Electrospun Poly(styrene) Fibers as a Protection for the First- and the Second-Generation Grubbs’ Catalyst

The study presents a novel method for protection of the first- and the second-generation Grubbs’ catalyst, by incorporation in poly(styrene) fibers through electrospinning technique. Both catalysts are sensitive to the presence of the amine hardeners in the epoxy-based self-healing composites and require protection from deactivation to retain their ability to promote polymerization reaction of the healing agent. Comparison of healing efficiencies of both catalysts suggested that poly(styrene) fibers offer better protection and dispersion for the first-generation Grubbs’ catalyst, although all the samples exhibited high-healing efficiency. Difference in stereoselectivity between two catalysts was also indicated.     

On thermal and vibrational properties of LaGaO3 single crystals

The thermal expansion and vibrational properties of [1 0 0] and [0 0 1] LaGaO₃ single crystals have been studied by thermal mechanical analysis and micro-Raman spectroscopy. A first-order orthorhombic to rhombohedral phase transition has been confirmed by both techniques, as well as by in situ heating using optical microscopy. The appearance of a metastable intermediate phase, tentatively assigned as monoclinic, has been detected both by optical microscopy and Raman spectroscopy upon heating of the [1 0 0] and [0 0 1] LaGaO₃ single crystals. Not only temperature, but the stress-induced orthorhombic to rhombohedral phase transition has also been detected by Raman mapping of the residual impression made by Vickers indentation. The position map of bands belonging to the lower-temperature/pressure orthorhombic and the higher-temperature/pressure rhombohedral phase show that the rhombohedral phase is located inside the impression, where the applied indentation stresses are the highest, whereas no rhombohedral phase is detected outside the impression, where the surface has not been altered by contact stresses.     

Oxygen migration on the graphene surface. 2. Thermochemistry of basal-plane diffusion (hopping)

Thermodynamic affinities, activation energies and diffusion coefficients for oxygen mobility on the graphene surface are calculated using density functional theory (DFT). We report and discuss the effects of geometry, charge distribution and heteroatom substitution on the migration of epoxy oxygen on the basal plane: both the driving force and the ease of surface hopping are very sensitive to their variations. A significant decrease in the hopping energy barrier is observed when graphene contains free edge sites and oxygen functionalities, as well as upon an increase in electron density; conversely, the barrier increases as a consequence of electron removal, and the propensity for graphene ‘unzipping’ also increases. There is a correlation between the hopping barrier and the C–O bond strength of the leaving epoxide group. Under the most favorable conditions investigated, oxygen mobility is quite high, of the same order as that of gas-phase O₂ in micropores (ca. 10⁻⁹ m²/s). This is consistent with the increasingly acknowledged role of basal-plane oxygen as a protagonist (e.g., reaction intermediate), instead of a spectator, in the wide variety of adsorption and reaction processes involving sp²-hybridized carbon materials.     

Oxidation inhibition effects of phosphorus and boron in different carbon fabrics

To improve oxidation inhibition, elemental boron and two phosphorus compounds were doped into an activated carbon cloth and a carbon felt. The hypothesis was that P can block active sites by virtue of the formation of C-P-O or C-O-P bonds at graphene edges while substitutional B can alter the chemical reactivity of the residual free active sites by reducing the electron density in the graphene layer. To increase the final dopant concentration, the carbon felt was activated in nitric acid. The crystallinity of activated carbon cloth was improved by heat treatment and substitutional B; that of carbon felt was also improved, but not necessarily due to substitutional B. In all cases the oxidation reactivity is suppressed by heat treatment and in the presence of dopants. The oxidation inhibition mechanism in P-doped samples appears to be active sites blockage because of a proportional increase of oxidation inhibition with increasing P loading. The results for B-doped samples are consistent with our previous studies in which B was found to exhibit both a catalytic and an inhibiting effect on carbon oxidation. Samples doped with both P and B showed the most effective oxidation inhibition and their oxidation behavior is described in detail.     

A framework for building intelligent manufacturing systems

The paper describes a systematic approach to design and development of software for intelligent manufacturing systems. The approach is based on a multilevel, general object oriented model of intelligent systems. Current methods and software design and development tools for intelligent manufacturing systems either stress particular components of intelligence (e.g., high level domain expertise, or learning capabilities, or fuzziness of decisions), or their domain dependence (e.g., monitoring and control systems, or CAPP systems). It is usually difficult to make extensions of such methods and tools, nor is it easy to reuse their components in developing intelligent manufacturing systems. Considerable efforts are being dedicated to the development of interoperable software components, distributed object environments, and flexible and scalable applications to overcome some of these problems. The approach described in the paper starts with a well founded software engineering principle, making clear distinction between generic, low level intelligent software components, and domain-dependent, high level components of an intelligent manufacturing system. It is extensible and adjustable. It also suggests some steps toward design of future software development tools for intelligent manufacturing systems. Several intelligent systems have been developed using the approach. One of these systems, in the cement manufacturing domain, is briefly overviewed, illustrating how the approach is used in practice. Finally, some informal discussion on the performance and complexity of the approach is presented     

HPLC flavonoid profiles as markers for the botanical origin of European unifloral honeys

The HPLC phenolic profiles of 52 selected unifloral honey samples produced in Europe were analysed to detect possible markers for the floral origin of the different honeys. Lime‐tree (five markers), chestnut (five markers), rapeseed (one marker), eucalyptus (six markers) and heather (three markers) honeys had specific markers with characteristic UV spectra. In addition, the flavanone hesperetin was confirmed as a marker for citrus honey, as well as kaempferol for rosemary honey and quercetin for sunflower honey. Abscisic acid, which had been reported to be a possible marker for heather honey, was also detected in rapeseed, lime‐tree and acacia honeys. Ellagic acid in heather honey and the hydroxycinnamates caffeic, p‐coumaric and ferulic acids in chestnut, sunflower, lavender and acacia honeys were also detected. The characteristic propolis‐derived flavonoids pinocembrin, pinobanksin and chrysin were present in most samples in variable amounts. © 2001 Society of Chemical Industry     

Inhibition of catalytic oxidation of carbon/carbon composites by boron-doping

The inhibition effect of high temperature boron-doping on the catalytic oxidation of carbon/carbon composites was investigated. Boron-doping at 2500 °C was found to improve the oxidation resistance of catalyst-loaded composites. Evident inhibition mechanisms include the reduction of active site number by increasing the crystallite size and the site blockage by formed boron oxide. Boron-doping at less than 1.0 wt.% was found to almost completely suppress the catalytic effect of calcium acetate after a slight carbon conversion. This inhibition effect was much less significant in the case of potassium-catalyzed oxidation where only a slight inhibition effect was observed. This is believed to be the essential result of the unique properties of potassium catalyst. Due to its wetting ability and mobility, potassium catalyst could form and maintain good interfacial contact with any exposed carbon surface regions.     

Catalytic oxidation of carbon/carbon composite materials in the presence of potassium and calcium acetates

The catalytic effects of potassium acetate (KAC) and calcium acetate (CaAC) on the oxidation of carbon/carbon composites (C/C composites) used in aircraft brake system have been characterized. Potassium exhibited a very strong catalytic effect on the oxidation of the selected carbon samples, including C/C composite blocks impregnated with aqueous KAC solution and graphite powder physically mixed with KAC powder. The initial amount of catalyst loading and the pre-treatment in inert gas were found to affect its catalytic effectiveness. Impregnated calcium was also a good catalyst for the oxidation of C/C composites, but its effectiveness is much lower than that of potassium and is much less sensitive to catalyst loading amount and pre-treatment. Calcium acetate physically mixed with graphite powder only showed a slight catalytic effect. The experimental results suggested that the interfacial contact between catalyst and carbon is the key factor determining catalytic effectiveness, in agreement with previous studies using porous carbon materials. Due to its unique wetting ability and mobility on the carbon surface, potassium can form and maintain such contact with carbon and is, therefore, more effective in the C-O₂ reaction than calcium. The formation and development of such contact, which can also be affected by catalyst loading and pre-treatment process, can explain well the influence of these experimental conditions on the catalytic effect of potassium. The decreasing trend of reactivity with increasing burn-off in calcium-catalyzed oxidation is a result of interfacial contact loss because calcium does not have the necessary mobility to maintain such contact during reaction.