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.     

A Micellar Route to Ordered Arrays of Magnetic Nanoparticles: From Size‐Selected Pure Cobalt Dots to Cobalt–Cobalt Oxide Core–Shell Systems

Starting with Co‐salt‐loaded inverse micelles, which form if the diblock copolymer polystyrene‐block‐poly(2‐vinylpyridine) is dissolved in a selective solvent like toluene and CoCl₂ is added to the solution, monomicellar arrays of such micelles exhibiting a significant hexagonal order can be prepared on top of various substrates with tailored intermicellar distances and structure heights. In order to remove the polymer matrix and to finally obtain arrays of pure Co nanoparticles, the micelles are first exposed to an oxygen plasma, followed by a treatment in a hydrogen plasma. Applying in‐situ X‐ray photoelectron spectroscopy, it is demonstrated that: 1) The oxygen plasma completely removes the polymer, though conserving the original order of the micellar array. Furthermore, the resulting nanoparticles are entirely oxidized with a chemical shift of the Co 2p_3/2 line pointing to the formation of Co₃O₄. 2) By the subsequent hydrogen plasma treatment the nanoparticles are fully reduced to metallic Co. 3) By exposing the pure Co nanoparticles for 100 s to various oxygen partial pressures pequation/tex2gif-inf-5.gif, a stepwise oxidation is observed with a still metallic Co core surrounded by an oxide shell. The data allow the extraction of the thickness of the oxide shell as a function of the total exposure to oxygen (pequation/tex2gif-inf-7.gif × time), thus giving the opportunity to control the ferromagnetic–antiferromagnetic composition of an exchange‐biased magnetic system.     

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     

Inhibition of sulfide on the simultaneous removal of nitrate and p‐cresol by a denitrifying sludge

BACKGROUND: Many industrial discharges, such as those generated from petrochemical refineries, contain large amounts of sulfurous, nitrogenous and organic contaminants. Denitrification has emerged as a suitable technology for the simultaneous removal of these pollutants in a single reactor unit; however, more evidence is demanded to clarify the limitations of denitrification on the simultaneous removal of sulfide and phenolic contaminants and to optimize the biological process. The aim of this study was to evaluate the capacity of a denitrifying sludge to simultaneously convert sulfide and p‐cresol via denitrification. RESULTS: Sulfide was the preferred electron donor over p‐cresol, imposing a 5 h lag phase (required for complete sulfide removal) on organotrophic denitrification. Addition of sulfide (20 mg S^2? L^?1) to p‐cresol‐amended denitrifying cultures also decreased the reduction rate of nitrate and nitrite, as well as the production rate of nitrogen gas. Nitrite reduction rate was the most affected step by sulfide, decreasing from 35 to 21 mg N (g VSS d)^?1. A synergistic inhibitory effect of nitrate and sulfide was also observed on nitrite reduction. Despite the effects of sulfide on the respiratory rates monitored, complete removal of nitrate, sulfide and p‐cresol could be achieved after 48 h of incubation. CONCLUSION: Our results suggest that simultaneous removal of sulfide and p‐cresol could be achieved in denitrifying reactors, but a large hydraulic residence time may be required to sustain an efficient process due to inhibitory effects of sulfide. Copyright © 2008 Society of Chemical Industry     

Photodegradation mechanism and stabilization of polyphenylene oxide and rigid‐rod polymers

Poly(2,4‐dimethyl‐1,4‐phenylene oxide) (PPO), poly(benzo[1,2‐d:5,4‐d′]bisoxazole‐2,6‐diyl‐1,4‐phenylene) (PBO) and poly(benzo[1,2‐d:4,5‐d′]bisthiazole‐2,6‐diyl‐1,4‐phenylene) (PBZT), which are polymers with extended conjugated structures, undergo a self‐sensitized photo‐induced electron‐transfer reaction. A second component is not required. This article presents many similar observations on these polymers when they are exposed to light and evidence to support the proposed photo‐induced electron‐transfer mechanism. Methods to stabilize these polymers against photo‐oxidation are also described. Workers investigating other conjugated polymeric systems may find the experimental methods, observations and polymer stabilization approaches discussed in this review useful. Copyright © 2005 Society of Chemical Industry     

Application of artificial neural networks to the analysis of two‐dimensional fluorescence spectra in recombinant E coli fermentation processes

A two‐dimensional (2D) spectrofluorometer was used to monitor various fermentation processes with recombinant E coli for the production of 5‐aminolevulinic acid (ALA). The whole fluorescence spectral data obtained during a process were analyzed using artificial neural networks, ie self‐organizing map (SOM) and feedforward backpropagation neural network (BPNN). The SOM‐based classification of the whole spectral data has made it possible to qualitatively associate some process parameters with the normalized weights and variances, and to select some useful combinations of excitation and emission wavelengths. Based on the classified fluorescence spectra a supervised BPNN algorithm was used to predict some of the process parameters. It was also shown that the BPNN models could elucidate some sections of the process's performance, eg forecasting the process's performance. Copyright © 2005 Society of Chemical Industry     

A comparison of lightness contrast effects in CRT and surface colours

The simultaneous contrast effect is investigated in this article. A total of 174 and 154 test/induction combinations were studied for CRT and surface colours respectively. Each combination was assessed by nine observers using a matching technique. The test and induction colours used for CRT colours were similar to surface colours using fabric samples. The results indicated a strong lightness contrast effect for both CRT and surface media; that is, the lightness of a test colour surrounded by a lighter induction colour was reduced for both CRT and surface colours. However, the effect in CRT medium was more pronounced than in the surface medium. © 2004 Wiley Periodicals, Inc. Col Res Appl, 30, 13–20, 2005; Published online in Wiley InterScience (www.interscience.wiley.com). DOI 10.1002/col.20074     

Inside Front Cover: Three‐Dimensionally Ordered Gold Nanocrystal/Silica Superlattice Thin Films Synthesized via Sol–Gel Self‐Assembly (Adv. Funct. Mater. 7/2006)

The synthesis of three‐dimensionally ordered, transparent gold‐nanocrystal (NC)/silica superlattice thin films using the self‐assembly (by spin‐coating) of water‐soluble gold nanocrystal micelles and soluble silica is reported by Fan and co‐workers on p. 891. The robust, 3D NC/silica superlattice films are of interest for the development of collective optical and electronic phenomena, and, importantly, for the integration of NC arrays into device architectures. Nanocrystals and their ordered arrays hold many important applications in fields such as catalysis, surface‐enhanced Raman spectroscopy based sensors, memory storage, and electronic and optical nanodevices. Herein, a simple and general method to synthesize ordered, three‐dimensional, transparent gold nanocrystal/silica superlattice thin films by self‐assembly of gold nanocrystal micelles with silica or organosilsesquioxane by spin‐coating is reported. The self‐assembly process is conducted under acidic sol–gel conditions (ca. pH 2), ensuring spin‐solution homogeneity and stability and facilitating the formation of ordered and transparent gold nanocrystal/silica films. The monodisperse nanocrystals are organized within inorganic host matrices as a face‐centered cubic mesostructure, and characterized by transmission electron spectroscopy and X‐ray diffraction.