Molecular simulation of thermophysical properties of aromatic polymers containing oxetane ring in the main chain

Molecular simulation techniques have been applied to newly synthesized aromatic polymers, containing oxetane rings in the main chain, to characterize the shape of rod‐like macromolecules. Single chains and periodic unit cells of a series of aromatic polymers with degree of polymerization 15 were used in the simulations, in accordance with the experimentally obtained one. The total potential energy was minimized and then NVE and NPT molecular dynamics simulations were performed for 1,000 ps at 11 temperatures between 10 and 1,000 K. The coefficient of asymmetry was calculated from the computer‐generated structures. The predictive capability of the NPT molecular dynamics simulation and Polymer Properties modules of Cerius² were used to estimate the orientational properties (order parameter), glass transition temperature, cohesive energy, and decomposition temperature of the polymers simulated. In general, there is a good‐to‐excellent agreement between simulated results and available experimental data of the above investigated properties. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 2334–2352, 1999     

Strong rotating flow in stationary droplets in low power budget using wire electrode configuration

We explore a simple strategy of generating strong rotating flow in a stationary surface‐droplet, using an intricate interplay of local electrical and thermal fields. Wire electrodes are employed to generate on‐spot heating without necessitating any elaborate micro‐fabrication, which causes strong local gradients in electrical properties to induce mobile charges into the droplet. Applying a low voltage (～10 V), strong rotational velocity of the order of mm/s can be achieved in the system, within the standard operating ranges of operating and geometrical parameters. Further, altering the diameter of the electrode, vortices can be tuned locally or globally in low power budget, without incurring any droplet oscillations. These results may turn out to be of immense consequence in enhancing micromixing in a plethora of droplet based applications ranging from thermal management to medical diagnostics to be potentially employed in resource‐limited settings.     

Reduced-order modelling of thermoacoustic instabilities in a two-heater Rijke tube

The topic of thermoacoustic instabilities in combustors is well-investigated, as it is important in the field of combustion, primarily in gas-turbine engines. In recent years, much attention has been focused on monitoring, diagnosis, prognosis, and control of high-amplitude pressure oscillations in confined combustion chambers. The Rijke tube is one of the most simple, yet very commonly used, laboratory apparatuses for emulation of thermoacoustic instabilities, which is also capable of capturing the physics of the thermally driven acoustics. A Rijke tube apparatus can be constructed with an electrical heater acting as the heat source, thus making it more flexible to operate and safer to handle than a fuel-burning Rijke tube or a fuel-fired combustor. Augmentation of the heat source of the Rijke tube with a secondary heater at a downstream location facilitates better control of thermoacoustic instabilities. Along this line, much work has been reported on the investigation of thermoacoustics by using computational fluid dynamics (CFD) modelling as well as reduced-order modelling for both single-heater and two-heater Rijke tube systems. However, since reduced-order models are often designed and built upon certain empirical relations, they may not account for the dynamic behaviour of the heater itself, which is a critical factor in the analysis and synthesis of real-time robust control systems. This issue is addressed in the current paper, where modifications have been made to existing models by incorporating heater dynamics. The model results are systematically validated with experimental data, generated from an in-house (electrically heated) Rijke tube apparatus.     

Augmented Lagrangian Digital Image Correlation

Experimental Mechanics - Digital image correlation (DIC) is a powerful experimental technique for measuring full-field displacement and strain. The basic idea of the method is to compare images of...     

Pd-catalysed C–H functionalisation of free carboxylic acids

Pd-catalysed C–H functionalisation of free carboxylic acids has drawn significant attention over the last few years due to the predominance of carboxylic acid moieties in pharmaceuticals and agrochemicals. But their coordinating ability was overlooked and masked by exogenous directing groups for a long time. Even other crucial roles of carboxylic acids as additives and steric inducers that directly influence the mode of a reaction have been widely neglected. This review aims to embrace all of the diverse aspects of carboxylic acids except additive and steric effects by concisely and systematically describing their versatile role in Pd-catalysed proximal and distal C–H activation reactions that could be implemented in the pharmaceutical and agrochemical industries. In addition, the mechanistic perspectives along with several recent strategies developed in the last few years discussed here will serve as educational resources for future research.

Pd-catalysed C–H functionalisation of free carboxylic acids has drawn significant attention over the last few years due to the predominance of carboxylic acid moieties in pharmaceuticals and agrochemicals.     

Synthesis and characterization of anhydride-functional polycaprolactone

Polycaprolactone-graft-maleic anhydride (PCL-g-MA) copolymer was prepared by grafting maleic anhydride onto PCL in a batch mixer and in an extruder using dicumyl peroxide as the initiator. The graft content was determined with the volumetric method by converting the anhydride functions to acid groups and then titrating with ethanolic potassium hydroxide. The grafted polymer was extracted with xylene to remove any unreacted monomer before the estimation step. The effect of temperature and the various concentrations of the initiator and monomer used for the grafting reaction were investigated. The presence of residual initiator in the reaction product was checked using thin-layer chromatography. Molecular weight determination was carried out for the pure and grafted polymer using gel permeation chromatography to determine if chain scission was present. Results indicate that maleic anhydride is grafted onto PCL using free radical initiators. The grafting reaction was confirmed by FTIR and NMR techniques. FTIR spectra showed absorption bands around 1785 and 1858 cm⁻¹. NMR spectra gave signals for methine proton at 3.47 ppm. For a given peroxide level, a higher temperature or residence (reaction) time gave higher percentage of grafted MA. There was an optimum temperature and initiator concentration after which the percentage of MA grafted on PCL decreased. The number-average molecular weight, tensile strength, and the percent elongation of PCL-g-MA were comparable to those of PCL before grafting. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 1139–1148, 1997