Mineralogical,geochemical and radiological characterisation of Selmo Formation in Batman area,Turkey

This work deals with the mineralogical, geochemical and radiological characterisations of Selmo Formation in Batman neighbourhood. The upper Miocene–Pliocene Selmo Formation is common in the centre of Batman and composed of carbonated sandy claystones and silty–sandy stone lenses. The common whole minerals of the samples are quartz, feldspars, calcite and dolomite. The clay minerals are smectite, illite, chlorite and mixed-layer clay (chlorite–smectite). The geochemical mean values of the samples are 51.7% SiO₂; 12.6% Al₂O₃; 6.2% Fe₂O₃; 3.6% MgO; 6.3% CaO; 1.1% Na₂O; 1.7% K₂O; 0.8% TiO₂; 0.2% P₂O₅; 0.1% MnO; and 0.03% Cr₂O₃. In addition, baseline maps for the concentrations of each radionuclide, the radium equivalent activity and the outdoor gamma dose rate distributions have been plotted for the study area. The mean activity concentrations of ²²⁶Ra, ²³²Th, ⁴⁰K and ¹³⁷Cs were determined to be 32, 24, 210 and 9 Bq kg^?1, respectively. The assessments of the radiological hazard indices, such as radium equivalent activity, absorbed dose rate in air, annual effective dose equivalent, excess lifetime cancer risk, external hazard index and internal hazard index, were calculated and compared with the internationally accepted reference values. This study shows that the concentrations of radioactivities in the measured samples were within the recommended safety limits and did not pose to be any significant source of radiation hazard.     

Synthesis and polymerizations of six aminophosphonate‐containing methacrylates

Two different groups of novel aminophosphonate‐containing methacrylates were synthesized. The route to the first group involves reactions of ethyl α‐bromomethacryate (EBBr) and t‐butyl α‐bromomethacryate (TBBr) with diethyl aminomethylphosphonate and diethyl 2‐aminoethylphosphonate. Bulk and solution polymerizations at 60–80 °C with 2,2′‐azobis(isobutyronitrile) (AIBN) gave crosslinked or soluble polymers depending on monomer structure and polymerization conditions. Increasing bulkiness from ethyl to t‐butyl decreases the polymerization rate, correlated well with the chemical shift differences of double bond carbons and consistent with the lower molecular weights of t‐butyl ester polymers (M_n = 1800–7900 vs. 50,000–72,000). The route to the second group involves the Michael addition reaction between diethyl aminomethylphosphonate and diethyl 2‐aminoethylphosphonate with 3‐(acryloyloxy)‐2‐hydroxypropyl methacrylate (AHM) to give secondary amines. The photopolymerization using differential scanning calorimeter showed that these monomers have similar or higher reactivities than AHM, even though AHM has two double bonds. The high rates of polymerization of these monomers were attributed to both hydrogen bonding interactions due to additional NH groups as well as chain transfer reactions. All the homopolymers obtained produced char (17–35%) on combustion. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011.     

A density functional theory study of ethylene adsorption on Ni10(1 1 1), Ni13(1 0 0) and Ni10(1 1 0) surface cluster models and Ni13 nanocluster

Ethylene adsorption was studied by use of DFT/B3LYP with basis set 6-31G(d,p) in Gaussian’03 software. It was found that ethylene has adsorbed molecularly on all clusters with π adsorption mode. Relative energy values were calculated to be −50.86 kcal/mol, −20.48 kcal/mol, −32.44 kcal/mol and −39.27 kcal/mol for Ni₁₃ nanocluster, Ni₁₀(1 1 1), Ni₁₃(1 0 0) and Ni₁₀(1 1 0) surface cluster models, respectively. Ethylene adsorption energy is inversely proportional to Ni coordination number when Ni₁₀(1 1 1), Ni₁₃(1 0 0) and Ni₁₀(1 1 0) cluster models and Ni₁₃ nanocluster are compared with each other.     

Trapping centers and their distribution in Tl2Ga2Se3S layered single crystals

Thermally stimulated current (TSC) measurements with current flowing perpendicular to the layers were carried out on Tl₂Ga₂Se₃S layered single crystals in the temperature range of 10-260 K. The experimental data were analyzed by using different methods, such as curve fitting, initial rise and isothermal decay methods. The analysis revealed that there were three trapping centers with activation energies of 12, 76 and 177 meV. It was concluded that retrapping in these centers was negligible, which was confirmed by the good agreement between the experimental results and the theoretical predictions of the model that assumes slow retrapping. The capture cross section and the concentration of the traps have been also determined. An exponential distribution of electron traps was revealed from the analysis of the TSC data obtained at different light illumination temperatures. This experimental technique provided values of 10 and 88 meV/decade for the traps distribution related to two different trapping centers.     

Spectroscopic ellipsometry study of above-band gap optical constants of layered structured TlGaSe2, TlGaS2 and TlInS2 single crystals

Spectroscopic ellipsometry measurements on TlGaSe₂, TlGaS₂ and TlInS₂ layered crystals were carried out on the layer-plane (0 0 1) surfaces, which are perpendicular to the optic axis c^?, in the 1.2–6.2 eV spectral range at room temperature. The real and imaginary parts of the pseudodielectric function as well as pseudorefractive index and pseudoextinction coefficient were found as a result of analysis of ellipsometric data. The structures of critical points in the above-band gap energy range have been characterized from the second derivative spectra of the pseudodielectric function. The analysis revealed four, five and three interband transition structures with critical point energies 2.75, 3.13, 3.72 and 4.45 eV (TlGaSe₂), 3.03, 3.24, 3.53, 4.20 and 4.83 eV (TlGaS₂), and 3.50, 3.85 and 4.50 eV (TlInS₂). For TlGaSe₂ crystals, the determined critical point energies were assigned tentatively to interband transitions using the available electronic energy band structure.     

Ellipsometry study of interband transitions in TlGaS2xSe2(1−x) mixed crystals (0≤x≤1)

In this paper, the spectroscopic ellipsometry measurements on TlGaS_2xSe_2(1?x) mixed crystals (0≤x≤1) were carried out on the layer-plane (001) surfaces with light polarization E⊥c^? in the 1.2–6.2 eV spectral range at room temperature. The real and imaginary parts of the dielectric function, refractive index and extinction coefficient were calculated from ellipsometric data using the ambient-substrate optical model. The critical point energies in the above-band gap energy range have been obtained from the second derivative spectra of the dielectric function. Particularly for TlGaSe₂ crystals, the determined critical point energies were assigned tentatively to interband transitions using the available electronic energy band structure. The effect of the isomorphic anion substitution (sulfur for selenium) on critical point energies in TlGaS_2xSe_2(1?x) mixed crystals was established.     

An ONIOM and DFT study of water and ammonia adsorption on anatase TiO2 (001) cluster

Density functional theory (DFT) calculations at ONIOM DFT B3LYP/ 6‐31G**‐MD/UFF level are employed to study molecular and dissociative water and ammonia adsorption on anatase TiO₂ (001) surface represented by partially relaxed Ti₂₀O₃₅ ONIOM cluster. DFT calculations indicate that water molecule is dissociated on anatase TiO₂ (001) surface by a nonactivated process with an exothermic relative energy difference of 58.12 kcal/mol. Dissociation of ammonia molecule on the same surface is energetically more favorable than molecular adsorption of ammonia (?37.17 kcal/mol vs. ?23.28 kcal/mol). The vibration frequency values also are computed for the optimized geometries of adsorbed water and ammonia molecules on anatase TiO₂ (001) surface. The computed adsorption energy and vibration frequency values are comparable with the values reported in the literature. Finally, several thermodynamical properties (ΔH°, ΔS°, and ΔG°) are calculated for temperatures corresponding to the experimental studies. © 2010 Wiley Periodicals, Inc. Int J Quantum Chem, 2011     

An ONIOM and DFT study of water adsorption on rutile TiO2 (110) cluster

Density functional theory (DFT) calculations performed at ONIOM DFT B3LYP/6‐31G**‐MD/UFF level are employed to study molecular and dissociative water adsorption on rutile TiO₂ (110) surface represented by partially relaxed Ti₂₅O₃₇ ONIOM cluster. DFT calculations indicate that dissociative water adsorption is not favorable because of high activation barrier (23.2 kcal/mol). The adsorption energy and vibration frequency of both molecularly and dissociatively adsorbed water molecule on rutile TiO₂ (110) surface compare well with the values reported in the literature. © 2009 Wiley Periodicals, Inc. Int J Quantum Chem, 2011     

Thermally stimulated current measurements in undoped Ga3InSe4 single crystals

The trap levels in nominally undoped Ga₃InSe₄ crystals were investigated in the temperature range of 10-300 K using the thermally stimulated currents technique. The study of trap levels was accomplished by the measurements of current flowing along the c-axis of the crystal. During the experiments we utilized a constant heating rate of 0.8 K/s. Experimental evidence is found for one hole trapping center in the crystal with activation energy of 62 meV. The analysis of the experimental TSC curve gave reasonable results under the model that assumes slow retrapping. The capture cross-section of the trap was determined as 1.0×10⁻²⁵ cm² with concentration of 1.4×10¹⁷ cm⁻³.     

Adsorption of water and ammonia on TiO2-anatase cluster models

Density functional theory (DFT) calculations performed at B3LYP/6-31G^∗∗ level are employed to study water and ammonia adsorption and dissociation on (1 0 1) and (0 0 1) TiO₂ anatase surfaces both represented by totally fixed and partially relaxed Ti₂O₉H₁₀ cluster models. PM3 semiempirical calculations were also conducted both on Ti₂O₉H₁₀ and Ti₉O₃₃H₃₀ clusters in order to assess the effect of cluster size. Following dissociation, the adsorption of H₂O and NH₃ by H-bonding on previously H₂O and NH₃ dissociated systems, respectively are also considered. It is found that the adsorption energies and geometries of water and ammonia molecules on (1 0 1) and (0 0 1) anatase cluster models depend on surface relaxation. The vibration frequency values are also calculated for the optimized geometries. The adsorption energies and vibration frequency values computed are compared with the available theoretical and experimental literature.