Supercritical carbonation of calcareous composites:influence of curing

This paper reports the effect of curing on the susceptibility of cementitious composites to carbonation using supercritical carbon dioxide. Samples made using a compression moulding technique were cured in water before and/or after carbonation and the effect on porosity, microstructure, solid phase assemblage and flexural strength was determined. In terms of development of mechanical strength, no benefit was gained from any period of pre- or post-carbonation curing regime. Yet samples cured prior to carbonation underwent minimal chemical reaction between supercritical carbon dioxide and calcium hydroxide, unhydrated cement or C-S-H. Thus there was no correlation between chemical degree of reaction and strength development. The effects responsible for the marked strength gain in supercritically carbonated samples must involve subtle changes in the microstructure of the C-S-H gel, not simple pore filling by calcium carbonate as is often postulated. © 2013 Elsevier Ltd. All rights reserved.\.

Supercritical carbonation of calcareous composites:influence of mix design

This work combined compression moulding with subsequent super-critical carbonation treatment (100 bar, 60 °C, 24 h) to fabricate cement and/or lime based ceramic composites with various aggregates. Composites were examined using mechanical testing, XRD, He pycnometry and thin-section petrography. Composites with lime-only binders were significantly weaker than those with cement-lime binders regardless of the degree of carbonation. Flexural strengths in excess of >10 MPa were routinely achieved in large (>100 mm) specimens. Aggregate type (calcareous vs. siliceous) had a significant effect on the microstructure and properties of the composites. Calcareous aggregates appear to augment the strength enhancement effected during super-critical carbonation by encouraging preferential precipitation of calcite at the binder-aggregate interface.

Catalytic supercritical water gasification of plastics with supported RuO2:a potential solution to hydrocarbons-water pollution problem

Here we report on a potential catalytic process for efficient clean-up of plastic pollution in waters, such as the Great Pacific Garbage Patch (CPGP). Detailed catalytic mechanisms of RuO2 during supercritical water gasification of common polyolefin plastics including low-density polyethylene (LDPE), high-density polyethylene (HDPE), polypropylene (PP) and polystyrene (PP), have been investigated in a batch reactor at 450 °C, 60 min. All four plastics gave very high carbon gasification efficiencies (CGE) and hydrogen gasification efficiencies (HGE). Methane was the highest gas component, with a yield of up to 37 mol kg−1LDPE using the 20 wt% RuO2 catalyst. Evaluation of the gas yields, CGE and HGE revealed that the conversion of PS involved thermal degradation, steam reforming and methanation; whereas hydrogenolysis was a possible additional mechanism during the conversion of aliphatic plastics. The process has the benefits of producing a clean-pressurized methane-rich fuel gas as well as cleaning up hydrocarbons-polluted waters.

Supercritical water gasification of RDF and its components over RuO2/γ-Al2O3 catalyst:new insights into RuO2 catalytic reaction mechanisms

Five samples including a composite refuse derived fuel (RDF) and four combustible components of municipal solid wastes (MSW) have been reacted under supercritical water conditions in a batch reactor. The reactions have been carried out at 450 °C for 60 min reaction time, with or without 20 wt% RuO2/gamma-alumina catalyst. The reactivities of the samples depended on their compositions; with the plastic-rich samples, RDF and mixed waste plastics (MWP), giving similar product yields and compositions, while the biogenic samples including mixed waste wood (MWW) and textile waste (TXT) also gave similar reaction products. The use of the heterogeneous ruthenium-based catalyst gave carbon gasification efficiencies (CGE) of up to 99 wt%, which was up by at least 83% compared to the non-catalytic tests. In the presence of RuO2 catalyst, methane, hydrogen and carbon dioxide became the dominant gas products for all five samples. The higher heating values (HHV) of the gas products increased at least two-fold in the presence of the catalyst compared to non-catalytic tests. Results show that the ruthenium-based catalyst was active in feedstock steam reforming, methanation and possible direct hydrogenolysis of C-C bonds. This work provides new insights into the catalytic mechanisms of RuO2 during SCWG of carbonaceous materials, along with the possibility of producing high yields of methane from MSW fractions.

Supercritical carbonation of lime based sustainable structural ceramics

Abstract Structural ceramics were manufactured from industrial byproducts and lime by a compression moulding/vacuum dewatering technique. Treatment of these ceramics with supercritical carbon dioxide was found to both significantly increase their flexural strength and activate cementation in the industrial byproducts at least as efficiently as heat curing. Flexural strengths of up to 10 MPa were achieved. Strength improvements were associated with decreased porosity and conversion of calcium hydroxide to calcium carbonate. Life cycle assessment of proposed products made from such materials indicated that the total reduction in embodied carbon dioxide achieved, as a result of combining use of byproducts with recombination of carbon dioxide, was up to 70%. © 2010 Institute of Materials, Minerals and Mining.

Direct femtosecond laser inscription in transparent dielectrics

Since 1996 direct femtosecond inscription in transparent dielectrics has become the subject of intensive research. This enabling technology significantly expands the technological boundaries for direct fabrication of 3D structures in a wide variety of materials. It allows modification of non-photosensitive materials, which opens the door to numerous practical applications. In this work we explored the direct femtosecond inscription of waveguides and demonstrated at least one order of magnitude enhancement in the most critical parameter - the induced contrast of the refractive index in a standard borosilicate optical glass. A record high induced refractive contrast of 2.5×10-2 is demonstrated. The waveguides fabricated possess one of the lowest losses, approaching level of Fresnel reflection losses at the glassair interface. High refractive index contrast allows the fabrication of curvilinear waveguides with low bend losses. We also demonstrated the optimisation of the inscription regimes in BK7 glass over a broad range of experimental parameters and observed a counter-intuitive increase of the induced refractive index contrast with increasing translation speed of a sample. Examples of inscription in a number of transparent dielectrics hosts using high repetition rate fs laser system (both glasses and crystals) are also presented. Sub-wavelength scale periodic inscription inside any material often demands supercritical propagation regimes, when pulse peak power is more than the critical power for selffocusing, sometimes several times higher than the critical power. For a sub-critical regime, when the pulse peak power is less than the critical power for self-focusing, we derive analytic expressions for Gaussian beam focusing in the presence of Kerr non-linearity as well as for a number of other beam shapes commonly used in experiments, including astigmatic and ring-shaped ones. In the part devoted to the fabrication of periodic structures, we report on recent development of our point-by-point method, demonstrating the shortest periodic perturbation created in the bulk of a pure fused silica sample, by using third harmonics (? =267 nm) of fundamental laser frequency (? =800 nm) and 1 kHz femtosecond laser system. To overcome the fundamental limitations of the point-by-point method we suggested and experimentally demonstrated the micro-holographic inscription method, which is based on using the combination of a diffractive optical element and standard micro-objectives. Sub-500 nm periodic structures with a much higher aspect ratio were demonstrated. From the applications point of view, we demonstrate examples of photonics devices by direct femtosecond fabrication method, including various vectorial bend-sensors fabricated in standard optical fibres, as well as a highly birefringent long-period gratings by direct modulation method. To address the intrinsic limitations of femtosecond inscription at very shallow depths we suggested the hybrid mask-less lithography method. The method is based on precision ablation of a thin metal layer deposited on the surface of the sample to create a mask. After that an ion-exchange process in the melt of Ag-containing salts allows quick and low-cost fabrication of shallow waveguides and other components of integrated optics. This approach covers the gap in direct fs inscription of shallow waveguide. Perspectives and future developments of direct femtosecond micro-fabrication are also discussed.

Simultaneous chemical reaction and distillation of formaldehyde

The thesis is concerned with the development and testing of a mathematical model of a distillation process in which the components react chemically. The formaldehyde-methanol-water system was selected and only the reversible reactions between formaldehyde and water giving methylene glycol and between formaldehyde and methanol producing hemiformal were assumed to occur under the distillation conditions. Accordingly the system has been treated as a five component system. The vapour-liquid equilibrium calculations were performed by solving iteratively the thermodynamic relationships expressing the phase equilibria with the stoichiometric equations expressing the chemical equilibria. Using optimisation techniques, the Wilson single parameters and Henry's constants were calculated for binary systems containing formaldehyde which was assumed to be a supercritical component whilst Wilson binary parameters were calculated for the remaining binary systems. Thus the phase equilibria for the formaldehyde system could be calculated using these parameters and good accuracy was obtained when calculated values were compared with experimental values. The distillation process was modelled using the mass and energy balance equations together with the phase equilibria calculations. The plate efficiencies were obtained from a modified A.I.Ch.E. Bubble Tray method. The resulting equations were solved by an iterative plate to plate calculation based on the Newton Raphson method. Experiments were carried out in a 76mm I.D., eight sieve plate distillation column and the results were compared with the mathematical model calculations. Overall, good agreement was obtained but some discrepancies were observed in the concentration profiles and these may have been caused by the effect of limited physical property data and a limited understanding of the reactions mechanism. The model equations were solved in the form of modular computer programs. Although they were written to describe the steady state distillation with simultaneous chemical reaction of the formaldehyde system, the approach used may be of wider application.

Transition in inclined internally heated fluid layers

Non-linear solutions and studies of their stability are presented for flows in a homogeneously heated fluid layer under the influence of a constant pressure gradient or when the mass flux across any lateral cross-section of the channel is required to vanish. The critical Grashof number is determined by a linear stability analysis of the basic state which depends only on the z-coordinate perpendicular to the boundary. Bifurcating longitudinal rolls as well as secondary solutions depending on the streamwise x-coordinate are investigated and their amplitudes are determined as functions of the supercritical Grashof number for various Prandtl numbers and angles of inclination of the layer. Solutions that emerge from a Hopf bifurcation assume the form of propagating waves and can thus be considered as steady flows relative to an appropriately moving frame of reference. The stability of these solutions with respect to three-dimensional disturbances is also analyzed in order to identify possible bifurcation points for evolving tertiary flows.

Femtosecond laser microfabrication of subwavelength structures in photonics

This paper describes experimental and numerical results of the plasma-assisted microfabrication of subwavelength structures by means of point-by point femtosecond laser inscription. It is shown that the spatio-temporal evolution of light and plasma patterns critically depend on input power. Subwavelength inscription corresponds to the supercritical propagation regimes when pulse power is several times self-focusing threshold. Experimental and numerical profiles show quantitative agreement.

Identifying the active phase in Cs-promoted MgO nanocatalysts for triglyceride transesterification

Background: Biodiesel is a clean-burning, renewable and biodegradable diesel fuel substitute derived from animal fats and plant oils, which may play an important role in replacing diminishing fossil fuel reserves and combating climate change. Conventional biodiesel production uses soluble base catalysts, such as Na or K alkoxides, to convert oils into fuel, and as a result requires energy intensive aqueous quench cycles to isolate the biodiesel product. Results: Cs-doping nanoparticulate MgO, prepared via a novel, supercritical sol-gel method, yields a solid base catalyst with improved activity for the transesterification of pure triacylglycerides (TAGs) and olive oil. Conclusion: Here, X-ray absorption spectroscopy (XAS) is used to probe the local chemical environment of Cs atoms in order to identify the nature of the catalytically active species as CsMg(CO)(HO). © 2013 Society of Chemical Industry.

Cs promoted triglyceride transesterification over MgO nanocatalysts

The influence of Cs on the structure and basicity of nanocrystalline MgO was assessed via electron microscopy, CO2 chemisorption, XRD and XPS. Caesium incorporation via co-precipitation under supercritical conditions generates Cs2Mg(CO3)2 nanocrystallites with an enhanced density and strength of surface base sites. Wet impregnation proved less effective for modifying MgO nanocrystals. A strong synergy between Cs and Mg components in the co-precipitated material dramatically enhanced the rate of tributyrin transesterification with methanol relative to undoped MgO and homogeneous Cs2CO3 catalysts. On-stream deactivation of Cs-doped MgO reflects heavy surface carbon deposition and loss of the high activity Cs2Mg(CO3)2 phase due to limited Cs dissolution.

Catalysts in production of biodiesel:a review

Biodiesel is a renewable substitute fuel for petroleum diesel fuel which is made from nontoxic, biodegradable, renewable sources such as refined and used vegetable oils and animal fats. Biodiesel is produced by transesterification in which oil or fat is reacted with a monohydric alcohol in the presence of a catalyst. The process of transesterification is affected by the mode of reaction, molar ratio of alcohol to oil, type of alcohol, nature and amount of catalysts, reaction time, and temperature. Various studies have been carried out using different oils as the raw material and different alcohols (methanol, ethanol, butanol), as well as different catalysts, notably homogeneous ones such as sodium hydroxide, potassium hydroxide, sulfuric acid, and supercritical fluids or enzymes such as lipases. Recent research has focused on the application of heterogeneous catalysts to produce biodiesel, because of their environmental and economic advantages. This paper reviews the literature regarding both catalytic and noncatalytic production of biodiesel. Advantages and disadvantages of different methods and catalysts used are discussed. We also discuss the importance of developing a single catalyst for both esterification and transesterification reactions.

Free energy functional expansion as the generalized approach to the equation of state of dense fluids

A version of the thermodynamic perturbation theory based on a scaling transformation of the partition function has been applied to the statistical derivation of the equation of state in a highpressure region. Two modifications of the equations of state have been obtained on the basis of the free energy functional perturbation series. The comparative analysis of the experimental PV T- data on the isothermal compression for the supercritical fluids of inert gases has been carried out. © 2012.

Femtosecond laser microfabrication of subwavelength structures in photonics

This paper describes experimental and numerical results of the plasma-assisted microfabrication of subwavelength structures by means of point-by point femtosecond laser inscription. It is shown that the spatio-temporal evolution of light and plasma patterns critically depend on input power. Subwavelength inscription corresponds to the supercritical propagation regimes when pulse power is several times self-focusing threshold. Experimental and numerical profiles show quantitative agreement.