Crystallization of Stoichiometric SbSI Glass

Congruent crystallization of antimony sulphoiodide (SbSI) glass of stoichiometric composition, which is prepared successfully for the first time using rapid melt‐quenching, has been investigated using differential scanning calorimetry (DSC). The results for glass powder show a glass transition at 127°C and two separate exothermal peaks with maxima around 140°C and 190°C. The ratio of the intensities of the exothermal peak at ~190°C to the peak at ~140°C increases as the particle size and heating rate are increased, but their total enthalpy remains constant at 62 ± 2 J/g for all DSC runs. Surface heating of the glass induced by a 520 nm CW laser shows two contracted regions: needle‐like crystalline formations at low temperature and bulk crystallization at high temperature. The observed phenomena and DSC results suggest two different kinds of crystallization of the SbSI phase: one‐dimensional crystallization at low temperature which starts from the sample surface and three‐dimensional bulk crystallization that continues the transformation to crystalline state at higher temperatures. The origin of the two different crystallizations can be traced to the strong anisotropy of the SbSI crystal structure due to the weak van der Waals interaction between covalent‐ionic chains (Sb₂S₂I₂)_n.     

Influence of polyimide precursor synthesis route and ortho-position functional group on thermally rearranged (TR) polymer properties: Conversion and free volume

Thermal rearrangement of polyimides with ortho-position groups to polybenzoxazoles and related structures has been of recent interest for producing gas separation membranes. This study explores the influence of synthesis route and ortho-position functional group on the thermal rearrangement process and the fractional free volume of thermally rearranged (TR) polymers produced from polyimides derived from 3,3′-dihydroxy-4,4′-diamino-biphenyl and 2,2′-bis-(3,4-dicarboxyphenyl) hexafluoropropane dianhydride (HAB–6FDA). Acetate, propanoate, and pivalate ortho-position functional groups were considered. Thermogravimetric analysis (TGA) was used to study thermal rearrangement at temperatures between 350 and 450 °C, and evolved gases from TGA were analyzed via mass spectrometry to characterize the byproducts of thermal rearrangement and thermal degradation. CO₂ was the major byproduct of thermal rearrangement for all samples, and its evolution began well before the onset of thermal degradation. When non-hydroxyl ortho-position groups were present in the polymers, several byproducts other than CO₂ were also observed due to the loss of these ortho-position groups before thermal rearrangement. Free volume generally increased with increasing extent of thermal rearrangement, but precise values of free volume could not be accurately determined for polymers with propanoate and pivalate ortho-position functional groups due to uncertainties in the chemical structure of partially converted materials. For polymers with acetate and hydroxyl ortho-position groups, free volume could be determined within the uncertainty of density measurements. Thermal rearrangement behavior and free volume results for acetate containing polymers synthesized via different routes were very similar. Based on these results, the chemical structure of the ortho-position functional group has a larger impact on TR polymer properties than the polyimide precursor synthesis route.     

Effect of lubricating oil contamination on evaporation in refrigerants R12 and R22

An investigation has been made into the effect of oil concentration on evaporation heat transfer coefficients in refrigerant-oil mixtures flowing in a horizontal tube. A new correlation is presented for heat transfer coefficients in convective evaporation of refrigerant-oil mixtures that predicts the results of the present study within approximately ±20%. The paper reports measurements of evaporation heat transfer coefficients in refrigerants R12 and R22, both oil-free and with two concentrations of Shell Clavus 32 oil. A 1·8 m long ⅜ in O/D copper tube (8·05 mm I/D) was used, at evaporation temperatures of −5°C, 0°C and +5°C. Heat flux and mixture mass velocity were kept constant at 2500 W m⁻² and 155 kg m⁻² s⁻¹, respectively, and measured coefficients were in the range of 1400 to 3900 W m⁻² K⁻¹. The results showed that, for a complete evaporator, 2% oil may be expected to increase the heat transfer coefficient by 12%, but 10% oil returns the coefficient to oil-free values.     

The polyurea structure and the role of Amine-Terminated Polyethers and Polyesters in Polyurethanes

The Reaction Injection Molding (RIM) technology has made it possible to master the fast reaction of di- and polyamines with di- and polyisocyanates, leading to the preferred polyurea structure. Telechelics with amino end groups are gaining increased interest for the manufacture of polyurethane-polyurea materials by this technology. They make it possible to substitute all urethane groups in the elastomers with urea groups. The telechelics which are considered are amine-terminated polyethers (ATPE) and polyesters based on the typical soft-segment forming polycondensation polymers which are widely used in polyurethane chemistry. Isocyanate-terminated prepolymers of toluene diisocyanate and polyether polyols can be hydrolyzed in aqueous alkaline media via the carbamate intermediate to the amineterminated prepolymers. The reactivity of these aromatic ATPEs was ideally fit for the RIM process. ATPEs by the hydrolysis process are somewhat limited if products with low viscosities are required. In the reaction of chloro-nitrobenzenes with polyether polyols followed by the hydrogenation of the nitro groups of the terminal phenoxy moieties, we found a path for the synthesis of low viscosity aromatic ATPEs. Capping of polyether polyols with acetoacetate groups and subsequent reaction of the acetoacetylated polyethers with amines, leads to polyethers with terminal imine or enamine groups, which are derivates of aminocrotonic acid. We determined that this approach is a universal method for the synthesis of a large variety of aromatic as well as aliphatic ATPEs with low viscosities. Trifluoroacetic acid turned out to be the ideal catalyst for the reaction of the acetoacetylated polyethers with aromatic diamines, one amino group forming the imine link, the second one remaining intact and providing the desired reactivity towards isocyanates. Aliphatic diamines do not require a catalyst for this reaction. They lead to aminocrotonates with aliphatic amino groups that have high reactivity towards isocyanates, which is to be expected from aliphatic amines. The reaction of the chloroformates of polyether polyols with diamines can also be used to synthesize a variety of ATPEs. We recently developed an approach to low viscosity ATPEs having secondary amino end groups. The hydroxyl groups of the polyether polyols are converted to chloride or methanesulfonyl. The polyethers terminated with these leaving-groups are reacted with primary aliphatic or aromatic amines to give the secondary ATPEs in very good yields.     

Development and validation of a new LC–MS/MS method for the simultaneous determination of six major ergot alkaloids and their corresponding epimers. Application to some food and feed commodities

A liquid chromatography–tandem mass spectrometry (LC–MS/MS) method was developed and validated for the simultaneous determination of six major ergot alkaloids, ergometrine, ergosine, ergotamine, ergocornine, ergokryptine and ergocristine, as well as their corresponding epimers in food and feed samples. The method involves extraction under alkaline conditions and subsequent clean-up by applying a simple and rapid liquid–liquid partitioning procedure prior to LC–MS/MS analysis. Evaluation of the method revealed good linearity, accuracy and precision. The limits of quantification varied from 0.1 to 1 μg/kg depending on the analyte and matrix. The average extraction and clean-up recoveries in different matrices were between 45 (only for ergometrine in biscuit) and 90%. The uncertainty associated with the analytical method was not higher than 51% and 30%, at concentration levels of 2.5 and 150 μg/kg respectively. Analyte epimerization proved to be minimal during the analytical procedure. The method has been successfully applied to the determination of ergot alkaloids in some Belgian food and feed commodities. Ergot alkaloids were found in 104 out of 122 samples investigated. Ergosine was the most frequently occurring alkaloid, while the highest levels were observed for ergotamine, ergocristine or ergosine, depending on the product type. The total alkaloid content in positive samples varied from 1 to 1145 μg/kg.     

Thermodynamic Modeling of the Miscibility Gaps and the Metastable Liquidi in the MgO-SiO2, CaO-SiO2, and SrO-SiO2 Systems

A range of compositions and temperatures below the monotectic temperature exists where there are thermodynamic restrictions that prevent the equilibrium solid from forming directly from the undercooled homogeneous liquid. In this region, the solid can form only after liquid-liquid phase separation has occurred. As suggested by earlier research, the thermodynamic restrictions on the crystallization process may be useful to control the crystallized grain structure in glass-ceramic systems. Thus, understanding the thermodynamic limitations on the formation of the solid in monotectic systems could have commercial significance. In the present paper, the metastable liquidus boundaries, liquid miscibility gaps, and spinodal curves in binary MgO-SiO₂, CaO-SiO₂, and SrO-SiO₂ systems are calculated by using analytical expressions for the Gibbs free energies of the liquid phases. Calculating the metastable liquidus rather than using a simple extrapolation as originally proposed in the aforementioned previous research provides greater control of the heat-treatment processes and, thus, greater control over the resulting microstructure.     

Low-frequency Beats Produced by Interference of Laser Modes

Abstract

A helium-neon laser operating in three or more axial modes can generate, at a photo detector with a nonlinear response to intensity, beat signals with frequencies corresponding to the second differences between the frequencies of these modes. This paper presents a quantum-field theoretical treatment of the formation of such low-frequency beats, as well as experimental data demonstrating that interference effects corresponding to the production of such beats can be observed even at light levels at which the probability of at least one photon from each of the three modes being present simultaneously in the optical path is negligible.     

One-trial cocaine-induced behavioral sensitization in preweanling rats: Role of contextual stimuli.

Using a one-trial procedure, preweanling rats exhibit robust sensitization regardless of whether drug pretreatment and testing occur in the same or different environments. The purpose of the present study was to determine whether one-trial context-specific and context-independent sensitization of preweanling rats could be dissociated by varying the pretreatment dose of cocaine, by varying the pretreatment drug, or by minimizing interoceptive cues. In Experiments 1a and 1b, rats were pretreated with a broad dose range of cocaine (0–40 mg/kg) before placement in a novel activity chamber or the home cage. In Experiment 2, rats were pretreated with a locomotor-enhancing drug (e.g., methylphenidate, U50,488, or MK-801) before placement in a novel activity or anesthesia chamber. In Experiment 3, rats were anesthetized with isoflurane before cocaine administration to minimize the effects of interoceptive and injection cues. In all experiments, rats were challenged with cocaine on the test day (24 hr later), with locomotion being measured in activity chambers. Results showed that (a) the pretreatment dose of cocaine (10–40 mg/kg) did not differentially affect context-specific and context-independent sensitization; (b) cross-sensitization between methylphenidate and cocaine was observed in the context-specific condition, but not when using a context-independent procedure; and (c) sensitization was evident if injection and interoceptive cues were minimized. One possibility is that associative processes do not modulate the one-trial sensitization of preweanling rats. Alternatively, “unitization” may cause preweanling rats to treat the different environments as equivalent, thus permitting robust sensitization even when drug pretreatment and testing occur in different environments. (PsycINFO Database Record (c) 2010 APA, all rights reserved)