Process envelopes for stabilisation/solidification of contaminated soil using lime-slag blend.

PURPOSE: Stabilisation/solidification (S/S) has emerged as an efficient and cost-effective technology for the treatment of contaminated soils. However, the performance of S/S-treated soils is governed by several intercorrelated variables, which complicates the optimisation of the treatment process design. Therefore, it is desirable to develop process envelopes, which define the range of operating variables that result in acceptable performance. METHODS: In this work, process envelopes were developed for S/S treatment of contaminated soil with a blend of hydrated lime (hlime) and ground granulated blast furnace slag (GGBS) as the binder (hlime/GGBS = 1:4). A sand contaminated with a mixture of heavy metals and petroleum hydrocarbons was treated with 5%, 10% and 20% binder dosages, at different water contents. The effectiveness of the treatment was assessed using unconfined compressive strength (UCS), permeability, acid neutralisation capacity and contaminant leachability with pH, at set periods. RESULTS: The UCS values obtained after 28 days of treatment were up to ∼800 kPa, which is quite low, and permeability was ∼10(-8) m/s, which is higher than might be required. However, these values might be acceptable in some scenarios. The binder significantly reduced the leachability of cadmium and nickel. With the 20% dosage, both metals met the waste acceptance criteria for inert waste landfill and relevant environmental quality standards. CONCLUSIONS: The results show that greater than 20% dosage would be required to achieve a balance of acceptable mechanical and leaching properties. Overall, the process envelopes for different performance criteria depend on the end-use of the treated material.

New chiral E- and Z-isomers of the 1R,4R-2-arylidene-p-menthane-3-ones in induced cholesteric and ferroelectric liquid crystals

A novel pair of the E- and Z-isomeric 1R,4R-2-(4-heptyloxyphenyl)-benzylidene-p-menthan-3-ones has been prepared and the influence of distinctions in their molecular geometry on macroscopic properties of liquid crystal systems with the induced supra-molecular helical structure has been studied. The significantly lower helical twisting power of the chiral Z-isomer in comparison with that of E- one has been confirmed in the case of induced cholesteric systems based on 4-pentyl-4-cyanobiphenyl. The phase behavior and ferroelectric characteristics have been investigated for smectic-C* compositions based on the eutectic mixture of the homological 4-hexyloxyphenyl-4'-hexyloxy- and 4-hexyloxyphenyl-4'-octyloxybenzoates containing the novel isomeric chiral dopants. The spontaneous polarisation of the opposite signs induced by the isomeric chiral components has been revealed for the compositions studied. Distinctions in phase states, absolute values of the spontaneous polarization, smectic tilt angle and rotation viscosity of the systems obtained are discussed.

Microwave power effects on the properties of phosphorus-doped SiC:H films prepared using ECR-CVD

There has been a growing interest in hydrogenated silicon carbide films (SiC:H) prepared using the electron cyclotron resonance-chemical vapour deposition (ECR-CVD) technique. Using the ECR-CVD technique, SiC:H films have been prepared from a mixture of methane, silane and hydrogen, with phosphine as the doping gas. The effects of changes in the microwave power (from 150 to 900 W) on the film properties were investigated in a series of phosphorus-doped SiC:H films. In particular, the changes in the deposition rate, optical bandgap, activation energy and conductivity were investigated in conjunction with results from Raman scattering and Fourier transform infra-red (FTIR) analysis. It was found that increase in the microwave power has the effect of enhancing the formation of the silicon microcrystalline phase in the amorphous matrix of the SiC:H films. This occurs in correspondence to a rapid increase in the conductivity and a reduction in the activation energy, both of which exhibit small variations in samples deposited at microwave powers exceeding 500 W. Analysis of IR absorption results suggests that hydrogen is bonded to silicon in the Si-H stretching mode and to carbon in the sp3 CHn rocking/wagging and bending mode in films deposited at higher microwave powers.

Nonparametric mixtures of factor analyzers

The mixtures of factor analyzers (MFA) model allows data to be modeled as a mixture of Gaussians with a reduced parametrization. We present the formulation of a nonparametric form of the MFA model, the Dirichlet process MFA (DPMFA). The proposed model can be used for density estimation or clustering of high dimensiona data. We utilize the DPMFA for clustering the action potentials of different neurons from extracellular recordings, a problem known as spike sorting. DPMFA model is compared to Dirichlet process mixtures of Gaussians model (DPGMM) which has a higher computational complexity. We show that DPMFA has similar modeling performance in lower dimensions when compared to DPGMM, and is able to work in higher dimensions. ©2009 IEEE.

CFD-DEM simulation of propagation of sound waves in fluid particles fluidised medium

In this work, speed of sound in 2 phase mixture has been explored using CFD-DEM (Computational Fluid Dynamcis - Discrete Element Modelling). In this method volume averaged Navier Stokes, continuity and energy equations are solved for fluid. Particles are simulated as individual entities; their behaviour is captured by Newton's laws of motion and classical contact mechanics. Particle-fluid interaction is captured using drag laws given in literature.The speed of sound in a medium depends on physical properties. It has been found experimentally that speed of sound drops significantly in 2 phase mixture of fluidised particles because of its increased density relative to gas while maintaining its compressibility. Due to the high rate of heat transfer within 2 phase medium as given in Roy et al. (1990), it has been assumed that the fluidised gas-particle medium is isothermal.The similar phenomenon has been tried to be captured using CFD-DEM numerical simulation. The disturbance is introduced and fundamental frequency in the medium is noted to measure the speed of sound for e.g. organ pipe. It has been found that speed of sound is in agreement with the relationship given in Roy et al. (1990). Their assumption that the system is isothermal also appears to be valid.

Metal Retention Experiments for the Design of Soil-Mix Technology Permeable Reactive Barriers

Soil-mix technology is effective for the construction of permeable reactive barriers (PRBs) for in situ groundwater treatment. The objective of this study was to perform initial experiments for the design of soil-mix technology PRBs according to (i) sorption isotherm, (ii) reaction kinetics and (iii) mass balance of the contaminants. The four tested reactive systems were: (i) a granular zeolite (clinoptilolite-GZ), (ii) a granular organoclay (GO), (iii) a 1:1-mixture GZ and model sandy clayey soil and (iv) a 1:1:1-mixture of GZ, GO and model soil. The laboratory experiments consisted of batch tests (volume 900mL and sorbent mass 18g) with a multimetal solution of Pb, Cu, Zn, Cd and Ni. For the adsorption experiment, the initial concentrations ranged from 0.01 to 0.5mM (2.5 to 30mg/L). The maximum metal retention was measured in a batch test (300mg/L for each metal, volume 900mL, sorbent mass 90-4.5g). The reactive material efficiency order was found to be GZ>GZ-soil mix>GZ-soil-GO mix>GO. Langmuir isotherms modelled the adsorption, even in presence of a mixed cations solution. Adsorption was energetically favourable and spontaneous in all cases. Metals were removed according to the second order reaction kinetics; GZ and the 1:1-mix were very similar. The maximum retention capacity was 0.1-0.2mmol/g for Pb in the presence of clinoptilolite; for Cu, Zn, Cd and Ni, it was below 0.05mmol/g for the four reactive systems. Mixing granular zeolite, organoclay and model soil increased the chemisorption. Providing that GZ is reactive enough for the specific conditions, GZ can be mixed to obtain the required sorption. Granular clinoptilolite addition to soil is recommended for PRBs for metal contaminated groundwater. The laboratory experiments consisted of batch tests with a multimetal solution of Pb, Cu, Zn, Cd and Ni. The four reactive materials chosen were granular zeolite, clinoptilolite and model sandy clayey soil, granular organoclay and a mix of clinoptilolite, model soil and organoclay. The reactive material efficiency order was found to be granular clinoptilolite>clinoptilolite-soil mix>clinoptilolite-soil-organoclay mix>granular organoclay. © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The microstructure and mechanical properties of ball-milled stainless steel powder: The effect of hot-pressing vs. laser sintering

The microstructure and mechanical properties of sintered stainless steel powder, of composition AISI 420, have been measured. Ball-milled powder comprising nanoscale grains was sintered to bulk specimens by two alternative routes: hot-pressing and microlaser sintering. The laser-sintered alloy has a porosity of 6% and comprises a mixture of delta ferrite and tempered martensite, and the relative volume fraction varies along the axis of the specimen due to a thermal cycle that evolves with progressive deposition. In contrast, the hot-pressed alloy has a porosity of 0.7% and exhibits a martensitic lath structure with carbide particles at the boundaries of the prior austenite grains. These differences in microstructure lead to significant differences in mechanical properties. For example, the uniaxial tensile strength of the hot-pressed material is one-half of its compressive strength, due to void initiation at the carbide particles at the prior austenite grain boundaries. Nanoindentation measurements reveal a size effect in hardness and also reveal the sensitivity of hardness to the presence of mechanical polishing and electropolishing. © 2011 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

The performance of closed reactor grade plutonium-thorium fuel cycles in reduced-moderation pressurised water reactors

The production of long-lived transuranic (TRU) waste is a major disadvantage of fission-based nuclear power. Previous work has indicated that TRU waste can be virtually eliminated in a pressurised water reactor (PWR) fuelled with a mixture of thorium and TRU waste, when all actinides are returned to the reactor after reprocessing. However, the optimal configuration for a fuel assembly operating this fuel cycle is likely to differ from the current configuration. In this paper, the differences in performance obtained in a reduced-moderation PWR operating this fuel cycle were investigated using WIMS. The chosen configuration allowed an increase of at least 20% in attainable burn-up for a given TRU enrichment. This will be especially important if the practical limit on TRU enrichment is low. The moderator reactivity coefficients limit the enrichment possible in the reactor, and this limit is particularly severe if a negative void coefficient is required for a fully voided core. Several strategies have been identified to mitigate this. Specifically, the control system should be designed to avoid a detrimental effect on moderator reactivity coefficients. The economic viability of this concept is likely to be dependent on the achievable thermal-hydraulic operating conditions. © 2012 Elsevier Ltd. All rights reserved.

The influence of matrix integrity on stress-fiber remodeling in 3D.

Matrix anisotropy is important for long term in vivo functionality. However, it is not fully understood how to guide matrix anisotropy in vitro. Experiments suggest actin-mediated cell traction contributes. Although F-actin in 2D displays a stretch-avoidance response, 3D data are lacking. We questioned how cyclic stretch influences F-actin and collagen orientation in 3D. Small-scale cell-populated fibrous tissues were statically constrained and/or cyclically stretched with or without biochemical agents. A rectangular array of silicone posts attached to flexible membranes constrained a mixture of cells, collagen I and matrigel. F-actin orientation was quantified using fiber-tracking software, fitted using a bi-model distribution function. F-actin was biaxially distributed with static constraint. Surprisingly, uniaxial cyclic stretch, only induced a strong stretch-avoidance response (alignment perpendicular to stretching) at tissue surfaces and not in the core. Surface alignment was absent when a ROCK-inhibitor was added, but also when tissues were only statically constrained. Stretch-avoidance was also observed in the tissue core upon MMP1-induced matrix perturbation. Further, a strong stretch-avoidance response was obtained for F-actin and collagen, for immediate cyclic stretching, i.e. stretching before polymerization of the collagen. Results suggest that F-actin stress-fibers avoid cyclic stretch in 3D, unless collagen contact guidance dictates otherwise.

The influence of matrix integrity on stress-fiber remodeling in 3D

Matrix anisotropy is important for long term in vivo functionality. However, it is not fully understood how to guide matrix anisotropy in vitro. Experiments suggest actin-mediated cell traction contributes. Although F-actin in 2D displays a stretch-avoidance response, 3D data are lacking. We questioned how cyclic stretch influences F-actin and collagen orientation in 3D. Small-scale cell-populated fibrous tissues were statically constrained and/or cyclically stretched with or without biochemical agents. A rectangular array of silicone posts attached to flexible membranes constrained a mixture of cells, collagen I and matrigel. F-actin orientation was quantified using fiber-tracking software, fitted using a bi-model distribution function. F-actin was biaxially distributed with static constraint. Surprisingly, uniaxial cyclic stretch, only induced a strong stretch-avoidance response (alignment perpendicular to stretching) at tissue surfaces and not in the core. Surface alignment was absent when a ROCK-inhibitor was added, but also when tissues were only statically constrained. Stretch-avoidance was also observed in the tissue core upon MMP1-induced matrix perturbation. Further, a strong stretch-avoidance response was obtained for F-actin and collagen, for immediate cyclic stretching, i.e. stretching before polymerization of the collagen. Results suggest that F-actin stress-fibers avoid cyclic stretch in 3D, unless collagen contact guidance dictates otherwise. © 2012 Elsevier Ltd.

The effect of addition of ZrO2 to Fe2O3 for hydrogen production by chemical looping

In this paper, a synthetic mixture of ZrO2 and Fe 2O3 was prepared by coprecipitation for use in chemical looping and hydrogen production. Cycling experiments in a fluidized bed showed that a material composed of 30 mol % ZrO2 and 70 mol % Fe 2O3 was capable of producing hydrogen with a consistent yield of 90 mol % of the stoichiometric amount over 20 cycles of reduction and oxidation at 1123 K. Here, the iron oxide was subjected to cycles consisting of nearly 100% reduction to Fe followed by reoxidation (with steam or CO 2 and then air) to Fe2O3. There was no contamination by CO of the hydrogen produced, at a lower detection limit of 500 ppm, when the conversion of Fe3O4 to Fe was kept below 90 mol %. A preliminary investigation of the reaction kinetics confirmed that the ZrO2 support does not inhibit rates of reaction compared with those observed with iron oxide alone. © 2012 American Chemical Society.

Cement-fly ash stabilisation/solidification of contaminated soil: Performance properties and initiation of operating envelopes

This study was aimed at evaluating the mechanical and pH-dependent leaching performance of a mixed contaminated soil treated with a mixture of Portland cement (CEMI) and pulverised fuel ash (PFA). It also sought to develop operating envelopes, which define the range(s) of operating variables that result in acceptable performance. A real site soil with low contaminant concentrations, spiked with 3000mg/kg each of Cd, Cu, Pb, Ni and Zn, and 10,000mg/kg of diesel, was treated with one part CEMI and four parts PFA (CEMI:PFA=1:4) using different binder and water contents. The performance was assessed over time using unconfined compressive strength (UCS), hydraulic conductivity, acid neutralisation capacity (ANC) and pH-dependent leachability of contaminants. With binder dosages ranging from 5% to 20% and water contents ranging from 14% to 21% dry weight, the 28-day UCS was up to 500kPa and hydraulic conductivity was around 10-8m/s. With leachant pH extremes of 7.2 and 0.85, leachability of the contaminants was in the range: 0.02-3500mg/kg for Cd, 0.35-1550mg/kg for Cu, 0.03-92mg/kg for Pb, 0.01-3300mg/kg for Ni, 0.02-4010mg/kg for Zn, and 7-4884mg/kg for total petroleum hydrocarbons (TPHs), over time. Design charts were produced from the results of the study, which show the water and/or binder proportions that could be used to achieve relevant performance criteria. The charts would be useful for the scale-up and design of stabilisation/solidification (S/S) treatment of similar soil types impacted with the same types of contaminants. © 2013 Elsevier Ltd.

Recycle of transuranium elements in light water reactors for reduction of geological storage requirements

This paper presents results of a feasibility study aimed at developing a zero-transuranic-discharge fuel cycle based on the U-Th-TRU ternary cycle. The design objective is to find a fuel composition (mixture of thorium, enriched uranium, and recycled transuranic components) and fuel management strategy resulting in an equilibrium charge-discharge mass flow. In such a fuel cycle scheme, the quantity and isotopic vector of the transuranium (TRU) component is identical at the charge and discharge time points, thus allowing the whole amount of the TRU at the end of the fuel irradiation period to be separated and reloaded into the following cycle. The TRU reprocessing activity losses are the only waste stream that will require permanent geological storage, virtually eliminating the long-term radiological waste of the commercial nuclear fuel cycle. A detailed three-dimensional full pressurized water reactor (PWR) core model was used to analyze the proposed fuel composition and management strategy. The results demonstrate the neutronic feasibility of the fuel cycle with zero-TRU discharge. The amount of TRU and enriched uranium loaded reach equilibrium after about four TRU recycles. The reactivity coefficients were found to be within a range typical for a reference PWR core. The soluble boron worth is reduced by a factor of ∼2 from a typical PWR value. Nevertheless, the results indicate the feasibility of an 18-month fuel cycle design with an acceptable beginning-of-cycle soluble boron concentration even without application of burnable poisons.

Motor learning of novel dynamics is not represented in a single global coordinate system: evaluation of mixed coordinate representations and local learning.

Successful motor performance requires the ability to adapt motor commands to task dynamics. A central question in movement neuroscience is how these dynamics are represented. Although it is widely assumed that dynamics (e.g., force fields) are represented in intrinsic, joint-based coordinates (Shadmehr R, Mussa-Ivaldi FA. J Neurosci 14: 3208-3224, 1994), recent evidence has questioned this proposal. Here we reexamine the representation of dynamics in two experiments. By testing generalization following changes in shoulder, elbow, or wrist configurations, the first experiment tested for extrinsic, intrinsic, or object-centered representations. No single coordinate frame accounted for the pattern of generalization. Rather, generalization patterns were better accounted for by a mixture of representations or by models that assumed local learning and graded, decaying generalization. A second experiment, in which we replicated the design of an influential study that had suggested encoding in intrinsic coordinates (Shadmehr and Mussa-Ivaldi 1994), yielded similar results. That is, we could not find evidence that dynamics are represented in a single coordinate system. Taken together, our experiments suggest that internal models do not employ a single coordinate system when generalizing and may well be represented as a mixture of coordinate systems, as a single system with local learning, or both.

CO2-gasification of a lignite coal in the presence of an iron-based oxygen carrier for chemical-looping combustion

Chemical-looping combustion (CLC) has the inherent property of separating the product CO2 from flue gases. Instead of air, it uses an oxygen carrier, usually in the form of a metal oxide, to provide oxygen for combustion. All techniques so far proposed for chemical looping with solid fuels involve initially the gasification of the solid fuel in order for the gaseous products to react with the oxygen carrier. Here, the rates of gasification of coal were compared when gasification was undertaken in a fluidised bed of either (i) an active Fe-based oxygen carrier used for chemical looping or (ii) inert sand. This enabled an examination of the ability of chemical looping materials to enhance the rate of gasification of solid fuels. Batch gasification and chemical-looping combustion experiments with a German lignite and its char are reported, using an electrically-heated fluidised bed reactor at temperatures from 1073 to 1223 K. The fluidising gas was CO2 in nitrogen. The kinetics of the gasification were found to be significantly faster in the presence of the oxygen carrier, especially at temperatures above 1123 K. A numerical model was developed to account for external and internal mass transfer and for the effect of the looping agent. The model also included the effects of the evolution of the pore structure at different conversions. The presence of Fe2O3 led to an increase in the rate of gasification because of the rapid oxidation of CO by the oxygen carrier to CO2. This resulted in the removal of CO and maintained a higher mole fraction of CO2 in the mixture of gas around the particle of char, i.e. within the mass transfer boundary layer surrounding the particle. This effect was most prominent at about 20% conversion when (i) the surface area for reaction was at its maximum and (ii) because of the accompanying increase in porosity and pore size, intraparticle resistance to gas mass transfer within the particle of char had fallen, compared with that in the initial particle. Excellent agreement was observed between the rates predicted by the numerical model and those observed experimentally. ©2013 Elsevier Ltd. All rights reserved.