A Novel Microemulsion Phase Transition: Toward the Elucidation of Third-Phase Formation in Spent Nuclear Fuel Reprocessing

We present evidence that the transition between organic and third phases, which can be observed in the plutonium uranium reduction extraction (PUREX) process at high metal loading, is an unusual transition between two isotropic bicontinuous microemulsion phases. As this system contains so many components, however, we have been seeking first to investigate the properties of a simpler system, namely, the related metal-free, quaternary water/<i>n</i>-dodecane/nitric acid/tributyl phosphate (TBP) system. This quaternary system has been shown to exhibit, under appropriate conditions, three coexisting phases: a light organic phase, an aqueous phase, and the so-called third phase. In the current work, we focused on the coexistence of the light organic phase with the third phase. Using Gibbs ensemble Monte Carlo (GEMC) simulations, we found coexistence of a phase rich in nitric acid and dilute in <i>n</i>-dodecane (the third phase) with a phase more dilute in nitric acid but rich in <i>n</i>-dodecane (the light organic phase). The compositions and densities of these two coexisting phases determined using the simulations were in good agreement with those determined experimentally. Because such systems are generally dense and the molecules involved are not simple, the particle exchange rate in their GEMC simulations can be rather low. To test whether a system having a composition between those of the observed third and organic phases is indeed unstable with respect to phase separation, we used the Bennett acceptance ratio method to calculate the Gibbs energies of the homogeneous phase and the weighted average of the two coexisting phases, where the compositions of these phases were taken both from experimental results and from the results of the GEMC simulations. Both demixed states were determined to have statistically significant lower Gibbs energies than the uniform, mixed phase, providing confirmation that the GEMC simulations correctly predicted the phase separation. Snapshots from the simulations and a cluster analysis of the organic and third phases revealed structures akin to bicontinuous microemulsion phases, with the polar species residing within a mesh and with the surface of the mesh formed by amphiphilic TBP molecules. The nonpolar <i>n</i>-dodecane molecules were observed in these snapshots to be outside this mesh. The only large-scale structural differences observed between the two phases were the dimensions of the mesh. Evidence for the correctness of these structures was provided by the results of small-angle X-ray scattering (SAXS) studies, where the profiles obtained for both the organic and third phases agreed well with those calculated from simulations. Finally, we looked at the microscopic structures of the two phases. In the organic phase, the basic motif was observed to be one nitric acid molecule hydrogen-bonded to a TBP molecule. In the third phase, the most common structure was that of the hydrogen-bonded TBP–HNO₃–HNO₃ chain. A cluster analysis provided evidence for TBP forming an extended, connected network in both phases. Studies of the effects of metal ions on these systems will be presented elsewhere

Comparative Molecular Dynamics Study on Tri‑<i>n</i>‑butyl Phosphate in Organic and Aqueous Environments and Its Relevance to Nuclear Extraction Processes

A refined model for tri-<i>n</i>-butyl phosphate (TBP), which uses a new set of partial charges generated from our ab initio density functional theory calculations, has been proposed in this study. Molecular dynamics simulations are conducted to determine the thermodynamic properties, transport properties, and the microscopic structures of liquid TBP, TBP/water mixtures, and TBP/<i>n</i>-alkane mixtures. These results are compared with those obtained from four other TBP models, previously described in the literature. We conclude that our refined TBP model appears to be the only TBP model from this set that, with reasonable accuracy, can simultaneously predict the properties of TBP in bulk TBP, in organic diluents, and in aqueous solution. The other models only work well for two of the three systems mentioned above. This new TBP model is thus appropriate for the simulation of liquid–liquid extraction systems in the nuclear extraction process, where one needs to simultaneously model TBP in both aqueous and organic phases. It is also promising for the investigation of the microscopic structure of the organic phase in these processes and for the characterization of third-phase formation, where TBP again interacts simultaneously with both polar and nonpolar molecules. Because the proposed TBP model uses OPLS-2005 Lennard-Jones parameters, it may be used with confidence to model mixtures of TBP with other species whose parameters are given by the OPLS-2005 force field

Photonic Crystals Fabricated by Block Copolymerization-Induced Microphase Separation

We present a method for fabricating photonic crystals (PCs) by polymerization-induced microphase separation of block copolymers (BCPs). Molecular weight of BCP for PCs is so large that it has been difficult for conventional solution casting and annealing methods to complete the microphase separation to form periodically ordered submicron structures. Our method overcomes the difficulty by inducing the microphase separation and transitions during the polymerization, when the molecular weight of the BCPs is small enough for the microphase separation and transitions. The microphase-separated structure is then enlarged while maintaining the self-similarity. We succeeded in fabricating PCs with reflection wavelength λ_m ≈ 1000 nm and a full width at half-maximum Δλ = 0.05λ_m by living-radical bulk block copolymerization of poly­(methyl methacrylate)-<i>block</i>-polystyrene

Small-Angle Neutron Scattering Study on Specific Polymerization Loci Induced by Copolymerization of Polymerizable Surfactant and Styrene during Miniemulsion Polymerization

We have investigated the origin of a specific polymerization loci that yielded copolymer particles with a bimodal gel permeation chromatographic profile in the early stage of miniemulsion polymerization of styrene (St) with the polymerizable surfactant <i>N</i>-<i>n</i>-dodecyl-<i>N</i>-2-methacryloyloxyethyl-<i>N</i>,<i>N</i>-dimethylammonium bromide (C₁₂DMAEMA). The formation of particles by miniemulsion polymerization using C₁₂DMAEMA was investigated as a function of the polymerization time (<i>t</i>_p) and was compared with that using the nonpolymerizable surfactant cetyltrimethylammonium bromide (CTAB). St was miniemulsified with C₁₂DMAEMA or CTAB and was polymerized with either a water-soluble initiator, 2,2′-azobis­(2-amidinopropane) dihydrochloride (V50), or an oil-soluble initiator, 2,2′-azobis­(isobutyronitrile) (AIBN), at 60 °C in the presence of polystyrene (PSt) as a hydrophobe. Gel permeation chromatography (GPC) and elemental analysis indirectly predicted two different polymerization loci in the St/C₁₂DMAEMA/V50 polymerization system. Time-resolved small-angle neutron scattering (SANS) was used to directly observe and examine the specific polymerization loci in the miniemulsion polymerization solutions. The droplets formed in the St/C₁₂DMAEMA/V50/PSt at the initial stage of the polymerization were not fully stabilized by C₁₂DMAEMA and poly­(C₁₂DMAEMA-<i>ran</i>-St) and were found to build up the large aggregates. The spherical droplets were stabilized later in the polymerization (<i>t</i>_p > 20 min) by forming a homogeneous dispersion in the water phase. In contrast, the droplets stabilized by CTAB in St/CTAB/V50/PSt maintained their size and shape throughout the polymerization. As a result, in both polymerization systems of St/C₁₂DMAEMA/V50/PSt and St/CTAB/V50/PSt, the particle size was found to depend strongly on the size of the droplets formed in the early stage of polymerization. Porod analysis of the power law scattering observed by SANS provided direct evidence for the specific polymerization loci, which appeared in the early stage of the polymerization system of St/C₁₂DMAEMA/V50/PSt on the surface of the droplet, and was the origin of the bimodal peaks in the GPC chromatogram

Small-angle neutron scattering study of specific interaction and coordination structure formed by mono-acetyl-substituted dibenzo-20-crown-6-ether and cesium ions

<p>This study uses small-angle neutron scattering (SANS) to elucidate the coordination structure of the complex of mono-acetyl-substituted dibenzo-20-crown-6-ether (ace-DB20C6) with cesium ions (Cs⁺). SANS profiles obtained for the complex of ace-DB20C6 and Cs⁺ (ace-DB20C6/Cs) in deuterated dimethyl sulfoxide indicated that Cs⁺ coordination resulted in a more compact structure than the free ace-DB20C6. The data were fitted well with SANS profiles calculated using Debye function for scattering on an absolute scattering intensity scale. For this theoretical calculation of the scattering profiles, the coordination structure proposed based on density functional theory calculation was used. Consequently, we conclude that the SANS analysis experimentally supports the proposed coordination structure of ace-DB20C6/Cs and suggests the following: (1) the complex of ace-DB20C6 and Cs⁺ is formed with an ace-DB20C6/Cs molar ratio of 1/1 and (2) the two benzene rings of ace-DB20C6 fold around Cs⁺ above the center of the crown ether ring of ace-DB20C6.</p