The caesium radioisotopes ¹³⁴Cs, ¹³⁵Cs, and ¹³⁷Cs are highly problematic medium-lived species produced during nuclear fission, due to their high radioactivity and environmental mobility. While many ion exchange materials can readily isolate Cs⁺ ions from neutral or basic aqueous solutions, only ammonium phosphomolybdate (AMP) functions effectively in acidic conditions, removing caesium even down to trace levels. Composites of AMP in a porous polymeric support such as polyacrylonitrile (PAN) can be used to selectively remove Cs⁺ ions from acidic aqueous decontamination liquors as well as other liquid wastes, and are promising for the isolation of Cs⁺ isotopes in spent fuel reprocessing. While both AMP and PAN have demonstrable acid stability, and PAN has known resistance to gamma radiation, AMP-PAN composites have received only a limited analysis of their physiochemical and ion exchange performance following irradiation. In this publication, we explore the effect of high levels of gamma irradiation on the ion exchange properties of AMP and AMP-PAN as a Cs⁺-selective adsorbent under spent fuel dissolver liquor concentrations and acidity. We demonstrate no significant reduction in performance with respect to uptake kinetics or capacity upon irradiation, abiding by the same absorption mechanism observed in the established literature.

Managing certain by-products of the nuclear fuel cycle, such as the radioactive isotopes of caesium: ¹³⁴Cs, ¹³⁵Cs and ¹³⁷Cs is challenging due to their environmental mobility and radioactivity. While a great many materials can isolate Cs+ ions from neutral or basic aqueous solutions via ion exchange, few of these, with the exception of ammonium phosphomolybdate (AMP), function effectively in acidic media. The use of AMP, and its porous composite in polyacrylonitrile (PAN) for management of Cs radioisotopes in various nuclear wastes have been known for decades and are well studied, yet the effects of radiation on the physiochemical properties of such composites have only received limited attention to date. In a previous publication, we demonstrated that a 100 kGy gamma irradiation dose has negligible effect on the ion exchange performance of AMP and AMP–PAN with respect to capacity or kinetics under the Cs+ concentrations and acidity found in spent nuclear fuel (SNF) recycling. As a continuation of this prior study, in this publication we explore the effects of gamma irradiation on the physiochemical properties of AMP and AMP–PAN using a range of characterisation methods. The effects of the same gamma dose on the oxidation state of Mo in AMP and AMP–PAN, the thermal degradation of both AMP and AMP–PAN, combined with a first study into the high-temperature degradation AMP, are reported. The implications of irradiation, its possible mechanism, the conditions present in SNF recycling, and for the end-of-life disposal or recycling of these materials are also discussed.

This article describes the design and operation of a new thermal analysis instrument which uses microwaves to simultaneously heat and detect thermally induced transformations in samples with masses in the range of 50 mg to 0.5 g. The data acquisition and control software developed for the instrument support a range of experimental techniques including constant power, linearly ramped power, linearly ramped temperature, and various modulated methods. Microwave thermal analysis utilizes the fact that physical or chemical alterations in a material, caused by processes such as melting, decomposition, or solid-solid phase changes, cause variations in its dielectric properties. These can be revealed by a variety of means including changes in the sample temperature, the differential temperature, or the shape of the power profile during linear heating experiments. The scope of the instrument is demonstrated with the decomposition of basic copper carbonate. The large temperature increase $\text{(∼100\hspace{0.05em}°}\mathrm{C})$ observed on the formation of the strongly coupling oxide indicates the potential sensitivity of using the thermal effects of dielectric changes as a means of detection. Further fine detail can be revealed by the use of derivative plots of either the applied power or the temperature.