EFFECTS OF TRITIUM GAS EXPOSURE ON ELECTRICALLY CONDUCTING POLYMERS

Abstract

Effects of beta (tritium) and gamma irradiation on the surface electrical conductivity of two types of conducting polymer films are documented to determine their potential use as a sensing and surveillance device for the tritium facility. It was shown that surface conductivity was significantly reduced by irradiation with both gamma and tritium gas. In order to compare the results from the two radiation sources, an approximate dose equivalence was calculated. The materials were also sensitive to small radiation doses (<10{sup 5} rad), showing that there is a measurable response to relatively small total doses of tritium gas. Spectroscopy was also used to confirm the mechanism by which this sensing device would operate in order to calibrate this sensor for potential use. It was determined that one material (polyaniline) was very sensitive to oxidation while the other material (PEDOT-PSS) was not. However, polyaniline provided the best response as a sensing material, and it is suggested that an oxygen-impermeable, radiation-transparent coating be applied to this material for future device prototype fabrication. A great deal of interest has developed in recent years in the area of conducting polymers due to the high levels of conductivity that can be achieved, some comparable to that of metals [Gerard 2002]. Additionally, the desirable physical and chemical properties of a polymer are retained and can be exploited for various applications, including light emitting diodes (LED), anti-static packaging, electronic coatings, and sensors. The electron transfer mechanism is generally accepted as one of electron 'hopping' through delocalized electrons in the conjugated backbone, although other mechanisms have been proposed based on the type of polymer and dopant [Inzelt 2000, Gerard 2002]. The conducting polymer polyaniline (PANi) is of particular interest because there are extensive studies on the modulation of the conductivity by changing either the oxidation state of the main backbone chain, or by protonation of the imine groups [de Acevedo, 1999]. There are several types of radiation sensors commercially available, including ionization chambers, geiger counters, proportional counters, scintillators and solid state detectors. Each type has advantages, although many of these sensors require expensive electronics for signal amplification, are large and bulky, have limited battery life or require expensive materials for fabrication. A radiation sensor constructed of a polymeric material could be flexible, light, and the geometry designed to suit the application. Very simple and inexpensive electronics would be necessary to measure the change in conductivity with exposure to radiation and provide an alarm system when a set change of conductivity occurs in the sensor that corresponds to a predetermined radiation dose having been absorbed by the polymer. The advantages of using a polymeric sensor of this type rather than those currently in use are the flexibility of sensor geometry and relatively low cost. It is anticipated that these sensors can be made small enough for glovebox applications or have the ability to monitor the air tritium levels in places where a traditional monitor cannot be placed. There have been a few studies on the changes in conductivity of polyaniline specifically for radiation detection [de Acevedo, 1999; Lima Pacheco, 2003], but there have been no reports on the effects of tritium (beta radiation) on conducting polymers, such as polyaniline or polythiophene. The direct implementation of conducting polymers as radiation sensor materials has not yet been commercialized due to differing responses with total dose, dose rate, etc. Some have reported a large increase in the surface conductivity with radiation dose while others report a marked decrease in conductive properties; these differing observations may reflect the competing mechanisms of chain scission and cross-linking. However, it is clear that the radiation dose effects on conducting polymers must be fully understood before these materials can be used as sensing devices. This report presents the results of irradiations of two conductive polymers: polyaniline and polythiophene. Samples of doped polyaniline and polythiophene were coated onto polyester (polyethyleneterephalate, PET) substrates and were exposed to both tritium gas (beta irradiation) and {sup 60}Co gamma irradiation. The samples were subsequently characterized after various total doses. Infrared spectroscopy was utilized to characterize the gamma-exposed samples post-irradiation. Although the sources of radiation are different in kind (charged particle versus photon) and their energies differ, there will be great value in using noncontaminating gamma irradiation to model the effects of tritium beta radiation.