Complex fiber bundle model for optimization of heterogeneous materials

We propose a complex fiber bundle model for the optimization of heterogeneous materials, which consists of many simple bundles. We also present an exact and compact recursion relation for the failure probability of a simple fiber bundle model with local load sharing, which is more efficient than the ones reported previously. Using a ''renormalization method'' and the recursion relation developed for the simple bundle, we calculate the failure probabilities of the complex fiber bundle. When the total number of fibers is given, we find that there exists an optimum way to organize the complex bundle, in which one gets a stronger bundle than in other ways.

Monte Carlo simulation of complex cohesive fracture in random heterogeneous quasi-brittle materials

A numerical method is developed to simulate complex two-dimensional crack propagation in quasi-brittle materials considering random heterogeneous fracture properties. Potential cracks are represented by pre-inserted cohesive elements with tension and shear softening constitutive laws modelled by spatially varying Weibull random fields. Monte Carlo simulations of a concrete specimen under uni-axial tension were carried out with extensive investigation of the effects of important numerical algorithms and material properties on numerical efficiency and stability, crack propagation processes and load-carrying capacities. It was found that the homogeneous model led to incorrect crack patterns and load–displacement curves with strong mesh-dependence, whereas the heterogeneous model predicted realistic, complicated fracture processes and load-carrying capacity of little mesh-dependence. Increasing the variance of the tensile strength random fields with increased heterogeneity led to reduction in the mean peak load and increase in the standard deviation. The developed method provides a simple but effective tool for assessment of structural reliability and calculation of characteristic material strength for structural design.

Modulating the selectivity for CO and butane oxidation over heterogeneous catalysis through amorphous catalyst coatings

The preparation of porous films directly deposited onto the surface of catalyst particles is attracting increasing attention. We report here for the first time a method that can be carried out at ambient pressure for the preparation of porous films deposited over 3 mm diameter catalyst particles of silica-supported Pt-Fe. Characterization of the sample prepared at ambient pressure (i.e., open air, OA) and its main structural differences as compared with a Na-A (LTA) coated catalyst made using an autoclave-based method are presented. The OA-coated material predominantly exhibited an amorphous film over the catalyst surface with between 4 and 13% of crystallinity as compared with fully crystallized LTA zeolite crystals. This coated sample was highly selective for CO oxidation in the presence of butane with no butane oxidation observed up to 350 degrees C. This indicates, for the first time, that the presence of a crystalline membrane is not necessary for the difference in light off temperature between CO and butane to be achieved and that amorphous films may also produce this effect. An examination of the space velocity dependence and adsorption of Na+ on the catalysts indicates that the variation in CO and butane oxidation activity is not caused by site blocking predominantly, although the Pt activity was lowered by contact with this alkali.

Behavior of the heterogeneous electron-transfer rate constants of arenes and substituted anthracenes in room-temperature ionic liquids

We report the anodic oxidation of several arenes and anthracenes within room-temperature ionic liquids (RTILs). In particular, the heterogeneous electron-transfer rates (k(0)) for substituted anthracenes and arenes are also investigated in 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([C(2)mim][NTf2]) and found not to obey the outer-sphere Marcus-type behavior of these compounds in contrast to the behavior in traditional organic solvents,in particular the predictions for k(0) with molecular size and solvent static dielectric constant. To obtain the electron-transfer rate for 9-phenylanthracene, the dimerization and heterogeneous electron-transfer kinetics of its electrogenerated radical cations is studied in [C(2)mim][NTf2] and eight other RTILs and are both found to be largely independent of the solution viscosity.

Bronsted-Evans-Polanyi relation of multistep reactions and volcano curve in heterogeneous catalysis

Multistep surface processes involving a number of association reactions and desorption processes may be considered as hypothetical one-step desorption processes. Thus, heterogeneous catalytic reactions can be treated kinetically as consisting of two steps: adsorption and desorption. It is also illustrated that the hypothetical one-step desorption process follows the BEP relation. A volcano curve can be obtained from kinetic analysis by including both adsorption and desorption processes.

Heterogeneous oxidation of pyrimidine and alkyl thioethers in ionic liquids over mesoporous Ti or Ti/Ge catalysts

Heterogeneous catalytic oxidation of a series of thioethers (2-thiomethylpyrimidine, 2-thiomethyl-4,6-dimethyl-pyrimidine, 2-thiobenzylpyrimidine, 2-thiobenzyl-4,6-dimethylpyrimidine, thioanisole, and n-heptyl methyl sulfide) was performed in ionic liquids by using MCM-41 and UVM-type mesoporous catalysts containing Ti, or Ti and Ge. A range of triflate, tetrafluoroborate, trifluoroacetate, lactate and bis(trifluoromethanesulfonyl)imide-based ionic liquids were used. The oxidations were carried out by using anhydrous hydrogen peroxide or the urea-hydrogen peroxide adduct and showed that ionic liquids are very effective solvents, achieving greater reactivity and selectivity than reactions performed in dioxane. The effects of halide and acid impurities on the reactions were also investigated. Recycling experiments on catalysts were carried out in order to evaluate Ti leaching and its effect on activity and selectivity.

FE Simulation of Viscoplastic Consistency Model

Finite element (FE) simulations provides an inexpensive alternative for material testingof new metal alloys. Carrying out experimental testing is expensive. Nanoindentation is particularly costly due to the equipment needed to work on such a scale. FE simulations provide an inexpensive means of material testing if accurately carried out. This paper will demonstrate the applicability and accuracy of using FE modelling for basic material tests and will propose that the viscoplastic model may be used for nanoindentation testing. The simulations will test the Young’s modulus of materials during analysis when an Abaqus VUMAT is used. The viscoplastic model is incorporated into a subroutine and is tested at the macroscopic scale against previous published results.

Micromechanical Modelling of Non-Homogenous Materials by Meshless Methods

A detailed study of bi-material composites, using meshless methods (MMs), is presented in this paper. Firstly, representative volume elements (RVEs) for different bi-material combinations are analysed by the element-free Galerkin (EFG) method in order to confirm the effective properties of heterogeneous material through homogenization. The results are shown to be in good agreement with experimental results and those obtained using the finite element method (FEM) which required a higher node density. Secondly, a functionally graded material (FGM), with a crack, is analysed using the EFG method. This investigation was motivated by the possibility of replacing the distinct fibrematrix interface with a FGM interface. Finally, an illustrative example showing crack propagation, in a two-dimension micro-scale model of a SiC/Al composite is presented. 

Evaporative Moisture Loss from Heterogeneous Stone: Material- Environment Interactions During Drying

The complexities of evaporation from structurally and mineralogically heterogeneous sandstone (Locharbriggs Sandstone) are investigated through a laboratory-based experiment in which a variety of environmental conditions are simulated. Data reported demonstrate the significance of material-environment interactions on the spatial and temporal variability of evaporative dynamics. Evaporation from porous stone is determined by the interplay between environmental, material and solution properties, which govern the rate and mode by which water is transmitted to, and subsequently removed from, an evaporating surface. Initially evaporation is marked by high rates of moisture loss controlled by external atmospheric conditions; then, when a critical level of surface moisture content is reached, hydraulic continuity between the stone surface and subsurface is disrupted and the drying front recedes
beneath the surface, evaporation rates decrease and are controlled by the ability of the material to transport water vapour to the surface. Pore size distribution and connectivity, as well as other material properties, control the timing of each stage of evaporation and the nature of the transition.

These experimental data highlight the complexity of evaporation, demonstrating that different regions of the same stone can exhibit varying moisture dynamics during drying and that the rate and nature of evaporative loss differs under different environmental conditions. The results identify the importance of material-environment interactions during drying and that stone micro-environmental conditions cannot be inferred from ambient data alone.
These data have significance for understanding the spatial distribution of stone surface weathering-related morphologies in both the natural and built environments where mineralogical and/or structural heterogeneity creates differences in moisture flux and hence variable drying rates. Such differences may provide a clearer explanation for the initiation and subsequent development of complex weathering responses where areas of significant deterioration can be found alongside areas that exhibit little or no evidence surface breakdown.

Highlights from Faraday Discussion: Designing New Heterogeneous Catalysts, London, UK, April 2016

The Faraday Discussion on the design of new heterogeneous catalysts took place from 4-6 April 2016 in London, United Kingdom. It brought together world leading scientists actively involved in the synthesis, characterisation, modelling and testing of solid catalysts, attracting more than one hundred delegates from a broad spectrum of backgrounds and experience levels-academic and industrial researchers, experimentalists and theoreticians, and students. The meeting was a reflection of how big of an impact the ability to control and design catalysts with specific properties for particular processes can potentially have on the chemical industry, environment, economy and society as a whole. In the following, we give an overview of the topics covered during this meeting and briefly highlight the content of each presentation.