Thermodynamic properties of Ln-O (Ln = La, Pr, Nd) solid solutions and their deoxidation by molten salt electrolysis

The lanthanide metals lanthanum, praseodymium and neodymium containing 2,200, 2,600, 1,850 mass ppm oxygen, respectively, were deoxidized to 20-30 ppm level at 1,073 K by an electrochemical method. The metal to be deoxidized was used as the cathode in an electrolysis cell which consisted of a graphite anode and molten CaCl2 electrolyte. The calcium metal produced at the cathode by electrolysis effectively deoxidized the lanthanide metal. Calcium oxide produced by deoxidation, dissolved in the melt. The liberation of carbon monoxide/dioxide at the anode was found to prevent accumulation of oxygen in the melt. For a quantitative discussion of the limits of deoxidation achievable by this technique, a thermodynamic investigation of the lanthanide-oxygen (Ln-O ; Ln = La, Pr, Nd) solid solutions was conducted. The lanthanide metal, yttrium and titanium samples were immersed in calcium-saturated CaCl2 melt, containing a small quantity of dissolved CaO, at 1,093 K. The oxygen potential of the melt and the Ln-O solid solutions were obtained from the oxygen content of yttrium samples at equilibrium, and the known thermodynamic properties of yttrium-oxygen solid solution. The results were confirmed by using Y/Y2O3 equilibrium to control the oxygen potential of the molten salt reservoir. The oxygen affinity of the metals was found to decrease in the order : Y > Ti > Nd > Pr > La. The deoxidation results are consistent with the thermodynamic properties of the RE-O solid solutions.

Phase relations in the system Cu-La-O and thermodynamic properties of CuLaO2 and CuLa2O4

Phase relations in the system Cu-La-O at 1200 K have been determined by equilibrating samples of different average composition at 1200 K, and phase analysis of quenched samples using optical microscopy, XRD, SEM and EDX. The equilibration experiments were conducted in evacuated ampoules, and under flowing inert gas and pure oxygen. There is only one stable binary oxide La2O3 along the binary La-O, and two oxides Cu2O and CuO along the binary Cu-O. The Cu-La alloys were found to be in equilibrium with La2O3. Two ternary oxides CuLaO2 and CuLa2O4+

La-Doped Ba2In2O5 Electrolyte: Pechini Synthesis, Microstructure, Electrical Conductivity, and Application for CO Gas Sensing

Dense (Ba1―xLax)2In2O5+x (BLIO) electrolytes with different compositions (x = 0.4, 0.5, 0.6) were fabricated using powders obtained by the Pechini method. The formation of BLIO powders was investigated by using X-ray diffraction and scanning electron microscopy coupled with energy-dispersive X-ray spectroscopy. The calcination temperature and time were optimized. The sintered (Ba1―xLax)2In2O5+x electrolytes showed a relative density greater than ∼97%, and the major phase of three electrolyte compositions was indexed as a cubic perovskite. The electrical conductivity of BLIO ceramics at elevated temperatures in air was measured by ac-impedance spectroscopy. The activation energies for conduction in BLIO were 102 kJ mol―1 between 473 and 666 K and 118 kJ mol―1 between 769 and 873 K, which are comparable to that for 8 mol % yttria-stabilized cubic zirconia. Mixed-potential gas sensors utilizing BLIO-based electrolytes exhibited good sensitivity to different CO concentrations from ∼100 to ∼500 ppm and excellent selectivity to methane at around 873 K.

Reactive interdiffusion: deviation from local equilibrium in the Fe-NiTiO3 couple

Deviation from local equilibrium between Fe–Ni alloy and (Fe,Ni)TiO3 solid solution in the reaction–diffusion zone of the Fe–NiTiO3 couple at 1273 K is evaluated by comparing the measured compositions in the zone with experimentally determined equilibrium tie-lines. The deviation is quantified by computing the Gibbs energy change for the reaction, Fe + NiTiO3 → FeTiO3 + Ni, from measured compositions in the zone and activity data available in the literature. Except near the extremities of the zone, the computed Gibbs energy change is constant, 8.2 kJ mol−1 higher than the standard Gibbs energy change for the reaction.

Large reduction of leakage current by graded-layer La doping in (Ba0.5, Sr0.5)TiO3 thin films

A large reduction in the leakage current behavior in (Ba, Sr)TiO3 (BST) thin films was observed by graded-layer donor doping. The graded doping was achieved by introducing La-doped BST layers in the grown BST films. The films showed a large decrease (about six orders of magnitude) in the leakage current in comparison to undoped films at an electric field of 100 kV/cm. The large decrease in leakage current was attributed to the formation of highly resistive layers, originating from compensating defect chemistry involved for La-doped films grown in oxidizing environment. Temperature-dependent leakage-current behavior was studied to investigate the conduction mechanism and explanations of the results were sought from Poole–Frenkel conduction mechanism.

Colossal magnetoresistance in epitaxial La(1-x-y)NayMnO3 thin film

We have synthesized La0.83Na0.11MnO2.93 by heating La2O3 and MnCO3 in NaCl melt at 900 °C. The exact composition was arrived by analyzing each ion by an independent chemical method. The compound crystallized in a rhombohedral structure and showed an insulator-to-metal transition at 290 K. Epitaxial thin films were fabricated on LaAlO3 (100) using a pulsed laser deposition technique. The film also showed an insulator-to-metal transition at 290 K. Magnetoresistance [ΔR/R0 = (RH−R0)/R0] was −71% near the insulator-to-metal transition temperature of 290 K at 6 T magnetic field.

Enhancement of charge and energy storage in sol-gel derived pure and La-modified PbZrO3 thin films

Antiferroelectric lanthanum-modified PbZrO3 thin films with La contents between 0 and 6 at. % have been deposited on Pt(111)/Ti/SiO2/Si substrate by sol-gel route. On the extent of La-modification, maximum polarization (Pmax) and recoverable energy density (W) have been enhanced followed by their subsequent reduction. A maximum Pmax ( ∼ 0.54 C/m2 at ∼ 60 MV/m) as well as a maximum W ( ∼ 14.9 J/cc at ∼ 60 MV/m) have been achieved on 5% La modification. Both Pmax and W have been found to be strongly dependent on La-induced crystallographic orientations.

Dielectric properties of (110) oriented PbZrO3 and La-modified PbZrO3 thin films grown by sol-gel process on Pt(111)/Ti/SiO2/Si substrate

Highly (110) preferred orientated antiferroelectric PbZrO3 (PZ) and La-modified PZ thin films have been fabricated on Pt/Ti/SiO2/Si substrates using sol-gel process. Dielectric properties, electric field induced ferroelectric polarization, and the temperature dependence of the dielectric response have been explored as a function of composition. The Tc has been observed to decrease by ∼ 17 °C per 1 mol % of La doping. Double hysteresis loops were seen with zero remnant polarization and with coercive fields in between 176 and 193 kV/cm at 80 °C for antiferroelectric to ferroelectric phase transformation. These slim loops have been explained by the high orientation of the films along the polar direction of the antiparallel dipoles of a tetragonal primitive cell and by the strong electrostatic interaction between La ions and oxygen ions in an ABO3 perovskite unit cell. High quality films exhibited very low loss factor less than 0.015 at room temperature and pure PZ; 1 and 2 mol % La doped PZs have shown the room temperature dielectric constant of 135, 219, and 142 at the frequency of 10 kHz. The passive layer effects in these films have been explained by Curie constants and Curie temperatures. The ac conductivity and the corresponding Arrhenius plots have been shown and explained in terms of doping effect and electrode resistance.

Growth and consumption rates of the phase layers during interdiffusion in a diffusion couple with finite end member

The relations for the growth and consumption rates of a layer with finite thickness as an end member and the product phases in the interdiffusion zone are developed. We have used two different methodologies, the diffusion based and the physico-chemical approach to develop the same relations. We have shown that the diffusion based approach is rather straightforward; however, the physico-chemical approach is much more versatile than the other method. It was found that the position of the marker plane becomes vague in the second stage of the interdiffusion process in pure A thin layer/B couple, where two phases grow simultaneously.

Effect of AC&DC field on the dielectric response of (Pb,La)TiO3 thin films

Lanthanum doped lead titanate thin films are the potential candidates for the capacitors, actuators and pyroelectric sensor applications due to their excellent dielectric, and ferroelectric properties. Lanthanum doped lead titanate thin films are grown on platinum coated Si substrates by excimer laser ablation technique. A broad diffused phase transition with the maximum dielectric permittivity (ϵmax) shifting to higher temperatures with the increase of frequency, along with frequency dispersion below Tc, which are the signatures of the relaxor like characteristics were observed. The dielectric properties are investigated from −60°C to 200°C with an application of different dc fields. With increasing dc field, the dielectric constant is observed to reduce and phase transition temperature shifted to higher temperature. With the increased ac signal amplitude of the applied frequency, the magnitude of the dielectric constant is increasing and the frequency dispersion is observed in ferroelectric phase, whereas in paraelectric phase, there is no dispersion has been observed. The results are correlated with the existing theories.

A cyclic peptide mimic of an RNA recognition motif of human La protein is a potent inhibitor of hepatitis C virus

Due to limited available therapeutic options, developing new lead compounds against hepatitis C virus is an urgent need. Human La protein stimulates hepatitis C virus translation through interaction with the hepatitis C viral RNA. A cyclic peptide mimicking the beta-turn of the human La protein that interacts with the viral RNA was synthesized. It inhibits hepatitis C viral RNA translation significantly better than the corresponding linear peptide at longer post-treatment times. The cyclic peptide also inhibited replication as measured by replicon RNA levels using real time RT-PCR. The cyclic peptide emerges as a promising lead compound against hepatitis C.

Human la protein interaction with GCAC near the initiator AUG enhances hepatitis C virus RNA replication by promoting linkage between 5 ` and 3 ` untranslated regions

Human La protein has been implicated in facilitating the internal initiation of translation as well as replication of hepatitis C virus (HCV) RNA. Previously, we demonstrated that La interacts with the HCV internal ribosome entry site (IRES) around the GCAC motif near the initiator AUG within stem-loop IV by its RNA recognition motif (RRM) (residues 112 to 184) and influences HCV translation. In this study, we have deciphered the role of this interaction in HCV replication in a hepatocellular carcinoma cell culture system. We incorporated mutation of the GCAC motif in an HCV monocistronic subgenomic replicon and a pJFH1 construct which altered the binding of La and checked HCV RNA replication by reverse transcriptase PCR (RT-PCR). The mutation drastically affected HCV replication. Furthermore, to address whether the decrease in replication is a consequence of translation inhibition or not, we incorporated the same mutation into a bicistronic replicon and observed a substantial decrease in HCV RNA levels. Interestingly, La overexpression rescued this inhibition of replication. More importantly, we observed that the mutation reduced the association between La and NS5B. The effect of the GCAC mutation on the translation-to-replication switch, which is regulated by the interplay between NS3 and La, was further investigated. Additionally, our analyses of point mutations in the GCAC motif revealed distinct roles of each nucleotide in HCV replication and translation. Finally, we showed that a specific interaction of the GCAC motif with human La protein is crucial for linking 5' and 3' ends of the HCV genome. Taken together, our results demonstrate the mechanism of regulation of HCV replication by interaction of the cis-acting element GCAC within the HCV IRES with human La protein.

Combining indentation and diffusion couple techniques for combinatorial discovery of high temperature shape memory alloys

We demonstrate the possibility of accelerated identification of potential compositions for high-temperature shape memory alloys (SMAs) through a combinatorial material synthesis and analysis approach, wherein we employ the combination of diffusion couple and indentation techniques. The former was utilized to generate smooth and compositionally graded inter-diffusion zones (IDZs) in the Ni-Ti-Pd ternary alloy system of varying IDZ thickness, depending on the annealing time at high temperature. The IDZs thus produced were then impressed with an indenter with a spherical tip so as to inscribe a predetermined indentation strain. Subsequent annealing of the indented samples at various elevated temperatures, T-a, ranging between 150 and 550 degrees C allows for partial to full relaxation of the strain imposed due to the shape memory effect. If T-a is above the austenite finish temperature, A(f), the relaxation will be complete. By measuring the depth recovery, which serves as a proxy for the shape recovery characteristic of the SMA, a three-dimensional map in the recovery temperature composition space is constructed. A comparison of the published Af data for different compositions with the Ta data shows good agreement when the depth recovery is between 70% and 80%, indicating that the methodology proposed in this paper can be utilized for the identification of promising compositions. Advantages and further possibilities of this methodology are discussed.

En Masse relay selection algorithms for multi-source, multi-relay, decode-and-forward cooperative systems

Opportunistic relay selection in a multiple source-destination (MSD) cooperative system requires quickly allocating to each source-destination (SD) pair a suitable relay based on channel gains. Since the channel knowledge is available only locally at a relay and not globally, efficient relay selection algorithms are needed. For an MSD system, in which the SD pairs communicate in a time-orthogonal manner with the help of decode-and-forward relays, we propose three novel relay selection algorithms, namely, contention-free en masse assignment (CFEA), contention-based en masse assignment (CBEA), and a hybrid algorithm that combines the best features of CFEA and CBEA. En masse assignment exploits the fact that a relay can often aid not one but multiple SD pairs, and, therefore, can be assigned to multiple SD pairs. This drastically reduces the average time required to allocate an SD pair when compared to allocating the SD pairs one by one. We show that the algorithms are much faster than other selection schemes proposed in the literature and yield significantly higher net system throughputs. Interestingly, CFEA is as effective as CBEA over a wider range of system parameters than in single SD pair systems.

Specific Sequence of a Beta Turn in Human La Protein May Contribute to Species Specificity of Hepatitis C Virus

Human La protein is known to be an essential host factor for translation and replication of hepatitis C virus (HCV) RNA. Previously, we have demonstrated that residues responsible for interaction of human La protein with the HCV internal ribosomal entry site (IRES) around the initiator AUG within stem-loop IV form a beta-turn in the RNA recognition motif (RRM) structure. In this study, sequence alignment and mutagenesis suggest that the HCV RNA-interacting beta-turn is conserved only in humans and chimpanzees, the species primarily known to be infected by HCV. A 7-mer peptide corresponding to the HCV RNA-interacting region of human La inhibits HCV translation, whereas another peptide corresponding to the mouse La sequence was unable to do so. Furthermore, IRES-mediated translation was found to be significantly high in the presence of recombinant human La protein in vitro in rabbit reticulocyte lysate. We observed enhanced replication with HCV subgenomic and full-length replicons upon overexpression of either human La protein or a chimeric mouse La protein harboring a human La beta-turn sequence in mouse cells. Taken together, our results raise the possibility of creating an immunocompetent HCV mouse model using human-specific cell entry factors and a humanized form of La protein.