Adsorption and desorption kinetics of hydrocarbons in FCC catalysts studied using a tapered element oscillating microbalance (TEOM). Part 2: numerical simulations

The factors affecting the adsorption and desorption kinetics in a TEOM are reviewed in detail with particular attention given to the assumptions required to obtain physical transport parameters from the data. Two models are presented to simulate TEOM adsorption data in the case that concentration differences down the catalyst bed can be neglected, as is appropriate when the amount of catalyst used is small, the carrier gas flowrate is large, and/or the adsorbate partial pressure is low. In the first model, the effective diffusion coefficient, D_e, is taken to be constant. In the second model, the effective diffusion coefficient is assumed to obey the Darken equation, D_e=D₀/(1−θ). The TEOM results obtained on n-hexane, n heptane, n-octane, toluene and p-xylene on a commercial FCC catalyst and on pure rare-earth exchanged zeolite Y under non-reacting conditions (373-) are analysed in detail. It is found that intracrystalline diffusion is not the limiting factor affecting the overall rates of adsorption and desorption for the systems studied. Instead, it is the transport of molecules between the adsorbed and vapour phases at the edge of zeolite crystallites that is the limiting transport step affecting the overall kinetics. For the FCC catalyst, the limiting step is the transport of molecules at the zeolite-matrix interface rather than, say, the matrix-vapour interface. Local rate constants for the desorption of the hydrocarbons at the rate-controlling interface have been obtained.     

Fast training procedure for Viola–Jones type object detectors using Laplacian clutter models

This paper presents a fast training strategy for the Viola–Jones (VJ) type object-detection systems. The VJ object- detection system, popular for its high accuracy at real-time testing speeds, has a drawback that it is slow to train. A face detector, for example, can take days to train. In content-based image retrieval (CBIR), where search needs to be performed instantaneously, VJ’s long training time is not affordable. Therefore, VJ’s method is hardly used for such applications. This paper proposes two modifications to the training algorithm of VJ-type object detection systems which reduces the training time to the order of seconds. Firstly, Laplacian clutter (non-object) models are used to train the weak classifier, thus eliminating the need to read and evaluate thousands of clutter images. Secondly, the training procedure is simplified by removing the time-consuming AdaBoost-based feature selection procedure. An object detector, trained with 500 images, approximately takes 2 s for training in a conventional 3 GHz machine. Our results show that the accuracy of the detector, built with the proposed approach, is inferior to that of VJ for difficult object class such as frontal faces. However, for objects with lesser degree of intra-class variations such as hearts, state-of-the-art accuracy can be obtained. Importantly, for CBIR applications, the fast testing speed of the VJ type object detector is maintained.     

Uniaxial stretching of poly(keto‐ether‐imide) films

Narrow strips of various fully imidized polyimide films were stretched under constant load either isothermally or during a temperature ramp. The effects of process variables (load and temperature) on modulus, failure strain, and tensile strength of the stretched films were characterized and room temperature moduli of up to 16 GPa were documented. Several materials that undergo strain‐induced crystallization were identified as candidates for further property optimization. Polym. Eng. Sci. 44:1360–1367, 2004. © 2004 Society of Plastics Engineers.     

A DSC study of curative interactions. II. The interaction of 2,2′-dibenzothiazole with ZnO,sulfur, and stearic acid

The interaction of combinations of sulfur, 2,2′-dibenzothiazole (MBTS), ZnO, and stearic acid were studied by differential scanning calorimetry. A MBTS/stearic acid interaction was indicated as evidenced by the effect the MBTS/stearic acid combination had on the melting of sulfur, the S_α → S_β transition being suppressed in favor of a S_α → S_γ transition. The dissolution/interaction of MBTS in molten sulfur was also delayed by the MBTS/stearic acid interaction, which, it is proposed, involved protonation of the N atom in MBTS by stearic acid. MBTS did not affect the formation of zinc stearate from ZnO and stearic acid, but when sulfure was added to the mixture, the ZnO/stearic acid reaction did not go to completion. No direct evidence for the formation of 2,2′-dibenzothiazole polysulphides was found, but the absence of the S_γ → S_μ transition in sulfur/MBTS mixes was interpreted as indirect evidence of a reaction between these curatives. There was no evidence for the formation of a sulfur/MBTS/ZnO compound of the type generally attributed the role of an active sulfurating agent in accelerated sulfur vulcanization.     

Oxygen permeation of blends of copolymers of siloxanes and poly(methylmethacrylate)

A series of low molecular weight (≈40000) copolymers of methylmethacrylate (MMA) and 4-(methacryloyloxy)butylpentamethyldisiloxane (MBPD) have been synthesized by free radical polymerization in dimethylformamide solution. The microstructure, as derived from ¹³C NMR spectra, indicates that the copolymers are about 80% syndiotactic with an overall random distribution of mers. At room temperature, copolymers rich in MMA are clear, rigid glasses but become liquid at high MBPD content. Blends of these copolymers with PMMA are all heterogeneous with visible phase separation over most of the composition range. Differential scanning calorimetry studies show the presence of two T_g's when the relative concentration of PMMA to copolymer is high. Blends of two co-polymers of similar siloxane content produce clear films with no indication of phase separation. The permeability to oxygen at 25°C increases from 0.20 for pure PMMA to 3.0 (fmol/m·s·Pa.) for a copolymer of MMA/MBPD of the mole ratio of 3:1. Evaluation of the permeation behaviors of the blends suggests that blends rich in siloxane exist as a layered structure with the PMMA rich component dominating the observed permeability.     

Service of forsterite refractories in regenerator roofs of open-hearth furnaces

Conclusions The Panteleimonov Refractories Plant produced a large industrial batch of forsterite roof brick for the lower structure of open-hearth furnaces. Tests carried out at the Donetsk Metallurgical Factory showed that it is desirable to use these forsterite refractories: the life of the regenerator roofs was four campaigns in the main roof with an adequately large residual thickness.Investigations established that the changes in the forsterite brick during service in the roof of regenerators are similar to the changes in bricks during service in other structural elements, but the destruction processes occur much more slowly.Translated from Ogneupory, No. 8, pp. 31–38, August, 1968.     

Continuous solvent extraction of sunflower,seed, groundnuts,palmkernels, rapeseed,and copra

In principle, the oil milling process is straightforward. The wide variety of equipment in use reflects, however, a multiparametric process. The main limiting parameters are kind of seed, oil content, particle strength, particle structure, temperature, moisture, particle size, residence time, mechanical forces, etc. Additionally, the seed specific parameters vary not only between kinds of seed but also for the same seed, due to different conditions in climate, soil, and harvesting. Therefore, equipment design must be widely based on statistical averages of the limiting parameters. In other words, exact precalculation of the single technological steps is impossible. As a consequence, for more than 5,000 years, the oil milling process has been in the stage of being optimized. The acutal technical standard is very satisfying, but there is still a strong need for further research and development. Currently, as in the past, the oil milling process seems to be not so much a science as an art.     

Hot-Pressing Behavior of Si3N4

The densification behavior of Si₃N₄ containing MgO was studied in detail. It was concluded that MgO forms a liquid phase (most likely a magnesium silicate). This liquid wets and allows atomic transfer of Si₃N₄. Evidence of a second-phase material between the Si₃N₄ grains was obtained through etching studies. Transformation of α- to β-Si₃N₄ during hot-pressing is not necessary for densification.     

ABA block copolymers without tapering by isokinetic living anionic polymerization in a series of stirred tank reactors

Equations for the molecular weight distribution and the average molecular weights of a living anionic polymerization with very rapid or slow initiation are presented for a series of stirred tank reactors. It is shown that polydispersity of the polymer in the last vessel of a cascade takes for nearly complete conversion of monomer then a minimum, when the reaction is performed isokinetically with concern to monomer conversion, i.e. when monomer conversion in each vessel of a cascade of n tanks is 1/n. Now, polydispersity of the polymer in the mth vessel of the cascade (1 ≤ m ≤ n) is D_m = 1 + 1/m. Values of all systems variables needed for isokinetic control of the polymerization may be precalculated from kinetic models. For vessels of equal size and with equal residence times reaction temperature is suggested as control variable increasing stepwise from vessel to vessel. The proposed procedure was checked for the systems styrene/n-butyllithium/toluene, styrene/s-butyllithium/benzene, and isoprene/s-butyllithium/n-heptane. A satisfying agreement between calculated and measured values of the objectives monomers conversion, number average molecular weight, and polydispersity was found. It is proposed to use the described procedure for the preparation of ABA block copolymers with negligible tapering between the blocks by living anionic polymerization in a series of stirred tank reactors.     

Dielectric relaxation of poly(chlorostyrenes) and their copolymers in the primary transition region

Dielectric relaxation measurements were carried out on a series of bulk poly(chlorostyrene) homopolymers and random copolymers over the frequency range from 50 to 100 kHz and at temperatures in the neighbourhood of the glass transitions of the polymers thus encompassing the α relaxation. Homopolymers examined were polystyrene (PS), poly(2-chlorostyrene) (P2CS), poly(3-chlorostyrene) (P3CS), and poly(4-chlorostyrene) (P4CS). Copolymers were poly(styrene-co-2-chlorostyrene) (PS2CS), poly(styrene-co-4-chlorostyrene) (PS4CS), and poly(2-chlorostyrene-co-4-chlorostyrene) (P2CS4CS). The dielectric data were analysed to yield dipole moments and Kirkwood—Fröhlich correlation parameters. The shapes of the dielectric loss curves were also taken into account. Glass transition temperatures were determined by differential scanning calorimetry (d.s.c.). It was concluded that the phenyl ring rotates freely in the α relaxation regions of PS, P4CS, and P3CS, but not in P2CS. The dipole moments of the copolymers are correlated with dyad distributions calculated from reactivity ratios.