Thermal decomposition of RDX from reactive molecular dynamics

We use the recently developed reactive force field ReaxFF with molecular dynamics to study thermal induced chemistry in RDX [cyclic-[CH(2)N(NO(2))](3)] at various temperatures and densities. We find that the time evolution of the potential energy can be described reasonably well with a single exponential function from which we obtain an overall characteristic time of decomposition that increases with decreasing density and shows an Arrhenius temperature dependence. These characteristic timescales are in reasonable quantitative agreement with experimental measurements in a similar energetic material, HMX [cyclic-[CH(2)N(NO(2))](4)]. Our simulations show that the equilibrium population of CO and CO(2) (as well as their time evolution) depend strongly of density: at low density almost all carbon atoms form CO molecules; as the density increases larger aggregates of carbon appear leading to a C deficient gas phase and the appearance of CO(2) molecules. The equilibrium populations of N(2) and H(2)O are more insensitive with respect to density and form in the early stages of the decomposition process with similar timescales.     

Atomistic-scale simulations of the initial chemical events in the thermal initiation of triacetonetriperoxide

To study the initial chemical events related to the detonation of triacetonetriperoxide (TATP), we have performed a series of molecular dynamics (MD) simulations. In these simulations we used the ReaxFF reactive force field, which we have extended to reproduce the quantum mechanics (QM)-derived relative energies of the reactants, products, intermediates, and transition states related to the TATP unimolecular decomposition. We find excellent agreement between the QM-predicted reaction products and those observed from 100 independent ReaxFF unimolecular MD cookoff simulations. Furthermore, the primary reaction products and average initiation temperature observed in these 100 independent unimolecular cookoff simulations match closely with those observed from a TATP condensed-phase cookoff simulation, indicating that unimolecular decomposition dominates the thermal initiation of the TATP condensed phase. Our simulations demonstrate that thermal initiation of condensed-phase TATP is entropy-driven (rather than enthalpy-driven), since the initial reaction (which mainly leads to the formation of acetone, O(2), and several unstable C(3)H(6)O(2) isomers) is almost energy-neutral. The O(2) generated in the initiation steps is subsequently utilized in exothermic secondary reactions, leading finally to formation of water and a wide range of small hydrocarbons, acids, aldehydes, ketones, ethers, and alcohols.     

Studies on borate esters 1 : The ph dependence of the stability of esters of boric acid and borate in aqueous medium as studied by 11B NMR

The pH dependent stability of esters of boric acid and borate with glycol, glycolic acid, oxalic acid and glyceric acid as dihydroxy compounds has been studied. ¹¹B NMR provides a suitable analytical tool for the quantitative determination and structure elucidation of the various esters in aqueous medium. The pH dependent stability of esters of boric acid and borate is formulated in a general rule of thumb: esters of boric acid and borate with dihydroxy compounds in aqueous medium show the highest stability at that pH where the sum of the charges of the free esterifying species is equal to the charge of the ester.     

Selective hydrosilylation of styrene using an in situ formed platinum(1,3-dimesityl-dihydroimidazol-2-ylidene) catalyst

A highly active and selective in situ formed platinum(N-heterocyclic carbene) catalyst for the hydrosilylation of styrene with triethylsilane is described, which unlike all other known hydrosilylation catalysts, selectively yields hydrosilylation products, but (almost) no dehydrogenative silylation products.     

On weighting two criteria with a parameter in combinatorial optimization problems

Two criteria in a combinatorial problem are often combined in a weighted sum objective using a weighting parameter between 0 and 1. For special problem types, e.g., when one of the criteria is a bottleneck value, efficient algorithms are known that solve for a given value of the weighting parameter.     

Threshold crack speed controls dynamical fracture of silicon single crystals

Fracture experiments of single silicon crystals reveal that after the critical fracture load is reached, the crack speed jumps from zero to approximately 2 km/sec, indicating that crack motion at lower speeds is forbidden. This contradicts classical continuum fracture theories predicting a continuously increasing crack speed with increasing load. Here we show that this threshold crack speed may be due to a localized phase transformation of the silicon lattice from 6-membered rings to a 5-7 double ring at the crack tip.     

On the Development of Titanium κ1-Amidinate Complexes,Commercialized as Keltan ACE™ Technology,Enabling the Production of an Unprecedented Large Variety of EPDM Polymer Structures

ARLANXEO Elastomers has developed and commercialized Keltan ACE™ technology, a class of half-sandwich cyclopentadienyl κ¹-amidinate metal complexes, which are extremely active for the production of first-class ethylene/propylene/diene copolymers (EPDM). In this review, the development and some of the key features of the Keltan ACE™ catalyst system are presented. Many different ACE catalysts have been synthesized over the past years, including bridged and bimetallic catalysts. With Keltan ACE™, a complete range of EPDM products with similar polymer characteristics as their Ziegler–Natta (ZN) counterparts can be produced, including variations containing very high 5-ethylidene-2-norbornene (ENB) contents, controlled long chain branching, very high molecular weight, as well as oil-extended products. Moreover, other EPDM structures can be polymerized. The Keltan ACE™ catalyst technology also allows the production of EPDMs with very high amounts of dicyclopentadiene (DCPD) or 5-vinyl 2-norbornene (VNB) without excessive gelation and reactor fouling, that is, products that cannot or are extremely difficult to obtain via classical ZN catalysis. In a next step, high-VNB-EPDM can be postreactor modified, for example, via metathesis chemistry. In addition, EPDM polymers with a very broad or even bimodal molecular weight distribution can be obtained in a single reactor with certain ACE catalyst structures at particular activator/precatalyst ratios. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 2877–2891     

The partial inverse minimum spanning tree problem when weight increase is forbidden

In a partial inverse optimization problem there is an underlying optimization problem with a partially given solution. The objective is to find a minimal perturbation of some of the problem’s parameter values, in such a way that the partial solution becomes a part of the optimal solution.     

An in situ temperature‐programmed XPS study of the surface chemical reactions of thiophene with Ag/titania

The Ag/titania sorbent for the ultradeep desulfurization of liquid fuels was characterized by electron spin resonance and was found to contain nearly the stoichiometric titania, without significant concentration of Ti³⁺ or the reactive oxygen species. The surface chemical reactions of thiophene adsorbed on the Ag/titania were studied by temperature‐programmed XPS from 25 to 525 °C upon in situ thermal annealing in high vacuum and in situ oxidation by oxygen gas. The titania support is not chemically reactive under those conditions. Silver oxide in the Ag/titania sorbent is converted to Ag₂ S without formation of the transient surface sulfates or sulfites and is further oxidized by molecular oxygen. Copyright © 2010 John Wiley & Sons, Ltd.     

Towards governance on noise between municipality and terminal operator by the use of simulation modelling

The development of multimodal transport terminals in urban areas generates various serious environmental problems. The available tools for the analyses of the use of such terminals offer insufficient support for decision-making on the location and design of these terminals from the sustainability perspective. New approaches are needed. This article contributes to satisfy this need, triggered by the planning of a new Barge Terminal in the Dutch city of Tilburg (BTT). Presently, the existing terminal in Tilburg is operating near full capacity and the construction of a new terminal is considered the best strategy to cope with steady growth. The main question concerns the optimal design of the new barge terminal to offer a high operational performance, however without exceeding the environmental quality standards, in particular noise. The article presents a simulation approach to assist in the process of finding a balance between the operational performance and the noise effects of alternative designs of the new terminal.