Stability of Ca-montmorillonite hydrates: A computer simulation study

Classic simulations are used to study interlayer structure, swelling curves, and stability of Ca-montmorillonite hydrates. For this purpose, NPzzT$ and MuPzzT ensembles are sampled for ground level and given burial conditions. For ground level conditions, a double layer hydrate having 15.0 A of basal spacing is the predominant state for relative vapor pressures (p/po) ranging in 0.6-1.0. A triple hydrate counting on 17.9 A of interlaminar distance was also found stable for p/po=1.0. For low vapor pressures, the system may produce a less hydrated but still double layer state with 13.5 A or even a single layer hydrate with 12.2 A of interlaminar distance. This depends on the established initial conditions. On the other hand, the effect of burial conditions is two sided. It was found that it enhances dehydration for all vapor pressures except for saturation, where swelling is promoted.Comment: 8 pages, 9 figure

Aging after shear rejuvenation in a soft glassy colloidal suspension: evidence for two different regimes

The aging dynamics after shear rejuvenation in a glassy, charged clay suspension have been investigated through dynamic light scattering (DLS). Two different aging regimes are observed: one is attained if the sample is rejuvenated before its gelation and one after the rejuvenation of the gelled sample. In the first regime, the application of shear fully rejuvenates the sample, as the system dynamics soon after shear cessation follow the same aging evolution characteristic of normal aging. In the second regime, aging proceeds very fast after shear rejuvenation, and classical DLS cannot be used. An original protocol to measure an ensemble averaged intensity correlation function is proposed and its consistency with classical DLS is verified. The fast aging dynamics of rejuvenated gelled samples exhibit a power law dependence of the slow relaxation time on the waiting time.Comment: 7 pages, 6 figure

Shear Viscosity of Clay-like Colloids in Computer Simulations and Experiments

Dense suspensions of small strongly interacting particles are complex systems, which are rarely understood on the microscopic level. We investigate properties of dense suspensions and sediments of small spherical Al_2O_3 particles in a shear cell by means of a combined Molecular Dynamics (MD) and Stochastic Rotation Dynamics (SRD) simulation. We study structuring effects and the dependence of the suspension's viscosity on the shear rate and shear thinning for systems of varying salt concentration and pH value. To show the agreement of our results to experimental data, the relation between bulk pH value and surface charge of spherical colloidal particles is modeled by Debye-Hueckel theory in conjunction with a 2pK charge regulation model.Comment: 15 pages, 8 figure

Lime stabilisation for earthworks: a UK perspective

Lime stabilisation is a versatile technique applied during earthworks operations. Modern soil recycling units are much more efficient at pulverising fill material and intermixing the added binder/water than machinery available 20 years ago. While supplier innovation adds flexibility to the site working method, specifications have not been sufficiently updated to permit optimal application. This review paper details the physico-chemical changes instigated through the lime-clay soil reaction, updating previous reviews. It aims to assist scientific debate, current practitioners and future specification changes. For example, the application of the minimum 24 h mellowing periods (mandatory to UK specifications) with high reactivity, quicklime powders is concluded to cause increased air voids in the compacted fill. Increased air voids are associated with reduced long-term strength and potential volume change from water ingress, which is of particular concern for sulfate swelling. Shorter mellowing periods and/or use of hydrated lime may lesson this issue; however, a 'one size fits all' approach is discouraged in preference to site-specific methodologies refined to suit the fill material and project requirements. The discussion also summarises working methods which may lower the risk of sulfate swell and defines areas requiring further practical research

Irreversible Aging Dynamics and Generic Phase Behavior of Aqueous Suspensions of Laponite

In this work we study the aging behavior of aqueous suspension of Laponite having 2.8 weight % concentration using rheological tools. At various salt concentration all the samples demonstrate orientational order when observed using crossed polarizers. In rheological experiments we observe inherent irreversibility in the aging dynamics which forces the system not to rejuvenate to the same state in the shear melting experiment carried out at a later date since preparation. The extensive rheological experiments carried out as a function of time elapsed since preparation demonstrate the self similar trend in the aging behavior irrespective of the concentration of salt. We observe that the exploration of the low energy states as a function of aging time is only kinetically affected by the presence of salt. We estimate that the energy barrier to attain the low energy states decreases linearly with increase in the concentration of salt. The observed superposition of all the elapsed time and the salt concentration dependent data suggests that the aging that occurs in low salt concentration systems over a very long period is qualitatively similar to the aging behavior observed in systems with high salt concentration over a shorter period.Comment: 27 pages, 8 figures. Langmuir, in pres

Lime Cake as an Alternative Stabiliser for Loose Clayey Loams

Lime Cake (precipitated calcium carbonate PCC), a by-product of sugar production, is proposed as a stabiliser for improvement of loose silty clayey loams. Two inorganic pedogenic and organic precipitated calcium carbonate polymorphs are artificially synthesized into a base loosely compacted loamy soil. Formation, micromorphology, quality of cementing bonds, and physiochemical interactions in the interlayer are modelled at molecular level and verified by a suite of micro-analytical spectrometry techniques. Emphasis is put into determining the impacts of polysaccharides on soil strength and implications on soil pore anatomy. Erodibility, compressibility, volumetric change, and hydro-mechanical behaviour of base, and modified soils at yield and post-yield states are studied. Anomalies in suction-controlled post-yield stress–strain behaviour of modified soils are discussed and explained within the tenets of mechanics of composite soils with double porosity. PCC-reinforcement offers the closest possible packing at optimum water content. Desiccation cracking remains likely, but at relatively higher lower-bound water contents. Under low confinement levels and unsaturated state, strain-hardening prevails. Loss of shear strength on saturation is minimal. When saturated, PCC-reinforced soil develops substantially high levels of shear strength at all strain levels. Higher levels of confinement are needed for organic fibrous and onion-skin coating matters to effectively encrust the soil pore network; such high levels, however, leads to formation of an unwelcomed brittle, strain–softening stress–stress behaviour

Clay micromechanics : an analysis of elementary mechanisms of clay particle interactions to gain insight into compression behaviour of clay

The macroscopic response of geomaterials is controlled by the processes occurring at the microscale. Understanding these processes is key to interpret experimental data, understand fundamental modes of stress-strain behaviour, inform ‘continuum’ macroscopic constitutive models, and develop quantitative predictive tools based on Discrete Element Method (DEM) approaches. Unlike granular materials, mechanisms at the particle scale controlling macro-mechanical behaviour of clays are still largely ignored. This paper presents an analysis of elementary mechanisms of clay particle interactions with the aim of gaining an insight into behaviour of clay and advance the process of defining suitable contact laws to be implemented into DEM formulations

Development of novel adenoviral vectors to overcome challenges observed with HAdV-5 based constructs

Recombinant vectors based on human adenovirus serotype 5 (HAdV-5) have been extensively studied in pre-clinical models and clinical trials over the last two decades. However, the thorough understanding of the HAdV-5 interaction with human subjects has uncovered major concerns about its product applicability. High vector-associated toxicity and widespread pre-existing immunity have been shown to significantly impede the effectiveness of HAdV-5 mediated gene transfer. It is therefore that the in depth knowledge attained working on HAdV-5 is currently being used to develop alternative vectors. Here, we provide a comprehensive overview of data obtained in recent years disqualifying the HAdV-5 vector for systemic gene delivery as well as novel strategies being pursued to overcome the limitations observed with particular emphasis on the ongoing vectorization efforts to obtain vectors based on alternative serotypes