Theoretical insights on a series of difluoramino group–based energetic molecules

A series of difluoramino group–based energetic molecules was designed and the relative properties were investigated by density functional theory. The results show that all the designed molecules have high positive heat of formation which ranges from 479.48 to 724.02 kJ/mol, detonation velocity ranges from 8.01 to 11.26 km/s, detonation pressure ranges from 28.03 to 63.46 GPa, and impact sensitivity ranges from 18.2 to 54.5 cm. Then, compounds D2, D3, D5, E4, E5, E6, and F2 were selected as the potential high energy density materials based on detonation properties and sensitivities. Natural bond orbital charges, electronic density, frontier molecular orbital, electrostatic potential on the surface, and thermal dynamic parameters of the screened molecules (compounds D2, D3, D5, E4, E5, E6, and F2) were also predicted at B3LYP/6‐31G(d,p) level to give a better understanding on the chemical and physical properties of them.     

Matrix‐isolation IR spectroscopy of R‐(+)‐3‐methylcyclopentanone in para‐hydrogen crystal

High‐resolution infrared (IR) spectra of R‐(+)‐3‐methylcyclopentanone (R3MCP) in para‐hydrogen (pH₂) crystal were recorded and compared with the corresponding IR spectra of R3MCP in Argon (Ar) isolation matrix as well as the IR spectra of the neat crystalline R3MCP at low deposition temperature of 4 ± 0.05 K. Moreover, IR spectra of R3MCP, hosted in pH₂ crystal, were recorded using a high‐resolution Fourier transform IR spectrometer as a function of sample concentration and over the range 10–300 ppm. Furthermore, density functional theory calculations of simulated IR spectra for the optimized geometries of R3MCP equatorial‐methyl and axial‐methyl conformers are compared with experimental spectra for the purpose of investigating molecular conformation. Upon comparison between theoretical and experimental IR spectra, vibrational modes arising from equatorial and axial conformers have been successfully assigned and related to the individual conformer's structure. Copyright © 2015 John Wiley & Sons, Ltd.     

Temperature dependence of the noise amplitude in graphene and graphene oxide

Graphene and related materials such as carbon nanotubes and graphene oxide are promising materials for future applications in chemical sensing and electronics. Electronic noise in these materials is typically very high due to the low number of carriers and the inverse dependence of 1/f noise on the number of carriers. We have investigated the changes in 1/f noise amplitude with temperature in exfoliated graphene and reduced graphene oxide devices. We show that using reduced graphene oxide results in an intriguing environmental coupling to noise amplitude. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

dielectric relaxation in VDF<Subscript>60</Subscript>/Tr<Subscript>40</Subscript> and VDF<Subscript>88</Subscript>/Te<Subscript>12</Subscript> polar copolymers embedded in porous glass matrices

The dielectric properties of composite materials prepared by embedding P(VDF₆₀/Tr₄₀) and P(VDF₈₈/Te₁₂) polar copolymers in porous glass matrices with a mean flow-through pore diameter of around 320 nm were investigated in the temperature range 200–450 K. Strong dielectric relaxation, the characteristic time of which conformed to the Williams-Landel-Ferry law, was observed in the vicinity of glass transition point T _g of an amorphous fraction of polymer inclusions. An increase (≈10 K) in the T _g temperature of the amorphous fraction of incorporated polymeric materials was detected.     

pH-dependent kinetics of MgCl2 adsorption under a fatty-acid Langmuir film

The effect of subphase pH (5.5 and 10.5) on the structure of behenic-acid monolayers was investigated during Mg²⁺ adsorption by means of Grazing Incidence X-ray Diffraction (GIXD) and Brewster Angle Microscopy (BAM). The final phase corresponding to an ion superlattice commensurate to the behenic-acid cell is pH-independent. In contrast, the sequence of phases evidenced from the initial L₂-phase to this final state presents at pH 10.5 an additional stage associated to a film condensation toward the L' ₂-phase. The structures of the intermediate states preceding the superstructure nucleation are slightly different, both with a short-range fatty-acid order. Finally, a laser light effect that could result from visible light absorption by the inorganic complexes is evidenced in the final state as well as in the intermediate phases.     

Highly sensitive and selective trimethylamine sensors based on WO3 nanorods decorated with Au nanoparticles

One-dimensional tungsten oxide (WO₃) gas sensing materials have been widely used for the detection of trimethylamine (TMA) gas. Furthermore, it is believed that an effective method to improve the gas sensing performance is to introduce noble metals into sensing materials. In this work, a novel gas sensing material was prepared by decorating Au nanoparticles on WO₃ nanorods. Based on field emission scanning electron microscopy (FESEM/EDS), X-ray diffraction (XRD), and transmission electron microscopy (TEM), the morphology and microstructure of as-prepared samples were characterized. Results show that Au nanoparticles with diameter of 13–15 nm are loaded on the surface of WO₃ nanorods with length of about 1–2 µm and width of 50–80 nm. Gas sensing tests reveal that the Au@WO₃ sensor has remarkably enhanced response to TMA gas compared with pure WO₃ nanorods. In addition, and the gas sensing mechanism has been investigated based on the experimental results. The superior sensing features indicate the present Au@WO₃ nanocomposites are promising for gas sensors, which can be used in the detection of the trimethylamine gas and this work provides insights and strategies for the fabrication of sensing materials.     

Functionalized SBA-15 organosilicas as sorbents of zinc(II) ions

SBA-15 nanoporous silicas functionalized with amine-, thiol-, vinyl-, phenyl- and cyano surface groups were synthesized by using the amphiphilic block copolymer P123 as the structure-directing agent. The obtained materials have a well-developed porous structure - the values of specific surface area are in the range 800-950 m²/g and the sizes of cylindrical mesopores are in the range 7.4-8.6 nm. It was established that the size of the mesopores strongly depends even on small amounts of co-monomers co-condensing with TEOS. Adsorption of Zn(II) ions at the SBA-15/NaCl interface was investigated by means of the radioactive isotope tracer technique over the pH range of 3-11. Surface charge density, adsorption density, pH_50% and ΔpH_10-90% parameters for different concentrations of the carrying electrolyte were evaluated and discussed.     

Defect chemistry and oxygen transport of (La0.6Sr0.4 − xMx)0.99Co0.2Fe0.8O3 − δ, M = Ca (x = 0.05, 0.1), Ba (x = 0.1, 0.2), Sr: Part I: Defect chemistry

This paper is the first part of a two part series, where the effects of varying the A-site dopant on the defect chemistry, the diffusion coefficient and the surface catalytic properties of the materials (La_0.6Sr_0.4 − xM_x)_0.99Co_0.2Fe_0.8O_3 − δ, M = Sr, Ca (x = 0.05, 0.1), Ba (x = 0.1, 0.2) (LSMFC) have been investigated. In part I, the findings on the defect chemistry are reported, while the transport properties are reported in part II. Substitution of Sr²⁺ ions with Ca²⁺ ions (smaller ionic radius) and Ba²⁺ ions (larger ionic radius) strains the crystal structure differently for each composition while keeping the average valence of the cations constant. The Ba²⁺ containing materials show the largest oxygen loss at elevated temperatures, while the purely Sr²⁺ doped material showed the smallest oxygen loss. This was reflected in the partial oxidation entropy of the materials. The measured oxygen loss was modelled with point defect chemistry models. Measurements at very low p_O2 showed several phase transitions.     

Electrical and electrochemical behaviour of several LiFe<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>Co<Subscript>1 − <Emphasis Type="Italic">x</Emphasis></Subscript>PO<Subscript>4</Subscript> solid solutions as cathode materials for lithium ion batteries

Several olivine phosphates were investigated in the last years as cathode materials for secondary lithium ion batteries. Among these compounds, LiFe _x Co_1 − x PO₄ solid solutions might be interesting candidates because they should combine the high potential value of Co³⁺/Co²⁺ (higher than 4.5 V vs Li⁺/Li) with the relatively high charge–discharge rate of LiFePO₄. Solid solutions were prepared by solid-state route and characterised by X-ray powder diffraction, cyclic voltammetry, impedance spectroscopy and the Hebb–Wagner method. The results show that also low amount of iron induces high electronic conductivity in the solid solutions.     

Two-phase reaction mechanism during chemical lithium insertion into α-MoO<Subscript>3</Subscript>

The phase transition during chemical lithium insertion into α-MoO₃ was investigated by chemical analysis, X-ray diffraction (XRD) and electrochemical characterisation. The samples have been prepared by reaction of various amounts of water-free lithium iodide with fine-particulate orthorhombic molybdenum trioxide in n-hexane (non-aqueous media), which yielded materials with different Li/Mo ratio. XRD investigations of these materials proved that the crystal structure of the layered α-MoO₃ has been changed after the chemical lithiation. The phase transition ranged from 0.25 < x < 0.5 in Li _x MoO₃ upon chemical lithium insertion into α-MoO₃. The XRD lines of lithium inserted phase Li _x MoO₃ grew at the expense of the XRD lines of the pristine α-MoO₃ as lithium ions were chemically inserted until the disappearance of lines related to α-MoO₃. The electrochemical performance of the lithiated samples is improved in comparison with the starting material (non-lithiated α-MoO₃).     

Spectroscopic characterization,photoinduced processes and cytotoxic properties of substituted N‐ethyl selenadiazoloquinolones

7‐R‐9‐ethyl‐6,9‐dihydro‐6‐oxo‐[1,2,5]selenadiazolo[3,4‐h]quinolines (R = H, COOC₂H₅, COOCH₃, COOH and COCH₃, E1h , E2h , E3h , E4h , E5h ) and 6‐ethyl‐6,9‐dihydro‐9‐oxo‐[1,2,5]selenadiazolo[3,4‐f]quinoline ( E1f ) were characterized by UV/vis, FT‐IR and fluorescence spectroscopy. The electronic absorption spectra of the derivatives E1h , E2h , E3h and E5h in the aprotic solvents dimethylsulfoxide (DMSO) and acetonitrile (ACN) reveal low‐energy absorption maxima with λ_max > 400 > nm, shifted hypsochromically in water. In DMSO, N‐ethyl selenadiazoloquinolones behave as strong fluorescent agents (λ_em ≥ 550 nm) with the exception of the carboxylic acid derivative E4h which shows only poor emission. Photoinduced reactions of N‐ethyl selenadiazoloquinolones were investigated by means of electron paramagnetic resonance (EPR) spectroscopy. Photoexcitation of N‐ethyl selenadiazoloquinolones in aerated DMSO with either 385 nm or 400 nm wavelengths, monitored by EPR spin trapping technique, results in the generation of superoxide radical anions; under an inert atmosphere, the generation of methyl radicals originating from the solvent predominates. Upon exposure at either 365 nm, 385 nm or 400 nm, aerated ACN solutions of selenadiazoloquinolones in the presence of sterically hindered amines produce nitroxide radicals via a reaction with photogenerated singlet oxygen. The 7‐substituted derivatives of 9‐ethyl‐6,9‐dihydro‐6‐oxo‐[1,2,5]selenadiazolo[3,4‐h]quinoline behave as photosensitizers activating molecular oxygen upon photoexcitation and possess the sufficient photochemical stability under the given experimental conditions. The cytotoxic effects of non‐photoactivated and UVA photoactivated N‐ethyl substituted selenadiazoloquinolones on cancer (human HeLa and murine L1210) and non‐cancer (NIH‐3T3) cell lines were monitored by the MTT test. The derivative E2h demonstrates the highest cytotoxic/photocytotoxic activity on the neoplastic cell lines. Copyright © 2013 John Wiley & Sons, Ltd.     

Temperature Dependence of the Transmission Spectra of Silicate Glasses Containing CdS<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>Se<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript> Semiconducting Nanocrystals

The transmission spectra of silicate glasses containing CdS_{1 − x} Se _x semiconducting nanocrystals of various sizes are investigated in the temperature range 20–300°C. It is shown that for explaining optical properties of these materials, not only the nanocrystal sizes, but also the structural changes occurring in nanocrystals during their formation must be taken into account.     

Pure and Sn-, Ga- and Mn-doped ZnO gas sensors working at different temperatures for formaldehyde,humidity, NH<Subscript>3</Subscript>, toluene and CO

ZnO and Sn-, Ga- and Mn-doped ZnO nanoparticles were prepared by a coprecipitation method, and characterized by scanning electron microscopy (SEM), energy dispersive spectra (EDS), X-ray diffraction (XRD) and Raman spectra. The gas sensing properties were studied using formaldehyde, relative humidity, NH₃, toluene and CO as the probes. The results show that all particles have wurtzite ZnO phase, though Sn–ZnO has a relatively smaller particle (and crystallite) size than the other three samples. Gas sensing property tests reveal that the temperature where the gas sensing maximum is gained (T _M) is changed by different dopants: Sn–ZnO and Mn–ZnO have relatively lower T _M (∼100°C lower) compared with that of pure ZnO, while Ga–ZnO has the same T _M as pure ZnO except in CO sensing. Thermoluminescence (TL) spectra were used to investigate the mechanism of T _M change. The peak positions of Ga–ZnO and ZnO are the same at 300–350°C, while that of Sn–ZnO shifts to 250–300°C, which might contribute to the same T _M of Ga–ZnO and pure ZnO and relatively lower T _M of Sn–ZnO. In the case of Mn–ZnO, the luminescence emission is evidently limited by its black color.     

RETRACTED ARTICLE: Quantum effects on translation and rotation of molecular chlorine in solid para-hydrogen

Structure and quantum effects of a Cl₂ molecule embedded in fcc and hcp para-hydrogen (pH₂) crystals are investigated in the zero-temperature limit. The interaction is modelled in terms of Cl₂–pH₂ and pH₂–pH₂ pair potentials from ab initio CCSD(T) and MP2 calculations. Translational and rotational motions of the molecules are described within three-dimensional anharmonic Einstein and Devonshire models, respectively, where the crystals are either treated as rigid or allowed to relax. The pH₂ molecules, as well as the heavier Cl₂ molecule, show large translational zero-point energies (ZPEs) and undergo large-amplitude translational motions. This gives rise to substantial reductions in the cohesive energies and expansions of the lattices, in agreement with experimental results for pure hydrogen crystals. The rotational dynamics of the Cl₂ impurity is restricted to small-amplitude librations, again with high librational ZPEs, which are described in terms of two-dimensional non-degenerate anharmonic oscillators. The lattice relaxation causes qualitative changes of the rotational energy surfaces, which finally favour librations around the crystallographic directions pointing towards the nearest neighbours, both for fcc and hcp lattices. Implications on the reactant orientation in the experimentally observed laser-induced chemical reaction, Cl + H₂ → HCl + H, are discussed.     

Hexadecapole deformation studies in<Superscript>148,150</Superscript>Nd

Theγ-ray yields from inelastically excited 2⁺ and 4⁺ levels of^{144,146,148,150}Nd nuclei using¹⁶O beam at near barrier energies in coincidence with the back-scattered projectiles were measured. The 2⁺ and 4⁺ level cross-sections were deduced from the measuredγ-ray yields and fitted to the DWBA calculations to obtain the reduced transition matrix elementsM(E4: 0⁺ → 4⁺). The deducedM(E4) values for¹⁴⁸Nd and¹⁵⁰Nd nuclei, 0.16(0.05) and 0.22(0.12) eb², respectively are consistent with theoretical predictions.     

Magnetic Properties of Monomer and Dimer Tetrahedral VO<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript> Entities Dispersed on Amorphous Silica-based Materials: Prediction of EPR Parameters from Relativistic DFT Calculations and Broken Symmetry Approach to Exchange Couplings

Molecular structures of the isolated tetrahedral oxovanadium(IV) and bridged μ-oxo-divanadium(IV) complexes hosted by the clusters mimicking surfaces of amorphous silica-based materials were investigated using density functional theory (DFT) calculations. Principal values of the g and A tensors for the monomer vanadyl species were obtained using the coupled-perturbed DFT level of theory and the spin–orbit mean-field approximation (SOMF). Magnetic exchange interaction for the μ-oxo bridged vanadium(IV) dimer was investigated within the broken symmetry approach. An antiferromagnetic coupling of the individual magnetic moments of the vanadium(IV) centers in the [VO–O–VO]²⁺ bridges was revealed and discussed in detail. The coupling explains pronounced decrease of the electron paramagnetic resonance signal (EPR) intensity, observed for the reduced VO _x /SiO₂ samples with the increasing coverage of vanadia, in terms of transformation of the paramagnetic monomer species into the dimers with S = 0 ground state.     

Large optical nonlinearity in CaCu<Subscript>3</Subscript>Ti<Subscript>4</Subscript>O<Subscript>12</Subscript> thin films

CaCu₃Ti₄O₁₂ (CCTO) thin films were successfully prepared on LaAlO₃ substrates by pulsed laser deposition technique. We measured the nonlinear optical susceptibility of the thin films using Z-scan method at a wavelength of 532 nm with pulse durations of 25 ps and 7 ns. The large values of the third-order nonlinear optical susceptibility, χ ⁽³⁾, of the CCTO film were obtained to be 2.79×10⁻⁸ esu and 3.30×10⁻⁶ esu in picosecond and nanosecond time regimes, respectively, which are among the best results of some representative nonlinear optical materials. The origin of optical nonlinearity of CCTO films was discussed. The results indicate that the CCTO films on LaAlO₃ substrates are promising candidate materials for applications in nonlinear optical devices.     

δ/γ transformation in non-equilibrium solidified peritectic Fe-Ni alloy

Through phase transformation kinetic analysis and experimental observation, the δ/γ transformation occurring in the non-equilibrium peritectic Fe-4.33at.%Ni alloys was systematically investigated. According to JMA solid-state transformation kinetic theory, the Time-Temperature-Transformation (TTT) curves of the δ/γ transformation in peritectic Fe-Ni alloy were calculated. On this basis, the physical correlation between the δ/γ transformation and the initial undercooling of melt (△T) was elucidated. The results indicate that the change of △T can alter not only the overall δ/γ transformation pathways but also the transformation fraction with respect to each transformation mechanism.     

High-g Shocking Testing of the <i>Martlet</i> Wireless Sensing System

This article reports the latest development of a wireless sensing system, named Martlet, on high-g shock acceleration measurement. The Martlet sensing node design is based on a Texas Instruments Piccolo microcontroller, with clock frequency programmable up to 90 MHz. The high clock frequency of the microcontroller enables Martlet to support high-frequency data acquisition and high-speed onboard computation. In addition, the extensible design of the Martlet node conveniently allows incorporation of multiple sensor boards. In this study, a high-g accelerometer interface board is developed to allow Martlet to work with the selected microelectromechanical system (MEMS) high-g accelerometers. Besides low-pass and high-pass filters, amplification gains are also implemented on the high-g accelerometer interface board. Laboratory impact experiments are conducted to validate the performance of the Martlet wireless sensing system with the high-g accelerometer board. The results of this study show that the performance of the wireless sensing system is comparable to the cabled system.     

Effect of co-sensitization in new hybrid photo-refractive materials based on PVK polymer matrix and inorganic LiNbO<Subscript>3</Subscript> nano-crystals

A new class of photo-refractive (PR) composite materials based on poly(N-vinylcarbazole) (PVK) (co-)sensitized with nano-crystalline lithium niobate (LiNbO₃) is presented. The steady-state performance, as well as the kinetics of the photo-refractive grating formation, was investigated by degenerate four-wave mixing (DFWM) and two-beam-coupling (TBC) experiments. We found an optimum content of LiNbO₃ nano-particles of only 10⁻³ wt.%. Even at concentrations as low as 10⁻⁷ wt.% a notable effect of the nano-crystals was detected. This yields materials with improved PR performance compared to that of the standard PR polymer material sensitized by TNF only. The role of LiNbO₃ nano-particles is discussed in detail: The particles support generation and transport of the free-charge carriers. Furthermore, they increase the electron trap density.