Two-Dimensional Correlation Analysis of Temperature-Dependent FT-IR Spectra of Oleic Acid

In the present study, variable temperature FT-IR spectroscopic investigations were used to characterize the spectral changes in oleic acid during heating oleic acid in the temperature range from -30 degrees;C to 22 degrees C. In order to extract more information about the spectral variations taking place during the phase transition process, 2D correlation spectroscopy (2DCOS) was employed for the stretching (C?O) and rocking (CH2) band of oleic acid. However, the interpretation of these spectral variations in the FT-IR spectra is not straightforward, because the absorption bands are heavily overlapped and change due to two processes: recrystallization of the ?-phase and melting of the oleic acid. Furthermore, the solid phase transition from the ?- to the a-phase was also observed between -4 degrees C and -2 degrees C. Thus, for a more detailed 2DCOS analysis, we have split up the spectral data set in the subsets recorded between -30 degrees C to -16 degrees C, -16 degrees C to 10 degrees C, and 10 degrees C to 22 degrees C. In the corresponding synchronous and asynchronous 2D correlation plots, absorption bands that are characteristic of the crystalline and amorphous regions of oleic acid were separated.

Ultrafast quasiparticle relaxation dynamics in superconducting iron pnictide Ca(Fe0.944Co0.056)(2)As-2

Nonequilibrium quasiparticle relaxation dynamics is reported in superconducting Ca(Fe0.944Co0.056)(2)As-2 single crystals by measuring transient reflectivity changes using femtosecond time-resolved pump-probe spectroscopy. Large changes in the temperature-dependent differential reflectivity values in the vicinity of the spin density wave (T-SDW) and superconducting (T-SC) transition temperatures of the sample have been inferred to have charge gap opening at those temperatures. We have estimated the zero-temperature charge gap value in the superconducting state to be similar to 1.8k(B)T(SC) and an electron-phonon coupling constant lambda of similar to 0.1 in the normal state that signifies the weak coupling in iron pnictides. From the peculiar temperature-dependence of the quasiparticle dynamics in the intermediate temperature region between T-SC and T-SDW we infer a temperature scale where the charge gap associated with the spin ordered phase is maximum and closes on either side while approaching the two phase transition temperatures.

Free energy barriers for homogeneous crystal nucleation in a eutectic system of binary hard spheres

In this study, the free energy barriers for homogeneous crystal nucleation in a system that exhibits a eutectic point are computed using Monte Carlo simulations. The system studied is a binary hard sphere mixture with a diameter ratio of 0.85 between the smaller and larger hard spheres. The simulations of crystal nucleation are performed for the entire range of fluid compositions. The free energy barrier is found to be the highest near the eutectic point and is nearly five times that for the pure fluid, which slows down the nucleation rate by a factor of 10(-31). These free energy barriers are some of highest ever computed using simulations. For most of the conditions studied, the composition of the critical nucleus corresponds to either one of the two thermodynamically stable solid phases. However, near the eutectic point, the nucleation barrier is lowest for the formation of the metastable random hexagonal closed packed (rhcp) solid phase with composition lying in the two-phase region of the phase diagram. The fluid to solid phase transition is hypothesized to proceed via formation of a metastable rhcp phase followed by a phase separation into respective stable fcc solid phases.

Determination of favorable inter-particle interactions for formation of substitutionally ordered solid phases from a binary mixture of oppositely charged colloidal suspensions

The solid phase formed by a binary mixture of oppositely charged colloidal particles can be either substitutionally ordered or substitutionally disordered depending on the nature and strength of interactions among the particles. In this work, we use Monte Carlo molecular simulations along with the Gibbs-Duhem integration technique to map out the favorable inter-particle interactions for the formation of substitutionally ordered crystalline phases from a fluid phase. The inter-particle interactions are modeled using the hard core Yukawa potential but the method can be easily extended to other systems of interest. The study obtains a map of interactions depicting regions indicating the type of the crystalline aggregate that forms upon phase transition.

Anomalous optical phonons in Cs-0.9(NH4)(0.1)H2AsO4: a temperature-dependent Raman study

We determine the nature of coupled phonons in mixed crystal of Cs-0.9(NH4)(0.1)H2AsO4 using inelastic light scattering studies in the temperature range of 5 K to 300 K covering a spectral range of 60-1100 cm(-1). The phase transition in this system are marked by the splitting of phonon modes, appearance of new modes and anomalies in the frequency as well as linewidth of the phonon modes near transition temperature. In particular, we observed the splitting of symmetric (v(1)) and antisymmetric (v(3)) stretching vibrations associated with AsO4 tetrahedra below transition temperature (T-c(*) similar to 110 K) attributed to the lowering of site symmetry of AsO4 in orthorhombic phase below transition temperature. In addition, the step-up (hardening) and step-down (softening) of the AsO4 bending vibrations (v(4) (S9, S11) and v(2) (S6)) below transition temperature signals the rapid development of long range ferroelectric order and proton ordering. The lowest frequency phonon (S1) mode observed at similar to 92 cm(-1) shows anomalous blue shift (similar to 12 %) from 300 K to 5 K with no sharp transition near T-c(*) unlike other observed phonon modes signaling its potential coupling with the proton tunneling mode. (C) 2013 Author(s).

Effect of electro-mechanical coupling on actuation behavior of a carbon nanotube cellular structure

We demonstrate the effect of mechanical strain on the electrostrictive behavior of catalytically grown cellular structure of carbon nanotube (CNT). In the small strain regime, where the stress-strain behavior of the material is linear, application of an electric-field along the mechanical loading direction induces an instantaneous increase in the stress and causes an increase in the apparent Young's modulus. The instantaneous increase in the stress shows a cubic-polynomial dependence on the electric-field, which is attributed to the non-linear coupling of the mechanical strain and the electric-field induced polarization of the CNT. The electrostriction induced actuation becomes >100 times larger if the CNT sample is pre-deformed to a small strain. However, in the non-linear stress-strain regime, although a sharp increase in the apparent Young's modulus is observed upon application of an electric-field, no instantaneous increase in the stress occurs. This characteristic suggests that the softening due to the buckling of individual CNT compensates for any instantaneous rise in the electrostriction induced stress at the higher strains. We also present an analytical model to elucidate the experimental observations. (C) 2013 Elsevier Ltd. All rights reserved.

MECHANISM OF CELL LYSIS IN MICROFLUIDIC CHANNEL WITH INTEGRATED NANOCOMPOSITE ELECTRODES

This paper reports on the characterization of an integrated micro-fluidic platform for controlled electrical lysis of biological cells and subsequent extraction of intracellular biomolecules. The proposed methodology is capable of high throughput electrical cell lysis facilitated by nano-composite coated electrodes. The nano-composites are synthesized using Carbon Nanotube and ZnO nanorod dispersion in polymer. Bacterial cells are used to demonstrate the lysis performance of these nanocomposite electrodes. Investigation of electrical lysis in the microchannel is carried out under different parameters, one with continuous DC application and the other under DC biased AC electric field. Lysis in DC field is dependent on optimal field strength and governed by the cell type. By introducing the AC electrical field, the electrokinetics is controlled to prevent cell clogging in the micro-channel and ensure uniform cell dispersion and lysis. Lysis mechanism is analyzed with time-resolved fluorescence imaging which reveal the time scale of electrical lysis and explain the dynamic behavior of GFP-expressing E. coli cells under the electric field induced by nanocomposite electrodes. The DNA and protein samples extracted after lysis are compared with those obtained from a conventional chemical lysis method by using a UV-Visible spectroscopy and fluorimetry. The paper also focuses on the mechanistic understanding of the nano-composite coating material and the film thickness on the leakage charge densities which lead to differential lysis efficiency.

Concentration Fluctuations and Segmental Dynamics in Weakly Dynamic Asymmetric Blends in the Presence of Surface-Functionalized Multiwall Carbon Nanotubes

Surface-functionalized multiwall carbon nanotubes (MWCNTs) are incorporated in poly(methyl methacrylate)/styrene acrylonitrile (PMMA/SAN) blends and the pretransitional regime is monitored in situ by melt rheology and dielectric spectroscopy. As the blends exhibit weak dynamic asymmetry, the obvious transitions in the melt rheology due to thermal concentration fluctuations are weak. This is further supported by the weak temperature dependence of the correlation length ( approximate to 10-12 angstrom) in the vicinity of demixing. Hence, various rheological techniques in both the temperature and frequency domains are adopted to evaluate the demixing temperature. The spinodal decomposition temperature is manifested in an increase in the miscibility gap in the presence of MWCNTs. Furthermore, MWCNTs lead to a significant slowdown of the segmental dynamics in the blends. Thermally induced phase separation in the PMMA/SAN blends lead to selective localization of MWCNTs in the PMMA phase. This further manifests itself in a significant increase in the melt conductivity.

Electrocaloric Effect in 0.85PMN-0.15PT Thin Films Deposited by Pulsed Laser Deposition

The electrocaloric effect (ECE) of 0.85PbMg(1/3)Nb(2/3)O(3-)0.15PbTiO(3) (0.85PMN-0.15PT) thin films deposited on (111) Pt/TiO2/SiO2/Si substrate by pulsed laser deposition (PLD) has been calculated. The reversible adiabatic temperature was calculated indirectly using the Maxwell's relation Delta T = -T/C rho integral(E2)(E1) (partial derivative P/partial derivative T)(sigma,E)dE. Permittivity and P-E measurements show an anomaly at 11 degrees C on heating only. This anomaly previously reported are claimed to arise due to the PNR depolarization upon heating. The absence of this anomaly during cooling suggests that no structural phase transition takes place. A negative electrocaloric effect is observed which is explained by the increase in the entropy term.