International Conference on Advancements and Futuristic Trends in Mechanical and Materials Engineering (October 5-7, 2012)

i
Punjab Technical University, Jalandhar-Kapurthala Highway, Kapurthala, Punjab-144601 (INDIA)


Space Radiations and Its Effect on Ultra High Temperature Resistant
Polymeric Nano Composite
1
H. M. S. Iqbal,
1
R. Benedictus and
2
S. Bhowmik
1
Faculty of Aerospace Engineering, Delft University of Technology, Kluyverweg 1, 2629 HS Delft,
The Netherlands
2
Singapore Institute of Manufacturing Technology, 71, Nanyang Drive, Singapore, 638075
E-mail: s.bhowmik@tudelft.nl

ABSTRACT

This investigation highlights effect of space radiation especially gamma and electron radiation on ultra high
temperature resistant polymeric nanocomposite based on Polybenzimidazole (PBI) and Carbon Nano Fiber (CNF).
Thermal and mechanical properties of PBI and PBI nanocomposite were investigated using thermogravimetric
analysis (TGA) and tensile testing. It is observed that due to dispersion of CNF into polymer matrix there is a
considerable improvement of tensile strength. It is further observed that when the basic PBI is exposed to gamma
and electron radiation there is considerable deterioration of tensile strength however, due to inclusion of CNF into
PBI matrix the extent of deterioration of tensile strength reduces. Therefore, it can be concluded that CNF might
have acted as radiation barrier material that could absorb high energy radiation.

Introduction
Polymeric materials are widely used in spacecraft
for load bearing structures, antennas, fuel tank,
electrical insulation, sealant, thermal control coating
and many other applications. These materials are
ideally suited for space applications due to their light
weight, flexibility in use, good thermal and electrical
insulation properties, and ease in manufacturing [1 -
5]. Depending on the applications, materials are
exposed to high vacuum, thermal cycling, high
energy UV radiations, atomic oxygen and high-
energy electrons, protons and heavy ions. Over a
design lifetime of 20 years, a satellite in
geosynchronous earth orbit could be exposed to a
high-energy radiation dose of about 1520 MGy, or
possibly more in some circumstances [4, 6]. These
high energy radiations in space are one of the main
concerns regarding the thermal, mechanical and
optical properties of these materials. Therefore, it is
important to understand the effect of these high
energy radiations on polymeric materials.
In this context, efforts are made in present work to
study the effects of different radiations on thermal,
mechanical and optical properties of PBI.





Experimental
Materials
26% concentrated solution of Polybenzimidazole
(PBI) in Dimethyleacetamide (DMAc) was supplied
by CELAZOLE, PBI performance products. 99%
concentrated N,N-Dimethylacetamide (DMAc) is
purchased from Aldrich chemicals. Carbon
nanofibres were supplied by Pyrograf Products, Inc.
with diameter ranging from 70 nm to 200 nm and
length ranging from 50 m to 200 m.
Solution casting of PBI and nano-filled PBI
films
Nano-composite films of PBI were prepared
using 2 wt% of CNFs. pre-calculated amount of
CNFs was carefully weighed and then added to the
DMAc solvent. These nanofibers were dispersed in
DMAc by ultrasonic mixing for 30 minutes at 60 C.
After ultrasonic mixing of CNFs, they were added to
PBI solution. The ultrasonic process in combination
with mechanical stirring was continued for next 15
minutes. The mixture was then used to cast the film
on the glass plate. Films were prepared in the same
way as the films prepared from unfilled PBI.

International Conference on Advancements and Futuristic Trends in Mechanical and Materials Engineering (October 5-7, 2012)

ii
Punjab Technical University, Jalandhar-Kapurthala Highway, Kapurthala, Punjab-144601 (INDIA)


Exposure to Electron radiations and Gamma
radiations
Unfilled and nano-filled PBI samples were
irradiated at LEONI Studer Hard AG, Switzelands.
The samples are exposed to electron and gamma
radiations with energy of 1 MeV. The samples were
irradiated with gamma radiations and electron
radiations for a total dose of 100 KGy and 1000 KGy
respectively. The dose rate at the sample positions
was approximately 4 kGy / sec.
Characterization
Thermal Gravimetric Analysis (TGA)
Thermal gravimetric analysis (TGA) was
conducted to study the effect of radiation on thermal
stability of unfilled and nano-filled PBI. Tests were
performed using Perkins Elmer Thermal Analysis
Instrument (Pyris Diamond Thermogravimetric
Analyzer). The weight of all the samples was
maintained between 4 to 5 mg. The samples were
heated from a temperature range of 25 C to 550 C
at a heating rate of 10 C/min. The furnace was
purged with nitrogen gas at a flow rate of 25ml/min
to prevent oxidation.
Tensile Testing
Tensile testing of irradiated unfilled and nano-
filled PBI films was carried out using Zwick tensile
machine at a test speed of 2 mm/min. Rectangular
specimens of 80x6x0.06 mm
3
were cut from
controlled and irradiated samples. An extensometer
was also used to determine the Youngs Modulus and
strain values. Three to five specimens for each
material were tested for the reproducibility of the
results.
Results and Discussion
Thermal gravimetric analysis (TGA)
TGA curve of unexposed PBI has shown two
steps decomposition as shown in figure 1. The initial
weight loss occurred between 40C and 200C is
around 10%. This weight loss occurred due to
evaporation of water. After first degradation step, a
stable plateau is appeared until a temperature of
400C. Only 2% weight loss occurred from 200C
and 400C which indicates that PBI exhibits high
thermal stability up to the temperature of 400C.
After this temperature, PBI has shown second
thermal degradation step but still this is not a sharp
degradation step. PBI has exhibited high thermal
stability even up to a temperature of 550C and
revealed only 16% weight loss. The loss in weight in
second degradation step was due to the loss of
gaseous products. At very high temperature,
ammonia and methane evolved from heterocyclic and
aromatic ring respectively [14].


52
62
72
82
92
102
0 100 200 300 400 500 600
M
a
s
s

(
%
)
Temperature (C)
PBI-C PBI-E
PBI-G PBI-M

Figure 1 Comparison of thermal stability of
controlled sample of unfilled PBI and PBI samples
exposed to Electron, gamma and mixed radiations

TGA curve of irradiated PBI samples in figure 1
revealed that exposure of PBI to different radiations
has not altered the thermal stability of PBI at low
temperature. However, these radiations have
improved the thermal stability of PBI at higher
temperature. The improvement in thermal stability is
more pronounced for the samples exposed to gamma
radiations and mixed radiations. Samples irradiated
by electron radiations have shown a slight increase in
thermal stability at high temperature. The total dose
value of electron irradiated PBI samples was high as
compare to the dose value of gamma radiations and
mixed radiations. At low dose values, it is expected
that radiations has induced cross-linking effect in the
polymer. As the dose value is increased, chain
scission reactions also started. But the net affect of
electron radiations in this study is radiation induced
cross-linking which resulted in slight increase in
thermal stability of unfilled PBI. Exposure of PBI to
gamma radiations and mixed radiations has
eliminated the second degradation step and polymer
has maintained a stable plateau until a temperature of
550C. These results indicate that chemical thermal
stability of unfilled PBI is not affected by irradiation.
Samples of PBI reinforced with CNFs were also
exposed to various radiations. Figure 2 represents a
comparison of thermal stability of controlled and
irradiated samples of nano-filled PBI.
International Conference on Advancements and Futuristic Trends in Mechanical and Materials Engineering (October 5-7, 2012)

iii
Punjab Technical University, Jalandhar-Kapurthala Highway, Kapurthala, Punjab-144601 (INDIA)


52
62
72
82
92
102
0 100 200 300 400 500 600
Temperature (C)
M
a
s
s

(
%
)
PBI- 2CNF- C
PBI- 2CNF- E
PBI- 2CNF- G
PBI- 2CNF- M

Fig. 2 Comparison of thermal stability of controlled
sample of nano-filled PBI exposed to Electron,
gamma and mixed radiations

TGA curve of baseline nano-filled PBI sample
has shown two steps decomposition. The initial
weight loss occurred between 40C and 200C is
around 11% which is about the same weight loss as
depicted by controlled sample of unfilled PBI. These
results indicate that addition of CNFs has not
changed the moisture absorption characteristics of
PBI. Also, the overall thermal stability behavior of
PBI has not changed after adding CNFs. However,
addition of CNFs to PBI has improved its thermal
stability after exposure to different radiations. Nano-
filled PBI exposed to electron radiations for higher
dose value has shown similar kind of improvement in
thermal stability as it has shown the improvement in
thermal stability after exposure to other radiations
which was not the case for unfilled PBI. These results
indicate that addition of CNFs to PBI has improved
the resistance of PBI to electron radiations for higher
dose values. The improvement in the thermal stability
of nano-filled PBI is more likely due the increased
cross-linking in the presence of CNFs. Cross-linking
restrict the mobility of the polymeric chains which
ultimately delayed the decomposition of the
materials.

Tensile Test Results
Retention of mechanical properties of a material after
irradiation is an important factor which determines the
sustainability of a polymer for use in radiation
environment. Therefore, to evaluate the performance of
PBI under radiation environment, tensile testing of
unfilled and nano-filled PBI is performed before and
after exposure to different radiations. A comparison of
stress-strain curve of baseline PBI and irradiated PBI
samples is shown in figure 3.
0
40
80
120
160
200
0 5 10 15 20
T
e
n
s
i
l
e

S
t
r
e
n
g
t
h

(
M
P
a
)
Strain (%)
PBI-C PBI-G
PBI-E PBI-M

Figure 3 Comparison of tensile properties of unfilled
PBI before and after exposure to various radiations

As in present study, PBI is exposed to different
radiations with different dose levels. Therefore, a
direct comparison of tensile properties of PBI
exposed to different radiations is not possible. The
ultimate objective of this study was to evaluate the
performance of PBI when exposed to different
radiations. Stress-strain curves obtained after exposing
unfilled PBI to different radiations reveal that electron
radiations and gamma radiation has very slight affect on
tensile strength of PBI. However, mixed radiations
have more detrimental effect on tensile strength of
unfilled PBI. Samples exposed to gamma radiations
exhibited a minor increase in both tensile strength
and tensile modulus. At the same time, these samples
have shown a decrease in tensile strain of about 18%.
The small increase in tensile strength and decrease in
tensile strain after exposure to gamma radiation is
more likely due to the radiation induced cross-linking
in PBI. These results indicate that gamma radiations
with a total dose value of 100KGy have not greatly
influenced the tensile strength properties of unfilled
PBI but it has an influence on failure strain. Tensile
testing of electron irradiated PBI samples reveals that
tensile strength of unfilled PBI is very slightly
decreased. However, these radiations have reduced
the strain of unfilled PBI to about 41%. These results
demonstrate that PBI can withstand high electron
radiation dose values without being affected in term
of tensile strength. Exposure of unfilled PBI samples
to mixed radiations has significantly reduced the
tensile strength and tensile modulus. A decrease of
16% in the tensile strength and 9% in the tensile
International Conference on Advancements and Futuristic Trends in Mechanical and Materials Engineering (October 5-7, 2012)

iv
Punjab Technical University, Jalandhar-Kapurthala Highway, Kapurthala, Punjab-144601 (INDIA)


modulus is observed. These results indicate that a
more pronounced change in tensile properties of PBI
is observed after exposure to mixed radiation.
A comparison of stress-strain curve of nano-filled PBI of
baseline sample and irradiated samples is shown in
figure 4.
0
40
80
120
160
200
0 3 6 9 12 15
T
e
n
s
i
l
e

S
t
r
e
n
g
t
h

(
M
P
a
)
Strain (%)
PBI-2CNF-C
PBI-2CNF-G

Figure 4 Comparison of tensile properties of nano-
filled PBI before and after exposure to different
radiations
Figure 4 shows that nano-filled PBI exposed to gamma
radiations exhibited higher tensile strength than
controlled samples. An improvement of about 7% is
observed in the tensile strength of nano-filled PBI
after exposure to gamma radiations. However, a
reduction of about 11% in the tensile strain is
observed for the samples exposed to gamma
radiations. This decrease in strain of nano-filled PBI
is less as compare to the decrease in strain of unfilled
PBI when exposed to gamma radiations. These
results indicate that addition of CNFs to PBI has
improved the performance of PBI in gamma radiation
environment.

Conclusion
In present work, efforts are made to study the
effects of different radiations on thermal, and
mechanical properties of PBI and nano-filled PBI
samples. TGA curves controlled and irradiated
samples show that all three kinds of radiations have
induced the cross-linking in PBI which ultimately has
increased the thermal stability particularly at high
temperature. Tensile testing of controlled and
irradiated samples of unfilled and nano-filled PBI
shows that gamma radiations and electron radiations
has slightly degraded the tensile strength of unfilled
PBI. However, these radiations have affected the
failure strain to some extent. Addition of CNFs to
PBI has increased the resistance of PBI against
radiations.

Acknowledgements: The authors give their high
gratitude to Leoni Studer AG, Switzerland for
radiation test facilities.

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