Contact angle hysteresis at the nanometer scale

Using atomic force microscopy with nonconventional carbon tips, the pinning of a liquid contact line on individual nanometric defects was studied. This mechanism is responsible for the occurrence of the contact angle hysteresis. The presence of weak defects which do not contribute to the hysteresis is evidenced for the first time. The dissipated energy associated with strong defects is also measured down to values in the range of kT, which correspond to defect sizes in the order of 1 nm.     

Structural determination by atmospheric pressure photoionization tandem mass spectrometry of some compounds isolated from the SARA fractions obtained from bitumen

We have identified compounds obtained from the SARA fractions of bitumen by using atmospheric pressure photoionization mass spectrometry and low‐energy collision tandem mass spectrometric analyses with a QqToF‐MS/MS hybrid instrument. The identified compounds were isolated from the maltene saturated oil and the aromatic fractions of the SARA components of a bitumen. The QqToF instrument had sufficient mass resolution to provide accurate molecular weight information and to enhance the tandem mass spectrometry results. The APPI‐QqToF‐MS analysis of the separated compounds showed a series of protonated molecules [M + H]⁺ and molecular ions [M]^+? of the same mass but having different chemical structures, in the maltene saturated oil and the aromatic SARA fractions. These isobaric ions were a molecular ion [M₂]^+? at m/z 418.2787 and a protonated molecule [M₅ + H]⁺ at m/z 287.1625 in the saturated oil fraction, and molecular ions [M₆]^+? at m/z 418.1584 and [M₇]^+? at m/z 287.1285 in the aromatic fraction. The identification of this series of chemical compounds was achieved by performing CID‐MS/MS analyses of the molecular ions [M]^+? ([M₁]^+? at m/z 446. 2980, [M₂]^+? at m/z 418.2787, [M₃]^+? at m/z 360.3350 and [M₄]^+? at m/z 346.2095) in the saturated oil fraction and of the [M₅ + H]⁺ ion at m/z 287.1625 also in the saturated oil fraction. The observed CID‐MS/MS fragmentation differences were explained by proposed different breakdown processes of the precursor ions. The presented tandem mass spectrometric study shows the capability of MS/MS experiments to differentiate between different classes of chemical compounds of the SARA components of bitumen and to explain the reasons for the observed mass spectrometric differences. However, greater mass resolution than that provided by the QqToF‐MS/MS instrument would be required for the analysis of the asphaltene fraction of bitumen. Copyright © 2011 John Wiley & Sons, Ltd.     

Calorimetry in nonstandard conditions: The noncrystalline phases of linear polyethylene

A linear Union Carbide PE (UC) has been analyzed by nonstandard calorimetry with a common DSC calorimeter and a Setaram C80 calorimeter. Nonstandard calorimetry entails using a low rate of heating (0.5–1 K/min), a small mass (0.5–1.5 mg), and an open cell (O‐cell) instead of the standard C‐cell. Events in O‐cells overlap less and occur with a faster kinetics than in C‐cells. PE crystals are nascent, solution‐grown (S‐grown), press‐grown (P‐grown), and strained by extrusion. In Part A, the traces show that the phase‐changes in the melt, previously observed in a C80 calorimeter (slow T‐ramp) and characterized by ΔH_network, can be observed with a common DSC in nonstandard conditions. In Part B, the difference between the C‐ and O‐cells and the changes in the main peak enthalpy (ΔH_ortho) are of interest. The main result is that, in O‐cells, the value of ΔH_ortho around T_ortho, exceeds unambiguously in certain conditions ΔH_ortho found for perfect orthorhombic crystals. The main endotherm contains then another contribution, namely ΔH_network. Crystal reorganization during the slow T‐ramp is followed in the C‐ and O‐cells on S‐grown crystals. In O‐cells, lamellar thickening observed in the slow‐ramp is more extensive. The ease of phase‐change depends on the sample history. It is as follows: strained‐part extruded > nascent > S‐grown > P‐grown. Co‐operative chain motions are more hindered in the standard C‐cells than in the O‐cells. In Part C, lower values of m succeed in bringing phase‐changes in P‐grown (O‐cells) samples. The origin of the events is discussed: three processes are thought to contribute to the phase‐changes namely, melting of strained short‐range order, activation of vibrations in the CH₂ groups, and fast decay of chain orientation which occurs simultaneously with melting. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 1932–1949, 2007     

A critique on the structural analysis of lignins and application of novel tandem mass spectrometric strategies to determine lignin sequencing

This review is devoted to the application of MS using soft ionization methods with a special emphasis on electrospray ionization, atmospheric pressure photoionization and matrix‐assisted laser desorption/ionization MS and tandem MS (MS/MS) for the elucidation of the chemical structure of native and modified lignins. We describe and critically evaluate how these soft ionization methods have contributed to the present‐day knowledge of the structure of lignins. Herein, we will introduce new nomenclature concerning the chemical state of lignins, namely, virgin released lignins (VRLs) and processed modified lignins (PML). VRLs are obtained by liberation of lignins through degradation of vegetable matter by either chemical hydrolysis and/or enzymatic hydrolysis. PMLs are produced by subjecting the VRL to a series of further chemical transformations and purifications that are likely to alter their original chemical structures. We are proposing that native lignin polymers, present in the lignocellulosic biomass, are not made of macromolecules linked to cellulose fibres as has been frequently reported. Instead, we propose that the lignins are composed of vast series of linear related oligomers, having different lengths that are covalently linked in a criss‐cross pattern to cellulose and hemicellulose fibres forming the network of vegetal matter. Consequently, structural elucidation of VRLs, which presumably have not been purified and processed by any other type of additional chemical treatment and purification, may reflect the structure of the native lignin. In this review, we present an introduction to a MS/MS top–down concept of lignin sequencing and how this technique may be used to address the challenge of characterizing the structure of VRLs. Finally, we offer the case that although lignins have been reported to have very high or high molecular weights, they might not exist on the basis that such polymers have never been identified by the mild ionizing techniques used in modern MS. Copyright © 2015 John Wiley & Sons, Ltd.     

Reinvestigation of the OP4-(Li/Na)CoO2-layered system and first evidence of the (Li/Na/Na)CoO2 phase with OPP9 oxygen stacking

The composition and synthesis conditions of the (Li/Na)CoO(2) phase with an ordered 1:1 Li/Na stacking alternating with CoO(2) slabs were determined from a careful study of the P2-Na(～0.7)CoO(2)-O3-LiCoO(2) system. An in situ X-ray diffraction (XRD) thermal study emphasizes the metastable character of this phase that can be stabilized only by very fast quenching. Its composition, (Li(0.42)Na(0.37))CoO(2), is significantly different from the ideally expected one, (Li(0.50)Na(0.35))CoO(2), and its structure, confirmed by Rietveld refinement of the XRD pattern, presents an ideal alternate ordering of lithium, cobalt, and sodium layers within OP4-type oxygen packing. The presence of vacancies in both alkali-ion layers was confirmed by electrochemical intercalation of lithium and sodium. For the first time, a new type of layered oxide exhibiting OPP9-type oxygen packing was evidenced. Between the CoO(2) slabs, alkali ions are intercalated in the following order: Li(octa)-Na(prism)-Na(prism). This material crystallizes in the R3m space group with a(hex) = 2.828 ? and c(hex) = 46.85 ? cell parameters.     

Arc voltage of a fast triggered vacuum gap

At high current, the performance of triggered vacuum gaps (TVGs) is limited by constriction of the vacuum arc. Several concentrated modes can be defined, i.e., foot point, anode spot, and intense arc mode. In all cases, small, luminous, high-temperature spots (from melting to boiling temperature) appear on the anode surface. In accordance with the anodic mode, the arc voltage has different characteristics (quiet and low or with high-frequency noise). The arc voltage is measured for different electrode configurations for a conduction time of 27 μs and for peak current up to 45 kA. For small gap distances (1-1.5 mm), the arc voltage is quiet and low (20 to 30 V) and almost independent of the peak current. For greater distances, the arc voltage increases with the distance and the peak current. If the peak current is higher than the threshold interruption current, the arc voltage is high and noisy. These overvoltages, with a frequency of about one megahertz, can reach more than 1000 V. These overvoltages disappear completely after about 15 μs, and the voltage decreases     

A study of the Na x TiO2 system by electrochemical deintercalation

The electrochemical deintercalation from the sheet oxide NaTiO₂ leads to new Na _x TiO₂ materials. The deintercalation is reversible over the range 0.70?x≤1, whereas irreversible modifications of the host structure occur by overvoltage (x?0.70). This behavior, which can be explained by migration of some titanium ions from the slabs to the intersheet space, may be considered as a 2D→3D structural transition.     

New secondary batteries for room temperature applications using a vitreous electrolyte

In order to obtain room temperature high energy secondary batteries, a B₂S₃Li₂SLiI vitreous electrolyte has been used. Lithium or a lithium-aluminium alloy have been tested as negative electrode in symmetrical cells and then utilized in four different types of experimental Li (or LiAl) /glass/TiS₂ batteries. The best results have been obtained with a composite TiS₂-liquid electrolyte positive electrode.     

Expression of stress proteins in cultured human cells as a sensitive indicator of metal toxicity

Human cell lines cultured under standardized conditions are found to react after a wide variety of aggressive but sub-lethal treatments by expressing stress proteins, mainly of the HSP68, HSP70 and HSP90 families. The stress reaction is a repair mechanism which rapidly takes place after minute damages caused to cell structures. It was therefore proposed to develop a sensitive biomarker to monitor environmental pollution, especially related to metals, based on the evaluation of stress protein production. This was achieved by computer-assisted densitometric analysis of autoradiographies of electrophoretically separated ³⁵S-labelled proteins. The results indicate that our biological models consisting in HT29 and HepG2 cell-lines react to low concentrations of cadmium or nickel by a clear-cut increase of stress proteins expression. In most cases, this effect is much more significant and much more rapid to observe than changes in growth curves. It may constitute a reliable index of cell susceptibility to environmental aggressions.