Radiation damage significantly weakens plastics by altering their molecular structure. Ionizing radiation like gamma rays break the covalent bonds within polymer chains. This causes plastics to become brittle as the broken bonds recombine crosswise instead of lengthwise. The structural changes reduce a plastic's tensile strength and elongation. Radiation also releases hydrogen from polymer chains, decreasing the plastic's volume as hydrogen diffuses out. Understanding these effects is crucial for designing nuclear facilities and maintenance schedules using plastics.

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Radiation Damage to Plastics
Shawn Robinson
Colorado School of Mines
Nuclear Materials

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Introduction
Radiation damage is an important issue in the design and maintenance of nuclear
facilities. Nuclear radiation such as alpha, beta, gamma, and neutron each have their unique
effect on materials. Plastics known as polymers show drastic changes in material properties after
irradiation. The polymer now acts as a brittle material with significantly reduced strength.
Polymers do not have an arranged lattice structure like metals. The material structure of
polymers is damaged by ionizing radiation. After studying the damage mechanisms of ionizing
radiation, radiation damage to plastics materials can be understood.
Radiation Damage
Particles in the emitted radiation impact at high energies when compared to the bonds in
the crystal lattice of a material. These particles slam into the crystal lattice, knocking off or
displacing atoms. Radiation damage continues over the lifetime of a material in a nuclear facility,
and as a result, bulk defect in materials can arise with varying severity. It is important to know
the impact of alpha, neutron, gamma, and beta particles on various types of materials and their
resulting bulk defects in the crystal lattice. This is crucial to the design of the nuclear facility
when material considerations are made. Awareness of how the radiation damage affects the
performance of the materials ensures reliably and safety in the system. Each type of particle
leaves its own type of radiation damage on a given material so it is good to have an
understanding of what each particle’s effect on a lattice is individually. Once this is understood,
the expected defects in a material would be a random combination of the various types possible,
since constant bombardment of random particles in the nuclear reaction.

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Ionizing Radiation
Gamma, beta, and alpha particles interact with the electron cloud of a material, departing
their energy to the electron in an atom which can strip the electrons off an atom, leaving them as
charged ions in a high energy state. [1] This is what is called ionizing radiation, and its effect on
atoms in a lattice of a material can cause some covalent or ionic bonds to break since the atoms
are stripped of their electrons, changing their charge. The strength of a material is dependent on
its chemical bonds, which rely on either the sharing of electrons or the pair of like charges.
Therefore, ionizing radiation can cause serious impact to crystal lattice.
Radiation Damage to Plastics
Ionizing radiation has a great effect on covalent bonds, which comprise most polymers.
The ionizing radiation reconfigures the covalent bonds by breaking the current chains or creating
different chains. [1] This weakening of the polymer’s bonds compromises its structural integrity.
In knowing the type of damage to expect in a radioactive environment, we can predict the
problems that may arise in material performance of plastics. After the polymer chain is broken, it
re-links to any available bond yielding a shorter or longer chain than it was originally. In the
event of shorter bond chains, the plastic becomes soft and weaker, possibly becoming liquefied
with increasing radiation. Teflon, Plexiglas, Lucite and butyl are mentioned as plastics most
likely to fail by these means. [1] On the other hand, when bonds in the plastic recombine into
longer chains, the resulting plastic become harder and more brittle. Brittle failure is common in
plastics such as polyethylene, polystyrene, silicone, neoprene and natural rubber.

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Figures 1-2 are of a samples of a commercial grade plastic scanned before and after
radiation damage was iduced. In the study, commecial plastics were assesed for the ability to be
used as structural materials for low level waste disposal. The sample composite was made by
mixing glass fibers into the plastic to increase the structural and chemical stability of the
plastic.[4] The image on the left shows the composite mixture before irradiation and the right is
after the material expirenced a slightly higher radiation dose than would be expected in the
lifetime of a structual material used for low level nuclear waste disposal. After irradiation the
effects of the radiation damage become visually apparent. Cross-linking and gasification of the
plastic causes a volume reduction of the material as the specific gravity is increased[4]. Once the
a significant portion of the gas has diffused out of the matarial, the bonds holding the polymer
chains are weakened, leaving a weak support material for the glass rods. Ionizing radiation still
Figure 1a 2a PlasticGlassComposite [4] Figure 2a 2b PlasticGlassComposite afterirradiation[4]

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damages plastic more significantly. Attempts to mix the plastic with support materials only acted
as localization points for the radiation damage, as the glass fibers were not easilty ionized or
damaged by the incoming radiation.
Radiation damage to Rubber
Rubber materials are also susceptible to brittle failure. Rubber relies on long bond chains
to remain flexible, with the amount of cross linking between the chains determining the stiffness
or tension available to it [1]. Natural rubber is more resistant to having its bonds broken down by
radiation damage than artificial plastics [1]. In all cases, the tensile strength of the rubber is
reduced as it becomes brittle or liquefied. In an actual system, seals and O-rings in air and D2O
systems of containment failed due to radiation and temperature damage. This part malfunction
can cause this major subsystem to fail. Upon scheduled outages, valves and rings are inspected
and replaced on an as needed/ call-up frequency to avoid failure of these system components.
Plastics undergo a more drastic change when exposed to radiation damage when compared to
metals because the actual chemical bonds in the plastic are changed or displaced, resulting in a
new degraded material.
Discussion.
In a study at Oakridge National lab, various commercial plastics were irradiated. This
study was a follow up study on commercial plastics where changes after radiation and oxygen
aging were studied. The plastics and elastomers were put into the maximum flux region of the
ORNL graphite reactor to study the effects of various types of radiation damage. Fast and
thermal neutrons were tested to determine the type of damage modes on the plastic. Gamma
damage was the most significant to the study, so by wrapping the experiment in cadmium, more

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n-gamma reactions were produced when the cadmium was hit with a neutron, thus increasing the
effect of ionizing radiation on the plastic being tested. An attempt to “alloy” or mix the plastics
with different types of rubber was made to mitigate the damage done to the material.[2] This
attempt failed due to the dependency on the bond chains which were broken regardless of the
plastic or rubber used. In application, failures such as these have been seen in the insulation on
some power and instrument cables, where the plastic became so brittle it just fell off the cables.
Terminal blocks have been seen decomposing in junction boxes where radiation fields were
high.[1] It is very important to be aware of this possibility when making material of plastics
since they might not be able to perform regular maintenance because of their location, and you’d
want to ensure the long lifetime and function of a plastic component, whatever the function may
be. In the text there is a useful chart to show the expected impact form radiation damage on
plastics as a function of the type of plastic and the total absorbed dose in Mrad. This can be used
to determine which plastic is best for commissioning for a task depending on the expected
replacement time and damage incurred over the lifetime of that part. By knowing the radiation
fields around the facility, you could know which materials are at risk on certain timescales. From
the chart most plastics start to experience some moderate damage after absorbing 10 Mrads, and
severe damage around 800-1000 Mrad.

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Testing.
Polymers have low neutron cross sections, so most of the damaging in the plastic comes
from ionizing gammas that break the covalent bonds [1]. Broken bonds were expected to
decrease tensile strength after radiation exposure. Using cadmium experiment covers converted
some of the thermal neutrons into gamma radiation [3]. More damage to the polymer can be
expected with increasing amounts of gamma radiation. Commercial plastics were irradiated to a
determined exposure time. They were tested for some of their material properties, such as
hardness and tensile strength. Once maximum stress-strain curves were plotted as a function of
exposure time, the effect of the damage became apparent. With this data it is better understood
what the effects of nuclear radiation will be on the final strength of various commercial plastics.
Figure 3 Chart of radiationexposuretopolymers[1]

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With this knowledge, a design engineer can determine how much the radiation is going to
degrade function of the part, and determine a modified design of this plastic part. If redesign is
not possible a removal/ replacement plan can be made to retrieve a part before failure at a
predicted time. [2] These experiments were very useful because they used ASTM procedure for
material testing, which most US engineers can understand, and make their own design
adjustments using standard stress strain formulas. If such a part were retrieved from service for
testing and material analysis, it would mostly likely disintegrate from embrittlement, or liquefy
before the test was complete, although chemical analysis could probably still be done.
Material using standard “dog-bone” and sample coupons for the irradiated polymers
gives a template for comparing results between many experiments. Using the test from many
studies on the effects of stress on these damaged materials gives a comparison data, and after
cross checking, the tensile test data was comparable between polymers of various studies.
Figure 4 Plastictestsamples[2]

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Figure 5 reveals the tensile stress data for a natural rubber sample irradiated to varying
severity. The un-irradiated curve characterizes a polymer, having a decent stress value at failure,
as well as a high percent elongation or stain value. After irradiation, the polymer has less than
50% of its usual maximum stress and strain values. Stress curves of the irradiated polymer
appears as brittle material or weak ceramic. This results from the cross linking that stiffens the
polymer after experienced ionizing radiation. [5]
Effects on Material properties
Radiation damage can cause a volume change in a plastic material. [2] Ionizing radiation
breaks the hydrocarbon chains releasing hydrogen. Now, the gaseous hydrogen diffuses through
the plastic, leaving shorter chains with more cross linking between hydrocarbon chains. This
results in a volume shrinkage in the polymer, since gas was released from the plastic. [2].
After irradiation of the various commercial polymers, radiation embrittlement was
observed for most of the plastics and natural rubber [4]. In this process the long covalent bond
chains within the plastic were cut by the radiation so that their length is shortened. The severed
bonds recombined horizontally instead of vertically. This formed a new polymer and stiffened
Figure 5 Tensile strengthof irradiatedplastics[2]

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the material as a bulk defect. The horizontal cross-linking of the bonds chains resulted in less
give and stretch than if oriented vertically. As a result, the plastic was stripped of its elastic
characteristics. The remaining material is brittle. Commercial grade rubbers, butyl rubber and
Thiokol underwent a liquid transformation as a result of radiation damage. In these elastomers,
the horizontal bonds and responsible for the stiffness and “rubbery” characteristic that returns
and retains rubber in its formed shape [1]. Radiation damages these bonds cutting the amount of
cross-linking between the bonds, which softens up the material. Over time, the amount of bonds
is reduced to the point that the rubber becomes liquid-like and cannot return to its original shape.
Two plastics Hycar and Silastic saw an initial increase in tensile strength due to radiation
hardening [1][4]. After continued radiation damage the tensile strength is reduced. These
commercial plastic can experience damage till the point where they can reach less than 1% of
their original elongation, and behave more as a brittle ceramic material than as plastic/
elastomer.[2]
Figure 6 polymerpropertiesafterirradiation[2]

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Fig 7 serves as a visual to the effects of gas diffusion in plastic-cloth filters used in D2O
systems. The hydrogen in the hydro-carbon bonds holding the plastic together are released after
gamma radiation. The lose hydrogen diffuses out of the material, causing a volume reduction in
the material that is left. Hydrogen acts as the spacing in polymer chains. When released, the
material is likely to crumble since the material left is made up of mostly carbon and oxygen.
Color and translucence of the polymer are also affected by radiation damage. UV rays excite the
polymer chains, tinging the plastic from yellow to black as the radiation is induced [5]. The
effect of the UV radiation was not as significant as that of gamma, but since there was a color
change, there is evidence of a chemical reaction in the material.
Figure 7 Plasticclothfiltervolume reduction[2]

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Conclusion.
Nuclear radiation significantly affects the material properties of commercial grade
plastics. Radiation damage can be occurred over the lifetime of a part. Among the various types
of radiation, gamma rays cause the most material damage. The rays ionize hydrocarbon bond
within a polymer. Hydrogen diffuses through the plastic, reducing the volume of the polymer.
The broken bonds in the plastic recombine wherever possible. This change is volume and
orientation of the bonds is “cross linking”. Cross-linking is the main defect from radiation
damage in polymers. This now brittle material has reduced maximum tensile strength and
elongation values. A good plastic material for a radiation environment would have to most
resistance to cross-linking and shrinkage. By having a higher ionization energy between atoms,
some plastics can be more resistant to radiation damage than others.

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References
[1] D. Dawson, R. Fleck. A. Wadham, Radiation Damage to Materials, course 228, module 4,
Obj. 4.5 b, p 8, P. Bird. WNTD, (June 1993).
[2] C. D. Bopp, 0. Sisman, RADIATION STABILITY OF PLASTICS AND ELASTOMERS,
ORNL-1373, Oak Ridge National Lab, Tennessee, (1954)
[3] H. BERGER, “Track-etch radiography: alpha, proton, and neutron,” Argonne National
Laboratory Material Science Division (Apr 1973).
[4] H. Bonin, M. Walker, V. Bui, APPLICATION OF POLYMERS FOR THE LONG-TERM
STORAGE AND DISPOSAL OF LOW- AND INTERMEDIATE-LEVEL RADIOACTIVE
WASTE, Royal Military College of Canada, Department of Chemistry and Chemical
Engineering P.O. Box 17000, Station FORCES, Kingston, Ontario K7K 7B4, Canada, (April
2003)
[5] I. Rosman, K. Zimmer, Damage to Plastic Scintillators by ionizing radiation, pg 56-62, (May
1956)