In situ SANS study of the surface and pore filling adsorption of subcritical and supercritical CO2 in porous silica as a function of pore size

We applied small-angle neutron scattering (SANS) and ultra small-angle neutron scattering (USANS) to monitor evolution of the CO2 adsorption in porous silica as a function of CO2 pressure and temperature in pores of different sizes. The range of pressures (0 < P < 345 bar) and temperatures (T=18 OC, 35 OC and 60 OC) corresponded to subcritical, near critical and supercritical conditions of bulk fluid. We observed that the adsorption behavior of CO2 is fundamentally different in large and small pores with the sizes D > 100 Å and D < 30 Å, respectively. Scattering data from large pores indicate formation of a dense adsorbed film of CO2 on pore walls with the liquid-like density (ρCO2)ads≈0.8 g/cm3. The adsorbed film coexists with unadsorbed fluid in the inner pore volume. The density of unadsorbed fluid in large pores is temperature and pressure dependent: it is initially lower than (ρCO2)ads and gradually approaches it with pressure. In small pores compressed CO2 gas completely fills the pore volume. At the lowest pressures of the order of 10 bar and T=18 OC, the fluid density in smallest pores available in the matrix with D ~ 10 Å exceeds bulk fluid density by a factor of ~ 8. As pressure increases, progressively larger pores become filled with the condensed CO2. Fluid densification is only observed in pores with sizes less than ~ 25 – 30 Å. As the density of the invading fluid reaches (ρCO2)bulk~ 0.8 g/cm3, pores of all sizes become uniformly filled with CO2 and the confinement effects disappear. At higher densities the fluid in small pores appears to follow the equation of state of bulk CO2 although there is an indication that the fluid density in the inner volume of large pores may exceed the density of the adsorbed layer. The equivalent internal pressure (Pint) in the smallest pores exceeds the external pressure (Pext) by a factor of ~ 5 for both sub- and supercritical CO2. Pint gradually approaches Pext as D → 25 – 30 Å and is independent of temperature in the studied range of 18 OC ≤ T ≤ 60 OC. The obtained results demonstrate certain similarity as well as differences between adsorption of subcritical and supercritical CO2 in disordered porous silica. High pressure small angle scattering experiments open new opportunities for in situ studies of the fluid adsorption in porous media of interest to CO2 sequestration, energy storage, and heterogeneous catalysis.

Porohyperelastic finite element model for the kangaroo humeral head cartilage based on experimental study and the consolidation theory

Solid-extracellular fluid interaction is believed to play an important role in the strain-rate dependent mechanical behaviors of shoulder articular cartilages. It is believed that the kangaroo shoulder joint is anatomically and biomechanically similar to human shoulder joint and it is easy to get in Australia. Therefore, the kangaroo humeral head cartilage was used as the suitable tissue for the study in this paper. Indentation tests from quasi-static (10-4/sec) to moderately high strain-rate (10-2/sec) on kangaroo humeral head cartilage tissues were conduced to investigate the strain-rate dependent behaviors. A finite element (FE) model was then developed, in which cartilage was conceptualized as a porous solid matrix filled with incompressible fluids. In this model, the solid matrix was modeled as an isotropic hyperelastic material and the percolating fluid follows Darcy’s law. Using inverse FE procedure, the constitutive parameters related to stiffness, compressibility of the solid matrix and permeability were obtained from the experimental results. The effect of solid-extracellular fluid interaction and drag force (the resistance to fluid movement) on strain-rate dependent behavior was investigated by comparing the influence of constant, strain dependent and strain-rate dependent permeability on FE model prediction. The newly developed porohyperelastic cartilage model with the inclusion of strain-rate dependent permeability was found to be able to predict the strain-rate dependent behaviors of cartilages.

Mathematical modelling of gas production and compositional shift of a CSG (coal seam gas) field: Local model development

In this work we discuss the development of a mathematical model to predict the shift in gas composition observed over time from a producing CSG (coal seam gas) well, and investigate the effect that physical properties of the coal seam have on gas production. A detailed (local) one-dimensional, two-scale mathematical model of a coal seam has been developed. The model describes the competitive adsorption and desorption of three gas species (CH4, CO2 and N2) within a microscopic, porous coal matrix structure. The (diffusive) flux of these gases between the coal matrices (microscale) and a cleat network (macroscale) is accounted for in the model. The cleat network is modelled as a one-dimensional, volume averaged, porous domain that extends radially from a central well. Diffusive and advective transport of the gases occurs within the cleat network, which also contains liquid water that can be advectively transported. The water and gas phases are assumed to be immiscible. The driving force for the advection in the gas and liquid phases is taken to be a pressure gradient with capillarity also accounted for. In addition, the relative permeabilities of the water and gas phases are considered as functions of the degree of water saturation.

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.

A comparative study of different porous amorphous silica minerals supported TiO2 catalysts

Three porous amorphous silica minerals, including diatomite, opal and porous precipitated SiO2wereadopted to prepare supported TiO2catalysts by hydrolysis–deposition method. The prepared compoundmaterials were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), Fouriertransform infrared spectroscopy (FT-IR), transmission electron microscopy (TEM) and X-ray photo-electron spectroscopy (XPS). Through morphology and physical chemistry properties of the resultingTiO2/amorphous SiO2catalysts, it was proposed that the nature of silica supports could affect the particlesize and the crystal form of TiO2and then further influence the photocatalytic property of TiO2/amorphousSiO2catalysts. The catalytic properties of these porous amorphous silica supported photocatalysts(TiO2/SiO2) were investigated by UV-assisted degradation of Rhodamine B (RhB). Compared with pureTiO2(P25) and the other two TiO2/amorphous SiO2catalysts, TiO2/diatomite photocatalyst exhibits bet-ter catalytic performance at different calcined temperatures, the decoloration rate of which can be upto over 85% even at a relatively low calcined temperature. The TiO2/diatomite photocatalyst possessesmixed-phase TiO2with relatively smaller particles size, which might be responsible for higher photo-catalytic activity. Moreover, the stable and much inerter porous microstructure of diatomite could beanother key factor in improving its activity.

Matrix metalloproteinase biosensor based on a porous silicon reflector

Matrix metalloproteinases (MMPs) are proteolytic enzymes important to wound healing. In non-healing wounds, it has been suggested that MMP levels become dysfunctional, hence it is of great interest to develop sensors to detect MMP biomarkers. This study presents the development of a label-free optical MMP biosensor based on a functionalised porous silicon (pSi) thin film. The biosensor is fabricated by immobilising a peptidomimetic MMP inhibitor in the porous layer using hydrosilylation followed by amide coupling. The binding of MMP to the immobilised inhibitor translates into a change of effective optical thickness (EOT) over the time. We investigate the effect of surface functionalisation on the stability of pSi surface and evaluate the sensing performance. We successfully demonstrate MMP detection in buffer solution and human wound fluid at physiologically relevant concentrations. This biosensor may find application as a point-of-care device that is prognostic of the healing trajectory of chronic wounds.

Towards a rule-based matrix for evaluating distress mechanisms in bridges

The effective management of bridge stock involves making decisions as to when to repair, remedy, or do nothing, taking into account the financial and service life implications. Such decisions require a reliable diagnosis as to the cause of distress and an understanding of the likely future degradation. Such diagnoses are based on a combination of visual inspections, laboratory tests on samples and expert opinions. In addition, the choice of appropriate laboratory tests requires an understanding of the degradation mechanisms involved. Under these circumstances, the use of expert systems or evaluation tools developed from “realtime” case studies provides a promising solution in the absence of expert knowledge. This paper addresses the issues in bridge infrastructure management in Queensland, Australia. Bridges affected by alkali silica reaction and chloride induced corrosion have been investigated and the results presented using a mind mapping tool. The analysis highights that several levels of rules are required to assess the mechanism causing distress. The systematic development of a rule based approach is presented. An example of this application to a case study bridge has been used to demonstrate that preliminary results are satisfactory.

An evaluation of alternative media for pebble matrix filtration using clay balls and recycled crushed glass

Protecting slow sand filters (SSFs) from high-turbidity waters by pretreatment using pebble matrix filtration (PMF) has previously been studied in the laboratory at University College London, followed by pilot field trials in Papua New Guinea and Serbia. The first full-scale PMF plant was completed at a water-treatment plant in Sri Lanka in 2008, and during its construction, problems were encountered in sourcing the required size of pebbles and sand as filter media. Because sourcing of uniform-sized pebbles may be problematic in many countries, the performance of alternative media has been investigated for the sustainability of the PMF system. Hand-formed clay balls made at a 100-yearold brick factory in the United Kingdom appear to have satisfied the role of pebbles, and a laboratory filter column was operated by using these clay balls together with recycled crushed glass as an alternative to sand media in the PMF. Results showed that in countries where uniform-sized pebbles are difficult to obtain, clay balls are an effective and feasible alternative to natural pebbles. Also, recycled crushed glass performed as well as or better than silica sand as an alternative fine media in the clarification process, although cleaning by drainage was more effective with sand media. In the tested filtration velocity range of ð0:72–1:33Þ m=h and inlet turbidity range of (78–589) NTU, both sand and glass produced above 95% removal efficiencies. The head loss development during clogging was about 30% higher in sand than in glass media.

A variable-stepsize Jacobian-free exponential integrator for simulating transport in heterogeneous porous media : application to wood drying

A Jacobian-free variable-stepsize method is developed for the numerical integration of the large, stiff systems of differential equations encountered when simulating transport in heterogeneous porous media. Our method utilises the exponential Rosenbrock-Euler method, which is explicit in nature and requires a matrix-vector product involving the exponential of the Jacobian matrix at each step of the integration process. These products can be approximated using Krylov subspace methods, which permit a large integration stepsize to be utilised without having to precondition the iterations. This means that our method is truly "Jacobian-free" - the Jacobian need never be formed or factored during the simulation. We assess the performance of the new algorithm for simulating the drying of softwood. Numerical experiments conducted for both low and high temperature drying demonstrates that the new approach outperforms (in terms of accuracy and efficiency) existing simulation codes that utilise the backward Euler method via a preconditioned Newton-Krylov strategy.

Grain size distributions of Magneli phases and metallic titanium in chondritic porous interplanetary dust particles

A mineralogical survey of chondritic interplanetary dust particles (IDPs)showed that these micrometeorites differ significantly in form and texture from components of carbonaceous chondrites and contain some mineral assemblages which do not occur in any meteorite class1. Models of chondritic IDP mineral evolution generally ignore the typical (ultra-) fine grain size of consituent minerals which range between 0.002-0.1µm in size2. The chondritic porous (CP) subset of chondritic IDPs is probably debris from short period comets although evidence for a cometary origin is still circumstantial3. If CP IDPs represent dust from regions of the Solar System in which comet accretion occurred, it can be argued that pervasive mineralogical evolution of IDP dust has been arrested due to cryogenic storage in comet nuclei. Thus, preservation in CP IDPs of "unusual meteorite minerals", such as oxides of tin, bismuth and titanium4, should not be dismissed casually. These minerals may contain specific information about processes that occurred in regions of the solar nebula, and early Solar System, which spawned the IDP parent bodies such as comets and C, P and D asteroids6. It is not fully appreciated that the apparent disparity between the mineralogy of CP IDPs and carbonaceous chondrite matrix may also be caused by the choice of electron-beam techniques with different analytical resolution. For example, Mg-Si-Fe distributions of Cl matrix obtained by "defocussed beam" microprobe analyses are displaced towards lower Fe-values when using analytical electron microscope (AEM)data which resolve individual mineral grains of various layer silicates and magnetite in the same matrix6,7. In general, "unusual meteorite minerals" in chondritic IDPs, such as metallic titanium, Tin01-n(Magneli phases) and anatase8 add to the mineral data base of fine-grained Solar System materials and provide constraints on processes that occurred in the early Solar System.

Formation of nanostructured porous Cu-Au surfaces : the influence of cationic sites on (electro)-catalysis

The fabrication of nanostructured bimetallic materials through electrochemical routes offers the ability to control the composition and shape of the final material that can then be effectively applied as (electro)-catalysts. In this work a clean and transitory hydrogen bubble templating method is employed to generate porous Cu–Au materials with a highly anisotropic nanostructured interior. Significantly, the co-electrodeposition of copper and gold promotes the formation of a mixed bimetallic oxide surface which does not occur at the individually electrodeposited materials. Interestingly, the surface is dominated by Au(I) oxide species incorporated within a Cu2O matrix which is extremely effective for the industrially important (electro)-catalytic reduction of 4-nitrophenol. It is proposed that an aurophilic type of interaction takes place between both oxidized gold and copper species which stabilizes the surface against further oxidation and facilitates the binding of 4-nitrophenol to the surface and increases the rate of reaction. An added benefit is that very low gold loadings are required typically less than 2 wt% for a significant enhancement in performance to be observed. Therefore the ability to create a partially oxidized Cu–Au surface through a facile electrochemical route that uses a clean template consisting of only hydrogen bubbles should be of benefit for many more important reactions.

Local stress-strain distribution and load transfer across cartilage matrix at micro-scale using combined microscopy-based finite element method

Articular cartilage is the load-bearing tissue that consists of proteoglycan macromolecules entrapped between collagen fibrils in a three-dimensional architecture. To date, the drudgery of searching for mathematical models to represent the biomechanics of such a system continues without providing a fitting description of its functional response to load at micro-scale level. We believe that the major complication arose when cartilage was first envisaged as a multiphasic model with distinguishable components and that quantifying those and searching for the laws that govern their interaction is inadequate. To the thesis of this paper, cartilage as a bulk is as much continuum as is the response of its components to the external stimuli. For this reason, we framed the fundamental question as to what would be the mechano-structural functionality of such a system in the total absence of one of its key constituents-proteoglycans. To answer this, hydrated normal and proteoglycan depleted samples were tested under confined compression while finite element models were reproduced, for the first time, based on the structural microarchitecture of the cross-sectional profile of the matrices. These micro-porous in silico models served as virtual transducers to produce an internal noninvasive probing mechanism beyond experimental capabilities to render the matrices micromechanics and several others properties like permeability, orientation etc. The results demonstrated that load transfer was closely related to the microarchitecture of the hyperelastic models that represent solid skeleton stress and fluid response based on the state of the collagen network with and without the swollen proteoglycans. In other words, the stress gradient during deformation was a function of the structural pattern of the network and acted in concert with the position-dependent compositional state of the matrix. This reveals that the interaction between indistinguishable components in real cartilage is superimposed by its microarchitectural state which directly influences macromechanical behavior.

H2-O2 porous fuel injection in a radical farming scramjet

This paper reports on the experimental testing of oxygen compatible ceramic matrix composite porous injectors in a nominally two-dimensional hydrogen fuelled and oxygen enriched radical farming scramjet in the T4 shock tunnel facility. All experiments were performed at a dynamic pressure of 146 kPa, an equivalent flight Mach number of 9.7, a stagnation pressure and enthalpy of 40MPa and 4.3 MJ/kg respectively and at a fuelling condition that resulted in an average equivalence ratio of 0.472. Oxygen was pre-mixed with the fuel prior to injection to achieve enrichment percentages of approximately 13%, 15% and 17%. These levels ensured that the hydrogen-oxidiser mix injected into the engine always remained too fuel rich to sustain a flame without any additional mixing with the captured air. Addition of pre-mixed oxygen with the fuel was found to significantly alter the performance of the engine; enhancing both combustion and ignition and converting a previously observed limited combustion condition into one with sustained and noticeable combustion induced pressure rise. Increases in the enrichment percentage lead to further increases in combustion levels and acted to reduce ignition lengths within the engine. Suppressed combustion runs, where a nitrogen test gas was used, confirmed that the pressure rise observed in these experiments as attributed to the oxygen enrichment and not associated with the increased mass injected.

Dielectric performance of polymer nanocomposites synthesized by atmospheric-pressure plasma-treated silica nanoparticles

In this study, atmospheric-pressure plasmas were applied to modify the surface of silane-coated silica nanoparticles. Subsequently nanocomposites were synthesized by incorporating plasma-treated nanoparticles into an epoxy resin matrix. Electrical testing showed that such novel dielectric materials obtained high partial discharge resistance, high dielectric breakdown strength, and enhanced endurance under highly stressed electric field. Through spectroscopic and microscopic analysis, we found surface groups of nanoparticles were activated and radicals were created after the plasma treatment. Moreover, a uniform dispersion of nanoparticles in nanocomposites was observed. It was expected that the improved dielectric performance of the nanocomposites can attribute to stronger chemical bonds formed between surface groups of plasma-treated nanoparticles and molecules in the matrix. This simple yet effective and environmentally friendly approach aims to synthesize the next generation of high-performance nanocomposite dielectric insulation materials for applications in high-voltage power systems.