Heat Induced Structure Modifications in Polymer‐Layered Silicate Nanocomposites

Summary: The success of the use of layered silicates in polymer nanocomposites, to improve physical and chemical properties is strictly related to a deeper knowledge of the mechanistic aspects on which the final features are grounded. This work shows the temperature induced structural rearrangements of nanocomposites based on poly[ethylene‐co‐(vinyl acetate)] (EVA) intercalated‐organomodified clay (at 3–30 wt.‐% silicate addition) which occur in the range between 75 and 350 °C. In situ high temperature X‐ray diffraction (HT‐XRD) studies have been performed under both nitrogen and air to monitor the modifications of the nanocomposite structure at increasing temperatures under inert/oxidative atmosphere. Heating between 75 and 225 °C, under nitrogen or air, causes the layered silicate to migrate towards the nanocomposite surface and to increase its interlayer distance. The degradation of both the clay organomodifier and the VA units of the EVA polymer seems to play a key role in driving the evolution of the silicate phase in the low temperature range. The structural modifications of the nanocomposites in the high temperature range (250–350 °C), depended on the atmosphere, either inert or oxidizing, in which the samples were heated. Heating under nitrogen led to deintercalation and thus a decrease of the silicate interlayer space, whereas exfoliation was the main process under air leading to an increase of the silicate interlayer space.

Heat induced structural modification of EVA‐clay nanocomposite under nitrogen and air.     

Thermodynamic interactions of branched polyethylene in polar and nonpolar systems

The thermodynamic properties of polymer solutions are frequently described in terms of the Flory-Huggins equation. This equation includes a parameter χ, which depends upon the intermolecular forces acting between the molecules in a solution. The experimental determination of χ was performed by an improved microtechnique and extended to a wide range of polar and nonpolar diluents of polyethylene. Careful correlations are prescribed for calculating χ from pure-component properties; they are based on an extension of the Hildebrand-Scatchard theory of solutions and on the theory of intermolecular forces. Polar (τ) and nonpolar (δ) solubility parameters are presented for a variety of solvents. For polyethylene—nonpolar solvent systems we have emphasized the factor deciding the sign of heat of mixing, while for polyethylene-polar solvent systems we have determined the contribution of dipole-induced dipole interactions ψ (δτ) in interchange-energy density B and, hence, χ.     

Ceramic Microtubes from Preceramic Polymers

A novel process for the production of ceramic microtubes involving the microextrusion of preceramic polymers was studied. Microtubes with a wide range of inner and outer diameters and several centimeters long were produced from two silicone resins. A coextrusion approach was also used to extend the forming capability of the technique. The addition of carbon black resulted in electrically conductive silicon oxycarbide (SiOC) ceramic microtubes. SiOC microtubes possessed a high bending strength, ranging from ∼30–1100 MPa.     

Cold sintering of diatomaceous earth

Diatomite, a natural silicate-based sedimentary rock, was densified by cold sintering at room temperature and 150°C under various pressures (100, 200, and 300 MPa) and using different NaOH water solutions (0–3 M). The relative density of cold sintered diatomite can be as high as 90%, a condition that can be achieved by conventional firing only at 1200–1300°C. The cold sintered materials maintain the same mineralogical composition of the starting powder (quartz, glass, and illite) and are constituted by well-deformed and flattened grains oriented orthogonally to the applied pressure. Conversely, an evident phase evolution takes place upon conventional firing with the formation of cristobalite and mullite. The bending strength of cold sintered artifacts can exceed 40 MPa and increases to ≈80 MPa after post-annealing at 800°C, such mechanical strength is much larger than that of conventionally pressed samples sintered at 800°C, which is only ≈1 MPa.     

Preparation and structural characterization of perovskite-type LaxLn1−x″CoO3 by the thermal decomposition of heteronuclear complexes, LaxLn1−x″| Co(CN)6| · nH2O (Ln″ = Sm and Ho)

Perovskite-type La_xLn_1−x″CoO₃ oxides are prepared by the thermal decomposition of La_xLn_1−x″ [Co(CN)₆] · nH₂O hetero-nuclear complexes. Except for LaCoO₃ (hexagonal), the structures observed for La_xSm_1−xCoO₃ are othorhombic. While the perovskite-type oxide HoCoO₃ is not formed by decomposition at 1000°C of the corresponding hexacyano complex, the partial replacing of Ho with La is effective in forming the pervoskite-type oxide having an orthorhombic structure containing Ho even at 800°C. A monotonous correlation (quasi-linear relationship) was found between the b- and c-lattice constants of the orthorhombic structures of the perovskite-type oxides and the effective radii of Ln ions, defined as r_eff = xr_1.a + (1 − x)r_1.0″. The distortion parameter for the orthorhombie cell (3″a/b−1) increaseswith decrease in r_eff and is expected to be 0.270 for perovskite-type HoCoO₃. The crystal structure of the La_xLn_1−x″, CoO₃ oxides is mainly controlled by the effective radii of Ln ions.     

Statics Aware Grid Shells

We introduce a framework for the generation of polygonal gridshell architectural structures, whose topology is designed in order to excel in static performances. We start from the analysis of stress on the input surface and we use the resulting tensor field to induce an anisotropic nonEuclidean metric over it. This metric is derived by studying the relation between the stress tensor over a continuous shell and the optimal shape of polygons in a corresponding gridshell. Polygonal meshes with uniform density and isotropic cells under this metric exhibit variable density and anisotropy in Euclidean space, thus achieving a better distribution of the strain energy over their elements. Meshes are further optimized taking into account symmetry and regularity of cells to improve aesthetics. We experiment with quad meshes and hexdominant meshes, demonstrating that our gridshells achieve better static performances than stateoftheart gridshells.     

A reclaimer scheduling problem arising in coal stockyard management

We study a number of variants of an abstract scheduling problem inspired by the scheduling of reclaimers in the stockyard of a coal export terminal. We analyze the complexity of each of the variants, providing complexity proofs for some and polynomial algorithms for others. For one, especially interesting variant, we also develop a constant factor approximation algorithm.     

Maximum density of quantum information in a scalable CMOS implementation of the hybrid qubit architecture

Scalability from single-qubit operations to multi-qubit circuits for quantum information processing requires architecture-specific implementations. Semiconductor hybrid qubit architecture is a suitable candidate to realize large-scale quantum information processing, as it combines a universal set of logic gates with fast and all-electrical manipulation of qubits. We propose an implementation of hybrid qubits, based on Si metal-oxide-semiconductor (MOS) quantum dots, compatible with the CMOS industrial technological standards. We discuss the realization of multi-qubit circuits capable of fault-tolerant computation and quantum error correction, by evaluating the time and space resources needed for their implementation. As a result, the maximum density of quantum information is extracted from a circuit including eight logical qubits encoded by the [[7, 1, 3]] Steane code. The corresponding surface density of logical qubits is 2.6 Mqubit/cm\(^2\).     

HPC on the Grid: The Theophys Experience

The Grid Virtual Organization (VO) “Theophys”, associated to the INFN (Istituto Nazionale di Fisica Nucleare), is a theoretical physics community with various computational demands, spreading from serial, SMP, MPI and hybrid jobs. That has led, in the past 20 years, towards the use of the Grid infrastructure for serial jobs, while the execution of multi-threaded, MPI and hybrid jobs has been performed in several small-medium size clusters installed in different sites, with access through standard local submission methods. This work analyzes the support for parallel jobs in the scientific Grid middlewares, then describes how the community unified the management of most of its computational need (serial and parallel ones) using the Grid through the development of a specific project which integrates serial e parallel resources in a common Grid based framework. A centralized national cluster is deployed inside this framework, providing “Wholenodes” reservations, CPU affinity, and other new features supporting our High Performance Computing (HPC) applications in the Grid environment. Examples of the cluster performance for relevant parallel applications in theoretical physics are reported, focusing on the different kinds of parallel jobs that can be served by the new features introduced in the Grid.     

A novel fluorescence lifetime imaging system that optimizes photon efficiency

Fluorescence lifetime imaging (FLIM) is a powerful microscopy technique for providing contrast of biological and other systems by differences in molecular species or their environments. However, the cost of equipment and the complexity of data analysis have limited the application of FLIM. We present a mathematical model and physical implementation for a low cost digital frequency domain FLIM (DFD-FLIM) system, which can provide lifetime resolution with quality comparable to time-correlated single photon counting methods. Our implementation provides data natively in the form of phasors. On the basis of the mathematical model, we present an error analysis that shows the precise parameters for maximizing the quality of lifetime acquisition, as well as data to support this conclusion. The hardware and software of the proposed DFD-FLIM method simplifies the process of data acquisition for FLIM, presents a new interface for data display and interpretation, and optimizes the accuracy of lifetime determination.