An investigation of the thermal stability and sulphur tolerance of Ag/Y-Al2O3 catalysts for the SCR of NOx with hydrocarbons and hydrogen

The sulphur tolerance and thermal stability of a 2 wt% Ag/gamma-Al2O3 catalyst was investigated for the H-2-promoted SCR of NO, with octane and toluene. The aged catalyst was characterised by XRD and EXAFS analysis. It was found that the effect of ageing was a function of the gas mix and temperature of ageing. At high temperatures (800 degrees C) the catalyst deactivated regardless of the reaction mix. EXAFS analysis showed that this was associated with the Ag particles on the surface of the catalyst becoming more ordered. At 600 and 700 degrees C, the deactivating effect of ageing was much less pronounced for the catalyst in the H-2-promoted octane-SCR reaction and ageing at 600 degrees C resulted in an enhancement in activity for the reaction in the absence of H-2. For the toluene + H-2-SCR reaction the catalyst deactivated at each ageing temperature. The effect of addition of low levels of sulphur (1 ppm SO2) to the feed was very much dependent on the reaction temperature. There was little deactivation of the catalyst at low temperatures ( 500 degrees C). The results can be explained by the activity of the catalyst for the oxidation Of SO2 to SO3 and the relative stability of silver and aluminium sulphates. The catalyst could be almost fully regenerated by a combination of heating and the presence of hydrogen in the regeneration mix. The catalyst could not be regenerated in the absence of hydrogen. (c) 2006 Published by Elsevier B.V.

Process efficiency in polymer extrusion: Correlation between the energy demand and melt thermal stability

Thermal stability is of major importance in polymer extrusion, where product quality is dependent upon the level of melt homogeneity achieved by the extruder screw. Extrusion is an energy intensive process and optimisation of process energy usage while maintaining melt stability is necessary in order to produce good quality product at low unit cost. Optimisation of process energy usage is timely as world energy prices have increased rapidly over the last few years. In the first part of this study, a general discussion was made on the efficiency of an extruder. Then, an attempt was made to explore correlations between melt thermal stability and energy demand in polymer extrusion under different process settings and screw geometries. A commodity grade of polystyrene was extruded using a highly instrumented single screw extruder, equipped with energy consumption and melt temperature field measurement. Moreover, the melt viscosity of the experimental material was observed by using an off-line rheometer. Results showed that specific energy demand of the extruder (i.e. energy for processing of unit mass of polymer) decreased with increasing throughput whilst fluctuation in energy demand also reduced. However, the relationship between melt temperature and extruder throughput was found to be complex, with temperature varying with radial position across the melt flow. Moreover, the melt thermal stability deteriorated as throughput was increased, meaning that a greater efficiency was achieved at the detriment of melt consistency. Extruder screw design also had a significant effect on the relationship between energy consumption and melt consistency. Overall, the relationship between the process energy demand and thermal stability seemed to be negatively correlated and also it was shown to be highly complex in nature. Moreover, the level of process understanding achieved here can help to inform selection of equipment and setting of operating conditions to optimise both energy and thermal efficiencies in parallel. 

High temperature thermal stability studies of ultrathin Al2O3 layers deposited on native oxide and sulphur passivated InGaAs surfaces

High resolution synchrotron radiation core level photoemission measurements have been used to undertake a comparative study of the high temperature stability of ultrathin Al2O3 layers deposited by atomic layer deposition (ALD) on both sulphur passivated and native oxide covered InGaAs. The residual interfacial oxides between sulphur passivated InGaAs and the ultrathin Al2O3 layer can be substantially removed at high temperature (up to 700 °C) without impacting on the InGaAs stoichiometry while significant loss of indium was recorded at this temperature on the native oxide InGaAs surface.

Expanded iron uta spectra - Probing the thermal stability limits in AGN clouds

The Fe unresolved transition arrays (UTAs) produce prominent features in the 15-17 Å wavelength range in the spectra of active galactic nuclei (AGNs). Here, we present new calculations of the energies and oscillator strengths of inner-shell lines from Fe XIV, Fe XV, and Fe XVI. These are crucial ions since they are dominant at inflection points in the gas thermal stability curve, and UTA excitation followed by autoionization is an important ionization mechanism for these species. We incorporate these, and data reported in previous papers, into the plasma simulation code Cloudy. This updated physics is subsequently employed to reconsider the thermally stable phases in absorbing media in AGNs. We show how the absorption profile of the Fe XIV UTA depends on density, due to the changing populations of levels within the ground configuration. © 2013. The American Astronomical Society. All rights reserved.

High temperature thermal stability investigations of ammonium sulphide passivated InGaAs and interface formation with Al2O3 studied by synchrotron radiation based photoemission

High resolution synchrotron radiation core level photoemission measurements have been used to undertake a comparative study ofthe high temperature thermal stability ofthe ammonium sulphide passivated InGaAs surface and the same surface following the atomic layer deposition (ALD) of an ultrathin (∼1 nm) Al2O3 layer. The solution based ex situ sulphur passivation was found to be effective at removing a significant amount of the native oxides and protecting the surface against re-oxidation upon air exposure. The residual interfacial oxides which form between sulphur passivated InGaAs and the ultrathin Al2O3 layer can be substantially removed at high temperature (up to 700 ◦C) without impacting on the InGaAs stoichiometry while significant loss of indium was recorded at this temperature on the uncovered sulphur passivated InGaAs surface.

High temperature thermal stability of the HfO2/Ge (100) interface as a function of surface preparation studied by synchrotron radiation core level photo emission

High resolution soft x-ray photoemission spectroscopy (SXPS) have been used to study the high temperature thermal stability of ultra-thin atomic layer deposited (ALD) HfO2 layers (∼1 nm) on sulphur passivated and hydrofluoric acid (HF) treated germanium surfaces. The interfacial oxides which are detected for both surface preparations following HfO2 deposition can be effectively removed by annealing upto 700 °C without any evidence of chemical interaction at the HfO2/Ge interface. The estimated valence and conduction band offsets for the HfO2/Ge abrupt interface indicated that effective barriers exist to inhibit carrier injection.

Thermal stability of myofibrillar protein from Indian major carps

The characteristics and stability of natural actomyosin (NAM) from rohu (Labeo rohita), catla (Catla catla) and mrigal (Cirrhinus mrigala) were investigated. The total extractable actomyosin (AM) was higher (7.60mgml−1) in the case of rohu compared with that from catla and mrigal (5mgml−1). Although the specific AM ATPase activity was similar (0.43–0.5 μmolPmin−1 mgP−1) among the three species, the total ATPase activity was lower in mrigal (25 μmol g−1 meat) compared with the other species (37 μmol g−1 meat). The inactivation rate constants (kd) of AM Ca ATPase activity showed differences in the stabilities of actomyosin among these fish, the actomyosin from catla being least stable. The NAM from these species was stable up to 20 ◦C at pH 7.0. Catla AM became unstable at 30 ◦C, while rohu and mrigal AM could withstand up to 45 ◦C. The thermal denaturation with respect to solubility, turbidity, ATPase activity, sulphhydryl group and surface hydrophobicity showed noticeable changes at around these temperatures

Stereochemistry and thermal stability of tartaric acid on the intrinsically chiral Cu{531} surface

Intrinsically chiral metal surfaces provide enantiospecific reaction environments without the need of coadsorbed modifiers. Amongst the intrinsically chiral copper surfaces, Cu{531} has the smallest unit cell and the highest density of chiral sites. XPS, NEXAFS and TPD were employed to investigate the adsorption and decomposition behaviour of the two chiral enantiomers of tartaric acid on this surface. The results obtained from XPS and NEXAFS show that at saturation coverage both enantiomers of tartaric acid adsorb in a μ4 configuration through the two carboxylic groups,which are rotatedwith respect to each other by 90°±≈15°within the surface plane. At intermediate coverage the R,R enantiomer adopts a similar configuration, but the S,S enantiomer is different and shows a high degree of dissociation. Growth of multilayers is observed at high exposures when the sample is kept at below 370 K. TPD experiments show that multilayers desorb between 390 K and 470 K and decomposition of the chemisorbed layer occurs between 470 K and 600 K. The desorption spectra support a two-step decomposition mechanism with a O_C_C_O or HO–HC_CH–OH intermediate that leads to production of CO2 and CO. Enantiomeric differences are observed in the desorption features related to the decomposition of the chemisorbed layer.

Thermal stability of extracellular hemoglobin of Glossoscolex paulistus: Determination of activation parameters by optical spectroscopic and differential scanning calorimetric studies

Glossoscolex paulistus hemoglobin (HbGp) was studied by dynamic light scattering (DLS), optical absorption spectroscopy (UV-VIS) and differential scanning calorimetry (DSC). At pH 7.0, cyanomet-HbGp is very stable, no oligomeric dissociation is observed, while denaturation occurs at 56 degrees C, 4 degrees C higher as compared to oxy-HbGp. The oligomeric dissociation of HbGp occurs simultaneously with some protein aggregation. Kinetic studies for oxy-HbGp using UV-VIS and DES allowed to obtain activation energy (E(a)) values of 278-262 kJ/mol (DES) and 333 kJ/mol (UV-VIS). Complimentary DSC studies indicate that the denaturation is irreversible, giving endotherms strongly dependent upon the heating scan rates, suggesting a kinetically controlled process. Dependence on protein concentration suggests that the two components in the endotherms are due to oligomeric dissociation effect upon denaturation. Activation energies are in the range 200-560 kJ/mol. The mid-point transition temperatures were in the range 50-65 degrees C. Cyanomet-HbGp shows higher mid-point temperatures as well as activation energies, consistent with its higher stability. DSC data are reported for the first time for an extracellular hemoglobin. (C) 2010 Elsevier B.V. All rights reserved.

Mechanisms governing the enhanced thermal stability of acid and base treated polypyrrole

One of the major problems associated with the use of polypyrrole (PPy) in a practical engineering application is its poor thermal stability at elevated temperatures, especially in the presence of oxygen and moisture. Several authors have shown that enhanced stability can be achieved through treatment with simple acids and bases. This paper presents a summary of the possible structural changes which occur as a result of these treatments and those that appear to be related to enhanced conductivity stability. A slight increase in conductivity (10–20%) is observed for acid treated PPy films which is found to be the result of protonation of the pyrrole structure. This effect is dramatically enhanced by treatment at high temperatures where an increase in conductivity of >84% can be achieved. Base treatment of the PPy films results in the deprotonation of the pyrrole structure leading to the loss of conductivity (>40%). Preliminary X-ray Photoelectron Spectroscopy (XPS) results indicate that both acid and base treatment resulted in the elimination of reactive sites for oxygen. Long term thermal ageing of these treated films were conducted at 150 °C in air. The conductivity decay behaviour was found to follow multiple first order chemical reaction kinetics.

Ion exchange, anisotropic structure and thermal stability of polypyrrole films

The thermal stability of electrochemically prepared polypyrrole (PPy) films with p-toluene sulfonate (pTS) or perchlorate (CIOP₄⁻) counter ion (PPy/pTS and PPy/ClO₄⁻) is improved by simple treatment with aqueous sulfuric acid, sodium sulfate or sodium bisulfate. The degree of stabilization achieved depends on the solution, temperature and duration of treatment. PPy/pTS is easily stabilized and thick films (43μm) retain 90 % of the initial conductivity after long period (300 h) at 150 °C, while thinner films (12 μm) retain slightly less (70 %). A model for the conductivity decay has been proposed. Although the mechanism for improved stability is not yet clear it is apparent that the level of ion exchange and the original polymer microstructure are important. The early stages of ion exchange are not symmetrical and diffusion is facilitated at the electrode side of the film. Furthermore, X-ray diffraction shows no evidence of morphological change after treatment of thick PPy/pTS but in thin PPy/pTS and PPy/ClO₄⁻ films an additional peak is indicative of more ordered structure following treatment. These observation may imply that there is a higher density of crosslinks and branching at the growth side than at the electrode side of the film.