Influence of Cooling Rate on the Enthalpy Relaxation and Fragility of a Metallic Glass

Structural relaxation behavior of a rapidly quenched (RQ) and a slowly cooled Pd40Cu30Ni10P20 metallic glass was investigated and compared. Differential scanning calorimetry was employed to monitor the relaxation enthalpies at the glass transition temperature, T-g , and the Kolrausch-Williams-Watts (KWW) stretched exponential function was used to describe its variation with annealing time. It was found that the rate of enthalpy recovery is higher in the ribbon, implying that the bulk is more resistant to relaxation at low temperatures of annealing. This was attributed to the possibility of cooling rate affecting the locations where the glasses get trapped within the potential energy landscape. The RQ process traps a larger amount of free volume, resulting in higher fragility, and in turn relaxes at the slightest thermal excitation (annealing). The slowly cooled bulk metallic glass (BMG), on the other hand, entraps lower free volume and has more short-range ordering, hence requiring a large amount of perturbation to access lower energy basins.

Manifestation of geometric frustration on magnetic and thermodynamic properties of the pyrochlores Sm2X2O7 (X=Ti,Zr)

We present here magnetization, specific heat, and Raman studies on single-crystalline specimens of the first pyrochlore member Sm2Ti2O7 of the rare-earth titanate series. Its analogous compound Sm2Zr2O7 in the rare-earth zirconate series is also investigated in the polycrystalline form. The Sm spins in Sm2Ti2O7 remain unordered down to at least T=0.5 K. The absence of magnetic ordering is attributed to very small values of exchange (θcw∼−0.26 K) and dipolar interaction (μeff∼0.15 μB) between the Sm3+ spins in this pyrochlore. In contrast, the pyrochlore Sm2Zr2O7 is characterized by a relatively large value of Sm-Sm spin exchange (θcw∼−10 K); however, long-range ordering of the Sm3+ spins is not established at least down to T=0.67 K due to frustration of the Sm3+ spins on the pyrochlore lattice. The ground state of Sm3+ ions in both pyrochlores is a well-isolated Kramers doublet. The higher-lying crystal field excitations are observed in the low-frequency region of the Raman spectra of the two compounds recorded at T=10 K. At higher temperatures, the magnetic susceptibility of Sm2Ti2O7 shows a broad maximum at T=140 K, while that of Sm2Zr2O7 changes monotonically. Whereas Sm2Ti2O7 is a promising candidate for investigating spin fluctuations on a frustrated lattice, as indicated by our data, the properties of Sm2Zr2O7 seem to conform to a conventional scenario where geometrical frustration of the spin excludes their long-range ordering.

Microwave-Assisted Synthesis of NiO Nanoparticles

NiO has been synthesized by microwave-induced chemical synthesis route using metalorganic complex of nickel in a domestic-type microwave oven (2.45 GHz). A novel metalorganic complex of nickel, viz., a beta-ketoester of nickel, synthesized and characterized as apart of this work, was employed as the precursor material. We varied the experimental parameters, such as the choice of solvent and microwave power, to obtain nanoparticles of NiO. The NiO nanoparticles were characterized by XRD, SEM, and TEM. The particle size of the NiO was found to vary from 7-40 nm. The magnetic behavior of the nanoparticles of NiO was examined with a vibrating sample magnetometer, revealing that as the particle size diminishes, the magnetic ordering in NiO changes, leading to a small, measurable coercivity.

Magneto-transport and optical properties of diluted magnetic semiconductor Ga1-xMnxSb

We have studied magneto-transport and optical properties of Ga1-xMnxSb crystals (x = 0.01, 0.02, 0.03 and 0.04) grown by horizontal Bridgman method. Negative magnetoresistance and anomalous Hall effect have been observed below 10K. Temperature dependence of magnetization measurement shows a magnetic ordering below 10K which could arise from Ga1-xMnxSb alloy formation. Also, saturation in magnetization observed even at room temperature suggests the existence of ferromagnetic MnSb clusters. Reduction in band gap is observed with increasing Mn concentration in the crystals. Temperature dependence of band gap follows Bose-Einstein's model.

Quantum spin nematics, dimerization, and deconfined criticality in Quasi-1D spin-one magnets

We study theoretically the destruction of spin nematic order due to quantum fluctuations in quasi-one-dimensional spin-1 magnets. If the nematic ordering is disordered by condensing disclinations, then quantum Berry phase effects induce dimerization in the resulting paramagnet. We develop a theory for a Landau-forbidden second order transition between the spin nematic and dimerized states found in recent numerical calculations. Numerical tests of the theory are suggested.

Random existence of charge ordered stripes and its influence on the magnetotransport properties of La0.6Sr0.4MnO3 perovskite substituted with diamagnetic ions at Mn sublattice

Phase-singular solid solutions of La0.6Sr0.4Mn1-yMeyO3 (0 <= y <= 0.3) [Me=Li1+, Mg2+, Al3+, Ti4+, Nb5+, Mo6+ or W6+] [LSMey] perovskite of rhombohedral symmetry (space group: R (3) over barc) have been prepared wherein the valence of the diamagnetic substituent at Mn site ranged from 1 to 6. With increasing y-content in LSMey, the metal-insulator (TM-I) transition in resistivity-temperature rho(T) curves shifted to low temperatures. The magnetization studies M(H) as well as the M(T) indicated two groups for LSMey. (1) Group A with Me=Mg, Al, Ti, or Nb which are paramagnetic insulators (PIs) at room temperature with low values of M (< 0.5 mu(B)/Mn); the magnetic transition [ferromagnetic insulator (FMI)-PI] temperature (T-C) shifts to low temperatures and nearly coincides with that of TM-I and the maximum magnetoresistance (MR) of similar to 50% prevails near T-C (approximate to TM-I). (2) Group-B samples with Me=Li, Mo, or W which are FMIs with M-s=3.3-3.58 mu(B)/Mn and marginal reduction in T-C similar to 350 K as compared to the undoped LSMO (T-C similar to 378 K). The latter samples show large temperature differences Delta T=T-c-TM-I, reaching up to similar to 288 K. The maximum MR (similar to 60%) prevails at low temperatures corresponding to the M-I transition TM-I rather than around T-C. High resolution lattice images as well as microscopy analysis revealed the prevalence of inhomogeneous phase mixtures of randomly distributed charge ordered-insulating (COI) bistripes (similar to 3-5 nm width) within FMI charge-disordered regions, yet maintaining crystallographically single phase with no secondary precipitate formation. The averaged ionic radius < r(B)>, valency, or charge/radius ratio < CRR > cannot be correlated with that of large Delta T; hence cannot be used to parametrize the discrepancy between T-C and TM-I. The M-I transition is controlled by the charge conduction within the electronically heterogeneous mixtures (COI bistripes+FMI charge disordered); large MR at TM-I suggests that the spin-ordered FM-insulating regions assist the charge transport, whereas the T-C is associated with the bulk spin ordered regions corresponding to the FMI phase of higher volume fraction of which anchors the T-C to higher temperatures. The present analysis showed that the double-exchange model alone cannot account for the wide bifurcation of the magnetic and electric transitions, contributions from the charge as well as lattice degrees of freedom to be separated from spin/orbital ordering. The heterogeneous phase mixtures (COI+FMI) cannot be treated as of granular composite behavior. (c) 2008 American Institute of Physics.

Understanding Membranes through the Molecular Design of Lipids

Lipids are amphiphilic molecules that are composed of hydrophilic and hydrophobic regions. A typical membranous aggregate (vesicles, water-filled lipid nanospheres) is formed upon the self-organization of lipids in water from a diverse collection of amphiphiles producing a dynamic supramolecular structure that shows phase behavior and ordering as required for specific biological functions. The determination of various physical properties of lipid aggregates is the key to determining structure-function relationships. Over the years, we have designed and synthesized a wide variety of lipid molecular systems for the investigation of their membrane-forming properties and have used them for purposes such as gene delivery and enzyme activation. In this feature article, we focus on our work on various types of lipids including ion-paired amphiphiles, cholesterol-based lipids, aromatic lipids, macrocyclic lipids containing disulfide tethers; cationic dimeric lipids, and so forth. The emphasis is oil experimental design and bottom-line conclusions.

Stochastic simulations of the origins and implications of long-tailed distributions in gene expression

Gene expression noise results in protein number distributions ranging from long-tailed to Gaussian. We show how long-tailed distributions arise from a stochastic model of the constituent chemical reactions and suggest that, in conjunction with cooperative switches, they lead to more sensitive selection of a subpopulation of cells with high protein number than is possible with Gaussian distributions. Single-cell-tracking experiments are presented to validate some of the assumptions of the stochastic simulations. We also examine the effect of DNA looping on the shape of protein distributions. We further show that when switches are incorporated in the regulation of a gene via a feedback loop, the distributions can become bimodal. This might explain the bimodal distribution of certain morphogens during early embryogenesis.

Correlation of structural disorder with the reversible discharge capacity of nickel hydroxide electrode

Hydrothermal treatment of a slurry of badly crystalline (beta(bc)) nickel hydroxide at different temperatures (65-170 degrees C) results in the progressive ordering of the structure by the step-wise elimination of disorders. Interstratification is eliminated at 140 degrees C, while cation vacancies are eliminated at 170 degrees C. A small percentage of stacking faults continue to persist even in `crystalline' samples. Electrochemical investigations show that the crystalline nickel hydroxide has a very low (0.4 e/Ni) reversible charge storage capacity. An incidence of at least 15% stacking faults combined with cation vacancies is essential for nickel hydroxide to perform close to its theoretical (1 e/ Ni) discharge capacity. (c) 2005 The Electrochemical Society.

Infrared absorption spectra of single crystals of glycine silver nitrate and monoglycine nitrate

he infrared absorption spectra of glycine silver nitrate (GAgNO3) and glycine nitrate (GHNO3) show that the glycine group exists completely in the zwitter ion form in the former and in both forms in the latter. The spectrum of GAgNO3 at liquid air temperature did not reveal any striking change which can be attributed to a freezing of the rapid reorientation of the NH3+ group taking place at higher temperatures. The position of the COO− stretching frequencies indicate that this group is co-ordinated only weakly to the Ag+ ion. The summation frequencies reported by Schroeder, Wier and Lippincott (1962) for AgNO3 were not observed in the present study on GAgNO3. It shows however that ferroelectricity in GAgNO3 is in all probability due to the motion of the Ag+ ion in the oxygen co-ordination polyhedron and is not directly connected with the ordering of the hydrogen bonds below Curie point.

ESR and optical absorption studies in copper diethyldithiocarbamate

ESR investigations at X band and optical-absorption measurements have been reported in single crystals of copper (n) diethyldithiocarbamate Cu[S 2CN(C2H5)2]2 diluted to 0.2% with the corresponding zinc complex. The measurements have been made both at room and liquid-oxygen temperatures. ESR measurements gave the following values for the parameters in spin Hamiltonian g11=2.1085, g=2.023(6), A63= 142.4×10-4 cm-1, A65 = 152.0×10-4 cm-1, B = 22.4×10-4 cm-1, Q~3×10-4 cm-1. Polarized optical absorption study has made possible a proper assignment of the absorption bands to their corresponding transitions. This has led to information regarding the ordering of the MO levels of the complex. The coefficients used in the MO description of the complex have been calculated from the observed parameters. The results show that the metal ligand BIσ bond is purely covalent and that the out-of-plane w bonding is appreciably covalent whereas the in-plane Π bonding is ionic. Further, it is noted that the metal ligand binding is more covalent with sulfur as ligand than with oxygen or nitrogen.

Detoxication of benzoate by glycine conjugation in the silkworm, Bombyx mori L

The role of hippuric acid formation as a mechanism for detoxication of benzoic acid in the silkworm has been investigated. Benzoate is inhibitory to the growth of the silkworm and excreted as hippuric acid, which is not toxic. Hippuric acid is not a normal constituent of excreta. Synthesis of hippuric acid has been shown to occur in the intestines of the silkworm. Hippuricase activity is present in the fat body and silk-gland tissue.

Intracellular distribution of coenzyme Q in rat liver

Coenzyme Q was found to be distributed in rat liver cell fractions. Mitochondria accounted for only 40–60% of the total. The presence of coenzyme Q in nuclei, isolated by several methods, could always be correlated with the presence of oxidative enzymes. It has been established that coenzyme Q is a constituent of microsomes. Administered coenzyme Q10-C14 was preferentially taken up by mitochondrial and microsomal fractions. Exogenous coenzyme Q appears to be rapidly metabolized.

Ultrasonic studies in chemically active liquid media (1) aqueous solution of N2O4

Using a pulse method the ultrasonic absorption has been studied in the frequency range of 2 to 10 Mc/s in dilute aqueous solutions of nitrogen tetroxide gas at room temperature. The absorption peaks (αλ vs frequency) observed in this study are attributed to the ionic dissociation reaction of the nitrous acid into its constituent ions. The rate constants of the forward and backward reactions are calculated using the theory of Tabuchi. The variation of the logarithm of the rate constant of the bimolecular ionic reaction, namely, log10 kb, with the square root of ionic strength qualitatively follows Brönsted's theory for ionic reactions in solutions.

Intrinsic Electron localization in manganites

We mention here an unusual disorder effect in manganites, namely the ubiquitous hopping behavior for electron transport observed in them over a wide range of doping. We argue that the implied Anderson localization is intrinsic to manganites, because of the existence of polarons in them which are spatially localized, generally at random sites (unless there is polaron ordering). We have developed a microscopic two fluid lb model for manganites, where l denotes lattice site localized l polarons, and b denotes band electrons. Using this, and the self-consistent theory of localization, we show that the occupied b states are Anderson localized in a large range of doping due to the scattering of b electrons from l polarons. Numerical simulations which further include the effect of long range Coulomb interactions support this, as well the existence of a novel polaronic Coulomb glass. A consequence is the inevitable hopping behaviour for electron transport observed in doped insulating manganites.