Exact and analytic-numerical solutions of lagging models of heat transfer in a semi-infinite medium

Different non-Fourier models of heat conduction have been considered in recent years, in a growing area of applications, to model microscale and ultrafast, transient, nonequilibrium responses in heat and mass transfer. In this work, using Fourier transforms, we obtain exact solutions for different lagging models of heat conduction in a semi-infinite domain, which allow the construction of analytic-numerical solutions with prescribed accuracy. Examples of numerical computations, comparing the properties of the models considered, are presented.

A VLT/FLAMES survey for massive binaries in Westerlund 1. IV. Wd1-5 – binary product and a pre-supernova companion for the magnetar CXOU J1647-45?

Context. The first soft gamma-ray repeater was discovered over three decades ago, and was subsequently identified as a magnetar, a class of highly magnetised neutron star. It has been hypothesised that these stars power some of the brightest supernovae known, and that they may form the central engines of some long duration gamma-ray bursts. However there is currently no consenus on the formation channel(s) of these objects. Aims. The presence of a magnetar in the starburst cluster Westerlund 1 implies a progenitor with a mass ≥40 M⊙, which favours its formation in a binary that was disrupted at supernova. To test this hypothesis we conducted a search for the putative pre-SN companion. Methods. This was accomplished via a radial velocity survey to identify high-velocity runaways, with subsequent non-LTE model atmosphere analysis of the resultant candidate, Wd1-5. Results. Wd1-5 closely resembles the primaries in the short-period binaries, Wd1-13 and 44, suggesting a similar evolutionary history, although it currently appears single. It is overluminous for its spectroscopic mass and we find evidence of He- and N-enrichement, O-depletion, and critically C-enrichment, a combination of properties that is difficult to explain under single star evolutionary paradigms. We infer a pre-SN history for Wd1-5 which supposes an initial close binary comprising two stars of comparable (~ 41 M⊙ + 35 M⊙) masses. Efficient mass transfer from the initially more massive component leads to the mass-gainer evolving more rapidly, initiating luminous blue variable/common envelope evolution. Reverse, wind-driven mass transfer during its subsequent WC Wolf-Rayet phase leads to the carbon pollution of Wd1-5, before a type Ibc supernova disrupts the binary system. Under the assumption of a physical association between Wd1-5 and J1647-45, the secondary is identified as the magnetar progenitor; its common envelope evolutionary phase prevents spin-down of its core prior to SN and the seed magnetic field for the magnetar forms either in this phase or during the earlier episode of mass transfer in which it was spun-up. Conclusions. Our results suggest that binarity is a key ingredient in the formation of at least a subset of magnetars by preventing spin-down via core-coupling and potentially generating a seed magnetic field. The apparent formation of a magnetar in a Type Ibc supernova is consistent with recent suggestions that superluminous Type Ibc supernovae are powered by the rapid spin-down of these objects.

A VLT/FLAMES survey for massive binaries in Westerlund 1. III. The WC9d binary W239 and implications for massive stellar evolution

Context. There is growing evidence that a treatment of binarity amongst OB stars is essential for a full theory of stellar evolution. However the binary properties of massive stars – frequency, mass ratio & orbital separation – are still poorly constrained. Aims. In order to address this shortcoming we have undertaken a multiepoch spectroscopic study of the stellar population of the young massive cluster Westerlund 1. In this paper we present an investigation into the nature of the dusty Wolf-Rayet star and candidate binary W239. Methods. To accomplish this we have utilised our spectroscopic data in conjunction with multi-year optical and near-IR photometric observations in order to search for binary signatures. Comparison of these data to synthetic non-LTE model atmosphere spectra were used to derive the fundamental properties of the WC9 primary. Results. We found W239 to have an orbital period of only ~5.05 days, making it one of the most compact WC binaries yet identified. Analysis of the long term near-IR lightcurve reveals a significant flare between 2004-6. We interpret this as evidence for a third massive stellar component in the system in a long period (>6 yr), eccentric orbit, with dust production occuring at periastron leading to the flare. The presence of a near-IR excess characteristic of hot (~1300 K) dust at every epoch is consistent with the expectation that the subset of persistent dust forming WC stars are short (<1 yr) period binaries, although confirmation will require further observations. Non-LTE model atmosphere analysis of the spectrum reveals the physical properties of the WC9 component to be fully consistent with other Galactic examples. Conclusions. The simultaneous presence of both short period Wolf-Rayet binaries and cool hypergiants within Wd 1 provides compelling evidence for a bifurcation in the post-Main Sequence evolution of massive stars due to binarity. Short period O+OB binaries will evolve directly to the Wolf-Rayet phase, either due to an episode of binary mediated mass loss – likely via case A mass transfer or a contact configuration – or via chemically homogenous evolution. Conversely, long period binaries and single stars will instead undergo a red loop across the HR diagram via a cool hypergiant phase. Future analysis of the full spectroscopic dataset for Wd 1 will constrain the proportion of massive stars experiencing each pathway; hence quantifying the importance of binarity in massive stellar evolution up to and beyond supernova and the resultant production of relativistic remnants.

The supergiant B[e] star LHA 115-S 18 - binary and/or luminous blue variable?

Context. The mechanism by which supergiant (sg)B[e] stars support cool, dense dusty discs/tori and their physical relationship with other evolved, massive stars such as luminous blue variables is uncertain. Aims. In order to investigate both issues we have analysed the long term behaviour of the canonical sgB[e] star LHA 115-S 18. Methods. We employed the OGLE II-IV lightcurve to search for (a-)periodic variability and supplemented these data with new and historic spectroscopy. Results. In contrast to historical expectations for sgB[e] stars, S18 is both photometrically and spectroscopically highly variable. The lightcurve is characterised by rapid aperiodic ` aring' throughout the 16 years of observations. Changes in the high excitation emission line component of the spectrum imply evolution in the stellar temperature - as expected for luminous blue variables - although somewhat surprisingly, spectroscopic and photometric variability appears not to be correlated. Characterised by emission in low excitation metallic species, the cool circumstellar torus appears largely unaffected by this behaviour. Finally, in conjunction with intense, highly variable He ii emission, X-ray emission implies the presence of an unseen binary companion. Conclusions. S18 provides observational support for the putative physical association of (a subset of) sgB[e] stars and luminous blue variables. Given the nature of the circumstellar environment of S18 and that luminous blue variables have been suggested as SN progenitors, it is tempting to draw a parallel to the progenitors of SN1987A and SN2009ip. Moreover the likely binary nature of S18 strengthens the possibility that the dusty discs/tori that characterise sgB[e] stars are the result of binary-driven mass-loss; consequently such stars may provide a window on the short lived phase of mass-transfer in massive compact binaries.

Steam reforming of ethanol over bimetallic RhPt/La2O3: Long-term stability under favorable reaction conditions

Recently, the steam reforming of biofuels has been presented as a potential hydrogen source for fuel cells. Because this scenario represents an interesting opportunity for Colombia (South America), which produces large amounts of bioethanol, the steam reforming of ethanol was studied over a bimetallic RhPt/La2O3 catalyst under bulk mass transfer conditions. The effect of temperature and the initial concentrations of ethanol and water were evaluated at space velocities above 55,000 h−1 to determine the conditions that maximize the H2/CO ratio and reduce CH4 production while maintaining 100% conversion of ethanol. These requirements were accomplished when 21 mol% H2O and 3 mol% C2H5OH (steam/ethanol molar ratio = 7) were reacted at 600 °C. The catalyst stability was assessed under these reaction conditions during 120 h on stream, obtaining ethanol conversions above 99% during the entire test. The effect of both H2 and air flows as catalyst regeneration treatments were evaluated after 44 and 67 h on stream, respectively. The results showed that H2 treatment accelerated catalyst deactivation, and air regeneration increased both the catalyst stability and the H2 selectivity while decreasing CH4 generation. Fresh and spent catalyst samples were characterized by TEM/EDX, XPS, TPR, and TGA. Although the Rh and Pt in the fresh catalyst were completely reduced, the spent samples showed a partial oxidation of Rh and small amounts of carbonaceous residue. A possible Rh–Pt–Rh2O3 structure was proposed as the active site on the catalyst, which was regenerated by air treatment.

Thermal decomposition of the different particles size fractions of almond shells and olive stones. Thermal behaviour changes due to the milling processes

The aim of this study is to investigate the effect of particle size on the non-isothermal pyrolysis of almond shells (AS) and olive stones (OS) and to show possible differences in the composition of the different fractions obtained after milling and sieving. The results obtained from the study of different particle size of AS and OS samples show significant differences in the solid residue obtained and in the shape and overlapping degree of the peaks, especially with the smaller particle size. These differences can be due to different factors: (a) the amount of inorganic matter, which increases as particle size decreases, (b) heat and mass transfer processes, (c) different sample composition as a consequence of the milling process which may provoke changes in the structure and the segregation of the components (in addition to the ashes) increasingly changes the composition of the sample as the particle size decreases.

Structured carbons as supports for hydrogenation hybrid catalysts prepared by the immobilization of a Rh diamine complex

A CNF-monolith sample (carbon nanofibres grown on a ceramic monolith), and a granular carbon xerogel have been used as supports for hybrid catalysts where the active species is an Rh diamine complex. The advantages of these supports are their open porous structure and their morphology, which make catalyst handling easier and avoid difficult separation processes. The obtained catalysts are noticeably more active than the homogeneous Rh complex and are stable against leaching. At first use, partial reduction of the Rh complex takes place and nanometer-sized Rh particles develop, which increases the catalyst activity. Despite the open porous structure, mass transport limitations are present, especially in the case of the carbon xerogel based catalyst. Differences in internal mass transfer limitations are essentially due to the different diffusional path lengths.

Opportunities for ceria-based mixed oxides versus commercial platinum-based catalysts in the soot combustion reaction. Mechanistic implications

The aim of this paper is to study the activities of ceria–zirconia and copper/ceria–zirconia catalysts, comparing with a commercial platinum/alumina catalyst, for soot combustion reaction under different gas atmospheres and loose contact mode (simulating diesel exhaust conditions), in order to analyse the kinetics and to deduce mechanistic implications. Activity tests were performed under isothermal and TPR conditions. The NO oxidation to NO2 was studied as well. It was checked that mass transfer limitations were not influencing the rate measurements. Global activation energies for the catalysed and non-catalysed soot combustion were calculated and properly discussed. The results reveal that ceria-based catalysts greatly enhance their activities under NOx/O2 between 425 °C and 450 °C, due to the “active oxygen”-assisted soot combustion. Remarkably, copper/ceria–zirconia shows a slightly higher soot combustion rate than the Pt-based catalyst (under NOx/O2, at 450 °C).

Removal of paracetamol on biomass-derived activated carbon: Modeling the fixed bed breakthrough curves using batch adsorption experiments

The remediation of paracetamol (PA), an emerging contaminant frequently found in wastewater treatment plants, has been studied in the low concentration range (0.3–10 mg L−1) using as adsorbent a biomass-derived activated carbon. PA uptake of up to 100 mg g−1 over the activated carbon has been obtained, with the adsorption isotherms being fairly explained by the Langmuir model. The application of Reichemberg and the Vermeulen equations to the batch kinetics experiments allowed estimating homogeneous and heterogeneous diffusion coefficients, reflecting the dependence of diffusion with the surface coverage of PA. A series of rapid small-scale column tests were carried out to determine the breakthrough curves under different operational conditions (temperature, PA concentration, flow rate, bed length). The suitability of the proposed adsorbent for the remediation of PA in fixed-bed adsorption was proven by the high PA adsorption capacity along with the fast adsorption and the reduced height of the mass transfer zone of the columns. We have demonstrated that, thanks to the use of the heterogeneous diffusion coefficient, the proposed mathematical approach for the numerical solution to the mass balance of the column provides a reliable description of the breakthrough profiles and the design parameters, being much more accurate than models based in the classical linear driving force.