Correction of second‐order‐diffraction errors in spectrophotometry

Conventional diffraction gratings are designed so that most of the light striking the grating is diffracted toward the “first‐order beam” direction, but in practice, some of the light may be diffracted towards the “second‐order beam” direction, so that the light striking a particular sensor pixel may be a combination of both first‐ and second‐order components. This causes errors in the output of diffraction‐grating based UV–visible spectrometers. A new method has been developed to correct such errors by calibrating the optical system with a UV‐excluded standard (such as an orange tile) and a UV‐included standard (such as a white tile). These two calibrations can predict the relationship between first‐order‐only signals and first‐and‐second‐order combined signals at sensor pixels (nominal wavelengths) where there is second‐order light, and thus help correct the second‐order diffraction error. This compensation method applied on the reflectance measurement of a set of color ceramic tiles showed significant improvement on the accuracy of the result. © 2016 Wiley Periodicals, Inc. Col Res Appl, 42, 189–192, 2017     

A comprehensive model of colour appearance for related and unrelated colours of varying size viewed under mesopic to photopic conditions

CIE has recommended two previous appearance models, CIECAM97s and CIECAM02. However, these models are unable to predict the appearance of a comprehensive range of colours. The purpose of this study is to describe a new, comprehensive colour appearance model, which can be used to predict the appearance of colours under various viewing conditions that include a range of stimulus sizes, levels of illumination that range from scotopic through to photopic, and related and unrelated stimuli. In addition, the model has a uniform colour space that provides a colour‐difference formula in terms of colour appearance parameters. © 2016 Wiley Periodicals, Inc. Col Res Appl, 42, 293–304, 2017     

One‐pot synthesis of {Mo6I8}4+‐doped polystyrene microspheres via a free radical dispersion copolymerisation reaction

Molybdenum octahedral clusters, when incorporated into an appropriate polymer matrix, are considered as promising agents for a range of biological applications. This work describes the one‐pot synthesis, morphology and cellular toxicity of nano‐sized polystyrene beads doped with luminescent cluster complexes [{Mo₆X₈}(NO₃)₆]^2? (X = Cl, Br or I). Specifically, the particles were obtained by free radical dispersion copolymerisation of styrene and methacrylic acid or 4‐vinylpyridine in the presence of the cluster complexes. The effects of the cluster loading in the reaction mixture on both the content of the final material and number‐average molar mass of the copolymers were evaluated. © 2017 Society of Chemical Industry     

Morphologically dependent alternating‐current and direct‐current breakdown strength in silica–polypropylene nanocomposites

In this article, we report the synthesis of a new bimodal surface ligand morphology on silica nanoparticles. Combining grafting‐to and grafting‐from approaches, in this study, we demonstrated the efficacy of anthracene surface modification for improving the dielectric breakdown strength (DBS) under alternating‐current and direct‐current conditions and that of a matrix‐compatible polymer brush for controlling the nanofiller (NF) dispersion. Ligand‐modified spherical colloidal SiO₂ nanoparticles (～14 nm in diameter) were mixed into polypropylene, and the resulting dispersion was improved over the unmodified particles, as shown with transmission electron microscopy. The results suggest that the electronic structure of the anthracene‐modified particle surface was critical to the improvement in DBS. In addition, the DBS of the composite was shown to depend on the dispersion state of the filler and the mode of stress; this indicated that the individually dispersed nanoparticles were not necessarily the optimal morphology for all stress conditions. Additionally, the precise nature of the matrix‐compatible brush was less important than the NF dispersion it produced. The bimodal grafted architectural design has provided a promising solution for the control of the dispersion and surface properties, especially for high‐molecular‐weight polymer matrices. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44347.     

Intensified and safe ozonolysis of fatty acid methyl esters in liquid CO2 in a continuous reactor

We demonstrate a continuous reactor for performing the ozonolysis of fatty acid methyl esters (FAMEs) using liquid CO₂ as solvent. The fast reaction kinetics allows the use of small‐volume reactors to completely convert the FAMEs, forming secondary ozonides as the primary products. The short residence times also help maximize the yields of the secondary ozonides by minimizing over‐oxidation and the formation of oligomeric products. The liquid CO₂ medium promotes safe reactor operation by providing an essential fraction of overall reactor cooling and by diluting the vapor phase organics. We also demonstrate a continuous stirred reactor for the safe thermal decomposition of the secondary ozonides to their corresponding acids and aldehydes. Using a lumped kinetic model for the thermal decomposition of the ozonolysis products, we estimate activation energy values of 108.6 ± 0.6 kJ mol^?1 for the decomposition of secondary ozonides and 122 ± 3 kJ mol^?1 for the decomposition of the undesired oligomeric species. © 2017 American Institute of Chemical Engineers AIChE J, 63: 2819–2826, 2017     

Equation‐oriented simulation and optimization of process flowsheets incorporating detailed spiral‐wound multistream heat exchanger models

Multiple chemical processes rely on multistream heat exchangers (MHEXs) for heat integration, particularly at cryogenic temperatures. Owing to their geometric complexity, the detailed design of MHEXs is typically iterative: the exchanger geometric parameters are selected to match process specifications resulting from a flowsheet optimization step; then, the flowsheet is reoptimized with the predictions of the MHEX model, and these steps are repeated until a convergence criterion is met. This paper presents a novel framework that allows—for the first time, to our knowledge—for the simultaneous optimization of the process flowsheet and the detailed MHEX design. Focusing on spiral‐wound MHEXs, we develop an equation‐oriented exchanger model using industry‐accepted heat transfer and pressure drop correlations for single‐phase and multiphase streams. We embed this model in our previously developed pseudo‐transient equation‐oriented process simulation and optimization framework. We demonstrate our approach on an industrial case study, the PRICO^® natural gas liquefaction process. © 2017 American Institute of Chemical Engineers AIChE J, 63: 3778–3789, 2017     

Effects of protein properties on adsorption and transport in polymer‐grafted ion exchangers: A multiscale modeling study

We use multiscale modeling to study how the molecular properties of a protein affect its adsorption and transport in ion exchange chromatography matrices with either open pores or charged polymers grafted into the pore structure. Coarse‐grained molecular dynamics (MD) simulations of lysozyme, bovine serum albumin, and immunoglobulin show that higher protein net charge leads to greater partitioning into the polymer‐grafted pore space but slower diffusion there due to favorable electrostatic interactions, while larger size decreases both pore space partitioning and diffusion due to steric effects of the polymers. Mass transfer simulations based on the MD results show that the polymer‐grafted systems can enhance the adsorption kinetics if pore space partitioning and diffusion are both sufficiently high. The simulations illustrate that to achieve fast adsorption kinetics, there is a tradeoff between favorable binding and rapid diffusion which largely depends on the charge and size of the protein. © 2017 American Institute of Chemical Engineers AIChE J, 63: 4564–4575, 2017