Crack stability in edge-notched clamped beam specimens: modeling and experiments

Stability of a fracture toughness testing geometry is important to determine the crack trajectory and R-curve behavior of the specimen. Few configurations provide for inherent geometric stability, especially when the specimen being tested is brittle. We propose a new geometrical construction called the single edge notched clamped bend specimen (SENCB), a modified form of three point bending, yielding stable cracking under load control. It is shown to be particularly suitable for small-scale structures which cannot be made free-standing, (e.g., thin films, coatings). The SENCB is elastically clamped at the two ends to its parent material. A notch is inserted at the bottom center and loaded in bending, to fracture. Numerical simulations are carried out through extended finite element method to derive the geometrical factor f(a/W) and for different beam dimensions. Experimental corroborations of the FEM results are carried out on both micro-scale and macro-scale brittle specimens. A plot of vs a/W, is shown to rise initially and fall off, beyond a critical a/W ratio. The difference between conventional SENB and SENCB is highlighted in terms of and FEM simulated stress contours across the beam cross-section. The `s of bulk NiAl and Si determined experimentally are shown to match closely with literature values. Crack stability and R-curve effect is demonstrated in a PtNiAl bond coat sample and compared with predicted crack trajectories from the simulations. The stability of SENCB is shown for a critical range of a/W ratios, proving that it can be used to get controlled crack growth even in brittle samples under load control.

Computational Study of the Formation of Short Centrosymmetric N-center dot center dot center dot S Supramolecular Synthon and Related Weak Interactions in Crystalline 1,2,4-Triazoles

A comprehensive analysis of the crystal packing and the energetic features of a series of four biologically active molecules belonging to the family of substituted 4-(benzylideneamino)-3-(4-fluoro-3-phenoxyphenyl)-1H-1,2,4-triazole-5-(4 H)-thione derivatives have been performed based on the molecular conformation and the supramolecular packing. This involves the formation of a short centrosymmetric R-2(2)(8) NH...S supramolecular synthon in the solid state, including the presence of CH...S, CH...O, CH...N, CH...F, CH...Cl, CF...FC, CCl...ClC, and CH...pi intermolecular interactions along with pp stacking to evaluate the role of noncovalent interactions in the crystal. The presence of such synthons has a substantial contribution toward the interaction energy (-18 to -20 kcal/mol) as obtained from the PIXEL calculation, wherein the Coulombic and polarization contribution are more significant than the dispersion contribution. The geometrical characteristics of such synthons favor short distance, and the population of related molecules having these geometries is rare as has been obtained from the Cambridge Structural Database (CSD). Furthermore, their interaction energies have been compared with those present in our molecules in the solid state. The topological characteristics of the NH...S supramolecular synthon, in addition to related weak interactions, CH...N, CH...Cl, CF...FC, and CCl...ClC, have been estimated using the quantum theory of atoms in molecules (QTAIM). In addition, an analysis of the Hirshfeld surface and associated fingerprint plots of these four molecules also have provided a platform for the evaluation of the contribution of different atom...atom contacts, which contribute toward the packing of the molecules in solids.

Rotational spectra of propargyl alcohol dimer: A dimer bound with three different types of hydrogen bonds

Pure rotational spectra of the propargyl alcohol dimer and its three deuterium isotopologues have been observed in the 4 to 13 GHz range using a pulsed-nozzle Fourier transform microwave spectrometer. For the parent dimer, a total of 51 transitions could be observed and fitted within experimental uncertainty. For two mono-substituted and one bi-substituted deuterium isotopologues, a total of 14, 17, and 19 transitions were observed, respectively. The observed rotational constants for the parent dimer A = 2321.8335(4) MHz, B = 1150.4774(2) MHz, and C = 1124.8898(2) MHz] are close to those of the most stable structure predicted by ab initio calculations. Spectra of the three deuterated isotopologues and Kraitchman analysis positively confirm this structure. Geometrical parameters and ``Atoms in Molecules'' analysis on the observed structure reveal that the two propargyl alcohol units in the dimer are bound by three different types of hydrogen bonds: O-H center dot center dot center dot O, O-H center dot center dot center dot pi, and C-H center dot center dot center dot pi. To the best of our knowledge, propargyl alcohol seems to be the smallest molecule forming a homodimer with three different points of contact. (C) 2014 AIP Publishing LLC.

A nodal domain theorem for integrable billiards in two dimensions

Eigenfunctions of integrable planar billiards are studied - in particular, the number of nodal domains, nu of the eigenfunctions with Dirichlet boundary conditions are considered. The billiards for which the time-independent Schrodinger equation (Helmholtz equation) is separable admit trivial expressions for the number of domains. Here, we discover that for all separable and nonseparable integrable billiards, nu satisfies certain difference equations. This has been possible because the eigenfunctions can be classified in families labelled by the same value of m mod kn, given a particular k, for a set of quantum numbers, m, n. Further, we observe that the patterns in a family are similar and the algebraic representation of the geometrical nodal patterns is found. Instances of this representation are explained in detail to understand the beauty of the patterns. This paper therefore presents a mathematical connection between integrable systems and difference equations. (C) 2014 Elsevier Inc. All rights reserved.

Electronically nonadiabatic decomposition mechanisms of clusters of zinc and dimethylnitramine

Electronically nonadiabatic decomposition mechanisms of dimethylnitramine (DMNA) in presence of zinc metal clusters are explored. Complete active space self-consistent field (CASSCF) calculation is employed for DMNA-Zn and ONIOM (Our own N-layered integrated molecular orbital and molecular mechanics) methodology is coupled with CASSCF methodology for DMNA-Zn-10 cluster. Present computational results show that DMNA-Zn clusters undergo electronically nonadiabatic reactions, rendering nitro-nitrite isomerization followed by NO elimination. The overall reactions are also found to be highly exothermic in nature. This is the first report on electronically nonadiabatic decomposition pathways of DMNA-Zn-n neutral clusters. (C) 2014 Elsevier B.V. All rights reserved.

MRT Letter: Two-Photon Excitation-Based 2pi Light-Sheet System for Nano-Lithography

We propose two-photon excitation-based light-sheet technique for nano-lithography. The system consists of 2 -configured cylindrical lens system with a common geometrical focus. Upon superposition, the phase-matched counter-propagating light-sheets result in the generation of identical and equi spaced nano-bump pattern. Study shows a feature size of as small as few tens of nanometers with a inter-bump distance of few hundred nanometers. This technique overcomes some of the limitations of existing nano-lithography techniques, thereby, may pave the way for mass-production of nano-structures. Potential applications can also be found in optical microscopy, plasmonics, and nano-electronics. Microsc. Res. Tech. 78:1-7, 2015. (c) 2014 Wiley Periodicals, Inc.

Graded IR Filters: Distinguishing Between Single and Multipoint NO2 center dot center dot center dot I Halogen Bonded Supramolecular Synthons (P, Q, and R Synthons)

The NO2 center dot center dot center dot I supramolecular synthon is a halogen bonded recognition pattern that is present in the crystal structures of many compounds that contain these functional groups. These synthons have been previously distinguished as P, Q, and R types using topological and geometrical criteria. A five step IR spectroscopic sequence is proposed here to distinguish between these synthon types in solid samples. Sets of known compounds that contain the P, Q, and R synthons are first taken to develop IR spectroscopic identifiers for them. The identifiers are then used to create graded IR filters that sieve the synthons. These filters contain signatures of the individual NO2 center dot center dot center dot I synthons and may be applied to distinguish between P, Q, and R synthon varieties. They are also useful to identify synthons that are of a borderline character, synthons in disordered structures wherein the crystal structure in itself is not sufficient to distinguish synthon types, and in the identification of the NO2 center dot center dot center dot I synthons in compounds with unknown crystal structures. This study establishes clear differences for the three different geometries P, Q, and Rand in the chemical differences in the intermolecular interactions contained in the synthons. Our IR method can be conveniently employed when single crystals are not readily available also in high throughput analysis. It is possible that such identification may also be adopted as an input for crystal structure prediction analysis of compounds with unknown crystal structures.

The cold mode: a phenomenological model for the evolution of density perturbations in the intracluster medium

Cool cluster cores are in global thermal equilibrium but are locally thermally unstable. We study a non-linear phenomenological model for the evolution of density perturbations in the intracluster medium (ICM) due to local thermal instability and gravity. We have analysed and extended a model for the evolution of an overdense blob in the ICM. We find two regimes in which the overdense blobs can cool to thermally stable low temperatures. One for large t(cool)/t(ff) (t(cool) is the cooling time and t(ff) is the free-fall time), where a large initial overdensity is required for thermal runaway to occur; this is the regime which was previously analysed in detail. We discover a second regime for t(cool)/t(ff) less than or similar to 1 (in agreement with Cartesian simulations of local thermal instability in an external gravitational field), where runaway cooling happens for arbitrarily small amplitudes. Numerical simulations have shown that cold gas condenses out more easily in a spherical geometry. We extend the analysis to include geometrical compression in weakly stratified atmospheres such as the ICM. With a single parameter, analogous to the mixing length, we are able to reproduce the results from numerical simulations; namely, small density perturbations lead to the condensation of extended cold filaments only if t(cool)/t(ff) less than or similar to 10.

Spatial filter based light-sheet laser interference technique for three-dimensional nanolithography

We propose a laser interference technique for the fabrication of 3D nano-structures. This is possible with the introduction of specialized spatial filter in a 2 pi cylindrical lens system (consists of two opposing cylindrical lens sharing a common geometrical focus). The spatial filter at the back-aperture of a cylindrical lens gives rise to multiple light-sheet patterns. Two such interfering counter-propagating light-sheet pattern result in periodic 3D nano-pillar structure. This technique overcomes the existing slow point-by-point scanning, and has the ability to pattern selectively over a large volume. The proposed technique allows large-scale fabrication of periodic structures. Computational study shows a field-of-view (patterning volume) of approximately 12: 2mm(3) with the pillar-size of 80 nm and inter-pillar separation of 180 nm. Applications are in nano-waveguides, 3D nano-electronics, photonic crystals, and optical microscopy. (C) 2015 AIP Publishing LLC.

Excited electronic state decomposition mechanisms of clusters of dimethylnitramine and aluminum

In this report, electronically non-adiabatic decomposition pathways of clusters of dimethylnitramine and aluminum (DMNA-Al and DMNA-Al-2) are discussed in comparison to isolated dimethylnitramine (DMNA). Electronically excited state processes of DMNA-Al and DMNA-Al-2 are explored using the complete active space self-consistent field (CASSCF) and the restricted active space self-consistent field (RASSCF) theories, respectively. Similar to the nitro-nitrite isomerization reaction pathway of DMNA, DMNA-Al-n clusters also exhibit isomerization pathway. However, it involves several other steps, such as, first Al-O bond dissociation, then N-N bond dissociation followed by isomerization and finally NO elimination. Furthermore, DMNA-Al-n clusters exhibit overall exothermic decomposition reaction pathway and isolated DMNA shows overall endothermic reaction channel.

Effects of hydrogen bonding on amide-proton chemical shift anisotropy in a proline-containing model peptide

Longitudinal relaxation due to cross-correlation between dipolar ((HN-1H alpha)-H-1) and amide-proton chemical shift anisotropy (H-1(N) CSA) has been measured in a model tripeptide Piv-(L)Pro-(L)Pro-(L)Phe-OMe. The peptide bond across diproline segment is known to undergo cis/trans isomerization and only in the cis form does the lone Phe amide-proton become involved in intramolecular hydrogen bonding. The strength of the cross correlated relaxation interference is found to be significantly different between cis and trans forms, and this difference is shown as an influence of intramolecular hydrogen bonding on the amide-proton CSA. (C) 2015 Elsevier B.V. All rights reserved.

Microstructure and Crystallographic Texture Evolution During the Friction-Stir Processing of a Precipitation-Hardenable Aluminum Alloy

Friction-stir processing (FSP) has been proven as a successful method for the grain refinement of high-strength aluminum alloys. The most important attributes of this process are the fine-grain microstructure and characteristic texture, which impart suitable properties in the as-processed material. In the current work, FSP of the precipitation-hardenable aluminum alloy 2219 has been carried out and the consequent evolution of microstructure and texture has been studied. The as-processed materials were characterized using electron back-scattered diffraction, x-ray diffraction, and electron probe microanalysis. Onion-ring formation was observed in the nugget zone, which has been found to be related to the precipitation response and crystallographic texture of the alloy. Texture development in the alloy has been attributed to the combined effect of shear deformation and dynamic recrystallization. The texture was found heterogeneous even within the nugget zone. A microtexture analysis revealed the dominance of shear texture components, with C component at the top of nugget zone and the B and A(2)* components in the middle and bottom. The bulk texture measurement in the nugget zone revealed a dominant C component. The development of a weaker texture along with the presence of some large particles in the nugget zone indicates particle-stimulated nucleation as the dominant nucleation mechanism during FSP. Grain growth follows the Burke and Turnbull mechanism and geometrical coalescence.

Synthesis and characterization of monometallic rhenium(I) complexes and their application as selective sensors for copper(II) ions

Novel imine functionalized monometallic rhenium(I) polypyridine complexes (1-4) comprising two phenol moieties attached to 2,20-bipyridine ligands L1-L4 have been synthesized and characterized. These complexes exhibit selective and sensitive detection towards copper(II) ions and this is observed through changes in UV-visible absorption, luminescence and time-resolved spectroscopic techniques. An enormous enhancement is observed in emission intensity, quantum yield and luminescence lifetime with the addition of copper(II) ions, and this can be attributed to the restriction of C=N isomerization in the Re(I) complexes. The strong binding between copper(II) ions and these complexes reveals that the binding constant values are in the range of 1.1 x 10(3)-6.0 x 103 M-1. The absorption spectral behavior of the complexes is supported by DFT calculations.

CROSS-SECTIONAL ANALYSIS OF PRE-TWISTED THICK BEAMS USING VARIATIONAL ASYMPTOTIC METHOD

An asymptotically-exact methodology is presented for obtaining the cross-sectional stiffness matrix of a pre-twisted moderately-thick beam having rectangular cross sections and made of transversely isotropic materials. The anisotropic beam is modeled from 3-D elasticity, without any further assumptions. The beam is allowed to have large displacements and rotations, but small strain is assumed. The strain energy of the beam is computed making use of the constitutive law and the kinematical relations derived with the inclusion of geometrical nonlinearities and initial twist. Large displacements and rotations are allowed, but small strain is assumed. The Variational Asymptotic Method is used to minimize the energy functional, thereby reducing the cross section to a point on the reference line with appropriate properties, yielding a 1-D constitutive law. In this method as applied herein, the 2-D cross-sectional analysis is performed asymptotically by taking advantage of a material small parameter and two geometric small parameters. 3-D strain components are derived using kinematics and arranged as orders of the small parameters. Warping functions are obtained by the minimization of strain energy subject to certain set of constraints that renders the 1-D strain measures well-defined. Closed-form expressions are derived for the 3-D non-linear warping and stress fields. The model is capable of predicting interlaminar and transverse shear stresses accurately up to first order.

Interaction-induced singular Fermi surface in a high-temperature oxypnictide superconductor

In the family of iron-based superconductors, LaFeAsO-type materials possess the simplest electronic structure due to their pronounced two-dimensionality. And yet they host superconductivity with the highest transition temperature T-c approximate to 55K. Early theoretical predictions of their electronic structure revealed multiple large circular portions of the Fermi surface with a very good geometrical overlap (nesting), believed to enhance the pairing interaction and thus superconductivity. The prevalence of such large circular features in the Fermi surface has since been associated with many other iron-based compounds and has grown to be generally accepted in the field. In this work we show that a prototypical compound of the 1111-type, SmFe0.92Co0.08AsO, is at odds with this description and possesses a distinctly different Fermi surface, which consists of two singular constructs formed by the edges of several bands, pulled to the Fermi level from the depths of the theoretically predicted band structure by strong electronic interactions. Such singularities dramatically affect the low-energy electronic properties of the material, including superconductivity. We further argue that occurrence of these singularities correlates with the maximum superconducting transition temperature attainable in each material class over the entire family of iron-based superconductors.