Separation of n-paraffins by selective adsorption

A study has been undertaken of the vapor-phase adsorptive separation of n-alkanes from Kuwait kerosene (Kuwait National Petroleum Company, heavy kerosene) using zeolite molecular sieves. Due to the shortage of information on the adsorption of multicomponent systems in the open literature, the present investigation was initiated to study the effect of feed flowrate, temperature, and zeolite particle size on the height of mass transfer zone (MTZ) and the dynamic capacity of the adsorbent for multicomponent n-alkanes adsorption on a fixed-bed of zeolite type-5A. The optimum operating conditions for separation of the n-alkanes has been identified so that the effluent would also be of marketable quality. The effect of multicycle adsorption-desorption stages on the dynamic behaviour of zeolite using steam as a desorbing agent has been studied and compared with n-pentane and n-hexane as desorbing agents. The separation process comprised one cycle of adsorption using a fixed-bed of zeolite type-5A. The bed was fed with vaporized kerosene until saturation had been achieved whereby the n-alkanes were adsorbed and the denormalized material eluted. The process of adsorption-desorption was carried out isobarically at one atmosphere. A mathematical model has been developed to predict the breakthrough time using the method of characteristics. The results were in a reasonable agreement with the experimental values. This model has also been utilized to develop the equilibrium isotherm. Optimum operating conditions were achieved at a feed flowrate of 33.33 x 10-9 m3/s, a temperature of 643 K, and a particle size of (1.0 - 2.0) x 10-3 m. This yielded an HMTZ value and a dynamic capacity of 0.206 m and 9.6S3 x 10-2 kg n-alkanes/kg of zeolite respectively. These data will serve as a basis for design of a commercial plant. The purity of liquid-paraffin product desorbed using steam was 83.24 wt%. The dynamic capacity was noticed to decrease sharply with the cycle number, without intermediate reactivation of zeolite, while it was kept unchanged by intermediate reactivation. Normal hexane was found to be the best desorbing agent, the efficiency of which was mounted to 88.2%.

Blurred edges look faint, and faint edges look sharp:The effect of a gradient threshold in a multi-scale edge coding model

A multi-scale model of edge coding based on normalized Gaussian derivative filters successfully predicts perceived scale (blur) for a wide variety of edge profiles [Georgeson, M. A., May, K. A., Freeman, T. C. A., & Hesse, G. S. (in press). From filters to features: Scale-space analysis of edge and blur coding in human vision. Journal of Vision]. Our model spatially differentiates the luminance profile, half-wave rectifies the 1st derivative, and then differentiates twice more, to give the 3rd derivative of all regions with a positive gradient. This process is implemented by a set of Gaussian derivative filters with a range of scales. Peaks in the inverted normalized 3rd derivative across space and scale indicate the positions and scales of the edges. The edge contrast can be estimated from the height of the peak. The model provides a veridical estimate of the scale and contrast of edges that have a Gaussian integral profile. Therefore, since scale and contrast are independent stimulus parameters, the model predicts that the perceived value of either of these parameters should be unaffected by changes in the other. This prediction was found to be incorrect: reducing the contrast of an edge made it look sharper, and increasing its scale led to a decrease in the perceived contrast. Our model can account for these effects when the simple half-wave rectifier after the 1st derivative is replaced by a smoothed threshold function described by two parameters. For each subject, one pair of parameters provided a satisfactory fit to the data from all the experiments presented here and in the accompanying paper [May, K. A. & Georgeson, M. A. (2007). Added luminance ramp alters perceived edge blur and contrast: A critical test for derivative-based models of edge coding. Vision Research, 47, 1721-1731]. Thus, when we allow for the visual system's insensitivity to very shallow luminance gradients, our multi-scale model can be extended to edge coding over a wide range of contrasts and blurs. © 2007 Elsevier Ltd. All rights reserved.

Grouping and the pitch of a mistuned fundamental component:effects of applying simultaneous multiple mistunings to the other harmonics

Mistuning a harmonic produces an exaggerated change in its pitch. This occurs because the component becomes inconsistent with the regular pattern that causes the other harmonics (constituting the spectral frame) to integrate perceptually. These pitch shifts were measured when the fundamental (F0) component of a complex tone (nominal F0 frequency = 200 Hz) was mistuned by +8% and -8%. The pitch-shift gradient was defined as the difference between these values and its magnitude was used as a measure of frame integration. An independent and random perturbation (spectral jitter) was applied simultaneously to most or all of the frame components. The gradient magnitude declined gradually as the degree of jitter increased from 0% to ±40% of F0. The component adjacent to the mistuned target made the largest contribution to the gradient, but more distant components also contributed. The stimuli were passed through an auditory model, and the exponential height of the F0-period peak in the averaged summary autocorrelation function correlated well with the gradient magnitude. The fit improved when the weighting on more distant channels was attenuated by a factor of three per octave. The results are consistent with a grouping mechanism that computes a weighted average of periodicity strength across several components. © 2006 Elsevier B.V. All rights reserved.

Dispersal in a population of the lichen Hypogymnia physodes

Dispersal of a Hypogymnia physodes (L.) Nyl. population was studied on an isolated Prunus blireiana L. tree at a site in North Seattle, U.S.A. Lichen propagules were trapped on adhesive strips pinned to four sites on the tree for 7 successive days. Soredia of H. physodes were frequently deposited on the strips but thallus fragments were rare. More soredia were deposited on the upper and lower branches than on the trunk, few soredia were deposited on the underside of the branches. The total daily deposition of soredia on the tree was positively correlated with average daily wind speed. Dispersal downwind from the tree was studied with squares of adhesive contact paper pinned to boards and located at intervals up to 25 m from the tree. Soredia and a few thallus fragments were recorded 25 m and 10 m, respectively, downwind on a day when average wind speed was 10.3 m/sec. The dispersal of soredia by wind from four individual thalli was studied over 10 successive days. Soredia were deposited from each thallus on each day mostly within 2 cm of the source. Higher wind speeds were necessary to dispersae soredia on days when the relative humidity was high. Soredia and thallus fragments were also dispersed by splash dispersal. More soredia were splashed furthest at a splash height of 90 cm. These results suggest that initial colonization of the tree by H. physodes may have occurred by wind-dispersed soredia. Subsequent spread probably occurred from established thalli mainly by the dispersal of soredia by wind and rain splash.

Computer simulation of liquid flow patterns on distillation trays

This thesis describes work carried out to improve the fundamental modelling of liquid flows on distillation trays. A mathematical model is presented based on the principles of computerised fluid dynamics. It models the liquid flow in the horizontal directions allowing for the effects of the vapour through the use of an increased liquid turbulence, modelled by an eddy viscosity, and a resistance to liquid flow caused by the vapour being accelerated horizontally by the liquid. The resultant equations are similar to the Navier-Stokes equations with the addition of a resistance term.A mass-transfer model is used to calculate liquid concentration profiles and tray efficiencies. A heat and mass transfer analogy is used to compare theoretical concentration profiles to experimental water-cooling data obtained from a 2.44 metre diameter air-water distillation simulation rig. The ratios of air to water flow rates are varied in order to simulate three pressures: vacuum, atmospheric pressure and moderate pressure.For simulated atmospheric and moderate pressure distillation, the fluid mechanical model constantly over-predicts tray efficiencies with an accuracy of between +1.7% and +11.3%. This compares to -1.8% to -10.9% for the stagnant regions model (Porter et al. 1972) and +12.8% to +34.7% for the plug flow plus back-mixing model (Gerster et al. 1958). The model fails to predict the flow patterns and tray efficiencies for vacuum simulation due to the change in the mechanism of liquid transport, from a liquid continuous layer to a spray as the liquid flow-rate is reduced. This spray is not taken into account in the development of the fluid mechanical model. A sensitivity analysis carried out has shown that the fluid mechanical model is relatively insensitive to the prediction of the average height of clear liquid, and a reduction in the resistance term results in a slight loss of tray efficiency. But these effects are not great. The model is quite sensitive to the prediction of the eddy viscosity term. Variations can produce up to a 15% decrease in tray efficiency. The fluid mechanical model has been incorporated into a column model so that statistical optimisation techniques can be employed to fit a theoretical column concentration profile to experimental data. Through the use of this work mass-transfer data can be obtained.

The use of flow control devices to improve the flow pattern and throughput of sieve trays

Compared to packings trays are more cost effective column internals because they create a large interfacial area for mass transfer by the interaction of the vapour on the liquid. The tray supports a mass of froth or spray which on most trays (including the most widely used sieve trays) is not in any way controlled. The two important results of the gas/liquid interaction are the tray efficiency and the tray throughput or capacity. After many years of practical experience, both may be predicted by empirical correlations, despite the lack of understanding. It is known that the tray efficiency is in part determined by the liquid flow pattern and the throughput by the liquid froth height which in turn depends on the liquid hold-up and vapour velocity. This thesis describes experimental work on sieve trays in an air-water simulator, 2.44 m in diameter. The liquid flow pattern, for flow rates similar to those used in commercial scale distillation, was observed experimentally by direct observation; by water-cooling, to simulate mass transfer; use of potassium permanganate dye to observe areas of longer residence time; and by height of clear liquid measurements across the tray and in the downcomer using manometers. This work presents experiments designed to evaluate flow control devices proposed to improve the gas liquid interaction and hence improve the tray efficiency and throughput. These are (a) the use of intermediate weirs to redirect liquid to the sides of the tray so as to remove slow moving/stagnant liquid and (b) the use of vapour-directing slots designed to use the vapour to cause liquid to be directed towards the outlet weir thus reducing the liquid hold-up at a given rate i.e. increased throughput. This method also has the advantage of removing slow moving/stagnant liquid. In the experiments using intermediate weirs, which were placed in the centre of the tray. it was found that in general the effect of an intermediate weir depends on the depth of liquid downstream of the weir. If the weir is deeper than the downstream depth it will cause the upstream liquid to be deeper than the downstream liquid. If the weir is not as deep as deep as the downstream depth it may have little or no effect on the upstream depth. An intermediate weir placed at an angle to the direction of flow of liquid increases the liquid towards the sides of the tray without causing an increase in liquid hold-up/ froth height. The maximum proportion of liquid caused to flow sideways by the weir is between 5% and 10%. Experimental work using vapour-directing slots on a rectangular sieve tray has shown that the horizontal momentum that is imparted to the liquid is dependent upon the size of the slot. If too much momentum is transferred to the liquid it causes hydraulic jumps to occur at the mouth of the slot coupled with liquid being entrained, The use of slots also helps to eliminate the hydraulic gradient across sieve trays and provides a more uniform froth height on the tray. By comparing the results obtained of the tray and point efficiencies, it is shown that a slotted tray reduces both values by approximately 10%. This reduction is due to the fact that with a slotted tray the liquid has a reduced residence time Ion the tray coupled also with the fact that large size bubbles are passing through the slots. The effectiveness of using vapour-directing slots on a full circular tray was investigated by using dye to completely colour the biphase. The removal of the dye by clear liquid entering the tray was monitored using an overhead camera. Results obtained show that the slots are successful in their aim of reducing slow moving liquid from the sides of the tray, The net effect of this is an increase in tray efficiency. Measurements of slot vapour-velocity found it to be approximately equal to the hole velocity.

Use of colour image analysis for assessment of fire damaged concrete

The aim of this project was to carry out a fundamental study to assess the potential of colour image analysis for use in investigations of fire damaged concrete. This involved:(a) Quantification (rather than purely visual assessment) of colour change as an indicator of the thermal history of concrete.(b) Quantification of the nature and intensity of crack development as an indication of the thermal history of concrete, supporting and in addition to, colour change observations.(c) Further understanding of changes in the physical and chemical properties of aggregate and mortar matrix after heating.(d) An indication of the relationship between cracking and non-destructive methods of testing e.g. UPV or Schmidt hammer. Results showed that colour image analysis could be used to quantify the colour changes found when concrete is heated. Development of red colour coincided with significant reduction in compressive strength. Such measurements may be used to determine the thermal history of concrete by providing information regarding the temperature distribution that existed at the height of a fire. The actual colours observed depended on the types of cement and aggregate that were used to make the concrete. With some aggregates it may be more appropriate to only analyse the mortar matrix. Petrographic techniques may also be used to determine the nature and density of cracks developing at elevated temperatures and values of crack density correlate well with measurements of residual compressive strength. Small differences in crack density were observed with different cements and aggregates, although good correlations were always found with the residual compressive strength. Taken together these two techniques can provide further useful information for the evaluation of fire damaged concrete. This is especially so since petrographic analysis can also provide information on the quality of the original concrete such as cement content and water / cement ratio. Concretes made with blended cements tended to produce small differences in physical and chemical properties compared to those made with unblended cements. There is some evidence to suggest that a coarsening of pore structure in blended cements may lead to onset of cracking at lower temperatures. The use of DTA/TGA was of little use in assessing the thermal history of concrete made with blended cements. Corner spalling and sloughing off, as observed in columns, was effectively reproduced in tests on small scale specimens and the crack distributions measured. Relationships between compressive strength/cracking and non-destructive methods of testing are discussed and an outline procedure for site investigations of fire damaged concrete is described.

Drivers of peak sales for pharmaceutical brands

Peak sales are an important metric in the pharmaceutical industry. Specifically, managers are focused on the height-of-peak-sales and the time required achieving peak sales. We analyze how order of entry and quality affect the level of peak sales and the time-to-peak-sales of pharmaceutical brands. We develop a growth model that includes these two variables as well as control variables for own and competitive marketing activities. We find that early entrants achieve peak sales later, and they have higher peak-sales levels. High-quality brands achieve peak sales earlier, and their peak-sales levels are higher. In addition, quality has a moderating effect on the order of entry effect on time-to-peak-sales. Our results indicate that late entrants have longer expected time-to-peak-sales when they introduce a brand with high quality.

Reactive processing of polymers:functionalisation of ethylene-propylene diene terpolymer (EPDM) in the presence and absence of a co-agent and effect of functionalised EPDM on compatibilisation of poly(ethylene terephthalate)/EPDM blends

Ethylene-propylene diene terpolymer (EPDM) was functionalized with glycidyl methacrylate (GMA) during melt processing by free radical grafting with peroxide initiation in the presence and absence of a reactive comonomer trimethylolpropane triacrylate (Tris). Increasing the peroxide concentration resulted in an increase in the GMA grafting yield, albeit the overall grafting level was low and was accompanied by higher degree of crosslinking of EPDM which was found to be the major competing reaction. The presence of Tris in the grafting system gave rise to higher grafting yield produced at a much lower peroxide concentration though the crosslinking reactions remained high but without the formation of GMA-homopolymer in either of the two systems. The use of these functionalized EPDM (f-EPDM) samples with PET as compatibilisers in binary and ternary blends of PET/EPDM/f-EPDM was evaluated. The influence of the different functionalisation routes of the rubber phase (in presence and absence of Tris) and the effect of the level of functionality and microstructure of the resultant f-EPDM on the extent of the interfacial reaction, morphology and mechanical properties was also investigated. It is suggested that the mechanical properties of the blends are strongly influenced by the performance of the graft copolymer, which is in turn, determined by the level of functionality, molecular structure of the functionalized rubber and the interfacial concentration of the graft copolymer across the interface. The cumulative evidence obtained from torque rheometry, scanning electron microscopy, SEM, dynamic mechanical analysis (DMA), tensile mechanical tests and Fourier transform infrared (FTIR) supports this. It was shown that binary and ternary blends prepared with f-EPDM in the absence of Tris and containing lower levels of g-GMA effected a significant improvement in mechanical properties. This increase, particularly in elongation to break, could be accounted for by the occurrence of a reaction between the epoxy groups of GMA and the hydroxyl/carboxyl end groups of PET that would result in a graft copolymer which could, most probably, preferentially locate at the interface, thereby acting as an 'emulsifier' responsible for decreasing the interfacial tension between the otherwise two immiscible phases. This is supported by results from FTIR analysis of the fractionated PET phase of these blends which confirm the formation of an interfacial reaction, DMA results which show a clear shift in the T s of the blend components and SEM results which reveal very fine morphology, suggesting effective compatibilisation that is concomitant with the improvement observed in their tensile properties. Although Tris has given rise to highest amount of g-GMA, it resulted in lower mechanical properties than the optimized blends produced in the absence of Tris. This was attributed to the difference in the microstructure of the graft and the level of functionality in these samples resulting in less favourable structure responsible for the coarser dispersion of the rubber phase observed by SEM, the lower extent of T shift of the PET phase (DMA), the lower height of the torque curve during reactive blending and FTIR analysis of the separated PET phase that has indicated a lower extent of the interfacial chemical reaction between the phases in this Tris-containing blend sample. © 2005 Elsevier Ltd. All rights reserved.

Why is it possible to detect doped regions of semiconductors in low voltage SEM:a review and update

There is an urgent need for fast, non-destructive and quantitative two-dimensional dopant profiling of modern and future ultra large-scale semiconductor devices. The low voltage scanning electron microscope (LVSEM) has emerged to satisfy this need, in part, whereby it is possible to detect different secondary electron yield values (brightness in the SEM signal) from the p-type to the n-type doped regions as well as different brightness levels from the same dopant type. The mechanism that gives rise to such a secondary electron (SE) contrast effect is not fully understood, however. A review of the different models that have been proposed to explain this SE contrast is given. We report on new experiments that support the proposal that this contrast is due to the establishment of metal-to-semiconductor surface contacts. Further experiments showing the effect of instrument parameters including the electron dose, the scan speeds and the electron beam energy on the SE contrast are also reported. Preliminary results on the dependence of the SE contrast on the existence of a surface structure featuring metal-oxide semiconductor (MOS) are also reported. Copyright © 2005 John Wiley & Sons, Ltd.