On the thermal stabilization of carbon-supported SiO2 catalysts by phosphorus:evaluation in the oxidative dehydrogenation of ethylbenzene to styrene and a comparison with relevant catalysts

A strategy to enhance the thermal stability of C/SiO2 hybrids for the O2-based oxidative dehydrogenation of ethylbenzene to styrene (ST) by P addition is proposed. The preparation consists of the polymerization of furfuryl alcohol (FA) on a mesoporous precipitated SiO2. The polymerization is catalyzed by oxalic acid (OA) at 160 °C (FA:OA = 250). Phosphorous was added as H3PO4 after the polymerization and before the pyrolysis that was carried out at 700 °C and will extend the overall activation procedure. Estimation of the apparent activation energies reveals that P enhances the thermal stability under air oxidation, which is a good indication for the ODH tests. Catalytic tests show that the P/C/SiO2 hybrids are readily active, selective and indeed stable in the applied reactions conditions for 60 h time on stream. Coke build-up during the reaction attributed to the P-based acidity is substantial, leading to a reduction of the surface area and pore volume. The comparison with a conventional MWCNT evidences that the P/C/SiO2 hybrids are more active and selective at high temperatures (450–475 °C) while the difference becomes negligible at lower temperature. However, the comparison with reference P/SiO2 counterparts shows a very similar yield than the hybrids but more selective to ST. The benefit of the P/C/SiO2 hybrid is the lack of stabilization period, which is observed for the P/SiO2 to create an active coke overlayer. For long term operation, P/SiO2 appears to be a better choice in terms of selectivity, which is crucial for commercialization.

Mechanisms of transfer film formation on data recording heads

The increasing demand for high capacity data storage requires decreasing the head-to-tape gap and reducing the track width. A problem very often encountered is the development of adhesive debris on the heads at low humidity and high temperatures that can lead to an increase of space between the head and media, and thus a decrease in the playback signal. The influence of stains on the playback signal of reading heads is studied using RAW (Read After Write) tests and their influence on the wear of the heads by using indentation technique. The playback signal has been found to vary and the errors to increase as stains form a patchy pattern and grow in size to form a continuous layer. The indentation technique shows that stains reduce the wear rate of the heads. In addition, the wear tends to be more pronounced at the leading edge of the head compared to the trailing one. Chemical analysis of the stains using ferrite samples in conjunction with MP (metal particulate) tapes shows that stains contain iron particles and polymeric binder transferred from the MP tape. The chemical anchors in the binder used to grip the iron particles now react with the ferrite surface to create strong chemical bonds. At high humidity, a thin layer of iron oxyhydroxide forms on the surface of the ferrite. This soft material increases the wear rate and so reduces the amount of stain present on the heads. The stability of the binder under high humidity and under high temperature as well as the chemical reactions that might occur on the ferrite poles of the heads influences the dynamic behaviour of stains. A model of stain formation taking into account the channels of binder degradation and evolution upon different environmental conditions is proposed.

Surface wave techniques for the study of engineering structures and materials

A wire drive pulse echo method of measuring the spectrum of solid bodies described. Using an 's' plane representation, a general analysis of the transient response of such solids has been carried out. This was used for the study of the stepped amplitude transient of high order modes of disks and for the case where there are two adjacent resonant frequencies. The techniques developed have been applied to the measurenent of the elasticities of refractory materials at high temperatures. In the experimental study of the high order in-plane resonances of thin disks it was found that the energy travelled at the edge of the disk and this initiated the work on one dimensional Rayleigh waves.Their properties were established for the straight edge condition by following an analysis similar to that of the two dimensional case. Experiments were then carried out on the velocity dispersion of various circuits including the disk and a hole in a large plate - the negative curvature condition.Theoretical analysis established the phase and group velocities for these cases and experimental tests on aluminium and glass gave good agreement with theory. At high frequencies all velocities approach that of the one dimensional Rayleigh waves. When applied to crack detection it was observed that a signal burst travelling round a disk showed an anomalous amplitude effect. In certain cases the signal which travelled the greater distance had the greater amplitude.An experiment was designed to investigate the phenanenon and it was established that the energy travelled in two nodes with different velocities.It was found by analysis that as well as the Rayleigh surface wave on the edge, a seoond node travelling at about the shear velocity was excited and the calculated results gave reasonable agreement with the experiments.

The influence of climate on the dispersal of lichen soredia

The relationship between the daily deposition of soredia of Hypogymnia physodes (L.) Nyl. and local climatic records was studied in the field during three periods at a site in Seattle, WA, U.S.A: (1) 11 August – 16 September 1986 (Study A); (2) 16 December – 11 January 1987 (Study B) and (3) 8 July 1988 – 30 January 1989 (Study C). The soredia were trapped on adhesive strips placed at various locations on a Prunus blireiana L. tree for 24 hr periods. A correlation matrix of the data from all three studies revealed a negative correlation between soredial deposition and relative humidity; and a positive correlation with rainfall and temperature. A multiple regression and forward stepwise regression analysis selected relative humidity as the most significant climatic variable, i.e. more soredia tended to be deposited when relative humidity was low. Analysis of individual studies by multiple regression revealed: (1) no significant relationships between soredial deposition and climate in Study A; (2) positive relationships with temperature and wind speed in Study B and (3) positive relationships with wind speed and rainfall in the summer/autumn months of Study C; in the winter months no relationships with climate were found because few soredia were deposited. The data suggest that in the field seasonal photoperiod differences combined with moderately high temperatures and high relative humidity may promote soredial formation and accumulation on thalli prior to soredia dispersal. In addition, low relative humidity may promote soredial release while wind and raindrops may be possible agents of dispersal.

Mechanisms of drying of skin forming materials

The literature relating to evaporation from single droplets of pure liquids, and to the drying of droplets containing solids and of droplet sprays has been reviewed. The heat and mass transfer rates for a single droplet suspended from a nozzle were studied within a 42mm I.D. horizontal wind tunnel designed to supply hot dry air, to simulate conditions encountered in a practical spray dryer. A novel rotating glass nozzle was developed to facilitate direct measurements of droplet weight and core temperature. This design minimised heat conduction through the nozzle. Revised correlations were obtained for heat and mass transfer coefficients, for evaporation from pure water droplets suspended from a rotating nozzle. Nu = 2.0 + 0.27 (l/B)°-18Re°-5Pr°-83 Sh = 2.0 + 0.575 ((T0-T.)/Tomfc) -o.o4Reo.5 ^0.33 Experimental drying studies were carried out on single droplets of different types of skin-forming materials, namely, custard, gelatin, skim milk and fructose at air temperatures ranging from 19°C to 198°C. Dried crusts were recovered and examined by Scanning Electron Microscopy. Skin-forming materials were classified into three types according to the mechanisms of skin formation. In the first type (typified by droplets of custard and starch) skin formed due to gelatinisation at high temperatures. Increasing the drying temperature resulted in increased crust resistance to mass transfer due to increased granule swelling and the crust resistance was completely transferred to a skin resistance at drying temperatures > 150°C. In the second type e.g. gelatin droplets the skin formed immediately drying had taken place at any drying temperature. At drying temperature > 60° C a more resistant skin was formed. In the third type (typified by droplets of skim milk and fructose) the skin appeared on the droplet surface at a certain stage of the drying process under any drying conditions. As the drying temperature was increased the resistance of the skin to mass transfer increased. The drying rate history of any material depended upon the nature of the skin formed which, in turn, depended upon the drying conditions. A mathematical model was proposed for the drying of the first type of skin-forming material. This was based on the assumption that, once all the granules gelatinised at the gelatinisation temperature, a skin appeared instantaneously on the droplet surface. The experimentally-observed times at which the skin appeared on the droplets surfaces were in excellent agreement with those predicted from the model. The work should assist in understanding the fundamentals of paniculate drying processes, particularly when skin-formation occurs and may be a crucial factor in volatiles retention.

The oxidation behaviour of sintered iron

The oxidation behaviour of porous, sintered iron was studied by thermo-gravimetric analysis (TGA), at temperatures between 300oC and 700oC, in a flowing atmosphere of 20% O2/80% N2. Samples for TGA tests were compacted from pure iron powder, at 150MPa to 550MPa, and vacuum sintered at 1120oC. The mass gain of samples during oxidation was recorded continuously for a period of 24 hours. It was found that the oxidation mass gain of PM samples depended on the permeability of the pore structure and the temperature. At low temperatures, the oxidising gas was able to permeate through the pore structure, causing the oxidation of a large active surface area. At high temperatures the active surface area was smaller, because oxygen diffusing into the pore structure, from the external atmosphere, was adsorbed by pore surfaces close to the external surface of the compact. Although the weight of the external oxide scale on compacts increased with increasing oxidation temperature, the absence of oxide in the core porosity in compacts oxidised at higher temperatures resulted in smaller mass gains than were observed for compacts oxidised at lower temperatures. The heat generated by the oxidation of the large active surface areas of porous samples was studied by thermo-calorimetric analysis (TCA). It was determined that this phenomenon could raise the core temperature of samples significantly above the ambient furnace temperature, and affecting the morphology of the oxide scale formed. The effects (on oxidation behaviour at 500oC) of small, elemental alloy additions of Al, Cu, P and Si to pure iron powder were studied. It was found that elements that promote pore rounding during sintering caused a significant reduction in the mass gain rate of the PM alloys, compared to the PM pure iron. The oxidation resistance due to these elements prevented pore closure by oxide growth, so that the active surface area of these PM alloys remained high. The PM alloys were also studied by thermo-mechanical analysis (TMA, dilatometry), to determine their dimensional stability during sintering and subsequent elevated temperature service. The oxidation experiment was augmented with optical and electron microscopy, and X-ray analysis of alloy and scale compositions.

Studies on the composition and nutritional value of the cultivated mushroom, agaricus bisporus (Lange) Sing

The effects of various cultural conditions on the composition and nutritional quality of Agaricus bisporus (Lange) Sing. were investigated. Variation in composition was found between different classes of sample. Sampling techniques were standardised to allow for major variations in the different developmental stages and culture ages. Fruitbodies were found to be of low calorific value but contained protein of high digestibility and quality, containing all the essential amino acids required by man. Quantitative estimates of the sulphur-containing amino acids indicated that fruitbodies were deficient in methionine and cysteine. The extent of water application and the supplementation of conventional substrates with various nitrogen-containing substances, influenced yield and composition, establishing the importance of these two factors in the physiology of fruitbodies and cultural management. Storage conditions influenced composition, high temperatures being deleterious to the nutritional value of fruitbodies. Submerged culture techniques were used to investigate the effects of various nutrients on growth and composition of mushroom mycelium, with special reference to the sulphur-containing amino acids. Yield and composition were greatly affected by the carbon:nitrogen ratio of the medium and by the nitrogen source. Significant increases in mycelial methionine content were observed on the addition of inorganic sulphate, the methionine derivative N-acetyl-L-methionine, and L-methionine. A greater increase in methionine content was obtained when the biomass of a thermophilic bacterium isolated from compost was used as a nitrogen source.

Electronic properties of homoepitaxial (111) highly boron-doped diamond films

The use of diamond as a semiconductor for the realization of transistor structures, which can operate at high temperatures (>700 K), is of increasing interest. In terms of bipolar devices, the growth of n-type phosphorus doped diamond is more efficient on the (111) growth plane; p-type boron-doped diamond growth has been most usually grown in the (100) direction and, hence, this study into the electronic properties, at high temperatures, of boron-doped diamond (111) homoepitaxial layers. It is shown that highly doped layers (hole carrier concentrations as high as 2×1020 cm-3) can be produced without promoting the onset of (unwanted) hopping conduction. The persistence of valance-band conduction in these films enables relatively high mobility values to be measured ( ~ 20 cm2/V?s) and, intriguingly, these values are not significantly reduced at high temperatures. The layers also display very low compensation levels, a fact that may explain the high mobility values since compensation is required for hopping conduction. The results are discussed in terms of the potential of these types of layers for use with high temperature compatible diamond transistors.

Comparison between femtosecond laser and fusion-arc inscribed long period gratings in photonic crystal fibre

The use of high intensity femtosecond laser sources for inscribing fibre gratings has attained significant interest. The principal advantage of high-energy pulses is their ability for grating inscription in any material type without preprocessing or special core doping. In the field of fibre optical sensing LPGs written in photonic crystal fibre have a distinct advantage of low temperature sensitivity over gratings written in conventional fibre and thus minimal temperature cross-sensitivity. Previous studies have indicated that LPGs written by a point-by-point inscription scheme using a low repetition femtosecond laser exhibit post-fabrication evolution leading to temporal instabilities at room temperatures with respect to spectral location, strength and birefringence of the attenuation bands. These spectral instabilities of LPGs are studied in photonic crystal fibres (endlessly single mode microstructure fibre) to moderately high temperatures 100°C to 200°C and their performance compared to fusion-arc fabricated LPG. Initial results suggest that the fusion-arc fabricated LPG demonstrate less spectral instability for a given constant and moderate temperature, and are similar to the results obtained when inscribed in a standard single mode fibre.

Low-temperature decoherence of qubit coupled to background charges

We have found an exact expression for the decoherence rate of a Josephson charge qubit coupled to fluctuating background charges. At low temperatures T the decoherence rate Γ is linear in T while at high temperatures it saturates in agreement with a known classical solution which, however, reached at surprisingly high T. In contrast to the classical picture, impurity states spread in a wide interval of energies (> T) may essentially contribute to Γ.

Novel organo-modifier for thermally-stable polymer-layered silicate nanocomposites

A new novel approach for the stabilisation of polymer-clay nanocomposites has been investigated based on reacting chemically an antioxidant function, a hindered phenol moiety, with an organic modifier based on a quaternary ammonium salt. The chemically linked antioxidant-containing organic modifier (AO-OM) was then introduced into natural montmorillonite (MMt) through a cation-exchange reaction resulting in antioxidant-containing organo-modified clay (AO-OM-MMt). The new antioxidant-containing modified clay, along with other organo-modified clays having a similar organo-modifier but without the reacted antioxidant, were characterised by spectroscopic, thermogravimetric and x-ray diffraction techniques and tested for their thermo-oxidative stability. PA11-based clay nanocomposites samples containing the AO-OM-MMt and the other organo-modified clays, both without and with an added (i.e. not chemically reacted) hindered phenol antioxidant (similar to the one used in the AO-OM) were prepared by melt processing and examined for their processing and long-term thermal-oxidative stability at high temperatures. It was shown that although the new organo-modifier, AO-OM, was also susceptible to the Hoffman elimination reaction, the nanocomposites containing this newly modified clay (PA11/AO-OM-MMt) showed higher melt processing and long-term thermo-oxidative stability, along with excellent clay dispersion and exfoliation, compared to the other PA11-nanocomposites examined here (with and without the conventionally added antioxidant). It is suggested here that the excellent overall performance observed for the PA11/AO-OM-MMt nanocomposites is due to an in-situ partial release of low molecular weight antioxidant species having stabilising functionalities that are capable of acting locally at the interface between the inorganic clay platelets and the polymeric matrix which is a critical area for the onset of degradation processes.

Facile synthesis and proposed mechanism of α,ω‐oxetanyl-telechelic poly(3-nitratomethyl-3-methyl oxetane) by an SN2(i) nitrato displacement method in basic media

The synthesis of a novel heterocyclic–telechelic polymer, α,ω-oxetanyl-telechelic poly(3-nitratomethyl-3-methyl oxetane), is described. Infrared spectroscopy (IR), gel permeation chromatography (GPC), and nuclear magnetic resonance (NMR) spectroscopy have been used to confirm the successful synthesis, demonstrating the presence of the telechelic-oxetanyl moieties. Synthesis of the terminal functionalities has been achieved via displacement of nitrato groups, in a manner similar to that employed with other leaving groups such as azido, bromo, and nitro, initiated by nucleophiles. In the present case, displacement occurs on the ends of a nitrato-functionalized polymer driven by the formation of sodium nitrate, which is supported by the polar aprotic solvent N,N-dimethyl formamide. The formation of an alkoxide at the polymer chain ends is favored and allows internal back-biting to the nearest carbon bearing the nitrato group, intrinsically in an SN2(i) reaction, leading to α,ω-oxetanyl functionalization. The telechelic-oxetanyl moieties have the potential to be cross-linked by chemical (e.g., acidic) or radiative (e.g., ultraviolet) curing methods without the use of high temperatures, usually below 100°C. This type of material was designed for future use as a contraband simulant, whereby it would form the predominant constituent of elastomeric composites comprising rubbery polymer with small quantities of solids, typically crystals of contraband substances, such as explosives or narcotics. This method also provides an alternative approach to ring closure and synthesis of heterocycles.

Protocol optimization for the mild detemplation of mesoporous silica nanoparticles resulting in enhanced texture and colloidal stability

Porosity development of mesostructured colloidal silica nanoparticles is related to the removal of the organic templates and co-templates which is often carried out by calcination at high temperatures, 500-600 °C. In this study a mild detemplation method based on the oxidative Fenton chemistry has been investigated. The Fenton reaction involves the generation of OH radicals following a redox Fe3+/Fe2+ cycle that is used as catalyst and H2O2 as oxidant source. Improved material properties are anticipated since the Fenton chemistry comprises milder conditions than calcination. However, the general application of this methodology is not straightforward due to limitations in the hydrothermal stability of the particular system under study. The objective of this work is three-fold: 1) reducing the residual Fe in the resulting solid as this can be detrimental for the application of the material, 2) shortening the reaction time by optimizing the reaction temperature to minimize possible particle agglomeration, and finally 3) investigating the structural and textural properties of the resulting material in comparison to the calcined counterparts. It appears that the Fenton detemplation can be optimized by shortening the reaction time significantly at low Fe concentration. The milder conditions of detemplation give rise to enhanced properties in terms of surface area, pore volume, structural preservation, low Fe residue and high degree of surface hydroxylation; the colloidal particles are stable during storage. A relative particle size increase, expressed as 0.11%·h-1, has been determined.

CO2 absorption into aqueous amine blended solutions containing monoethanolamine (MEA), N,N-dimethylethanolamine (DMEA), N,N-diethylethanolamine (DEEA) and 2-amino-2-methyl-1-propanol (AMP) for post-combustion capture processes

Presently monoethanolamine (MEA) remains the industrial standard solvent for CO2 capture processes. Operating issues relating to corrosion and degradation of MEA at high temperatures and concentrations, and in the presence of oxygen, in a traditional PCC process, have introduced the requisite for higher quality and costly stainless steels in the construction of capture equipment and the use of oxygen scavengers and corrosion inhibitors. While capture processes employing MEA have improved significantly in recent times there is a continued attraction towards alternative solvents systems which offer even more improvements. This movement includes aqueous amine blends which are gaining momentum as new generation solvents for CO2 capture processes. Given the exhaustive array of amines available to date endless opportunities exist to tune and tailor a solvent to deliver specific performance and physical properties in line with a desired capture process. The current work is focussed on the rationalisation of CO2 absorption behaviour in a series of aqueous amine blends incorporating monoethanolamine, N,N-dimethylethanolamine (DMEA), N,N-diethylethanolamine (DEEA) and 2-amino-2-methyl-1-propanol (AMP) as solvent components. Mass transfer/kinetic measurements have been performed using a wetted wall column (WWC) contactor at 40°C for a series of blends in which the blend properties including amine concentration, blend ratio, and CO2 loadings from 0.0-0.4 (moles CO2/total moles amine) were systematically varied and assessed. Equilibrium CO2 solubility in each of the blends has been estimated using a software tool developed in Matlab for the prediction of vapour liquid equilibrium using a combination of the known chemical equilibrium reactions and constants for the individual amine components which have been combined into a blend.From the CO2 mass transfer data the largest absorption rates were observed in blends containing 3M MEA/3M Am2 while the selection of the Am2 component had only a marginal impact on mass transfer rates. Overall, CO2 mass transfer in the fastest blends containing 3M MEA/3M Am2 was found to be only slightly lower than a 5M MEA solution at similar temperatures and CO2 loadings. In terms of equilibrium behaviour a slight decrease in the absorption capacity (moles CO2/mole amine) with increasing Am2 concentration in the blends with MEA was observed while cyclic capacity followed the opposite trend. Significant increases in cyclic capacity (26-111%) were observed in all blends when compared to MEA solutions at similar temperatures and total amine concentrations. In view of the reasonable compromise between CO2 absorption rate and capacity a blend containing 3M MEA and 3M AMP as blend components would represent a reasonable alternative in replacement of 5M MEA as a standalone solvent.