size of Bubble Lowest & Highest Activation Energy

Irradiation During Growth Temperatures For Growth
Time (hr) (diam in mm) For Growth (°C) (cal/mole)

6-1/2 0. 10-0.30 130-135 81, 800

6-1/2 0. 70-1.10 130-135 48, 000
6-1/2 1.40-2.00 130-135 42,200

20 0.30-0.60 98.5-108 51,700

20 0.70-1. 00 98.5-108 28, 200

20 1.00-1.30 98. 5-108 21,700

40 0. 10-0.30 89. 5-93. 5 86,000

40 0.20-0.40 89.5-93.5 84,800

40 0.40-0.70 89.5-93.5 61,300

15
C. EXTERNAL STRESS EFFECTS
Figure 11 represents a series of samples with similar treatments, except for

Figure 11. Bubble Growth in Compression Specimens

(Samples irradiated 24 hr at 42°C, and heated to­
gether at 104°C for 30 min under the compressive
loads indicated)

different external stresses during heating. The stresses were applied by weight­
ing one face of the samples. Small bubbles were present (not visible in the photo­
graph), in a number proportional to the external weight, but the visible bubbles
are most numerous with the intermediate weight. More bubbles are formed as
the compression is increased, but the intermediate stress cannot suppress their
growth. Bubble growth under a stress of 9 psi or greater is restricted, perhaps
because the pressure exerted on the matrix by the bubble is equal to or less
than the compressive stress. The compressive stress caused the samples to de­
crease up to 10% in thickness in the normal test period of 4 hr.
Compression should decrease the growth of large bubbles. The reverse

16
appears to be true in the samples stressed at 6. 5 and 7. 5 psi. This anomaly
suggests that the driving forces for bubble growth, such as heat of solution and
effective gas concentration, are increased by compression.
Figure 12 shows tensile test samples which were tested with and without

(a) 4X (b) 4X
Figure 12. Bubble Growth in Tensile Specimens
(a) Irradiated 22 hr at 42° C, heated at 105° C for 1 hr (unstressed)
(b) Irradiated 22 hr at 42° C, heated at 105° C for 2 hr (10 psi stress)

stress. A tensile stress of 8 to 10 psi was developed in the gauge section of the
stressed sample, which caused an elongation of 10% in 4 hr. The number of
bubbles formed in the gauge section was compared to the number formed in the
remainder of the sample. Twenty to thirty percent more bubbles were found in
the gauge section of the stressed samples than in the unstressed samples under
equivalent conditions. Figure 12 (b) indicates, however, that the test conditions
do not affect bubble growth, since the bubbles are of uniform size throughout,
even though the stress in the gauge section is greater than in the ends of the
sample. The expected growth under tensile stress may not occur, because of gas
loss to the air from the narrow gauge section. Gas escape, during heating in an
oil bath, was observed in nearly all samples. It was most rapid from cracks
which extended into the sample.
The reasons for increased nucleation under both compression and tension may
have something in common, such as the generation of microcracks to act as
nucleation sites.
D, IRRADIATIONS ABOVE 42° C
Samples were irradiated at 105, 130, and 150°C. Figure 13 (a) represents
a sample which was held at 130° C during a 6 hr irradiation, and Figure 13 (b)
represents a sample with 6 hr irradiation at 42° C, followed by 6 hr heating at
130°C. Plastic irradiated at high temperature grows fewer but larger bubbles

(b) 2X

Figure 13. Bubble Growth During and After Irradiation

(a) Irradiated 6 hr at 130°C
(b) Irradiated 6 hr at 42°C and heated 6 hr at
130°C after irradiation

than plastic irradiated at low temperature and annealed at high temperature. A

o
similar difference is noted in uranium. This is attributed partly to the gas con-

18
centration in the matrix, which is low during high-temperature irradiation, but
is relatively high after low-temperature irradiation. High gas concentration
causes much nucleation (Figure 13 (b) ) on heating, but low concentration and
high gas mobility on high-temperature irradiation allow the gases to diffuse long
distances to a few nucleation sites (Figure 13(a)).
A correlation was made, based on initial bubble appearance in samples pre­
pared by both high-temperature and 42° C irradiation and annealing. On high-
temperature irradiation, bubbles appeared initially between 2 and 3 hr at 150° C,
between 3 and 3-1/2 hr at 130° C, and between 6 and 7 hr at 105° C. However, no
bubbles appeared, after 42° C irradiation and postirradiation heating, under the
same time and temperature conditions. Some of the gas produced on irradiation
probably has a chance to escape from the sample after low-temperature irradia­
tion and standing (for several days), prior to postirradiation heating. The lower
gas concentration is expected to decrease the chances for nucleation.
Another experiment was performed, in which the possibility of gas escape
was minimized. Samples were treated in successive cycles of irradiation for 1
hr at 42° C, followed by heating for 1 hr at each of the respective test tempera­
tures: 105, 130, and 150° C. Little time elapsed between successive cycles of
irradiation and heating. Bubbles appeared after 8 cycles at 105°C and 5 cycles
at either 130 or 150° C. More time for gas loss to the air was available in this
experiment than during high-temperature irradiation, and the first appearance
of bubbles was delayed beyond those times noted for bubble appearance during
high-temperature irradiation. The variation in bubble appearance in the various
tests indicates that initial bubble appearance is fairly sensitive to gas concen­
tration.
Temperature-gas concentration relationships to cause initial bubble appear­
ance are shown in Figure 14. This plot generalizes high-temperature irradia­
tion behavior and the behavior after low-temperature irradiation and postirradi­
ation annealing. The plot was made as follows: From Figure 1, the unirradia-
3 3
ted plastic was shown to contain about 1. 6 cm gas/cm plastic (See Section IV-
B), which is called the equilibrium concentration. The gas produced in the
plastic on 42°C irradiation, followed by postirradiation heating for 1/2 hr at
150°C, is found from Figure 2 and is plotted as a percentage of the equilibrium
concentration on the abscissa of Figure 14. The ordinate of Figure 14 represents

19
 0.9

© ANNEALED AFTER 42 °C IRRADIATION

A HIGH TEMPERATURE IRRADIATION

0.5 --------------------------------------------------------------------------------------------------------------- ------------------

0 100 200 300
GAS SUPERSATURATION (percent of equilibrium)
Figure 14. Effect of Temperature and Composition on Bubble Appearance

the temperature ratio (T/Tm) for initial bubble appearance; where (T) is the
absolute temperature for initial bubble appearance, and (T^j) is 573° K, the as­
sumed melting point of the plastic. The plastic, of course, softens over a range
of temperature and decomposes, rather than melts. In Figure 14, the lower
curve represents initial bubble appearance during high-temperature irradiation;
and the upper curve, during heating at 0. 5°C/min after 42° C irradiation. Below
each curve, the gas is in solid solution; and, above each curve, the gas is seg­
regating into bubbles. After irradiation at 42°C and annealing at 100°C, the
3 3
plastic retains about 1. 5 cm gas/cm plastic; but, on irradiation at 100° C,
3 3
only 0. 5 cm gas/cm plastic is retained without visible bubble formation, a
quantitative indication of the effect shown in Figure 13.
Figure 15 shows 3 plastic sandwiches, one welded with methylene dichloride,
one welded with methylene dichloride with 5 p alumina in the interface, and a
third wetted with methylene dichloride but not welded. They were irradiated at
100°C for 2 hr. The largest number of bubbles was formed at the welded inter­
face containing alumina, a smaller number at the welded interface without

20
 (a)

2X

Interface
Interface
bonded interface
with bonded
only- unbonded
alumina

(b)

Figure 15. Effect of Nucleation Sites on Bubble Formation

(Two views of 3 plastic sandwiches irradiated at 100°C for 2 hr)
(a) Normal to the interface
(b) Parallel to the interface

alumina, and none at the unwelded interface or in the matrix of the specimens.
The fine alumina particles are the most effective nucleation sites; although, in
this experiment, some of the bubbles may have been formed with gas from the
alumina. Many bubbles formed at the welded interface without alumina, although
few bubbles formed in a similar sample during low temperature irradiation and
annealing (Figure 5(d)).

21
 V. GENERAL DISCUSSION

Any comparison of the behavior of plastic and uranium is limited by the

differences between their properties. While gross behavior is different, it is
assumed that processes related to swelling are similar. Similar processes are:
a) Gas flow appears to obey diffusion laws in plastic and in
5, 8
uranium. ’
b) Bubble nucleation and growth are sensitive to temperature and gas
concentration.^’ ®
c) Internal surfaces increase diffusion. ^
d) A few large bubbles are produced by high-temperature irradiation
and relatively many small bubbles are produced by low-temperature
irradiation and postirradiation heating. ^
Dissimilarities, other than property differences, are also evident:
a) The gases are more chemically active, more soluble, and diffuse
more rapidly in irradiated plastic than in irradiated uranium.
b) The bubble growth in plastic does not greatly deplete the available
gas in plastic, as it does in uranium. ®
With these similarities and limitations in mind, the following data on plastic
may provide corollaries for uranium:
a) Tensile stress, compressive stress, and increased gas concentra­
tion increase bubble nucleation.
b) Uniaxial compressive stress inhibits bubble growth only when the
compressive stress is great enough to cause considerable defor­
mation to the matrix.
c) Gas diffusivity decreases when opposing a gas pressure.
d) Existing bubbles, angular particles, and internal surfaces are ef­
fective centers for gas collection.
e) Bubble growth varies with bubble size, even beyond the size for
effective restraint from surface tension.
The data suggest that, if bubble formation and growth is also controlled by
stress and gas concentration in metal fuels, the fission rate may effect the num­
ber and size of bubbles in the fuel.
The total gas from fission, if distributed as many small bubbles, would

22
cause less swelling than if distributed as a few large bubbles, since the growth of
small bubbles is controlled by surface tension; whereas only fuel strength, a re-
3 11 12
latively weak restraint, controls the growth of large bubbles. ’ * Each gas
atom under high restraint in a small bubble occupies less space than under low
restraint in a large bubble. Increased fission rate, by increasing the stress and
equilibrium gas concentration, may increase the number of small bubbles, and
decrease swelling. However, it has been calculated that increased fission rate
will decrease swelling by also decreasing the time available under irradiation for
2
bubble growth.
Bubble growth in plastic is decreased by uniaxial compression. By analogy
to the behavior of plastic, the bubble growth which would occur in unrestrained
fuel slugs may be decreased by restraining the fuel with strong jackets.
13
In this study, and in other studies on aluminum and magnesium alloys,
foreign particles and internal surfaces appear to increase large bubble formation
and growth. Large bubbles:
1) add their own large volume to swelling
2) decrease the distance through which gas has to diffuse to reach a
bubble
3) connect to form lens shaped voids and cracks.
If impurity particles are accidentally increased by poor fuel melting practice,
large nonuniformly space particles seem to result which would lead to large,
interconnected bubbles on irradiation. However, the bubbles formed on increased
fission rate (due to the increased stress and gas concentration) appear to nucleate
homogeneously, and would grow with random distribution from essentially zero
diameter. Bubbles homogeneously nucleated would be within the size ( <1000 A)
range where surface tension restraint is very large; whereas bubbles, hetro-
geneously formed on impurity particles greater than 1 p in size, would probably
be as large as or larger than the particles on which they nucleated. Therefore,
with other factors equal, nuclei-free, coarse-grained fuel should swell the least.
This argument neglects the effects of increases in fuel strength, which may be
caused by increasing impurity content, but such increases are calculated to have
14
little effect at moderate burnup rates.

23
 VI. CONCLUSIONS

In irradiated plastic:
1) Bubble nucleation is increased by either compression or tension
on the sample, and by increased gas concentration.
2) Bubbles nucleate readily at impurity particles in the matrix, less
readily at internal surfaces, and least readily in the pure matrix.
3) A few large bubbles are produced during high-temperature irra­
diation, and relatively many small bubbles are produced during
low-temperature irradiation and postirradiation heating.
4) Bubble growth is more rapid for bubbles which form at internal
surfaces than for bubbles formed within the matrix.
5) Bubble growth is decreased by a compressive stress.
6) Bubble growth rates increase with bubble size.
By analogy to the behavior of irradiated plastic, the data indicate that, in
metal fuel:
1) Increased fission rate will decrease swelling by increasing the
formation of small bubbles, since their growth is controlled by
large surface tension restraint.
2) A single-phase, coarse-grained fuel, free of nuclei, will swell the
least, by decreasing the formation and growth of large bubbles
which are restrained only by the matrix, a restraint which is much
less than surface tension restraint.
3) A few large bubbles will be produced on high-temperature irradia­
tion and relatively many small bubbles will be produced on low-
temperature irradiation and postirradiation heating.
4) If large restraints are imposed on fuel slugs by heavy jackets, the
growth of large bubbles will be decreased.
5) Bubbles formed by homogeneous nucleation will tend to remain
small and bubbles formed on large particles and grain boundaries
will grow relatively large.

24
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