Sine-Gordon Theory for the Equation of State of Classical Hard-Core Coulomb Systems. I. Low Fugacity Expansion

We present an exact field theoretical representation of the statistical mechanics of classical hard-core Coulomb systems. This approach generalizes the usual sine-Gordon theory valid for point-like charges or lattice systems to continuous Coulomb fluids with additional short-range interactions. This formalism is applied to derive the equation of state of the restricted primitive model of electrolytes in the low fugacity regime up to order ρ^5/2 (ρ number density). We recover the results obtained by Haga by means of Mayer graphs expansions.     

Depth profiling of tin-coated glass by laser ablation inductively coupled plasma emission spectrometry with acoustic signal measurement

A pulsed, frequency-quadrupled Nd:YAG laser (266 nm, 10 Hz) coupled to an inductively coupled plasma atomic emission spectrometer (ICP-AES) was employed for depth profiling by ablation of a pyrolytically deposited Sn layer (300 nm) on float glass. The procedure consisted of performing individual ablation cycles (layer-by-layer). A raster with stroke distance of either 50 μm or 200 μm (the raster density) was used as an ablation pattern. The ablation was stopped after each cycle and the peak area of the resulting transient optical signal of the ICP discharge was plotted against the cycle number. The ablation rate of 90 to 20 nm per cycle at a low-energy pulse (6 mJ to 1 mJ) was determined by profilometry. A beam masking was employed to attenuate the laser shot energy and to eliminate the peripheral irregularity of the beam profile. Almost uniform removal of the square area (1 mm × 1 mm) of the coating by ablation was achieved by combining the fitted raster density, beam masking, focusing and beam energy. Different ablation processes were distinguished in cases of the tin coating and the uncoated glass surface. While the coating was mainly evaporated, the uncoated glass surface exhibited a crumbling associated with production of glass powder. This was confirmed by electron microscopy observations. The measured acoustic signal followed the behavior of the emission intensity of the Sn line and was supposed to be proportional to the amount of Sn vapors. The emission intensity depth profile of the Sn coating with graded structure was obtained, which qualitatively corresponded with the depth profile measured by secondary ion mass spectrometry.     

Polymer-solvent complexes and intercalates prepared under various conditions

The relevancy of temperature-composition phase diagrams for the study of polymer-solvent complexes and intercalates is discussed. In particular the use of Tamman's diagrams for determining the stoichiometric composition is evaluated. Examples of the validity of this approach are taken from isotactic or syndiotactic polystyrene compounds. Also, the effect of the path followed for reaching a T, C coordinate is examined. It is shown that cooling hot, homogeneous solutions at composition C or allowing solvent to diffuse in a solid polymer matrix at temperature T yields basically the same thermal behaviour.     

Ammoides pusilla Essential Oil: A Potent Inhibitor of the Growth of Fusarium avenaceum and Its Enniatin Production

Enniatins are mycotoxins produced by Fusarium species contaminating cereals and various agricultural commodities. The co-occurrence of these mycotoxins in large quantities with other mycotoxins such as trichothecenes and the possible synergies in toxicity could lead to serious food safety problems. Using the agar dilution method, Ammoides pusilla was selected among eight Tunisian plants for the antifungal potential of its essential oil (EO) on Fusarium avenaceum mycelial growth and its production of enniatins. Two EO batches were produced and analyzed by GC/MS-MS. Their activities were measured using both contact assays and fumigant tests (estimated IC50 were 0.1 µL·mL⁻¹ and 7.6 µL·L⁻¹, respectively). The A. pusilla EOs and their volatiles inhibited the germination of spores and the mycelial growth, showing a fungistatic but not fungicidal activity. The accumulation of enniatins was also significantly reduced (estimated IC50 were 0.05 µL·mL⁻¹ for the contact assays and 4.2 µL·L⁻¹ for the fumigation assays). The most active batch of EO was richer in thymol, the main volatile compound found. Thymol used as fumigant showed a potent fungistatic activity but not a significant antimycotoxigenic activity. Overall, our data demonstrated the bioactivity of A. pusilla EO and its high potential to control F. avenaceum and its enniatins production in agricultural commodities.     

All-optical manipulation of azo-dye molecules

A challenging issue in the field of the design of devices for photonic applications is to achieve complete manipulation of the molecular order. Azo-dye aromatic polymers have been shown to offer interesting prospects for material engineering using light matter interactions. Dual-frequency irradiation using appropriate combinations of circular beams polarizations are demonstrated to enable full control of the molecular polar rotation. More recent results on photoinduced surface-relief gratings have also opened the way of molecular translation control using optical fields. Understanding of the relevant parameters of molecular translation processes is a key issue for optimization of such an optomechanical effect: a simple model accounting qualitatively for the essential features of photoinduced surface-relief gratings will be presented.     

Complex formation through heterogeneous nucleation of thermoreversible gelation

The preparation method and the molecular structure of a composite material consisting of a ternary system polymer/bicoppercomplex/solvent are presented. The properties of each binary system are exposed first. The polymer solutions produce thermoreversible gels while the bicopper organic complex forms a randomly-dispersed, self-assembling structure in organic solvents. It is shown that, in a common solvent, the bicopper complex acts as a nucleation agent for the gelation of the polymer (heterogeneous nucleation). As a result, bicopper complex filaments are encapsulated in a polymer matrix.     

Chemical analysis of polymers using transmission electron microscopy/electron energy-loss spectroscopy: The example of poly(ethylene terephthalate)

We have performed EELS analysis of poly (ethylene terephthalate) (PET) in the analytical TEM in order to evaluate the possibility to obtain chemical analysis of the polymer at sub-micrometer scale. Due to irradiation damage, it revealed necessary to work at the lowest possible electron dose, typically below 10³ C.m⁻², and with the specimen cooled to liquid nitrogen temperature. In the acquired spectra, we propose an identification of the different chemical bondings in agreement with XANES experiments.     

Encapsulation of magnetic self-assembled systems in thermoreversible gels

We describe two different ways of encapsulating within the fibrils of thermoreversible polymer gels the filaments of a supermolecular polymer formed by self-assembly of a bicopper complex. Heterogeneous nucleation is brought about with gels made from isotactic poly(styrene) while compound formation occurs with gels made from poly(hexyl isocyanate). These ways depend upon the interaction between the wings of the supermolecular polymer and the side groups of the polymer. In all cases, the filaments retain their 1-D structure. Preliminary results from magnetic susceptibility measurements show a striking difference between the pure and the encapsulated supermolecular polymer.     

Kinetics of styrene uptake by a polyurethane network during the formation of interpenetrating polymer networks

Due to insolubility of the components, formation of interpenetrating polymer networks (IPNs) requires particular ways of synthesis. Among others, IPNs can be prepared by the sequential technique where a network is swollen in a monomer and its crosslinker, which are then polymerized in situ. The simplest case is to swell at equilibrium; however this leads to IPNs of a given composition. For obtaining other compositions, swelling has to be stopped before equilibrium, or the swollen network (gel) has to be deswollen to a certain extent. Therefore, diffusivity of the monomer within the gel has to be known. The kinetics of monomer uptake was studied for a polyether urethane/styrene-divinylbenzene system which gives transparent materials despite the difference in refractive indexes. This allows direct visual observations of the monomer progress within the network. The results are not fully in agreement with the theories of Tanaka and of Candau which both predict the progression of a solvent in a polymeric gel. Two regimes of swelling depending on the concentration distribution of the monomer within the gel were found.