Hardness and structure characterization of Ti(6)Al(4)V films produced by reactive magnetron sputtering on a conventional austenitic stainless steel

Ti(6)Al(4)V thin films were grown by magnetron sputtering on a conventional austenitic stainless steel. Five deposition conditions varying both the deposition chamber pressure and the plasma power were studied. Highly textured thin films were obtained, their crystallite size (C) 2008 Elsevier Ltd. All rights reserved.

Improved comparison plot method for pore structure characterization of MCM-41

MCM-41 samples of various pore dimensions are synthesized. Plotting of nitrogen adsorption data at 77 K versus the statistical film thickness (comparison plot) reveals three distinct stages, with a characteristic of two points of inflection. The steep intermediate stage caused by capillary condensation occurred in the highly uniform mesopores. From the slopes of the sections before and after the condensation, the surface area of the mesopores is calculated. The linear portion of the last section is extrapolated to the adsorption axis of the comparison plot, and this intercept is used to obtain the volume of the mesopores. From the surface area and pore volume, average mesopore diameter is calculated, and the value thus obtained is in good agreement with the pore dimension obtained from powder X-ray diffraction measurements. The principle of the calculation as well as problems associated are discussed in detail.

Synthesis and crystal structure characterization of iron(II), cobalt(II) and nickel(II) complexes with 1,3-bis(2-pyridylmethylthio)propane

Three new mononuclear complexes of nitrogen-sulfur donor sets, formulated as (Fe-II(L)Cl-2] (1), [Co-II(L)Cl-2] (2) and [Ni-II(L)Cl-2] (3) where L = 1,3-bis(2-pyridylmethylthio)propane, were synthesized and isolated in their pure form. All the complexes were characterized by physicochemical and spectroscopic methods. The solid state structures of complexes I and 3 have been established by single crystal X-ray crystallography. The structural analysis evidences isomorphous crystals with the metal ion in a distorted octahedral geometry that comprises NSSN ligand donors with trans located pyridine rings and chlorides in cis positions. In dimethylformamide solution, the complexes were found to exhibit Fe-II/Fe-III, co(II)/co(III) and Ni-II/Ni-III quasi-reversible redox couples in cyclic voltammograms with E-1/2 values (versus Ag/AgCl at 298 K) of +0.295, +0.795 and +0.745 V for 1, 2 and 3, respectively. (C) 2009 Elsevier Ltd. All rights reserved.

Copper(II) complexes of tetradentate N2S2 donor sets: synthesis, crystal structure characterization and reactivity

Two mononuclear and one dinuclear copper(II) complexes, containing neutral tetradentate NSSN type ligands, of formulation [Cu-II(L-1)Cl]ClO4 (1), [Cu-II(L-2)Cl]ClO4 (2) and [Cu-2(II)(L-3)(2)Cl-2](ClO4)(2) (3) were synthesized and isolated in pure form [where L-1 = 1,2-bis(2-pyridylmethylthio)ethane, L-2 = 1,3-bis(2-pyridylmethylthio)propane and L-3 = 1,4-bis(2-pyridylmethylthio)butane]. All these green colored copper(II) complexes were characterized by physicochemical and spectroscopic methods. The dinuclear copper(II) complex 3 changed to a colorless dinuclear copper(I) species of formula [Cu-2(1)(L-3)(2)](ClO4)(2),0.5H(2)O (4) in dimethylformamide even in the presence of air at ambient temperature, while complexes I and 2 showed no change under similar conditions. The solid-state structures of complexes 1, 2 and 4 were established by X-ray crystallography. The geometry about the copper in complexes 1 and 2 is trigonal bipyramidal whereas the coordination environment about the copper(I) in dinuclear complex 4 is distorted tetrahedral. (C) 2008 Elsevier Ltd. All rights reserved.

Structure characterization of molecular complexes for non-linear optical materials. II. 1 : 1 complexes of 4-methyl-morpholine-N-oxide (1) and 3-picoline-N-oxide (2) with 2,4,6-trinitrophenol, studied by X-ray, AM1 and DFT calculations

(1) C6H2N3O7- center dot C5H12NO2+, Mr = 346.26, P2(1)/c, a = 7.2356(6), b = 10.5765(9), c = 19.593(2) angstrom, 3 beta=95.101(6)degrees, V = 1493.5(2) angstrom(3), Z = 4, R-1 = 0.0414; (2) C6H2N3O7- center dot C6H8NO+, Mr = 38.24, P2(1)/n, a = 7.8713(5), b = 6.1979(7), c = 28.697(3) angstrom, beta = 90.028(7)degrees, V = 1400.0(2) angstrom(3), Z = 4, R-1 = 0.0416. The packing units in both compounds consist of hydrogen bonded cation-anion pairs. The (hyper)polarizabilities have been calculated for the crystallographic and optimized molecules, by AM1 and at the DFT/B3LYP(6-31G**) level.

Pore structure characterization of kaolin, metakaolin, and their acid-treated products using small-angle X-ray scattering

Pore structure of dealuminated kaolin and metakaolin was studied by small-angle X-ray scattering (SAXS). Both parent kaolin and metakaolin have about 10% of the total pore volume provided by globular pores with 105 Å mean pore size. Their surface area is about 14 m2/g. Acid dealumination of kaolin causes an increase of its globular pore volume without an appreciable change in the mean pore size, its surface area increasing up to about 90 m2/g. Acid dealumination of metakaolin enhances the globular pore volume, although there is generation of slit-shaped pores with a narrow thickness distribution whose mean value is 14 Å. This interlayer spacing causes an increase in surface area of about 190 m2/g by SAXS. © 1994.

Structure, characterization and near-infrared emission of a novel 6-connected uninodal 3D network of Nd(III) containing 2,5-thiophenedicarboxylate anion

The novel coordination polymer with the formula {[Nd2(2,5-tdc)3(dmf)2(H2O)2].dmf.H2O}n (2,5-tdc2-=2,5-thiophedicarboxylate anion and dmf=dimethylformamide) has been synthesized and characterized by thermal analysis (TG/DTA), vibrational spectroscopy (FTIR) and single crystal X-ray diffraction analysis (XRD). Structure analysis reveals that Nd(III) ions show dicapped trigonal prism coordination geometry. The 2,5-tdc2- ligands connect four Nd(III) centers, adopting (κ1 - κ1) - (κ1 - κ1) - μ4 coordination mode, generating an interesting 6-connected uninodal 3D network. Photophysical properties were studied using diffuse reflectance spectroscopy (DR) and excitation/emission spectra. The photoluminescence data show the near infrared emission (NIR) with the characteristic 4F3/2→4IJ (J=9/2, 11/2 and 13/2) transitions of Nd(III) ion, indicating that 2,5-tdc2- is able to act as a sensitizer for emission in NIR region. © 2013 Elsevier B.V.

The Aerosol OT + n-butanol + n-heptane + water system: Phase behavior, structure characterization, and application to Pt70Fe30 nanoparticle Synthesis

A phase diagram of the pseudo-ternary Aerosol OT (AOT) + n-butanol/n-heptane/water system, at a mass ratio of AOT/n-butanol = 2, is presented. Conductivity measurements showed that within the vast one-phase microemulsion region observed, the structural transition from water-in-oil to oil-in-water microemulsion occurs continuously without phase separation. This pseudo-ternary system was applied to the synthesis of carbon-supported Pt 70Fe30 nanoparticles, and it was found that nanoparticles prepared in microemulsions containing n-butanol have more Fe than those prepared in ternary microemulsions of AOT/n-heptane/water under similar conditions. It was verified that introducing n-butanol as a cosurfactant into the AOT/n-heptane/water system lead to complete reduction of the Fe ions that allowed obtaining alloyed PtFe nanoparticles with the desired composition, without the need of preparing functionalized surfactants and/or the use of inert atmosphere. © 2007 American Chemical Society.

Synthesis and structure characterization of chromium oxide prepared by solid thermal decomposition reaction

Mesoporous chromium oxide (Cr2O3) nanocrystals were first synthesized by the thermal decomposition reaction of Cr(NO3)(3)(circle)9H(2)O using citric acid monohydrate (CA) as the mesoporous template agent. The texture and chemistry of chromium oxide nanocrystals were characterized by N-2 adsorption-desorption isotherms, FTIR, X-ray diffraction (XRD), UV-vis, and thermoanalytical methods. It was shown that the hydrate water and CA are the crucial factors in influencing the formation of mesoporous Cr2O3 nanocrystals in the mixture system. The decomposition of CA results in the formation of a mesoporous structure with wormlike pores. The hydrate water of the mixture provides surface hydroxyls that act as binders, making the nanocrystals aggregate. The pore structures and phases of chromium oxide are affected by the ratio of precursor-to-CA, thermal temperature, and time.

Raman Spectroscopy and DFT calculations for the Electronic Structure Characterization of Conjugated Polymers

In the last three decades, there has been a broad academic and industrial interest in conjugated polymers as semiconducting materials for organic electronics. Their applications in polymer light-emitting diodes (PLEDs), polymer solar cells (PSCs), and organic field-effect transistors (OFETs) offer opportunities for the resolution of energy issues as well as the development of display and information technologies1. Conjugated polymers provide several advantages including low cost, light weight, good flexibility, as well as solubility which make them readily processed and easily printed, removing the conventional photolithography for patterning2. A large library of polymer semiconductors have been synthesized and investigated with different building blocks, such as acenes or thiophene and derivatives, which have been employed to design new materials according to individual demands for specific applications. To design ideal conjugated polymers for specific applications, some general principles should be taken into account, including (i) side chains (ii) molecular weights, (iii) band gap and HOMO and LUMO energy levels, and (iv) suited morphology.3-6 The aim of this study is to elucidate the impact that substitution exerts on the molecular and electronic structure of π-conjugated polymers with outstanding performances in organic electronic devices. Different configurations of the π-conjugated backbones are analyzed: (i) donor-acceptor configuration, (ii) 1D lineal or 2D branched conjugated backbones, and (iii) encapsulated polymers (see Figure 1). Our combined vibrational spectroscopy and DFT study shows that small changes in the substitution pattern and in the molecular configuration have a strong impact on the electronic characteristics of these polymers. We hope this study can advance useful structure-property relationships of conjugated polymers and guide the design of new materials for organic electronic applications.

Ageing on commercial automotive catalysts, a structure reactivity study

Increasingly stringed regulations for diesel engine emissions have a significant impact on the required efficiency of DOC. Lowered DOC oxidation efficiency due to thermal aging effects influences the efficiency of the exhaust aftertreatment systems downstream of the DOC. In this work carried out in the Jean Le Rond d’Alembert Institute the effect of hydrothermal aging on the reactivity and structure of a commercial DOC was investigated. The characterization of the catalytic performance was carried out on a synthetic gas bench using carrots catalyst under conditions close to the realistic conditions i.e. using a synthetic gas mixture, representative of the exhaust gases from diesel engines. Different structural characterization techniques were performed: textural and morphological proprieties were analyzed by BET and TEM, the characterization of the presented crystallographic phases was performed by DRX and the determination of the number of reducible species was possible by TPR. TEM results shown, an increase of the metal particle size with the aging caused by the agglomeration of metal particles, revealing the presence of metal sintering. DRX results also suggest the presence of support sintering. Furthermore, DRX and BET results unexpectedly reveal that the most drastic aging conditions used actually activated the catalyst surface. As expected, the aging affected negatively the catalyst performance on the oxidation of methane and CO, however an improvement of the NO oxidation performance with the aging was observed. Nevertheless, for the aging conditions used, catalytic activity results show that the influence of aging in DOC performance was not significant, and therefore, more drastic aging conditions must be used.

Characterization of thirteen microsatellite markers in river and brook lampreys (Lampetra fluviatilis and L-planeri)

We describe the development based on 454 pyrosequencing technology of thirteen microsatellite markers for two closely related species of lamprey: Lampetra fluviatilis and L. planeri. The number of alleles per locus ranged from 2 to 5 in L. fluviatilis and from 2 to 6 in L. planeri. Gene diversity ranged from 0.062 to 0.718 in L. fluviatilis and from 0.322 to 0.677 in L. planeri. These markers will be helpful to study population genetic structure of both species and resolve their taxonomic status as separate species or ecotypes of a single species.

Encapsulation of naproxen in nanostructured system: structural characterization and in vitro release studies

Nanoparticles were produced by solvent emulsification evaporation method with the following characteristics: nanometric size (238 ± 3 nm), narrow polydispersity index (0.11), negative zeta potential (-15.1 mV), good yield of the process (73 ± 1.5%), excellent encapsulation efficiency (81.3 ± 4.2%) and spherical shape. X-rays diffraction demonstrated the loss of drug crystallinity after encapsulation; however, the profile of the diffractograms of the poly-ε-caprolactone (PCL) nanoparticles was kept. Differential scanning calorimetry thermograms, correspondingly, exhibited the loss of drug melting peak and the increasing of the melting point of the PCL nanoparticles, evidencing an interaction drug-polymer. Naproxen release was low and sustained obeying the Higuchi´s kinetic. The results show that nanoparticles are promising sustained release system to the naproxen.

Modulating the electronic structure of amino acids: interaction of model lewis acids with anthranilic acid

On the basis of theoretical B3LYP calculations, Yáñez and co-workers (J. Chem. Theory Comput. 2012, 8, 2293) illustrated that beryllium ions are capable of significantly modulating (changing) the electronic structures of imidazole. In this computational organic chemistry study, the interaction of this β-amino acid and five model Lewis acids (BeF1+, Be2+, AlF2(1+), AlF2+, and Al3+) were investigated. Several aspects were addressed: natural bond orbitals, including second order perturbation analysis of intra-molecular charge delocalization and the natural population analysis atomic charges; molecular geometries; selected infrared stretching frequencies (C-N, C-O, and N-H), and selected ¹H-NMR chemical shifts. The data illustrate that this interaction can weaken the H-O bond and goes beyond strengthening the intra-molecular hydrogen bond (N...H-O) to cause a spontaneous transfer of the proton to the nitrogen atom in five cases generating zwitterion structures. Many new features are observed. Most importantly, the zwitterion structures include a stabilizing hydrogen bond (N-H...O) that varies in relative strength according to the Lewis acid. These findings explain the experimental observations of α-amino acids (for example: J. Am. Chem. Soc. 2001, 123, 3577) and are the first reported fundamental electronic structure characterization of β-amino acids in zwitterion form.

Effects of processing on the structure of zein/oleic acid films investigated by X-ray diffraction

Zein films plasticized with oleic acid were formed by solution casting, by the stretching of moldable resins, and by blown film extrusion. The effects of the forming process on film structure were investigated by X-ray diffraction. Wide-angle X-ray scattering (WAXS) patterns showed d-spacings at 4.5 and 10 angstrom, which were attributed to the zein alpha-helix backbone and inter-helix packing, respectively. The 4.5.angstrom d-spacing remained stable under processing while the 10 angstrom d-spacing varied with processing treatment. Small-angle X-ray scattering (SAXS) detected a long-range periodicity for the formed films but not for unprocessed zein, which suggests that the forming process-promoted film structure development is possibly aided by oleic acid. The SAXS d-spacing varied among the samples (130-238 angstrom) according to zein origin and film-forming method. X-ray scattering data suggest that the zein molecular structure resists processing but the zein supramolecular arrangements in the formed films are dependent on processing methods.