Sonochemical dissolution of nanoscale ThO2 and partial conversion into a thorium peroxo sulfate

The influence of the sample morphology and experimental conditions towards the sonochemical dissolution of nanoscale ThO₂ samples in sulfuric acid media is described. Significant sonochemical dissolution rates and yields are observed at 20 kHz under Ar/O₂ atmosphere in dilute 0.5 M H₂SO₄ at room temperature, contrasting with the generally-reported high refractory behavior for ThO₂. The dissolution of ThO₂ combines the physical effects driven by acoustic cavitation phenomenon, the complexing affinity of Th(IV) in sulfuric medium and the sonochemical generation of H₂O₂. These sonochemical conditions further allow the observation of the partial conversion of ThO₂ into a scarce Th(IV) peroxo sulfate with 1D morphology resulting from one or both following processes: dissolution/reprecipitation or formation of an intermediate Th(IV) surface complex.     

Analysis of oxygen shell splitting in hydrothermally grown single crystal ThO2(200)

Single crystals of ThO₂ have been synthesized using hydrothermal growth and studied using the X‐ray absorption fine structure (XAFS) technique. The extended X‐ray absorption fine structure (EXAFS) has been extracted from the XAFS and analyzed using a novel, computational Latin hypercube sampling method. The methodology not only confirms the expected space group and crystal structure, it also identifies the origin of a previously reported split O shell. Since EXAFS is a local order analysis technique, the O shell splitting is identified as an O atom occupying an interstitial site. This result is significant for examining O^2– transport in a ThO₂ matrix and corroborating research indicating partial Th 5f occupancy that is similar to hyper‐stoichiometric UO_2+x compounds. (© 2015 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

Atomistic simulation of CO2 solubility in poly(ethylene oxide) oligomers

We have performed atomistic molecular dynamics simulations coupled with thermodynamic integration to obtain the excess chemical potential and pressure-composition phase diagrams for CO₂ in poly(ethylene oxide) oligomers. Poly(ethylene oxide) dimethyl ether, CH₃O(CH₂CH₂O)_nCH₃ (PEO for short) is a widely applied physical solvent that forms the major organic constituent of a class of novel nanoparticle-based absorbents. Good predictions were obtained for pressure–composition–density relations for CO₂ + PEO oligomers (2 ≤ n ≤ 12), using the Potoff force field for PEO [J. Chem. Phys. 136, 044514 (2012)] together with the TraPPE model for CO₂ [AIChE J. 47, 1676 (2001)]. Water effects on Henry’s constant of CO₂ in PEO have also been investigated. Addition of modest amounts of water in PEO produces a relatively small increase in Henry’s constant. Dependence of the calculated Henry’s constant on the weight percentage of water falls on a temperature-dependent master curve, irrespective of PEO chain length.     

Atomistic view of the recombinative desorption of H2 from H/Si(100)

Scanning tunneling microscopy is employed to investigate the recombinative desorption of H2 from hydrogenated Si(100) surfaces consisting of dihydride (SiH2) and monohydride (SiH) surface species organized in (1 x 1), (3 x 1), and (2 x 1) configurations. The results show that desorption from dihydrides involves a pair of neighboring dihydrides linked along the tetrahedral bond direction. Dihydrides in (3 x 1) domains are separated in the same direction by monohydrides, and desorption from a pair is geometrically impossible. The same desorption mechanism nevertheless applies via first a position switching of dihydrides with neighboring monohydrides.     

Fire suppression using trifluoroiodomethane (CF3I)-carbon dioxide (CO2) mixtures

With the regulatory prohibition for using Halon 1301 (CF₃Br) in fire suppression systems onboard newly certified aircraft, significant research efforts have been undertaken to develop suitable halon replacements with comparable suppression performance that are also eco-friendly with low Ozone Depletion Potential (ODP) and Global Warming Potential (GWP). This paper determined the fire suppression effectiveness for mixtures of trifluoroiodomethane (CF₃I) with carbon dioxide (CO₂) under development as a drop-in halon replacement for onboard aircraft fire suppression systems. Through both experimental measurements and flame simulations using detailed chemical kinetics, we demonstrated that the extinguishment performance of CF₃I-CO₂ blends can be superior to that of the individual components alone. The extinction concentrations were determined for different CF₃I-to-CO₂ ratios introduced into ambient air using a heptane cup burner. The extinction concentrations for pure CF₃I in air (3.36 ± 0.13% vol.) and CO₂ in air (20.74 ± 0.64% vol.) are in close agreement with previously reported values, and first-time extinction concentration data for CF₃I-CO₂ blends are reported. To elucidate important reaction pathways, detailed chemical mechanisms have been compiled for modeling methane-, propane- and heptane-air flame inhibition at ambient conditions. These mechanisms were constructed from published sub-mechanisms for C₇ and C₁-C₃ hydrocarbons and hydrofluorocarbons with additional oxidation chemistry developed for trifluoroiodomethane. The latter sub-mechanism contains 14 species and 91 reactions. Using the CANTERA software package, critical concentration values of CF₃I-CO₂ mixtures in air for extinguishing methane, propane, and n-heptane counterflow flames were determined and compared against experimental non-premixed flame extinction data.     

Supercritical fluid extraction of rare earth elements,thorium and uranium from monazite concentrate and phosphogypsum using carbon dioxide containing tributyl phosphate and di-(2-ethylhexyl)phosphoric acid

Supercritical fluid extraction (SCFE) using carbon dioxide containing tributyl phosphate (TBP), di-(2-ethylhexyl)phosphoric acid (D2EHPA) and their adducts with HNO₃ is applied for extraction of rare earth elements (REE), thorium (Th) and uranium (U) from monazite concentrate (MC) and phosphogypsum (PG). REE extraction from MC and their separation from Th and U are carried out from the product of MC–Na₂CO₃ baking (MCS), which is obtained under microwave irradiation, after which the phosphates of REE, Th and U present in the MC are converted into their oxides. Up to 50% of REE can be recovered as the adducts of TBP and D2EHPA with HNO₃ from the resulting powdered MCS under SCFE conditions, whereas Th and U remain in the solid phase. After a complete dissolution of the MCS residue in the mixture of 4 M HCl and 0.05 M HF, Th and U are quantitatively extracted using supercritical carbon dioxide (SC CO₂) containing D2EHPA and thus separated from the REE that remain in an acidic solution. The conditions of quantitative isolation of REE, Th and U from PG are determined. The schemes for complex processing of MC and PG aimed at REE recovery and their separation from Th and U are suggested.     

Fermionic composite models from confining SU(2)L

A class of fermionic composite models with SU(2)_L as confining group is discussed utilizing the notion of complementarity. The models are, in some sense, fermionic realizations of the bosonic Abbott-Farhi model, avoiding fundamental scalars. Model A has SU(2)_L as confining group; model B has an additional chiral SU(M) and coincides with a model by Abbott, Fahri and Schwimmer; model C has an additional vector SU(M) and provides for a closer realization of the original basonic model.     

Neutral current constraints in the SU(2) ⊗ U(1) models

We present a systematic analysis of hadronic neutral currents in low energy neutrino reactions applicable to SU(2) ? U(1) models with any number of quarks. We point out a relation to determine the Weinberg angle independent of the models for the heavy quarks. We discuss the constraints of atomic neutral current experiments on the SU(2) ? U(1) gauge models.     

Sulfur dioxide (SO2) gas transfer process enhanced by corona discharge

The sulfur dioxide (SO₂) gas transfer process in a corona discharge field has been studied. The experiments were conducted to investigate the effects of voltage, length, and height of the discharge area on the electric transfer of SO₂ as well as on the desulphurization efficiency. Experimental results show that corona discharge can facilitate the SO₂ gas transfer process. The rate and efficiency of desulphurization increase with increasing voltage, length of discharge area, and input power. The addition of a uniform electric field to the corona-discharge field improves the electronic transfer of SO₂. Measured desulphurization efficiency was as high as 95%, and the augmentation of desulphurization efficiency due to corona discharge was nearly 50% under the conditions tested.     

The hidden SO(4) symmetry of general SU(2) thirring models

General four-fermion interactions in two dimensions with SU(2) invariance are shown to possess a hidden SO(4) symmetry. As a consequence physical states belong to irreducible representations of the two commuting O(3) subgroups and their interactions decouple accordingly. Two independnet stable trajectories of the renormalization group are shown to exist perturbatively and are consistently reproduced by abelian bosonization.     

Fitting models to correlated data (large samples)

The study of the ordered series of residuals of a fit proved to be useful in evaluating separately the pure experimental error and the model bias leading to a possible improvement of the modeling [J. Mol. Spectrosc. 217 (2003) 32]. In the present work this procedure is extended to homogeneous correlated data. This new method allows a separate estimation of pure experimental error, model bias, and data correlation; furthermore, it brings a new insight into the difference between goodness of fit and model relevance. It can be considered either as a study of ‘random systematic errors’ or as an extended approach of the Durbin-Watson problem [Biometrika 37 (1950) 409] taking into account the model error. In the present work an empirical approach is proposed for large samples (n?500) where numerical tests are done showing the accuracy and the limits of the method.     

Features of Phonon Spectra of CeO2, ThO2, and NpO2 Crystals Due to the Structure of their Sublattices

Russian Physics Journal - In the CeO2, ThO2, and NpO2 crystals, the acoustic branches of the phonon spectra correspond predominantly to the vibrations of metal ions, and the optical branches...     

Exact consequences of universality in SU(2) × U(1) gauge models

Exact consequences of universality within SU(2) × U(1) gauge models, with leptons in doublets and singlets, and for arbitrary vacuum expectation values of the Higgs fields, imply an extended Weinberg-Salam structure for leptons, with all neutrinos massless (the inverse statement is obvious). We also discuss approximate universality.     

Phenomenology ofSO(10) unified superstring models with intermediate scaleSU R(2) breaking

Electroweak breaking and the supersymmetric particle spectrum are discussed in superstring theories where the gauge group after compactification isSO(10)×E _s ^′ , and where the gauge symmetry after flux breaking isSU(3)×SU(2)×SU(2)×U(1).