Multiple emissive triarylborane-A(2)H(2) and triarylborane-Zn-A(2)H(2) porphyrin conjugates

Triarylborane-A(2)H(2) (1) and triarylborane-Zn-A(2)H(2) porphyrins (2) have been synthesized by acid catalyzed condensation of 4-dimesitylboryl-benzaldehyde and dipyrromethane under ambient conditions. Compounds 1 and 2 showed multiple emission bands upon excitation at the triarylborane dominated absorption region (350 nm). Detailed experimental and computational studies show that the multiple emission features of 1 and 2 arise as a result of a partial energy transfer from the donor (triarylborane) to the acceptor (porphyrin) moieties. Compounds 1 and 2 showed very high selectivities towards fluoride ions compared to other competing anions.

Structural, Optical, and Piezoelectric Response of Lead-Free Ba0.95Mg0.05Zr0.1Ti0.9O3 Nanocrystalline Powder

Nanocrystalline powders of Ba1-xMgxZr0.1Ti0.9O3 (x = 0.025-0.1) were synthesized via citrate assisted sol-gel method. Interestingly, the one with x = 0.05 in the system Ba1-xMgxZr0.1Ti0.9O3 exhibited fairly good piezoelectric response aside from the other physical properties. The phase and structural confirmation of synthesized powder was established by X-ray powder diffraction (XRD) and Raman Spectroscopic techniques. Two distinct Raman bands i.e., 303 and 723 cm(-1) characteristic of tetragonal phase were observed. Thermogravimetric analysis (TGA) was performed to evaluate the phase decomposition of the as-synthesized Ba0.95Mg0.05Zr0.1Ti0.9O3 sample as a function of temperature. The average crystallite size associated with Ba0.95Mg0.05Zr0.1Ti0.9O3 was calculated using Scherrer formula based on the XRD data and was found to be 25 nm. However, Scanning and Transmission Electron Microscopy studies revealed the average crystallite size to be in the range of 30-40 nm, respectively. Kubelka-Munk function was employed to determine the optical band gap of these nanocrystallites. A piezoelectric response of 26 pm/V was observed for Ba0.95Mg0.05Zr0.1Ti0.9O3 nanocrystal by Piezoresponse Force Microscopy (PFM) technique. Photoluminescence (PL) study carried out on these nanocrystals exhibited a blue emission (470 nm) at room temperature.

Effect of particle size of sand and surface asperities of reinforcement on their interface shear behaviour

This paper investigates the effect of particle size of sand and the surface asperities of reinforcing material on their interlocking mechanism and its influence on the interfacial shear strength under direct sliding condition. Three sands of different sizes with similar morphological characteristics and four different types of reinforcing materials with different surface features were used in this study. Interface direct shear tests on these materials were performed in a specially developed symmetric loading interface direct shear test setup. Morphological characteristics of sand particles were determined from digital image analysis and the surface roughness of the reinforcing materials was measured using an analytical expression developed for this purpose. Interface direct shear tests at three different normal stresses were carried out by shearing the sand on the reinforcing material fixed to a smooth surface. Test results revealed that the peak interfacial friction and dilation angles are hugely dependent upon the interlocking between the sand particles and the asperities of reinforcing material, which in turn depends on the relative size of sand particles and asperities. Asperity ratio (AS/D-50) of interlocking materials, which is defined as the ratio of asperity spacing of the reinforcing material and the mean particle size of sand was found to govern the interfacial shear strength with highest interfacial strength measured when the asperity ratio was equal to one, which represents the closest fitting of sand particles into the asperities. It was also understood that the surface roughness of the reinforcing material influences the shear strength to an extent, the influence being more pronounced in coarser particles. Shear bands in the interface shear tests were analysed through image segmentation technique and it was observed that the ratio of shear band thickness (t) to the median particle size (D-50) was maximum when the AS/D-50 was equal to one. (C) 2015 Elsevier Ltd. All rights reserved.

Triplet excited electronic state switching induced by hydrogen bonding: A transient absorption spectroscopy and time-dependent DFT study

The solvent plays a decisive role in the photochemistry and photophysics of aromatic ketones. Xanthone (XT) is one such aromatic ketone and its triplet-triplet (T-T) absorption spectra show intriguing solvatochromic behavior. Also, the reactivity of XT towards H-atom abstraction shows an unprecedented decrease in protic solvents relative to aprotic solvents. Therefore, a comprehensive solvatochromic analysis of the triplet-triplet absorption spectra of XT was carried out in conjunction with time dependent density functional theory using the ad hoc explicit solvent model approach. A detailed solvatochromic analysis of the T-T absorption bands of XT suggests that the hydrogen bonding interactions are different in the corresponding triplet excited states. Furthermore, the contributions of non-specific and hydrogen bonding interactions towards differential solvation of the triplet states in protic solvents were found to be of equal magnitude. The frontier molecular orbital and electron density difference analysis of the T-1 and T-2 states of XT indicates that the charge redistribution in these states leads to intermolecular hydrogen bond strengthening and weakening, respectively, relative to the S-0 state. This is further supported by the vertical excitation energy calculations of the XT-methanol supra-molecular complex. The intermolecular hydrogen bonding potential energy curves obtained for this complex in the S-0, T-1, and T-2 states support the model. In summary, we propose that the different hydrogen bonding mechanisms exhibited by the two lowest triplet excited states of XT result in a decreasing role of the n pi* triplet state, and are thus responsible for its reduced reactivity towards H-atom abstraction in protic solvents. (C) 2016 AIP Publishing LLC.

Electron-hole asymmetry in the electron-phonon coupling in top-gated phosphorene transistor

Using in situ Raman scattering from phosphorene channel in an electrochemically top-gated field effect transistor, we show that phonons with A(g) symmetry depend much more strongly on concentration of electrons than that of holes, wheras phonons with B-g symmetry are insensitive to doping. With first-principles theoretical analysis, we show that the observed electon-hole asymmetry arises from the radically different constitution of its conduction and valence bands involving pi and sigma bonding states respectively, whose symmetry permits coupling with only the phonons that preserve the lattice symmetry. Thus, Raman spectroscopy is a non-invasive tool for measuring electron concentration in phosphorene-based nanoelectronic devices.

Enhanced Plasticity of Zr-Based Bulk Metallic Glass Matrix Composite with Ductile Reinforcement

A composite material containing uniformly distributed micrometer-sized Nb particles in a Zr-based amorphous matrix was prepared by suction cast. The resulting material exhibits high fractured strength over 1550 MPa and enhanced plastic strain of about 29.7% before failure in uniaxial compression test at room temperature. Studies of the serrations on the stress-strain curves and the shear bands on the fractured samples reveal that the amplitude of the stress drop of each serration step corresponds to the extent of the propagation of a single shear band through the materials. The composite exhibits more serration steps and smaller amplitude of stress drop due to the pinning of shear band propagation by ductile Nb particles.

Formation, Thermal Stability and Deformation Behavior of Graphite-Flakes Reinforced Cu-based Bulk Metallic Glass Matrix Composites

Graphite-flake reinforced Cu47Ti34Zr11 Ni-8 bulk metallic glass matrix composite was fabricated by water-cooled copper mould cast. Most of the graphite flakes still keep unreacted and distribute uniformly in the amorphous matrix except that some reactive wetting occurs by the formation of TiC particles around the flakes. It reveals that the presence of graphite flakes does not affect the onset of the glass transition temperature, crystallization reaction and liquidus of the metallic glass. The resulting material shows obvious serrated flow and higher fracture strength under room temperature compressive load, comparing with the monolithic bulk metallic glass (BMG). Three types of interaction between the shear bands and graphite flakes, namely, shear band termination, shear bands branching and new shear bands formation near the graphite flakes can be observed by quasi-static uniaxial compression test and bonded interface technique through Vickers indentation.

Perceptual thresholds for detecting modifications applied to the acoustical properties of a violin

This study is the first step in the psychoacoustic exploration of perceptual differences between the sounds of different violins. A method was used which enabled the same performance to be replayed on different "virtual violins," so that the relationships between acoustical characteristics of violins and perceived qualities could be explored. Recordings of real performances were made using a bridge-mounted force transducer, giving an accurate representation of the signal from the violin string. These were then played through filters corresponding to the admittance curves of different violins. Initially, limits of listener performance in detecting changes in acoustical characteristics were characterized. These consisted of shifts in frequency or increases in amplitude of single modes or frequency bands that have been proposed previously to be significant in the perception of violin sound quality. Thresholds were significantly lower for musically trained than for nontrained subjects but were not significantly affected by the violin used as a baseline. Thresholds for the musicians typically ranged from 3 to 6 dB for amplitude changes and 1.5%-20% for frequency changes. interpretation of the results using excitation patterns showed that thresholds for the best subjects were quite well predicted by a multichannel model based on optimal processing. (c) 2007 Acoustical Society of America.

Mechanism on Progressive Failure of a Faulted Rock Slope Due to Slip-Weakening

Slip-weakening is one of the characteristics of geological materials under certain loadings. Non-uniform rock structure may exist in the vicinity of the slip surface for a rock slope. Some portion of the slip surface may be penetrated but the other not. For the latter case, the crack or the fault surface will undergo shear deformation before it becomes a successive surface under a certain loading. As the slipped portion advances,slip-weakening occurs over a distance behind the crack tip. In the weakening zone, the shear strength will decrease from its peak value to residual friction level. The stress will redistribute along the surface of crack and in the weakening zone. Thus the changed local stress concentration leads the crack to extend and the ratio of penetration of the slip surface to increase. From the view of large-scale for the whole slip surface, the shear strength will decrease due to the damage of interior rock structure, and the faulted rock behaves as a softening material. Such a kind of mechanism performs in a large number of practical landslides in the zones experienced strong earthquakes. It should be noted that the mechanism mentioned above is different from that of the breakage of structural clay,in which the geological material is regarded as a medium containing structural lumps and structural bands. In this paper, the softening behavior of a faulted rock should be regarded as a comprehensive result of the whole complicated process including slip-weakening, redistribution of stress, extension of crack tip, and the penetration of the slip surface. This process is accompanied by progressive failure and abrupt structural damage. The size of slip-weakening zone is related to the undergoing strain. Once the relative slide is initiated (local or integrated), the effect of slip-weakening will behave in a certain length behind the crack tip until the formation of the whole slip surface.

Serrated Plastic Flow in a Zr-Based Bulk Metallic Glass During Nanoindentation

We investigate plastic deformation of Zr41.2Ti13.8Cu12.5Ni10Be22.5 bulk metallic glass using depth sensing nanoindentation. Numerous serrations in the load-displacement curves during indentation, shear bands and pile-ups around the indent were observed. The results revealed that the serrated plastic flow behaviour in this alloy depends strongly on the indentation strain rate.

Thermoplastic shear localisation in titanium alloys during dynamic deformation

Cylindrical specimens (4 mm diameter and 4 mm height) of titanium alloy bar were given various heat treatments to provide a wide range of microstructures and mechanical parameters. These specimens were then subjected to high plastic strain at a large strain rate (103 s-1 ) during dynamic compression by a split Hopkinson bar at ambient temperature. The microstructures of the localised shear bands were examined by optical and transmission electron microscopy. The results show that there are two types of localised shear bands: deformed and white shear bands. A detailed observation reveals that there is no difference in the nature of the deformed and white shear bands, but they occur at different stages of localised deformation. It is found that there is a burst of strain, corresponding to a critical strain rate at which the white shear band occurs and no phase transformation occurs in the shear bands.

Ductile Metallic Glasses in Supercooled Martensitic Alloys

We report ductile bulk metallic glasses based on martensitic alloys. The slowly cooled specimens contain a mixture of parent 'austenite' and martensite phase. The slightly faster cooled bulk metallic glasses with 2-5 nm sized 'austenite'-like crystalline cluster reveal high strength and large ductility (16%). Shear bands propagate in a slither mode in this spatially inhomogeneous glassy structure and undergo considerable 'thickening' from 5-25 nm. A 'stress induced displacive transformation' is proposed to be responsible for both plasticity and work-hardening-like behavior of these 'M-Glasses'.

Strain Rate-Dependent Compressive Deformation Behavior of Nd-Based Bulk Metallic Glass

Compressive deformation behavior of the Nd60Fe20Co10Al10 bulk metallic glass was characterized over a wide strain rate range (6.0 x 10(-4) to 1.0x10(3) s(-1)) at room temperature. Fracture stress was found to increase and fracture strain decrease with increasing applied strain rate. Serrated flow and a large number of shear bands were observed at the quasi-static strain rate (6.0 x 10(-4)s(-1)). The results suggest that the appearance of a large number of shear bands is probably associated with flow serration observed during compression; and both shear banding and flow serration are a strain accommodation and stress relaxation process. At dynamic strain rates (1.0 x 10(3) s(-1)), the rate of shear band nucleation is not sufficient to accommodate the applied strain rate and thus causes an early fracture of the test sample. The fracture behavior of the Nd60Fe20Co10Al10 bulk metallic glass is sensitive to strain rate.

Shear localization and recrystallization in dynamic deformation of 8090 Al-Li alloy

The microstructural evolution in localized shear deformation was investigated in an 8090 Al-Li alloy by split Hopkinson pressure bar (strain rate of approximately 10(3) s(-1)) at ambient temperature and 77 K. The alloy was tested in the peak-, over-, under-, and natural-aged conditions, that provide a wide range of microstructural parameters and mechanical properties. Two types of localized shear bands were distinguished by optical microscopy: the deformed shear band and the white-etching shear band. They form at different stages of deformation during localization. There are critical strains for the occurrence of deformed and white-etching localized shear deformation, at the imposed strain rate. Observations by transmission electron microscopy reveal that the white-etching bands contain fine equiaxed grains; it is proposed that they are the result of recrystallization occurring during localization. The deformed-type bands are observed after testing at 77 K in all heat treatment conditions, but they are not as well defined as those developed at ambient temperature. Cracking often occurs along the localized shear at ambient temperature. The decrement in temperature is favorable for the nucleation, growth and coalescence of the microcracks along the shear bands, inducing fracture.

Characterization of Plastic Flow in Two Zr-Based Bulk Metallic Glasses

Plastic deformation behaviors of Zr65Al10Ni10CU15 and Zr52.5Al10Ni10Cu15Be12.5 bulk metallic glasses (BMGs) are studied by using the depth-sensing nanoindentation, microindentation and uniaxial compression. The Be-containing BMG exhibits a significantly improved overall plastic strain compared with the Be-free alloy during compressive tests. Both BMGs show a loading-rate-dependent serrated flow during nanoindentation measurements, but the Be-containing alloy exhibits a much lower critical loading rate for the disappearance of the serration than the Be-free BMG. The shear band patterns developed during plastic deformation are investigated by microindentation technique, wherein much higher shear band density is found in the Be-containing alloy than in the Be-free alloy, indicating an easier nucleation of shear bands in the former BMG. The difference in the plastic deformation behavior of the two BMGs can be explained by a free volume model.