A simulation study on the abatement of CO2 emissions by de-absorption with monoethanolamine

Because of the adverse effect of CO2 from fossil fuel combustion on the earth's ecosystems, the most cost-effective method for CO2 capture is an important area of research. The predominant process for CO2 capture currently employed by industry is chemical absorption in amine solutions. A dynamic model for the de-absorption process was developed with monoethanolamine (MEA) solution. Henry's law was used for modelling the vapour phase equilibrium of the CO2, and fugacity ratios calculated by the Peng-Robinson equation of state (EOS) were used for H2O, MEA, N-2 and O-2. Chemical reactions between CO2 and MEA were included in the model along with the enhancement factor for chemical absorption. Liquid and vapour energy balances were developed to calculate the liquid and vapour temperature, respectively.

Patching up dipoles: can dipolar particles be viewed as patchy colloids?

We investigate whether the liquid-vapour phase transition of strongly dipolar fluids can be understood using a model of patchy colloids. These consist of hard spherical particles with three short-ranged attractive sites (patches) on their surfaces. Two of the patches are of type A and one is of type B. Patches A on a particle may bond either to a patch A or to a patch B on another particle. Formation of an AA (AB) bond lowers the energy by epsilon AA (epsilon AB). In the limit [image omitted], this patchy model exhibits condensation driven by AB-bonds (Y-junctions). Y-junctions are also present in low-density, strongly dipolar fluids, and have been conjectured to play a key role in determining their critical behaviour. We map the dipolar Yukawa hard-sphere (DYHS) fluid onto this 2A + 1B patchy model by requiring that the latter reproduce the correct DYHS critical point as a function of the isotropic interaction strength epsilon Y. This is achieved for sensible values of epsilon AB and the bond volumes. Results for the internal energy and the particle coordination number are in qualitative agreement with simulations of DYHSs. Finally, by taking the limit [image omitted], we arrive at a new estimate for the critical point of the dipolar hard-sphere fluid, which agrees with extrapolations from simulation.

Cr2O3 thin films grown at room temperature by low pressure laser chemical vapour deposition

Chromia (Cr2O3) has been extensively explored for the purpose of developing widespread industrial applications, owing to the convergence of a variety of mechanical, physical and chemical properties in one single oxide material. Various methods have been used for large area synthesis of Cr2O3 films. However, for selective area growth and growth on thermally sensitive materials, laser-assisted chemical vapour deposition (LCVD) can be applied advantageously. Here we report on the growth of single layers of pure Cr2O3 onto sapphire substrates at room temperature by low pressure photolytic LCVD, using UV laser radiation and Cr(CO)(6) as chromium precursor. The feasibility of the LCVD technique to access selective area deposition of chromia thin films is demonstrated. Best results were obtained for a laser fluence of 120 mJ cm(-2) and a partial pressure ratio of O-2 to Cr(CO)(6) of 1.0. Samples grown with these experimental parameters are polycrystalline and their microstructure is characterised by a high density of particles whose size follows a lognormal distribution. Deposition rates of 0.1 nm s(-1) and mean particle sizes of 1.85 mu m were measured for these films. (C) 2011 Elsevier B.V. All rights reserved.

Laser-assisted deposition of thin films from photoexcited vapour phases

Laser-assisted chemical vapour deposition (LCVD) has been extensively studied in the last two decades. A vast range of applications encompass various areas such as microelectronics, micromechanics, microelectromechanics and integrated optics, and a variety of metals, semiconductors and insulators have been grown by LCVD. In this article, we review briefly the LCVD process and present two case studies of thin film deposition related to laser thermal excitation (e.g., boron carbide) and non-thermal excitation (e.g., CrO(2)) of the gas phase.

Phase diagrams of particles with dissimilar patches: X-junctions and Y-junctions

We use Wertheim's first-order perturbation theory to investigate the phase behaviour and the structure of coexisting fluid phases for a model of patchy particles with dissimilar patches (two patches of type A and f(B) patches of type B). A patch of type alpha = {A, B} can bond to a patch of type beta = {A, B} in a volume nu(alpha beta), thereby decreasing the internal energy by epsilon(alpha beta). We analyse the range of model parameters where AB bonds, or Y-junctions, are energetically disfavoured (epsilon(AB) < epsilon(AA)/2) but entropically favoured (nu(AB) >> nu(alpha alpha)), and BB bonds, or X-junctions, are energetically favoured (epsilon(BB) > 0). We show that, for low values of epsilon(BB)/epsilon(AA), the phase diagram has three different regions: (i) close to the critical temperature a low-density liquid composed of long chains and rich in Y-junctions coexists with a vapour of chains; (ii) at intermediate temperatures there is coexistence between a vapour of short chains and a liquid of very long chains with X-and Y-junctions; (iii) at low temperatures an ideal gas coexists with a high-density liquid with all possible AA and BB bonds formed. It is also shown that in region (i) the liquid binodal is reentrant (its density decreases with decreasing temperature) for the lower values of epsilon(BB)/epsilon(AA). The existence of these three regions is a consequence of the competition between the formation of X- and Y-junctions: X-junctions are energetically favoured and thus dominate at low temperatures, whereas Y-junctions are entropically favoured and dominate at higher temperatures.

Re-entrant phase behaviour of network fluids: A patchy particle model with temperature-dependent valence

We study a model consisting of particles with dissimilar bonding sites ("patches"), which exhibits self-assembly into chains connected by Y-junctions, and investigate its phase behaviour by both simulations and theory. We show that, as the energy cost epsilon(j) of forming Y-junctions increases, the extent of the liquid-vapour coexistence region at lower temperatures and densities is reduced. The phase diagram thus acquires a characteristic "pinched" shape in which the liquid branch density decreases as the temperature is lowered. To our knowledge, this is the first model in which the predicted topological phase transition between a fluid composed of short chains and a fluid rich in Y-junctions is actually observed. Above a certain threshold for epsilon(j), condensation ceases to exist because the entropy gain of forming Y-junctions can no longer offset their energy cost. We also show that the properties of these phase diagrams can be understood in terms of a temperature-dependent effective valence of the patchy particles. (C) 2011 American Institute of Physics. [doi: 10.1063/1.3605703]

A 3-phase model for VIS/NIR mu C-Si : H p-i-n detectors

The spectral response and the photocurrent delivered by entirely microcrystalline p-i-n-Si:H detectors an analysed under different applied bias and light illumination conditions. The spectral response and the internal collection depend not only on the energy range but also on the illumination side. Under [p]- and [n]-side irradiation, the internal collection characteristics have an atypical shape. It is high for applied bias and lower than the open circuit voltage, shows a steep decrease near the open circuit voltage (higher under [n]-side illumination) and levels off for higher voltages. Additionally, the numerical modeling of the VIS/NIR detector, based on the band discontinuities near the grain boundaries and interfaces, complements the study and gives insight into the internal physical process.

Phase diagrams of binary mixtures of patchy colloids with distinct numbers and types of patches: Theempty fluid regime

We investigate the effect of distinct bonding energies on the onset of criticality of low functionality fluid mixtures. We focus on mixtures ofparticles with two and three patches as this includes the mixture where "empty" fluids were originally reported. In addition to the number of patches, thespecies differ in the type of patches or bonding sites. For simplicity, we consider that the patches on each species are identical: one species has threepatches of type A and the other has two patches of type B. We have found a rich phase behavior with closed miscibility gaps, liquid-liquid demixing, and negative azeotropes. Liquid-liquid demixing was found to pre-empt the "empty" fluid regime, of these mixtures, when the AB bonds are weaker than the AA or BB bonds. By contrast, mixtures in this class exhibit "empty" fluid behavior when the AB bonds are stronger than at least one of the other two. Mixtureswith bonding energies epsilon(BB) = epsilon(AB) and epsilon(AA) < epsilon(BB), were found to exhibit an unusual negative azeotrope. (C) 2011 American Institute of Physics. [doi:10.1063/1.3561396]

Reentrant Phase Diagram of Network Fluids

We introduce a microscopic model for particles with dissimilar patches which displays an unconventional "pinched'' phase diagram, similar to the one predicted by Tlusty and Safran in the context of dipolar fluids [Science 290, 1328 (2000)]. The model-based on two types of patch interactions, which account, respectively, for chaining and branching of the self-assembled networks-is studied both numerically via Monte Carlo simulations and theoretically via first-order perturbation theory. The dense phase is rich in junctions, while the less-dense phase is rich in chain ends. The model provides a reference system for a deep understanding of the competition between condensation and self-assembly into equilibrium-polymer chains.

Computing the phase diagram of binary mixtures: A patchy particle case study

We investigate the phase behaviour of 2D mixtures of bi-functional and three-functional patchy particles and 3D mixtures of bi-functional and tetra-functional patchy particles by means of Monte Carlo simulations and Wertheim theory. We start by computing the critical points of the pure systems and then we investigate how the critical parameters change upon lowering the temperature. We extend the successive umbrella sampling method to mixtures to make it possible to extract information about the phase behaviour of the system at a fixed temperature for the whole range of densities and compositions of interest. (C) 2013 AIP Publishing LLC.

Phase growth control in low temperature PLD Co: TiO2 films by pressure

This paper reports on the structural and optical properties of Co-doped TiO2 thin films grown onto (0001)Al2O3 substrates by non-reactive pulsed laser deposition (PLD) using argon as buffer gas. It is shown that by keeping constant the substrate temperature at as low as 310 degrees C and varying only the background gas pressure between 7 Pa and 70 Pa, it is possible to grow either epitaxial rutile or pure anatase thin films, as well as films with a mixture of both polymorphs. The optical band gaps of the films are red shifted in comparison with the values usually reported for undoped TiO2, which is consistent with n-type doping of the TiO2 matrix. Such band gap red shift brings the absorption edge of the Co-doped TiO2 films into the visible region, which might favour their photocatalytic activity. Furthermore, the band gap red shift depends on the films' phase composition, increasing with the increase of the Urbach energy for increasing rutile content. (C) 2012 Elsevier B.V. All rights reserved.

SCANNERS: constraining the phase diagram of a complex scalar singlet at the LHC

We present the first version of a new tool to scan the parameter space of generic scalar potentials, SCANNERS (Coimbra et al., SCANNERS project., 2013). The main goal of SCANNERS is to help distinguish between different patterns of symmetry breaking for each scalar potential. In this work we use it to investigate the possibility of excluding regions of the phase diagram of several versions of a complex singlet extension of the Standard Model, with future LHC results. We find that if another scalar is found, one can exclude a phase with a dark matter candidate in definite regions of the parameter space, while predicting whether a third scalar to be found must be lighter or heavier. The first version of the code is publicly available and contains various generic core routines for tree level vacuum stability analysis, as well as implementations of collider bounds, dark matter constraints, electroweak precision constraints and tree level unitarity.

Regulation of antioxidant enzymes gene expression in the yeast Saccharomyces cerevisiae during stationary phase

Gene expression of three antioxidant enzymes, Mn superoxide dismutase (MnSOD), Cu,Zn superoxide dismutase (Cu,ZnSOD), and glutathione reductase (GR) was investigated in stationary phase Saccharomyces cerevisiae during menadione-induced oxidative stress. Both GR and Cu,ZnSOD mRNA steady state levels increased, reaching a plateau at about 90 min exposure to menadione. GR mRNA induction was higher than that of Cu,ZnSOD (about 14-fold and 9-fold after 90 min, respectively). A different pattern of response was obtained for MnSOD mRNA, with a peak at about 15 min (about 8-fold higher) followed by a decrease to a plateau approximately 4-fold higher than the control value. However, these increased mRNA levels did not result in increased protein levels and activities of these enzymes. Furthermore, exposure to menadione decreased MnSOD activity to half its value, indicating that the enzyme is partially inactivated due to oxidative damage. Cu,ZnSOD protein levels were increased 2-fold, but MnSOD protein levels were unchanged after exposure to menadione in the presence of the proteolysis inhibitor phenylmethylsulfonyl fluoride. These results indicate that the rates of Cu,ZnSOD synthesis and proteolysis are increased, while the rates of MnSOD synthesis and proteolysis are unchanged by exposure to menadione. Also, the translational efficiency for both enzymes is probably decreased, since increases in protein levels when proteolysis is inhibited do not reflect the increases in mRNA levels. Our results indicate that oxidative stress modifies MnSOD, Cu,ZnSOD, and GR gene expression in a complex way, not only at the transcription level but also at the post-transcriptional, translational, and post-translational levels.

How patchy can one get and still condense? The role of dissimilar patches in the interactions of colloidal particles

We investigate the influence of strong directional, or bonding, interactions on the phase diagram of complex fluids, and in particular on the liquid-vapour critical point. To this end we revisit a simple model and theory for associating fluids which consist of spherical particles having a hard-core repulsion, complemented by three short-ranged attractive sites on the surface (sticky spots). Two of the spots are of type A and one is of type B; the interactions between each pair of spots have strengths [image omitted], [image omitted] and [image omitted]. The theory is applied over the whole range of bonding strengths and results are interpreted in terms of the equilibrium cluster structures of the coexisting phases. In systems where unlike sites do not interact (i.e. where [image omitted]), the critical point exists all the way to [image omitted]. By contrast, when [image omitted], there is no critical point below a certain finite value of [image omitted]. These somewhat surprising results are rationalised in terms of the different network structures of the two systems: two long AA chains are linked by one BB bond (X-junction) in the former case, and by one AB bond (Y-junction) in the latter. The vapour-liquid transition may then be viewed as the condensation of these junctions and we find that X-junctions condense for any attractive [image omitted] (i.e. for any fraction of BB bonds), whereas condensation of the Y-junctions requires that [image omitted] be above a finite threshold (i.e. there must be a finite fraction of AB bonds).

Shear-induced lamellar phase of an ionic liquid crystal at room temperature

The phase behaviour of a number of N-alkylimidazolium salts was studied using polarizing optical microscopy, differential scanning calorimetry and X-ray diffraction. Two of these compounds exhibit lamellar mesophases at temperatures above 50 degrees C. In these systems, the liquid crystalline behaviour may be induced at room temperature by shear. Sheared films of these materials, observed between crossed polarisers, have a morphology that is typical of (wet) liquid foams: they partition into dark domains separated by brighter (birefringent) walls, which are approximately arcs of circle and meet at "Plateau borders" with three or more sides. Where walls meet three at a time, they do so at approximately 120 degrees angles. These patterns coarsen with time and both T1 and T2 processes have been observed, as in foams. The time evolution of domains is also consistent with von Neumann's law. We conjecture that the bright walls are regions of high concentration of defects produced by shear, and that the system is dominated by the interfacial tension between these walls and the uniform domains. The control of self-organised monodomains, as observed in these systems, is expected to play an important role in potential applications.