Pore structure and column efficiency of silica monoliths in high performance liquid chromatography (HPLC)

Five different methods were critically examined to characterize the pore structure of the silica monoliths. The mesopore characterization was performed using: a) the classical BJH method of nitrogen sorption data, which showed overestimated values in the mesopore distribution and was improved by using the NLDFT method, b) the ISEC method implementing the PPM and PNM models, which were especially developed for monolithic silicas, that contrary to the particulate supports, demonstrate the two inflection points in the ISEC curve, enabling the calculation of pore connectivity, a measure for the mass transfer kinetics in the mesopore network, c) the mercury porosimetry using a new recommended mercury contact angle values. rnThe results of the characterization of mesopores of monolithic silica columns by the three methods indicated that all methods were useful with respect to the pore size distribution by volume, but only the ISEC method with implemented PPM and PNM models gave the average pore size and distribution based on the number average and the pore connectivity values.rnThe characterization of the flow-through pore was performed by two different methods: a) the mercury porosimetry, which was used not only for average flow-through pore value estimation, but also the assessment of entrapment. It was found that the mass transfer from the flow-through pores to mesopores was not hindered in case of small sized flow-through pores with a narrow distribution, b) the liquid penetration where the average flow-through pore values were obtained via existing equations and improved by the additional methods developed according to Hagen-Poiseuille rules. The result was that not the flow-through pore size influences the column bock pressure, but the surface area to volume ratio of silica skeleton is most decisive. Thus the monolith with lowest ratio values will be the most permeable. rnThe flow-through pore characterization results obtained by mercury porosimetry and liquid permeability were compared with the ones from imaging and image analysis. All named methods enable a reliable characterization of the flow-through pore diameters for the monolithic silica columns, but special care should be taken about the chosen theoretical model.rnThe measured pore characterization parameters were then linked with the mass transfer properties of monolithic silica columns. As indicated by the ISEC results, no restrictions in mass transfer resistance were noticed in mesopores due to their high connectivity. The mercury porosimetry results also gave evidence that no restrictions occur for mass transfer from flow-through pores to mesopores in the small scaled silica monoliths with narrow distribution. rnThe prediction of the optimum regimes of the pore structural parameters for the given target parameters in HPLC separations was performed. It was found that a low mass transfer resistance in the mesopore volume is achieved when the nominal diameter of the number average size distribution of the mesopores is appr. an order of magnitude larger that the molecular radius of the analyte. The effective diffusion coefficient of an analyte molecule in the mesopore volume is strongly dependent on the value of the nominal pore diameter of the number averaged pore size distribution. The mesopore size has to be adapted to the molecular size of the analyte, in particular for peptides and proteins. rnThe study on flow-through pores of silica monoliths demonstrated that the surface to volume of the skeletons ratio and external porosity are decisive for the column efficiency. The latter is independent from the flow-through pore diameter. The flow-through pore characteristics by direct and indirect approaches were assessed and theoretical column efficiency curves were derived. The study showed that next to the surface to volume ratio, the total porosity and its distribution of the flow-through pores and mesopores have a substantial effect on the column plate number, especially as the extent of adsorption increases. The column efficiency is increasing with decreasing flow through pore diameter, decreasing with external porosity, and increasing with total porosity. Though this tendency has a limit due to heterogeneity of the studied monolithic samples. We found that the maximum efficiency of the studied monolithic research columns could be reached at a skeleton diameter of ~ 0.5 µm. Furthermore when the intention is to maximize the column efficiency, more homogeneous monoliths should be prepared.rn

Characteristics of modal sound radiation of finite cylindrical shells

Characteristics of modal sound radiation of finite cylindrical shells are studied using finite element and boundary element methods in this paper. In the low frequency range, modal radiation efficiencies of finite cylindrical shells are found to asymptotically approach those of the corresponding infinite cylindrical shell when structural trace wavelengths of the cylindrical shells are greater than the acoustic wavelength. Modal radiation efficiencies for each group of modes having the same circumferential modal index decrease as the axial modal index increases. They converge to each other when the axial trace wavelength is much greater than the circumferential trace wavelength. The mechanism leading to lower radiation efficiency of modes with higher circumferential modal index of short cylinders is explained. Similar to those of flat plate panels, change in slope or waviness is observed in modal radiation efficiency curves of modes with higher order axial modal index at medium frequencies. This is attributed to the interference of sound radiated by neighbouring vibrating cells when the distance between nodal lines of a vibrating mode is in the same order or smaller than the acoustic wavelength. Effects of the internal sound field on modal radiation efficiencies of a finite open-end cylinder are discussed.

Sound radiation from a perforated panel set in a baffle with a different perforation ratio

A finite flexible perforated panel set in a differently perforated rigid baffle is considered. The radiation efficiency from such a panel is derived using a 2-D wavenumber domain formulation. This generalization is later used to represent a more practical case of a perforated panel fixed in an unperforated baffle. The perforations are in the form of an array of uniformly distributed circular holes. A complex impedance model for the holes available in the literature is used. An averaged fluid particle velocity is derived using the continuity equation and the surface pressure is derived using an appropriate momentum equation. The discontinuity in the perforate impedance (due to different hole dimensions or perforation ratio) at the panel-baffle interface is carefully taken into account. It is found that there exists a `coupling' of different wavenumbers of the spatially mean fluid particle velocity field. The change in the resonance frequencies and the modeshapes of the panel due to the perforations is taken into account using the Receptance method. Analytical expressions for the radiated power and radiation efficiency are derived in an integral form and numerical results are presented. Several comparisons are made to understand the radiation efficiency curves. Since both the resistive and reactive components of the hole impedance are taken into account, the model is directly applicable to micro-perforated panels also. (C) 2016 Elsevier Ltd. All rights reserved.

Shear effects on the properties and separation characteristics of whey protein precipitates

Selective isoelectric whey protein precipitation and aggregation is carried out at laboratory scale in a standard configuration batch agitation vessel. Geometric scale-up of this operation is implemented on the basis of constant impeller power input per unit volume and subsequent clarification is achieved by high speed disc-stack centrifugation. Particle size and fractal geometry are important in achieving efficient separation while aggregates need to be strong enough to resist the more extreme levels of shear that are encountered during processing, for example through pumps, valves and at the centrifuge inlet zone. This study investigates how impeller agitation intensity and ageing time affect aggregate size, strength, fractal dimension and hindered settling rate at laboratory scale in order to determine conditions conducive for improved separation. Particle strength is measured by observing the effects of subjecting aggregates to moderate and high levels of process shear in a capillary rig and through a partially open ball-valve respectively. The protein precipitate yield is also investigated with respect to ageing time and impeller agitation intensity. A pilot scale study is undertaken to investigate scale-up and how agitation vessel shear affects centrifugal separation efficiency. Laboratory scale studies show that precipitates subject to higher impeller shear-rates during the addition of the precipitation agent are smaller but more compact than those subject to lower impeller agitation and are better able to resist turbulent breakage. They are thus more likely to provide a better feed for more efficient centrifugal separation. Protein precipitation yield improves significantly with ageing, and 50 minutes of ageing is required to obtain a 70 - 80% yield of α-lactalbumin. Geometric scale-up of the agitation vessel at constant power per unit volume results in aggregates of broadly similar size exhibiting similar trends but with some differences due to the absence of dynamic similarity due to longer circulation time and higher tip speed in the larger vessel. Disc stack centrifuge clarification efficiency curves show aggregates formed at higher shear-rates separate more efficiently, in accordance with laboratory scale projections. Exposure of aggregates to highly turbulent conditions, even for short exposure times, can lead to a large reduction in particle size. Thus, improving separation efficiencies can be achieved by the identification of high shear zones in a centrifugal process and the subsequent elimination or amelioration of such.

Reconstruction of atomic ionization probabilities in intense laser fields

Application of a parallel-projection inversion technique to z-scan spectra of multiply charged xenon and krypton ions, obtained by non-resonant field ionization of neutral targets, has for the first time permitted the direct observation of intensity-dependent ionization probabilities. These ionization efficiency curves have highlighted the presence of structure in the tunnelling regime, previously unobserved under full-volume techniques.

Development of remote monitoring process tools for biomass fired bubbling fluidized bed boilers

Remote monitoring of a power boiler allows the supplying company to make sure that equipment is used as supposed to and gives a good chance for process optimization. This improves co-operation between the supplier and the customer and creates an aura of trust that helps securing future contracts. Remote monitoring is already in use with recovery boilers but the goal is to expand especially to biomass-fired BFB-boilers. To make remote monitoring possible, data has to be measured reliably on site and the link between the power plant and supplying company’s server has to work reliably. Data can be gathered either with the supplier’s sensors or with measurements originally installed in the power plant if the plant in question is not originally built by the supplying company. Main goal in remote monitoring is process optimization and avoiding unnecessary accidents. This can be achieved for instance by following the efficiency curves and fouling in different parts of the process and comparing them to past values. The final amount of calculations depends on the amount of data gathered. Sudden changes in efficiency or fouling require further notice and in such a case it’s important that dialogue toward the power plant in question also works.

Mass spectral studies of some pentafluorophenyl derivatives of group V /|nby Andrew Tanner Rake. -- 260 St. Catharines, Ont. : [s. n.],

The mass spectra of compounds of t he series (C6F5 )3-n MP~ (n = 1,2,3, M = P and As ), (C6F5>3Sb, Ph) Sb and (C6F5 )2SbPh have been studied in detail and the important modes of fragmentation were e1ucidated, a ided by metastable ions. Various trends attributed to the central atom and or the . substituent groups have been noted and, where applicable, compared to recent studies on related phenyl and pentafluorophenyl compounds of groups IV and V. The mass spectra of fluorine containing organometallic compounds exhibit characteristic migrations of fluorine to t he central atom, giving an increasing abundance of MF+, MF2+' and RMF+ (R = Ph or C6F5) ions on descending the group_ The mass spectra of pentafluorophenyl , antimony, and arsenic compounds show a greater fragmentation of the aromatic ring than those of phosphorus. The mixed phenyl pentafluorophenyl derivatives show a characteristic pattern depending on the number of phenyl grm.lps present but show t he general characteristics of both the tris(phenyl) and tris(pentafluorophenyl) compounds. The diphenyl pentafluorophenyl der ivatives show the loss of biphenyl ion as the most import ant step, the los s of phenyl t o give the i on PhMC6F5 + being of secondary importance. The ,bis(pentafluorophenyl) phenyl derivatives fragment primarily by loss of PhC6F5 to give C6F5M+ ions, the abundance of t hese increasing r apidly from phosphorus to arsenic. This species then, exhibits a characteristic fragmentation observed in the tris(penta- fluorophenyl ) compounds. However, the abundance of (C6F5)2M+ species in these compounds i s small. I ons of the type C6H4MC6F4 + and tetrafluorobiphenylene ions C6H4C6F4 + also are observed on substitution of a phenyl group for a penta- fluorophenyl group. The fully fluorinated species (C6F4)2M+ is not observed, although octafluorobiphenylene ions , (C6F4)2+' are evident in several spectra . The appearance potentials of the major ions were obtatned from the ionisation efficiency curves. Attempts were made to correlate these to the effect of the central atom in substituent groups, but the large errors involved prevented the reaching of quantitative conclusions, although it would appear that the electron is removed from the ligand in the ionisation of t he parent molecule .

Análise da relação desempenho/custo de alguns coletores solares comerciais

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Evaluation of alkali flooding combined with intermittent flow in carbonate reservoir

The majority of carbonate reservoir is oil-wet, which is an unfavorable condition for oil production. Generally, the total oil recovery after both primary and secondary recovery in an oil-wet reservoir is low. The amount of producible oil by enhanced oil recovery techniques is still large. Alkali substances are proven to be able to reverse rock wettability from oil-wet to water-wet, which is a favorable condition for oil production. However, the wettability reversal mechanism would require a noneconomical aging period to reach the maximum reversal condition. An intermittent flow with the optimum pausing period is then combined with alkali flooding (combination technique) to increase the wettability reversal mechanism and as a consequence, oil recovery is improved. The aims of this study are to evaluate the efficiency of the combination technique and to study the parameters that affect this method. In order to implement alkali flooding, reservoir rock and fluid properties were gathered, e.g. interfacial tension of fluids, rock wettability, etc. The flooding efficiency curves are obtained from core flooding and used as a major criterion for evaluation the performance of technique. The combination technique improves oil recovery when the alkali concentration is lower than 1% wt. (where the wettability reversal mechanism is dominant). The soap plug (that appears when high alkali concentration is used) is absent in this combination as seen from no drop of production rate. Moreover, the use of low alkali concentration limits alkali loss. This combination probably improves oil recovery also in the fractured carbonate reservoirs in which oil is uneconomically produced. The results from the current study indicate that the combination technique is an option that can improve the production of carbonate reservoirs. And a less quantity of alkali is consumed in the process.

Vapor phase composition as an indicator of thermal stability of the Sm, Eu, and Yb chlorides

The Sm, Eu, and Yb tri- and dichlorides were investigated by Knudsen effusion mass spectrometry. It was found out by the analysis of mass spectra and ionization efficiency curves that the vapor composition is complex due to the partial high temperature decomposition/disproportionation of the samples. Up to five vapor species were identified for both LnCl3 (LnCl3, LnCl2, Ln2Cl4, Ln2Cl5, and Ln2Cl6) and LnCl2 (LnCl3, LnCl2, LnCl, Ln, and Ln2Cl4). The quantitative evaluation of vapor composition was made. It indicates that the disproportionation of SmCl2 and EuCl2 is negligible in the temperature range studied whereas that of YbCl2 and the decomposition of SmCl3 and YbCl3 cannot be neglected.

Wind intermittency and CO2 reductions: the case of the spanish power system

Renewable energy sources are believed to reduce drastically greenhouse gas emissions that would otherwise be generated from fossil fuels used to generate electricity. This implies that a unit of renewable energy will replace a unit of fossil-fuel, with its CO2 emissions, on an equivalent basis (with no other effects on the grid). But, the fuel economy and emissions in the existing power systems are not proportional with the electricity production of intermittent sources due to cycling of the fossil fuel plants that make up the balance of the grid (i.e. changing the power output makes thermal units to operate less efficiently). This study focuses in the interactions between wind generation and thermal plants cycling, by establishing the levels of extra fuel use caused by decreased efficiencies of fossil back-up for wind electricity in Spain. We analyze the production of all thermal plants in 2011, studying different scenarios where wind penetration causes major deviations in programming, while we define a procedure for quantifying the carbon reductions by using emission factors and efficiency curves from the existing installations. The objectives are to discuss the real contributions of renewable energies to the environmental targets as well as suggest alternatives that would improve the reliability of future power systems.

Two empirical hydrocyclone models revisited

There has been an abundance of literature on the modelling of hydrocyclones over the past 30 years. However, in the comminution area at least, the more popular commercially available packages (e.g. JKSimMet, Limn, MODSIM) use the models developed by Nageswararao and Plitt in the 1970s, either as published at that time, or with minor modification. With the benefit of 30 years of hindsight, this paper discusses the assumptions and approximations used in developing these models. Differences in model structure and the choice of dependent and independent variables are also considered. Redundancies are highlighted and an assessment made of the general applicability of each of the models, their limitations and the sources of error in their model predictions. This paper provides the latest version of the Nageswararao model based on the above analysis, in a form that can readily be implemented in any suitable programming language, or within a spreadsheet. The Plitt model is also presented in similar form. (C) 2004 Elsevier Ltd. All rights reserved.

Efeito da concentração de sólidos e de variáveis operacionais no desempenho de um hidrociclone concentrador

The hydrocycloning operation has a goal to separate solid-liquid suspensions and liquid-liquid emulsions through the centrifugal force action. Hydrocyclones are equipment with reduced size and used in both clarification and thickening. This device is used in many areas, like petrochemical and minerals process, and accumulate advantages like versatility and low cost of maintenance. However, the demand to improve the process and to reduce the costs has motivated several studies of equipment optimization. The filtering hydrocyclone is a non-conventional equipment developed at FEQUI/UFU with objective to improve the hydrocycloning separation efficiency. The purpose of this study is to evaluate the operating conditions of feed concentration and underflow diameter on the performance of a filtering geometry optimized to minimization of energy costs. The filtration effect was investigated through the comparison between the performance of the Optimized Filtering Hydrocyclone (HCOF) and the Optimized Concentrator Hydrocyclone (HCO). Because of the resemblance of hydrocyclones performance, the filtration did not represent significant effect on the performance of the HCOF. It was found that in this geometry the decrease of the variable underflow diameter was very favorable to thickening operation. The suspension concentration of quartzite at 1.0% of solids in volume was increased about 42 times when the 3 mm underflow diameter was used. The increase on the feed solid percentage was good for decreasing the energy spent, so that a minimum number of Euler of 730 was achieved at CVA = 10.0%v. However, a greater amount of solids in suspension leads to a lower efficiency of the equipment. Therefore, to minimize the underflow-to-throughput ratio and keep a high efficiency level, it is indicated to work with dilute suspension (CVA = 1.0%) and 3 mm underflow diameter (η = 67%). But if it is necessary to work with high feed concentration, the use of 5 mm underflow diameter provides a rise in the efficiency. The HCO hydrocyclone was compared to the traditional family of hydrocyclones Rietema and presented advantages like higher efficiency (34% higher in average) and lower energy costs (20% lower in average). Finally, the efficiency curves and project equation have been raised for the HCO hydrocyclone each with satisfactory adjust.

Mining patterns and factors contributing to crash severity on road curves

Road curves are an important feature of road infrastructure and many serious crashes occur on road curves. In Queensland, the number of fatalities is twice as many on curves as that on straight roads. Therefore, there is a need to reduce drivers’ exposure to crash risk on road curves. Road crashes in Australia and in the Organisation for Economic Co-operation and Development(OECD) have plateaued in the last five years (2004 to 2008) and the road safety community is desperately seeking innovative interventions to reduce the number of crashes. However, designing an innovative and effective intervention may prove to be difficult as it relies on providing theoretical foundation, coherence, understanding, and structure to both the design and validation of the efficiency of the new intervention. Researchers from multiple disciplines have developed various models to determine the contributing factors for crashes on road curves with a view towards reducing the crash rate. However, most of the existing methods are based on statistical analysis of contributing factors described in government crash reports. In order to further explore the contributing factors related to crashes on road curves, this thesis designs a novel method to analyse and validate these contributing factors. The use of crash claim reports from an insurance company is proposed for analysis using data mining techniques. To the best of our knowledge, this is the first attempt to use data mining techniques to analyse crashes on road curves. Text mining technique is employed as the reports consist of thousands of textual descriptions and hence, text mining is able to identify the contributing factors. Besides identifying the contributing factors, limited studies to date have investigated the relationships between these factors, especially for crashes on road curves. Thus, this study proposed the use of the rough set analysis technique to determine these relationships. The results from this analysis are used to assess the effect of these contributing factors on crash severity. The findings obtained through the use of data mining techniques presented in this thesis, have been found to be consistent with existing identified contributing factors. Furthermore, this thesis has identified new contributing factors towards crashes and the relationships between them. A significant pattern related with crash severity is the time of the day where severe road crashes occur more frequently in the evening or night time. Tree collision is another common pattern where crashes that occur in the morning and involves hitting a tree are likely to have a higher crash severity. Another factor that influences crash severity is the age of the driver. Most age groups face a high crash severity except for drivers between 60 and 100 years old, who have the lowest crash severity. The significant relationship identified between contributing factors consists of the time of the crash, the manufactured year of the vehicle, the age of the driver and hitting a tree. Having identified new contributing factors and relationships, a validation process is carried out using a traffic simulator in order to determine their accuracy. The validation process indicates that the results are accurate. This demonstrates that data mining techniques are a powerful tool in road safety research, and can be usefully applied within the Intelligent Transport System (ITS) domain. The research presented in this thesis provides an insight into the complexity of crashes on road curves. The findings of this research have important implications for both practitioners and academics. For road safety practitioners, the results from this research illustrate practical benefits for the design of interventions for road curves that will potentially help in decreasing related injuries and fatalities. For academics, this research opens up a new research methodology to assess crash severity, related to road crashes on curves.

Association Rule Sharing Model for Privacy Preservation and Collaborative Data Mining Efficiency

The disclosure of information and its misuse in Privacy Preserving Data Mining (PPDM) systems is a concern to the parties involved. In PPDM systems data is available amongst multiple parties collaborating to achieve cumulative mining accuracy. The vertically partitioned data available with the parties involved cannot provide accurate mining results when compared to the collaborative mining results. To overcome the privacy issue in data disclosure this paper describes a Key Distribution-Less Privacy Preserving Data Mining (KDLPPDM) system in which the publication of local association rules generated by the parties is published. The association rules are securely combined to form the combined rule set using the Commutative RSA algorithm. The combined rule sets established are used to classify or mine the data. The results discussed in this paper compare the accuracy of the rules generated using the C4. 5 based KDLPPDM system and the CS. 0 based KDLPPDM system using receiver operating characteristics curves (ROC).