Non-aqueous phase liquid behavior in the subsurface: Transportation, source zone characterization and remediation

Contaminant behaviour in soils and fractured rock is very complex, not least because of the heterogeneity of the subsurface environment. For non-aqueous phase liquids (NAPLs), a liquid density contrast and interfacial tension between the contaminant and interstitial fluid adds to the complexity of behaviour, increasing the difficulty of predicting NAPL behaviour in the subsurface. This paper outlines the need for physical model tests that can improve fundamental understanding of NAPL behaviour in the subsurface, enhance risk assessments of NAPL contaminated sites, reduce uncertainty associated with NAPL source remediation and improve current technologies for NAPL plume remediation. Four case histories are presented to illustrate physical modelling approaches that have addressed problems associated with NAPL transport, remediation and source zone characterization. © 2006 Taylor & Francis Group, London.

Phase separation induced by Au catalysts in ternary InGaAs nanowires.

We report a novel phase separation phenomenon observed in the growth of ternary In(x)Ga(1-x)As nanowires by metalorganic chemical vapor deposition. A spontaneous formation of core-shell nanowires is investigated by cross-sectional transmission electron microscopy, revealing the compositional complexity within the ternary nanowires. It has been found that for In(x)Ga(1-x)As nanowires high precursor flow rates generate ternary In(x)Ga(1-x)As cores with In-rich shells, while low precursor flow rates produce binary GaAs cores with ternary In(x)Ga(1-x)As shells. First-principle calculations combined with thermodynamic considerations suggest that this phenomenon is due to competitive alloying of different group-III elements with Au catalysts, and variations in elemental concentrations of group-III materials in the catalyst under different precursor flow rates. This study shows that precursor flow rates are critical factors for manipulating Au catalysts to produce nanowires of desired composition.

Single sublattice endotaxial phase separation driven by charge frustration in a complex oxide.

Complex transition-metal oxides are important functional materials in areas such as energy and information storage. The cubic ABO3 perovskite is an archetypal example of this class, formed by the occupation of small octahedral B-sites within an AO3 network defined by larger A cations. We show that introduction of chemically mismatched octahedral cations into a cubic perovskite oxide parent phase modifies structure and composition beyond the unit cell length scale on the B sublattice alone. This affords an endotaxial nanocomposite of two cubic perovskite phases with distinct properties. These locally B-site cation-ordered and -disordered phases share a single AO3 network and have enhanced stability against the formation of a competing hexagonal structure over the single-phase parent. Synergic integration of the distinct properties of these phases by the coherent interfaces of the composite produces solid oxide fuel cell cathode performance superior to that expected from the component phases in isolation.

Evolution of vertical phase separation in P3HT:PCBM thin films induced by thermal annealing

The achievement of the desirable morphology at the nanometer scale of bulk heterojunctions consisting of a conjugated polymer with fullerene derivatives is a prerequisite in order to optimize the power conversion efficiency of organic solar cells. The various experimental conditions such as the choice of solvent, drying rates and annealing have been found to significantly affect the blend morphology and the final performance of the photovoltaic device. In this work, we focus on the effects of post deposition thermal annealing at 140 °C on the blend morphology, the optical and structural properties of bulk heterojunctions that consist of poly(3-hexylthiophene) (P3HT) and a methanofullerene derivative (PCBM). The post thermal annealing modifies the distribution of the P3HT and the PCBM inside the blend films, as it has been found by Spectroscopic Ellipsometry studies in the visible to far-ultraviolet spectral range. Phase separation was identified by AFM and GIXRD as a result of a slow drying process which took place after the spin coating process. The increase of the annealing time resulted to a significant increase of the P3HT crystallinity at the top regions of the blend films. © 2011 Elsevier B.V. All rights reserved.

Non-destructive optical characterization of phase separation in bulk heterojunction organic photovoltaic cells

The dithiophene donor-acceptor copolymers that are bridged either with carbon (C-PCPDTBT) or silicon atoms (Si-PCPDTBT) belong to a promising family of materials for use in photoactive layers for organic photovoltaic cells (OPVs). In this work, we implement the non-destructive Spectroscopic Ellipsometry technique in the near infrared to the far ultraviolet spectral region in combination with advanced theoretical modeling to investigate the vertical distribution of the C-PCPDTBT and Si-PCPDTBT polymer and fullerene ([6,6]-phenyl C71-butyric acid methyl ester - PC70BM) phases in the blend, as well as the effect of the polymer-to-fullerene ratio on the distribution mechanism. It was found that the C-PCPDTBT:PC70BM blends have donor-enriched top regions and acceptor-enriched bottom regions, whereas the donor and acceptor phases are more homogeneously intermixed in the Si-PCPDTBT:PC70BM blends. We suggest that the chemical incompatibility of the two phases as expressed by the difference in their surface energy, may be a key element in promoting the segregation of the lower surface phase to the top region of the photoactive layer. We found that the increase of the photoactive layer thickness reduces the polymer enrichment at the cathode, producing a more homogeneous phase distribution of donor and acceptor in the bulk that leads to the increase of the OPV efficiency. © 2014 Elsevier B.V.

Thermal annealing effect on the nanomechanical properties and structure of P3HT:PCBM thin films

Nanostructured polymer-fullerene thin films are among the most prominent materials for application in high efficient polymer solar cells. Specifically, poly(3-hexylthiophene) (P3HT) and fullerene derivatives (PCBM) blends are used as the donor/acceptor materials forming a bulk heterojunction. Although P3HT:PCBM properties have been extensively studied, less light has been set on its nanomechanical properties, which affect the device service life. In this work Atomic Force Acoustic Microscopy (AFAM), Atomic Force Spectroscopy and Nanoindentation were used to study the effect of the fullerene presence and the annealing on the P3HT:PCBM nanomechanical behavior. The P3HT:PCBM thin films were prepared by spin coating on glass substrates and then annealed at 100 °C and 145 °C for 30 min. Large phase separation was identified by optical and Atomic Force Microscopy (AFM) for the annealed samples. Needle-like PCBM crystals were formed and an increase of the polymer crystallinity degree with the increase of the annealing temperature was confirmed by X-ray diffraction. AFAM characterization revealed the presence of aggregates close to stiff PCBM crystals, possibly consisting of amorphous P3HT material. AFM force-distance curves showed a continuous change in stiffness in the vicinity of the PCBM crystals, due to the PCBM depletion near its crystals, and the AFM indentation provided qualitative results about the changes in P3HT nanomechanical response after annealing. © 2011 Elsevier B.V. All rights reserved.

Development of a nanoporous and multilayer drug-delivery platform for medical implants.

Biodegradable polymers can be applied to a variety of implants for controlled and local drug delivery. The aim of this study is to develop a biodegradable and nanoporous polymeric platform for a wide spectrum of drug-eluting implants with special focus on stent-coating applications. It was synthesized by poly(DL-lactide-co-glycolide) (PLGA 65:35, PLGA 75:25) and polycaprolactone (PCL) in a multilayer configuration by means of a spin-coating technique. The antiplatelet drug dipyridamole was loaded into the surface nanopores of the platform. Surface characterization was made by atomic force microscopy (AFM) and spectroscopic ellipsometry (SE). Platelet adhesion and drug-release kinetic studies were then carried out. The study revealed that the multilayer films are highly nanoporous, whereas the single layers of PLGA are atomically smooth and spherulites are formed in PCL. Their nanoporosity (pore diameter, depth, density, surface roughness) can be tailored by tuning the growth parameters (eg, spinning speed, polymer concentration), essential for drug-delivery performance. The origin of pore formation may be attributed to the phase separation of polymer blends via the spinodal decomposition mechanism. SE studies revealed the structural characteristics, film thickness, and optical properties even of the single layers in the triple-layer construct, providing substantial information for drug loading and complement AFM findings. Platelet adhesion studies showed that the dipyridamole-loaded coatings inhibit platelet aggregation that is a prerequisite for clotting. Finally, the films exhibited sustained release profiles of dipyridamole over 70 days. These results indicate that the current multilayer phase therapeutic approach constitutes an effective drug-delivery platform for drug-eluting implants and especially for cardiovascular stent applications.

Effect of process parameters on the morphology and nanostructure of roll-to-roll printed P3HT:PCBM thin films for organic photovoltaics

Roll-to-roll (R2R) gravure exhibits significant advantages such as high precision and throughput for the printing of photoactive and conductive materials and the fabrication of flexible organic electronics such as organic photovoltaics (OPVs). Since the photoactive layer is the core of the OPV, it is important to investigate and finally control the process parameters and mechanisms that define the film morphology in a R2R process. The scope of this work is to study the effect of the R2R gravure printing and drying process on the nanomorphology and nanostructure of the photoactive P3HT:PCBM thin films printed on PEDOT:PSS electrodes towards the fabrication of indium tin oxide (ITO)-free flexible OPVs. In order to achieve this, P3HT:PCBM blends of different concentration were R2R printed under various speeds on the PEDOT:PSS layers. Due to the limited drying time during the rolling, an amount of solvent remains in the P3HT:PCBM films and the slow-drying process takes place which leads to the vertical and lateral phase separation, according to the Spectroscopic Ellipsometry and Atomic Force Microscopy analysis. The enhanced slow-drying leads to stronger phase separation, larger P3HT crystallites according to the Grazing Incidence X-Ray Diffraction data and to weaker mechanical response as it was shown by the nanoindentation creep. However, in the surface of the films the P3HT crystallization is controlled by the impinged hot air during the drying, where the more the drying time the larger the surface P3HT crystallites. The integration of the printed P3HT:PCBM and PEDOT:PSS layers in an OPV device underlined the feasibility of fabricating ITO-free flexible OPVs by R2R gravure processes. © 2013 Elsevier B.V.

Effects of buffer layer properties and annealing process on bulk heterojunction morphology and organic solar cell performance

The performance of polymer-fullerene bulk heterojunction (BHJ) solar cells is strongly dependent on the vertical distribution of the donor and acceptor regions within the BHJ layer. In this work, we investigate in detail the effect of the hole transport layer (HTL) physical properties and the thermal annealing on the BHJ morphology and the solar cell performance. For this purpose, we have prepared solar cells with four distinct formulations of poly(3,4- ethylenedioxythiophene) poly(styrenesulfonate) (PEDOT:PSS) buffer layers. The samples were subjected to thermal annealing, applied either before (pre-annealing) or after (post-annealing) the cathode metal deposition. The effect of the HTL and the annealing process on the BHJ ingredient distribution - namely, poly(3-hexylthiophene) (P3HT) and [6,6]-phenyl C61 butyric acid methyl ester (PCBM) - has been studied by spectroscopic ellipsometry and atomic force microscopy. The results revealed P3HT segregation at the top region of the films, which had a detrimental effect on all pre-annealed devices, whereas PCBM was found to accumulate at the bottom interface. This demixing process depends on the PEDOT:PSS surface energy; the more hydrophilic the surface the more profound is the vertical phase separation within the BHJ. At the same time those samples suffer from high recombination losses as evident from the analysis of the J-V measurements obtained in the dark. Our results underline the significant effect of the HTL-active and active-ETL (electron transport layer) interfacial composition that should be taken into account during the optimization of all polymer-fullerene solar cells. © 2012 The Royal Society of Chemistry.

Dynamical behavior of damped driven coupled single electron simple harmonic oscillators

Coherent coupling between a large number of qubits is the goal for scalable approaches to solid state quantum information processing. Prototype systems can be characterized by spectroscopic techniques. Here, we use pulsed-continuous wave microwave spectroscopy to study the behavior of electrons trapped at defects within the gate dielectric of a sol-gel-based high-k silicon MOSFET. Disorder leads to a wide distribution in trap properties, allowing more than 1000 traps to be individually addressed in a single transistor within the accessible frequency domain. Their dynamical behavior is explored by pulsing the microwave excitation over a range of times comparable to the phase coherence time and the lifetime of the electron in the trap. Trap occupancy is limited to a single electron, which can be manipulated by resonant microwave excitation and the resulting change in trap occupancy is detected by the change in the channel current of the transistor. The trap behavior is described by a classical damped driven simple harmonic oscillator model, with the phase coherence, lifetime and coupling strength parameters derived from a continuous wave (CW) measurement only. For pulse times shorter than the phase coherence time, the energy exchange between traps, due to the coupling, strongly modulates the observed drain current change. This effect could be exploited for 2-qubit gate operation. The very large number of resonances observed in this system would allow a complex multi-qubit quantum mechanical circuit to be realized by this mechanism using only a single transistor.

The effect of wake passing on a flow separation in a low pressure turbine cascade

This paper describes an investigation into the effect that passing wakes have on a separation bubble that exists on the pressure surface and near the leading edge of a low pressure turbine blade. Previous experimental studies have shown that the behaviour of this separation is strongly incidence dependent and that it responds to its disturbance environment. The results presented in this paper examine the effect of wake passing in greater detail. Two dimensional, Reynolds averaged, numerical predictions are first used to examine qualitatively the unsteady interaction between the wakes and the separation bubble. The separation is predicted to consist of spanwise vortices whose development is in phase with the wake passing. However, comparison with experiments shows that the numerical predictions exaggerate the coherence of these vortices and also overpredict the time-averaged length of the separation. Nonetheless, experiments strongly suggest that the predicted phase locking of the vortices in the separation onto the wake passing is physical.

The phase of iron catalyst nanoparticles during carbon nanotube growth

We study the Fe-catalyzed chemical vapor deposition of carbon nanotubes by complementary in situ grazing-incidence X-ray diffraction, in situ X-ray reflectivity, and environmental transmission electron microscopy. We find that typical oxide supported Fe catalyst films form widely varying mixtures of bcc and fcc phased Fe nanoparticles upon reduction, which we ascribe to variations in minor commonly present carbon contamination levels. Depending on the as-formed phase composition, different growth modes occur upon hydrocarbon exposure: For γ-rich Fe nanoparticle distributions, metallic Fe is the active catalyst phase, implying that carbide formation is not a prerequisite for nanotube growth. For α-rich catalyst mixtures, Fe3C formation more readily occurs and constitutes part of the nanotube growth process. We propose that this behavior can be rationalized in terms of kinetically accessible pathways, which we discuss in the context of the bulk iron-carbon phase diagram with the inclusion of phase equilibrium lines for metastable Fe3C. Our results indicate that kinetic effects dominate the complex catalyst phase evolution during realistic CNT growth recipes. © 2012 American Chemical Society.