Metakaolin as a cement extender

The effect of 10% and 20% replacement metakaolin on a number of aspects of hydration chemistry and service performance of ordinary Portland cement pastes has been investigated. The analysis of expressed pore solutions has revealed that metakaolin-blended specimen pastes possess enhanced chloride binding capacities and reduced pore solution pH values when compared with their unblended counterparts. The implications of the observed changes in pore solution chemistry with respect to chloride induced reinforcement corrosion and the reduction in expansion associated with the alkali aggregate reaction are discussed. Differential thermal analysis, mercury intrusion porosimetry, and nuclear magnetic resonance spectroscopy have been employed in the analysis of the solid phase. It is suggested that hydrated gehlenite (a product of pozzolanic reaction) is operative in the removal and solid state binding of chloride ions from the pore solution of metakaolin-blended pastes. Diffusion coefficients obtained in a non-steady state chloride ion diffusion investigation have indicated that cement pastes containing 10% and 20% replacement metakaolin exhibit superior resistance to the penetration of chloride ions in comparison with those of plain OPC of the same water:cement ratio. The chloride induced corrosion behaviour of cement paste samples, of water:cement ratio 0.4, containing 0% , 10%, and 20% replacement metakaolin, has been monitored using the linear polarization technique. No significant corrosion of embedded mild steel was observed over a 200 day period.

Technology of repair for corroded reinforced concrete

A number of factors relating to various methods of repair for chloride initiated corrosion damage of reinforced concrete have been studied. A novel methodology has been developed to facilitate the measurement of macro and micro-cell corrosion rates for steel electrodes embedded in mortar prisms containing a chloride gradient. The galvanic bar specimen comprised electrically isolatable segmental mild steel electrodes and was constructed such that macro-cell corrosion currents were determinable for a number of electrode combinations. From this, the conditions giving rise to an incipient anode were established. The influence of several reinforcement and substrate primer systems upon macro-cell corrosion, arising from an incipient anode, within a patch repair have been investigated. Measurements of electrochemical noise were made in order to investigate the suitability of the technique as an on-site means of assessing corrosion activity within chloride contaminated reinforced concrete. For this purpose the standard deviation of potential noise was compared to macro-cell galvanic current data and micro-cell corrosion intensity determined by linear polarisation. Hydroxyl ion pore solution analyses were carried out on mortar taken from cathodically protected specimens. These specimens, containing sodium chloride, were cathodically protected over a range of polarisation potentials. Measurement of the hydroxyl ion concentrations were made in order to examine the possibility of alkali-silica reactions initiated by cathodic protection of reinfored concrete. A range of mortars containing a variety of generic type additives were examined in order to establish their resistances to chloride ion diffusion. The effect of surfactant addition rate was investigated within a cement paste containing various dosages of naphthalene sulphonate.

Corrosion and passivation of steel in concrete

A study of several chemical and electrochemical factors which affect the behaviour of embedded steel in cement pastes and concrete has been made. The effects of internal and external sources of chloride ions on the pore solution chemistry of Portland cement pastes, with and without additions of anodic corrosion inhibitors, have been studied using a pore solution expression device which has enabled samples of pore solution to be expressed from hardened cement pastes and analysed for various ionic species. Samples of pure alite and tricalcium aluminate have been prepared and characterised with respect to morphology, free lime content and fineness. Kinetics of diffusion of chloride ions in hardened pastes of alite and alite blended with tricalcium aluminate have been investigated and an activation energy obtained for the diffusion process in alite. The pore structures of the hardened pastes and the chloride ion binding capacity of alite have also been determined. Concrete cylinders containing embedded steel with four different surface conditions were exposed to various environments. The electrochemical behaviour of the steel was monitored during the period of exposure by means of rest potential measurements and the steel corrosion products analysed before and after being embedded. An examination was made of the nature of the interfacial zones produced between the embedded steel and cement. Rest potential measurements were monitored for steel embedded in alite paste in the presence of chloride ions and cement paste containing various levels of inhibitors in combination with chloride ions. In the latter case the results were supported by polarisation resistance determinations.

Quantitative interpretation of diffusion-ordered NMR spectra:can we rationalize small molecule diffusion coefficients?

Appealingly simple: A new method is described that allows the diffusion coefficient of a small molecule to be estimated given only the molecular weight and the viscosity of the solvent used. This method makes possible the quantitative interpretation of the diffusion domain of diffusion-ordered NMR spectra (see picture). © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

MRI pressure and stress measurement in novel homogeneous soft solids

This paper presents MRI measurements of a novel semi solid MR contrast agent to pressure. The agent is comprised of potassium chloride cross linked carageenan gum at a concentration of 2% w/v, with micron size lipid coated bubbles of air at a concentration of 3% v/v. The choice for an optimum suspending medium, the methods of production and the preliminary MRI results are presented herein. The carageenan gum is shown to be ideally elastic for compressions relating to volume changes less than 15%, in contrast to the inelastic gellan gum also tested. Although slightly lower than that of gellan gum, carageenan has a water diffusion coefficient of 1.72×10-9 m2.s-1 indicating its suitability to this purpose. RARE imaging is performed whilst simultaneously compressing test and control samples and a maximum sensitivity of 1.6% MR signal change per % volume change is found which is shown to be independent of proton density variations due to the presence of microbubbles and compression. This contrast agent could prove useful for numerous applications, and particularly in chemical engineering. More generally the method allows the user to non-invasively image with MRI any process that causes, within the solid, local changes either in bubble size or bubble shape. © 2008 American Institute of Physics.

Co3O4 nanostructures with a high rate performance as anode materials for lithium-ion batteries, prepared via book-like cobalt-organic frameworks

The self-assembly of cobalt coordination frameworks (Co-CPs) with a two-dimensional morphology is demonstrated by a solvothermal method. The morphology of the Co-CPs has been controlled by various solvothermal conditions. The two-dimensional nanostructures agglomerated by Co3O4 nanoparticles remained after the pyrolysis of the Co-CPs. The as-synthesized Co3O4 anode material is characterized by cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS) and galvanostatic charge-discharge measurements. The morphology of Co3O4 plays a crucial role in the high performance anode materials for lithium batteries. The Co3O4 nanoparticles with opened-book morphology deliver a high capacity of 597 mA h g-1 after 50 cycles at a current rate of 800 mA g-1. The opened-book morphology of Co3O4 provides efficient lithium ion diffusion tunnels and increases the electrolyte/Co3O4 contact/interfacial area. At a relatively high current rate of 1200 mA g-1, Co3O4 with opened-book morphology delivers an excellent rate capability of 574 mA h g-1.

Osmotic dehydration in plant tissues

The primary aim of the thesis is to provide a comprehensive investigation of the osmotic dehydration processes in plant tissue. Effort has been concentrated on the modelling for simulating the processes. Two mathematical models for simulating the mass transfer during osmotic dehydration processes in plant tissues are developed and verified using existing experimental data. Both models are based on the mechanism of diffusion and convection of any mobile material that can transport in plant tissues. The mass balance equation for the transport of each constituent is established separately for intracellular and extra-cellular volumes with taking into account the mass transfer across the cell membrane the intracellular and extra-cellular volumes and the shrinkage of the whole tissue. The contribution from turgor pressure is considered in both models. Model two uses Darcy’s law to build the relation between shrinkage velocity and hydrostatic pressure in each volume because the plant tissue can be considered as the porous medium. Moreover, it has been extended to solve the multi-dimensional problems. A lot of efforts have been made to the parameter study and the sensitivity analyses. The parameters investigated including the concentration of the osmotic solution, diffusion coefficient, permeability of the cell membrane, elastic modulus of the cell wall, critical cell volume etc. The models allow us to quantitatively simulate the time evolution of intracellular and extra-cellular volumes as well as the time evolution of concentrations in each cross-section.

Cathodic protection of reinforced concrete:anodic processes in cements and related electrolytes

The nature and kinetics of electrode reactions and processes occurring for four lightweight anode systems which have been utilised in reinforced concrete cathodic protection systems have been studied. The anodes investigated were flame sprayed zinc, conductive paint and two activated titanium meshes. The electrochemical properties of each material were investigated in rapidly stirred de-oxygenated electrolytes using anodic potentiodynamic polarisation. Conductive coating electrodes were formed on glass microscope slides, whilst mesh strands were immersed directly. Oxygen evolution occurred preferentially for both mesh anodes in saturated Ca (OH)2/CaC12 solutions but was severely inhibited in less alkaline solutions and significant current only passed in chloride solutions. The main reactions for conductive paint was based on oxygen evolution in all electrolytes, although chlorides increased the electrical activity. Self-corrosion of zinc was controlled by electrolyte composition and the experimental set-up, chlorides increasing the electrical activity. Impressed current cathodic protection was applied to 25 externally exposed concrete slabs over a period of 18 months to investigate anode degradation mechanisms at normal and high current densities. Specimen chloride content, curing and reinforcement depth were also variables. Several destructive and non-destructive methods for assessing the performance of anodes were evaluated including a site instrument for quantitative "instant-off- potential measurements. The impact of cathodic protection on the concrete substrate was determined for a number of specimens using appropriate methods. Anodic degradation rates were primarily influenced by current density, followed by cemendtious alkalinity, chloride levels and by current distribution. Degradation of cementitious overlays and conductive paint substrates proceeded by sequential neutralisation of cement phases, with some evidence of paint binder oxidation. Sprayed zinc progressively formed an insulating layer of hydroxide complexes, which underwent pitting_ attack in the presence of sufficient chlorides, whilst substrate degradation was minimal. Adhesion of all anode systems decreased with increasing current density. The influence of anode material on the ionic gradients which can develop during cathodic protection was investigated. A constant current was passed through saturated cement paste prisms containing calcium chloride to central cathodes via anodes applied or embedded at each end. Pore solution was obtained from successive cut paste slices for anion and cation analyses. Various experimental errors reduced the value of the results. Characteristic S-shaped profiles were not observed and chloride ion profiles were ambiguous. Mesh anode specimens were significantly more durable than the conductive coatings in the high humidity environment. Limited results suggested zinc ion migration to the cathode region. Electrical data from each investigation clearly indicated a decreasing order of anode efficiency by specific anode material.

SO2 sequestration in large volcanic eruptions:high-temperature scavenging by tephra

It is well accepted that the climate impact of large explosive volcanic eruptions results from reduction of solar radiation following atmospheric conversion of magmatic SO emissions into HSO aerosols. Thus, understanding the fate of SO in the eruption plume is crucial for better assessing volcanic forcing of climate. Here we focus on the potential of tephra to interact with and remove SO gas from the eruptive plume. Scavenging of SO by tephra is generally assumed to be driven by in-plume, low-temperature reactions between HSO condensates and tephra particles. However, the importance of SO gas-tephra interaction above the dew point temperature of HSO (190-200°C) has never been constrained. Here we report the results of an experimental study where silicate glasses with representative volcanic compositions were exposed to SO in the temperature range 25-800°C. We show that above 600°C, the uptake of SO on glass exhibits optimal efficiency and emplaces surficial CaSO deposits. This reaction is sustained via Ca diffusion from the bulk to the surface of the glass particles. At 800°C, the diffusion coefficient for Ca in the glasses was in the range 10-10cms. We suggest that high temperature SO scavenging by glass-rich tephra proceeds by the same Ca diffusion-driven mechanism. Using a simple mathematical model, we estimated SO scavenging efficiencies at 800°C varying from

The critical role of intracavity dynamics in high-power mode-locked fiber lasers

We present a theoretical description of the generation of ultra-short, high-energy pulses in two laser cavities driven by periodic spectral filtering or dispersion management. Critical in driving the intra-cavity dynamics is the nontrivial phase profiles generated and their periodic modification from either spectral filtering or dispersion management. For laser cavities with a spectral filter, the theory gives a simple geometrical description of the intra-cavity dynamics and provides a simple and efficient method for optimizing the laser cavity performance. In the dispersion managed cavity, analysis shows the generated self-similar behavior to be governed by the porous media equation with a rapidly-varying, mean-zero diffusion coefficient whose solution is the well-known Barenblatt similarity solution with parabolic profile. © 2010 Copyright SPIE - The International Society for Optical Engineering.

Intracavity dynamics in mode-locked lasers

We present a theoretical description of the generation of ultra-short, high-energy pulses in two laser cavities driven by periodic spectral filtering or dispersion management. Critical in driving the intra-cavity dynamics is the nontrivial phase profiles generated and their periodic modification from either spectral filtering or dispersion management. For laser cavities with a spectral filter, the theory gives a simple geometrical description of the intra-cavity dynamics and provides a simple and efficient method for optimizing the laser cavity performance. In the dispersion managed cavity, analysis shows the generated self-similar behavior to be governed by the porous media equation with a rapidly-varying, mean-zero diffusion coefficient whose solution is the well-known Barenblatt similarity solution with parabolic profile. © 2010 American Institute of Physics.

Intracavity dynamics for power and energy enhancement in mode-locked lasers

We present a theoretical description of the generation of ultra-short, high-energy pulses in two laser cavities driven by periodic spectral filtering or dispersion management. Critical in driving the intra-cavity dynamics is the nontrivial phase profiles generated and their periodic modification from either spectral filtering or dispersion management. For laser cavities with a spectral filter, the theory gives a simple geometrical description of the intra-cavity dynamics and provides a simple and efficient method for optimizing the laser cavity performance. In the dispersion managed cavity, analysis shows the generated self-similar behavior to be governed by the porous media equation with a rapidly-varying, mean-zero diffusion coefficient whose solution is the well-known Barenblatt similarity solution with parabolic profile.

Ion bombardment induced compositional changes in compound semiconductor surfaces studied by XPS combined with LEISS

Surface compositional change of GaP, GaAs, GaSb, InP, InAs, InSb, GeSi and CdSe single crystals due to low keV noble gas ion beam bombardment has been investigated by combining X-ray Photoelectron Spectroscopy (XPS) and Low Energy Ion Scattering Spectroscopy (LEISS). The purpose of using this complementary analytical method is to obtain more complete experimental evidence of ion beam modification in surfaces of compound semiconductors and GeSi alloy to improve the understanding of the mechanisms responsible for these effects. Before ion bombardment the sample surfaces were analysed nondestructively by Angular Resolved XPS (ARXPS) and LEISS to get the initial distribution of surface composition. Ion bombardment experiments were carried out using 3keV argon ions with beam current of 1μA for a period of 50 minutes, compositional changes in the surfaces of compound semiconductors and GeSi alloy were monitored with normal XPS. After ion bombardment the surfaces were re-examined with ARXPS and LEISS. Both XPS and LEISS results showed clearly that ion bombardment will change the compositional distribution in the compound semiconductor and GeSi surfaces. In order to explain the observed experimental results, two major theories in this field, Sigmund linear collision cascade theory and the thermodynamic models based on bombardment induced Gibbsian surface segregation and diffusion, were investigated. Computer simulation using TRIM code was also carried out for assistance to the theoretical analysis. Combined the results obtained from XPS and LEISS analyses, ion bombardment induced compositional changes in compound semiconductor and GeSi surfaces are explained in terms of the bombardment induced Gibbsian surface segregation and diffusion.

Effect of the Hofmeister anions upon the swelling of a self-assembled pH-responsive hydrogel

We report the effect of a range of monovalent sodium salts on the molecular equilibrium swelling of a simple synthetic microphase separated poly(methyl methacrylate)-block-poly(2-(diethylamino)ethyl methacrylate)-block-poly(methyl methacrylate) (PMMA88-b-PDEA223-b-PMMA88) pH-responsive hydrogel. Sodium acetate, sodium chloride, sodium bromide, sodium iodide, sodium nitrate and sodium thiocyanate were selected for study at controlled ionic strength and pH; all salts are taken from the Hofmeister series (HS). The influence of the anions on the expansion of the hydrogel was found to follow the reverse order of the classical HS. The expansion ratio of the gel measured in solutions containing the simple sodium halide salts (NaCl, NaBr, and NaI) was found to be strongly related to parameters which describe the interaction of the ion with water; surface charge density, viscosity coefficient, and entropy of hydration. A global study which also included nonspherical ions (NaAce, NaNO3 and NaSCN) showed the strongest correlation with the viscosity coefficient. Our results are interpreted in terms of the Collins model,(1) where larger ions have more mobile water in the first hydration cage immediately surrounding the gel, therefore making them more adhesive to the surface of the stationary phase of the gel and ultimately reducing the level of expansion.