Variation in glass transition temperature of polymer nanocomposite films driven by morphological transitions

We report the variation of glass transition temperature in supported thin films of polymer nanocomposites, consisting of polymer grafted nanoparticles embedded in a homopolymer matrix. We observe a systematic variation of the estimated glass transition temperature T-g, with the volume fraction of added polymer grafted nanoparticles. We have correlated the observed T-g variation with the underlying morphological transitions of the nanoparticle dispersion in the films. Our data also suggest the possibility of formation of a low-mobility glass or gel-like layer of nanoparticles at the interface, which could play a significant role in determining T-g of the films provided. (C) 2013 American Institute of Physics. http://dx.doi.org/10.1063/1.4773442]

Doping by diffusion of dopants from the substrate: synthesis of doped ZnO nanowires

We report on the substrate assisted doping of ZnO nanowires grown by a vapor transport technique. The nanowires were grown non-catalytically on multiwalled carbon nanotubes (MWCNTs) and soda lime glass (SLG). Carbon from MWCNTs and sodium from SLG diffuse into ZnO during the growth and are distributed uniformly and provide doping. An advantage associated with the technique is that no conventional external dopant source is required to obtain doped ZnO nanowires. The diameter, length and hence the aspect ratio can easily be varied by changing the growth conditions. The transport studies on both carbon and sodium doped ZnO support the p-type nature of ZnO. The p-type nature of carbon doped ZnO is stable for at least eight months.

On the mechanism and the length scales involved in the ductile fracture of a bulk metallic glass

Some bulk metallic glasses (BMGs) exhibit high crack initiation toughness due to shear band mediated plastic flow at the crack tip and yet do not display additional resistance to crack growth due to the lack of a microstructure. Thus, at crack initiation, the fracture behavior of BMGs transits from that of ductile alloys to that of brittle ceramics. In this paper, we attempt to understand the physics behind the characteristic length from the notch root at which this transition occurs, through testing of four-point bend specimens made of a nominally ductile Zr-based BMG in three different structural states. In the as-cast state, both symmetric (mode I) and asymmetric (mixed mode) bend specimens are tested. The process of shear band mediated plastic flow followed by crack initiation at the notch root was monitored through in situ imaging. Results show that stable crack growth occurs inside a dominant shear band through a distance of, similar to 60 mu m, irrespective of the structural state and mode mixity, before attaining criticality. Detailed finite element simulations show that this length corresponds to the distance from the notch root over which a positive hydrostatic stress gradient prevails. The mean ridge heights on fractured surfaces are found to correlate with the toughness of the BMG. The Argon and Salama model, which is based on the meniscus instability phenomenon at the notch root, is modified to explain the experimentally observed physics of fracture in ductile BMGs. (C) 2012 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

A Finite Element Method Based Approach for Evaluating the Sensitivity of Faraday-Type Electromagnetic Flow Meter for Liquid Sodium Flow

Faraday-type electromagnetic flow meters are employed for measuring the flow rate of liquid sodium in fast breeder reactors. The calibration of such flow meters, owing to the required elaborative arrangements is rather difficult. On the other hand, theoretical approach requires solution of two coupled electromagnetic partial differential equation with profile of the flow and applied magnetic field as the inputs. This is also quite involved due to the 3D nature of the problem. Alternatively, Galerkin finite element method based numerical solution is suggested in the literature as an attractive option for the required calibration. Based on the same, a computer code in Matlab platform has been developed in this work with both 20 and 27 node brick elements. The boundary conditions are correctly defined and several intermediate validation exercises are carried out. Finally it is shown that the sensitivities predicted by the code for flow meters of four different dimensions agrees well with the results given by analytical expression, thereby providing strong validation. Sensitivity for higher flow rates, for which analytical approach does not exist, is shown to decrease with increase in flow velocity.

Comprehensive investigations on DNa center dot center dot center dot A (D = H/F) complexes show why `sodium bonding' is not commonly observed

A comprehensive study of D-Na center dot center dot center dot A (D = H/F) complexes has been done using advanced ab initio and atoms in molecule (AIM) theoretical analyses. The correlation between electron density at bond critical point and binding energy gives a distinguishing feature for hydrogen bonding, different from the `electrostatic complexes' formed by LiD and NaD. Moreover, the LiD/NaD dimers have both linear and anti-parallel minima, as expected for electrostatic dipole-dipole interactions. The HF dimer has a quasi-linear minimum and the anti-parallel structure is a saddle point. Clearly, characterizing hydrogen bonding as `nothing but electrostatic interaction between two dipoles' is grossly in error.

Deposition and characterization of pure and Cd doped SnO2 thin films by the nebulizer spray pyrolysis (NSP) technique

Pure and cadmium doped tin oxide thin films were deposited on glass substrates from aqueous solution of cadmium acetate, tin (IV) chloride and sodium hydroxide by the nebulizer spray pyrolysis (NSP) technique. X-ray diffraction reveals that all films have tetragonal crystalline structure with preferential orientation along (200) plane. On application of the Scherrer formula, it is found that the maximum size of grains is 67 nm. Scanning electron microscopy shows that the grains are of rod and spherical in shape. Energy dispersive X-ray analysis reveals the average ratio of the atomic percentage of pure and Cd doped SnO2 films. The electrical resistivity is found to be 10(2) Omega cm at higher temperature (170 degrees C) and 10(3) Omega cm at lower temperature (30 degrees C). Optical band gap energy was determined from transmittance and absorbance data obtained from UV-vis spectra. Optical studies reveal that the band gap energy decreases from 3.90 eV to 3.52 eV due to the addition of Cd as dopant with different concentrations.

Mammalian neuronal sodium channel Blocker mu-conotoxin BuIIIB has a structured N-terminus that influences potency

Among the mu-conotoxins that block vertebrate voltage-gated sodium channels (VGSCs), some have been shown to be potent analgesics following systemic administration in mice. We have determined the solution structure of a new representative of this family, mu-BuIIIB, and established its disulfide connectivities by direct mass spectrometric collision induced dissociation fragmentation of the peptide with disulfides intact The major oxidative folding product adopts a 1-4/2-5/3-6 pattern with the following disulfide bridges: Cys5-Cys17, Cys6-Cys23, and Cys13-Cys24. The solution structure reveals that the unique N-terminal extension in mu-BuIIIB, which is also present in mu-BuIIIA and mu-BuIIIC but absent in other mu-conotoxins, forms part of a short a-helix encompassing Glu3 to Asn8. This helix is packed against the rest of the toxin and stabilized by the Cys5-Cys17 and Cys6-Cys23 disulfide bonds. As such, the side chain of Val1 is located close to the aromatic rings of Trp16 and His20, which are located on the canonical helix that displays several residues found to be essential for VGSC blockade in related mu-conotoxins. Mutations of residues 2 and 3 in the N-terminal extension enhanced the potency of mu-BuIIIB for Na(v)1.3. One analogue, D-Ala2]BuIIIB, showed a 40-fold increase, making it the most potent peptide blocker of this channel characterized to date and thus a useful new tool with which to characterize this channel. On the basis of previous results for related mu-conotoxins, the dramatic effects of mutations at the N-terminus were unanticipated and suggest that further gains in potency might be achieved by additional modifications of this region.

Comparison of ZnO films deposited on indium tin oxide and soda lime glass under identical conditions

ZnO films have been grown via a vapour phase transport (VPT) on soda lime glass (SLG) and indium-tin oxide (ITO) coated glass. ZnO film on ITO had traces of Zn and C which gives them a dark appearance while that appears yellowish-white on SLG. X-ray photoelectron spectroscopy studies confirm the traces of C in the form of C-O. The photoluminescence studies reveal a prominent green luminescence band for ZnO film on ITO. (C) 2013 Author(s).

Crystal growth and nonlinear optical properties of sodium D-isoascorbate monohydrate

Optical quality single crystals of sodium D-isoascorbate monohydrate were grown by a slow cooling technique. The crystal possesses a bulky prismatic morphology. Thermal analyses indicate that the crystals are stable up to 125 degrees C. The optical transmission window ranges from 307 nm to 1450 nm. The principal refractive indices have been measured employing Brewster's angle method. The crystallographic and the principal dielectric axes coincide with each other such that a lies along Z, b along X and c along Y. The optic axis is oriented 58 degrees (at 532 nm) to the crystallographic a axis in the XZ plane and the crystal is negative biaxial. Type 1 and type 2 phase matching curves are generated and experimentally verified. No polarization dependence of the light absorption was observed confirming the validity of Kleinman's symmetry conjecture, leading to a single nonvanishing nonlinear tensor component. According to Hobden's classification the crystal belongs to class 3. The crystal also exhibits second order noncollinear conic sections. The single shot and multiple shot surface laser damage thresholds are determined to be 32.7 GW cm(-2) and 6.5 GW cm(-2) respectively for 1064 nm radiation.

Structure-property correlation in BaO-TiO2-B2O3 glasses: glass stability, optical, hydrophobic, and dielectric properties

Glasses in the x(BaO-TiO2)-B2O3 (x = 0.25, 0.5, 0.75, and 1 mol.) system were fabricated via the conventional melt-quenching technique. Thermal stability and glass-forming ability as determined by differential thermal analysis (DTA) were found to increase with increasing BaO-TiO2 (BT) content. However, there was no noticeable change in the glass transition temperature (T-g). This was attributed to the active participation of TiO2 in the network formation especially at higher BT contents via the conversion of the TiO6 structural units into TiO4 units, which increased the connectivity and resulted in an increase in crystallization temperature. Dielectric and optical properties at room temperature were studied for all the glasses under investigation. Interestingly, these glasses were found to be hydrophobic. The results obtained were correlated with different structural units and their connectivity in the glasses.

Low loss waveguide on chalcogenide glass using ultrafast laser at low repetition rate

In this work, we synthesized bulk amorphous GeGaS glass by conventional melt quenching technique. Amorphous nature of the glass is confirmed using X-ray diffraction. We fabricated the channel waveguides on this glass using the ultrafast laser inscription technique. The waveguides are written on this glass 100 mu m below the surface of the glass with a separation of 50 ae m by focusing the laser beam into the material using 0.67 NA lens. The laser parameters are set to 350 fs pulse duration at 100 KHz repetition rate. A range of writing energies with translation speeds 1 mm/s, 2 mm/s, 3 mm/s and 4 mm/s were investigated. After fabrication the waveguides facets were ground and polished to the optical quality to remove any tapering of the waveguide close to the edges. We characterized the loss measurement by butt coupling method and the mode field image of the waveguides has been captured to compare with the mode field image of fibers. Also we compared the asymmetry in the shape of the waveguide and its photo structural change using Raman spectra.

Photo-thermal modifications in ultrafast laser inscribed chalcogenide glass waveguides

We report here, a finite difference thermal diffusion (FDTD) model for controlling the cross-section and the guiding nature of the buried channel waveguides fabricated on GeGaS bulk glasses using the direct laser writing technique. Optimization of the laser parameters for guiding at wavelength 1550 nm is done experimentally and compared with the theoretical values estimated by FDTD model. The mode field diameter (MFD) between 5.294 mu m and 24.706 mu m were attained by suitable selection of writing speed (1mm/s to 4 mm/s) and pulse energy (623 nJ to 806 nJ) of the laser at a fixed repletion rate of 100 kHz. Transition from single-mode to multi-mode waveguide is observed at pulse energy 806nJ as a consequence of heat accumulation. The thermal diffusion model fits well for single-mode waveguides with the exception of multi-mode waveguides.

A naturally occurring amino acid substitution in the voltage-dependent sodium channel selectivity filter affects channel gating

The pore of sodium channels contains a selectivity filter made of 4 amino acids, D/E/K/A. In voltage sensitive sodium channel (Nav) channels from jellyfish to human the fourth amino acid is Ala. This Ala, when mutated to Asp, promotes slow inactivation. In some Nav channels of pufferfishes, the Ala is replaced with Gly. We studied the biophysical properties of an Ala-to-Gly substitution (A1529G) in rat Nav1.4 channel expressed in Xenopus oocytes alone or with a beta 1 subunit. The Ala-to-Gly substitution does not affect monovalent cation selectivity and positively shifts the voltage-dependent inactivation curve, although co-expression with a beta 1 subunit eliminates the difference between A1529G and WT. There is almost no difference in channel fast inactivation, but the beta 1 subunit accelerates WT current inactivation significantly more than it does the A1529G channels. The Ala-to-Gly substitution mainly influences the rate of recovery from slow inactivation. Again, the beta 1 subunit is less effective on speeding recovery of A1529G than the WT. We searched Nav channels in numerous databases and noted at least four other independent Ala-to-Gly substitutions in Nav channels in teleost fishes. Thus, the Ala-to-Gly substitution occurs more frequently than previously realized, possibly under selection for alterations of channel gating.

Role of substrate temperature on the properties of Na-doped ZnO thin film nanorods and performance of ammonia gas sensors using nebulizer spray pyrolysis technique

Sodium doped zinc oxide (Na:ZnO) thin films were deposited on glass substrates at substrate temperatures 300,400 and 500 degrees C by a novel nebulizer spray method. X-ray diffraction shows that all the films are polycrystalline in nature having hexagonal structure with high preferential orientation along (0 0 2) plane. High resolution SEM studies reveal the formation of Na-doped ZnO films having uniformly distributed nano-rods over the entire surface of the substrates at 400 degrees C. The complex impedance of the ZnO nano-rods shows two distinguished semicircles and the diameter of the arcs got decreased in diameter as the temperature increases from 170 to 270 degrees C and thereafter slightly increased. (c) 2013 Elsevier B.V. All rights reserved.

Effect of Net-Fluence on waveguide formation in ultrafast laser inscribed chalcogenide glass

Waveguides were fabricated on GeGaSEr chalcogenide glass using ultrafast laser inscription method. The thermal diffusion model is discussed for understanding the light matter interaction and shown the effect of net-fluence in waveguide formation on chalcogenide glass. (C) 2012 Optical Society of America