COSMO‐based computer‐aided molecular/mixture design: A focus on reaction solvents

In this article, we investigate reaction solvent design using COSMO‐RS thermodynamics in conjunction with computer‐aided molecular design (CAMD) techniques. CAMD using COSMO‐RS has the distinct advantage of being a method based in quantum chemistry, which allows for the incorporation of quantum‐level information about transition states, reactive intermediates, and other important species directly into CAMD problems. This work encompasses three main additions to our previous framework for solvent design (Austin et al., Chem Eng Sci. 2017;159:93–105): (1) altering the group contribution method to estimate hydrogen‐bonding and non‐hydrogen‐bonding σ‐profiles; (2) ab initio modeling of strong solute/solvent interactions such as H‐bonding or coordinate bonding; and (3) solving mixture design problems limited to common laboratory and industrial solvents. We apply this methodology to three diverse case studies: accelerating the reaction rate of a Menschutkin reaction, controlling the chemoselectivity of a lithiation reaction, and controlling the chemoselectivity of a nucleophilic aromatic substitution reaction. We report improved solvents/mixtures in all cases. © 2017 American Institute of Chemical Engineers AIChE J, 63: 104–122, 2018     

Polypropylene/silica micro‐ and nanocomposites modified with poly(styrene‐b‐ethylene‐co‐butylene‐b‐styrene)

The effects of different silica loadings and elastomeric content on interfacial properties, morphology and mechanical properties of polypropylene/silica 96/4 composites modified with 5, 10, 15, and 20 vol % of poly(styrene‐b‐ethylene‐co‐butylene‐b‐styrene) SEBS added to total composite volume were investigated. Four silica fillers differing in size (nano‐ vs. micro‐) and in surface properties (untreated vs. treated) were chosen as fillers. Elastomer SEBS was added as impact modifier and compatibilizer at the same time. The morphology of ternary polymer composites revealed by light and scanning electron microscopies was compared with morphology predicted models based on interfacial properties. The results indicated that general morphology of composite systems was determined primarily by interfacial properties, whereas the spherulitic morphology of polypropylene matrix was a result of two competitive effects: nucleation effect of filler and solidification effect of elastomer. Tensile and impact strength properties were mainly influenced by combined competetive effects of stiff filler and tough SEBS elastomer. Spherulitic morphology of polypropylene matrix might affect some mechanical properties additionally. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41486.     

Acceleration of kinetic monte carlo simulations of free radical copolymerization: A hybrid approach with scaling

Kinetic Monte Carlo (KMC) has been widely used in the simulation of polymeric reactions. The power of KMC is highlighted by its ability to keep track of the length and sequence of every radical or polymer chain, while it is computationally more expensive than deterministic kinetic models. This paper introduces an acceleration method that significantly reduces the computational cost of KMC simulations, while keeping the same features as the full kinetic Monte Carlo simulations. Case studies are used to demonstrate the general applicability of this method to free radical copolymerization. © 2017 American Institute of Chemical Engineers AIChE J, 63: 4013–4021, 2017     

Experimental and calculated liquid-liquid interfacial tension in demixing metal alloys

Liquid-liquid interracial tension in binary and temary Al-based monotectic systems has been determined experimentally with a tensiometric method in a wide temperature interval. The temperature dependence of the interfacial tension is well described by a power law function of the type σαβ - （1 - T/Tc）δ with the critical exponent δ= 1.3 and a critical temperature Tc. Theoretical models describing the liquid-liquid interface in monotectic alloys and their applicability for calculation of the interfacial tension and its temperature dependence in binary systems are considered.     

Integrated material flow and radioactivity distribution methodology within the calculation tool for evaluation of parameters for decommissioning of nuclear installations

Decommissioning of nuclear facilities becomes an important issue in all areas of nuclear technology, mainly in their energetic applications. Decommissioning process has to be planned in the safe, ecological and economic manner. It determines the requirements on appropriate evaluation of needed technologies, media, amount of solid materials released into the environment, radioactivity of effluents, amount of radioactive waste for disposal, number and exposure of personnel and finally the financial demands. A detailed evaluation of these parameters may be done by analytical calculation approach. This approach models a real process of decommissioning with its individual basic activities. The methodology of integrated material flow and radioactivity distribution within this calculation evaluation tool is applied and implemented to describe the real decommissioning activities and their mutual relations to obtain more accurate outputs.     

Magnetocaloric and magneto-transport properties of Gd10Co20Si70 alloy

We report the results of magnetic, thermodynamic, transport and magnetocaloric effect (MCE) studies of newly synthesized Gd_(10)Co_(20)Si_(70) alloy. These measurements confirm an antiferromagnetic transition at T_N=9 K. Both MCE and magnetoresistance (MR) show quadratic dependence on the applied magnetic field, indicating the presence of spin fluctuations in the alloy. The maximum values of the magnetic entropy change determined from the isothermal magnetization data for magnetic field change of 7 and9 T are found to be 10.5 and 15.6 J/kg·K, respectively. As a consequence of the spin fluctuations effect, the MCE peaks are pulled towards high temperature side as asymmetrically broadened peak. The MR attains a large positive value of 73%at 2 K in 8 T. The large MR and reversible MCE make this alloy an attractive multifunctional magnetic material.     

Carbon‐Nanotube–PDMS Composite Coatings on Optical Fibers for All‐Optical Ultrasound Imaging

Polymer–carbon nanotube composite coatings have properties that are desirable for a wide range of applications. However, fabrication of these coatings onto submillimeter structures with the efficient use of nanotubes has been challenging. Polydimethylsiloxane (PDMS)–carbon nanotube composite coatings are of particular interest for optical ultrasound transmission, which shows promise for biomedical imaging and therapeutic applications. In this study, methods for fabricating composite coatings comprising PDMS and multiwalled carbon nanotubes (MWCNTs) with submicrometer thickness are developed and used to coat the distal ends of optical fibers. These methods include creating a MWCNT organogel using two solvents, dip coating of this organogel, and subsequent overcoating with PDMS. These coated fibers are used as all‐optical ultrasound transmitters that achieve high ultrasound pressures (up to 21.5 MPa peak‐to‐peak) and broad frequency bandwidths (up to 39.8 MHz). Their clinical potential is demonstrated with all‐optical pulse‐echo ultrasound imaging of an aorta. The fabrication methods in this paper allow for the creation of thin, uniform carbon nanotube composites on miniature or temperature‐sensitive surfaces, to enable a wide range of advanced sensing capabilities.     

Mie‐Resonant Membrane Huygens' Metasurfaces

All‐dielectric metasurfaces have become a new paradigm for flat optics as they allow flexible engineering of the electromagnetic space of propagating waves. Such metasurfaces are usually composed of individual subwavelength elements embedded into a host medium or placed on a substrate, which often diminishes the quality of the resonances. The substrate imposes limitations on the metasurface functionalities, especially for infrared and terahertz frequencies. Here a novel concept of membrane Huygens' metasurfaces is introduced. The metasurfaces feature an inverted design, and they consist of arrays of holes made in a thin membrane of high‐index dielectric material, with the response governed by the electric and magnetic Mie resonances excited within dielectric domains of the membrane. Highly efficient transmission combined with the 2π phase coverage in the freestanding membranes is demonstrated. Several functional metadevices for wavefront control are designed, including beam deflector, a lens, and an axicon. Such membrane metasurfaces provide novel opportunities for efficient large‐area metadevices, whose advanced functionality is defined by structuring rather than by chemical composition.