Structure of Ce1-xSnxO2 and its relation to oxygen storage property from first-principles analysis

CeO2-SnO2 solid solution has been reported to possess high oxygen storage/release property which possibly originates from local structural distortion. We have performed first-principles based density functional calculations of Ce1-xSnxO2 structure (x=0, 0.25, 0.5, 1) to understand its structural stability in fluorite in comparison to rutile structure of the other end-member SnO2, and studied the local structural distortion induced by the dopant Sn ion. Analysis of relative energies of fluorite and rutile phases of CeO2, SnO2, and Ce1-xSnxO2 indicates that fluorite structure is the most stable for Ce1-xSnxO2 solid solution. An analysis of local structural distortions reflected in phonon dispersion show that SnO2 in fluorite structure is highly unstable while CeO2 in rutile structure is only weakly unstable. Thus, Sn in Ce1-xSnxO2-fluorite structure is associated with high local structural distortion whereas Ce in Ce1-xSnxO2-rutile structure, if formed, will show only marginal local distortion. Determination of M-O (M=Ce or Sn) bond lengths and analysis of Born effective charges for the optimized structure of Ce1-xSnxO2 show that local coordination of these cations changes from ideal eightfold coordination expected of fluorite lattice to 4+4 coordination, leading to generation of long and short Ce-O and Sn-O bonds in the doped structure. Bond valence analyses for all ions show the presence of oxygen with bond valence similar to 1.84. These weakly bonded oxygen ions are relevant for enhanced oxygen storage/release properties observed in Ce1-xSnxO2 solid solution. (C) 2010 American Institute of Physics.

Relationship between Low Strain Shear Modulus and Standard Penetration Test N Values

A low strain shear modulus plays a fundamental role in the estimation of site response parameters In this study an attempt has been made to develop the relationships between standard penetration test (SPT) N values with the low strain shear modulus (G(max)) For this purpose, field experiments SPT and multichannel analysis of surface wave data from 38 locations in Bangalore, India, have been used, which were also used for seismic microzonation project The in situ density of soil layer was evaluated using undisturbed soil samples from the boreholes Shear wave velocity (V-s) profiles with depth were obtained for the same locations or close to the boreholes The values for low strain shear modulus have been calculated using measured V-s and soil density About 215 pairs of SPT N and G(max) values are used for regression analysis The differences between fitted regression relations using measured and corrected values were analyzed It is found that an uncorrected value of N and modulus gives the best fit with a high regression coefficient when compared to corrected N and corrected modulus values This study shows better correlation between measured values of N and G(max) when compared to overburden stress corrected values of N and G(max)

Consideration on thermal decomposition of calcium hydroxide pellets for energy storage

The reversible chemical reaction of Ca(OH)2/CaO appears to be attractive for storage of solar thermal energy, in view of the nonpolluting and nontoxic nature of the reactants. This paper presents some data on thermal decomposition of calcium hydroxide pellets along with its additives of aluminum, aluminum hydroxide, zinc, and copper. The addition of aluminum and zinc powder enhanced the rate of decomposition considerably at 450°C, but copper had no effect. Considerations on the effect of additives are also discussed in some detail, though their effects are not established with certainty. There is some evidence that heat transfer into the pellet, and the number of potential nucleation sites due to thermal stresses, influence the kinetics and mechanism of decomposition.

Explicit Construction of Optimal Exact Regenerating Codes for Distributed Storage

Erasure coding techniques are used to increase the reliability of distributed storage systems while minimizing storage overhead. Also of interest is minimization of the bandwidth required to repair the system following a node failure. In a recent paper, Wu et al. characterize the tradeoff between the repair bandwidth and the amount of data stored per node. They also prove the existence of regenerating codes that achieve this tradeoff. In this paper, we introduce Exact Regenerating Codes, which are regenerating codes possessing the additional property of being able to duplicate the data stored at a failed node. Such codes require low processing and communication overheads, making the system practical and easy to maintain. Explicit construction of exact regenerating codes is provided for the minimum bandwidth point on the storage-repair bandwidth tradeoff, relevant to distributed-mail-server applications. A sub-space based approach is provided and shown to yield necessary and sufficient conditions on a linear code to possess the exact regeneration property as well as prove the uniqueness of our construction. Also included in the paper, is an explicit construction of regenerating codes for the minimum storage point for parameters relevant to storage in peer-to-peer systems. This construction supports a variable number of nodes and can handle multiple, simultaneous node failures. All constructions given in the paper are of low complexity, requiring low field size in particular.

Effect of Nanostructuring and Ex situ Amorphous Carbon Coverage on the Lithium Storage and Insertion Kinetics in Anatase Titania

Implications of nanostructuring and conductive carbon interface on lithium insertion/removal capacity and insertion kinetics innanoparticles of anatase polymorph of titania is discussed here.Sol-gel synthesized nanoparticles of titania (particle size similar to 6 nm) were hydrothermally coated ex situ with a thin layer of amorphous carbon (layer thickness: 2-5 nm) and calcined at a temperature much higher than the sol-gel synthesis temperature. The carbon-titania composite particles (resulting size similar to 10 nm) displayed immensely superior cyclability and rate capability (higher current rates similar to 4 g(-1)) compared to unmodified calcined anatase titania. The conductive carbon interface around titania nanocrystal enhances the electronic conductivity and inhibits crystallite growth during electrochemical insertion/removal thus preventing detrimental kinetic effects observed in case of unmodified anatase titania. The carbon coating of the nanoparticles also stabilized the titania crystallographic structure via reduction in the accessibility of lithium ions to the trapping sites. This resulted in a decrease in the irreversible capacity observed in the case of nanoparticles without any carbon coating.

Electrochemical investigation of single-walled carbon nanotubes for hydrogen storage

Electrodes made of purified and open single walled carbon nanotubes behave like metal hydride electrodes in Ni-MH batteries, showing high electrochemical reversible charging capacity up to 800 mAh g(-1) corresponding to a hydrogen storage capacity of 2.9 wt% compared to known AB(5), AB(2) metal hydride electrodes. (C) 2000 Elsevier Science Ltd. All rights reserved.

Reducibility of Ce1-xZrxO2: origin of enhanced oxygen storage capacity

We combine first-principles calculations with EXAFS studies to investigate the origin of high oxygen storage capacity in ceria-zirconia solid solution, prepared by solution combustion method. We find that nanocrystalline Ce0.5Zr0.5O2 can be reduced to Ce0.5Zr0.5O1.57 by H-2 upto 850 degrees C with an OSC of 65 cc/gm which is extremely high. Calculated local atomic-scale structure reveals the presence of long and short bonds resulting in four-fold coordination of the cations, confirmed by the EXAFS studies. Bond valence analysis of the microscopic structure and energetics is used to evaluate the strength of binding of different oxide ions and vacancies. We find the presence of strongly and weakly bound oxygens, of which the latter are responsible for the higher oxygen storage capacity in the mixed oxides than in the pure CeO2.

Implications of Energy Profile and Storage on Energy Harvesting Sensor Link Performance

Energy harvesting sensors (EHS), which harvest energy from the environment in order to sense and then communicate their measurements over a wireless link, provide the tantalizing possibility of perpetual lifetime operation of a sensor network. The wireless communication link design problem needs to be revisited for these sensors as the energy harvested can be random and small and not available when required. In this paper, we develop a simple model that captures the interactions between important parameters that govern the communication link performance of a EHS node, and analyze its outage probability for both slow fading and fast fading wireless channels. Our analysis brings out the critical importance of the energy profile and the energy storage capability on the EHS link performance. Our results show that properly tuning the transmission parameters of the EHS node and having even a small amount of energy storage capability improves the EHS link performance considerably.

On the hardness and elastic modulus of bulk metallic glass matrix composites

The influences of the amorphous matrix and crystalline dendrite phases on the hardness and elastic moduli of Zr/Ti-based bulk metallic glass matrix composites have been assessed. While the moduli of the composites correspond to those predicted by the rule of mixtures, the hardness of the composites is similar to that of the matrix, suggesting that the plastic flow in the composites under constrained conditions such as indentation is controlled by the flow resistance of the contiguous matrix. (C) 2010 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Computing a matrix symmetrizer exactly using modified multiple modulus residue arithmetic

A symmetric solution X satisfying the matrix equation XA = AtX is called a symmetrizer of the matrix A. A general algorithm to compute a matrix symmetrizer is obtained. A new multiple-modulus residue arithmetic called floating-point modular arithmetic is described and implemented on the algorithm to compute an error-free matrix symmetrizer.

Correlation of Oxygen Storage Capacity and Structural Distortion in Transition-Metal-, Noble-Metal-, and Rare-Earth-Ion-Substituted CeO2 from First Principles Calculation

Oxygen storage/release (OSC) capacity is an important feature common to all three-way catalysts to combat harmful exhaust emissions. To understand the mechanism of improved OSC for doped CeO2, we undertook the structural investigation by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), H-2-TPR (temperature-programmed hydrogen reduction) and density functional theoretical (DFT) calculations of transition-metal-, noble-metal-, and rare-earth (RE)-ion-substituted ceria. In this report, we present the relationship between the OSC and structural changes induced by the dopant ion in CeO2. Transition metal and noble metal ion substitution in ceria greatly enhances the reducibility of Ce1-xMxO2-delta (M = Mn, Fe, Co, Ni, Cu, Pd, Pt, Ru), whereas rare-earth-ion-substituted Ce(1-x)A(x)O(2-delta) (A = La, Y) have very little effect in improving the OSC. Our simulated optimized structure shows deviation in cation oxygen bond length from ideal bond length of 2.34 angstrom (for CeO2). For example, our theoretical calculation for Ce28Mn4O62 structure shows that Mn-O bonds are in 4 + 2 coordination with average bond lengths of 2.0 and 3.06 angstrom respectively. Although the four short Mn-O bond lengths spans the bond distance region of Mn2O3, the other two Mn-O bonds are moved to longer distances. The dopant transition and noble metal ions also affects Ce coordination shell and results in the formation of longer Ce-O bonds as well. Thus longer cation oxygen bonds for both dopant and host ions results in enhanced synergistic reduction of the solid solution. With Pd ion substitution in Ce1-xMxO2-delta (M = Mn, Fe, Co, Ni, Cu) further enhancement in OSC is observed in H-2-TPR. This effect is reflected in our model calculations by the presence of still longer bonds compared to the model without Pd ion doping. The synergistic effect is therefore due to enhanced reducibility of both dopant and host ion induced due to structural distortion of fluorite lattice in presence of dopant ion. For RE ions (RE = Y, La), our calculations show very little deviation of bonds lengths from ideal fluorite structure. The absence of longer Y-O/La-O and Ce-O bonds make the structure much less susceptible to reduction.

Regenerating Codes for Distributed Storage Networks

In a storage system where individual storage nodes are prone to failure, the redundant storage of data in a distributed manner across multiple nodes is a must to ensure reliability. Reed-Solomon codes possess the reconstruction property under which the stored data can be recovered by connecting to any k of the n nodes in the network across which data is dispersed. This property can be shown to lead to vastly improved network reliability over simple replication schemes. Also of interest in such storage systems is the minimization of the repair bandwidth, i.e., the amount of data needed to be downloaded from the network in order to repair a single failed node. Reed-Solomon codes perform poorly here as they require the entire data to be downloaded. Regenerating codes are a new class of codes which minimize the repair bandwidth while retaining the reconstruction property. This paper provides an overview of regenerating codes including a discussion on the explicit construction of optimum codes.

Methylene blue sensitized dichromated gelatin holograms: a study of their storage life and reprocessibility

The results of an experimental investigation on the storage life and reprocessibility of methylene blue sensitized dichromated gelatin (MBDCG) holograms are reported. The major conclusions of the investigation are: (i) Storage of MBDCG holograms in normal laboratory conditions for long periods is possible and it diminishes somewhat their diffraction efficiency. (ii) The results on short time storage and long time storage are almost similar, thus indicating that the diffraction efficiency can be stabilized through storage in a relatively short period of time. (iii) The deterioration in the diffraction efficiency on storage is less [D(eta) < 20%] for gratings of low/medium initial efficiency (eta < 70%) and it is more for gratings of high initial efficiency. (iv) About 65-95% restoration of the diffraction efficiency can be accomplished through reprocessing. (v) The restoration of diffraction efficiency is almost perfect [R(eta) > 80%] for gratings of low/medium initial efficiency (eta <75%) whereas it is rather imperfect for gratings having high initial efficiency.

Effect of Storage Temperatures on the Mechanical Properties of the Composite Solid Propellants

Accelerated ageing studies for three composite propellant formulations, namely polystyrene (PS)/ ammonium perchlorate (AP), polymethylmethacrylate (PMMA)/AP and poly phenol formaldehyde (PPF)/AP have been carried out in the temperature range of 55-125°C. Measurements of the ultimate compression strength (Uc) and isothermal decomposition rate (TD rate) were monitored as a function of storage time and temperature. The change in Uc was found to be linearly dependent on the change in TD rate irrespective of the propellant systems. Analysis of the results further revealed that the cause of ageing for both Uc and burning rate (r) is the thermal decomposition of the propellant. The safe-life for the change in mechanical properties was found to be higher compared to the change in r for PS and PMMA based propellants.

Metallacarboranes: Toward Promising Hydrogen Storage Metal Organic Frameworks

Using first principles calculations, we show the high hydrogen storage capacity of metallacarboranes, where the transition metal (TM) atoms can bind up to 5 H-2-molecules. The average binding energy of similar to 0.3 eV/H favorably lies within the reversible adsorption range. Among the first row TM atoms, Sc and Ti are found to be the optimum in maximizing the H-2 storage (similar to 8 wt %) on the metallacarborane cluster. Being an integral part of the cage, TMs do not suffer from the aggregation problem, which has been the biggest hurdle for the success of TM-decorated graphitic materials for hydrogen storage. Furthermore, the presence of carbon atom in the cages permits linking the metallacarboranes to form metal organic frameworks, which are thus able to adsorb hydrogen via Kubas interaction, in addition to van der Waals physisorption.