Highly bent crystals formed by restrained π-stacked columns connected via alkylene linkers with variable conformations

A reproducible formation of strongly bent crystals was accomplished by structurally restraining macrocyclic π-conjugated molecules. The model π-units consist of two 9,10-bis(2-thienylethynyl)anthracenes with a strong propensity for stacking, which are connected in a macrocyclic fashion via two alkylene linkers. The correlation between the crystalline morphology and the macrocyclic structures restrained by a variety of flexible alkylene linker combinations was systematically studied. Bent crystals were obtained only with specific alkylene linkers of appropriate chain length. The alkylene linkers can adopt different conformations in the crystal packing, so as to fill voids within the macrocycle. The ability to form several similar molecular structures with different alkylene conformations gives rise to contaminations of different crystalline phases within a single crystal, and it is these phase contaminations which are responsible for the bending of the crystals.     

On the Dual Phosphorescence of Xanthone and Chromone in Glassy Hydrocarbon Hosts

Trace quantities of hydrogen‐bonding impurities in otherwise highly purified and dried glassy hydrocarbon matrices at 77 K can modify the relative triplet state energy levels, and hence the photophysical properties of two aromatic ketones, xanthone and chromone, to the extent that the intrinsic spectroscopic properties are obscured. The intrinsic spectroscopic properties of each are revealed in multicrystalline n‐alkane Shpol'skii matrices, and also can be observed in rigorously purified and dried hydrocarbon glasses at 77 K. The extreme sensitivity to stoichiometric, and even substoichiometric quantities of hydrogen‐bonding impurities arises from the near‐degeneracy of the two lowest‐lying triplet states, and the sensitive nature of the n→π* blueshift phenomena to specific hydrogen‐bonding interactions.     

Two‐dimensional reactive scattering with transmitted quantum trajectories

A simple and easy‐to‐implement method is presented for the study of time‐dependent reaction dynamics by propagating an ensemble of transmitted quantum trajectories. During the trajectory evolution, reflected trajectories are gradually removed and all the remaining trajectories represent the transmitted subensemble. The removal process of reflected trajectories avoids numerical instabilities arising from node formation in the reactant region, and allows stable long‐time propagation of transmitted trajectories. This method is applied to a two‐dimensional model chemical reaction. Excellent computational results are obtained for the time‐dependent reaction probabilities evaluated by the time integration of the probability flux. © 2014 Wiley Periodicals, Inc.     

Experimental study of multiple interior impacts

In this paper, experiments involving interior impacts on soft, lead targets are described. The term “interior impact” refers to the impact of a projectile at the bottom of a predrilled hole in the target. It is known that impact of low-velocity projectiles into such soft targets results in plastic flow and cavities similar to those obtained in high-velocity impact of hard targets. Therefore, comparatively simple rifle-propelled projectile impacts on soft targets may yield useful information for high-speed hard-target impacts. Double impacts with a short-time interval, on the order of microseconds, between projectile arrivals were conducted. The leading projectile creates a plastic flow in the target which partially seals the entrance hole. The trailing projectile must first force open the passage hole before achieving additional penetration. The total penetration was measured for different time intervals between the projectiles. A method was developed to obtain double impacts at the same point. The method utilizes a duplex round, which is made up of two separate projectiles fired from the same cartridge. With this round, a series of impact experiments was conducted. It was learned that occlusion, or the close up of the hole, is negligible for nearly simultaneous projectiles (less than 10 μs between impacts), and greatest with about 80 to 100 μs between impacts. The projectile velocity was measured by the use of properly placed photodiodes.     

High-strain-rate tests on titanium 6-6-2 utilizing a unique rate-testing machine

This paper presents the design of a unique materials-testing system capable of medium strain rates of from 10^?4 to 10²/s. The design incorporates both closed-loop hydraulic operation with that of open-loop pneumatic operation. A novel design permits accurate specimen alignment and a stiff frame which exceeds 17×10⁶ lb/in. (11.7×10⁴ MPa). The mechanine is able to perform conventional tension/compression tests, fatigue tests and, with slight modification, biaxial-stress-tube tests and triaxial-stress tests. The accurate alignment capability coupled with high frame stiffness and the pneumatic operation enables the testing of brittle materials with rigid grips. Titanium 6-6-2 was tested in both tension and compression at strain rates from 10^?4 to about 10/s at four selected temperatures. The material showed a slight strain-rate sensitivity. Yield stress was shown to increase with strain rate while ductility decreased at each test temperature.     

Effects of amorphous poly(vinyl acetate) on crystalline morphology of poly(3-hydroxybutyric acid-co-3-hydroxyvaleric acid)

The amorphous and crystalline phase behavior, spherulite morphology, and interactions between amorphous poly(vinyl acetate) (PVAc) and poly(3-hydroxybutyric acid-co-3-hydroxyvaleric acid) (PHBV) were examined using differential scanning calorimetry, polarized-light optical and scanning electron, atomic-force microscopy (DSC, POM, SEM, AFM), and small-angle X-ray scattering (SAXS). The PHBV/PVAc blend was found to be miscible with an almost linear T _g-composition relationship, indicating perfect homogeneity. Interaction parameter by melting point depression is a negative value of χ = −0.32, suggesting quite favorable interaction strength. With the intimate interaction between the amorphous PVAc and crystalline PHBV polymers, effects of PVAc on the spherulitic morphology of PHBV are quite significant. Owing to the higher T _g of PVAc (than that of PHBV), the spherulite growth rate of PHBV was depressed by increasing PVAc content in blends. Neat PHBV exhibits ring-banded spherulites when crystallized at T_c = 60 ~ 110^° C {T_{\rm{c}}} = {6}0\sim {11}0^\circ {\hbox{C}} ; however, with increasing PVAc content in the blends, the temperature range at which the PHBV/PVAc blends exhibit ring-banded spherulites remains similar but the regularity increases, and the inter-ring spacing significantly decreases. In addition, the spherulite size and ring-band patterns therein are strongly dependent on T _max (190 vs. 220 °C, respectively, for erasing prior nuclei), from which the blends were quenched to a T _c (60–110 °C) for crystallization. For PHBV/PVAc blends crystallized at the same T _c from different T _max, higher T _max tends to erase nuclei, leading to larger spherulites. However, such larger spherulites owing to higher T _max are not necessarily packed with thicker lamellae.     

Equilibrium phase diagram of drop-on-fiber: coexistent states and gravity effect

Drop-on-fiber is commonly observed in daily life and is closely related to digital microfluidics. The wetting behavior of droplet-on-fiber is different from that of droplet-on-plane due to the global cylindrical shape. It is generally believed that the equilibrium geometric shape of a droplet on a fiber takes either asymmetric clam-shell or axisymmetric barrel conformation in the absence of gravity. The barrel-to-clam-shell transition is determined by the stability condition. Nonetheless, experimental observations showed that both barrel and clam-shell conformations can coexist in some situations and thus indicated the existence of the multiple stable states. In this Article, the phase diagrams of droplet-on-fiber, that is, the plots of droplet volume against contact angle, are established on the basis of the finite-element simulation (Surface Evolver). When the gravity effect is absent, there are three regimes including barrel, clam-shell, and coexistence of barrel and clam-shell. As the gravity effect is considered, there exist three regimes, including (I) downward clam-shell, (II) coexistence of barrel and clam-shell, and (III) falling-off.     

Investigation of formation mechanism of Pt(111) nanoparticle layers grown on Ru(0001) core

A layer growth mechanism of Pt-Ru bimetallic nanoparticles has been proposed with supporting experiments and calculations by density functional theory (DFT). Elongated Pt atoms on Ru nanoparticles were synthesized via a two-step route, and their structural details were obtained by high-resolution transmission electron microscopy. Because of the intrinsic mismatch of lattice spacing between the two elements, such an unusual growth was analyzed with the DFT simulations to explore the mystery of the growth mechanism. Pt atoms would rearrange the packing order and adjust the Pt-Pt atomic distance, and so do the Ru nanoparticles in order to achieve the optimal energy status of the bimetallic system. The resultant Pt(111) layers could stack on top of the Ru(0001) core more tightly by fitting the pockets left between the Ru atoms. The findings give insight into the formation mechanism of the nanosized Pt-Ru bimetallic catalyst and pave the way for designing bimetallic catalysts with tailored properties at the atomic level.