Modelling a circulating fluidized bed riser reactor with gas—solids downflow at the wall

A predictive model was developed for the fully developed zone of a circulating fluidized bed (CFB) riser reactor operating in the fast fluidization regime that overcomes limitations of existing models. The model accounts for the upward flow of gas and solids in the core and downward flow of the two phases in the annulus. Additionally, a numerical solution methodology for the simulation of a riser reactor employing the hydrodynamic model was devised. A simulation was performed using the fast, main Claus reaction to demonstrate the effects of backmixing in the fast fluidization regime. It was found that the molar flow rates of the reactants leaving a fast fluidized CFB riser reactor were significantly higher than those leaving an identical reactor operating in the pneumatic transport regime.     

Dislocation Cores and Hardness Polarity of 4H-SiC

The hardness of opposite basal faces of 4H-SiC single crystals has been measured in the temperature range 25°–1200°C. A strong hardness anisotropy between the silicon-terminated (0001) and carbon-terminated (0001) faces of this polar crystal has been found. Transmission electron microscopy investigation of the dislocations in the plastic zone of the 1200°C indentations shows that they lie predominantly on the basal planes parallel to the indented face, and the extra-half planes of the nonscrew dislocations originate from the indented face. It is also found that, when the (0001) Si-terminated face is indented, the dislocations are either widely dissociated, with the width of the stacking fault ribbon much larger than the equilibrium value, or else they are single leading partials, with the corresponding trailing partials absent. In this case, all the leading partials are found to have a silicon core. On the other hand, the dislocations in the plastic zone of the carbon-terminated face are in the form of dissociated dislocations, with the width of the associated stacking fault ribbons appreciably less than the equilibrium value. Moreover, the leading partials of these dissociated dislocations have a carbon core. The results indicate that the hardness of the polar basal faces of 4H-SiC at elevated temperatures is partly determined by the nature of the dislocation cores nucleated by the indentation process. It is argued that this is due to the influence of the core on the generation and glide of the leading partial dislocations.     

Transport properties of natural gas through polyethylene nanocomposites at high temperature and pressure

Four titanium(IV) alkoxides, namely: Ti(IV) n-propoxide (1), Ti(IV) n-butoxide (2), Ti(IV) tert-butoxide (3), and Ti(IV) 2-ethylhexoxide (4), have been used as initiators in the bulk ring-opening polymerization (ROP) of ??-caprolactone (??-CL). The influence of the alkoxide group on the course of the ROP of ??-CL was investigated by means of ¹H-NMR and differential scanning calorimetry (DSC). The ¹H-NMR spectra confirmed that the ROP reaction of ??-CL proceeded via the widely accepted coordination-insertion mechanism for each of the four initiators. Isoconversional methods have been used to evaluate non-isothermal DSC data via the equations of Friedman, Kissinger-Akahira-Sunose (KAS) and Ozawa-Flynn-Wall (OFW). The kinetic studies showed that the polymerization rate for the four initiators (1-4) was in the order of 1?>?2????4?>?3. The lowest activation energies (40?C47, 42?C44, and 49?C52?kJ/mol for the Friedman, KAS and OFW methods respectively) were found in the polymerizations using Ti(IV) n-propoxide (1), while the highest activation energies (84?C107, 77?C87, and 80?C91?kJ/mol for the Friedman, KAS and OFW methods respectively) were obtained using Ti(IV) tert-butoxide (3). Differences in the rates of polymerization and the activation energies amongst the four initiators appeared to be governed mainly by the different degrees of steric hindrance in the initiator structure. These results represent important findings regarding the steric influence of the alkoxide groups on the kinetics of the ROP of ??-CL initiated by titanium(IV) alkoxides.     

In‐line near infrared spectroscopy monitoring of pharmaceutical powder moisture in a fluidised bed dryer: An efficient methodology for chemometric model development

This work proposes a novel chemometric methodology for in‐line near infrared spectroscopy (NIRS) monitoring of pharmaceutical powder moisture in a fluidised‐bed dryer. The collected spectra are analysed by multivariate chemometrics involving the preparation of numerous laboratory samples. A different methodology, using only plant samples, was tested in real‐time. A specially designed probe tip, allowing for robust in‐situ spectral acquisition, was designed. The results prove that NIRS can be as efficient as traditional quality analyses, e.g. loss‐on‐drying, in measuring powder moisture content in a fluidised bed dryer with a calibration model based only on plant samples. © 2011 Canadian Society for Chemical Engineering     

Effect of Oxime Ether Incorporation in Acyl Indole Derivatives on PPAR Subtype Selectivity

Compounds that simultaneously activate peroxisome proliferator‐activated receptor (PPAR) subtypes α and γ have the potential to effectively treat dyslipidemia and type 2 diabetes (T2D) in a single pharmaceutically active molecule. The frequently observed side effects of selective PPARγ agonists, such as edema and weight gain, were expected to be overcome by using additive PPARα activity, leading to dual PPARα/γ agonists with balanced activity for both subtypes. Herein we report the discovery, synthesis, and optimization of a new series of α‐ethoxyphenylpropionic acid bearing 5‐ or 6‐substituted indoles. The incorporation of oxime ethers on the carbonyl portion of the benzoyl group can bring the PPARα/γ potency ratio equal to or slightly greater than one, as is the case for compounds 20 c and 21 a . Compound 20 c shows high efficacy in an ob/ob mouse model of T2D and dyslipidemia, similar to that of rosiglitazone and tesaglitazar, but with a significant increase in body weight gain. In contrast, compound 21 a , less potent as a dual PPARα/γ activator than 20 c , showed an interesting pharmacological profile, as it elicits a decrease in body weight relative to reference compounds.     

Thiol-ene “clickable” carbon-chain polymers based on diallyl cyclopropane-1,1-dicarboxylate

A novel type of clickable polymers with a very high local density of allyl side groups was developed. These polymers were obtained by the anionic ring-opening (co)polymerization of diallyl cyclopropane-1,1-dicarboxylate using as an initiating system a protic precursor whose acid–base reaction with the t-BuP₄ phosphazene base generated the initiator in situ. The obtained polymers display geminated allyl groups on every third carbon alongside the macromolecular backbone. Homopolymers as well as block and statistical copolymers have been synthesized, with controlled molecular weights and narrow molecular weight distributions. The coupling of mercaptans with the allyl CC double bonds has been investigated both thermally and photochemically, with the influence of the type of initiation on the efficiency of the polymer modification being discussed in comparison with other “clickable” systems. Further functionalization by several thiols was performed, leading to a range of functional poly(cyclopropane-1,1-dicarboxylate)s.     

Effect of surface resistance on cyclohexane uptake curves in Silicalite-1 crystals

Adsorption kinetics of cyclohexane in a variety of Silicalite-1 samples were measured by gravimetric uptake experiments. The kinetic appears as dependent upon the history of the crystals. Samples stored for several months before calcination (with their micropores full of template) exhibit a kinetic drop by almost an order of magnitude. Surprisingly, physico-chemicals analysis do not show any differences between these samples (no modification of their crystallinity or morphology, and no residual carbon is detected in the pore network). The kinetic drop is therefore attributed to a modification of the crystals surface, induced by a long-time contact with the template or cyclohexane molecules.Aged and as-synthesized (non-calcined) samples were etched by an HF solution, so as to “purify” the surface of the crystals. After a few minutes of treatment, the aged samples recover their initial adsorption kinetic, confirming that the kinetic drop is induced by the partial blocking of the entrance of the pores. Moreover, some of the as-synthesized crystals also show a rise of their adsorption kinetic, showing that surface resistance can be present ab initio, depending on the synthesis conditions.In an attempt to produce an accelerated aging effect, hydrothermal treatments were performed on non-calcined crystals. However, the treatments conditions are too severe, and induce variations in the crystal structure.     

Cold Crystallization of PLLA Studied by Simultaneous SAXS and WAXS

Summary: The cold crystallization process of initially amorphous poly(L ‐lactic acid), PLLA, with two different molecular weights, during a heating at 2 °C/min, was investigated by DSC and time‐resolved simultaneous SAXS and WAXS, using synchrotron radiation. Equatorial scans of the isotropic 2D‐SAXS patterns showed that the average Bragg long period (L_B) of PLLA samples was approximately constant with the development of cold crystallization up to a temperature that corresponded to a melt/re‐crystallization process that took place before the nominal melting peak seen by DSC. L_B values were found to be higher for the high molecular weight material. This was in accordance with the higher melting temperature observed in the high molecular weight PLLA that implied the existence of thicker lamellae. WAXS results showed that the molecular weight did not apparently affect the crystal form and the final degree of crystallinity of PLLA. The Avrami parameters from WAXS and DSC were consistent, showing that the non‐isothermal cold crystallization of the two PLLA samples corresponded mainly to a three‐dimensional growth, although an imperfect crystallization process was involved at early times. The crystallization rate of PLLA, observed both by WAXS and DSC, decreased with increasing molecular weight.

SAXS profiles of PLLA2 as a function of temperature. The inset shows the 2D‐SAXS pattern obtained at 180 °C.     

Blends composed of poly(N‐isopropylacrylamide) and an ethylene/vinyl alcohol copolymer: Thermal and morphological studies

Blends of poly(N‐isopropylacrylamide) (PNIPAM) and an ethylene/vinyl alcohol copolymer (EVAL) were obtained through casting from dimethyl sulfoxide (DMSO) solutions and phase inversion in 50/50 DMSO/H₂O solutions. The miscibility and morphology of the PNIPAM/EVAL blends were investigated with thermal and morphological analysis. Differential scanning calorimetry indicated that the crystallinity of EVAL decreased with increasing PNIPAM content and that the blends cast from DMSO/H₂O solutions were miscible in the melt state. Measurements of the melting point depression allowed the determination of the interaction energy density (B) and Flory–Huggins interaction parameter (χ₁₂) with the Nishi–Wang equation. The negative B and χ₁₂ values obtained were examined in terms of the specific intermolecular interactions between the polymers. Scanning electron micrographs revealed that blends obtained by the casting method led to dense membranes, whereas the phase‐inversion method rendered typical macroporous membranes. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 501–505, 2004     

Synthesis of polar vinyl monomer–olefin copolymers by α‐diimine nickel catalyst

Vinyl acetate, methyl methacrylate, acrylonitrile and methyl vinyl ketone were investigated for co‐ and terpolymerization with ethylene and ethylene–propylene. Precursor [bis(N,N ′‐dimesitylimino)acenaphthene]dibromonickel, activated by methylaluminoxane was used as a catalyst system and trialkylaluminium was employed to block the polar groups for these polymerizations. Polymerization activities of the order of magnitude of 10⁶ in the case of vinyl acetate and methyl methacrylate, and 10⁵ in the case of acrylonitrile were achieved. Microanalysis and GPC of acrylonitrile copolymers found about 17 units of acrylonitrile per polymer chain. Copolymers with very different properties from the parent homopolymers were obtained in all cases except that of methyl vinyl ketone. © 2001 Society of Chemical Industry