Rhodium-Catalyzed Enantioselective Radical Addition of CX4 Reagents to Olefins

We describe the synthetically useful enantioselective addition of Br−CX₃ (X=Cl or Br) to terminal olefins to introduce a trihalomethyl group and generate optically active secondary bromides. Computational and experimental evidence supports an asymmetric atom-transfer radical addition (ATRA) mechanism in which the stereodetermining step involves outer-sphere bromine abstraction from a [(bisphosphine)Rh^IIBrCl] complex by a benzylic radical intermediate. This mechanism appears unprecedented in asymmetric catalysis.     

Molecular organization in MAPLE‐deposited conjugated polymer thin films and the implications for carrier transport characteristics

The morphological structure of poly(3‐hexylthiophene) (P3HT) thin films deposited by both Matrix Assisted Pulsed Laser Evaporation (MAPLE) and solution spin‐casting methods are investigated. The MAPLE samples possessed a higher degree of disorder, with random orientations of polymer crystallites along the side‐chain stacking, π–π stacking, and conjugated backbone directions. Moreover, the average molecular orientations and relative degrees of crystallinity of MAPLE‐deposited polymer films are insensitive to the chemistries of the substrates onto which they were deposited; this is in stark contrast to the films prepared by the conventional spin‐casting technique. Despite the seemingly unfavorable molecular orientations and the highly disordered morphologies, the in‐plane charge carrier transport characteristics of the MAPLE samples are comparable to those of spin‐cast samples, exhibiting similar transport activation energies (56 vs. 54 meV) to those reported in the literature for high mobility polymers. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017 , 55, 39–48     

Effects of Heterogeneous Fracture Aperture on Multiphase Production from Shale Reservoirs

Production simulation from fractured shale reservoirs is often performed by simplifying the hydraulic fractures as rectangular planes with homogeneous aperture. This study investigates the effects of heterogeneous fracture aperture and proppant distribution in realistic, non-rectangular fractures on the multi-phase production from shales. The heterogeneous hydraulic fractures are generated with the GEOS multiphysics simulator under realistic 3D stress field. These fractures are embedded into the TOUGH+ multi-phase flow simulator for production simulation. The results emphasize the importance of flow barriers within the hydraulic fractures, due both to low-aperture regions caused by the stress-shadow effect and the settling of proppant. The production rate is particularly sensitive to aperture heterogeneity if the flow barriers are close to the wellbore such that a great portion of fracture volume is isolated from the well. A stage-to-stage comparison reveals that production from different stages could vary significantly because the local stress field leads to different fracture area and aperture. The use of proppant prevents fracture closure, but if the propped regions are far from the well, they do not enhance production because flow barriers between these regions and the well act as bottlenecks. The present study highlights the importance of incorporating aperture heterogeneity into production simulation, provides insights on the relationship between flow barriers, proppant concentration, and well production, and proposes a practical method to mitigate numerical difficulties when modeling heterogeneous fractures.

     

On the Relationship Between the Statistics of the Resolved and True Rate of Dissipation of Mixture Fraction

The relationship between the one-point probability-density-function (PDF) of the dissipation rate of mixture fraction fluctuations and the corresponding resolved quantity available in large eddy simulation (LES) is analyzed. The investigation pursues two fronts: an a priori study using direct numerical simulation (DNS), and an analytic development that, using common turbulence physics simplifications, relates the one-point statistics of the resolved and true scalar dissipations. Particularly, the analysis reveals the connection between the multi-point correlations of the mixture fraction gradient and the one-point PDF of the resolved scalar dissipation. A DNS of a temporally evolving shear layer with and without heat release is used to quantify the accuracy of the analytical result. It is verified, both by filtering the DNS and from the theory, that increasing the filter cutoff width reduces the magnitude of the resolved scalar dissipation fluctuations, as expected and observed experimentally. Comparison with DNS indicates that the analytical relationship predicts the behavior of the resolved scalar dissipation PDF well at the center planes of the shear layer, where turbulence is locally more isotropic and homogeneous. Large-scale anisotropy and inhomogeneities in the DNS degrade the accuracy of the approximate analytical result close to the edges of the shear layer. These results may be improved with future investigations to account fully for the missing statistics in LES, which have the potential to allow a more accurate quantification of finite-rate chemistry effects in reacting flows.     

Shear-wave speeds and elastic moduli for different liquids Part 3. Experiments-update

Tables of values of shear-wave speeds, shear moduli and relaxation times for 18 new liquids are presented, supplementing the tables for 51 liquids given in Part 2. A brief discussion of errors and analysis of the oscilloscope traces is presented. The relation of the effective moduli measured on the wave-speed meter to independent measurements using phase-modulated birefringence and delayed die swell is discussed. A method of measuring wave speeds and rigidities for sheared media is proposed.     

Molecular dynamics simulations of ion-irradiation induced deflection of 2D graphene films

Ion-irradiation induced surface stress generation and the resulting deflection of 2D cantilever graphene films is studied using molecular dynamics (MD) simulations. The simulation results show that the free-end deflection is strongly dependent on the kinetic energy of the incident ions. At low incident energies (?10 eV), the graphene film bends towards the irradiated side (upward deflection in our simulations); a transition from bending towards the irradiated side (upward deflection) to bending away from the irradiated side (downward deflection) occurs when the incident energy is ～10 eV; the downward deflection peaks at ～50 eV. Further increases of the incident energy cause the magnitude of downward deflection to decrease. The evolution of free-end deflection with respect to the number of incidences is also dependent on the incident energy. The dependence of the deflection behavior of the graphene films on the incident energy revealed by our atomistic simulations suggests the generation of intrinsic stress of different levels in the growing films. Such behavior may be attributed to competing mechanisms of production and annihilation of interstitial- and vacancy-like defects in the growing film. Understanding the dependence of thin film deflection on the incident energy provides guidelines for controlling thin film shapes at the nanometer scale using ion-beam machining.     

Friction factor and holdup studies for lubricated pipelining—I. Experiments and correlations

Results from new experiments on the lubricated pipelining of emulsified waxy crude oil and No. 6 fuel oil are presented and compared with other sources of literature. A correlation formula which estimates the holdup fraction is introduced and evaluated for all available experimental data. A simple theory is given which is based on the concentric core-annular flow model and leads to a Reynolds number and friction factor which reduce a large body of experimental data onto one curve; with the best results in the high Reynolds number flow regime.     

Measurements of the tip leakage vortex structures and turbulence in the meridional plane of an axial water-jet pump

Particle image velocimetry (PIV) measurements at varying resolutions focus on the flow structures in the tip region of a water-jet pump rotor, including the tip-clearance flow and the rollup process of a tip leakage vortex (TLV). Unobstructed views of these regions are facilitated by matching the optical refractive index of the transparent pump with that of the fluid. High-magnification data reveal the flow non-uniformities and associated turbulence within the tip gap. Instantaneous data and statistics of spatial distributions and strength of vortices in the rotor passage reveal that the leakage flow emerges as a wall jet with a shear layer containing a train of vortex filaments extending from the tip of the blade. These vortices are entrained into the TLV, but do not have time to merge. TLV breakdown in the aft part of the blade passage further fragments these structures, increasing their number and reducing their size. Analogy is made between the circumferential development of the TLV in the blade passage and that of the starting jet vortex ring rollup. Subject to several assumptions, these flows display similar trends, including conditions for TLV separation from the shear layer feeding vorticity into it.     

Generalized Maxwell model for the viscoelastic behavior of a soda-lime-silica glass under low frequency shear loading

The linear viscoelastic behavior of a soda-lime-silica glass under low frequency shear loading is investigated in the glass transition range. Using the time-temperature superposition technique, the master curves of the shear dynamic relaxation moduli are obtained at a reference temperature of 566°C. A method to determine the viscoelastic constants from dynamic relaxation moduli is proposed. However, some viscoelastic constants cannot be directly measured from the experimental curves and others cannot be precisely obtained due to non-linearity effects at very low frequencies. The generalized Maxwell model is investigated from the experimental dynamic moduli without fixing the viscoelastic constants. A set of parameters is shown to be in good agreement with the experimental dynamic relaxation moduli, but does not give the correct values of the viscoelastic constants of the investigated glass. The soda-lime-silica glass exhibits a non-linear viscoelastic behavior at very low stress level which is usually observed for organic glasses. This non-linear behavior is questioned.     

Saint-Venant's principle in nonlinear plane elasticity with sufficiently small strains

A homogeneous, isotropic cylinder in an equilibrium state of plane strain, whose cross-section is a rectangle R : [0 < y ₁ < 2L; 0 < y ₂ < h] with h/L 1, is considered. There are no body forces and the long sides are stress free. At y ₁ = 0 and y ₁ = 2L, there are arbitrary loadings, each statically equivalent to a uniformly distributed tensile or compressive stress c. Within the theory of nonlinear elasticity and with the strains and strain gradients assumed to be sufficiently small (but with no such assumptions on the displacement gradients), it is proved that if (,=1,2) represents the Cauchy stress tensor and the Kronecker delta, then |–c₁₁| decays exponentially to zero in R with distance from the nearer end, and the decay constant depends only upon the material but is independent of L.