Uncoupled surface spin induced exchange bias in α-MnO 2 nanowires

We have studied the microstructure, surface states, valence fluctuations, magnetic properties, and exchange bias effect in MnO2 nanowires. High purity α-MnO 2 rectangular nanowires were synthesized by a facile hydrothermal method with microwave-assisted procedures. The microstructure analysis indicates that the nanowires grow in the [0 0 1] direction with the (2 1 0) plane as the surface. Mn3+ and Mn2+ ions are not found in the system by X-ray photoelectron spectroscopy. The effective magnetic moment of the manganese ions fits in with the theoretical and experimental values of Mn4+ very well. The uncoupled spins in 3d3 orbitals of the Mn 4+ ions in MnO 6 octahedra on the rough surface are responsible for the net magnetic moment. Spin glass behavior is observed through magnetic measurements. Furthermore, the exchange bias effect is observed for the first time in pure α-MnO2 phase due to the coupling of the surface spin glass with the antiferromagnetic α-MnO2 matrix. These α-MnO2 nanowires, with a spin-glass-like behavior and with an exchange bias effect excited by the uncoupled surface spins, should therefore inspire further study concerning the origin, theory, and applicability of surface structure induced magnetism in nanostructures.

High-pressure Raman and infrared spectroscopic studies of ZrP2O7

High-pressure Raman and mid-infrared spectroscopic studies were carried out on ZrP2O7 to 23.2 and 13 GPa respectively. In the pressure range 0.7-4.3 GPa the lattice mode at 248 cm(-1) disappears, new modes appear around 380 and 1111 cm(-1) and the strong symmetric stretching mode at 476 cm(-1) softens, possibly indicating a subtle phase transition. Above 8 GPa all the modes broaden, and all of the Raman modes disappear beyond 18 GPa. On decompression from the highest pressure, 23.2, to 0 GPa all of the modes reappear but with larger full width at half maximum. Lattice dynamics of the high temperature phase of ZrP2O7 were studied using first principles method and compared with experimental values. (C) 2009 Elsevier Ltd. All rights reserved.

Charge distribution in and electric moments of some aliphatic acids

Using the treatment of Smith et al., charge distribution in and consequently the dipole moments of several aliphatic acids have been evaluated. The electric moments of chloro (2·86 D), bromo (2·90 D), iodo (2·06 D) and trichloro (3·00 D) acetic acids have been measured in dioxan solution at 35°. The experimental values are compared with those calculated theoretically and discussed in terms of the various possible structures.

Thermal Conductivities of Organic Liquids-A New Correlation.

A new equation for predicting the thermal conductivities of organic liquids using dimension-less analysis is given. The equation (Equation Presented) correlates 51 different liquids tested within 11% average error and 17% standard deviation. A comparison of the proposed equation with the available correlations and its application to some industrially important liquids show that this equation can be safely used to calculate the thermal conductivities at 20°C. and 1 atm. pressure for organic liquids of known molecular weight. Cp and ΔHv - the only two parameters for which experimental values must be known for making use of this equation - can be calculated using other well known correlations. The proposed equation is not applicable to inorganic liquids.

Raman spectra of single crystals of adipic and sebacic acids and a study of the hydrogen bond vibrations in carboxylic acid dimers

Raman spectra of single crystals of adipic and sebacic acids have been photographed for the first time using λ 2537 excitation. The spectra have been divided into four regions: (a) internal frequencies; (b) summations and overtones; (c) external vibrations; and (d) low-frequency hydrogen bond oscillations. Tentative correlations have been given for all the internal frequencies and summations and overtones. A series of diffuse weak bands observed in the spectra of both these acids in the not, vert, similar2400–2800 cm−1 have been explained as a superposition of O---H frequencies lowered due to hydrogen bond formation over the summations and overtones of fundamentals mainly in the not, vert, similar1000–1500 cm−1 region. Rotatory type of external oscillations of the two formula units of these molecules in their unit cells have been identified at 76, 99, 118 and 165 cm−1 in adipic acid and 66, 95, 117 and 177 cm−1 in the spectrum of sebacic acid. A brief discussion of the low frequency hydrogen bond vibrations in these acids has been made. Making use of the Lippincott—Schroeder potential and assuming a highly anharmonic potential curve for the hydrogen bond, the vibrational frequencies of the bond have been theoretically evaluated. There is very good agreement between these and the experimental values. The results for adipic acid in cm−1 are: 304 (0 → 1), 270 (1 → 2), 241 (2 → 3), 222 (3 → 4) 201 (4 → 5), 183 (5 → 6). In the case of sebacic acid some of the intermediate and higher transitions are absent in the spectrum recorded by the author. From the above data for adipic acid the dissociation energy of the hydrogen bond was evaluated as 5·9 kcal/mole in fair agreement with the values derived from conventional methods.

Prediction of solid block masonry prism compressive strength using FE model

Masonry strength is dependent upon characteristics of the masonry unit,the mortar and the bond between them. Empirical formulae as well as analytical and finite element (FE) models have been developed to predict structural behaviour of masonry. This paper is focused on developing a three dimensional non-linear FE model based on micro-modelling approach to predict masonry prism compressive strength and crack pattern. The proposed FE model uses multi-linear stress-strain relationships to model the non-linear behaviour of solid masonry unit and the mortar. Willam-Warnke's five parameter failure theory developed for modelling the tri-axial behaviour of concrete has been adopted to model the failure of masonry materials. The post failure regime has been modelled by applying orthotropic constitutive equations based on the smeared crack approach. Compressive strength of the masonry prism predicted by the proposed FE model has been compared with experimental values as well as the values predicted by other failure theories and Eurocode formula. The crack pattern predicted by the FE model shows vertical splitting cracks in the prism. The FE model predicts the ultimate failure compressive stress close to 85 of the mean experimental compressive strength value.

An optimum criterion for eccentrically loaded R. C. columns

An analysis of eccentrically loaded short reinforced concrete columns using a variable failure strain criterion is presented. The method dispenses with the usual procedure of assuming a fixed value for the ultimate strain in concrete. The analysis is based on the use of a simple, single equation for the complete stress-strain curve of concrete and the adoption of a process of maximisation of moment with respect to extreme fibre concrete compressive strain. Columns of rectangular section and loaded eccentrically along one axis only are considered in this paper. A good agreement is observed between the theoretical and experimental values of some test results.

Phase change on transmission of microwaves through metal disc delay dielectrics

Expressions for the phase change Φ suffered by microwaves when transmitted through an artificial dielectric composed of metallic discs arranged in a three-dimensional array have been derived with different approaches as follows (i) molecular theory, (ii) electromagnetic theory and (iii) transmission line theory. The phase change depends on the distance t that the wave traverses inside the dielectric and also the spacing d between centre to centre of any two adjacent discs in the three principal directions. Molecular theory indicates Φ as an increasing function of t, whereas, the other two theories indicate Φ as an oscillatory function of t. The transmission line theory also exhibits Φ to be real or imaginary depending on t. Experimental values of Φ as a function of t have been obtained with the help of a microwave (3·2 cms wavelength) interferometer for two dielectrics having d as 1·91 cms and 2·22 cms respectively.

Vibrational analysis of boldine hydrochloride using QM/MM approach

A complete vibrational analysis was performed on the molecular structure of boldine hydrochloride using QM/MM method. The equilibrium geometry, harmonic vibrational frequencies and infrared intensities were calculated by QM/MM method with B3LYP/6-31G(d) and universal force field (UFF) combination using ONIOM code. We found the geometry obtained by the QM/MM method to be very accurate, and we can use this rapid method in place of time consuming ab initio methods for large molecules. A detailed interpretation of the infrared spectra of boldine hydrochloride is reported. The scaled theoretical wave numbers are in perfect agreement with the experimental values. The FT-IR spectra of boldine hydrochloride in the region 4000-500 cm(-1) were recorded in CsI (solid phase) and in chloroform with concentration 5 and 10 mg/ml.

A New Liquid Level Sensor for Process-Control Applications

Many process-control systems are air-operated. In such an environment, it would be desirable and economical to use pneumatic sensors. Bubble-back pressure sensors perform quite satisfactorily, but in case of viscous inflammable and slurry-like liquids with a tendency to froth, this level sensor is inadequate. The method suggested in this paper utilizes a pneumatic capacitor, one boundary of which is formed by the liquid level, to modulate a fluid amplifier feedback oscillator. The absence of moving parts and economy obtained makes this method attractive for process-control applications. The system has been mathematically modeled and simulated on an IBM 360/44 digital computer. Experimental values compare fairly well with the theoretical results. For the range tested, the sensor is found to have a linear frequency variation with the liquid level Extended running in the laboratory shows that the system is very reliable. This system has been found insensitive to temperature variations of up to 15ðC.

Influence of strain softening on the fracture of plain concrete beams

Fracture behaviour of notched and un-notched plain concrete slender beams subjected to three-point or four-point bending is analyzed through a one-dimensional model, also called Softening Beam Model. Fundamental equations of equilibrium are used to develop the model. The influence of structural size in altering the fracture mode from brittle fracture to plastic collapse is explained through the stress distribution across the uncracked ligament obtained by varying the strain softening modulus. It is found that at the onset of fracture instability, stress at the crack tip is equal to zero. The maximum load and fracture load are found to be different and a unique value for the fracture load is obtained. It is shown that the length of the fracture process zone depends on the value of the strain softening modulus. Theoretical limits for fracture process zone length are also calculated. Several nonlinear fracture parameters, such as, crack tip opening displacement, crack mouth opening displacement and fracture energy are computed for a wide variety of beam specimens reported in the literature and are found to compare very well with experimental and theoretical results. It is demonstrated that by following a simple procedure, both pre-peak and post-peak portions of load versus crack mouth opening displacement curve can be obtained quite accurately. Further, a simple procedure to calculate the maximum load is also developed. The predicted values of maximum load are found to agree well with the experimental values. The Softening Beam Model (SBM), proposed in this investigation is very simple and is based on rational considerations. It can completely describe the fracture process from the beginning of formation of the fracture process zone till the onset of fracture instability.A l'aide d'un modèle unidimensionnel dit ldquoSoftening Beam Modelrdquo (SBM), on analyse le comportement à rupture de poutres élancées pleines entaillées ou non, soumises en flexion en trois ou quatre points. Des équations fondamentales d'équilibre sont utilisées pour développer le modèle. On explique l'influence de la taille du composant sur l'altération du mode de rupture en rupture fragile et en effondrement plastique par la distribution par la distribution des contraintes sur le ligament non fissuré lorsque varie le module d'adoucissement. On trouve que la contrainte à l'extrémité de la fissure est nulle est nulle au début de l'instabilité de la rupture. La charge maximum et la charge à la rupture sont trouvées différentes, et on obtient une valeur unique de la charge à la rupture. On montre que la longueur de la zone concernée par le processus de rupture d'pend de la valeur du module d'adoucissement. On calcule également les limites théoriques de longueur de cette zone. Divers paramètres de rupture non linéaire sont calculés pour une large gamme d'éprouvettes en poutres reprises dans la littérature; on trouve qu'il existe une bonne concordance avec les résultats expérimentaux et théoriques. On démontre qu'en suivant une procédure simple on peut obtenir avec une bonne précision la courbe reliant les portions avant et après le pic de sollicitation en fonction du COD de la fissure. En outre, on développe une procédure simple pour calculer la charge maximum. Les valeurs prédites sont en bon accord avec les valeurs expérimentales. Le modèle SBM proposé est très simple et est basé sur des considérations rationnelles. Il est susceptible de décrire complètement le processus de rupture depuis le début de la formation de la zone intéressée jusqu'à l'amorçage de la rupture instable.

Activation barriers for d.c. conductivity in ionic glasses: Classical calculations using the small-cluster approximation

A small-cluster approximation has been used to calculate the activation barriers for the d.c. conductivity in ionic glasses. The main emphasis of this approach is on the importance of the hitherto ignored polarization energy contribution to the total activation energy. For the first time it has been demonstrated that the d.c. conductivity activation energy can be calculated by considering ionic migration to a neighbouring vacancy in a smali cluster of ions consisting of face-sharing anion polyhedra. The activation energies from the model calculations have been compared with the experimental values in the case of highly modified lithium thioborate glasses.

Geometry and quadratic nonlinearity of charge transfer complexes in solution using depolarized hyper-Rayleigh scattering

We report large quadratic nonlinearity in a series of 1:1 molecular complexes between methyl substituted benzene donors and quinone acceptors in solution. The first hyperpolarizability, beta(HRS), which is very small for the individual components, becomes large by intermolecular charge transfer (CT) interaction between the donor and the acceptor in the complex. In addition, we have investigated the geometry of these CT complexes in solution using polarization resolved hyper-Rayleigh scattering (HRS). Using linearly (electric field vector along X direction) and circularly polarized incident light, respectively, we have measured two macroscopic depolarization ratios D = I-2 omega,I-X,I-X/I-2 omega,I-Z,I-X and D' = I-2 omega,I-X,I-C/I-2 omega,I-Z,I-C in the laboratory fixed XYZ frame by detecting the second harmonic scattered light in a polarization resolved fashion. The experimentally obtained first hyperpolarizability, beta(HRS), and the value of macroscopic depolarization ratios, D and D', are then matched with the theoretically deduced values from single and double configuration interaction calculations performed using the Zerner's intermediate neglect of differential overlap self-consistent reaction field technique. In solution, since several geometries are possible, we have carried out calculations by rotating the acceptor moiety around three different axes keeping the donor molecule fixed at an optimized geometry. These rotations give us the theoretical beta(HRS), D and D' values as a function of the geometry of the complex. The calculated beta(HRS), D, and D' values that closely match with the experimental values, give the dominant equilibrium geometry in solution. All the CT complexes between methyl benzenes and chloranil or 1,2-dichloro-4,5-dicyano-p-benzoquinone investigated here are found to have a slipped parallel stacking of the donors and the acceptors. Furthermore, the geometries are staggered and in some pairs, a twist angle as high as 30 degrees is observed. Thus, we have demonstrated in this paper that the polarization resolved HRS technique along with theoretical calculations can unravel the geometry of CT complexes in solution. (C) 2011 American Institute of Physics. doi:10.1063/1.3514922]

Structural Behavior of Story-High Cement-Stabilized Rammed-Earth Walls under Compression

A rammed-earth wall is a monolithic construction made by compacting processed soil in progressive layers in a rigid formwork. There is a growing interest in using this low-embodied-carbon building material in buildings. The paper investigates the strength and structural behavior of story-high cement-stabilized rammed-earth (CSRE) walls, reviews literature on the strength of CSRE, and discusses results of the compressive strength of CSRE prisms, wallettes, and story-high walls. The strength of the story-high wall was compared with the strength of wallettes and prisms. There is a nearly 30% reduction in strength as the height-to-thickness ratio increases from about 5 to 20. The ultimate compressive strength of CSRE walls predicted using the tangent modulus theory is in close agreement with the experimental values. The shear failures noticed in the story-high walls resemble the shear failures of short-height prism and wallette specimens. The paper ends with a discussion of structural design and characteristic compressive strength of CSRE walls. DOI: 10.1061/(ASCE)MT.1943-5533.0000155. (C) 2011 American Society of Civil Engineers.

Pipelined ring algorithm for matrix multiplication on transputer networks: performance analysis and estimation

A parallel matrix multiplication algorithm is presented, and studies of its performance and estimation are discussed. The algorithm is implemented on a network of transputers connected in a ring topology. An efficient scheme for partitioning the input matrices is introduced which enables overlapping computation with communication. This makes the algorithm achieve near-ideal speed-up for reasonably large matrices. Analytical expressions for the execution time of the algorithm have been derived by analysing its computation and communication characteristics. These expressions are validated by comparing the theoretical results of the performance with the experimental values obtained on a four-transputer network for both square and irregular matrices. The analytical model is also used to estimate the performance of the algorithm for a varying number of transputers and varying problem sizes. Although the algorithm is implemented on transputers, the methodology and the partitioning scheme presented in this paper are quite general and can be implemented on other processors which have the capability of overlapping computation with communication. The equations for performance prediction can also be extended to other multiprocessor systems.