Comment on ‘‘Relaxation Kinetics of Nanoscale Indents in a Polymer Glass’’

A Comment on the Letter by A. Knoll, D. Wiesmann, B. Gotsmann, and U. Duerig, published in Physical Review Letter, 2009, vol. 102, p.117801

Phase behavior and rheological analysis of reverse liquid crystals and W/I2, W/H2 gel emulsions using an amphiphilic block copolymer.

This article reports the phase behavior determi- nation of a system forming reverse liquid crystals and the formation of novel disperse systems in the two-phase region. The studied system is formed by water, cyclohexane, and Pluronic L-121, an amphiphilic block copolymer considered of special interest due to its aggregation and structural proper- ties. This system forms reverse cubic (I2) and reverse hexagonal (H2) phases at high polymer concentrations. These reverse phases are of particular interest since in the two-phase region, stable high internal phase reverse emulsions can be formed. The characterization of the I2 and H2 phases and of the derived gel emulsions was performed with small-angle X-ray scattering (SAXS) and rheometry, and the influence of temperature and water content was studied. TheH2 phase experimented a thermal transition to an I2 phase when temperature was increased, which presented an Fd3m structure. All samples showed a strong shear thinning behavior from low shear rates. The elasticmodulus (G0) in the I2 phase was around 1 order of magnitude higher than in theH2 phase. G0 was predominantly higher than the viscousmodulus (G00). In the gel emulsions,G0 was nearly frequency-independent, indicating their gel type nature. Contrarily to water-in-oil (W/O) normal emulsions, in W/I2 and W/H2 gel emulsions, G0, the complex viscosity (|η*|), and the yield stress (τ0) decreased with increasing water content, since the highly viscous microstructure of the con- tinuous phase was responsible for the high viscosity and elastic behavior of the emulsions, instead of the volumefraction of dispersed phase and droplet size. A rheological analysis, in which the cooperative flow theory, the soft glass rheology model, and the slip plane model were analyzed and compared, was performed to obtain one single model that could describe the non-Maxwellian behavior of both reverse phases and highly concentrated emulsions and to characterize their microstructure with the rheological properties.

Occurrence and bioaccumulation study of PCDD and PCDF from mineral feed additives

Occurrence of polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) was evaluated in sepiolite as a widely employed binder and anti-caking agent for animal feed. Also, naturally contaminated kaolinitic clay was used for comparative purposes. Since sepiolite shows remarkable adsorption properties, particular interest was paid to the extraction steps as they become critical for the final determination of these pollutants in such matrixes. Furthermore, classical Soxhlet extraction using different extracting strategies as well as acid treatment were carried out with simultaneous liquid-liquid extraction. Results obtained depended on the extraction procedure applied. Acid treatment or Soxhlet extraction using a mixture of toluene:ethanol as solvent allowed to reach the minimum requirements of recovery rates. However, Soxhlet extraction using a mixture cyclohexane:toluene as extracting solvent did not allow to comply with minimum specifications for recovery. Significant differences were obtained in TEQ units when acid treatment was applied in comparison to Soxhlet extraction. This fact can be explained because the use of drastic acid conditions allows removing strongly adsorbed analytes which can be uniquely extracted after a total destruction of the crystalline structure of sepiolite. On the contrary, Soxhlet extraction was not able to destroy the structure of sepiolite and as a consequence the PCDDs/Fs were strongly adsorbed in the internal structure of the mineral. From biological point of view the availability of these toxicants constitutes a critical aspect playing an important role in the final decision choosing particular analytical procedures. Then, acid conditions in the digestive tract should be taken into account. In this scenario, a bioaccumulation study was conducted to evaluate the transference of PCDDs/PCDFs from the sepiolite into the animal tissues when fed with feed containing sepiolite. To this end, chickens were used as a model to examine the bioavailability of PCDDs/PCDFs. Four groups of chickens were exposed through their diet to a control feed, feed with 3% w/w sepiolite as additive, feed contaminated with PCDDs/PCDFs at concentration around 2.8 pg WHO-TEQ/g and feed with 2% of a contaminated kaolinitic clay (460 pg TEQ/g mineral). Livers of the four studied groups were analyzed throughout the exposure period. Results of this trial showed that the performance of broilers was not affected by the presence of dioxins at levels tested, and chickens did not show any abnormal behaviour. Dioxins intentionally added to the diet were absorbed and accumulated in the liver in a significant manner, whereas the PCDDs/Fs from sepiolite were not available for chickens since livers from broilers fed 3% sepiolite presented similar WHO-TEQ values than those from broilers fed control diet.

An approximate mathematical model for solidification of a flowing liquid in a microchannel

A mathematical model is developed to analyse the combined flow and solidification of a liquid in a small pipe or two-dimensional channel. In either case the problem reduces to solving a single equation for the position of the solidification front. Results show that for a large range of flow rates the closure time is approximately constant, and the value depends primarily on the wall temperature and channel width. However, the ice shape at closure will be very different for low and high fluxes. As the flow rate increases the closure time starts to depend on the flow rate until the closure time increases dramatically, subsequently the pipe will never close.

Extensional flow of nematic liquid crystal under electric field gradient

Systematic asymptotic methods are used to formulate a model for the extensional flow of a thin sheet of nematic liquid crystal. With no external body forces applied, the model is found to be equivalent to the so-called Trouton model for Newtonian sheets (and fi bers), albeit with a modi fied "Trouton ratio". However, with a symmetry-breaking electric field gradient applied, behavior deviates from the Newtonian case, and the sheet can undergo fi nite-time breakup if a suitable destabilizing field is applied. Some simple exact solutions are presented to illustrate the results in certain idealized limits, as well as sample numerical results to the full model equations.

The implementation of liquid chromatography tandem mass spectrometry for the official control of lipophilic toxins in seafood: Single-laboratory validation under four chromatographic conditions

We performed a comprehensive study to assess the fit for purpose of four chromatographic conditions for the determination of six groups of marine lipophilic toxins (okadaic acid and dinophysistoxins, pectenotoxins, azaspiracids, yessotoxins, gymnodimine and spirolides) by LC-MS/MS to select the most suitable conditions as stated by the European Union Reference Laboratory for Marine Biotoxins (EURLMB). For every case, the elution gradient has been optimized to achieve a total run-time cycle of 12 min. We performed a single-laboratory validation for the analysis of three relevant matrices for the seafood aquaculture industry (mussels, pacific oysters and clams), and for sea urchins for which no data about lipophilic toxins have been reported before. Moreover, we have compared the method performance under alkaline conditions using two quantification strategies: the external standard calibration (EXS) and the matrix-matched standard calibration (MMS). Alkaline conditions were the only scenario that allowed detection windows with polarity switching in a 3200 QTrap mass spectrometer, thus the analysis of all toxins can be accomplished in a single run, increasing sample throughput. The limits of quantification under alkaline conditions met the validation requirements established by the EURLMB for all toxins and matrices, while the remaining conditions failed in some cases. The accuracy of the method and the matrix effects where generally dependent on the mobile phases and the seafood species. The MMS had a moderate positive impact on method accuracy for crude extracts, but it showed poor trueness for seafood species other than mussels when analyzing hydrolyzed extracts. Alkaline conditions with EXS and recovery correction for OA were selected as the most proper conditions in the context of our laboratory. This comparative study can help other laboratories to choose the best conditions for the implementation of LC-MS/MS according to their own necessities.

Energy dispersive X-Ray fluorescence : measuring elements in solid and liquid matrices

The subject of this project is about “Energy Dispersive X-Ray Fluorescence ” (EDXRF).This technique can be used for a tremendous variety of elemental analysis applications.It provides one of the simplest, most accurate and most economic analytical methods for thedetermination of the chemical composition of many types of materials.The purposes of this project are:- To give some basic information about Energy Dispersive X-ray Fluorescence.- To perform qualitative and quantitative analysis of different samples (water-dissolutions,powders, oils,..) in order to define the sensitivity and detection limits of the equipment.- To make a comprehensive and easy-to-use manual of the ‘ARL QUANT’X EnergyDispersive X-Ray Fluorescence’ apparatus

Simple and fast methods based on solid-phase extraction coupled to liquid chromatography with UV detection for the monitoring of caffeine in natural and waste waters as marker of anthropogenic impact

Two concentration methods for fast and routine determination of caffeine (using HPLC-UV detection) in surface, and wastewater are evaluated. Both methods are based on solid-phase extraction (SPE) concentration with octadecyl silica sorbents. A common “offline” SPE procedure shows that quantitative recovery of caffeine is obtained with 2 mL of an elution mixture solvent methanol-water containing at least 60% methanol. The method detection limit is 0.1 μg L−1 when percolating 1 L samples through the cartridge. The development of an “online” SPE method based on a mini-SPE column, containing 100 mg of the same sorbent, directly connected to the HPLC system allows the method detection limit to be decreased to 10 ng L−1 with a sample volume of 100 mL. The “offline” SPE method is applied to the analysis of caffeine in wastewater samples, whereas the “on-line” method is used for analysis in natural waters from streams receiving significant water intakes from local wastewater treatment plants

New insights on the crystalline forms in binary systems of n-alkanes: Characterization of the solid ordered phases in the phase diagram tricosane + pentacosane

X-ray diffraction analyses of the pure components n-tricosane and n-pentacosane and of their binary mixed samples have enabled us to characterize the crystalline phases observed at low temperature. On the contrary to what was announced in literature on the structural behavior of mixed samples in odd-odd binary systems with D n = 2, the three domains are not all orthorhombic. This work has enabled us to show that two of the domains are, in fact, monoclinic, (Aa, Z = 4) and the other one is orthorhombic (Pca21, Z = 4). The conclusions drawn in this work can be easily transposed to other binary systems of n-alkanes.

Analysis of S-rich CuIn(S,Se)2 layers for photovoltaic applications: Influence of the sulfurization temperature on the crystalline properties of electrodeposited and sulfurized CuInSe2 precursors

This paper reports the microstructural analysis of S-rich CuIn(S,Se)2 layers produced by electrodeposition of CuInSe2 precursors and annealing under sulfurizing conditions as a function of the temperature of sulfurization. The characterization of the layers by Raman scattering, scanning electron microscopy, Auger electron spectroscopy, and XRD techniques has allowed observation of the strong dependence of the crystalline quality of these layers on the sulfurization temperature: Higher sulfurization temperatures lead to films with improved crystallinity, larger average grain size, and lower density of structural defects. However, it also favors the formation of a thicker MoS2 interphase layer between the CuInS2 absorber layer and the Mo back contact. Decreasing the temperature of sulfurization leads to a significant decrease in the thickness of this intermediate layer and is also accompanied by significant changes in the composition of the interface region between the absorber and the MoS2 layer, which becomes Cu rich. The characterization of devices fabricated with these absorbers corroborates the significant impact of all these features on device parameters as the open circuit voltage and fill factor that determine the efficiency of the solar cells.

Nanocrystalline SnO2 by liquid pyrolisis

Liquid pyrolysis is presented as a new production method of SnO2 nanocrystalline powders suitable for gas sensor devices. The method is based on a pyrolytic reaction of high tensioned stressed drops of an organic solution of SnCl4·5(H2O). The main advantages of the method are its capability to produce SnO2 nanopowders with high stability, its accurate control over the grain size and other structural characteristics, its high level of repeatability and its low industrialization implementation cost. The characterization of samples of SnO2 nanoparticles obtained by liquid pyrolysis in the range between 200ºC and 900ºC processing temperature is carried out by X-ray diffraction, transmission electron microscopy, Raman and X-ray photoelectron spectroscopy. Results are analyzed and discussed so as to validate the advantages of the liquid pyrolysis method.

Thermal nucleation of cavities in liquid helium at negative pressures

We have investigated the nucleation rate at which cavities are formed in 4He and 3He at negative pressures due to thermal fluctuations. To this end, we have used a density functional that reproduces the He liquid-gas interface along the coexistence line. The inclusion of thermal effects in the calculation of the barrier against nucleation results in a sizable decrease of the absolute value of the tensile strength above 1.5 K.