Steam reforming of model compounds and fast pyrolysis bio-oil on supported noble metal catalysts

The production of hydrogen by steam reforming of bio-oils obtained from the fast pyrolysis of biomass requires the development of efficient catalysts able to cope with the complex chemical nature of the reactant. The present work focuses on the use of noble metal-based catalysts for the steam reforming of a few model compounds and that of an actual bio-oil. The steam reforming of the model compounds was investigated in the temperature range 650-950 degrees C over Pt, Pd and Rh supported on alumina and a ceria-zirconia sample. The model compounds used were acetic acid, phenol, acetone and ethanol. The nature of the support appeared to play a significant role in the activity of these catalysts. The use of ceria-zirconia, a redox mixed oxide, lead to higher H-2 yields as compared to the case of the alumina-supported catalysts. The supported Rh and Pt catalysts were the most active for the steam reforming of these compounds, while Pd-based catalysts poorly performed. The activity of the promising Pt and Rh catalysts was also investigated for the steam reforming of a bio-oil obtained from beech wood fast pyrolysis. Temperatures close to, or higher than, 800 degrees C were required to achieve significant conversions to COx and H-2 (e.g., H-2 yields around 70%). The ceria-zirconia materials showed a higher activity than the corresponding alumina samples. A Pt/ceria-zirconia sample used for over 9 h showed essentially constant activity, while extensive carbonaceous deposits were observed on the quartz reactor walls from early time on stream. In the present case, no benefit was observed by adding a small amount of O-2 to the steam/bio-oil feed (autothermal reforming, ATR), probably partly due to the already high concentration of oxygen in the bio-oil composition. (c) 2005 Elsevier B.V. All rights reserved.

Speciation of Rare-Earth Metal Complexes in Ionic Liquids: A Multiple-Technique Approach

The dissolution process of metal complexes in ionic liquids was investigated by a multiple-technique approach to reveal the solvate species of the metal in solution. The task-specific ionic liquid betainium bis(trifluoromethylsulfonyl)imide ([Hbet][Tf2N]) is able to dissolve stoichiometric amounts of the oxides of the rare-earth elements. The crystal structures of the compounds [Eu-2(bet)(8)(H2O)(4)][Tf2N](6), [Eu-2(bet)(8)(H2O)(2)][Tf2N](6)center dot 2H(2)O, and [Y-2(bet)(6)(H2O)(4)][Tf2N](6) were found to consist of dimers. These rare-earth complexes are well soluble in the ionic liquids [Hbet][Tf2N] and [C(4)mim]- [Tf2N] (C(4)mim = 1-butyl-3-methylimidazolium). The speciation of the metal complexes after dissolution in these ionic liquids was investigated by luminescence spectroscopy, H-1, C-13, and Y-89 NMR spectroscopy, and by the synchrotron techniques EXAFS (extended X-ray absorption fine structure) and HEXS (high-energy X-ray scattering). The combination of these complementary analytical techniques reveals that the cationic dimers decompose into monomers after dissolution of the complexes in the ionic liquids. Deeper insight into the solution processes of metal compounds is desirable for applications of ionic liquids in the field of electrochemistry, catalysis, and materials chemistry.

Compressed Metal Powders that Remain Superhydrophobic After Abrasion

Superhydrophobic “lotus effect” materials are typically not sufficiently robust for most real world applications because their small surface features are both easily damaged and vulnerable to fouling. Here, a method for preparing a new type of superhydrophobic (? > 162°) composite material by compression of superhydrophobic metal particles is reported. This material, which has no natural analogue, has low-surface-energy microstructures extending throughout its whole volume. Removing its outer layer by abrasion or cutting deep into it does not result in loss of superhydrophobicity because it merely exposes a fresh portion of the underlying superhydrophobic material. The high contact angle is therefore retained even after accidental damage, and vigorous abrasion can be used to restore hydrophobicity after fouling.

Biosorption of toxic chromium from aqueous phase by lignin: mechanism, effect of other metal ions and salts

Surface reaction methodology was implicated in the optimization of hexavalent chromium removal onto lignin with respect to the process parameters. The influence of altering the conditions for removal of chromium(VI), for instance; solution pH, ionic strength, initial concentration, the dose of biosorbent, presence of other metals (Zn and Cu), presence of salts and biosorption-desorption studies, were investigated. It was found that the biosorption capacity of lignin depends on solution pH, with a maximum biosorption capacity for chromium at pH 2. Experimental equilibrium data were fitted to five different isotherm models by non-linear regression method, however, the biosorption equilibrium data were well interpreted by the Freundlich isotherm. The maximum biosorption capacities (q(max)) obtained using Dubinin-Radushkevich and Khan isotherms for Cr(VI) biosorption are 31.6 and 29.1 mg/g. respectively. Biosorption showed pseudo second order rate kinetics at different initial concentrations of Cr(VI). The intraparticle diffusion study indicated that film diffusion may be involved in the current study. The percentage removal of chromium on lignin decreased significantly in the presence of NaHCO3 and K2P2O7 salts. Desorption data revealed that nearly 70% of the Cr(VI) adsorbed on lignin could be desorbed using 0.1 M NaOH. It was evident that the biosorption mechanism involves the attraction of both hexavalent chromium (anionic) and trivalent chromium (cationic) onto the surface of lignin. (C) 2011 Elsevier B.V. All rights reserved.

Platinum Group Metals and Their Oxides in Semiconductor Photosensitisation BASIC PRINCIPLES, METAL PHOTODEPOSITION AND WATER PHOTOSPLITTING REACTIONS

The basic principles of semiconductor photochemistry, particularly using titania as a semiconductor photocatalyst, are discussed. When a platinum group metal or its oxide is deposited onto the surface of a sensitised semiconductor the overall efficiency of the reactions it takes part in are often improved, especially when the deposits are used as hydrogen and oxygen catalysts, respectively. Methods of depositing metal or metal oxide are examined, and a particular focus is given to a photodeposition process that uses a sacrificial electron donor. Platinum group metal and platinum group metal oxide coated semiconductor photocatalysts are prominent in heterogeneous systems that are capable of the photoreduction, oxidation and cleavage of water. There is a recent renaissance in work on water-splitting semiconductor-sensitised photosystems, but there are continued concerns over their irreproducibility, longevity and photosynthetic nature.

Optical transmission of periodic annular apertures in metal film on high-refractive index substrate: The role of the nanopillar shape

The influence of annular aperture parameters on the optical transmission through arrays of coaxial apertures in a metal film on high refractive index substrates has been investigated experimentally and numerically. It is shown that the transmission resonances are related to plasmonic crystal effects rather than frequency cutoff behavior associated with annular apertures. The role of deviations from ideal aperture shape occurring during the fabrication process has also been studied. Annular aperture arrays are often considered in many applications for achieving high optical transmission through metal films and understanding of nanofabrication tolerances are important. (C) 2010 American Institute of Physics.

Nanoporous metal organic framework materials for hydrogen storage

Hydrogen is expected to play an important role in future transportation as a promising alternative clean energy source to carbon-based fuels. One of the key challenges to commercialize hydrogen energy is to develop appropriate onboard hydrogen storage systems, capable of charging and discharging large quantities of hydrogen with fast enough kinetics to meet commercial requirements. Metal organic framework (MOF) is a new type of inorganic and organic hybrid nanoporous particulate materials. Its diverse networks can enhance hydrogen storage through tuning the structure and property of MOFs. The MOF materials so far developed adsorb hydrogen through weak dispersion interactions, which allow significant quantity of hydrogen to be stored at cryogenic temperatures with fast kinetics. Novel MOFs are being developed to strengthen the interactions between hydrogen and MOFs in order to store hydrogen under ambient conditions. This review surveys the development of such candidate materials, their performance and future research needs. (C) 2009 Chinese Society of Particuology and Institute of Process Engineering, Chinese Academy of Sciences. Published by Elsevier B.V. All rights reserved.

Multiscale simulation of nanometric cutting of single crystal copper and its experimental validation

In this paper a multiscale simulation study was carried out in order to gain in-depth understanding of machining mechanism of nanometric cutting of single crystal copper. This study was focused on the effects of crystal orientation and cutting direction on the attainable machined surface quality. The machining mechanics was analyzed through cutting forces, chip formation morphology, generation and evolution of defects and residual stresses on the machined surface. The simulation results showed that the crystal orientation of the copper material and the cutting direction significantly influenced the deformation mechanism of the workpiece materials during the machining process. Relatively lower cutting forces were experienced while selecting crystal orientation family {1 1 1}. Dislocation movements were found to concentrate in front of the cutting chip while cutting on the (1 1 1) surface along the View the MathML source cutting direction thus, resulting in much smaller damaged layer on the machined surface, compared to other orientations. This crystal orientation and cutting direction therefore recommended for nanometric cutting of single crystal copper in practical applications. A nano-scratching experiment was performed to validate the above findings.

Thermomechanical analyses of ultrasonic welding process using thermal and acoustic softening effects

Ultrasonic welding process is a rapid manufacturing process used to weld thin layers of metal at low temperatures and low energy consumption. Experimental results have shown that ultrasonic welding is a combination of both surface (friction) and volume (plasticity) softening effects. In the presented work, a very first attempt has been made to simulate the ultrasonic welding of metals by taking into account both of these effects (surface and volume). A phenomenological material model has been proposed which incorporates these two effects (i.e. surface and volume). The thermal softening due to friction and ultrasonic (acoustic) softening has been included in the proposed material model. For surface effects a friction law with variable coefficient of friction dependent upon contact pressure, slip, temperature and number of cycles has been derived from experimental friction tests. Thermomechanical analyses of ultrasonic welding of aluminium alloy have been performed. The effects of ultrasonic welding process parameters, such as applied load, amplitude of ultrasonic vibration, and velocity of welding sonotrode on the friction work at the weld interface are being analyzed. The change in the friction work at the weld interface has been explained on the basis of softening (thermal and acoustic) of the specimen during the ultrasonic welding process. In the end, a comparison between experimental and simulated results has been presented showing a good agreement. © 2008 Elsevier Ltd. All rights reserved.

Influence of microstructure on the cutting behaviour of silicon

We use molecular dynamics simulation to study the mechanisms of plasticity during cutting of monocrystalline and polycrystalline silicon. Three scenarios are considered: (i) cutting a single crystal silicon workpiece with a single crystal diamond tool, (ii) cutting a polysilicon workpiece with a single crystal diamond tool, and (iii) cutting a single crystal silicon workpiece with a polycrystalline diamond tool. A long-range analytical bond order potential is used in the simulations, providing a more accurate picture of the atomic-scale mechanisms of brittle fracture, ductile plasticity, and structural changes in silicon. The MD simulation results show a unique phenomenon of brittle cracking typically inclined at an angle of 45° to 55° to the cut surface, leading to the formation of periodic arrays of nanogrooves in monocrystalline silicon, which is a new insight into previously published results. Furthermore, during cutting, silicon is found to undergo solid-state directional amorphisation without prior Si-I to Si-II (beta tin) transformation, which is in direct contrast to many previously published MD studies on this topic. Our simulations also predict that the propensity for amorphisation is significantly higher in single crystal silicon than in polysilicon, signifying that grain boundaries eases the material removal process.

Modelling and characterization of ultrasonic consolidation process of Aluminium alloys

Ultrasonic consolidation process is a rapid manufacturing process used to join thin layers of metal at low temperatures and low energy consumption. In this work, finite element method has been used to simulate the ultrasonic consolidation of Aluminium alloys 6061 (AA-6061) and 3003 (AA-3003). A thermomechanical material model has been developed in the framework of continuum cyclic plasticity theory which takes into account both volume (acoustic softening) and surface (thermal softening due to friction) effects. A friction model based on experimental studies has been developed, which takes into account the dependence of coefficient of friction upon contact pressure, amount of slip, temperature and number of cycles. Using the developed material and friction model ultrasonic consolidation (UC) process has been simulated for various combinations of process parameters involved. Experimental observations are explained on the basis of the results obtained in the present study. The current research provides the opportunity to explain the differences of the behaviour of AA-6061 and AA-3003 during the ultrasonic consolidation process. Finally, trends of the experimentally measured fracture energies of the bonded specimen are compared to the predicted friction work at the weld interface resulted from the simulation at similar process condition. Similarity of the trends indicates the validity of the developed model in its predictive capability of the process. © 2008 Materials Research Society.

Microstructure and microtexture evolution of aluminum alloy 3003 under ultrasonic welding process for embedding SiC fibre

Ultrasonic welding process can be used for bonding metal foils which is the fundament of ultrasonic consolidation (UC). UC process can be used to embed reinforcement fibres such as SiC fibres within an aluminum matrix materials. In this research we are investigating the phenomena occurring in the microstructure of the parts during ultrasonic welding process to obtain better understanding about how and why the process works. High-resolution electron backscatter diffraction (EBSD) is used to study the effects of the vibration on the evolution of microstructure in AA3003. The inverse pole figures (IPF) and the correlated misorientation angle distribution of the mentioned samples are obtained. The characteristics of the crystallographic orientation, the grain structure and the grain boundary are analyzed to find the effect of ultrasonic vibration on the microstructure and microtexture of the bond. The ultrasonic vibration will lead to exceptional refinement of grains to a micron level along the bond area and affect the crystallographic orientation. Ultrasonic vibration results in a very weak texture. Plastic flow occurs in the grain after welding process and there is additional plastic flow around the fibre which leads to the fibre embedding. © 2009 Editorial Board of CHINA WELDING.

Evaluation of drilling process in Ti6Al4V using 3D FE simulation

Drilling of Ti6Al4V is investigated experimentally and numerically. A 3D finite element model developed based on Lagrangian approach using commercial finite element software ABAQUS/explicit. 3D complex drill geometry is included in the model. The drilling process simulations are performed at the combinations of three cutting speed and four feed rates. The effects of cutting parameters on the induced thrust force and torque are predicted by the developed model. For validation purpose, experimental trials have been performed in similar condition to the simulations. The forces and torques measured during experiment are compared to the results of the finite element analysis. The agreement of the experimental results for force and torque values with the FE results is very good. Moreover, surface roughness of the holes was measured for mapping of machining. Copyright © 2013 Inderscience Enterprises Ltd.

Rough Waters, Dark Shadows and Cross-Cutting Winds:the impact of European Union enlargement on Turkey’s EU accession negotiations

For a multiplicity of socio-economic, geo-political, strategic and identity-based reasons, Turkey’s progress towards EU membership is often treated as a sui generis case. Yet although Turkey’s accession negotiations with the European Union (EU) are essentially a bilateral – and often stormy – affair, they take place within a wider and dynamic process of enlargement in which not only can the gloomy – sometimes dark – shadows of past and prospective enlargements be clearly detected, but so too can the often chill winds from ongoing, parallel negotiations with other candidates. How the EU negotiates accession and what it expects from candidates has continued to evolve since the EU began drawing up its framework for negotiations with Turkey ten years ago. This paper charts this evolution by first identifying changes in the light of Croatia’s negotiating experience, the ‘lessons learnt’ by the EU in meeting the challenges of Bulgarian and Romanian accession, the EU’s handling of Iceland’s membership bid and accession negotiations, and the revised approach to negotiating accession evident in the more recent frameworks for accession negotiations with Montenegro and Serbia. The paper then explores the extent to which these changes have impacted on the approach the EU has adopted in framing and progressing accession negotiations with Turkey. In doing so, it questions both the consistency with which the EU’s negotiates accession and the extent to which Turkey’s progress towards EU membership is conditioned by the broader dynamics of EU enlargement as opposed to simply the dynamics within EU-Turkey relations and domestic Turkish reform efforts.