Flame spread across surfaces of PBX 9501

There is little flame spread data for homogeneous energetic materials and no data for nitramines. We report the results of flame spread experiments of PBX 9501 (HMX (cyclotetramethylenetetranitramine) based explosive). The horizontal flame spread rate, S_f, is of the same order of magnitude as normal deflagration and varies nearly as the square root of pressure, as our scaling analysis presented here predicts. In the vertical orientation, the flame propagation downward was observed to be slightly faster than horizontal flame spread, presumably because of the melt layer flowing downward on the sample. In an accident scenario, a charge may be fractured or the surface roughened. Consequently, we also examined the effect of roughness. Minor roughness created by explosives machining was found to have a negligible affect on flame spread. However, more significant roughness can increase the rate between two and three times over normal flame spread for the conditions considered here. In addition we examine the effect of sample edges and configuration. Corners result in more favorable heat loss and therefore affect flame spread rate. We argue that the increased spread rate on edges and rough surfaces is because of favorable heat transfer convergence.     

Monotonic optimization based decoding for linear codes

New efficient methods are developed for the optimal maximum-likelihood (ML) decoding of an arbitrary binary linear code based on data received from any discrete Gaussian channel. The decoding algorithm is based on monotonic optimization that is minimizing a difference of monotonic (d.m.) objective functions subject to the 0–1 constraints of bit variables. The iterative process converges to the global optimal ML solution after finitely many steps. The proposed algorithm’s computational complexity depends on input sequence length k which is much less than the codeword length n, especially for a codes with small code rate. The viability of the developed is verified through simulations on different coding schemes.     

Unusual superexchange pathways in an NiS2 triangular lattice with negative charge-transfer energy

We have studied the electronic structure of the Ni triangular lattice in NiGa(2)S(4) using photoemission spectroscopy and subsequent model calculations. The cluster-model analysis of the Ni 2p core-level spectrum shows that the S 3p to Ni 3d charge-transfer energy is approximately -1 eV and the ground state is dominated by the d(9)L configuration (L is a S 3p hole). Cell perturbation analysis for the NiS(2) triangular lattice indicates that the strong S 3p hole character of the ground state provides the enhanced superexchange interaction between the third-nearest-neighbor sites.     

Molecular mechanism for H2 release from BH3NH3, including the catalytic role of the Lewis acid BH3

Electronic structure calculations using various methods, up to the coupled-cluster CCSD(T) level, in conjunction with the aug-cc-pVnZ basis sets with n = D, T, and Q, extrapolated to the complete basis set limit, show that the borane molecule (BH3) can act as an efficient bifunctional acid-base catalyst in the H2 elimination reactions of XHnYHn systems (X, Y = C, B, N). Such a catalyst is needed as the generation of H2 from isoelectronic ethane and borane amine compounds proceeds with an energy barrier much higher than that of the X-Y bond energy. The asymptotic energy barrier for H2 release is reduced from 36.4 kcal/mol in BH3NH3 to 6.0 kcal/mol with the presence of BH3 relative to the molecular asymptote. The NH3 molecule can also participate in a similar catalytic process but induces a smaller reduction of the energy barrier. The kinetics of these processes was analyzed by both transition-state and RRKM theory. The catalytic effect of BH3 has also been probed by an analysis of the electronic densities of the transition structures using the atom-in-molecule (AIM) and electron localization function (ELF) approaches.     

Folding simulations with novel conformational search method

A novel scheme for fast conformational search has been developed by combining the replica exchange method (REM) with the generalized effective potential concept. The new method, referred to Q-REM [S. Jang et al. Phys. Rev. Lett. 91, 058305 (2003)], is expected to provide a useful alternative to the conventional REM for effective conformational sampling of complex systems. The authors have performed folding simulations of the Trp-cage miniprotein using Q-REM. All atom level simulations with generalized Born solvent access-area solvation model show that successful folding can be observed with much smaller number of replicas in Q-REM compared to the conventional REM. It can be concluded that the new method has potential to significantly improve sampling efficiency, allowing simulations of more challenging systems.     

Examining the effect of the dipole moment on charge separation in donor-acceptor polymers for organic photovoltaic applications

A new low band gap copolymer PBB3 containing [6,6']bi[thieno[3,4-b]thiophenyl]-2,2'-dicarboxylic acid bis-(2-butyloctyl) ester (BTT) and 4,8-bis(2-butyloctyl)benzo[1,2-b:4,5-b']dithiophene (BDT) units was synthesized and tested for solar cell efficiency. PBB3 showed a broad absorbance in the near-IR region with a substantially red-shifted (by more than 100 nm) λ(max) at 790 nm as compared to the PTB series of polymers, which have been previously reported. The PBB3 polymer also showed both a favorable energy level match with PCBM (with a LUMO energy level of -3.29 eV) and a favorable film domain morphology as evidenced by TEM images. Despite these seemingly optimal parameters, a bulk heterojunction (BHJ) photovoltaic device fabricated from a blend of PBB3 and PC(71)BM showed an overall power conversion efficiency (PCE) of only 2.04% under AM 1.5G/100 mW cm(-2). The transient absorption spectra of PBB3 showed the absence of cationic and pseudo charge transfer states that were observed previously in the PTB series polymers, which were also composed of alternating thienothiophene (TT) and BDT units. We compared the spectral features and electronic density distribution of PBB3 with those of PTB2, PTB7, and PTBF2. While PTB2 and PTB7 have substantial charge transfer characteristics and also relatively large local internal dipoles through BDT to TT moieties, PTBF2 and PBB3 have minimized internal dipole moments due to the presence of two adjacent TT units (or two opposing fluorine atoms in PTBF2) with opposite orientations or internal dipoles. PBB3 showed a long-lived excitonic state and the slowest electron transfer dynamics of the series of polymers, as well as the fastest recombination rate of the charge-separated (CS) species, indicating that electrons and holes are more tightly bound in these species. Consequently, substantially lower degrees of charge separation were observed in both PBB3 and PTBF2. These results show that not only the energetics but also the internal dipole moment along the polymer chain may be critical in maintaining the pseudocharge transfer characteristics of these systems, which were shown to be partially responsible for the high PCE device made from the PTB series of low band gap copolymers.     

Characterization of wettability effects on pressure drop of two-phase flow in microchannel

The Characterization of the effects of surface wettability and geometry on pressure drop of slug flow in isothermal horizontal microchannels is investigated for circular and square channels with hydraulic diameter (D _h ) of 700 μm. Flow visualization is employed to characterize the bubble in slug flow established in microchannels of various surface wettabilities. Pressure drop increases with decrease in surface wettability, while the channel geometry influences slug frequency. It is observed that the gas–liquid contact line in advancing and receding interfaces of bubble change with surface wettability in slug flows. Flow resistance, where capillary force is important, is estimated using Laplace–Young equation considering the change of dynamic contact angles of bubble. The experimental study also demonstrates that the liquid film presence elucidates the pressure drop variation of slug flows at various surface wettabilities due to diminishing capillary effect.     

'Illusional' nano-size effect due to artifacts of in-plane conductivity measurements of ultra-thin films

The nano-size effect, which indicates a drastic increase in conductivity in solid electrolyte materials of nano-scale microstructures, has drawn substantial attention in various research fields including in the field of solid oxide fuel cells (SOFCs). However, especially in the cases of the conductivity of ultra-thin films measured in an in-plane configuration, it is highly possible that the 'apparent' conductivity increase originates from electrical current flowing through other conduction paths than the thin film. As a systematic study to interrogate those measurement artifacts, we report various sources of electrical current leaks regarding in-plane conductivity measurements, specifically insulators in the measurement set-up. We have observed a 'great conductivity increase' up to an order of magnitude at a very thin thickness of a single layer yttria-stabilized zirconia (YSZ) film in a set-up with an intentional artifact current flow source. Here we propose that the nano-size effect, reported to appear in ultra-thin single layer YSZ, can be a result of misinterpretation.