BenzoDODA grafted polymeric resin-Plutonium selective solid sorbent.

A new ligand grafted polymeric resin (BenzoDODA SDVB) was synthesized by covalently attaching plutonium selective ligand (BenzoDODA) on to styrene divinyl benzene (SDVB) polymer matrix. BenzoDODA SDVB resin was evaluated for separation and recovery of plutonium(IV) from nitric acid medium. Sorption of Pu(IV) was found to decrease with the increase in nitric acid concentration, with very small sorption above 7.0M HNO3. Sorption kinetics was fast enough to achieve the equilibrium within 60min of contact where the kinetic data fitted well to pseudo-second-order model. Sorption isotherm data fitted well to Langmuir model suggesting chemical interaction between the BenzoDODA moiety and plutonium(IV) ions. Sorption studies with some of representative radionuclides of high level waste showed that BenzoDODA SDVB is selective and therefore could be a promising solid sorbent for separation and recovery of plutonium. Further, the theoretical calculations done on BenzoDODA SDVB resin suggested Pu(NO3)4·BenzoDODA (1:1) sorbed complex conformed to generally observed square antiprism geometry of the plutonium complexes, with contributions from oxygen atoms of four nitrate ions as well as from four oxygen atoms present in BenzoDODA (two phenolic ether oxygen atoms and two carbonyl oxygen atoms of amidic moiety).

Efficient transport of Am(III) from nitric acid medium using a new conformationally constrained (N,N,N',N'-tetra-2-ethylhexyl)7-oxabicyclo[2.2.1]heptane-2,3-dicarboxamide across a supported liquid membrane.

Am(III) is one of the most hazardous radionuclide present in nuclear fuel cycle. A new conformationally constrained diamide, (N,N,N',N'-tetra-2-ethylhexyl)7-oxabicyclo[2.2.1]heptane-2,3-dicarboxamide (OBDA) was studied for Am(III) transport from HNO3 medium across a Supported Liquid Membrane. Transport rate was observed to be significantly fast with ∼95% transport of Am(III) within 1h using 0.1M OBDA in the presence of 15% isodecyl alcohol (IDA)/n-dodecane as carrier. The mechanism of transport was investigated by studying various parameters like feed HNO3/NaNO3 concentration, OBDA concentration in the membrane, membrane pore size, membrane thickness etc. From these studies, the mechanism of transport was found to be diffusion controlled with diffusion co-efficient value of 5.1×10(-6)cm(2)/s. The membrane was found to be highly selective for tri- and tetra-valent actinides, and trivalent lanthanides. OBDA based membrane was found to be stable for at least for ten consecutive cycles of operation.

Removal of americium from aqueous nitrate solutions by sorption onto PC88A-impregnated macroporous polymeric beads.

The removal of Am (III) ions from aqueous solutions was studied by solid-liquid extraction using indigenously synthesized Extractant Impregnated Macroporous Polymeric Beads (EIMPBs). These beads were prepared by an in situ phase inversion method using polyethersulfone (PES) as base polymer and 2-ethylhexyl phosphonic acid mono-2-ethylhexyl ester (PC88A) as an extractant. The synthesized EIMPBs were characterized by FTIR, TGA and SEM techniques. The batch equilibration study using these beads for the uptake of Am (III) was carried out as a function of parameters, like pH, equilibration time, Am (III) concentration, etc. The blank polymeric beads, without PC88A, have shown negligible sorption of Am (III) under the experimental conditions. The experimental data on the sorption behavior of Am (III) on the polymeric beads fitted well in the pseudo-second-order kinetics model. The synthesized polymeric beads exhibited very good sorption capacity for Am (III) at pH 3. The reusability of the beads was also ascertained by repetitive sorption/desorption of Am (III) up to 10 cycles of operation, without any significant change in their sorption characteristics.

Supported liquid membrane transport studies on Am(III), Pu(IV), U(VI) and Sr(II) using irradiated TODGA.

Transport behaviour of actinides viz. Am(3+), Pu(4+) and UO(2)(2+) was investigated from nitric acid feed conditions using PTFE (polytetrafluoroethylene) flat sheet supported liquid membranes (SLM) containing an irradiated solvent system comprising of N,N,N',N'-tetra-n-octyldiglycolamide (TODGA) as the carrier extractant and N,N-di-n-hexyloctanamide (DHOA) as the phase modifier. The present studies were carried out in order to understand the effect of irradiation on the long term reusability of the SLM and the decontamination behaviour in the absorbed dose range of 0-100 MRad. The studies using irradiated carrier included those with irradiated TODGA without any phase modifier and with 0.1M as well as 0.5M DHOA as the phase modifier. Transport behaviour of all the metal ions were found to be seriously affected with increasing radiation dose which was reflected in the decreasing percentage transport (%T) as well as permeability co-efficient (P) values. Though Sr(II) transport was quite significant with all the three unirradiated solvent systems, it was surprisingly low (<5%) when solvents exposed to 100 MRad dose were used in the SLM. Separation factors (S.F.) of the actinides over Sr(II) were calculated and were found to increase at higher radiation doses suggesting possibility of getting better decontamination on prolonged use of the supported liquid membrane system.