Analysis of a Lennard-Jones fcc structure melting to the corresponding frozen liquid: differences between the bulk and the surface

We computed a Lennard Jones frozen liquid with a free surface using classical molecular dynamics. The structure factor curves on the free surface of this sample was calculated for different depths knowing that we have periodic boundary conditions on the other parts of the sample. The resulting structure factor curves show an horizontal shift of their first peak depending on how deep in the sample the curves are computed. We analyze our resulting curves in the light of spatial correlation functions during melting and at when the liquid is frozen. The conclusion is that near the free surface the sample is less dense than in the bulk and that the frozen liquid surface has a spatial correlation which does not differ very much from that of the bulk. This result is intrinsic to the melting of the Lennard Jones liquid and does not depend on any other parameter.Comment: 18 pages 9 figure

Morphological instabilities of a thin film on a Penrose lattice: a Monte Carlo study

We computed by a Monte Carlo method the thermal relaxation of a polycrystalline thin film deposited on a Penrose lattice. The thin film was modelled by a 2 dimensional array of elementary domains, which have each a given height. During the Monte Carlo process, the height of each of these elementary domains is allowed to change as well as their crystallographic orientation. After equilibrium is reached at a given numerical temperature, all elementary domains have changed their orientation into the same one and small islands appear, preferentially on the domains of the Penrose lattice located in the center of heptagons. This method is a new numerical approach to study the influence of the substrate and its defects on the islanding process of polycrystalline films.Comment: 9 pages,5 figure

Monte Carlo approach of the islanding of polycrystalline thin films

We computed by a Monte Carlo method derived from the Solid on Solid model, the evolution of a polycrystalline thin film deposited on a substrate during thermal treatment. Two types of substrates have been studied: a single crystalline substrate with no defects and a single crystalline substrate with defects. We obtain islands which are either flat (i.e. with a height which does not overcome a given value) or grow in height like narrow towers. A good agreement was found regarding the morphology of numerical nanoislands at equilibrium, deduced from our model, and experimental nanoislands resulting from the fragmentation of YSZ thin films after thermal treatment.Comment: 20 pages, 7 figure

Modified-atmosphere packaging of hen table eggs: Effects on pathogen and spoilage bacteria

Abstract As part of a more comprehensive research activity on the use of modified-atmosphere packaging for the improvement of quality and functional properties of table eggs, the effects of air, 100% CO2, and 100% O2 packaging were also evaluated on the survival of experimentally inoculated pathogen bacteria (Salmonella Enteritidis, Escherichia coli, and Listeria monocytogenes) as well as on spoilage bacteria (total aerobic mesophilic bacteria) on table eggs during 30 d of storage at 4, 25, and 37°C by colony count method. In general, temperatures played a major role, rather than gasses, in influencing the bacterial survival. In particular, the lowest microbial loads were registered at 4°C on E. coli and spoilage bacteria, whereas 37°C was the best storage temperature to avoid the psychrotropic microorganism L. monocytogenes development regardless of the gas used. One hundred percent CO2 packaging, in association with a low storage temperature (4°C), had a significant positive effect in reducing Salmonella loads. On eggs inoculated with L. monocytogenes and stored at 4°C as well as on eggs containing only spoilage bacteria and stored at 25°C, 100% CO2 resulted the best gas in comparison with air and O2. One hundred percent CO2 packaging showed no negative effect on pathogen survival compared with air. Although further improvements are required to control RH within packaging to limit bacteria growth/survival, in view of the positive effects of CO2 packaging on quality traits of table eggs, 100% CO2 packaging might represent a promising innovative technique for the maintenance of egg characteristics during transport, retail, and domestic storage

Silica-magnesium-titanium Ziegler-Natta catalysts. Part 1: Structure of the pre-catalyst at a molecular level

In this paper, which is the first part of a more extended work, we elucidate the molecular level structure of a highly active SiO2-supported Ziegler-Natta precatalyst obtained by reacting a dehydroxylated silica and a solution of an organomagnesium compound with TiCl4. The synergetic combination of Ti K-edge and Ti L3-edge X-ray Absorption spectroscopy (XAS) and diffuse reflectance UV–Vis spectroscopies, complemented by Density Functional Theory (DFT) simulations, indicate that small TiCl3 clusters similar to β-TiCl3 coexist with isolated monomeric Ti(IV) species. Ti K-edge Extended X-ray Absorption Fine Structure (EXAFS) Spectroscopy allows the quantification of these two phases and demonstrates that the Ti(IV) sites are 6-fold coordinated (either by six chlorine ligands or by five chlorine and one oxygen ligands), but highly distorted, similar to what is modelled for TiCl4-capped MgCl2 nanoplatelets. Finally, IR spectroscopy suggests that the MgCl2 phase has a molecular character (Far-IR) and that the only accessible Mg2+ sites are uncoordinated cations acting as Lewis acid sites (IR of CO adsorbed at 100 K). Based on these experimental findings, we propose the co-existence in the precatalyst of small TiCl3 clusters and of mixed oxo-chloride magnesium-titanium structures deposited at the silica surface. The evolution of the precatalyst in the presence of the activator and of the monomer is discussed in the second part of this work

Observing Brownian motion in vibration-fluidized granular matter

At the beginning of last century, Gerlach and Lehrer observed the rotational Brownian motion of a very fine wire immersed in an equilibrium environment, a gas. This simple experiment eventually permitted the full development of one of the most important ideas of equilibrium statistical mechanics: the very complicated many-particle problem of a large number of molecules colliding with the wire, can be represented by two macroscopic parameters only, namely viscosity and the temperature. Can this idea, mathematically developed in the so-called Langevin model and the fluctuation-dissipation theorem be used to describe systems that are far from equilibrium? Here we address the question and reproduce the Gerlach and Lehrer experiment in an archetype non-equilibrium system, by immersing a sensitive torsion oscillator in a granular system of millimetre-size grains, fluidized by strong external vibrations. The vibro-fluidized granular medium is a driven environment, with continuous injection and dissipation of energy, and the immersed oscillator can be seen as analogous to an elastically bound Brownian particle. We show, by measuring the noise and the susceptibility, that the experiment can be treated, in first approximation, with the same formalism as in the equilibrium case, giving experimental access to a ''granular viscosity'' and an ''effective temperature'', however anisotropic and inhomogeneous, and yielding the surprising result that the vibro-fluidized granular matter behaves as a ''thermal'' bath satisfying a fluctuation-dissipation relation

Evolution of iron speciation during hydration of C4 AF

International audienceIt is now well accepted and demonstrated that calcium silicate, calcium aluminate and calcium sulfo aluminate (ettringite, AFm) phases exhibit a good capability to fix metals and metalloids. Unfortunately the role of minor phases and especially calcium-ferric aluminate phase, shorthand C(4)AF is not well defined. In other systems like in soils or sediments iron phases play a key role in the fixation of pollutant. In cement sorption isotherms, indicated that various metals can be retained by the C(4)AF hydrated products. Therefore the capabilities of those phase to retain heavy metal should not be neglected. Previous investigations have shown that the minerals formed during the hydration of C(4)AF are similar to those formed from C3A (pure tri-calcium aluminate) under comparable conditions. Nevertheless no investigation was conducted at the molecular level and there is still a controversy whether Fe substitutes for Al in the hydrated minerals in whole or in part, or if it forms FeOOH clusters scattered throughout the matrix. In this context we have conducted XAS experiments using synchrotron radiation. It was found that the hydration of C(4)AF forms C(3)AH(6) (hydrogarnet) in which Fe randomly substitutes for Al as well as an amorphous FeOOH phase. Intermediate products like AFm (i.e., an ill organized lamellar phase) are also formed but rapidly evolve to C(3)AH(6); iron does not seem to be incorporated in the AFm structure

Thermal Decomposition Pathways of ZnxFe3- xO4Nanoparticles in Different Atmospheres

This article shows how initial composition and thermal treatment of nonstoichiometric zinc ferrite nanoparticles (nZFN) can be chosen to adjust the structure and cation distribution and enhance magnetism in the resulting nanoscale material. It also provides insight into new prospects regarding the production and design of nanoscale materials. Investigations were conducted before and after heating of nZFN in an inert atmosphere and a vacuum up to temperature of 1170 °C. Annealing leads to partial reduction of Fe ions, enhanced magnetism, and an increase in the size of the particles independent of the atmosphere. Use of the inert atmosphere delivers a solid solution of magnetite and zinc ferrite with a reduced Zn content in the structure as a result of sublimation of newly formed ZnO and reduction of Fe, and it favors crystallization. A preference for normal-spinel phase and enhancement of magnetic saturation from 20 Am2/kg up to 101 Am2/kg was observed. Vacuum annealing with high probability produces ZnO, Fe3O4, and Fe2O3 multiphase system with signs of amorphization, mainly on the surface. A large fraction of Fe ions is reduced and the volume ratio of Fe3O4 to Fe2O3 increases with heating time. The final solid product from a complete decomposition of ZFN is magnetite

Glioblastoma cusa fluid protein profiling: A comparative investigation of the core and peripheral tumor zones

The present investigation aimed to characterize the protein profile of cavitating ultrasound aspirator fluid of newly diagnosed and recurrent glioblastoma comparing diverse zones of collection, i.e., tumor core and tumor periphery, with the aid of 5\u2010aminolevulinic acid fluorescence. The samples were pooled and analyzed in triplicate by LC\u2010MS following the shotgun proteomic approach. The identified proteins were then grouped to disclose elements exclusive and common to the tumor state or tumor zones and submitted to gene ontology classification and pathway overrepresentation analysis. The proteins common to the distinct zones were further investigated by relative quantitation, following a label free approach, to disclose possible differences of expression. Nine proteins, i.e., tubulin 2B chain, CD59, far upstream element\u2010binding, CD44, histone H1.4, caldesmon, osteopontin, tropomyosin chain and metallothionein\u20102, marked the core of newly diagnosed glioblastoma with respect to tumor periphery. Considering the tumor zone, including the core and the fluorescence positive periphery, the serine glycine biosynthesis, pentose phosphate, 5\u2010 hydroxytryptamine degredation, de novo purine biosynthesis and huntington disease pathways resulted statistically significantly overrepresented with respect to the human genome of reference. The fluorescence negative zone shared several protein elements with the tumor zone, possibly indicating the presence of pathological aspects of glioblastoma rather than of normal brain parenchyma. On the other hand, its exclusive protein elements were considered to represent the healthy zone and, accordingly, exhibiting no pathways overrepresentation. On the contrary to newly diagnosed glioblastoma, pathway overrepresentation was recognized only in the healthy zone of recurrent glioblastoma. The TGF\u3b2 signaling pathway, exclusively classified in the fluorescence negative periphery in newly diagnosed glioblastoma, was instead the exclusive pathway classified in the tumor core of recurrent glioblastoma. These results, preliminary obtained on sample pools, demonstrated the potential of cavitron ultrasonic sur gical aspirate fluid for proteomic profiling of glioblastoma able to distinguish molecular features specific of the diverse tumor zones and tumor states, possibly contributing to the understanding of the highly infiltrative capability and recurrent rate of this aggressive brain tumor and opening to potential clinical applications to be further investigated