Infra-red spectrum of the tight (110) fold in n-C198H398

The alkane n-C₁₉₈H₃₉₈ has been crystallised in both extended chain and once-folded forms and annealed to produce materials with low concentrations of gauche bonds. The concentrations of the specific conformers detected by FTIR spectroscopy at −173 °C are calculated, using measurements on liquid n-hexadecane for calibration: values are all generally less than 2.0 per 100 carbon atoms, with extended chain samples showing values less than 1.0 per 100 carbon atoms. A subtraction spectrum (Once-folded chain sample minus Extended chain sample) shows positive bands at 1298, 1340, 1347 and 1369 cm⁻¹, which are predicted in earlier calculations for a (110) fold, while additional positive bands at 1353 and 1363 cm⁻¹ are assigned, respectively, to gg conformers and (tentatively) to strained gtg or gtg′ conformations.     

Low temperature air oxidation of n-alkanes in the presence of Na-smectite

This paper is the continuation of a study concerning the catalytic effects of clay on organic matter and especially n-alkanes during oxidation carried out at low temperature. The influences of clay minerals were investigated to understand their role better during natural oxidation of organic matter.n-Alkanes oxidation experiments in presence of Na-smectite were carried out at 100 °C during 512 h and reveal an important production of oxygen-bearing molecules to the detriment of initial n-alkanes. Thus, Na-smectite allows to initiate the auto-oxidation of n-alkanes due to its chemical (charged sheets) and/or physical (high specific area) properties. The evolution of oxygen-bearing molecules distribution enables to distinguish two competitive chemical pathways. On one hand, alcohols and ketones are produced with an aliphatic chain length similar to the starting n-alkanes. On the other hand, aliphatic chain cleavages occur and principally produce 1-alcohols, 2-ketones, carboxylic acids and 3-substitued γ-lactones. These oxygen-bearing compounds are more and more preponderant and evidence the fact that cleavage mechanisms become progressively dominant.     

Diffusivity of n-hexane in poly(ethylene-stat-octene)s assessed by molecular dynamics simulation

Molecular dynamics simulations have been used to study diffusion of n-hexane in wholly amorphous poly(ethylene-stat-octene)s with comonomer contents ranging from 0 to 11.5 mol%. The branches in the polymer increased the specific volume by affecting the packing of the chains in the rubbery state in accordance with experimental data. The diffusion of n-hexane at penetrant concentrations between 0.5 and 9.1 wt% was simulated within time-scales between 0.1 and 0.2 μs. The penetrant diffusivity unexpectedly decreased with increasing comonomer content. The penetrant molecule motion statistics showed that systems with high comonomer content showed a greater tendency for short distance motion (over a sampling period of 3 ps) whereas the systems with lower comonomer content showed penetrant motion over longer distances. It seems that the branches retarded local chain mobility of the polymer thereby trapping the penetrant molecules. All systems studied showed a minimum in penetrant diffusivity at ca. 1 wt% n-hexane and a marked increase in diffusivity at higher penetrant concentrations. The volumetric data for the different polymer-penetrant systems were consonant with additional volumes of the different components. Comparison between simulated diffusivities (for a wholly amorphous polymer) and experimentally obtained diffusivity data for semicrystalline polymers showed that constraining effect of the crystals were substantial for the highly crystalline systems and that it gradually decreased with decreasing crystallinity.     

Thermodynamic and structural analyses of the solid phases in multi-alkane mixtures similar to petroleum cuts at ambient temperature

Structural analyses were carried out by X-ray diffraction, at ambient temperature, on multi-alkane samples whose mole fraction distribution shows a shape of the ‘exponential decreasing’ type, as observed in petroleum cuts. Nine samples, whose normal-alkane number varies from 15 to 23, have been studied with mole fraction continuous distributions of normal-alkanes going from C₂₂-C₃₆ to C₁₄-C₃₆: each mixture differs from the previous sample by the addition of a lighter n-alkane. At the solid state, the multi-alkane solid samples C₂₂-C₃₆ and C₂₁-C₃₆ are two-phase, C₂₀-C₃₆ to C₁₅-C₃₆, three-phase, and the broader distribution C₁₄-C₃₆, four-phase. In these polyphase solid systems, whose heaviest n-alkane is always C₃₆, the average composition of the heavy and middle phases are constant and their structure are isostructural to the β′ ordered intermediate solid solution, observed in n-alkane binary or ternary molecular alloys; the mean carbon atom number of the light phase decreases as the global average carbon atom number of the synthetic mixtures in relation to the addition of light n-alkanes and its structure simultaneously evolves from the β′ ordered intermediate solid solution towards the β-RI(Fmmm) and the disordered solid solutions, observed in pure n-alkanes: the light n-alkane added between each distribution intercalates itself into the structure whose molecule stacking period (thickness) is compatible with its own carbon chain length, in order to reduce the molecular gaps.     

Physical properties of poly(n-alkyl acrylate) copolymers. Part 2. Crystalline/non-crystalline combinations

The physical properties of n-alkyl acrylate copolymers containing one crystallizeable monomer and one non-crystallizeable or slightly crystallizeable monomer, including thermal characteristics, structure as determined by small angle X-ray scattering, and gas permeability as a function of temperature, were examined in detail and compared to the corresponding homopolymers and copolymer systems containing two crystallizeable comonomers. The current copolymers exhibit melting point depression and, for a given average side-chain length, have lower heats of fusion than the corresponding homopolymers and crystalline/crystalline copolymers. Limited SAXS experiments revealed an increase in the d-spacings, above and below the melting point, with side-chain length consistent with expectations. The crystallites predominantly exhibit end-to-end packing similar to other poly(n-alkyl acrylates) previously studied. Poly(n-alkyl acrylates) exhibit a ‘jump’ in their gas permeability at the T_m of the side-chain lengths that is mainly caused by a switch in the side-chain morphology from crystalline to amorphous upon melting. The reduced crystallinity of the crystalline/non-crystalline copolymers results in a smaller permeation jump, which in some cases were extremely broad. All jump breadths correlate with the melting endotherms for these copolymers as determined by DSC similar to that for homopolymers and crystalline/crystalline copolymers. The magnitude of the jump correlates with the heat of fusion, irrespective of the comonomer type, in all cases.     

Removal of SO2 at low temperature using dead Bacillus licheniformis

In this paper we studied the adsorption and desorption behavior of SO₂ by the dead Bacillus licheniformis R08 biomass. The effects of water vapor, temperature and O₂ on the removal of SO₂ by the biomass were studied. FTIR and XPS were used to characterize the mechanism of the SO₂ adsorption on the biomass. The experimental results showed that water vapor and temperature deeply influenced the adsorption of SO₂ by the biomass. However, O₂ cannot oxidize SO₂ to SO₃ on the biomass. FTIR and XPS results showed that oxygenous and nitrogenous functional groups on the cell walls of biomass may be related to the SO₂ adsorption and three sulfur species were formed on the biomass in adsorption process. In the desorption process, weakly adsorbed SO₂ could be desorbed by increasing temperature and the biomass can be reused for 10 cycles.     

Synthesis and microstructure of (LaSr)MnO3 and (LaSr)FeO3 ceramics by a reaction-sintering process

(La_xSr_1−x)MnO₃ (LSMO) and (La_xSr_1−x)FeO₃ (LSFO) (x = 0.2–0.4) ceramics prepared by a simple and effective reaction-sintering process were investigated. Without any calcination involved, La₂O₃ and SrCO₃ were mixed with MnO₂ (LSMO) or Fe₂O₃ (LSFO) then pressed and sintered directly. LSMO and LSFO ceramics were obtained after 2 and 4 h sintering at 1350–1400 and 1200–1280 °C, respectively. Grain size decreased as La content increased in LSMO and LSFO ceramics.     

Influence of the Type of Reducing Agent (H2, CO, C3H6 and C3H8) on the Reduction of Stored NOX in a Pt/BaO/Al2O3 Model Catalyst

In this investigation, a comparative study for a NO _X storage catalytic system was performed focusing on the parameters that affect the reduction by using different reductants (H₂, CO, C₃H₆ and C₃H₈) and different temperatures (350, 250 and 150 °C), for a Pt/BaO/Al₂O₃ catalyst. Transient experiments show that H₂ and CO are highly efficient reductants compared to C₃H₆ which is somewhat less efficient. H₂ shows a significant reduction effect at relatively low temperature (150 °C) but with a low storage capacity. We find that C₃H₈does not show any NO _X reduction ability for NO _X stored in Pt/BaO/Al₂O₃ at any of the temperatures. The formation of ammonia and nitrous oxide is also discussed.     

TSC study of length ester side group effect on sub-vitreous relaxations in poly(n-alkyl methacrylates)

A comparative study by thermo-stimulated currents (TSC) of three poly(n-alkyl methacrylates) is performed. TSC complex spectra exhibit two dipolar relaxations considered in the following: the glass relaxation and a secondary relaxation related to motion of ester side groups. For each sample, the fractional polarisations protocol is applied to describe the fine structure of these complex spectra. It allows us to define the evolution of activation parameters with temperature. The influence of side chain architecture is then considered. It emphasises that the β mode is independent of the ester group length. On the contrary, the α mode is highly sensitive to structural change. These results are finally explained in terms of molecular mobility.     

Mn influence on the electrochemical behaviour of Li3V2(PO4)3 cathode material

The role played by the substitution of Mn on the electrochemical behaviour of Li₃V₂(PO₄)₃ has been investigated. Independently of the synthesis route, the Mn doping improves the electrochemical features with respect to the undoped samples. Different reasons can be taken into consideration to explain the electrochemical enhancement. In the sol–gel synthesis the capacity slightly enhances due to the Mn substitution on both the V sites, within the solubility limit x = 0.124 in Li₃V_2−xMn_x(PO₄)₃. In the solid state synthesis the significant capacity enhancement is preferentially due to the microstructural features of the crystallites and to the LiMnPO₄ phase formation.     

Waterborne polyurethane/poly(n-butyl acrylate-styrene) hybrid emulsions: Particle formation,film properties,and application

In this work, a hybrid synthesis technology has been used to fabricate waterborne polyurethane (WPU)/poly(n-butyl acrylate-styrene) (PBS) emulsions with dimethylol-propionic acid (DMPA) as chain extender. The influences of the PBS, styrene, and DMPA contents on the physical properties of the resultant emulsions and cast films have been investigated in detail using various characterization methods. The experimental results show that with an increase in the PBS or styrene content, the particle size in emulsions increases but the viscosity of the emulsions decreases and that the opposite applies for the DMPA content. For cast films, with an increase in the styrene or DMPA content, the tensile strength increases whereas the elongation decreases. The water absorption capacity of the film decreases with an increase in the styrene content or a decrease in the DMPA content. Furthermore, the emulsions synthesized have been used for paper sizing applications. The treated papers exhibit greatly improved water resistance, and the Cobb values at 30 and 60 s are only 10.23 and 11.89%, respectively, of those of unsized papers. The other paper properties, such as gloss, smoothness, folding resistance, and burst strength, are also considerably improved.     

Combustion synthesis of (Ti1−xNbx)2AlC solid solutions from elemental and Nb2O5/Al4C3-containing powder compacts

Preparation of the (Ti_1−xNb_x)₂AlC solid solution (formed from the M_n+1AX_n or MAX carbides, where n = 1, 2, or 3, M is an early transition metal, A is an A-group element, and X is C) with x = 0.2-0.8 was investigated by self-propagating high-temperature synthesis (SHS). Nearly single-phase (Ti,Nb)₂AlC was produced through direct combustion of constituent elements. Due to the decrease of reaction exothermicity, the combustion temperature and reaction front velocity decreased with increasing Nb content of (Ti_1−xNb_x)₂AlC formed from the elemental powder compacts. In addition, the samples composed of Ti, Al, Nb₂O₅, and Al₄C₃ were adopted for the in situ formation of Al₂O₃-added (Ti,Nb)₂AlC. The SHS process of the Nb₂O₅/Al₄C₃-containing sample involved aluminothermic reduction of Nb₂O₅, which not only enhanced the reaction exothermicity but also facilitated the evolution of (Ti,Nb)₂AlC. Based upon the XRD analysis, two intermediates, TiC and Nb₂Al, were detected in the (Ti,Nb)₂AlC/Al₂O₃ composite and their amounts were reduced by increasing the extent of thermite reduction involved in the SHS process. The laminated microstructure characteristic of the MAX carbide was observed for both monolithic and Al₂O₃-added (Ti,Nb)₂AlC solid solutions synthesized in this study.     

Raman and dielectric investigation of (Ba0.9−xSrxCa0.1)(Ti0.8Zr0.2)O3 ferroelectric ceramics

Solid solutions of (Ba_0.9−xSr_xCa_0.1)(Ti_0.8Zr_0.2)O₃ (BSCTZ) (0.1≤x≤0.4) were prepared using the conventional solid state reaction method. The effects of the substitution content on the crystallographic structure, phase transition and dielectric properties of the samples were investigated by dielectric and Raman spectroscopy over a wide temperature range from 100 to 500 K. All the samples were noted to undergo a diffuse phase transition from the tetragonal to the cubic phase and to exhibit a relaxor ferroelectric behavior.     

X-ray photoelectron spectroscopy and electrochemical behaviour of 4 V cathode, Li(Ni1/2Mn1/2)O2

Layered Li(Ni_1/2Mn_1/2)O₂ was prepared by the solution and mixed hydroxide methods, characterised by X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) and studied by cyclic voltammetry (CV) and charge discharge cycling in CC and CCCV modes at room temperature (r.t.) and at 50 °C. The XPS studies show about 8% of Ni³⁺ and Mn³⁺ ions are present in Li(Ni²⁺_1/2Mn_1/2⁴⁺)O₂ due to valency-degeneracy. The compound prepared at 950 °C, 12 h, solution method gives a second cycle discharge capacity of 150 mA h g⁻¹ (2.5-4.4 V) at a specific current of 30 mA g⁻¹ and retains 137 mA h g⁻¹ at the end of 40 cycles. CV shows that the redox process at 3.7-4.0 V corresponds to Ni²⁺↔Ni⁴⁺ and clear indication of Mn^3+/4+ couple was noted at 4.2-4.5 V. The observed capacity-fading (2.5-4.4 V) is shown to be contributed by the polarisation at the end of charging. The cathodic capacity is stable up to 40 cycles in the voltage window, 2.5-4.2 V both at room temperature and 50 °C.     

Influence of A-site Ba substitution on microwave dielectric properties of (BaxMg1−x)(A0.05Ti0.95)O3 (A=Zr,Sn) ceramics

The microwave dielectric properties of (Ba_xMg_1−x)(A_0.05Ti_0.95)TiO₃ (A=Zr, Sn) ceramics were investigated with regard to substitution of Ba for Mg of A-site. The microwave dielectric properties were correlated with the Ba content. With an increase in Ba content from 0.01 to 0.1, the dielectric constant and the τ_f value increased, but the Q×f value decreased. The sintered (Ba_xMg_1−x)(Zr_0.05Ti_0.95)TiO₃ (called B_xMZT) ceramics had a permittivity in the range of 19.1−20.6, quality factor from 180,000 to 25,000 GHz, and variation in temperature coefficient of resonant frequency from −35 to −39 ppm/°C with increasing composition x. For sintered (Ba_xMg_1−x)(Sn_0.05Ti_0.95)TiO₃ (called B_xMST) ceramics, the dielectric constant increased from 19 to 20.5, Q×f value increased from 120,000 to 37,000 (GHz), and the τ_f value increased from −50 to −3.3 ppm/°C as the x increased from 0.01 to 0.1. When A=Sn and x=0.1, (Ba_0.1Mg_0.9)(Sn_0.05Ti_0.95)TiO₃ ceramics exhibited dielectric constant of 20.5, Q×f value of 37,000 (GHz), and a near-zero τ_f value of −3.3 ppm/°C sintered at 1210 °C for 4 h.     

A study on structure and electrochemical properties of (La, Ce, Pr, Nd)2MgNi9 hydrogen storage electrode alloys

(La, Ce, Pr, Nd)₂MgNi₉ hydrogen storage alloys were prepared through induction melting followed by a long annealing treatment. The structure and electrochemical properties of annealed alloys have been investigated by orthogonal design experiments. Both the individual effects of each substituting element and their interaction in alloys were studied systemically. It has been shown that the structure of main phase in alloys belongs to PuNi₃-type with a space group R-3m. Substituting rare-earth elements have a significant effect on both the phase structure of alloys and microstructure. The anisotropic change in the crystal structure of alloys can cause the acceleration of pulverization of alloy particles and result in the deterioration of the cyclic stability of alloy electrodes. Misch metals can raise the plateau pressure of hydrogen absorption/desorption. The discharge capacity of alloy ranges from 342.97 to 380.68 mAh g⁻¹ depending on the sort and content of substituting elements. Both cerium and neodymium can obviously reduce the discharge capacity of alloy electrodes. When compared to the La₂MgNi₉ alloy electrode, mish metals can significantly improve the high rate dischargeability of alloy electrodes. The improvement of the kinetic characteristic of alloy electrodes mainly results from the increase of the hydrogen diffusion rate in alloy bulk.     

Effects of B-site ion (M) substitution on the ionic conductivity of (Li3xLa2/3−x)1+y/2(MyTi1−y)O3 (M=Al, Cr)

Effect on the ionic conductivity of B-site ion (M) substitution in (Li_3xLa_2/3−x)_1+y/2M_yTi_1−yO₃ (M=Al, Cr) has been investigated. It has been found that partial substitution of smaller Al³⁺ for Ti⁴⁺ is effective to enhance the ionic conductivity of Li_3xLa_2/3−xTiO₃. At 300 K, the maximum bulk conductivity of (1.58±0.01)×10⁻³ S cm⁻¹ is observed from the composition of (Li_0.39La_0.54)_1−y/2Al_yTi_1−yO₃ with y=0.02 (x=0.13), that is the highest yet reported for known perovskite solutions at room temperature. The conductivity enhancement is interpreted as being due to the substitution-induced bond-strength change rather than due to bottleneck size change for Li migration, TiO₆-octahedron tilting or A-site cation ordering.     

Structural, thermal and mechanical properties of transparent Yb:(Y0.97Zr0.03)2O3 ceramic

Yb doped (Y_0.97Zr_0.03)₂O₃ transparent ceramics were fabricated by solid state reaction and vacuum sintering. The microstructure, thermal and mechanical properties of Y₂O₃ ceramic, as well as the effect of Yb doping concentration on these properties were investigated in detail. The lattice parameter and unit cell volume decrease with the increasing of Yb content, whereas thermal expansive coefficient increases. With Yb content increasing from 0 to 8 at.%, the mean grain size increases from 15.82 μm to 26.54 μm, and the thermal conductivity at room temperature (RT) decreases from 11.97 to 6.39 W/m/K. The microhardness decreases with Yb content, and the microhardness and fracture toughness of (Y_0.97Zr_0.03)₂O₃ transparent ceramic is 11.11 GPa and 1.29 MPa m^1/2, respectively.     

Electrochemical and thermal studies of Li[NixLi(1/3−2x/3)Mn(2/3−x/3)]O2 (x = 1/12, 1/4, 5/12, and 1/2)

Samples of the layered cathode materials, Li[Ni_xLi_(1/3−2x/3)Mn_(2/3−x/3)]O₂ (x = 1/12, 1/4, 5/12, and 1/2), were synthesized at 900 °C. Electrodes of these samples were charged in Li-ion coin cells to remove lithium. The charged electrode materials were rinsed to remove the electrolyte salt and then added, along with EC/DEC solvent or 1 M LiPF₆ EC/DEC, to stainless steel accelerating rate calorimetry (ARC) sample holders that were then welded closed. The reactivity of the samples with electrolyte was probed at two states of charge. First, for samples charged to near 4.45 V and second, for samples charged to 4.8 V, corresponding to removal of all mobile lithium from the samples and also concomitant release of oxygen in a plateau near 4.5 V. Li[Ni_xLi_(1/3−2x/3)Mn_(2/3−x/3)]O₂ samples with x = 1/4, 5/12 and 1/2 charged to 4.45 V do not react appreciably till 190 °C in EC/DEC. Li[Ni_xLi_(1/3−2x/3)Mn_(2/3−x/3)]O₂ samples charged to 4.8 V versus Li, across the oxygen release plateau, start to significantly react with EC/DEC at about 130 °C. However, their high reactivity is similar to that of Li_0.5CoO₂ (4.2 V) with 1 μm particle size. Therefore, Li[Ni_xLi_(1/3−2x/3)Mn_(2/3−x/3)]O₂ samples showing specific capacity of up to 225 mAh/g may be acceptable for replacing LiCoO₂ (145 mAh/g to 4.2 V) from a safety point of view, if their particle size is increased.     

Generation of polyacetylene sulfoxide radicals through spin migration from the main-chain to the sulfoxide moiety in the side chain of poly[p-(n-butylsulfoxide)phenylacetylene] prepared with a [Rh(norbornadiene)Cl]2 catalyst

A phenylacetylene bearing an n-butylsulfoxide group, i.e., p-(n-butylsulfoxide)phenylacetylene (1) was prepared in high yields using the [Rh(norbornadiene)Cl]₂-NEt₃ catalyst in the presence of various solvents under mild conditions. The resulting polymer, poly[p-(n-butylsulfoxide)phenylacetylene] (poly(1)), was characterized in detail by ¹H NMR, ESR, laser Raman, and diffuse reflective UV-vis methods. The data clearly showed that cis-to-trans isomerization of the polymer can be induced when pressure is imposed to the polymer at room temperature, rotationally breaking the cis CC bonds to generate the cis and trans radicals. Further, the spin density in the cis radical was migrated from the main-chain to the sulfoxide moiety as the side chain of the phenyl ring to magnetically interact with the first two methylene protons in the n-butyl group giving a triplet line ESR spectrum with an extremely large g value, g = 2.0081.