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.     

Barrier effect of flame retardant systems in poly(methyl methacrylate): Study of the efficiency of the surface treatment by octylsilane of silica nanoparticles in combination with phosphorous fire retardant additives

In this work, flame retardant systems comprising ammonium polyphosphate (AP423) and hydrophilic (A200) or hydrophobic (R805) nanometric silica were incorporated into PMMA. The following techniques were performed to detail the fire behaviour of the composites: mass loss cone calorimetry, pyrolysis‐combustion flow calorimetry, pyrolysis‐gas chromatography–mass spectrometry, thermogravimetric analysis, X‐ray diffraction analysis, Fourier transform infrared spectroscopy and microscopic observations. The best fire behaviour was obtained with the surface‐treated silica in the presence of AP423. The formation of a new crystalline phase from the interactions between AP423 and R805 silica and a strong barrier effect due to a layered residue were the main modes of action of this system. Moreover, we have shown that the difference between the AP423 + R805 and AP423 + A200 systems was due to poor dispersion of the silica into the PMMA matrix in the latter formulation. Copyright © 2011 John Wiley & Sons, Ltd.     

Reactivity between liquid Si or Si alloys and graphite

The fundamental issues of the reaction at liquid Si/graphite interfaces between Si melting point (1412 °C) and 1600 °C are studied on the basis of results obtained with polycrystalline graphite concerning the growth kinetics of the interfacial reaction layer and the microstructure and morphology of this layer. Experiments were also performed using vitreous carbon substrates. Results are also reported for Si–Al alloys at 1000 °C. The elementary process controlling the growth kinetics is determined and a model is proposed to describe the different stages of the interfacial reaction.     

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.     

Polyamide 66 microspheres metallised with in situ synthesised gold nanoparticles for a catalytic application

A simple concept is proposed to metallise polyamide 66 (PA66) spherulite structures with in situ synthesised gold nanoparticles (Au NPs) using a wet chemical method. This cost-effective approach, applied to produce a PA66/Au NP hybrid material, offers the advantages of controlling the nanoparticle size, the size distribution and the organic-inorganic interactions. These are the key factors that have to be controlled to construct consistent Au nanostructures which are essential for producing the catalytic activities of interest. The hybrid materials obtained are characterised by means of scanning electron microscopy, transmission electron microscopy, attenuated total reflection-Fourier transform infrared spectrometry and X-ray diffraction spectrometry. The results show that PA66 microspheres obtained via the crystallisation process are coated with Au NPs of 13 nm in size. It was found that controlling the metal coordination is the key parameter to template the Au NPs on the spherulite surfaces. The preparation processes and the key factors leading to the formation of PA66 spherulites coated with Au NPs are discussed. Moreover, the efficiency of the coated spherulites as a potential catalyst is proved by demonstrating the reduction of methylene blue via UV-visible spectrometry.     

A new class of organosilane-modified polycarboxylate superplasticizers with low sulfate sensitivity

It is well-established that a competitive adsorption exists between polycarboxylate superplasticizers (SP) and sulfate ions solubilized in the interstitial solution of cement paste, which may cause a loss of the dispersing properties. This has been explained by competitive weak ionic interactions between functional carboxyl groups and sulfate ions with cement grains. In this study, SPs including trialkoxysilane functional groups have been synthesized. Adsorption and dispersing properties of these SPs were evaluated in the presence of different concentrations of Na₂SO₄ added in aqueous solution. It appeared that a partial substitution of carboxyl groups by trialkoxysilane in the polymer makes them more resistant to sulfate ions. We suggested that the high adsorption capacity of these SPs results from the formation of strong bonds between hydroxysilane groups and calcium silicate hydrate phases. The improved compatibility of these new silylated SPs has been demonstrated through the formulation of two different concrete equivalent mortars.