Coarse-grained modeling of model poly(urethane urea)s: Microstructure and interface aspects

Poly(urethane urea) elastomers are versatile and can be tailored to exhibit a broad range of mechanical response under high strain rate deformation. In this work, we utilize coarse-grained molecular dynamics simulations to elucidate the molecular mechanisms, particularly the effects of hard segment content, intermolecular interaction, and rigidity of the interface between the hard and soft segments on local morphology and rate-dependent stress-strain behavior in the ballistic regime. Simulation results qualitatively agree with available experimental data, where analysis of hard segment orientation during tensile and compression deformation and dynamic strain rate sensitivity was also performed. Further study of the intermolecular interaction on the stress-strain behavior reveals that it has a strong effect on strain hardening, particularly for a rigid interface, once the hard segment content reaches the percolation threshold. Simulation results also show that interface intermolecular interaction could become more dominant over interface rigidity in the initial stress-strain response, particularly below percolation.     

The collision efficiency in a shear flow

Fluid flows with cohesive particles are present in oil industry (e.g. natural gas/oil with hydrates, wax or asphaltenes), medicine (e.g. blood cells), nano- and ferro-fluidic applications (e.g. fluids with nanoparticles subject to the van der Waals and electrostatic interactions) and even in astrophysics (e.g. grains in planetary rings). Such flows may lead to formation of agglomerates that, for example in pipelines, may result in unwanted phenomena such as formation of deposits. The main process parameter governing this is the “collision efficiency”, which is the ratio of the number of collisions resulting in agglomeration to the total number of collisions. This is commonly considered to depend on the relativemagnitudes of attractive and repulsive interactions during a collision. The effect of the particles' mechanical properties on the agglomeration efficiency has, however, not yet been studied. In this paper the agglomeration efficiency is studied as a function of inter-particle friction, stiffness, density and volume fraction by numerical simulation. By running direct numerical simulations (DNS) with Lagrangian particle tracking of a shear flow laden with solid particles, the parameters influencing the agglomeration efficiency are demonstrated and their effects quantified. Finally, an expression that relates the collision efficiency to the salient dimensionless physical parameters is proposed.     

Investigation of the Sharkskin melt instability using optical Fourier analysis

An optical method allowing the characterization of melt flow instabilities typically occurring during an extrusion process of polymers and polymer compounds is presented. It is based on a camera-acquired image of the extruded compound with a reference length scale. Application of image processing and transformation of the calibrated image to the frequency domain yields the magnitude spectrum of the instability. The effectiveness of the before mentioned approach is shown on Styrene-butadiene rubber (SBR) compounds, covering a wide range of silica filler content, extruded through a Göttfert capillary rheometer. The results of the image-based analysis are compared with the results from the sharkskin option, a series of highly sensitive pressure transducers installed inside the rheometer. A simplified version of the code used to produce the optical analysis results is included as supplementary material. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48806.     

Synthesis and characterization of novel antimicrobial polymers containing pendent triclosan moieties

Novel antimicrobial copolymers were produced by first converting the commodity biocide, triclosan (TCS), to an epoxy-functional derivative, 2-((5-chloro-2-(2,4-dichlorophenoxy)phenoxy) methyl)oxirane (ETCS), and then reacting ETCS with polyethylenimine (PEI). While neither ETCS or PEI showed high antimicrobial activity toward either the Gram-positive bacterium, Staphylococcus epidermidis, or the Gram-negative bacterium, Escherichia coli, some the copolymers showed very high activity toward both bacteria. Antimicrobial activity for these copolymers was found to be highly dependent on both the molecular weight of the PEI utilized and the concentration of pendent groups derived from ETCS. In general, decreasing PEI molecular weight and increasing TCS pendent group concentration increased antimicrobial activity. Surface tension measurements showed that the molecular parameters affecting antimicrobial activity also affected surface activity in a similar fashion. Thus, it was speculated that the mechanism of antimicrobial activity associated with these copolymers involves interaction of the copolymers with the bacterial cell wall. A comparison of the antimicrobial activity of the most effective copolymers to TCS showed that the copolymers were more effective toward E. coli than pure TCS when compared using an equivalent TCS content (i.e. TCS pendent group content for the copolymers). This characteristic coupled with the fact that the TCS-containing copolymers are highly aqueous soluble liquids as opposed to a crystalline solid of limited solubility may afford utility of these copolymers for a variety of applications.     

Hydrothermal syntheses of ETS-10 like vanadosilicates using chiral organic molecules. Part I

Vanadosilicates with the structures of ETS-10 and AM-6 microporous materials have been hydrothermally synthesized using organic directing structures agent (SDAs) derivatives of decahydroquinoline, 3,5-dimethyl-piperidine, 2,6-dimethyl-piperidine and (S)-Sparteine. Derivatives of these chiral amines have not been explored before in the sol gel chemistry of vanadosilicates. Physicochemical characterization of the obtained vanadosilicate materials with these different chiral templates was carried out by X-ray diffraction (XRD), scanning electron microscopy (SEM), Raman and infrared (IR) spectroscopy, solid-state NMR spectroscopy, and differential thermogravimetric analysis (DTA)/thermogravimetric analysis (TGA). The results suggest that the presence of the chiral organic templates have different effects in terms of the final phase of the synthesized materials and their morphology. The products obtained using chiral template derivatives of decahydroquinoline reveal that certain products might be very enriched with chiral polymorph A while others present structures which are similar to other large-porous vanadosilicate such as AM-6 and AM-13. Derivatives of 2,6-dimethyl-piperidine and 3,5-dimethyl-piperidine have not favored any structure that resembles a chiral polymorph A, but only known vanadosilicates such as AM-6, AM-13. Derivatives of (S)-Sparteine, on the other hand, have not only favored the formation of structures enriched with a large amount of chiral polymorph A, but also their use has resulted in other unknown vanadosilicate structures whose physicochemical characterizations are in progress.     

Graphene decoration with metal nanoparticles: towards easy integration for sensing applications

A simple and versatile method for the decoration of CVD grown graphene with metal nanoparticles is presented. The mechanism of nanoparticle formation is galvanic displacement resulting in physically adsorbed clusters. The single layer graphene obtained by this method can be easily transferred. Integration onto a gas sensing transducer is presented as proof of concept.     

The Critical Role of Passive Permeability in Designing Successful Drugs

Passive permeability is a key property in drug disposition and delivery. It is critical for gastrointestinal absorption, brain penetration, renal reabsorption, defining clearance mechanisms and drug-drug interactions. Passive diffusion rate is translatable across tissues and animal species, while the extent of absorption is dependent on drug properties, as well as in vivo physiology/pathophysiology. Design principles have been developed to guide medicinal chemistry to enhance absorption, which combine the balance of aqueous solubility, permeability and the sometimes unfavorable compound characteristic demanded by the target. Permeability assays have been implemented that enable rapid development of structure-permeability relationships for absorption improvement. Future advances in assay development to reduce nonspecific binding and improve mass balance will enable more accurately measurement of passive permeability. Design principles that integrate potency, selectivity, passive permeability and other ADMET properties facilitate rapid advancement of successful drug candidates to patients.     

Pd-Decorated Tungsten as Pt-Free Bimetallic Catalysts for Hydrogen Oxidation Reaction in Alkaline Electrolyte

Developing Pt-free catalysts for hydrogen oxidation reaction (HOR) in alkaline solution is becoming a key challenge in the development of anion exchange membrane fuel cells and electrochemical reactors. Herein, we present the preparation, HOR activity, and stability of Pd-decorated tungsten (Pd-d-W) catalysts. The Pd-d-W catalysts were prepared by the chemically activated surface of tungsten nanoparticles by Pd ions. The resultant bimetallic catalysts consisted of crystalline phases of both Pd and W nanoparticles. The CO stripping voltammograms and H-desorption (H_des) peak potential of hydrogen desorption in Pd suggests that the enhancement of HOR catalytic activity observed in Pd-d-W catalyst can be ascribed to the modification of electronic property of Pd and availability of OH_ad near-surface Pd atoms.     

An Exemplar Imidazoline Surfactant for Corrosion Inhibitor Studies: Synthesis,Characterization, and Physicochemical Properties

An optimized one-pot recipe has been developed to synthesize a surfactant molecule, referred to as OMID, consisting of an imidazoline head group and aliphatic tail, which is an exemplar corrosion inhibitor for carbon steel in acidic solutions. As evidenced by gas chromatography, ¹H and ¹³C nuclear magnetic resonance, and Fourier-transform infrared data, a high-purity product was achieved without the use of either a solvent or catalyst. Critical micelle concentration values and corrosion inhibition efficiencies ( η %) were determined in aqueous solutions of hydrochloric acid and sulfuric acid using surface tensiometry and linear polarization resistance measurements, respectively. Hydrolysis of the imidazoline head group as a function of pH (0–11) was explored with ultraviolet–visible absorption spectroscopy. In addition, N 1s and C 1s X-ray photoelectron spectroscopy data were acquired from both surface-adsorbed OMID and a multilayer of the imidazoline head group of OMID. These latter data are highly relevant to those attempting to understand OMID inhibition chemistry.     

DEPOSITION OF A FINE POWDER IN HORIZONTAL PIPELINES AND BENDS

The deposition of a very fine powder in a horizontal, lean-phase pneumatic conveying conduit containing a 90° bend has been studied experimentally. The total deposition and the deposition pattern were studied as a function of superficial gas velocity, solids loading and bend geometry: one sharp and three smooth bends of different radii of curvature were used. Most deposition was seen in the sharp bend, while in the smooth bends the deposition did not vary much with radius of curvature. The deposition decreased significantly with increasing superficial gas velocity. The experimental results were compared with CFD simulations of the flow field. The observations are consistent with the notion of deposition in regions with low near-wall gas velocity, indicating that models for deposition should be sought in considerations of the deposit stability for this type of system.