Dynamics of dense sheared granular flows. Part II. The relative velocity distributions

The distribution of relative velocities between colliding particles in shear flows of inelastic spheres is analysed in the Volume fraction range 0.4-0.64. Particle interactions are considered to be due to instantaneous binary collisions, and the collision model has a normal coefficient of restitution e(n) (negative of the ratio of the post- and pre-collisional relative velocities of the particles along the line joining the centres) and a tangential coefficient of restitution e(t) (negative of the ratio of post- and pre-collisional velocities perpendicular to line joining the centres). The distribution or pre-collisional normal relative velocities (along the line Joining the centres of the particles) is Found to be an exponential distribution for particles with low normal coefficient of restitution in the range 0.6-0.7. This is in contrast to the Gaussian distribution for the normal relative velocity in all elastic fluid in the absence of shear. A composite distribution function, which consists of an exponential and a Gaussian component, is proposed to span the range of inelasticities considered here. In the case of roughd particles, the relative velocity tangential to the surfaces at contact is also evaluated, and it is found to be close to a Gaussian distribution even for highly inelastic particles.Empirical relations are formulated for the relative velocity distribution. These are used to calculate the collisional contributions to the pressure, shear stress and the energy dissipation rate in a shear flow. The results of the calculation were round to be in quantitative agreement with simulation results, even for low coefficients of restitution for which the predictions obtained using the Enskog approximation are in error by an order of magnitude. The results are also applied to the flow down an inclined plane, to predict the angle of repose and the variation of the volume fraction with angle of inclination. These results are also found to be in quantitative agreement with previous simulations.

Application of partition method to vibration problems of plates

The “partition method” or “sub-domain method” consists of expressing the solution of a governing differential equation, partial or ordinary, in terms of functions which satisfy the boundary conditions and setting to zero the error in the differential equation integrated over each of the sub-domains into which the given domain is partitioned. In this paper, the use of this method in eigenvalue problems with particular reference to vibration of plates is investigated. The deflection of the plate is expressed in terms of polynomials satisfying the boundary conditions completely. Setting the integrated error in each of the subdomains to zero results in a set of simultaneous, linear, homogeneous, algebraic equations in the undetermined coefficients of the deflection series. The algebraic eigenvalue problem is then solved for eigenvalues and eigenvectors. Convergence is examined in a few typical cases and is found to be satisfactory. The results obtained are compared with existing results based on other methods and are found to be in very good agreement.

The mechanism of manganese electrodeposition

The mechanism of manganese electrodeposition from a sulphate bath on to a stainless-steel substrate has been studied by using current efficiency data to resolve the totali-E curves. A simple, two-step electron transfer mechanism:is proposed to explain the following experimentally obtained parameters: cathodic and anodic transfer coefficients, reaction order and stoichiometric number. The mechanism also explains the effect of pH oni o,Mn and on the corrosion currents.

Dendritic structures produced on solidification of multicomponent aqueous solutions

Dendrite structures of ice produced on undirectional solidification of ternary and quaternary aqueous solutions have been studied. Upon freezing, solutions containing more than one solute produce plate-shaped dendrites of ice. The spacing between dendrites increase linearly with the distance from the chill surface and the square root of local solidification time (or square root of inverse freezing rate) for any fixed composition. For fixed freezing conditions, the dendrite spacings from multicomponent aqueous solutions were a function of the concentrations and diffusion coefficients of the individual solutes. The dendrite spacing produced by freezing of a solution was changed by the addition of a solute different from those already present. If the main diffusion coefficient of the added solute is higher than that of solutes already present, the dendrite spacing is increased and vice versa. The dendrite spacing in multi-component systems increases with the total solute concentration if the constituent solutes are present in equal amounts. The dendrite spacing obtained on freezing of these dilute multicomponent solutions can be expressed by regression equations of the type Image Full-size image (2K) where L is the dendrite spacing in microns, C1, C2 and C3 are concentrations of individual solutes, Θf is the total freezing time and A1 −A8 are constants. A Yates analysis of the dendrite spacings in a factorial design of quaternary solutions indicates that there are strong interactions between individual solutes in regard to their effect on the dendrite spacings. A mass transport analysis has been used to calculate the interdendritic supersaturation ΔC of the individual solutes, the supercooling in the interdendritic liquid ΔT, and the transverse growth velocity of the dendrites, VT. In ternary solutions if two solutes are present in equal amount the supersaturation of the solute with higher main diffusion coefficient is lower, and vice versa. If a solute with higher main diffusion coefficient is added to a binary solution, the interface growth velocity, the interdendritic supersaturation of the base solute and the interdendritic supercooling increase with the quantity of solute added.

Identification of a class of non-linear systems

This paper considers the on-line identification of a non-linear system in terms of a Hammerstein model, with a zero-memory non-linear gain followed by a linear system. The linear part is represented by a Laguerre expansion of its impulse response and the non-linear part by a polynomial. The identification procedure involves determination of the coefficients of the Laguerre expansion of correlation functions and an iterative adjustment of the parameters of the non-linear gain by gradient methods. The method is applicable to situations involving a wide class of input signals. Even in the presence of additive correlated noise, satisfactory performance is achieved with the variance of the error converging to a value close to the variance of the noise. Digital computer simulation establishes the practicability of the scheme in different situations.

Validity of a self-report recall tool for estimating sedentary behaviour in adults

BACKGROUND Sedentary behavior is continuing to emerge as an important target for health promotion. The purpose of this study was to determine the validity of a self-report use of time recall tool, the Multimedia Activity Recall for Children and Adults (MARCA) in estimating time spent sitting/lying, compared with a device-based measure. METHODS Fifty-eight participants (48% female, [mean±standard deviation] 28±7.4 years of age, 23.9±3.05 kg/m2) wore an activPAL device for 24-h and the following day completed the MARCA. Pearson correlation coefficients (r) were used to analyse convergent validity of the adult MARCA compared with activPAL estimates of total sitting/lying time. Agreement was examined using Bland-Altman plots. RESULTS According to activPAL estimates, participants spent 10.4 hr/day [standard deviation (SD)=2.06] sitting or lying down while awake. The correlation between MARCA and activPAL estimates of total sit/lie time was r=0.77 (95% confidence interval = 0.64-0.86; p<0.001). Bland-Altman analyses revealed a mean bias of +0.59 hr/day with moderately wide limits of agreement (-2.35 hours to +3.53 hr/day). CONCLUSIONS This study found a moderate to strong agreement between the adult MARCA and the activPAL, suggesting that the MARCA is an appropriate tool for the measurement of time spent sitting or lying down in an adult population.

Wind drift of snowfall between the radar volume and ground

This study evaluates how the advection of precipitation, or wind drift, between the radar volume and ground affects radar measurements of precipitation. Normally precipitation is assumed to fall vertically to the ground from the contributing volume, and thus the radar measurement represents the geographical location immediately below. In this study radar measurements are corrected using hydrometeor trajectories calculated from measured and forecasted winds, and the effect of trajectory-correction on the radar measurements is evaluated. Wind drift statistics for Finland are compiled using sounding data from two weather stations spanning two years. For each sounding, the hydrometeor phase at ground level is estimated and drift distance calculated using different originating level heights. This way the drift statistics are constructed as a function of range from radar and elevation angle. On average, wind drift of 1 km was exceeded at approximately 60 km distance, while drift of 10 km was exceeded at 100 km distance. Trajectories were calculated using model winds in order to produce a trajectory-corrected ground field from radar PPI images. It was found that at the upwind side from the radar the effective measuring area was reduced as some trajectories exited the radar volume scan. In the downwind side areas near the edge of the radar measuring area experience improved precipitation detection. The effect of trajectory-correction is most prominent in instant measurements and diminishes when accumulating over longer time periods. Furthermore, measurements of intensive and small scale precipitation patterns benefit most from wind drift correction. The contribution of wind drift on the uncertainty of estimated Ze (S) - relationship was studied by simulating the effect of different error sources to the uncertainty in the relationship coefficients a and b. The overall uncertainty was assumed to consist of systematic errors of both the radar and the gauge, as well as errors by turbulence at the gauge orifice and by wind drift of precipitation. The focus of the analysis is error associated with wind drift, which was determined by describing the spatial structure of the reflectivity field using spatial autocovariance (or variogram). This spatial structure was then used with calculated drift distances to estimate the variance in radar measurement produced by precipitation drift, relative to the other error sources. It was found that error by wind drift was of similar magnitude with error by turbulence at gauge orifice at all ranges from radar, with systematic errors of the instruments being a minor issue. The correction method presented in the study could be used in radar nowcasting products to improve the estimation of visibility and local precipitation intensities. The method however only considers pure snow, and for operational purposes some improvements are desirable, such as melting layer detection, VPR correction and taking solid state hydrometeor type into account, which would improve the estimation of vertical velocities of the hydrometeors.

Growth of ionization currents in nitrogen

Townsend's primary and secondary ionization coefficients α/p and γ were determined in nitrogen over a wide range of E/p (100-1000 V cm−1 Torr−1) and p (0·4 to 12 Torr at 0 °C) using the pressure variation technique. This technique, along with the Gosseries method of evaluation of ionization coefficients, seems to be more suitable at higher values of E/p, since the errors in these coefficients could be minimized by a suitable selection of p and d, thus eliminating the non-equilibrium ionization condition.

Photon-Induced Electron Pairing

The earlier work on the possibility of interband electron pairing in the presence of a strong radiation field has been further extended. Some additional terms, neglected earlier, have been taken into account and generalized to a situation where the electron-phonon coupling coefficients for the two conduction bands (valleys) are different. It is found that the pairing interaction is attractive and the strength depends on the photon density.

Molecular Interactions Chlorin Assemblies and NMR Separations

Photosynthesis is a chemical process in which the energy of the light quanta is transformed into chemical energy. Chlorophyll (Chl) molecules play a key role in photosynthesis; they function in the antennae systems and in the photosynthetic reaction center where the primary charge separation (CS) takes place. Bio-inspired mimicry of the CS is an essential unit in dye-sensitized solar cells. Aim of this study was to design and develop electron donor-acceptor (EDA) pairs from Chls and fullerenes (C60) or carbon nanotubes (CNT). The supramolecular approach was chosen, as long synthetic sequences required by the covalent approach lead to long reaction schemes and low yields. Here, a π-interaction between soluble CNTs and Chl was used in EDA construction. Also, a beta-face selective two-point bound Chl-C60 EDA was introduced. In addition, the photophysical properties of the supramolecular EDA dyads were analyzed. In organic chemistry, nuclear magnetic resonance (NMR) spectroscopy is the most vital analytical technique in use. Multi-dimensional NMR experiments have enabled a structural analysis of complex natural products and proteins. However, in mixture analysis NMR is still facing difficulties. In many cases overlapping signals can t be resolved even with the help of multi-dimensional experiments. In this work, an NMR tool based on simple host-guest chemistry between analytes and macromolecules was developed. Diffusion ordered NMR spectroscopy (DOSY) measures the mobilities of compounds in an NMR sample. In a liquid state NMR sample, each of the analytes has a characteristic diffusion coefficient, which is proportional to the size of the analyte. With normal DOSY experiment, provided that the diffusion coefficients of the analytes differ enough, individual spectra of analytes can be extracted. When similar sized analytes differ chemically, an additive can be introduced into the sample. Since macromolecules in a liquid state NMR sample can be considered practically stationary, even faint supramolecular interaction can change the diffusion coefficient of the analyte sufficiently for a successful resolution in DOSY. In this thesis, polyvinylpyrrolidone and polyethyleneglycol enhanced DOSY NMR techniques, which enable mixture analysis of similar in size but chemically differing natural products, are introduced.

High-throughput prediction of eucalypt lignin syringyl/guaiacyl content using multivariate analysis: a comparison between mid-infrared, near-infrared, and Raman spectroscopies for model development

BACKGROUND: In order to rapidly and efficiently screen potential biofuel feedstock candidates for quintessential traits, robust high-throughput analytical techniques must be developed and honed. The traditional methods of measuring lignin syringyl/guaiacyl (S/G) ratio can be laborious, involve hazardous reagents, and/or be destructive. Vibrational spectroscopy can furnish high-throughput instrumentation without the limitations of the traditional techniques. Spectral data from mid-infrared, near-infrared, and Raman spectroscopies was combined with S/G ratios, obtained using pyrolysis molecular beam mass spectrometry, from 245 different eucalypt and Acacia trees across 17 species. Iterations of spectral processing allowed the assembly of robust predictive models using partial least squares (PLS). RESULTS: The PLS models were rigorously evaluated using three different randomly generated calibration and validation sets for each spectral processing approach. Root mean standard errors of prediction for validation sets were lowest for models comprised of Raman (0.13 to 0.16) and mid-infrared (0.13 to 0.15) spectral data, while near-infrared spectroscopy led to more erroneous predictions (0.18 to 0.21). Correlation coefficients (r) for the validation sets followed a similar pattern: Raman (0.89 to 0.91), mid-infrared (0.87 to 0.91), and near-infrared (0.79 to 0.82). These statistics signify that Raman and mid-infrared spectroscopy led to the most accurate predictions of S/G ratio in a diverse consortium of feedstocks. CONCLUSION: Eucalypts present an attractive option for biofuel and biochemical production. Given the assortment of over 900 different species of Eucalyptus and Corymbia, in addition to various species of Acacia, it is necessary to isolate those possessing ideal biofuel traits. This research has demonstrated the validity of vibrational spectroscopy to efficiently partition different potential biofuel feedstocks according to lignin S/G ratio, significantly reducing experiment and analysis time and expense while providing non-destructive, accurate, global, predictive models encompassing a diverse array of feedstocks.

Application of partition method to vibration problems of plates

The “partition method” or “sub-domain method” consists of expressing the solution of a governing differential equation, partial or ordinary, in terms of functions which satisfy the boundary conditions and setting to zero the error in the differential equation integrated over each of the sub-domains into which the given domain is partitioned. In this paper, the use of this method in eigenvalue problems with particular reference to vibration of plates is investigated. The deflection of the plate is expressed in terms of polynomials satisfying the boundary conditions completely. Setting the integrated error in each of the subdomains to zero results in a set of simultaneous, linear, homogeneous, algebraic equations in the undetermined coefficients of the deflection series. The algebraic eigenvalue problem is then solved for eigenvalues and eigenvectors. Convergence is examined in a few typical cases and is found to be satisfactory. The results obtained are compared with existing results based on other methods and are found to be in very good agreement.

Fast FIR Algorithms for the Continuous Wavelet Transform From Constrained Least Squares

New algorithms for the continuous wavelet transform are developed that are easy to apply, each consisting of a single-pass finite impulse response (FIR) filter, and several times faster than the fastest existing algorithms. The single-pass filter, named WT-FIR-1, is made possible by applying constraint equations to least-squares estimation of filter coefficients, which removes the need for separate low-pass and high-pass filters. Non-dyadic two-scale relations are developed and it is shown that filters based on them can work more efficiently than dyadic ones. Example applications to the Mexican hat wavelet are presented.

The kinetics and reactivity of several polyatomic free radicals in reactions with NO2, O2, Cl2, and HCl

In this thesis, the kinetics of several alkyl, halogenated alkyl, and alkenyl free radical reactions with NO2, O2, Cl2, and HCl reactants were studied over a wide temperature range in time resolved conditions. Laser photolysis photoionisation mass spectrometer coupled to a flow reactor was the experimental method employed and this thesis present the first measurements performed with the experimental system constructed. During this thesis a great amount of work was devoted to the designing, building, testing, and improving the experimental apparatus. Carbon-centred free radicals were generated by the pulsed 193 or 248 nm photolysis of suitable precursors along the tubular reactor. The kinetics was studied under pseudo-first-order conditions using either He or N2 buffer gas. The temperature and pressure ranges employed were between 190 and 500 K, and 0.5 45 torr, respectively. The possible role of heterogeneous wall reactions was investigated employing reactor tubes with different sizes, i.e. to significantly vary the surface to volume ratio. In this thesis, significant new contributions to the kinetics of carbon-centred free radical reactions with nitrogen dioxide were obtained. Altogether eight substituted alkyl (CH2Cl, CHCl2, CCl3, CH2I, CH2Br, CHBr2, CHBrCl, and CHBrCH3) and two alkenyl (C2H3, C3H3) free radical reactions with NO2 were investigated as a function of temperature. The bimolecular rate coefficients of all these reactions were observed to possess negative temperature dependencies, while pressure dependencies were not noticed for any of these reactions. Halogen substitution was observed to moderately reduce the reactivity of substituted alkyl radicals in the reaction with NO2, while the resonance stabilisation of the alkenyl radical lowers its reactivity with respect to NO2 only slightly. Two reactions relevant to atmospheric chemistry, CH2Br + O2 and CH2I + O2, were also investigated. It was noticed that while CH2Br + O2 reaction shows pronounced pressure dependence, characteristic of peroxy radical formation, no such dependence was observed for the CH2I + O2 reaction. Observed primary products of the CH2I + O2 reaction were the I-atom and the IO radical. Kinetics of CH3 + HCl, CD3 + HCl, CH3 + DCl, and CD3 + DCl reactions were also studied. While all these reactions possess positive activation energies, in contrast to the other systems investigated in this thesis, the CH3 + HCl and CD3 + HCl reactions show a non-linear temperature dependency on the Arrhenius plot. The reactivity of substituted methyl radicals toward NO2 was observed to increase with decreasing electron affinity of the radical. The same trend was observed for the reactions of substituted methyl radicals with Cl2. It is proposed that interactions of frontier orbitals are responsible to these observations and Frontier Orbital Theory could be used to explain the observed reactivity trends of these highly exothermic reactions having reactant-like transition states.

Cooperativity in the inhibition of oxidative phosphorylation by chlorophenoxyisobutyrate

The kinetics of inhibition of oxidative phosphorylation by the antihypercholes-terolaemic compound p-chlorophenoxyisobutyrate reveal cooperativity characteristic of allosteric interactions. Hill plots and Dixon plots give clear indication that the compound interferes with two distinct steps in the energy-transfer pathway. The values of interaction coefficients calculated from the Hill plots were two and four in the direction of ATP synthesis and one and two in the reverse direction. This could mean either that the pathways of synthesis and breakdown of ATP are different, or that if the pathways are the same, only half the inhibitor-binding sites function in the reverse direction.