Molecular dynamics simulations of polyphosphazenes: poly[bis(chloro)phosphazene][NPCl2] n

Suitable parameter sets for the CHARMm force field were derived for the structural units in polychlorophosphazene [P=N, P N, P Cl] using the Dinur Hagler energy second derivative procedure based on quantum mechanical SCI calculations using the 6–31G^* basis set. To validate the reliability of the parameter set, structural results obtained with CHARMm for the adopted model compounds (OP₂NCl₅ and OP₃N₂Cl₅) were compared with those derived fromab initio quantum mechanics using the 6–31G^* basis set. Application of molecular dynamics (MD) simulations in combinatioin with the available X-ray diffraction data provided structural and conformational information on the polymer. The calculation made using the periodic boundary conditions (PBC) agree well with the polychlorophosphazene ordered in a monoclinic unit cell (a=5.98,b=12.99,c=4.92 A; β=111.7). This model was stabilized mainly by the image atoms contribution to the electrostatic energy term and had aquasi-planar conformation of the backbone chain (glide symmetry). The MD calculations also provided evidence that the difference between single and double PN bonds is less marked than that measured experimentally. This result is, however, in agreement with more recent and accurate X-ray studies on poly(methylphosphazene). Validation of the polymer model provided a complete picture, otherwise experimentally inaccessible, of the internal fluctuations of the polymeric chains.     

Tobacco craving predicts lapse to smoking among adolescent smokers in cessation treatment.

Previous research indicates that tobacco craving predicts relapse to smoking among adult smokers attempting to quit. We hypothesized a similar relationship between craving and lapse (any smoking following a period of abstinence) among adolescent smokers during the treatment phase of a clinical trial. A visit was considered a lapse visit if the participant reported smoking or had a carbon monoxide level of 7 ppm or greater subsequent to an abstinent visit. A total of 34 participants (mean age = 14.9 years [SD = 1.3]; mean cigarettes/day = 18.0 [SD = 7.6]; mean Fagerstr?m Test for Nicotine Dependence score = 6.8 [SD = 1.34]; 65% female), were included in the present analysis of 167 treatment visits. Logistic regression analyses showed a positive relationship between degree of craving, measured by the Questionnaire on Smoking Urges, and lapse during smoking cessation treatment (p = .013). Additionally, linear regression analyses demonstrated a strong positive association between cigarettes smoked per day and craving scores (p<.001). Taken together with other data, these findings suggest that degree of craving might influence tobacco abstinence for adolescent smokers. Thus monitoring and addressing craving appears useful to increase the success of adolescent smoking cessation.     

Semantic annotation of narrative media objects

This paper addresses the annotation of the narrative features of media objects. Based on a relevant narratological and computational background, we introduce an ontology?Cbased model called Drammar, an annotation schema for the narrative features of media objects based on Drammar and a software tool, Cinematic, for annotating these objects and validating the annotation. Annotated media objects can also be automatically edited into sequences, with the twofold goal of testing the validity of the annotation??through the reconstruction of the baseline sequence??and exploring the possibility of alternative sequences. The software tool encodes both the narrative model and the annotation itself in ontological format, and relies on external ontologies for representing world knowledge and limit the arbitrariness of the annotation. The paper opens the way to the design of a general annotation schema for narrative multimedia with the long?Cterm goal of building large corpora of annotated video material and of bridging the gap between the low?Clevel signal analysis and the high?Clevel semantic representation of the narrative content of the media objects. Finally, the paper illustrates a few projects elaborated with the Drammar annotation and the Cinematic tool, with purposes of artistic research and cross?Cmedia analysis, that provide an empirical validation of the annotation process.     

Determination of Binder Decomposition Kinetics for Specifying Heating Parameters in Binder Burnout Cycles

The decomposition kinetics of poly(vinyl butyral) binder from barium titanate multilayer ceramic capacitors with platinum metal electrodes were analyzed by thermogravimetric analysis as a function of the heating rate. The activation energy and pre-exponential factor for the decomposition kinetics were determined from two types of integral equations, from the Redhead method, and from the variation in heating rate method. The accuracy of the kinetic parameters determined from these methods was then evaluated for describing the observed rate of binder decomposition. Although the individual models yielded very different kinetic parameters, all were capable of describing the experimental data within ±15% accuracy. The kinetic parameters were then used in a coupled transport and kinetic model for describing the buildup of pressure within the ceramic green body as a function of the heating cycle. A methodology based on calculus of variations was also developed to predict the minimum duration for the binder burnout cycle.     

Strain-Induced Deformation in Magnesia–Alumina Layered Composites

Ceramic beams are induced in situ to form complex shapes at elevated temperature without the application of an external stress. This process has been demonstrated for thin alumina substrates coated with a layer of magnesia. The internal strain causing the substrates to deform at elevated temperature arises as a consequence of strain mismatch accompanying the penetration of the coating into the substrate. The magnitude of the deformation depends on the amount of coating applied, on the thickness of the substrate, on the density of the substrate, and on the temperature. During exposure of the beams to elevated temperature, the magnesia coating reacts with the alumina substrate to form the spinel phase; the resulting volume change accompanying the phase transformation is likely the predominant driving force for deformation.     

Adsorption of Cr(III), Ni(II), Zn(II), Co(II) ions onto phenolated wood resin

In this study, phenolated wood resin was used an adsorbent for the removal of Cr(III), Ni(II), Zn(II), Co(II) ions by adsorption from aqueous solution. The adsorption of metal ions from solution was carried at different contact times, concentrations and pHs at room temperature (25°C). For individual metal ion, the amount of metal ions adsorbed per unit weight of phenolated wood resin at equilibrium time increased with increasing concentration and pH. Also, when the amounts of metal ions adsorbed are compared to each other, it was seen that this increase was order of Cr(III) > Ni(II) > Zn(II) > Co(II). This increase was order of Cr(III) > Ni(II) > Co(II) > Zn(II) for commercial phenol–formaldehyde resin. Kinetic studies showed that the adsorption process obeyed the intraparticle diffusion model. It was also determined that adsorption isotherm followed Langmuir and Freundlich models. Adsorption isotherm obtained for commercial phenol–formaldehyde resin was consistent with Freundlich model well. Adsorption capacities from Langmuir isotherm for commercial phenol–formaldehyde resin were higher than those of phenolated wood resin, in the case of individual metal ions. Original adsorption isotherm demonstrated the monolayer coverage of the surface of phenolated wood resin. Adsorption kinetic followed the intraparticle diffusion model. The positive values of ΔG° determined using the equilibrium constants showed that the adsorption was not of spontaneous nature. It was seen that values of distribution coefficient (K_D) decreasing with metal ion concentration in solution at equilibrium (C_e) indicated that the occupation of active surface sites of adsorbent increased with metal ions. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 2838–2846, 2006     

Influence of ABS type on morphology and mechanical properties of PC/ABS blends

The morphology and the mechanical properties of polycarbonate (PC) blends with different acrylonitrile–butadiene–styrene (ABS) materials were investigated. PC/ABS blends based on a mass-made ABS with 16% rubber and large (0.5–1μm) rubber particles are compared to blends based on an emulsion-made ABS with 50% rubber and small, monodisperse (0.12 μm) rubber particles over the full range of blend compositions. The blends with the bulk ABS showed excellent impact strength for most compositions, and those containing 50 and 70% PC exhibited ductile to brittle transition temperatures below that of PC. The blends with the emulsion ABS showed excellent toughness in sharp notch Izod impact tests at room temperature and in standard notch Izod impact tests at low temperatures near the T_g of the rubber. By melt blending the various ABS materials with a styrene–acrylonitrile (SAN 25) copolymer, materials with lower rubber concentrations were obtained. These materials were used in blends with PC to make comparisons at constant rubber concentration of 5, 10, and 15%. The results of this investigation show that brittle ABS materials can produce tough PC–ABS blends. It is apparent that small rubber particles toughen PC–ABS blends at lower rubber concentrations and at lower temperatures than is possible with large rubber particles. However, additional work is needed to understand the nature of toughening in these PC–ABS blends with different rubber phase morphologies. It is of particular interest to understand the exceptional ductility of some of the blends at low temperatures. © 1994 John Wiley & Sons, Inc.     

XPS Characterization of reduced LaCoO3 perovskite

Three samples of LaCoO₃ were prepared by two different methods and calcined at 800 or 1000 °C. They had BET areas of 1, 12, and 16 m²/g and all of them showed pure perovskite X-ray diffraction patterns with identical unit cell dimensions. In a series of experiments the oxide, having larger surface area, was stepwise reduced in hydrogen at temperatures between 60 and 500 °C. The XPS spectra, taken at room temperature after evacuation at 400 °C at each reduction level, showed that the surface concentration of Co° was very low up to 300 °C but increased sharply between 300 and 350 °C (9–75%). This concentration further increased to 100% after 10 min reduction at 450 °C, but upon heating in hydrogen for an additional 10 min at 500 °C it decreased again to 75%. In another series of experiments the mixed oxide was reoxidized after each reduction. A fresh sample was reduced to 350 and 400 °C by contacting with hydrogen for 1 hr and evacuated at temperatures between 400 and 500 °C. Both high evacuation temperatures and reduction at 400 °C during 1 hr produced a sharp decrease in Co° surface concentration. These results are consistent with the catalytic behavior of this perovskite reported earlier by E. A. Lombardo et al. (4–7). A model is proposed to interpret the reduction of LaCoO₃.     

Experiencing Nature: Embodying Animals in Immersive Virtual Environments Increases Inclusion of Nature in Self and Involvement With Nature

Immersive virtual environments (IVEs) produce simulations that mimic unmediated sensory experiences. 3 experiments (N = 228) tested how different modalities increase environmental involvement by allowing users to inhabit the body of animals in IVEs or watch the experience on video. Embodying sensory‐rich experiences of animals in IVEs led to greater feeling of embodiment, perception of being present in the virtual world, and interconnection between the self and nature compared to video. Heightened interconnection with nature elicited greater perceptions of imminence of the environmental risk and involvement with nature, which persisted for 1 week. Although the effect sizes were small to moderate, findings suggest that embodied experiences in IVEs may be an effective tool to promote involvement with environmental issues.     

Healing Effect of Controlled Anti‐Electromigration on Conventional and High‐Tc Superconducting Nanowires

The electromigration process has the potential capability to move atoms one by one when properly controlled. It is therefore an appealing tool to tune the cross section of monoatomic compounds with ultimate resolution or, in the case of polyatomic compounds, to change the stoichiometry with the same atomic precision. As demonstrated here, a combination of electromigration and anti‐electromigration can be used to reversibly displace atoms with a high degree of control. This enables a fine adjustment of the superconducting properties of Al weak links, whereas in Nb the diffusion of atoms leads to a more irreversible process. In a superconductor with a complex unit cell (La_2?x Ce_x CuO₄), the electromigration process acts selectively on the oxygen atoms with no apparent modification of the structure. This allows to adjust the doping of this compound and switch from a superconducting to an insulating state in a nearly reversible fashion. In addition, the conditions needed to replace feedback controlled electromigration by a simpler technique of electropulsing are discussed. These findings have a direct practical application as a method to explore the dependence of the characteristic parameters on the exact oxygen content and pave the way for a reversible control of local properties of nanowires.