Methane and carbon dioxide adsorption on edge-functionalized graphene: a comparative DFT study

With a view towards optimizing gas storage and separation in crystalline and disordered nanoporous carbon-based materials, we use ab initio density functional theory calculations to explore the effect of chemical functionalization on gas binding to exposed edges within model carbon nanostructures. We test the geometry, energetics, and charge distribution of in-plane and out-of-plane binding of CO2 and CH4 to model zigzag graphene nanoribbons edge-functionalized with COOH, OH, NH2, H2PO3, NO2, and CH3. Although different choices for the exchange-correlation functional lead to a spread of values for the binding energy, trends across the functional groups are largely preserved for each choice, as are the final orientations of the adsorbed gas molecules. We find binding of CO2 to exceed that of CH4 by roughly a factor of two. However, the two gases follow very similar trends with changes in the attached functional group, despite different molecular symmetries. Our results indicate that the presence of NH2, H2PO3, NO2, and COOH functional groups can significantly enhance gas binding, making the edges potentially viable binding sites in materials with high concentrations of edge carbons. To first order, in-plane binding strength correlates with the larger permanent and induced dipole moments on these groups. Implications for tailoring carbon structures for increased gas uptake and improved CO2/CH4 selectivity are discussed. (C) 2012 American Institute of Physics. http://dx.doi.org/10.1063/1.4736568]

A physics-based flexural phonon-dependent thermal conductivity model for single layer graphene

In this paper, we address a physics-based closed-form analytical model of flexural phonon-dependent diffusive thermal conductivity (kappa) of suspended rectangular single layer graphene sheet. A quadratic dependence of the out-of-plane phonon frequency, generally called flexural phonons, on the phonon wave vector has been taken into account to analyze the behavior of kappa at lower temperatures. Such a dependence has further been used for the determination of second-order three-phonon Umklapp and isotopic scatterings. We find that these behaviors in our model are best explained through the upper limit of Debye cut-off frequency in the second-order three-phonon Umklapp scattering of the long phonon waves that actually remove the thermal conductivity singularity by contributing a constant scattering rate at low frequencies and note that the out-of-plane Gruneisen parameter for these modes need not be too high. Using this, we clearly demonstrate that. follows a T-1.5 and T-2 law at lower and higher temperatures in the absence of isotopes, respectively. However in their presence, the behavior of kappa sharply deviates from the T-2 law at higher temperatures. The present geometry-dependent model of kappa is found to possess an excellent match with various experimental data over a wide range of temperatures which can be put forward for efficient electro-thermal analyses of encased/supported graphene.

Anisotropic low field magnetoimpedance in (001) oriented La0.7Sr0.3MnO3 thin films

We report the evidence for the anisotropic magnetoimpedance behavior in (001) oriented La0.7Sr0.3MnO3 (LSMO) thin films, in low frequency-low magnetic field regime. (001) oriented LSMO thin films were deposited using pulsed laser deposition and characterized with X-ray diffraction and temperature dependent magnetization studies. In the in-plain configuration, an ac magnetoresistance (MRac) of similar to -0.5% was observed at 1000 Oe, at 100 Hz frequency in these films. The MRac was found to decrease with increase in frequency. We observe increases in MRac at low frequency, indicating major contribution for change of permeability from domain wall motion. At higher frequencies, it decreases due to decrease in transverse permeability, resulting from dampening of domain wall motion. Out-of-plane configuration showed MRac similar to 5.5% at 1000 Oe, at 100 Hz frequency. The MRac turned from positive to negative with increase in frequency in out-of-plane configuration. These changes are attributed to the change in permeability of the film with the frequency and applied magnetic field.

Electric field activated nonlinear anisotropic charge transport in doped polypyrrole

Electric field activated nonlinear transport is investigated in polypyrrole thin film in both in-plane and out-of-plane geometries down to 5 K and strong anisotropy is observed. A morphological model is suggested to explain the anisotropy through inter-chain and intra-chain transport. The deviation from the variable range hopping at low temperature is accounted by fluctuation assisted transport. From Zabrodaskii plots, it is found that electric field can tune the transport from insulating to metallic regime. Glazman-Matveev model is used to describe the nonlinear conduction. Field scaling analysis shows that conductance data at different temperature falls on to a single curve. Nonlinearity exponent, m(T) and characteristic length, L-E are estimated to characterize the transport in both the geometries. (C) 2013 AIP Publishing LLC.

Exchange bias in strained SrRuO3 thin films

Recently, it was found that the ferromagnetic SrRuO3 when combined with another ferromagnet in thin film form gives rise to exchange bias (EB) effect. However, we observed EB in single, strained, SrRuO3 thin films grown on diamagnetic LaAlO3 (100) substrates. It displays the training effect, which essentially confirms EB. The temperature dependence of the EB reveals the blocking temperature to be around similar to 75 K. The strength of the exchange bias decreases with the increase in thickness of the film. We observe tensile strain in the out of plane direction. Further, the presence of in-plane compressive strain is observed through asymmetric reciprocal space mapping. Finally, we find a direct link between strain and EB. The evolution of strain with thickness matches well with the nature of scaled EB. It has been shown earlier by first principle calculations that this strain can induce EB in thin films. (C) 2014 AIP Publishing LLC.

Investigation on two magnon scattering processes in pulsed laser deposited epitaxial nickel zinc ferrite thin film

Ferromagnetic resonance (FMR) measurements are employed to evaluate the presence of the two magnon scattering contribution in the magnetic relaxation processes of the epitaxial nickel zinc ferrite thin films deposited using pulsed laser deposition (PLD) on the (0 0 1) MgAl2O4 substrate. Furthermore, the reciprocal space mapping reveals the presence of microstructural defects which acts as an origin for the two magnon scattering process in this thin film. The relevance of this scattering process is further discussed for understanding the higher FMR linewidth in the in-plane configuration compared to the out-of-plane configuration. FMR measurements also reveal the presence of competing uniaxial and cubic anisotropy in the studied films.

Three-dimensional warping in strip-based composite four-bar mechanisms

This work intends to demonstrate the effect of geometrically non-linear cross-sectional analysis of certain composite beam-based four-bar mechanisms in predicting the three-dimensional warping of the cross-section. The only restriction in the present analysis is that the strains within each elastic body remain small (i.e., this work does not deal with materials exhibiting non-linear constitutive laws at the 3-D level). Here, all component bars of the mechanism are made of fiber-reinforced laminates. They could, in general, be pre-twisted and/or possess initial curvature, either by design or by defect. Each component of the mechanism is modeled as a beam based on geometrically non-linear 3-D elasticity theory. The component problems are thus split into 2-D analyses of reference beam cross-sections and non-linear 1-D analyses along the three beam reference curves. The splitting of the three-dimensional beam problem into two- and one-dimensional parts, called dimensional reduction, results in a tremendous savings of computational effort relative to the cost of three-dimensional finite element analysis, the only alternative for realistic beams. The analysis of beam-like structures made of laminated composite materials requires a much more complicated methodology. Hence, the analysis procedure based on Variational Asymptotic Method (VAM), a tool to carry out the dimensional reduction, is used here. The representative cross-sections of all component bars are analyzed using two different approaches: (1) Numerical Model and (2) Analytical Model. Four-bar mechanisms are analyzed using the above two approaches for Omega = 20 rad/s and Omega = pi rad/s and observed the same behavior in both cases. The noticeable snap-shots of the deformation shapes of the mechanism about 1000 frames are also reported using commercial software (I-DEAS + NASTRAN + ADAMS). The maximum out-of-plane warping of the cross-section is observed at the mid-span of bar-1, bar-2 and bar-3 are 1.5 mm, 250 mm and 1.0 mm, respectively, for t = 0:5 s. (C) 2015 Elsevier Ltd. All rights reserved.

PIV study on the dimple mid-plane of a narrow rectangular channel with dimples applied to one wall

This paper presents an investigation of the fluid flow in the fully developed portion of a rectangular channel (Aspect Ratio of 2) with dimples applied to one wall at channel Reynolds numbers of 20,000, 30,000, and 40,000. The dimples are applied in a staggered-row, racetrack configuration. Results for three different dimple geometries are presented: a large dimple, small dimple, and double dimple. Heat transfer and aerodynamic results from preceding works are presented in Nusselt number and friction factor augmentation plots as determined experimentally. Using particle image velocimetry, the region near the dimple feature is studied in detail in the location of the entrainment and ejection of vortical packets into and out of the dimple; the downstream wake region behind each dimple is also studied to examine the effects of the local flow phenomenon that result in improved heat transfer in the areas of the channel wall not occupied by a feature. The focus of the paper is to examine the secondary flows in these dimpled channels in order to support the previously presented heat transfer trends. The flow visualization is also intended to improve the understanding of the flow disturbances in a dimpled channel; a better understanding of these effects would lead the development of more effective channel cooling designs. Copyright © 2011 by ASME.

Structure of a peptide oxazolone: 2-(1'-benzyloxycarbonylamino-1'-methylethyl)-4,4-dimethyl-5-oxazolone

C16H20N204, monoclinic, P21, a = 6.270 (1),b= 11.119(3),c= ll.640(4)A, fl= 100.7 (2)°,Dm = 1-27 (flotation), Dc = 1-26 Mg m -3, Z = 2. The structure has been refined to a final R value of 0.041 for 1584 independent counter-measured reflections. The oxazolone ring in the molecule is nearly planar. The exocyclic O atom is 0.065 A out of the plane defined by the other four atoms in the ring belonging to the lactone group. The difference in length between the two adjacent C-O bonds in the ring is small, but significant. The crystal structure is stabilized by van der Waals interactions and a N--H... N hydrogen bond.

Interfacial structure and crystallographic studies of transformations in betat' and beta Cu---Zn alloys-II. martensitic formation of alpha1' plates in beta'

A TEM study of the interphase boundary structure of 9R orthorhombic alpha1' martensite formed in beta' Cu---Zn alloys shows that it consists of a single array of dislocations with Burgers vector parallel to left angle bracket110right-pointing angle beta and spaced about 3.5 nm apart. This Burgers vector lies out of the interface plane; hence the interface dislocations are glissile. Unexpectedly, though, the Burgers vectors of these dislocations are not parallel when referenced to the matrix and the martensite lattices. This finding is rationalized on published hard sphere models as a consequence of relaxation of a resultant of the Bain strain and lattice invariant shear displacements within the matrix phase.

Theory of the non-planar peptide unitstar, open

By means of CNDO/2 calculations on N-methyl acetamide, it is shown that the state of minimum energy of the trans-peptide unit is a non-planar conformation, with the NH and NC2α bonds being significantly out of the plane formed by the atoms C1α, C′, O and N.

On plane-wave propagation in a uniform pipe in the presence of a mean flow and a temperature gradient

A theoretical study on the propagation of plane waves in the presence of a hot mean flow in a uniform pipe is presented. The temperature variation in the pipe is taken to be a linear temperature gradient along the axis. The theoretical studies include the formulation of a wave equation based on continuity, momentum, and state equation, and derivation of a general four-pole matrix, which is shown to yield the well-known transfer matrices for several other simpler cases.

Structure and dynamics of benzene in one-dimensional channels

Molecular dynamics investigation of benzene in one-dimensional channel systems A1PO(4)-5, VPI-5, and carbon nanotube is reported. The results suggest that, in all the three host systems, the plane of benzene is almost perpendicular to the channel axis when the molecule is near the center of the channel and the plane of benzene is parallel to the channel axis when the molecule is near the wall of the channel. The density distribution of benzene as a function of channel length, z and the radial distance, r, from the channel axis is also different in the three host structures. Anisotropy in translational diffusion coefficient, calculated in body-fixed frame of benzene, suggests that benzene prefers to move with its plane parallel to the direction of motion in A1PO(4)-5 and VPI-5 whereas in carbon nanotube the motion occurs predominantly with the plane of the benzene perpendicular to the direction of motion.;Anisotropy associated with the rotational motion is seen to alter significantly in confinement as compared to liquid benzene. In A1PO(4)-5, the rotational anisotropy is reversed as compared to liquid benzene thereby suggesting that anisotropy arising out of molecular geometry can be reduced. Reorientational correlation times for C-6 and C-2 axes Of benzene are reported. Apart from the inertial decay of reorientational correlation function due to free, rotation, two other distinct regimes of decay are observed in narrower channels (AIPO(4)-5 and carbon nanotube): (i) an initial fast decay (0.5-2 ps) and (ii) a slower decay (>2 ps) of reorientational correlation function where C-6 decays slower than C-2 Similar to what is observed in liquid benzene. In the initial fast decay, it is seen that the decay for C-6 is faster than C-2 which is in contrast to what is observed in liquid benzene or for benzene confined in VPI-5.

A finite element analysis of quasistatic crack growth in a pressure sensitive constrained ductile layer

Polymeric adhesive layers are employed for bonding two components in a wide variety of technological applications, It has been observed that, unlike in metals, the yield behavior of polymers is affected by the state of hydrostatic stress. In this work, the effect of pressure sensitivity of yielding and layer thickness on quasistatic interfacial crack growth in a ductile adhesive layer is investigated. To this end, finite deformation, finite element analyses of a cracked sandwiched layer are carried out under plane strain, small-scale yielding conditions for a wide range of mode mixities. The Drucker-Prager constitutive equations are employed to represent the behavior of the layer. Crack propagation is simulated through a cohesive zone model, in which the interface is assumed to follow a prescribed traction-separation law. The results show that for a given mode mixity, the steady state Fracture toughness [K](ss) is enhanced as the degree of pressure sensitivity increases. Further, for a given level of pressure sensitivity, [K](ss) increases steeply as mode Il loading is approached. (C) 2000 Elsevier Science Ltd. All rights reserved.