Ion exchange equilibria between (Mn,Co)O solid solution and (Mn,Co)Cr2O4 and (Mn,Co)Al2O4 spinel solid solutions at 1100oC

The compositions of the (Mn,Co)O solid solution with rock salt structure in equilibrium with (Mn,Co)Cr2O4 and (Mn,Co)Al2O4 spinel solid solutions have been determined by X-ray diffraction measurements at 1100° C and an oxygen partial pressure of 10–10 atm. The ion exchange equilibria are quantitatively analysed, using values for activities in the (Mn,Co)O solid solution available in the literature, in order to obtain activities in the spinel solid solutions. The MnAl2O4-CoAl2O4 solid solution exhibits negative deviations from Raoult's law, consistent with the estimated cation disorder in the solid solution, while the MnCr2O4-CoCr2O4 solid solution shows slightly positive deviations. The difference in the Gibbs free energy of formation of the two pure chromites and aluminates derived from the results of this study are in good agreement with recent results obtained from solid oxide galvanic cells and gas-equilibrium techniques.

Inter and intra crystalline ion exchange equilibria in the system Fe Cr Al O

The tie lines delineating ion-exchange equilibria between FeCr2O4FeAl2O4 spinel solid solution and Cr2O3Al2O3 solid solution with corundum structure have been determined at 1373 K by electron microprobe and EDAX point count analysis of oxide phases equilibrated with metallic iron. Activities in the spinel solid solution are derived from the tie lines and the thermodynamic data on Cr2O3Al2O3 solid solution available in the literature. The oxygen potentials corresponding to the tie-line composition of oxide phases in equilibrium with metallic iron were measured using solid oxide galvanic cells with CaOZrO2 and Y2O3ThO2 electrolytes. These electrochemical measurements also yield activities in the spinel solid solution, in good agreement with those obtained from tie lines. The activity-composition relationship in the spinel solid solution is analysed in terms of the intra-crystalline ion exchange between the tetrahedral and octahedral sites of the spinel structures. The ion exchange is governed by site-preference energies of the cations and the entropy of cations mixing on each site.

On the magnetization reversal of the oxide-based exchange spring magnet

The role of the soft phase (Ni0.8Zn0.2Fe2O4) on the magnetization reversal and coercivity mechanism of the Ni0.8Zn0.2Fe2O4/BaFe12O19 nanocomposite has been investigated. The presence of the interacting field and the disorder in the nanocomposite has been confirmed by the variation of Jr/Jr(∞) vs Jd/Jr(∞) and the irreversible magnetization. To understand the relative strength of the pinning and the nucleation, the magnetic viscosity measurement has been done and the thermal activation volume has been estimated. From the Barbier plot and the activation volume measurement, the dominant mechanism governing the magnetization reversal process has been proposed.

Gold(I)-selenolate complexes: Synthesis, characterization and ligand exchange reactions

In this paper, the synthesis and characterization of some imidazole-based gold-selenolates are described. This study indicates that the nature of selenolate plays an important role in ligand exchange reactions in gold(I) selenolates. Furthermore, the reactivity of imidazole-based gold(I) selenolates toward nucleophiles such as selenols and phosphines is strikingly different from that of the N,N-dimethylaminobenzylamine-based gold(I) complexes. The presence of Se ... N non-bonded interactions in N,N-dimethylaminobenzylamine-based gold(I) complexes modulates the reactivity of Au(I) centre towards incoming nucleophiles.

Low temperature synthesis of layered NaxCoO2 and KxCoO2 from NaOH/KOH fluxes and their ion exchange properties

We report a low temperature synthesis of layered Na0×20CoO2 and K0×44CoO2 phases from NaOH and KOH fluxes at 400°C. These layered oxides are employed to prepare hexagonal HCoO2, LixCoO2 and Delafossite AgCoO2 phases by ion exchange method. The resulting oxides were characterised by powder X-ray diffraction, X-ray photoelectron spectroscopy, SEM and EDX analysis. Final compositions of all these oxides are obtained from chemical analysis of elements present. Na0×20CoO2 oxide exhibits insulating to metal like behaviour, whereas AgCoO2 is semiconducting.

Density matrix renormalization group algorithm for Bethe lattices of spin-1/2 or spin-1 sites with Heisenberg antiferromagnetic exchange

A density matrix renormalization group (DMRG) algorithm is presented for the Bethe lattice with connectivity Z = 3 and antiferromagnetic exchange between nearest-neighbor spins s = 1/2 or 1 sites in successive generations g. The algorithm is accurate for s = 1 sites. The ground states are magnetic with spin S(g) = 2(g)s, staggered magnetization that persists for large g > 20, and short-range spin correlation functions that decrease exponentially. A finite energy gap to S > S(g) leads to a magnetization plateau in the extended lattice. Closely similar DMRG results for s = 1/2 and 1 are interpreted in terms of an analytical three-site model.

Oscillatory exchange bias and training effects in nanocrystalline Pr0.5Ca0.5MnO3

We report on exchange bias effects in 10 nm particles of Pr0.5Ca0.5MnO3 which appear as a result of competing interactions between the ferromagnetic (FM)/anti-ferromagnetic (AFM) phases. The fascinating new observation is the demonstration of the temperature dependence of oscillatory exchange bias (OEB) and is tunable as a function of cooling field strength below the SG phase, may be attributable to the presence of charge/spin density wave (CDW/SDW) in the AFM core of PCMO10. The pronounced training effect is noticed at 5 K from the variation of the EB field as a function of number of field cycles (n) upon the field cooling (FC) process. For n > 1, power-law behavior describes the experimental data well; however, the breakdown of spin configuration model is noticed at n >= 1. Copyright 2012 Author(s). This article is distributed under a Creative Commons Attribution 3.0 Unported License. http://dx.doi.org/10.1063/1.3696033]

Charge order suppression, emergence of ferromagnetism and absence of exchange bias effect in Bi0.25Ca0.75MnO3 nanoparticles: Electron paramagnetic resonance and magnetization studies

We report the results of magnetization and electron paramagnetic resonance (EPR) studies on nanoparticles (average diameter similar to 30 nm) of Bi0.25Ca0.75MnO3 (BCMO) and compare them with the results on bulk BCMO. The nanoparticles were prepared using the nonaqueous sol-gel technique and characterized by XRD and TEM analysis. Magnetization measurements were carried out with a commercial physical property measurement system (PPMS). While the bulk BCMO exhibits a charge ordering transition at similar to 230 K and an antiferromagnetic (AFM) transition at similar to 130 K, in the nanoparticles, the CO phase is seen to have disappeared and a transition to a ferromagnetic (FM) state is observed at T-c similar to 120 K. However, interestingly, the exchange bias effect observed in other nanomanganite ferromagnets is absent in BCMO nanoparticles. EPR measurements were carried out in the X-band between 8 and 300 K. Lineshape fitting to a Lorentzian with two terms (accounting for both the clockwise and anticlockwise rotations of the microwave field) was employed to obtain the relevant EPR parameters as functions of temperature. The results confirm the occurrence of ferromagnetism in the nanoparticles of BCMO. (C) 2012 American Institute of Physics. http://dx.doi.org/10.1063/1.4730612]

A Rare Phenoxido/Acetato/Azido Bridged Trinuclear and an Unprecedented Phenoxido/Azido Bridged One-Dimensional Polynuclear Nickel(II) Complexes: Synthesis, Crystal Structure, and Magnetic Properties with Theoretical Investigations on the Exchange Mechanism

The reaction of a tridentate Schiff base ligand HL (2-(3-dimethylaminopropylimino)-methyl]-phenol) with Ni(II) acetate or perchlorate salts in the presence of azide as coligand has led to two new Ni(II) complexes of formulas Ni3L2(OAc)(2)(mu(1,1)-N-3)(2)(H2O)(2)]center dot 2H(2)O (1) and Ni2L2(mu(1,1)-N-3) (mu(1,3)-N-3)](n)(2). Single crystal X-ray structures show that complex 1 is a linear trinuclear Ni(II) compound containing a mu(2)-phenwddo, an end-on (EO) azido and a syn-syn acetato bridge between the terminal and the central Ni(II) ions. Complex 2 can be viewed as a one-dimensional (1D) chain in which the triply bridged (di-mu(2)-phenoxido and EO azido) dimeric Ni-2 units are linked to each other in a zigzag pattern by a single end-to-end (EE) azido bridge. Variable-temperature magnetic susceptibility studies indicate the presence of moderate ferromagnetic exchange coupling in complex 1 with J value of 16.51(6) cm(-1). The magnetic behavior of 2 can be fitted in an alternating ferro- and antiferromagnetic model J(FM) = +34.2(2.8) cm(-1) and J(AF) = -21.6(1.1) cm(-1)] corresponding to the triple bridged dinuclear core and EE azido bridge respectively. Density functional theory (DFT) calculations were performed to corroborate the magnetic results of 1 and 2. The contributions of the different bridges toward magnetic interactions in both compounds have also been calculated.

Truthful multi-armed bandit mechanisms for multi-slot sponsored search auctions

In pay-per-click sponsored search auctions which are currently extensively used by search engines, the auction for a keyword involves a certain number of advertisers (say k) competing for available slots (say m) to display their advertisements (ads for short). A sponsored search auction for a keyword is typically conducted for a number of rounds (say T). There are click probabilities mu(ij) associated with each agent slot pair (agent i and slot j). The search engine would like to maximize the social welfare of the advertisers, that is, the sum of values of the advertisers for the keyword. However, the search engine does not know the true values advertisers have for a click to their respective advertisements and also does not know the click probabilities. A key problem for the search engine therefore is to learn these click probabilities during the initial rounds of the auction and also to ensure that the auction mechanism is truthful. Mechanisms for addressing such learning and incentives issues have recently been introduced. These mechanisms, due to their connection to the multi-armed bandit problem, are aptly referred to as multi-armed bandit (MAB) mechanisms. When m = 1, exact characterizations for truthful MAB mechanisms are available in the literature. Recent work has focused on the more realistic but non-trivial general case when m > 1 and a few promising results have started appearing. In this article, we consider this general case when m > 1 and prove several interesting results. Our contributions include: (1) When, mu(ij)s are unconstrained, we prove that any truthful mechanism must satisfy strong pointwise monotonicity and show that the regret will be Theta T7) for such mechanisms. (2) When the clicks on the ads follow a certain click precedence property, we show that weak pointwise monotonicity is necessary for MAB mechanisms to be truthful. (3) If the search engine has a certain coarse pre-estimate of mu(ij) values and wishes to update them during the course of the T rounds, we show that weak pointwise monotonicity and type-I separatedness are necessary while weak pointwise monotonicity and type-II separatedness are sufficient conditions for the MAB mechanisms to be truthful. (4) If the click probabilities are separable into agent-specific and slot-specific terms, we provide a characterization of MAB mechanisms that are truthful in expectation.

Structural and magnetic properties of SmCo5/Co exchange coupled nanocomposite thin films

We investigated the structural and magnetic properties of SmCo5/Co exchange coupled nanocomposite thin films grown by magnetron sputtering from Sm and Co multitargets successively. The growth of the films was carried out at elevated substrate temperature followed by in situ annealing. On Si (100) substrate, X-ray diffraction confirms the formation of textured (110) SmCo5 hard phase, whereas on MgO (110) substrate, the diffraction pattern shows the epitaxial growth of SmCo5 phase with crystalline orientation along 100] direction. Secondary Ion Mass Spectroscopy reveals the structural transformation from multilayered (Sm/Co) to SmCo5/Co nano-composite films due to high reactivity of Sm at elevated temperature. Transmission electron microscopy indicates the existence of nanocrystalline phase of SmCo5 along with unreacted Co. Observed single phase behavior in magnetic hysteresis measurements indicates well exchange coupling between the soft and the hard phases in these nano-composite films. For samples with samarium layer thickness, t(sm)=3.2 nm and cobalt layer thickness, t(Co)= 11.4 nm, the values of (BH)(max) were obtained as 20.1 MGOe and 12.38 MGOe with H-c value similar to 3.0 kOe grown on MgO and Si substrates, respectively.

Exchange-spring mechanism of soft and hard ferrite nanocomposites

The paper reports exchange-spring soft and hard ferrite nanocomposites synthesized by chemical co-precipitation with or without the application of ultrasonic vibration. The composites contained BaFe12O19 as the hard phase and CoFe2O4/MgFe2O4 as the soft phase. X-ray diffraction patterns of the samples in the optimum calcined condition indicated the presence of soft ferrites as face-centred cubic (fcc) and hard ferrites as hexagonal close packed (hcp) structure respectively. Temperature dependence of magnetization in the range of 20-700 degrees C demonstrated distinct presence of soft and hard ferrites as magnetic phases which are characterized by wide difference in magnetic anisotropy and coercivity. Exchange-spring mechanism led these nanocomposite systems to exchange-coupled, which ultimately produced convex hysteresis loops characteristic of a single-phase permanent magnet. Fairly high value of coercivity and maximum energy product were observed for the samples in the optimum calcined conditions with a maximum applied field of 1600 kA/m (2 T).

Suppression Of Barkhausen Noise Due To Exchange Biasing In Fe-FeMn Bilalayers

Exchange biased Fe(FM)-FeMn(AFM) bilayers were grown by pulsed laser ablation in UHV and probed by SQUID magnetometer and planar Hall effect measurements. A suppression of barkhausen avalanches was observed during the switching of the bilayer when compared to that of pure Fe, which is indicative of a change in the reversal mechanism.

Mechanism design for green, truthful procurement auctions

Auction based mechanisms have become popular in industrial procurement settings. These mechanisms minimize the cost of procurement and at the same time achieve desirable properties such as truthful bidding by the suppliers. In this paper, we investigate the design of truthful procurement auctions taking into account an additional important issue namely carbon emissions. In particular, we focus on the following procurement problem: A buyer wishes to source multiple units of a homogeneous item from several competing suppliers who offer volume discount bids and who also provide emission curves that specify the cost of emissions as a function of volume of supply. We assume that emission curves are reported truthfully since that information is easily verifiable through standard sources. First we formulate the volume discount procurement auction problem with emission constraints under the assumption that the suppliers are honest (that is they report production costs truthfully). Next we describe a mechanism design formulation for green procurement with strategic suppliers. Our numerical experimentation shows that emission constraints can significantly alter sourcing decisions and affect the procurement costs dramatically. To the best of our knowledge, this is the first effort in explicitly taking into account carbon emissions in planning procurement auctions.