Soft X‐ray Ptychographic Imaging and Morphological Quantification of Calcium Silicate Hydrates (C–S–H)

Morphological details of calcium silicate hydrate (C–S–H) stemming from the hydration process of Portland cement (PC) phases are crucial for understanding the PC‐based systems but are still only partially known. Here we introduce the first soft X‐ray ptychographic imaging of tricalcium silicate (C₃S) hydration products. The results are compared using both scanning transmission X‐ray and electron transmission microscopy data. The evidence shows that ptychography is a powerful method to visualize the details of outer and inner product C–S–H of fully hydrated C₃S, which have fibrillar and an interglobular structure with average void sizes of 20 nm, respectively. The high‐resolution ptychrography image enables us to perform morphological quantification of C–S–H, and, for the first time, to possibly distinguish the contributions of inner and outer product C–S–H to the small angle scattering of cement paste. The results indicate that the outer product C–S–H is mainly responsible for the q^?3 regime, whereas the inner product C–S–H transitions to a q^?2 regime. Various hypotheses are discussed to explain these regimes.     

Time‐space PGD for the rapid solution of 3D nonlinear parametrized problems in the many‐query context

This work deals with the question of the resolution of nonlinear problems for many different configurations in order to build a ‘virtual chart’ of solutions. The targeted problems are three‐dimensional structures driven by Chaboche‐type elastic‐viscoplastic constitutive laws. In this context, parametric analysis can lead to highly expensive computations when using a direct treatment. As an alternative, we present a technique based on the use of the time‐space proper generalized decomposition in the framework of the LATIN method. To speed up the calculations in the parametrized context, we use the fact that at each iteration of the LATIN method, an approximation over the entire time‐space domain is available. Then, a global reduced‐order basis is generated, reused and eventually enriched, by treating, one‐by‐one, all the various parameter sets. The novelty of the current paper is to develop a strategy that uses the reduced‐order basis for any new set of parameters as an initialization for the iterative procedure. The reduced‐order basis, which has been built for a set of parameters, is reused to build a first approximation of the solution for another set of parameters. An error indicator allows adding new functions to the basis only if necessary. The gain of this strategy for studying the influence of material or loading variability reaches the order of 25 in the industrial examples that are presented. Copyright © 2015 John Wiley & Sons, Ltd.     

Facing the Urban housing crisis

L'auteur qui a beaucoup fait pour aider à développer la nouvelle communauté de Tapiola près d'Helsinki considère que le développement urbain depuis 1945 a été invariablement désastreux. L'urbanisme a, d'après lui, sous-évalué les besoins humains primaires des individus et n'a pas su appliquer la démocratie, ce qui a conduit à créer un mauvais système de contrôle de l'urbanisme.     

Inference on a Structural Break in Trend with Fractionally Integrated Errors

Perron and Zhu (2005) established the consistency, convergence rate and limiting distributions of parameter estimates in time trends with a change in slope with or without a concurrent level change for the cases with I(1) or I(0) errors. We extend their analysis to the general case of fractionally integrated errors with memory parameter d^?. Our results uncover interesting features; e.g., with a level shift allowed, the convergence rate for the break date estimate is the same for all d^?∈(?0.5,0.5). In other cases, it is decreasing as d^? increases. We also provide results about the so‐called spurious break issue.     

Designs of 3-Dimensional Networks and MOFs Using Mono- and Polymetallic Copper(I) Secondary Building Units and Mono- and Polythioethers: Materials Based on the Cu–S Coordination Bond

This mini-review surveys 23 structures of 3D coordination polymers built upon mono-, di- as well as cyclic and acylic polythioethers. An emphasis is put on the Secondary Building Units (SBU) and the physical properties. Importantly, the key feature is that the dominant SBU is not the rhomboid (Cu₂X₂S₄), but an inorganic polymer containing at least the chain of the type (CuX) _n . In the latter type of SBU, these chain formations are observed for X = I, but predominantly for X = CN. In addition, a large portion of the surveyed materials exhibit rich photophysical properties, but on several occasions, these materials exhibit properties often attributed to MOFs, mainly solvent exchange.     

Optimization of a multiperiod refinery planning problem under uncertainty

Uncertainty in refinery planning presents a significant challenge in determining the day-to-day operations of an oil refinery. Deterministic modeling techniques often fail to account for this uncertainty, potentially resulting in reduced profit. The stochastic programming framework explicitly incorporates parameter uncertainty in the problem formulation, thus giving preference to robust solutions. In this work, a nonlinear, multiperiod, industrial refinery problem is extended to a two-stage stochastic problem, formulated as a mixed-integer nonlinear program. A crude-oil sequencing case study is developed with binary scheduling decisions in both stages of the stochastic programming problem. Solution via a decomposition strategy based on the generalized Benders decomposition (GBD) algorithm is proposed. The binary decisions are designated as complicating variables that, when fixed, reduce the full-space problem to a series of independent scenario subproblems. Through the application of the GBD algorithm, a feasible mixed-integer solution is obtained that is more robust to uncertainty than its deterministic counterpart.     

Enhancing laccase stability and activity for dyes decolorization using ZIF-8@MWCNT nanocomposite

The continuous use of chemical dyes in various industries, and their discharge into industrial effluents, results in severe problems to human life and water pollution. Laccases have the ability to decolorize dyes and toxic chemicals in industrial effluents as green biocatalysts. Their possible industrial applications have been limited by poor reusability, low stability, and loss of free laccase action. In this research, laccase was immobilized on zeolitic imidazolate framework coated multi-walled carbon nanotubes (Laccase@ZIF-8@MWCNTs) via metal affinity adsorption to develop an easy separable and stable enzyme. The optimum reaction conditions for immobilized laccase are at a pH of 3.0 and a temperature of 60?℃. The immobilized laccase was enhanced in storage and thermal stability. The results indicated that Laccase@ZIF-8@MWCNTs still maintained 68% of its original activity after 10 times of repeated use. Most importantly, the biocatalytic system was applied for decolorization of different dyes (20?mg·L^?1) without a mediator, and up to 97.4% for Eriochrome black T and 95.6% Acid red 88 was achieved in 25 min. Biocatalysts with these properties may be used in a variety of environmental and industrial applications.     

Effect of Thermomechanical Fatigue on Precipitation Microstructure in Two Precipitation-Hardened Cast Aluminum Alloys

Thermal loading induces modifications of the precipitation microstructure of Al–Si–Cu–Mg alloys. This study focuses on the effect of deformation on precipitation microstructure during thermomechanical loadings. Several specimens were thermomechanically cycled while others were exposed to the same thermal cycles without any mechanical loading. The nature and morphological characteristics of the precipitation microstructure of the thermomechanically cycled specimens are compared to those of the thermally aged ones, using transmission electron microscopy (TEM), in order to assess the effect of deformation on the precipitation microstructure and especially on the kinetics of precipitate growth. The absence of any significant effect of superimposed straining during thermal cycling is discussed. Implications for the prevision of yield strength degradation during service operation are briefly presented.

     

Pentadecane functionalized graphite oxide sheets as a tool for the preparation of electrical conductive polyethylene/graphite oxide composites

Covalent functionalization of pentadecane-decorated thermally reduced graphite oxide (GO) sheets has been studied as a tool for the preparation of polyethylene/GO composites exhibiting rheological and electrical percolation thresholds. It was accomplished through pentadecane based radical addition onto unsaturated bonds located on the GO sheets' surface using dicumyl peroxide as hydrogen abstractor. This chemical functionalization influences the affinity of the formed pentadecane grafted GO sheets for various solvents. Then, the compounding of the composites pentadecane grafted GO/PE was performed at a processing temperature of 140 °C with 25, 20, 15, 10, 8 and 5 wt% loadings. Rheological and electrical percolation thresholds were found between 10 and 15 wt% for polyethylene/pentadecane functionalized graphene oxide composites while the composite graphite/PE at the same loading percentage did not reach any percolation threshold.