Characterisation of the adsorption sites of hydrogen on Pt/C fuel cell catalysts

A key component of a hydrogen fuel cell is a catalyst to dissociate dihydrogen to hydrogen atoms. In the present study, the adsorption of hydrogen on Pt/C fuel cell catalysts has been investigated by inelastic neutron scattering spectroscopy.

Monitoring a clean Pt(50%)/C catalyst with low energy neutron spectroscopy, after exposure to dihydrogen at 20 K, as it was heated to room temperature, showed three distinct temperature regimes: (i) a decrease in intensity from 10 to 60 K, (ii) a rise to a maximum between 60 and 120 K and then (iii) a slow fall-off towards room temperature. We assign the three regions as: (i) desorption of physisorbed dihydrogen, (ii) dissociation of dihydrogen to give an adsorbed layer and (iii) damping of the response by an increasing Debye–Waller factor.

The vibrational INS spectra of a series of Pt/C catalysts prepared under varying conditions were similar indicating that the same types of site are common to all the catalysts, although the relative proportions of each site are sample dependent. Features at 520, 950 and part of the intensity at 1300 cm⁻¹ are assigned to hydrogen on (1 1 1) faces, in good agreement with single crystal data. The mode at 640 cm⁻¹ is assigned as the doubly degenerate asymmetric stretch of Pt(1 0 0) faces with the symmetric stretch near 550 cm⁻¹.

We assign the bending mode of the on-top site to the feature at 470 cm⁻¹. The Pt–H stretch mode was observed at 2079 cm⁻¹. This is a significant result: this is the first time that hydrogen on the on-top sites has been observed on nanosized platinum particles supported on high surface area carbon black. The width of the INS peak is surprisingly large and may give additional information on the type and relative proportions of the crystallographic faces present on the catalyst particles.     

THE ADHESION OF ISOCYANATE-BASED POLYMERS TO STEEL

Isocyanate-based materials have been used for decades as the basis for high performance adhesives, coatings, and primers. The origin of the excellent adhesion of these materials to metals such as steel has been generally assumed to derive from the condensation of isocyanates with metal hydroxyls to form metal oxide-cyanate esters analogous to urethanes. In this work Fourier transform infrared reflection (FTIR) was used to demonstrate that these esters do indeed form, but that the esterification is preceded by the formation of carbamate salts between the isocyanate and the hydrated metal oxide.

Isocyanate pMDI Polyurethane Steel Adhesion Interface     

Rückgewinnung von Metallen aus niedrigkonzentrierten Lösungen

Recycling of metals from low concentrated solutions. A review is given of processes used for the separation of metals from aqueous solutions, especially low concentration waste waters. Purification processes for waste water used only to reach values set by law are compared with processes that allow recovery of metals. Precipitation with and without additives, adsorption, processes with ion exchange resins, solvent extraction and membrane processes, especially liquid membrane permeation, are described. As a result of these considerations, a qualitative comparison of all the described processes becomes possible. For the separation of zinc from a waste water stream, a special economic comparison is also shown between precipitation processes and the liquid membrane permeation process. Finally, the latest developments in the fields of solvent extraction and liquid membrane permeation are discussed.     

Image analysis for interfacial area and cocontinuity detection in polymer blends

A novel image processing method was developed to extract interfacial area concentration measurements from 2D micrographs of immiscible polymer blends. Although this method can be used for analyzing different types of 2D micrographs such as optical or transmission electron microscopy images, it was designed for analyzing scanning electron microscopy (SEM) images. The method operates by detecting edges within the images and using standard image processing operations to selectively eliminate false edges. SEM images of polyethylene oxide/polystyrene (PEO/PS) blends were analyzed using this image processing method to measure the amount of interfacial area in the samples. Interfacial area per unit volume exhibits maxima for blend compositions at the boundary between droplet and cocontinuous morphologies. In addition to the detection of cocontinuity, the interfacial area measurements facilitated by this method may be used in future investigations of blend dynamics, including coalescence, drop deformation, and blend rheology studies. These measurements may also be used to quantify the effects of compatibilizers on blend morphology.     

Effect of Dyebath Additives on Decolorization Efficiency in the Ozonation of Dyehouse Effluent

It is necessary to study the effect of dyebath additives on decolorization efficiency in order to optimize ozone-based decolorization processes as the consumption of ozone can be reduced through selecting ozone favorable additives. The effect of 5 dyebath additives viz. electrolytes (sodium chloride and sodium sulfate), chelating agent (ethylene diamine tetra acetic acid or EDTA), reducing agent (sodium dithionite), optical brightener (Uvitex BHT), and dispersing agent (Zetex DNVL) was investigated. All of the additives showed synergistic effect as addition of sodium chloride, sodium dithionite and Zetex DN-VL markedly improved decolorization efficiency, but EDTA and optical brightener showed negative effect. Sodium sulfate did not show any positive or negative effect on decolorization efficiency.     

Dose and enantiospecific responses of white pine cone beetles,Conophthorus coniperda,to alpha-Pinene in an eastern white pine seed orchard

The white pine cone beetle, Conophthorus coniperda, exhibited dose and enantiospecific responses to -pinene in stands of mature eastern white pine, Pinus strobus, in a seed orchard near Murphy, North Carolina, USA. (–)--Pinene significantly increased catches of cone beetles to traps baited with (± )-trans-pityol. (+)--Pinene did not increase catches of beetles to pityol-baited traps and interrupted the response of beetles to traps baited with (±)-trans-pityol and (–)--pinene. Maximal attraction of cone beetles to pityol-baited traps was obtained with lures releasing (–)--pinene at a rate of 103 mg/day at 23^°C. Lures releasing (–)--pinene at rates lower or higher than 103 mg/day resulted in reduced catches to traps baited with (±)-trans-pityol. The sex ratio in all catches was heavily male biased. Attraction of the clerid predator, Thanasimus dubius, to traps baited with (±)-trans-pityol increased significantly with the presence of -pinene, irrespective of enantiomeric composition. Maximal attraction of T. dubius to pityol-baited traps occurred with devices releasing (–)--pinene at the highest rate tested, 579 mg/d at 23^°C, a sub optimal rate for cone beetles.     

Processing of mesocarbon microbeads to high-performance materials: Part II. Reaction bonding by in situ silicon carbide and nitride formation

The processing of carbon-ceramic composites by utilizing the unique sintering ability of mesocarbon microbeads (MCMB) is reported. The ceramic constituents (silicon nitride and silicon carbide) are formed in situ by reactions between MCMB and silicon in different atmospheres. In comparison with direct addition of ceramic (SiC, Si₃N₄) phases, in situ formation shows several appealing features. By inducing the reaction of silicon with MCMB, the sintering ability of the composite is enhanced via reaction bonding mechanisms. Similarly, it is demonstrated that composite porosity is limited owing to silicon reaction with nitrogen. The reactive formation of nanoscale ceramic reinforcements via decomposition of the silicon-containing polymer (e.g. poly-carbomethyl-silane) is also reported. This approach results in formation of uniform nanosized (>100 nm) SiC layers strongly bonded to the surface of the carbon particles. The presented results contribute to the development of carbon-ceramic materials with high-operational properties.     

Extension of Master Sintering Curve Theory to Organic Decomposition

The ability to predict and control organic decomposition of a material under arbitrary thermal treatments is one of the main objectives of thermogravimetric studies. The development of this ability provides significant potential to ensure reliability and reproducibility for a given processing method and can be used in planning optimized thermal treatment strategies. Based on this report, the master sintering curve theory has been successfully extended to similar kinetically controlled phenomena. The theory has been applied to organic decomposition reaction kinetics to develop a master organic decomposition curve. The fundamental kinetics are assumed to be governed by an Arrhenius-type reaction rate, making master sintering and decomposition curves analogous to one another. The formulation and construction of a master decomposition curve are given in this paper. Simultaneous thermogravimetric and differential thermal analysis of a low-temperature co-fire glass/ceramic dielectric tape (Dupont 951 Green Tape^TM) is analyzed and used to demonstrate this new concept. The results reveal two independent organic decomposition reactions, the first occurring at ≈245°C and the second at ≈365°C. The analysis is used to produce a master decomposition curve and to calculate the activation energy for these reactions, at 86±6 and 142±4 kJ/mol, respectively. In addition, the weight loss of product and the rate of decomposition can be predicted under varying thermal paths (time–temperature trajectories) following a minimal set of preliminary experiments.     

Sludge Pre-Treatment through Ozone Application: Alternative Sludge Reuse Possibilities for Recirculating Aquaculture System Optimization

Recirculating Aquaculture Systems (RAS) reduce water consumption by efficient filtration to maintain appropriate levels of accumulating compounds and sludge. Sludge is mechanically separated by drum filters and disposed of to the detriment of overall system water budgets. Dissolved nitrogen compounds are reduced via nitrification–denitrification filters, requiring commercial external carbon sources. The reuse of sludge after ozone pre-treatment may represent the next step in RAS optimization. The present study analyzes the content of sludge from RAS and tests ozonation as a pre-treatment for recycling as carbon source. The dissociative effect of ozone and the physicochemical changes due to ozonation lead to a significant increase in soluble carbon availability. Predominantly long-chain fatty acid (FA) (saturated and unsaturated) with 16 and 18 carbon atoms independently of the treatment were found in the profiles. Saturated FA concentrations in solution increased after 20, 40, and 60 min ozonation. The solid content of the sludge was practically unaffected by ozonation in terms of FA profile: only saturated FA slightly increases after 40 min treatment. The implications of these findings for denitrifying bacteria are discussed.

Abbreviations: Recirculating Aquaculture Systems (RAS); Advanced Oxidation Processes (AOPs)     

Physical crosslinking effects in α,ω-dihydroxy terminated polybutadienes

Structure and molecular dynamics of α,ω-dihydroxy terminated polybutadienes of varying number averaged molecular weight (1320-10?500 g/mol) have been investigated by Fourier-transformed infrared (FTIR) spectroscopy, nuclear magnetic resonance (NMR) spectroscopy, dielectric relaxation spectroscopy (DRS), differential scanning calorimetry (DSC) and wide-angle X-ray scattering (WAXS). DSC and DRS revealed an increase in the glass transition temperature upon decrease of the molecular weight, accompanied by an increasing dynamic fragility m (or steepness index) of the dielectric α-process. This correlation between T_g and m for different molecular weights indicates the presence of a physical network, where H-bonded end-group clusters act as temporary crosslinks. From the dielectric relaxation strength Δ?_α(M_n), the fraction of associated hydroxy groups (f_bond) was estimated showing a peak value for the two but shortest polymers, a behaviour that strongly resembles the molecular weight dependence of the fragility. By considering the quantity f_bond(M_n) in a modified Fox-Flory approach, the measured T_g(M_n) behaviour could be reproduced in a satisfying way. FTIR results support this general picture and show a considerable dependence of the extent of hydrogen bonding and formation of hydroxy groups associates on the molecular weight. Further, WAXS and DSC results disprove the idea of formation of pseudo-crystalline hydrophobic microdomains in these compounds as suggested by other authors.