Assessing organo-clay dispersion in polymer layered silicate nanocomposites: A SAXS approach

A SAXS method for the quantitative assessment of the morphology of polymer layered silicate nanocomposites is proposed. Fitting the SAXS patterns, the number of clay layers, the periodicity of the layers in the tactoids, the thickness of the regions interposed between the clay platelets and their distributions can be measured. A good agreement with TEM data was obtained, avoiding the inconsistencies with microscopical observations often reported in the literature.     

Co- and Ni-exchanged ferrierite: The contribution of synchrotron X-ray diffraction data to siting of TMIs

High-silica zeolites exchanged with transition metal ions (TMIs) are the subject of great interest for their unusual catalytic activity and selectivity. Structural information like coordination and accessibility of TMIs in zeolites are important factors for understanding their catalytic activity. Siting of TMIs in zeolites is typically obtained by spectroscopic (EXAFS, EPR, UV–vis and IR) and computational methods, as in the case of Co-ferrierite. However, some controversy exists in the literature concerning the model for incorporation of bare Co ions in ferrierite. We show here that the results of our synchrotron X-ray powder diffraction studies on Co- and Ni-exchanged ferrierite (Si/Al = 8.5) are in a good agreement with the model of Co siting based on an indirect spectroscopic approach and help to validate this model. By direct structural evidences, a possible explanation for the larger catalytic activity of Co sites in the main channels of ferrierite can be inferred. A combination of data from in situ XRD continuous monitoring of the Co ion migration during calcination and crystal-chemical considerations allows to device a strategy for the design of optimised co-cations containing Co-ferrierite catalysts.     

On the dynamics of non-linear viscoelastic solids with material moduli that depend upon pressure

We investigate the dynamic response, of a generalization of an incompressible Kelvin-Voigt viscoelastic solid, whose viscosity depends on the pressure. Bodies with pressure-dependent material moduli have relevance to numerous technologically significant problems in geomechanics, the mechanics of granular media and powder compaction. We obtain analytical results for creep and recovery phenomena as well as solutions to the propagation of waves in such bodies. We are able to obtain explicit exact solutions that clearly illustrate the marked difference in the response of bodies with pressure-dependent material moduli as opposed to their counterparts whose moduli do not depend on the pressure. We also show that the governing equations for such materials can change type, and that their solutions exhibit singularities and localization.     

Evaluation of Slow Crack Growth Resistance in Ceramics for High-Temperature Applications

The slow (subcritical) crack growth (SCG) resistance of Si₃N₄ and SiC ceramics has been evaluated by a stepwise loading test on bending bars precracked by Vickers indentation. Three highly refractory materials were selected for the evaluation: i.e., (1) high-purity Si₃N₄ sintered by hot isostatic pressing (HIP) without additives and (2,3) α - and β - SiC pressureless sintered with B and C addition. Under the hypothesis of linear elastic behavior at high temperature, which was found satisfied in the present materials, the SCG resistance was expressed in terms of initial stress intensity factor critical for SCG failure within a predetermined lifetime. The present method was found useful in shortening the testing time and consistent with other traditional fatigue tests (e.g., static-fatigue test): It is recommended as a screening test for materials under research and development. Among the materials tested in the present study, the highest SCG resistance up to 1440°C was found in the high-purity Si₃N₄ without additives.     

3-D gust effect factor for slender vertical structures

Original studies on gust factor buffeting dealt with the alongwind displacement of structures. Research on this topic carried out since the nineties followed two distinct lines: the first determines the maximum effects due to the alongwind response; the second extends the original method from the alongwind response to crosswind and torsional responses. This paper represents the junction point of these research lines with reference to cantilever slender vertical structures. It derives the most relevant effects associated with the three-dimensional (3-D) wind-excited response of this structural type and shows that a suitable definition of one non-dimensional quantity, referred to as the 3-D gust effect factor, provides such effects at any level through a wide set of experimental, numerical and analytical procedures. A new definition of a 3-D equivalent static force consistent with this method is also introduced and critically compared with previous analogous statements.     

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.     

Low-Power Adaptive Biased Integrated Amplifiers

In this paper the author will present the working principle and the applications of a novel adaptive biasing topology, designed to decrease the stand-by power dissipation without affecting the transient performance of low-power amplifiers. The proposed circuit, whose principle and circuit topology can be implemented both in CMOS and in bipolar standard technologies, gives a biasing current whose value depends on the applied input differential voltage and can be set according to the requested transient performance constraints. The adaptive architecture can be utilized in the design of high-efficient low-power operational amplifiers, for the biasing of both the input stage (where the input source current is dynamically increased) and the output stage (where the output current can be controlled and limited). These amplifiers show a very good behaviour, evaluated in terms of two efficiency factors, if compared with those of other adaptive solutions and class-AB topologies, proposed in the literature. Simulation results and also measurements on a chip prototype, fabricated in a standard CMOS technology, are finally presented.     

In-vitro iron dialysability from legumes: Influence of phytate and extrusion cooking

In-vitro iron dialysability from five Italian legumes (mottled bean, white bean, faba bean, chickpea, lentil) and the influence of phytate and extrusion cooking on it were evaluated. Iron dialysability was 2·3 and 2·4% in mottled and white bean respectively, 1·2% infaba bean, 2·7% in chickpea and 1·1% in lentil. After extrusion cooking the flours showed a marked iron contamination and a decrease in iron dialysability, but these changes were significant only for mottled bean. Enzymic phytate removal induced an increase in iron dialysability > 100% in all the raw legumes except mottled bean which showed an increase of only 57%. This finding indicates that, although phytate consistently modifies iron dialysability, it is difficult to identify a quantitative relationship between phytate content and iron dialysability.