A Practical Method to Derive Sample Temperature during Nonisothermal Coupled Thermogravimetry Analysis and Differential Scanning Calorimetry Experiments

Nonisothermal thermogravimetry differential scanning calorimetry (TG‐DSC) mounting is intensively used for the determination of kinetic parameters and reaction heat along the chemical transformation of a solid. Nevertheless, when tests are performed with heating rates as high as those encountered in industrial processes, e.g., several tens of K min^–1, there is great uncertainty in the knowledge of the exact sample temperature. In this work, a method to derive a simple mathematical expression is proposed and fully described in order to calculate the real sample temperature throughout a temperature‐ramped test on a commercial apparatus. The furnace temperature and the heat flow signals were used, together with the crucible specific heat and the heating rate. A number of validation tests were performed to derive similar reaction rates for a reference. First‐order kinetic reactions were presented and reconciled over a large range of heating rates from 3 to 50 K min^–1.     

Effect of polymerization conditions on o‐phenylenediamine and o‐phenetidine oxidative copolymers

A series of new o‐phenylenediamine (OPD)/o‐phenetidine (PHT) copolymers with partly phenazine‐like structures has been successfully synthesized at three polymerization temperatures by chemically oxidative polymerization in four different polymerization media. The molecular structures and properties of the resulting OPD/PHT polymers were investigated by IR, UV–vis and high‐resolution ¹H NMR spectroscopies, and DSC, in order to ascertain the effect of reaction temperature, comonomer ratio and acid medium. The copolymerization mechanism of OPD with PHT monomers has been proposed. It is found that the statistical OPD/PHT copolymer obtained at a temperature of 118 °C has a higher degree of polymerization than that obtained at 12–17 °C. The OPD content in the copolymers calculated from NMR spectroscopic analysis is higher than that in the feed OPD content, whereas the OPD content calculated from element analysis is slightly lower than the feed OPD content. It can be predicted that denitrogenation takes place in the OPD units during the polymerization process at OPD/PHT molar ratios of 90/10 and 100/0. These OPD/PHT copolymers exhibit a much better solubility than the OPD homopolymer, hence suggesting an incorporation of PHT units into the phenazine structure of the homopolymer. The thermal behavior of the copolymers was also studied. Copyright © 2004 Society of Chemical Industry     

Oil Spill Cleanup from Sea Water by Sorbent Materials

Three sorbents were compared in order to determine their potential for oil spill cleanup. Polypropylene nonwoven web, rice hull, and bagasse with two different particle sizes were evaluated in terms of oil sorption capacities and oil recovery efficiencies. Polypropylene can sorb almost 7 to 9 times its weight from different oils. Bagasse, 18 to 45 mesh size, follows polypropylene as the second sorbent in oil spill cleanup. Bagasse, 14 to 18 mesh size, and rice hull have comparable oil sorption capacities, which are lower than those of the two former sorbents. It was found that oil viscosity plays an important role in oil sorption by sorbents. All adsorbents used in this work could remove the oil from the surface of the water preferentially.     

Magnetic Resonance Visualisation of Flow and Pore Structure in Packed Beds with Low Aspect Ratio

Different NMR techniques were combined to obtain the structure and velocity information for a systematic investigation of fixed beds with low aspect ratio (tube diameter to particle diamter, d_t/d_p) in the range 1.4 to 32. The structure of the void space was determined for a variety of packed beds of glass beads or regular and irregular porous pellets by magnetic resonance imaging (MRI). Based on the images the radial distribution of the voids within the bed was obtained. Ordering effects were found even for non‐spherical and polydisperse particles, and a maximum of the fluid density near the tube wall was confirmed for all pellet geometries and sizes. By combining MRI with velocity encoding, velocity profiles and distributions of flow velocity components of a single fluid phase through packed beds have been acquired. The radial velocity distribution follows an oscillatory pattern which largely reflects the ordering of the particles, which can be accessed from the density distribution of the interparticle fluid. Maximum velocities of up to four times the average value were found to occur near the tube wall. This wall effect was observed for all but the smallest particles, where the aspect ratio was d_t/d_p = 32. Moreover, a visualisation of flow pattern in the presence of packed particles was achieved by using a tagging technique, and the stationary flow field could be identified for an experimental time of several hours.     

Relating the Morphology of Poly(p‐phenylene vinylene)/Methanofullerene Blends to Solar‐Cell Performance

The performance of bulk‐heterojunction solar cells based on a phase‐separated mixture of donor and acceptor materials is known to be critically dependent on the morphology of the active layer. Here we use a combination of techniques to resolve the morphology of spin cast films of poly(p‐phenylene vinylene)/methanofullerene blends in three dimensions on a nanometer scale and relate the results to the performance of the corresponding solar cells. Atomic force microscopy (AFM), transmission electron microscopy (TEM), and depth profiling using dynamic time‐of‐flight secondary ion mass spectrometry (TOF‐SIMS) clearly show that for the two materials used in this study, 1‐(3‐methoxycarbonyl)propyl‐1‐phenyl‐[6,6]‐methanofullerene (PCBM) and poly[2‐methoxy‐5‐(3′,7′‐dimethyloctyloxy)‐1,4‐phenylene vinylene] (MDMO‐PPV), phase separation is not observed up to 50 wt.‐% PCBM. Nanoscale phase separation throughout the film sets in for concentrations of more than 67 wt.‐% PCBM, to give domains of rather pure PCBM in a homogenous matrix of 50:50 wt.‐% MDMO‐PPV/PCBM. Electrical characterization, under illumination and in the dark, of the corresponding photovoltaic devices revealed a strong increase of power conversion efficiency when the phase‐separated network develops, with a sharp increase of the photocurrent and fill factor between 50 and 67 wt.‐% PCBM. As the phase separation sets in, enhanced electron transport and a reduction of bimolecular charge recombination provide the conditions for improved performance. The results are interpreted in terms of a model that proposes a hierarchical build up of two cooperative interpenetrating networks at different length scales.     

Determination of water activities and osmotic and activity coefficients of the system NaCl–BaCl2–H2O at 298.15 K

The water activities of the mixed aqueous electrolyte NaCl–BaCl₂(aq) are measured at total molalities from 0.25 mol kg⁻¹ to about saturation for different ionic strength fractions (y) of NaCl with y=0.33,0.50,0.67. The results allow the deduction of osmotic coefficients. The experimental results are compared with the predictions of the Zdanovskii, Stokes, and Robinson (ZSR), Kusik and Meissner (KM), Robinson and Stokes (RS), Lietzke and Stoughton (LSII), Reilly, Wood, and Robinson (RWR), and Pitzer models. From these measurements, the Pitzer mixing ionic parameters are determined and used to predict the solute activity coefficients in the mixture. The excess Gibbs energy is also determined.     

Biofiltration of toluene in the absence and the presence of ethyl acetate under continuous and intermittent loading

BACKGROUND: Two peat biofilters were used for the removal of toluene from air for one year. One biofilter was fed with pure toluene and the other received 1:1 (by weight) ethyl acetate:toluene mixture. RESULTS: The biofilters were operated under continuous loading: the toluene inlet load (IL) at which 80% removal occurred was 116 g m^?3 h^?1 at 57 s gas residence time. Maximum elimination capacity of 360 g m^?3 h^?1 was obtained at an IL of 745 g m^?3 h^?1. The elimination of toluene was inhibited by the presence of ethyl acetate. Intermittent loading, with pollutants supplied for 16 h/day, 5 days/week, did not significantly affect the removal efficiency (RE). Biomass was fully activated in 2 h after night closures, but 6 h were required to recover RE after weekend closures. Live cell density remained relatively constant over the operational period, while the dead cell fraction increased. Finally, a 15 day starvation period was applied and operation then re‐started. Performance was restored with similar re‐acclimatization period to that after weekend closures, and a reduction in dead cell fraction was observed. CONCLUSION: This study demonstrates the capacity of the system to handle intermittent loading conditions that are common in industrial practices, including long‐term starvation. Copyright © 2008 Society of Chemical Industry