Radiation Effects

Ionization and Excitation

Ionizing radiations deposit their energy in aqueous and most biological systems in a

largely indiscriminate manner, leaving behind a complex mixture of short-lived ions,

free radicals, and electronically excited molecules. Such interaction processes are

known as ionization and excitation of the atoms or molecules, which can cause

chemical changes. In ionization process an electron of K-shell or L-shell is removed

from the atom or molecule leaving behind a positive ion. For polymers, as for most

organic molecules, the ionization potentials, i.e., the binding energies of the most

electrons are in the range to 10–15 eV. This defines the lower limit of the energy

required for ionization and corresponds to UV radiation. Earlier studies have shown

that the average energy required for the formation of one ion pair in gases is 25–35

eV. When the incident energy is insufficient to produce ionization, the atom

undergoes excited state before returning to the stable state by the emission of photon.

Highly excited molecules break down with a high probability, giving rise to free

radicals. In solid polymers, ions and free radicals may remain trapped for a

considerable length of time. These basic radiation-induced processes of ionization

and excitation can be summarized as follows:

-
Ionization: AB AB+ + e (3.15)

Excitation: AB AB* A + B (3.16)

Break down: AB** A + B (3.17)

3.1
Here is the symbol used to designate a radiation-induced event, AB denotes an
-
organic molecule, AB+ a positive ion, e an electron, AB* and AB** excited

molecules, A and B are uncharged fragments (free radicals). These various active

species are responsible for the changes observed in organic molecules subjected to

ionizing radiations. In polymers, some transformations are attributed to ions.

However, most reactions can be accounted by conventional free-radical processes.

Gases are generated in all irradiated polymers, as in any organic molecule. Hydrogen

accounts for a substantial fraction of the gas. Its formation results from a two-step

process. At first a carbon–hydrogen bond is broken by radiation.

PH P + H (3.18)

Here PH is a hydrogen-containing polymer, P a polymeric radical and H a

hydrogen atom. This step is followed by hydrogen atom abstraction:

H + PH H2 + P (3.19)

Short side-branches are selectively ruptured under irradiation. Thus, methane is a

major product in the radiolysis of polypropylene and polyisobutylene. Carbon

monoxide and carbon dioxide arise among the gases evolved from polyacrylates and

polymethacrylates. Halogenated polymers produce acidic gases: HCl from poly(vinyl

chloride) and HF from fluorinated polymers. In vitreous or partially crystalline

3.2
polymers, the gases generated by irradiation remain trapped and may give rise to

strains which produce cracks and may even rupture the irradiated specimen.

Radiolysis

If a molecule of water, H2O absorbs ionizing radiation, it can be broken up or ionized

into two ions; a hydrogen ion (H+) and hydroxyl ion (OH-). This mechanism is called

radiolysis of water. The H+ and OH - show that an electrical charge is carried by an

ion. These ions are chemically quite active (reaction up to about 10-16 s). However,

radiation is so energetic that it can also cause break-up of the water molecule without

forming ions, but into two uncharged species called free radicals, and in this case

 
H and OH . These radicals are very much more active chemically than ions and can

cause different chemical reactions when react with compounds or molecules in their

vicinity.

Recombination

The electrons abstracted from the irradiated molecules (AB+) are subjected to the

strong electric field of positive charges formed earlier. Therefore, charge

recombination is a frequent event, either during irradiation or after the end of

irradiation, as an after-effect. In this process the ionization potential (10 to 15 eV) is

recovered and this generates highly excited molecules, carrying an amount of energy

much larger than any bond strength. As a result, such highly excited molecules

(AB**) will break down into free radicals ( A , B ) (Denaro & Jayson, 1972):

3.3
 A B
-
AB+ + e AB** + (3.20)

Polymerization

In the process of radiation-induced polymerization, free radicals react with the

unsaturated molecules of a low molecular mass compound or monomers, and these

monomers combine with one another, thereby producing a polymer of high molecular

mass. A polymer, which composed of similar structural links of molecular chain, is

known as homopolymer and those formed from different kinds of structural links is

known as copolymer. Since radiation initiation is temperature independent, polymer

can be polymerized in the frozen state around aqueous crystals. The mechanism of the

radiation induced polymerization is concerning the kinetics of diffusion-controlled

reactions and consists of several stages: addition of hydroxyl radicals and hydrogen

atoms to carbon-carbon double bond of monomer with subsequent formation of

monomer radicals, which the rate constant is diffusion controlled; addition of

hydrated electrons to carbonyl groups and formation of radical anion of a very high

rate constant and the decay of radicals with parallel addition of monomer to the

growing chain, which terminates the polymerization process.

Crosslinking

Crosslinking is the process, which follows reactions (3.18) and (3.19) in which two

polymeric radicals combine to form an intermolecular bond or crosslinking.

P + P ' P P' (3.21)

3.4
P' is a polymeric radicals and P’ is a polymer cross-linker. As a result of its reaction,

involving two macromolecular fragments produces 3D cross-linking of polymer with

high molecular mass. The cross-linking polymer has a strong mechanical structure,

good thermal resistance and is insoluble in organic solvents. From a comparison of

reactions (3.18) and (3.19) with reaction (3.21), it appears that the formation of one

crosslink corresponds to the evolution of one hydrogen molecule. The yield of

crosslinking is enhanced in the presence of polyunsaturated compounds, such as

polyfunctional vinyl monomers. There is a competition between intermolecular and

intramolecular cross-linking modes. At lower polymer concentrations, the probability

of intermolecular recombination decreases.

Role of Radical Scavengers and Oxygen

Additives can alter the radiation-induced processes in aqueous solutions of polymers.

Selective scavengers of transient products of water radiolysis, like tetra-butanol for

OH or nitrous oxide for e-eq, can produce separate reaction with polymers. Oxygen is

a very special additive. The oxygen molecule contains two unpaired electrons which

readily react with a free radical, R  resulting in the formation of a peroxy-


radical RO2 :


R  + O2 RO2 (3.22)

3.5
Such peroxy-radicals are very reactive and abstract hydrogen atoms, H from

neighboring RH molecules:


RO2 + RH RO2 H + R (3.23)

A new radical, R  is generated in this process which carries the reaction on. This is

the basic chain reaction responsible for the oxidation of organic molecules. RO2 H is

an unstable hydroperoxide which slowly breaks down at room temperature, producing

more radicals and more oxidative damage. This oxidative chain reaction is prevented

by the use of proper anti-oxidants.

3.6