Insights into redox cycling of sulfur and iron in peatlands using high-resolution diffusive equilibrium thin film (DET) gel probe sampling

High spatial resolution vertical profiles of pore-water chemistry have been obtained for a peatland using diffusive equilibrium in thin films (DET) gel probes. Comparison of DET pore-water data with more traditional depth-specific sampling shows good agreement and the DET profiling method is less invasive and less likely to induce mixing of pore-waters. Chloride mass balances as water tables fell in the early summer indicate that evaporative concentration dominates and there is negligible lateral flow in the peat. Lack of lateral flow allows element budgets for the same site at different times to be compared. The high spatial resolution of sampling also enables gradients to be observed that permit calculations of vertical fluxes. Sulfate concentrations fall at two sites with net rates of 1.5 and 5.0nmol cm− 3 day− 1, likely due to a dominance of bacterial sulfate reduction, while a third site showed a net gain in sulfate due to oxidation of sulfur over the study period at an average rate of 3.4nmol cm− 3 day− 1. Behaviour of iron is closely coupled to that of sulfur; there is net removal of iron at the two sites where sulfate reduction dominates and addition of iron where oxidation dominates. The profiles demonstrate that, in addition to strong vertical redox related chemical changes, there is significant spatial heterogeneity. Whilst overall there is evidence for net reduction of sulfate within the peatland pore-waters, this can be reversed, at least temporarily, during periods of drought when sulfide oxidation with resulting acid production predominates.

Fast and accurate SCFT calculations for periodic block-copolymer morphologies using the spectral method with Anderson mixing

We study the numerical efficiency of solving the self-consistent field theory (SCFT) for periodic block-copolymer morphologies by combining the spectral method with Anderson mixing. Using AB diblock-copolymer melts as an example, we demonstrate that this approach can be orders of magnitude faster than competing methods, permitting precise calculations with relatively little computational cost. Moreover, our results raise significant doubts that the gyroid (G) phase extends to infinite $\chi N$. With the increased precision, we are also able to resolve subtle free-energy differences, allowing us to investigate the layer stacking in the perforated-lamellar (PL) phase and the lattice arrangement of the close-packed spherical (S$_{cp}$) phase. Furthermore, our study sheds light on the existence of the newly discovered Fddd (O$^{70}$) morphology, showing that conformational asymmetry has a significant effect on its stability.

Positioning Janus nanoparticles in block copolymer scaffolds

The periodic domains formed by block copolymer melts have been heralded as potential scaffolds for arranging nanoparticles in 3d space, provided we can control the positioning of the particles. Recent experiments have located particles at the domain interfaces by grafting mixed brushes to their surfaces. Here the underlying mechanism, which involves the transformation into Janus particles, is investigated with self-consistent field theory using a new multi-coordinate-system algorithm.

Efficiency of pseudo-spectral algorithms with Anderson mixing for the SCFT of periodic block-copolymer phases

This study examines the numerical accuracy, computational cost, and memory requirements of self-consistent field theory (SCFT) calculations when the diffusion equations are solved with various pseudo-spectral methods and the mean field equations are iterated with Anderson mixing. The different methods are tested on the triply-periodic gyroid and spherical phases of a diblock-copolymer melt over a range of intermediate segregations. Anderson mixing is found to be somewhat less effective than when combined with the full-spectral method, but it nevertheless functions admirably well provided that a large number of histories is used. Of the different pseudo-spectral algorithms, the 4th-order one of Ranjan, Qin and Morse performs best, although not quite as efficiently as the full-spectral method.

Effect of architecture on the phase behavior of AB-type block copolymer melts

Equilibrium phase diagrams are calculated for a selection of two-component block copolymer architectures using self-consistent field theory (SCFT). The topology of the phase diagrams is relatively unaffected by differences in architecture, but the phase boundaries shift significantly in composition. The shifts are consistent with the decomposition of architectures into constituent units as proposed by Gido and coworkers, but there are significant quantitative deviations from this principle in the intermediate-segregation regime. Although the complex phase windows continue to be dominated by the gyroid (G) phase, the regions of the newly discovered Fddd (O^70) phase become appreciable for certain architectures and the perforated-lamellar (PL) phase becomes stable when the complex phase windows shift towards high compositional asymmetry.

Detection of nitroaromatic vapours with diketopyrrolopyrrole thin films: exploring the role of structural order and morphology on thin film properties and fluorescence quenching efficiency

Sensitive optical detection of nitroaromatic vapours with diketo-pyrrolopyrrole thin films is reported for the first time and the impact of thin film crystal structure and morphology on fluorescence quenching behaviour demonstrated.

Determination of the embedded thermo-optical expansion coefficients of PbTe and ZnSe thin film infrared multilayers

This paper reports the first derived thermo-optical properties for vacuum deposited infrared thin films embedded in multilayers. These properties were extracted from the temperature-dependence of manufactured narrow bandpass filters across the 4-17 µm mid-infrared wavelength region. Using a repository of spaceflight multi-cavity bandpass filters, the thermo-optical expansion coefficients of PbTe and ZnSe were determined across an elevated temperature range 20-160 ºC. Embedded ZnSe films showed thermo-optical properties similar to reported bulk values, whilst the embedded PbTe films of lower optical density, deviate from reference literature sources. Detailed knowledge of derived coefficients is essential to the multilayer design of temperature-invariant narrow bandpass filters for use in non-cooled infrared detection systems. We further present manufacture of the first reported temperature-invariant multi-cavity narrow bandpass filter utilizing PbS chalcogenide layer material.

Effective interaction between monolayers of block copolymer compatiblizer in a polymer blend

The stability of ternary blends of two immiscible homopolymers and a block copolymer compatiblizer depends crucially on the effective interaction between the copolymermonolayers that form between the unlike homopolymer domains. Here, the interaction is calculated for blends involving A and B homopolymers of equal size with ABABdiblock copolymers of symmetric composition using both self-consistent field theory (SCFT) and strong-segregation theory (SST). If the homopolymers are larger than the copolymer molecules, an attractive interaction is predicted which would destroy the blend. This conclusion coupled with considerations regarding the elastic properties of the monolayer suggests that the optimum size of the homopolymer molecules is about 80% that of the copolymer molecule. A detailed examination of the theory demonstrates that the attraction results from the configurational entropy loss of the homopolymer molecules trapped between the copolymermonolayers. We conclude by suggesting how the monolayers can be altered in order to suppress this attraction and thus improve compatiblization.

Improving polymeric microemulsions with block copolymer polydispersity

Recent experiments have demonstrated that block copolymers are capable of stabilizing immiscible homopolymer blends producing bicontinuous microemulsion. The stability of these polymeric alloys requires the copolymer to form flexible, nonattractive monolayers along the homopolymer interfaces. We predict that copolymer polydispersity can substantially and simultaneously improve the monolayers in both of these respects. Furthermore, polydispersity should provide similar improvements in systems, such as colloidal suspensions and polymer/clay composites, that utilize polymer brushes to suppress attractive interactions.

Theoretical Analysis of Aggregation in Block-Copolymer Films: The Optical Signature

We focus this work on the theoretical investigation of the block-copolymer poly [oxyoctyleneoxy-(2,6-dimethoxy-1,4phenylene-1,2-ethinylene-phenanthrene-2,4diyl) named as LaPPS19, recently proposed for optoelectronic applications. We used for that a variety of methods, from molecular mechanics to quantum semiempirical techniques (AMI, ZINDO/S-CIS). Our results show that as expected isolated LaPPS19 chains present relevant electron localization over the phenanthrene group. We found, however, that LaPPS19 could assemble in a pi-stacked form, leading to impressive interchain interaction; the stacking induces electronic delocalization between neighbor chains and introduces new states below the phenanthrene-related absorption; these results allowed us to associate the red-shift of the absorption edge, seen in the experimental results, to spontaneous pi-stack aggregation of the chains. (C) 2009 Wiley Periodicals, Inc. Int J Quantum Chem 110: 885-892, 2010

Thermodynamics and Lithium Intercalation in CeO(2)-TiO(2) Thin Film

The kinetics and the thermodynamics of electrochemical intercalation of lithium into CeO(2)-TiO(2) films prepared by the sol-gel process were studied by galvanostatic intermittent titration technique (GITT) as function of the depth of lithium intercalation. The open-circuit-potential versus x in Li(x)(CeO(2)-TiO(2)) curve consists of two straight lines with different slopes, one in the range of 0.03 <= x <= 0.09 and the other of 0.09 < x <= 0.15. The standard Gibbs energy for lithium intercalation Delta G(1)(0) was 6kJ/mol for x = 0.09 in Li(x)(CeO(2)-TiO(2)) at room temperature. The chemical diffusion coefficient value, D(Li+), of lithium intercalation into thin film oxide was 2.14.10(-11) cm(2)/s at x = 0.15, and the value of the component diffusion coefficient D(Li+),(k) was about one order of magnitude lower than the coefficient of chemical diffusion.

An electrochemical sensor for (L)-dopa based on oxovanadium-salen thin film electrode applied flow injection system

An oxovanadium-salen complex (NAP-ethylene-bis(salicylidenciminato) oxovanadium) thin film deposited on a graphite-polyurethane electrode was investigated with regard to its potential use for detection of L-dopa in flow injection system. The oxovanadium(IV)/oxovanadium(V) redox couple of the modified electrode was found to mediate the L-dopa oxidation before its use in the FIA system. Experimental parameters, such as pH of the carrier solution, flow rate, sample volume injection and probable interferents were investigated. Under the optimized FIA conditions, the amperometric signal was linearly dependent on the L-dopa concentration over the range 1.0 x 10(-1) to 1.0 x 10(-4) mol L-1 (I-anodic, mu A) = 0.01 + 0.25 [L-dopa mu mol L-1]) with a detection limit (S/N = 3) of 8.0 x 10(-7) mol L-1 and a sampling frequency of 90 h(-1) was achieved. For a concentration of 1.0 x 10(-5) mol L-1 L-dopa, the R.S.D. of nine consecutive measurements was 3.7%. (c) 2006 Elsevier B.V. All rights reserved.

Nanohardness of a Ti thin film and its interface deposited by an electron beam on a 304 SS substrate

The results of nanohardness measurements at a film surface and film-substrate interface are presented and discussed. An electron beam device was used to deposit a Ti film on a 304 stainless steel (304 SS) substrate. The diluted interface was obtained by thermal activated atomic diffusion. The. Ti film and Ti film-304 SS interface were analyzed by energy dispersive spectrometry and were observed using atomic force microscopy. The nanohardness of the Ti film-304 SS system was measured by a nanoindentation technique. The results showed the Ti film-304 SS interface had a higher hardness value than the Ti film and 304 SS substrate. The Ti film surface had a lower hardness due to the presence of a TiO2 thin layer.

Thermal treatment of superconductor thin film of the BSCCO system using domestic microwave oven

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Photoelectrocatalytic treatment of p-nitrophenol using Ti/TiO2 thin-film electrode

The photoelectrochemical degradation of p-nitrophenol (PNP) was investigated using titanium dioxide thin-film photoelectrode. The effects of different supporting electrolytes, pH, applied potential and PNP concentration were examined and discussed. Complete photodegradation was obtained in perchlorate medium at pH 2 when the photoanode was biased at +1.0 V (versus SCE) during a 3-h experiment. Under these conditions, carbon removal of approximately 60% was achieved. (C) 2005 Elsevier B.V. All rights reserved.