Spin reversal and magnetization jumps in ErMexMn1-xO3 perovskites (Me = Ni, Co)

The erbium-based manganite ErMnO3 has been partially substituted at the manganese site by the transition-metal elements Ni and Co. The perovskite orthorhombic structure is found from x(Ni) = 0.2-0.5 in the nickel-based solid solution ErNixMn1-xO3, while it can be extended up to x(Co) = 0.7 in the case of cobalt, provided that the synthesis is performed under oxygenation conditions to favor the presence of Co3+. Presence of different magnetic entities (i.e., Er3+, Ni2+, Co2+, Co3+, Mn3+, and Mn4+) leads to quite unusual magnetic properties, characterized by the coexistence of antiferromagnetic and ferromagnetic interactions. In ErNixMn1-xO3, a critical concentration x(crit)(Ni) = 1/3 separates two regimes: spin-canted AF interactions predominate at x < x(crit), while the ferromagnetic behavior is enhanced for x > x(crit). Spin reversal phenomena are present both in the nickel- and cobalt-based compounds. A phenomenological model based on two interacting sublattices, coupled by an antiferromagnetic exchange interaction, explains the inversion of the overall magnetic moment at low temperatures. In this model, the ferromagnetic transition-metal lattice, which orders at T-c, creates a strong local field at the erbium site, polarizing the Er moments in a direction opposite to the applied field. At low temperatures, when the contribution of the paramagnetic erbium sublattice, which varies as T-1, gets larger than the ferromagnetic contribution, the total magnetic moment changes its sign, leading to an overall ferrimagnetic state. The half-substituted compound ErCo0.50Mn0.50O3 was studied in detail, since the magnetization loops present two well-identified anomalies: an intersection of the magnetization branches at low fields, and magnetization jumps at high fields. The influence of the oxidizing conditions was studied in other compositions close to the 50/50 = Mn/Co substitution rate. These anomalies are clearly connected to the spin inversion phenomena and to the simultaneous presence of Co2+ and Co3+ magnetic moments. Dynamical aspects should be considered to well identify the high-field anomaly, since it depends on the magnetic field sweep rate. (C) 2006 Elsevier B.V. All rights reserved.

Small-angle X-ray scattering study of the smart thermo-optical behavior of zirconyl aqueous colloids

The smart thermo-optical systems studied here are based on the unusual thermoreversible sol-gel transition of zirconyl chloride aqueous solution modified by sulfuric acid in the molar ratio Zr/SO4:3/1. The transparency to the visible light changes during heating due to light scattering. This feature is related to the aggregates growth that occurs during gelation. These reversible changes can be controlled by the amount of chloride ions in solution. The thermoreversible sol-gel transition temperature increases from 323 to 343 K by decreasing the molar ratio Cl/Zr from 7.0 to 1.3. In this work the effect of the concentration of chloride ions on the structural characteristics of the system has been analyzed by in situ SAXS measurements during the sol-gel transition carried out at 323 and 333 K. The experimental SAXS curves of sols exhibit three regions at small, medium and high scattering vectors characteristics of Guinier, fractal and Porod regimes, respectively. The radius of primary particles, obtained from the crossover between the fractal and Porod regimes, remains almost invariable with the chloride concentration, and the value (4 Angstrom) is consistent with the size of the molecular precursor. During the sol-gel transition the aggregates grow with a fractal structure and the fractal dimensionality decreases from 2.4 to 1.8. This last value is characteristic of a cluster-cluster aggregation controlled by a diffusion process. Furthermore, the time exponent of aggregate growth presents values of 0.33 and 1, typical of diffusional and hydrodynamic motions. A crossover between these two regimes is observed.

Specific and nonspecific collapse in protein folding funnels

Experiments with fast folding proteins are beginning to address the relationship between collapse and folding. We investigate how different scenarios for folding can arise depending on whether the folding and collapse transitions are concurrent or whether a nonspecific collapse precedes folding. Many earlier studies have focused on the limit in which collapse is fast compared to the folding time; in this work we focus on the opposite limit where, at the folding temperature, collapse and folding occur simultaneously. Real proteins exist in both of these limits. The folding mechanism varies substantially in these two regimes. In the regime of concurrent folding and collapse, nonspecific collapse now occurs at a temperature below the folding temperature (but slightly above the glass transition temperature).

Optimal Boussinesq model for shallow-water waves interacting with a microstructure

In this paper, we consider the propagation of water waves in a long-wave asymptotic regime, when the bottom topography is periodic on a short length scale. We perform a multiscale asymptotic analysis of the full potential theory model and of a family of reduced Boussinesq systems parametrized by a free parameter that is the depth at which the velocity is evaluated. We obtain explicit expressions for the coefficients of the resulting effective Korteweg-de Vries (KdV) equations. We show that it is possible to choose the free parameter of the reduced model so as to match the KdV limits of the full and reduced models. Hence the reduced model is optimal regarding the embedded linear weakly dispersive and weakly nonlinear characteristics of the underlying physical problem, which has a microstructure. We also discuss the impact of the rough bottom on the effective wave propagation. In particular, nonlinearity is enhanced and we can distinguish two regimes depending on the period of the bottom where the dispersion is either enhanced or reduced compared to the flat bottom case. © 2007 The American Physical Society.

Inverted critical adsorption of polyelectrolytes in confinement

What are the fundamental laws for the adsorption of charged polymers onto oppositely charged surfaces, for convex, planar, and concave geometries? This question is at the heart of surface coating applications, various complex formation phenomena, as well as in the context of cellular and viral biophysics. It has been a long-standing challenge in theoretical polymer physics; for realistic systems the quantitative understanding is however often achievable only by computer simulations. In this study, we present the findings of such extensive Monte-Carlo in silico experiments for polymer-surface adsorption in confined domains. We study the inverted critical adsorption of finite-length polyelectrolytes in three fundamental geometries: planar slit, cylindrical pore, and spherical cavity. The scaling relations extracted from simulations for the critical surface charge density sigma(c)-defining the adsorption-desorption transition-are in excellent agreement with our analytical calculations based on the ground-state analysis of the Edwards equation. In particular, we confirm the magnitude and scaling of sigma(c) for the concave interfaces versus the Debye screening length 1/kappa and the extent of confinement a for these three interfaces for small kappa a values. For large kappa a the critical adsorption condition approaches the known planar limit. The transition between the two regimes takes place when the radius of surface curvature or half of the slit thickness a is of the order of 1/kappa. We also rationalize how sigma(c)(kappa) dependence gets modified for semi-flexible versus flexible chains under external confinement. We examine the implications of the chain length for critical adsorption-the effect often hard to tackle theoretically-putting an emphasis on polymers inside attractive spherical cavities. The applications of our findings to some biological systems are discussed, for instance the adsorption of nucleic acids onto the inner surfaces of cylindrical and spherical viral capsids.

Crystallization process of amorphous GaSb films studied by Raman spectroscopy

Thermal annealings of amorphous gallium antimonide films were accompanied using Raman spectroscopy, both for stoichiometric and nonstoichiometric compositions. The films were prepared by flash evaporation on silicon substrates. Structural changes were induced by the heat treatments: an increasing degree of crystallization as a function of the annealing temperature is observed. Sb clusters are found to crystallize before GaSb does, and the dependence of the corresponding Raman peak intensity with the annealing temperature (occurring in two regimes) is explained. A mechanism for the crystallization of the amorphous GaSb is proposed, based on the prior migration of the Sb excess outside the GaSb region to be crystallized. © 1995 American Institute of Physics.

Immobilization of cholesterol oxidase in LbL films and detection of cholesterol using ac measurements

The preserved activity of immobilized biomolecules in layer-by-layer (LbL) films can be exploited in various applications. including biosensing. In this study, cholesterol oxidase (COX) layers were alternated with layers of poly(allylamine hydrochloride) (PAH) in LbL films whose morphology was investigated with atomic force microscopy (AFM). The adsorption kinetics of COX layers comprised two regimes, a fast, first-order kinetics process followed by a slow process fitted with a Johnson-Mehl-Avrami (JMA) function. with exponent similar to 2 characteristic of aggregates growing as disks. The concept based on the use of sensor arrays to increase sensitivity, widely employed in electronic tongues, was extended to biosensing with impedance spectroscopy measurements. Using three sensing units, made of LbL films of PAH/COX and PAHIPVS (polyvinyl sulfonic acid) and a bare gold interdigitated electrode, we were able to detect cholesterol in aqueous solutions down to the 10(-6) M level. This high sensitivity is attributed to the molecular-recognition interaction between COX and cholesterol, and opens the way for clinical tests to be made with low cost. fast experimental procedures. (C) 2008 Published by Elsevier B.V.

Classical bifurcation in a quadrupolar NMR system

The Josephson junction model is applied to the experimental implementation of classical bifurcation in a quadrupolar nuclear magnetic resonance system. There are two regimes, one linear and one nonlinear, which are implemented by the radio-frequency and the quadrupolar terms of the Hamiltonian of a spin system, respectively. These terms provide an explanation of the symmetry breaking due to bifurcation. Bifurcation depends on the coexistence of both regimes at the same time in different proportions. The experiment is performed on a lyotropic liquid crystal sample of an ordered ensemble of 133Cs nuclei with spin I = 7/2 at room temperature. Our experimental results confirm that bifurcation happens independently of the spin value and of the physical system. With this experimental spin scenario, we confirm that a quadrupolar nuclei system could be described analogously to a symmetric two-mode Bose-Einstein condensate.

X-Ray studies of the physics of matter around super-massive black-holes in nearby Seyfert galaxies

Seyfert galaxies are the closest active galactic nuclei. As such, we can use them to test the physical properties of the entire class of objects. To investigate their general properties, I took advantage of different methods of data analysis. In particular I used three different samples of objects, that, despite frequent overlaps, have been chosen to best tackle different topics: the heterogeneous BeppoS AX sample was thought to be optimized to test the average hard X-ray (E above 10 keV) properties of nearby Seyfert galaxies; the X-CfA was thought the be optimized to compare the properties of low-luminosity sources to the ones of higher luminosity and, thus, it was also used to test the emission mechanism models; finally, the XMM–Newton sample was extracted from the X-CfA sample so as to ensure a truly unbiased and well defined sample of objects to define the average properties of Seyfert galaxies. Taking advantage of the broad-band coverage of the BeppoS AX MECS and PDS instruments (between ~2-100 keV), I infer the average X-ray spectral propertiesof nearby Seyfert galaxies and in particular the photon index (~1.8), the high-energy cut-off (~290 keV), and the relative amount of cold reflection (~1.0). Moreover the unified scheme for active galactic nuclei was positively tested. The distribution of isotropic indicators used here (photon index, relative amount of reflection, high-energy cut-off and narrow FeK energy centroid) are similar in type I and type II objects while the absorbing column and the iron line equivalent width significantly differ between the two classes of sources with type II objects displaying larger absorbing columns. Taking advantage of the XMM–Newton and X–CfA samples I also deduced from measurements that 30 to 50% of type II Seyfert galaxies are Compton thick. Confirming previous results, the narrow FeK line is consistent, in Seyfert 2 galaxies, with being produced in the same matter responsible for the observed obscuration. These results support the basic picture of the unified model. Moreover, the presence of a X-ray Baldwin effect in type I sources has been measured using for the first time the 20-100 keV luminosity (EW proportional to L(20-100)^(−0.22±0.05)). This finding suggests that the torus covering factor may be a function of source luminosity, thereby suggesting a refinement of the baseline version of the unifed model itself. Using the BeppoSAX sample, it has been also recorded a possible correlation between the photon index and the amount of cold reflection in both type I and II sources. At a first glance this confirms the thermal Comptonization as the most likely origin of the high energy emission for the active galactic nuclei. This relation, in fact, naturally emerges supposing that the accretion disk penetrates, depending to the accretion rate, the central corona at different depths (Merloni et al. 2006): the higher accreting systems hosting disks down to the last stable orbit while the lower accreting systems hosting truncated disks. On the contrary, the study of the well defined X–C f A sample of Seyfert galaxies has proved that the intrinsic X-ray luminosity of nearby Seyfert galaxies can span values between 10^(38−43) erg s^−1, i.e. covering a huge range of accretion rates. The less efficient systems have been supposed to host ADAF systems without accretion disk. However, the study of the X–CfA sample has also proved the existence of correlations between optical emission lines and X-ray luminosity in the entire range of L_(X) covered by the sample. These relations are similar to the ones obtained if high-L objects are considered. Thus the emission mechanism must be similar in luminous and weak systems. A possible scenario to reconcile these somehow opposite indications is assuming that the ADAF and the two phase mechanism co-exist with different relative importance moving from low-to-high accretion systems (as suggested by the Gamma vs. R relation). The present data require that no abrupt transition between the two regimes is present. As mentioned above, the possible presence of an accretion disk has been tested using samples of nearby Seyfert galaxies. Here, to deeply investigate the flow patterns close to super-massive black-holes, three case study objects for which enough counts statistics is available have been analysed using deep X-ray observations taken with XMM–Newton. The obtained results have shown that the accretion flow can significantly differ between the objects when it is analyzed with the appropriate detail. For instance the accretion disk is well established down to the last stable orbit in a Kerr system for IRAS 13197-1627 where strong light bending effect have been measured. The accretion disk seems to be formed spiraling in the inner ~10-30 gravitational radii in NGC 3783 where time dependent and recursive modulation have been measured both in the continuum emission and in the broad emission line component. Finally, the accretion disk seems to be only weakly detectable in rk 509, with its weak broad emission line component. Finally, blueshifted resonant absorption lines have been detected in all three objects. This seems to demonstrate that, around super-massive black-holes, there is matter which is not confined in the accretion disk and moves along the line of sight with velocities as large as v~0.01-0.4c (whre c is the speed of light). Wether this matter forms winds or blobs is still matter of debate together with the assessment of the real statistical significance of the measured absorption lines. Nonetheless, if confirmed, these phenomena are of outstanding interest because they offer new potential probes for the dynamics of the innermost regions of accretion flows, to tackle the formation of ejecta/jets and to place constraints on the rate of kinetic energy injected by AGNs into the ISM and IGM. Future high energy missions (such as the planned Simbol-X and IXO) will likely allow an exciting step forward in our understanding of the flow dynamics around black holes and the formation of the highest velocity outflows.

Dynamics, rheology and critical properties of colloidal fluid mixtures

Liquids under the influence of external fields exhibit a wide range of intriguing phenomena that can be markedly different from the behaviour of a quiescent system. This work considers two different systems — a glassforming Yukawa system and a colloid-polymer mixture — by Molecular Dynamics (MD) computer simulations coupled to dissipative particle dynamics. The former consists of a 50-50 binary mixture of differently-sized, like-charged colloids interacting via a screened Coulomb (Yukawa) potential. Near the glass transition the influence of an external shear field is studied. In particular, the transition from elastic response to plastic flow is of interest. At first, this model is characterised in equilibrium. Upon decreasing temperature it exhibits the typical dynamics of glassforming liquids, i.e. the structural relaxation time τα grows strongly in a rather small temperature range. This is discussed with respect to the mode-coupling theory of the glass transition (MCT). For the simulation of bulk systems under shear, Lees-Edwards boundary conditions are applied. At constant shear rates γ˙ ≫ 1/τα the relevant time scale is given by 1/γ˙ and the system shows shear thinning behaviour. In order to understand the pronounced differences between a quiescent system and a system under shear, the response to a suddenly commencing or terminating shear flow is studied. After the switch-on of the shear field the shear stress shows an overshoot, marking the transition from elastic to plastic deformation, which is connected to a super-diffusive increase of the mean squared displacement. Since the average static structure only depends on the value of the shear stress, it does not discriminate between those two regimes. The distribution of local stresses, in contrast, becomes broader as soon as the system starts flowing. After a switch-off of the shear field, these additional fluctuations are responsible for the fast decay of stresses, which occurs on a time scale 1/γ˙ . The stress decay after a switch-off in the elastic regime, on the other hand, happens on the much larger time scale of structural relaxation τα. While stresses decrease to zero after a switch-off for temperatures above the glass transition, they decay to a finite value for lower temperatures. The obtained results are important for advancing new theoretical approaches in the framework of mode-coupling theory. Furthermore, they suggest new experimental investigations on colloidal systems. The colloid-polymer mixture is studied in the context of the behaviour near the critical point of phase separation. For the MD simulations a new effective model with soft interaction potentials is introduced and its phase diagram is presented. Here, mainly the equilibrium properties of this model are characterised. While the self-diffusion constants of colloids and polymers do not change strongly when the critical point is approached, critical slowing down of interdiffusion is observed. The order parameter fluctuations can be determined through the long-wavelength limit of static structure factors. For this strongly asymmetric mixture it is shown how the relevant structure factor can be extracted by a diagonalisation of a matrix that contains the partial static structure factors. By presenting first results of this model under shear it is demonstrated that it is suitable for non-equilibrium simulations as well.

Rupture forces of split aptamers

Rupture forces of ligand-receptor interactions, such as proteins-proteins, proteins-cells, and cells-tissues, have been successfully measured by atomic force spectroscopy (AFS). For these measurements, the ligands and receptors were chemically modified so that they can be immobilized on the tip and on a substrate, respectively. The ligand interact the receptor when the tip approaches the substrate. This interaction can be studied by measuring rupture force upon retraction. However, this technique is not feasible for measurements involving small molecules, since they form only few H-bonds with their corresponding receptors. Modifying small molecules for immobilization on surfaces may block or change binding sites. Thus, recorded rupture forces might not reflect the full scope of the involved small ligand-receptor interactions.rnIn my thesis, a novel concept that allows measuring the rupture force of small involved ligand-receptor interactions and does not require molecular modification for immobilization was introduced. The rupture force of small ligand-receptor interaction is not directly measured but it can be determined from measurements in the presence and in the absence of the ligand. As a model system, the adenosine mono phosphate (AMP) and the aptamer that binds AMP were selected. The aptamer (receptor) is a single stranded DNA that can partially self-hybridize and form binding pockets for AMP molecules (ligands). The bonds between AMP and aptamer are provided by several H-bonds and pair stacking.rnIn the novel concept, the aptamer was split into two parts (oligo a and oligo b). One part was immobilized on the tip and the other one on the substrate. Approaching the tip to the substrate, oligo a and oligo b partially hybridized and the binding pockets were formed. After adding AMP into the buffer solution, the AMP bound in the pockets and additional H-bonds were formed. Upon retraction of the tip, the rupture force of the AMP-split aptamer complex was measured. In the presence of excess AMP, the rupture force increased by about 10 pN. rnThe dissociation constant of the AMP-split aptamer complex was measured on a single molecular level (~ 4 µM) by varying the AMP concentrations and measuring the rupture force at each concentration. Furthermore, the rupture force was amplified when more pockets were added to the split aptamer. rnIn the absence of AMP, the thermal off-rate was slightly reduced compared to that in the presence of AMP, indicating that the AMP stabilized the aptamer. The rupture forces at different loading rates did not follow the logarithmic fit which was usually used to describe the dependence of rupture forces at different loading rates of oligonucleotides. Two distinguished regimes at low and high loading rates were obtained. The two regimes were explained by a model in which the oligos located at the pockets were stretched at high loading rates. rnThe contribution of a single H-bond formed between the AMP molecule and the split aptamer was measured by reducing the binding groups of the AMP. The rupture forces reduce corresponding to the reduction of the binding groups. The phosphate group played the most important role in the formation of H-bond network between the AMP molecule and the split aptamer. rn

Probing quantum chromodynamics with the ATLAS detector : charged-particle event shape variables and the dijet cross-section

Die Quantenchromodynamik ist die zugrundeliegende Theorie der starken Wechselwirkung und kann in zwei Bereiche aufgeteilt werden. Harte Streuprozesse, wie zum Beispiel die Zwei-Jet-Produktion bei hohen invarianten Massen, können störungstheoretisch behandelt und berechnet werden. Bei Streuprozessen mit niedrigen Impulsüberträgen hingegen ist die Störungstheorie nicht mehr anwendbar und phänemenologische Modelle werden für Vorhersagen benutzt. Das ATLAS Experiment am Large Hadron Collider am CERN ermöglicht es, QCD Prozesse bei hohen sowie niedrigen Impulsüberträgen zu untersuchen. In dieser Arbeit werden zwei Analysen vorgestellt, die jeweils ihren Schwerpunkt auf einen der beiden Regime der QCD legen:rnDie Messung von Ereignisformvariablen bei inelastischen Proton--Proton Ereignissen bei einer Schwerpunktsenergie von $sqrt{s} = unit{7}{TeV}$ misst den transversalen Energiefluss in hadronischen Ereignissen. rnDie Messung des zweifachdifferentiellen Zwei-Jet-Wirkungsquerschnittes als Funktion der invarianten Masse sowie der Rapiditätsdifferenz der beiden Jets mit den höchsten Transversalimpulsen kann genutzt werden um Theorievorhersagen zu überprüfen. Proton--Proton Kollisionen bei $sqrt{s} = unit{8}{TeV}$, welche während der Datennahme im Jahr 2012 aufgezeichnet wurden, entsprechend einer integrierten Luminosität von $unit{20.3}{fb^{-1}}$, wurden analysiert.rn

Quantum Energy Teleportation Between Spin Particles in a Gibbs State

Energy in a multipartite quantum system appears from an operational perspective to be distributed to some extent non-locally because of correlations extant among the system's components. This non-locality allows users to transfer, in effect, locally accessible energy between sites of different system components by local operations and classical communication (LOCC). Quantum energy teleportation is a three-step LOCC protocol, accomplished without an external energy carrier, for effectively transferring energy between two physically separated, but correlated, sites. We apply this LOCC teleportation protocol to a model Heisenberg spin particle pair initially in a quantum thermal Gibbs state, making temperature an explicit parameter. We find in this setting that energy teleportation is possible at any temperature, even at temperatures above the threshold where the particles' entanglement vanishes. This shows for Gibbs spin states that entanglement is not fundamentally necessary for energy teleportation; correlation other than entanglement can suffice. Dissonance-quantum correlation in separable states-is in this regard shown to be a quantum resource for energy teleportation, more dissonance being consistently associated with greater energy yield. We compare energy teleportation from particle A to B in Gibbs states with direct local energy extraction by a general quantum operation on B and find a temperature threshold below which energy extraction by a local operation is impossible. This threshold delineates essentially two regimes: a high temperature regime where entanglement vanishes and the teleportation generated by other quantum correlations yields only vanishingly little energy relative to local extraction and a second low-temperature teleportation regime where energy is available at B only by teleportation.

Filtration and oxidation characteristics of a diesel oxidation catalyst and a catalyzed particulate filter : development of a 1-D 2-layer model

The emissions, filtration and oxidation characteristics of a diesel oxidation catalyst (DOC) and a catalyzed particulate filter (CPF) in a Johnson Matthey catalyzed continuously regenerating trap (CCRT ®) were studied by using computational models. Experimental data needed to calibrate the models were obtained by characterization experiments with raw exhaust sampling from a Cummins ISM 2002 engine with variable geometry turbocharging (VGT) and programmed exhaust gas recirculation (EGR). The experiments were performed at 20, 40, 60 and 75% of full load (1120 Nm) at rated speed (2100 rpm), with and without the DOC upstream of the CPF. This was done to study the effect of temperature and CPF-inlet NO2 concentrations on particulate matter oxidation in the CCRT ®. A previously developed computational model was used to determine the kinetic parameters describing the oxidation characteristics of HCs, CO and NO in the DOC and the pressure drop across it. The model was calibrated at five temperatures in the range of 280 – 465° C, and exhaust volumetric flow rates of 0.447 – 0.843 act-m3/sec. The downstream HCs, CO and NO concentrations were predicted by the DOC model to within ±3 ppm. The HCs and CO oxidation kinetics in the temperature range of 280 - 465°C and an exhaust volumetric flow rate of 0.447 - 0.843 act-m3/sec can be represented by one ’apparent’ activation energy and pre-exponential factor. The NO oxidation kinetics in the same temperature and exhaust flow rate range can be represented by ’apparent’ activation energies and pre-exponential factors in two regimes. The DOC pressure drop was always predicted within 0.5 kPa by the model. The MTU 1-D 2-layer CPF model was enhanced in several ways to better model the performance of the CCRT ®. A model to simulate the oxidation of particulate inside the filter wall was developed. A particulate cake layer filtration model which describes particle filtration in terms of more fundamental parameters was developed and coupled to the wall oxidation model. To better model the particulate oxidation kinetics, a model to take into account the NO2 produced in the washcoat of the CPF was developed. The overall 1-D 2-layer model can be used to predict the pressure drop of the exhaust gas across the filter, the evolution of particulate mass inside the filter, the particulate mass oxidized, the filtration efficiency and the particle number distribution downstream of the CPF. The model was used to better understand the internal performance of the CCRT®, by determining the components of the total pressure drop across the filter, by classifying the total particulate matter in layer I, layer II, the filter wall, and by the means of oxidation i.e. by O2, NO2 entering the filter and by NO2 being produced in the filter. The CPF model was calibrated at four temperatures in the range of 280 – 465 °C, and exhaust volumetric flow rates of 0.447 – 0.843 act-m3/sec, in CPF-only and CCRT ® (DOC+CPF) configurations. The clean filter wall permeability was determined to be 2.00E-13 m2, which is in agreement with values in the literature for cordierite filters. The particulate packing density in the filter wall had values between 2.92 kg/m3 - 3.95 kg/m3 for all the loads. The mean pore size of the catalyst loaded filter wall was found to be 11.0 µm. The particulate cake packing densities and permeabilities, ranged from 131 kg/m3 - 134 kg/m3, and 0.42E-14 m2 and 2.00E-14 m2 respectively, and are in agreement with the Peclet number correlations in the literature. Particulate cake layer porosities determined from the particulate cake layer filtration model ranged between 0.841 and 0.814 and decreased with load, which is about 0.1 lower than experimental and more complex discrete particle simulations in the literature. The thickness of layer I was kept constant at 20 µm. The model kinetics in the CPF-only and CCRT ® configurations, showed that no ’catalyst effect’ with O2 was present. The kinetic parameters for the NO2-assisted oxidation of particulate in the CPF were determined from the simulation of transient temperature programmed oxidation data in the literature. It was determined that the thermal and NO2 kinetic parameters do not change with temperature, exhaust flow rate or NO2 concentrations. However, different kinetic parameters are used for particulate oxidation in the wall and on the wall. Model results showed that oxidation of particulate in the pores of the filter wall can cause disproportionate decreases in the filter pressure drop with respect to particulate mass. The wall oxidation model along with the particulate cake filtration model were developed to model the sudden and rapid decreases in pressure drop across the CPF. The particulate cake and wall filtration models result in higher particulate filtration efficiencies than with just the wall filtration model, with overall filtration efficiencies of 98-99% being predicted by the model. The pre-exponential factors for oxidation by NO2 did not change with temperature or NO2 concentrations because of the NO2 wall production model. In both CPF-only and CCRT ® configurations, the model showed NO2 and layer I to be the dominant means and dominant physical location of particulate oxidation respectively. However, at temperatures of 280 °C, NO2 is not a significant oxidizer of particulate matter, which is in agreement with studies in the literature. The model showed that 8.6 and 81.6% of the CPF-inlet particulate matter was oxidized after 5 hours at 20 and 75% load in CCRT® configuration. In CPF-only configuration at the same loads, the model showed that after 5 hours, 4.4 and 64.8% of the inlet particulate matter was oxidized. The increase in NO2 concentrations across the DOC contributes significantly to the oxidation of particulate in the CPF and is supplemented by the oxidation of NO to NO2 by the catalyst in the CPF, which increases the particulate oxidation rates. From the model, it was determined that the catalyst in the CPF modeslty increases the particulate oxidation rates in the range of 4.5 – 8.3% in the CCRT® configuration. Hence, the catalyst loading in the CPF of the CCRT® could possibly be reduced without significantly decreasing particulate oxidation rates leading to catalyst cost savings and better engine performance due to lower exhaust backpressures.

International Trade Regulation and the Mitigation of Climate Change. World Trade Forum

What can trade regulation contribute towards ameliorating the GHG emissions and reducing their concentrations in the atmosphere? This collection of essays analyses options for climate-change mitigation through the lens of the trade lawyer. By examining international law, and in particular the relevant WTO agreements, the authors address the areas of potential conflict between international trade law and international law on climate mitigation and, where possible, suggest ways to strengthen mutual supportiveness between the two regimes. They do so taking into account the drivers of human-induced climate change in energy markets and of consumption.