End Group Effects on Adhesion of Perfluoropolyether Lubricants to Solid Substrates

Interfacial interactions of several commercial perfluoropolyether (PFPE) and aromaticmodified lubricants with silicon oxide or carbon substrates were investigated through contact angle measurement, dipping tests, fluorescence spectroscopy and contact-start-stop testing. All commercial lubricants that have not been thermally treated are displaced from the solid substrate by contact with water. Contact angles of water on ZDOL, a PFPE doubly-terminated with hydroxyl groups, spun on silicon and carboncoated wafers were measured as a function of thermal annealing treatment. The adhesion of commercial lubricants to such previously thermally-bonded layers is stronger than to the bare silicon wafers. The thermal reaction of ZDOL on silica gel and carbon was investigated by thermogravimetric analysis and FTIR. The thermal reaction takes place when the baking temperature exceeds 70°C; at least part of this surface-bonding involves condensation of terminal hydroxyl groups with isolated surface silanols. Finally, stiction values for aromatic-modified lubricants are substantially lower than for the unmodified commercial PFPE lubricants, but there are still significant humidity effects.     

DYNAMIC TENSIONS IN FINITE OIL DROPLETS

In reacting systems, dynamic interfacial tension (IFT) values above 10-20 mN/m are often encountered. For such high tension values, infinitely long oil droplets will not be realised in spinning drop tensiometry. Hence, Vonnegut's solution will not be strictly valid. The experimentalist is then compelled to use one of the several alternative solution schemes proposed in the literature. We have obtained dynamic IFT data for 0.3125 mM oleic acid in hexadecane contacted with various NaOH solutions by the use of a novel experimental scheme called photo-micropendography. These tension values were then compared with spinning drop tensiometer data calculated by using three alternative solution schemes, namely, Vonnegut's method, the formula of Slattery and Chen and the analysis of Princen el al. The comparison showed that when the droplet's length/width ratio was below 2.5, Vonnegut's formula was severely in error. The solution scheme proposed by Slattery and Chen gave tension values close to those found by photo-micropendography over the entire range of IFT values exhibited by the oleic acid/caustic systems. However, the most consistent and reasonably accurate tension values resulted from the use of Table I in the paper by Princen, Zia and Mason. A simplified computer algorithm has been proposed for calculating dynamic interfacial tensions using the formulas and tables proposed by the latter authors. However, at length/width ratios above 2.5, the agreement between interfacial tensions determined by micropendography and spinning drop data calculated by the use of Vonnegut's solution was quite good.     

Thiol Redox and pKa Properties of Mycothiol,the Predominant Low‐Molecular‐Weight Thiol Cofactor in the Actinomycetes

The thiol pK_a and standard redox potential of mycothiol, the major low‐molecular‐weight thiol cofactor in the actinomycetes, are reported. The measured standard redox potential reveals substantial discrepancies in one or more of the other previously measured intracellular parameters that are relevant to mycothiol redox biochemistry.     

Effect of Mechanical Constraint on Domain Reorientation in Predominantly {111}‐Textured Lead Zirconate Titanate Films

Ferroelectric/ferroelastic domain reorientation was measured in 2.0 μm thick tetragonal {111}‐textured PbZr_0.30Ti_0.70O₃ thin films using synchrotron X‐ray diffraction (XRD). Lattice strain from the peak shift in the 111 Bragg reflection and domain reorientation were quantified as a function of applied electric field amplitude. Domain reorientation was quantified through the intensity exchange between the 112 and 211 Bragg reflections. Results from three different film types are reported: dense films that are clamped to the substrate (as‐processed), dense films that are partially released from the substrate, and films with 3% volume porosity. The highest amount of domain reorientation is observed in grains that are misoriented with respect to the {111} preferred (domain engineered) orientation. Relative to the clamped films, films that were released from the substrate or had porosity exhibited neither significant enhancement in domain reorientation nor in 111 lattice strain. In contrast, similar experiments on {100}‐textured and randomly oriented films showed significant enhancement in domain reorientation in released and porous films. Therefore, {111}‐textured films are less susceptible to changes in properties due to mechanical constraints because there is overall less domain reorientation in {111} films than in {100} films.     

Simple N‐Heterocyclic Carbenes as Ligands in Ullmann‐Type Ether and Thioether Formations

A simple N‐heterocyclic carbene (NHC) derived from 1‐methyl‐3‐ethylimidazolium tetrafluoroborate was found to be an efficient ligand for a range of copper‐catalyzed cross‐coupling reactions, leading to the formation of aromatic ethers and thioethers.

     

Flow distribution in spiral mandrel dies

An analysis of flow of a power law fluid in a spiral mandrel die is presented. The analysis is applied to study the effect of various die design parameters on the flow distribution at the end of the spiral mandrel section. Three variables that have a very strong effect on the flow distribution are the number of grooves, the initial clearance, and the groove helix angle. The distribution is improved by increasing the number of grooves, by using a non-zero initial clearance, and a relatively small helix angle. Two more variables that have a significant effect on the flow distribution are the taper angle and the initial groove depth. The optimum taper angle was found to be between 1 and 3 degrees. The distribution uniformity improves with the initial groove depth, while the pressure drop reduces at the same time.     

Fano resonances in nanoscale plasmonic systems: a parameter-free modeling approach

The interaction between plasmonic resonances, sharp modes, and light in nanoscale plasmonic systems often leads to Fano interference effects. This occurs because the plasmonic excitations are usually spectrally broad and the characteristic narrow asymmetric Fano line-shape results upon interaction with spectrally sharper modes. By considering the plasmonic resonance in the Fano model, as opposed to previous flat continuum approaches, here we show that a simple and exact expression for the line-shape can be found. This allows the role of the width and energy of the plasmonic resonance to be properly understood. As examples, we show how Fano resonances measured on an array of gold nanoantennas covered with PMMA, as well as the hybridization of dark with bright plasmons in nanocavities, are well reproduced with a simple exact formula and without any fitting parameters.     

Verification of cardiac tissue electrophysiology simulators using an N-version benchmark

Ongoing developments in cardiac modelling have resulted, in particular, in the development of advanced and increasingly complex computational frameworks for simulating cardiac tissue electrophysiology. The goal of these simulations is often to represent the detailed physiology and pathologies of the heart using codes that exploit the computational potential of high-performance computing architectures. These developments have rapidly progressed the simulation capacity of cardiac virtual physiological human style models; however, they have also made it increasingly challenging to verify that a given code provides a faithful representation of the purported governing equations and corresponding solution techniques. This study provides the first cardiac tissue electrophysiology simulation benchmark to allow these codes to be verified. The benchmark was successfully evaluated on 11 simulation platforms to generate a consensus gold-standard converged solution. The benchmark definition in combination with the gold-standard solution can now be used to verify new simulation codes and numerical methods in the future.