Monitoring phase behavior of sub- and supercritical CO2 confined in porous fractal silica with 85% porosity

Phase behavior of CO2 confined in porous fractal silica with volume fraction of SiO2 φs = 0.15 was investigated using small-angle neutron scattering (SANS) and ultrasmall-angle neutron scattering (USANS) techniques. The range of fluid densities (0<(FCO2)bulk<0.977 g/cm3) and temperatures (T=22 °C, 35 and 60 °C) corresponded to gaseous, liquid, near critical and supercritical conditions of the bulk fluid. The results revealed formation of a dense adsorbed phase in small pores with sizes D<40 A° at all temperatures. At low pressure (P <55 bar, (FCO2)bulk <0.2 g/cm3) the average fluid density in pores may exceed the density of bulk fluid by a factor up to 6.5 at T=22 °C. This “enrichment factor” gradually decreases with temperature, however significant fluid densification in small pores still exists at temperature T=60°C, i.e., far above the liquid-gas critical temperature of bulk CO2 (TC=31.1 °C). Larger pores are only partially filled with liquid-like adsorbed layer which coexists with unadsorbed fluid in the pore core. With increasing pressure, all pores become uniformly filled with the fluid, showing no measurable enrichment or depletion of the porous matrix with CO2.

Studies on the in-plane shear response of confined masonry shear walls

The prime aim of this research project is to evaluate the performance of confined masonry walls under in-plane shear with a view to contributing to the national masonry design standard through a set of design clauses. This aim stems from the criticisms of the current provisions of the in-plane shear capacity equations in the Australian Masonry Standard AS3700 (2011) being highly non-conservative. This PhD thesis is an attempt to address this gap in the knowledge through systematic investigation of the key parameters that affects the in-plane shear strength of the masonry walls through laboratory experiments and extensive finite element analyses.

Finite element analysis of the in-plane shear behaviour of masonry panels confined with reinforced grouted cores

A combined experimental and numerical program was conducted to study the in-plane shear behaviour of hollow concrete masonry panels containing reinforced grout cores. This paper is focused on the numerical program. A two dimensional macromodelling strategy was used to simulate the behaviour of the confined masonry (CM) shear panels. Both the unreinforced masonry and the confining element were modelled using macromasonry properties and the steel reinforcement was modelled as an embedded truss element located within the grout using perfectly bonded constraint. The FE model reproduced key behaviours observed in the experiments, including the shear strength, the deformation and the crack patterns of the unconfined and confined masonry panels. The predictions of the validated model were used to evaluate the existing in-plane shear expressions available in the national masonry standards and research publications.

Design expressions for the in-plane shear capacity of confined masonry shear walls containing squat panels

In-plane shear capacity formulation of reinforced masonry is commonly conceived as the sum of the capacities of three parameters, viz, the masonry, the reinforcement, and the precompression. The term “masonry” incorporates the aspect ratio of the wall without any regard to the aspect ratio of the panels inscribed (and hence confined) by the vertical and the horizontal reinforced grout cores. This paper proposes design expressions in which the aspect ratio of such panels is explicitly included. For this purpose, the grouted confining cores are regarded as a grid of confining elements within which the panels are positioned. These confined masonry panels are then considered as building blocks for multi-bay, multi-storied confined masonry shear walls and analyzed using an experimentally validated macroscopic finite-element model. Results of the analyzes of 161 confined masonry walls containing panels of height to length ratio less than 1.0 have been regressed to formulate design expressions. These expressions have been first validated using independent test data sets and then compared with the existing equations in some selected international design standards. The concept of including the unreinforced masonry panel aspect ratio as an additional term in the design expression for partially grouted/confined masonry shear walls is recommended based on the conclusions from this paper.

Covalently bonded networks through surface-confined polymerization

The prospect of synthesizing ordered, covalently bonded structures directly on a surface has recently attracted considerable attention due to its fundamental interest and for potential applications in electronics and photonics. This prospective article focuses on efforts to synthesize and characterize epitaxial one- and two-dimensional (1D and 2D, respectively) polymeric networks on single crystal surfaces. Recent studies, mostly performed using scanning tunneling microscopy (STM), demonstrate the ability to induce polymerization based on Ullmann coupling, thermal dehalogenation and dehydration reactions. The 2D polymer networks synthesized to date have exhibited structural limitations and have been shown to form only small domains on the surface. We discuss different approaches to control 1D and 2D polymerization, with particular emphasis on the surface phenomena that are critical to the formation of larger ordered domains.

Absence of reptation in highly confined polymers

We present results of mechanical stress relaxation measurements on polymers confined at the air-water interface in the form of a monolayer. Systematic measurements allow, to our knowledge, for the first time, observation of the scaling of the stress relaxation time of the highly confined polymers as a function of both surface concentration and molecular weight. The observed scaling is found to be very close to that expected for motion of unentangled polymer solutions with hydrodynamic interactions. Our experimental observations thus clearly rule out the possibility of entanglement and hence reptation as a mode of relaxation in such highly confined polymeric systems.

Space allowances for confined livestock and their determination from allometric principles

The amount of space provided to animals governs important elements of their behaviour and, hence, is critical for their health and welfare. We review the use of allometric principles and equations to estimate the static space requirements of animals when standing and lying, and the space required for animals to feed, drink, stand-up and lie-down. We use the research literature relating to transportation and intensive housing of sheep and cattle to assess the validity of allometric equations for estimating space allowances. We investigated these areas because transportation and intensive housing provide points along a continuum in terms of the duration of confinement, (from hours to months) and spatial requirements are likely to increase with increasing duration of confinement, as animals will need to perform a greater behavioural repertoire for long-term survival, health and welfare. We find that, although there are theoretical reasons why allometric relationships to space allowances may vary slightly for different classes of stock, space allowances that have been demonstrated to have adverse effects on animal welfare during transportation correlated well with an inability to accommodate standing animals, as estimated from allometry. For intensive housing, we were able to detect a space allowance below which there were adverse effects on welfare. For short duration transportation during which animals remain standing, a space allowance per animal described by the allometric equation: area (m^2) = 0.020W^0.66, where W = liveweight (kg), would appear to be appropriate. Where it is desirable for all animals to lie simultaneously, then a minimum space allowance per animal described by the allometric equation: area (m^2) = 0.027W^0.66 appears to permit this, given that animals in a group time-share space. However, there are insufficient data to determine whether this allowance onboard a vehicle/vessel would enable animals to move and access food and water with ease. In intensive housing systems, a minimum space allowance per animal described by the allometric equation: area (m^2) = 0.033W^0.66 appears to be the threshold below which there are adverse effects on welfare. These suggested space allowances require verification with a range of species under different thermal conditions and, for transportation, under different conditions of vehicular/vessel stability. The minimum length of trough per animal (L in m) required for feeding and drinking can be determined from L = 0.064W^0.33, with the number of animals required to feed/drink simultaneously taken into account, together with any requirement to minimise competition. This also requires verification with a range of species. We conclude that allometric relationships are an appropriate basis for the formulation of space allowances for livestock.

An Analysis of a Boundary Layer Diffusion Flame Over a Porous Flat Plate in a Confined Flow

A numerical analysis of the gas dynamic structure of a two-dimensional laminar boundary layer diffusion flame over a porous flat plate in a confined flow is made on the basis of the familiar boundary layer and flame sheet approximations neglecting buoyancy effects. The governing equations of aerothermochemistry with the appropriate boundary conditions are solved using the Patankar-Spalding method. The analysis predicts the flame shape, profiles of temperature, concentrations of variousspecies, and the density of the mixture across the boundary layer. In addition, it also predicts the pressure gradient in the flow direction arising from the confinement ofthe flow and the consequent velocity overshoot near the flame surface. The results of thecomputation performed for an n-pentane-air system are compared with experimental data andthe agreement is found to be satisfactory.

Jump Reorientation of Water Molecules Confined in Narrow Carbon Nanotubes

We used molecular dynamics (MD) simulations to study the reorientational dynamics of water molecules confined inside narrow carbon nanotubes immersed in a bath of water. Our simulations show that the confined water molecules exhibit bistability in their reorientational relaxation, which proceeds by angular jumps between the two stable states. The angular jump of a water molecule in the bulk involves the breaking of a hydrogen bond with one of its neighbors and the formation of a hydrogen bond with a different neighbor. In contrast, the angular jump of a confined water molecule corresponds to an interchange of the two hydrogen atoms that can form a hydrogen bond with the same neighbor. The free energy barrier between these two states is a few k(B)T. The analytic solution of a simplified two-state jump model that qualitatively explains the reorientational behavior observed in simulations is also presented.

Studies on micro explosive driven blast wave propagation in confined domains using NONEL tubes

Explosive driven micro blast waves are generated in the laboratory using NONEL tubes. The explosive mixture coated to the inner walls of the plastic Nonel tube comprises of HMX and Aluminum ( 18mg/m). The detonation is triggered electrically to generate micro blast waves from the open end of the tube. Flow visualization and over pressure measurements have been carried out to understand the propagation dynamics of these micro-blast waves in both confined and unconfined domains. The classical cubic root law used for large scale blast correlation appears to hold good even for these micro-blasts generated in the laboratory.

Evaluation of k-epsilon and RNG turbulence models for confined swirling and non-swirling flow

In a very recent study [1] the Renormalisation Group (RNG) turbulence model was used to obtain flow predictions in a strongly swirling quarl burner, and was found to perform well in predicting certain features that are not well captured using less sophisticated models of turbulence. The implication is that the RNG approach should provide an economical and reliable tool for the prediction of swirling flows in combustor and furnace geometries commonly encountered in technological applications. To test this hypothesis the present work considers flow in a model furnace for which experimental data is available [2]. The essential features of the flow which differentiate it from the previous study [1] are that the annular air jet entry is relatively narrow and the base wall of the cylindrical furnace is at 90 degrees to the inlet pipe. For swirl numbers of order 1 the resulting flow is highly complex with significant inner and outer recirculation regions. The RNG and standard k-epsilon models are used to model the flow for both swirling and non-swirling entry jets and the results compared with experimental data [2]. Near wall viscous effects are accounted for in both models via the standard wall function formulation [3]. For the RNG model, additional computations with grid placement extending well inside the near wall viscous-affected sublayer are performed in order to assess the low Reynolds number capabilities of the model.

Computation of confined swirling flow using RNG and k-epsilon turbulence models

In this work we numerically model isothermal turbulent swirling flow in a cylindrical burner. Three versions of the RNG k-epsilon model are assessed against performance of the standard k-epsilon model. Sensitivity of numerical predictions to grid refinement, differing convective differencing schemes and choice of (unknown) inlet dissipation rate, were closely scrutinised to ensure accuracy. Particular attention is paid to modelling the inlet conditions to within the range of uncertainty of the experimental data, as model predictions proved to be significantly sensitive to relatively small changes in upstream flow conditions. We also examine the characteristics of the swirl--induced recirculation zone predicted by the models over an extended range of inlet conditions. Our main findings are: - (i) the standard k-epsilon model performed best compared with experiment; - (ii) no one inlet specification can simultaneously optimize the performance of the models considered; - (iii) the RNG models predict both single-cell and double-cell IRZ characteristics, the latter both with and without additional internal stagnation points. The first finding indicates that the examined RNG modifications to the standard k-e model do not result in an improved eddy viscosity based model for the prediction of swirl flows. The second finding suggests that tuning established models for optimal performance in swirl flows a priori is not straightforward. The third finding indicates that the RNG based models exhibit a greater variety of structural behaviour, despite being of the same level of complexity as the standard k-e model. The plausibility of the predicted IRZ features are discussed in terms of known vortex breakdown phenomena.

Analysis of turbulent confined highly swirling flow

We report here a CFD model of highly swirling flow in a quarl burner using three versions of the k-epsilon model. Results for the recirculating zone, the bounding shear layer and the downstream flow are presented. We discuss, with suitable qualifications, how the model predictions can inform our understanding of this class of flows.

Influence of Hydrophilic Surface Specificity on the Structural Properties of Confined Water

The influence of chemical specificity of hydrophilic surfaces on the structure of confined water in the subnanometer regime is investigated using grand canonical Monte Carlo Simulations. The structural variations for water confined between hydroxylated silica surfaces are contrasted with water confined between mica surfaces. Although both surfaces are hydrophilic, our Study shows that hydration of potassium ions on the mica surface has a strong influence on the water Structure and solvation force response of confined water. In contrast to the disrupted hydrogen bond network observed for water confined between Mica Surfaces, water between silica surfaces retains its hydrogen bond network displaying bulklike structural features down to surface separations as small as 0.45 nm. Hydrogen bonding of all invariant contact water layer with the surface silanol groups aids in maintaining a constant number of hydrogen bonds per water molecule for the silica surfaces. As a consequence water depletion and rearrangement upon decreasing confinement is a strong function of the hydrophilic surface specificity, particularly at smaller separations. An oscillatory solvation force response is only observed for water confined between Silica surfaces, and bulklike features are observed for both Surfaces above a surface separation of about 1.2 nm. We evaluate and contrast the water density, dipole moment distributions, pi pair correlation functions, and solvation forces as a function of the surface separation.

Structure and Function of Hemoglobin Confined Inside Silica Nanotubes

Investigations on the structure and function of hemoglobin (Hb) confined inside sol-gel template synthesized silica nanotubes (SNTs) have been discussed here. Immobilization of hemoglobin inside SNTs resulted in the enhancement of direct electron transfer during an electrochemical reaction. Extent of influence of nanoconfinement on protein activity is further probed via ligand binding and thermal stability studies. Electrochemical investigations show reversible binding of n-donor liquid ligands, such as pyridine and its derivatives, and predictive variation in their redox potentials suggests an absence of any adverse effect on the structure and function of Hb confined inside nanometer-sized channels of SNTs. Immobilization also resulted in enhanced thermal stability of Hb. The melting or denaturation temperature of Hb immobilized inside SNTs increase by approximately 4 degrees C as compared with that of free Hb in solution.