Synthesis, structural and electrical characterization of a new organic inorganic bromide: [(C3H7)4N]2CoBr4.

A new organic inorganic hybrid [TPA]2CoBr4, where TPA = [(C3H7)4N]+ (i.e., tetra-propyl-ammonium) compound has been synthesized by slow evaporation method at room temperature. Single crystal X-ray diffraction (SC-XRD), X-ray powder diffraction (XRPD), thermal analyses, vibrational and complex impedance spectroscopy have been used to characterize both structural, thermal, electrical properties. [TPA]2CoBr4 crystallizes in the monoclinic system (C2/c space group) with the following cell parameters: a = 33.145 (5) Å, b = 14.234 (3) Å, c = 15.081 (2) Å and ß = 110.207 (5)°. In the crystal structure, the organic TPA cations which form layers stacked along the a-axis, are separated from each other by inorganic tetrahedral [CoBr4]2- anions. The XRPD pattern confirms both the high purity of the sample and the crystalline nature of the powder. The differential scanning calorimetry (DSC) analysis shows an endothermic peak at 394 K upon heating which is ascribed to a structural phase transition since no decomposition of the titled compound is evidenced by thermogravimetric analysis. The ac conductivity and the dielectric properties confirm the presence of the phase transition. At the structural phase transition around 394 K, a change from a quantum mechanical tunneling to a correlated barrier hopping conduction models is determined from the temperature dependence of the exponent s of the Jonscher's power law. The analysis of complex impedance spectra shows that the electrical properties of the material are heavily dependent on frequency and temperature, indicating a relaxation phenomenon and semiconductor-type behavior. One single semicircle is detectable in the Nyquist plots of the complex impedance spectra which can be satisfactorily fitted with a combination R//CPE elements assigned to the bulk response. This behavior suggests that the sample is electrically homogeneous. Capacitance analysis proves the high effective permittivity at radio frequencies in the sample.

Insight into the mechanism of carbon steel corrosion under aerobic and anaerobic conditions.

We particularly focused our study on identifying the corrosion products formed at 30 °C on carbon steel under aerobic and anaerobic conditions and on following their evolution with time due to enhanced microbial activity under environmental and geological conditions. The nature and structural properties of corrosion products were investigated by scanning electron microscopy/energy dispersive X-ray spectroscopy (SEM/EDS), X-ray diffraction (XRD) and confocal micro-Raman spectroscopy. Structural characterisation clearly showed the formation of iron oxides (magnetite and maghemite) under aerobic conditions. Under anaerobic conditions, the first corrosion product formed on the steel surface was nanocrystalline mackinawite, which was then followed by a fast transformation process into the pyrrhotite phase, and the Raman spectrum of monoclinic pyrrhotite was proposed for the first time. Finally, this study also shows that in the context of geological disposal of radioactive waste, the corrosion of carbon steel containers in anoxic and sulphidogenic environments sustained by sulphate-reducing bacteria may not be a problem notably due to the formation of a passive layer on the steel surface.

Statistical analysis of mounded surfaces: application to the evolution of ultrathin gold film morphology with deposition temperature.

Extracting characteristic dimensions from mounded surfaces such as grain size or intergrain lengths is usually made by statistical analysis. Different statistical functions are used in the literature to extract characteristic lengths. The main issue is that depending on the choice of the statistical function the results can be very different. In this paper, we demonstrate using a series of model mounded surfaces for which characteristic dimensions are known, that a method (namely, interfacial differential function, IDF) is the most effective method to determine the different characteristic lengths. The influence on the statistical treatment of the variation of the different characteristic lengths is then studied and confirms the ability of the IDF analysis. The IDF method was used to analyze the evolution of ultrathin gold film morphology as function of deposition temperature. This approach allows us to demonstrate that the roughness increase with deposition temperature is mainly due to a grain height increase and not to a grain coarsening phenomena as it was claimed before.

Self-assembled monolayers of bisphosphonates: influence of side chain steric hindrance.

Bisphosphonates form self-assembled monolayers (SAMs) spontaneously on stainless steel, silicon, and titanium oxidized surfaces. We used contact angle measurements, atomic force microscopy, and X-ray reflectivity analysis to study the formation of SAMs on a model surface of ultraflat titanium (rms = 0.2 nm). The results were extended to standard materials (mechanically polished titanium, stainless steel, and silicon) and showed that water-soluble bisphosphonic perfluoropolyether can easily form SAMs, with 100% surface coverage and a layer thickness of less than 3 nm. Hydrophobic (water contact angle >110 degrees on stainless steel or titanium) and lipophobic (methylene iodide contact angle >105 degrees on titanium) properties are discussed in terms of industrial applications.

Experimental evidence of the electrostatic contribution to the bending rigidity of charged membranes.

We address the issue of the origin of the bending rigidity of a charged membrane formed from amphiphilic molecules. Electrostatic effects are investigated by direct measurement of the force necessary to deform a catanionic membrane as function of the ionic strength of the medium by means of an atomic force microscope (AFM). Using continuum mechanical modeling of membrane deformation, we derive the bending rigidity of the catanionic membranes and monitor for the first time its decrease in response to increasing salt concentration.

Azobenzene-containing monolayer with photoswitchable wettability.

A compact monolayer containing azobenzene has been prepared on silicon substrates. The elaboration route consisted of covalent grafting of freshly synthesized azobenzene moieties onto an isocyanate-functionalized self-assembled monolayer (SAM). The highly packed and ordered isocyanate-functionalized SAM and the azobenzene-functionalized SAM were monitored and characterized by contact angle measurements and X-ray reflectivity (XR). Photoswitching of the wettability of the film induced by the reversible cis-trans isomerization of the azobenzene chromophores is experimentally shown from water and olive oil contact angle measurements.

Multiple glass-transition temperatures in thin supported films of isotactic PMMA as revealed by enhanced Raman scattering.

The glass-transition temperature, Tg, of isotactic PMMA thin films has been measured for four thicknesses by enhanced Raman spectroscopy and ellipsometry. This was made possible by inserting a silica spacer layer between the film and the substrate. The use of such a spacer drastically improves the sensitivity of Raman scattering measurements. The improvement in the sensitivity allows us to study phenomena involving changes in molecular dynamics, such as the phase transition, and to probe the existence in very thin films of several thickness-dependent transition temperatures, Tg(h). This in turn is interpreted as the occurrence in the film of a layered structure. The influence of the polymer concentration on the conformation of the surface adsorbed polymer layer and therefore on Tg(h) is discussed.

Substrate-induced modulation of the Raman scattering signals from self-assembled organic nanometric films.

Raman scattering signals recorded by microscopy from organic self-assembled monolayers (thin nanometric films of calibrated thickness) on silica substrates were found to be much stronger than those obtained from identical films assembled on bulk silicon substrates. This effect, observed in the backscattering geometry, is shown to result from interferences between the direct and reflected beams (including both the excitation and scattered radiation) in front of a smooth reflecting surface. Strong dependence of the effect on the distance between the sampled monolayer and the bulk silicon substrate allows enhancement of the Raman signals of organic monolayer films on silicon by factors up to approximately 70 by using appropriate silica spacers. The dependence of the Raman signal intensity on film thickness was also studied for thicker nanometric films comprising a series of self-assembled organosilane multilayers on bulk silicon and fused silica substrates, and the predicted deviation from linearity in the case of the silicon substrate is experimentally confirmed.

Vibrational study of Li6P6O18.3H2O and ab initio calculations in P6O18 and P6O18.3H2O.

The infrared and polarized Raman spectra of the trigonal Li(6)P(6)O(18).3H(2)O crystal are reported. The results are analysed using several group theory approaches, in terms of internal and external modes of the highly symmetric P(6)O(18) cyclophosphoric ring and water molecules. Equilibrium geometries and vibrational spectra of P(6)O(18) units, free and in interaction with water molecules (P(6)O(18).3H(2)O) have been determined by ab initio calculations using the basis set 6-31+G(d) of Hartree Fock method. Experimental frequencies and polarisation conditions are remarkably consistent with ab initio calculations. A detailed description of the normal modes of vibration of these systems is presented.