Atomic Energy, VoL 76, No.

5, 1994

RADIATION RESISTANCE OF POLYMER MATERIALS

1~. R. K i i n s h p o n t , V . K. M i l i n c h u k , a n d V . I. T u p i k o v UDC 66.018.86(035.5)

The properties of materials change under the action of ionizing radiation. The degree of change per unit absorbed
energy usually characterizes the radiation resistance of a material, i.e., the capability of the material to maintain the
normalized technical indicators within established limits. It is obvious that the most reliable information about the radiation
resistance and service life of a polymer material is obtained by performing tests under natural conditions. However, such
tests are rare because they are expensive, and often they are difficult to perform. For this reason, there arises the problem
of simulating the test conditions.
An important question is the possibility of performing accelerated tests, since the operating time scale of the
materials can differ by several factors from the time scales of the tests. The obvious method for accelerating tests by
increasing the dose rate and reducing the exposure is valid in those cases when the radiation-induced changes in the
characteristic properties of materials do not depend on the absorbed dose rate. In the opposite case, it is necessary to know
the dependence of the radiation-induced changes on the absorbed dose rate.
Besides the radiation environment, the operating conditions also include the composition of the surrounding
medium, the temperature, the mechanical loads, and the electromagnetic fields. Many of these factors affect the materials
together with the radiation, and the result of this action is not simply additive.
One of the main problems of radiation materials science is to construct models required for predicting the changes
in the properties of and determining the real service life of materials. The construction of such models is based on the
knowledge of the mechanism and kinetics of processes occurring in materials. In the absence of such information (which,
as a rule, is not available) only empirical models can be constructed, but their range of application is usually limited. The
objective of the present paper is to consider some problems arising in the assessment of the radiation resistance of materi-
als taking into account multifactor operating conditions.

CHARACTERISTIC INDICATORS OF THE RADIATION RESISTANCE OF MATERIALS

Every material has a complex of physical-chemical properties. In connection with the functions which a material
must perform, only certain of its properties, namely, the operating properties, are of interest. The change in the indicators
of the operational properties of materials (physical-mechanical, electrophysical, thermophysical, optical, and others) under
the action of ionizing radiation characterizes their radiation resistance. The characteristic indicators of the radiation
resistance of a polymer material were introduced in accordance with GOST 25645.321-87 [1]. In most cases, the common
characteristic indicators of the radiation resistance of materials used for different purposes are the physical-mechanical
properties, as stated in GOST 25645.331-91 [2], since other indicators become meaningless in the case of radiation-induced
damage to a material.
Every material has many characteristic indicators. For example, a structural material used for electric insulation
has 20 characteristic indicators [2]. At the same time, the dependence of the characteristic indicators on the absorbed dose
(for irreversible radiation-induced effects) or the absorbed dose rate (for reversible effects) is, as a rule, different for all
characteristic indicators. In other words, the radiation resistance is usually determined by one characteristic indicator, for
which the term "determining characteristic indicator of radiation resistance" (Table I) was introduced in [2].
The absorbed dose (and the absorbed dose rate for irreversible effects) for which a characteristic indicator changes
by a definite amount is used as a quantitative characteristic of radiation resistance. The relative change of a characteristic
indicator, depending on the functional purpose of the material, is called an arbitrary criterion of radiation resistance and
the dose at which the arbitrary criterion is reached is called the radiation index (see Tables I and 2).

Affiliate of the L. Ya. Karpov Scientific-Research Institute of Physical Chemistry. Translated from Atomnaya
I~nergiya, Vol. 76, No. 5, pp. 422-428, May, 1994. Original article submitted January 19, 1994.

384 1063-4258/94/7605-0384512.50 9 Plenum Publishing Corporation

 TABLE 1. Determining Characteristic Indicators of the Radiation Resistance of Materials
and Their Arbitrary Criteria

Functionalpurpose Determiningcharacteristic Arbitrary criterion Technical specifications

of the material indicator of radiation of radiation document (TSD) for the
resistance resistance, % method of determiningthe
indicator
Structural functions:
force Bendingstrength, MPa -50 GOST 4648
packing Residual deformationunder -20 GOST 9.701 - for rubbers,
compression, % TSD for the material
Glue Rupture strength of a glue -50 TSD for the material
bond, MPa
Heat-insulating,including Thermal conductivity, 25 GOST 23630.2
heat-shielding W/(m.K)
Temperature-controlcoat- Coefficient of absorptionof 50 for <0.3 TSD for the material
ings solar radiationat wavelengths
from 0.2 to 2.5 /~m
Radiation shieldingof Hydrogen content, mass % -1 TSD for the material
nuclear reactors

TABLE 2. Radiation Index of Characteristic Indicators of the

Three Most Widely Used Polymers in Technology (in MGy).
Irradiation in Air [3, 4l

Characteristic indicator Low-density Polytetraflu- Poly-

polyethylene oro-ethylene imide
Rupture strength 2.54 0.01 > 100
Thermal conductivity I0 > 1.2
Specific heat capacity 45
Density 5 0.01-0.03
Tangentof the loss angle 1 3 0.1
(1 kHz)
Electric strength 3-6 1 > 10
Radiation-inducedmass loss 10 1 500

S I M U L A T I O N OF THE R A D I A T I O N E N V I R O N M E N T

Under actual operating conditions, materials can be subjected to ionizing radiation of different types (-y-radiation,
accelerated charge particles, neutrons) with, as a rule, a wide energy distribution. In laboratory tests for radiation resis-
tance, one of the most important capabilities is to simulate the radiation environment, since in most cases it is incorrect to
replace radiation of one type by radiation of another type as well as the energy spectrum of the radiation and to switch
from pulsed to continuous irradiation or vice versa, and any such changes must be substantiated. Usually, the volume-
averaged absorbed dose under fixed irradiation conditions (average dose rate and temperature, medium, and so on) is used
as a measure of the radiation effect of ionizing radiation. The absorbed dose, however, is not always a unique measure of
such action, primarily because the energy of the ionizing radiation is reteased discretely and is limited to the region of the
track. The absorbed dose rate in tracks is significantly higher than the volume-averaged dose rate, and it depends on the
characteristics of the ionizing radiation. If radiation processes depend on the absorbed dose rate (or the response of the
system to the action of the radiation is related nonlinearly to the dose), then for the same volume-averaged dose the
radiation effects can be different. Radiation effects are often associated with linear energy transfer. This characteristic is
one-dimensional, and it does not describe the spatial pattern of the energy distribution in the volume of the track. There-
fore it also does not describe the local concentration of intermediate active particles, whose reactions give rise to changes
in the properties of the irradiated materials.

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 TABLE 3. Effect of the Type of Ionizing Radiation on the Change in the Indicators of the
Macroproperties of Polymers under Irradiation [6]

Polymer Dose, MGy Ratio of the postirradiation property

indicators to the initial indicators
.~-rays I protons ('I'00 MeV)I neutrons
Dielectric properties (tan ~)
Polyvinyl chloride 0,03 1,6 1,4 2,2
0,1 2,1 1,25 5,0
0,3 1,5 t
]
1,3 2,2
Low-density polyethy- 1 4.0 I 2,0 1,45
lene 3 6.3 2,3 1,7
Volume electric resistance
Polytetrafluoroethylene 0,0I 0,8 I 0,001 0,001
0,03 0.3 0,001 0,001
Tensile strength
Low-density polyethy- 0,3 1,3 1,3 0,95
lene 1,0 1,2 0,95 0,95
3,0 0.45 0,45 0,75
Polytetrafluoroethylene 0,001 0,6 0,25
0,003 0.45 0,18
0,0t 0,35 0,t8 0,5
Polyethyleneterephthalate 1.0 0.71 0,85
2,0 0.68 0,79

*Electrons (E = 2 MeV) and protons (E = 8 MeV) were used instead of y-rays.

Microdosimetric concepts, which take into account the stochastic nature of the interaction of the radiation with the
medium and the local character of the energy release, also do not permit a complete explanation of the differences in the
efficiency of the action of different types of radiation.
Systematic investigations of the specific nature of the action of ionizing radiation of different types (neutrons from
a nuclear reactor, accelerated protons, -y-rays from 6~ and accelerated electrons) on the change in the properties of
polymer materials have made it possible to draw some general conclusions [5]:
In the general case, the radiation-induced changes in the properties of polymer materials depend on the type of
radiation: the greatest changes are characteristic for neutron irradiation;
the differences owing to the type of radiation reach tens of percent, and in separate cases hundreds of percent;
the degree of inequivalence of the action depends on the chemical structure of the macromolecules, the composition
of the polymer compositions, and the physical structure of the polymer and character of the surrounding medium.
Increasing the absorbed dose nullifies the effect of the type of radiation (Table 3).

COMBINED EFFECT OF IONIZING RADIATION AND OTHER FACTORS

During operation in ionizing-radiation fields, other external factors also act on the materials - the environment
(vacuum, air, liquid medium), temperature, optical radiation, electric and magnetic fields, mechanical loads, and so on.
Materials are subjected to the combined action of ionizing radiation and other external factors. Under combined action,
much stronger changes are observed in the properties of materials than under the action of only ionizing radiation and
external destabilizing factors separately [6-11].
Environment. The environment changes in the process of irradiation as a result of both radiolysis of air and
radiation-induced release of gas from the materials (Table 4). Atmospheric components which are chemically active with
respect to polymers are: oxygen, ozone, and nitrogen dioxide. The last two corrosive chemical compounds are always
present when materials are irradiated in air, since they are products of the radiolysis of air. The stationary concentration of
ozone during irradiation of air falls in the range 0. I-0.3 vol. % [12]. When ozone interacts with polymers, the molecular
mass of the polymers decreases and oxygen-containing groups accumulate (carboxyl, carbonyl, peroxide, and others). In
time, surface cracks form and spread; ultimately this results in the destruction of the polymer material. The rate of ozone
aging increases in the presence of tensile stresses, which open cracks and reveal new surfaces [13].

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 TABLE 4

Polymer Compositionof hazardous gaseousproducts. % Radiation-chemical yield

Polyethylene Hydrogen(95-98) 3.2-4.5
Polypropylene Hydrogen (85-98), methane (2-12) 2.4-2.8
Polyamidr Hydrogen(50-70), carbon monoxide (30-40) 1.3-3
Polycarbonates Hydrogen(2), carbon monoxide (50), carbondioxide (40) 1.3
Polyimide Hydrogen(20-30), carbon monoxide (15-40), carbon dioxide (40-50)
Polyvinylchloride Hydrogenchloride(95) 20
Polytetrafluoroethylene Carbon monoxide, carbon dioxide, carbon tetrafluoride, perfluoroalkanes 0.45
Polydimethylsiloxane Hydrogen (35-40), methane (30-60) 2.5-39

The content of oxygen in polymers in air is (0.3-3). 10 -3 moles/kg, and the rate at which oxygen enters the poly-
mers is determined by the diffusion coefficient, which at 278-370 K lies in the range 0.04-15 cm2.sec - l . The macro-
radicals formed under the action of radiation in the presence of oxygen transform into peroxide radicals. The successive
alternation of the reactions in which oxygen is attached to macroradicals and reactions of peroxide radicals is characterized
by a chain oxidation process, which destroys polymers.
Optical Radiation. Secondary radiation arises during the interaction of electrons and protons with materials;
neutrons and x-ray bremsstrahlung arises in inelastic collisions with the atoms of the material; and, when the velocity of
the charged particles is higher than the propagation velocity of light in the medium, Cherenkov-Vavilov radiation arises.
The penetrating power of radiation of these types is higher than that of the primary charged particles, and for this reason
the secondary radiation can increase the absorbed dose not only in materials in the primary-radiation field, but also in
materials behind screens.
Cherenkov-Vavilov radiation arises in solids and liquids for electron energies of about 0.1 MeV and proton
energies of about 100 MeV [14]. Usually, light generated in the volume of the material acts both on the material itself and
on the products of radiolysis. Ultraviolet radiation can cause photochemical degradation of the material. Moreover, short-
lived and stable products of radiolysis, whose optical absorption spectrum is usually shifted into the long-wavelength region
compared to the initial material, i.e., these products extend the range of photosensitivity of the material, arise in the
materials.
Deactivation of excited molecules which are formed in the interaction with ionizing radiation or neutralization of
charged particles can also be an internal source of light in the irradiated material. It has been established experimentally
that radioluminescence and recombination luminescence in polymers strongly influence the radiation-chemical processes
[15]. So, ionizing radiation combined with optical radiation intensify the effect (photoradiation effect) [6, 7].
Additional destabilizing factors arise when ionizing radiation interacts with the materials of parts. These factors
include the specific chemical medium created by the products of radiolysis of the materials [3, 16], electrization of
materials [17], secondary ionizing radiation, and optical and UV radiation [14] induced by the effect of ionizing radiation,
and pulses of mechanical stresses produced by pulses of ionizing radiation (pressure waves) [18].
Electrization. One of the basic processes of the interaction of radiation with matter is ionization of molecules, as
a result of which electrons and positive ions (holes) are produced. The concentration and mobility of the charged particles
determines the radiation-induced electric conductivity, which can vary over wide limits. The nonuniform distribution of the
absorbed dose over the volume of the material gives rise to differential electrostatic charging of the materials. A conse-
quence of the differential charging is an electric spark discharge, which can penetrate into the surrounding space, along the
surface (above- or below-surface) without escaping into the surrounding space and through the layer of dielectric onto the
substrate (breakdown of the dielectric). Electric discharges gradually destroy materials. The electric fields arising during
electrization can influence the mechanism of the radiation-chemical processes and change the distribution of the absorbed
dose of ionizing radiation in the materials.
Mechanical Loads. Polymer materials in parts are usually in a loaded state or they have internal stresses, which
arise for different reasons, including the fabrication technology. The effect of the mechanical loads changes the molecular
dynamics, the structure of the polymer chain, and the supermolecular structure. These changes are reversible, if the
mechanical loads do not give rise to chemical changes. In the presence of radiation, mechanical loads give rise to new

387
chemical reactions in polymers, as a result of which a new irreversible state of a polymer, which cannot be achieved under
the action of ionizing radiation only, can arise.
The most extensive information has been accumulated about the combined effect of hydrostatic compression and
ionizing radiation, giving rise to a change in the rate and directionality of radiation-chemical reactions [19]. For example,
in polyethylene and some elastomers, the effectiveness of radiation-induced linkage increases; this leads to significant
changes of the physical-chemical and operating properties [8]. As a result of the combined action of high-energy radiation
and mechanical loads, the relaxation rate after removal of the load and the creep rate increase, and these rates depend on
the absorbed dose rate [3, 4, 9, I0]. As a rule, high-energy radiation accelerates the degradation of a material in stressed
regions [20].
In summary, it should be noted that information about the radiation resistance of polymer materials has been
obtained mainly for standard conditions of irradiation (room temperature, monoenergetic radiation, air), and from the
standpoint of radiation material science it can be used only for making a preliminary choice of materials. The suitability of
materials for various operating conditions can be determined on the basis of the complex of acting factors (including the
medium and temperature) and the functional purpose of the material.
Physical factors, with respect to which the materials are insensitive under ordinary conditions, can have a strong
destabilizing effect on the radiation-induced changes of the properties of polymer materials. The absorbed energy of the
radiation converts the polymer system into a nonequilibrium state and makes the system susceptible to external actions,
such as optical radiation, mechanical loads, electric and magnetic fields, and others.

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