Physical and chemical kinetics of structural build-up of cement suspensions

Abstract : The structural build-up of fresh cement-based materials has a great impact on their structural performance after casting. Accordingly, the mixture design should be tailored to adapt the kinetics of build-up given the application on hand. The rate of structural build-up of cement-based suspensions at rest is a complex phenomenon affected by both physical and chemical structuration processes. The structuration kinetics are strongly dependent on the mixture’s composition, testing parameters, as well as the shear history. Accurate measurements of build-up rely on the efficiency of the applied pre-shear regime to achieve an initial well-dispersed state as well as the applied stress during the liquid-solid transition. Studying the physical and chemical mechanisms of build-up of cement suspensions at rest can enhance the fundamental understanding of this phenomenon. This can, therefore, allow a better control of the rheological and time-dependent properties of cement-based materials. The research focused on the use of dynamic rheology in investigating the kinetics of structural build-up of fresh cement pastes. The research program was conducted in three different phases. The first phase was devoted to evaluating the dispersing efficiency of various disruptive shear techniques. The investigated shearing profiles included rotational, oscillatory, and combination of both. The initial and final states of suspension’s structure, before and after disruption, were determined by applying a small-amplitude oscillatory shear (SAOS). The difference between the viscoelastic values before and after disruption was used to express the degree of dispersion. An efficient technique to disperse concentrated cement suspensions was developed. The second phase aimed to establish a rheometric approach to dissociate and monitor the individual physical and chemical mechanisms of build-up of cement paste. In this regard, the non-destructive dynamic rheometry was used to investigate the evolutions of both storage modulus and phase angle of inert calcium carbonate and cement suspensions. Two independent build-up indices were proposed. The structural build-up of various cement suspensions made with different cement contents, silica fume replacement percentages, and high-range water reducer dosages was evaluated using the proposed indices. These indices were then compared to the well-known thixotropic index (Athix.). Furthermore, the proposed indices were correlated to the decay in lateral pressure determined for various cement pastes cast in a pressure column. The proposed pre-shearing protocol and build-up indices (phases 1 and 2) were then used to investigate the effect of mixture’s parameters on the kinetics of structural build-up in phase 3. The investigated mixture’s parameters included cement content and fineness, alkali sulfate content, and temperature of cement suspension. Zeta potential, calorimetric, spectrometric measurements were performed to explore the corresponding microstructural changes in cement suspensions, such as inter-particle cohesion, rate of Brownian flocculation, and nucleation rate. A model linking the build-up indices and the microstructural characteristics was developed to predict the build-up behaviour of cement-based suspensions The obtained results showed that oscillatory shear may have a greater effect on dispersing concentrated cement suspension than the rotational shear. Furthermore, the increase in induced shear strain was found to enhance the breakdown of suspension’s structure until a critical point, after which thickening effects dominate. An effective dispersing method is then proposed. This consists of applying a rotational shear around the transitional value between the linear and non-linear variations of the apparent viscosity with shear rate, followed by an oscillatory shear at the crossover shear strain and high angular frequency of 100 rad/s. Investigating the evolutions of viscoelastic properties of inert calcite-based and cement suspensions and allowed establishing two independent build-up indices. The first one (the percolation time) can represent the rest time needed to form the elastic network. On the other hand, the second one (rigidification rate) can describe the increase in stress-bearing capacity of formed network due to cement hydration. In addition, results showed that combining the percolation time and the rigidification rate can provide deeper insight into the structuration process of cement suspensions. Furthermore, these indices were found to be well-correlated to the decay in the lateral pressure of cement suspensions. The variations of proposed build-up indices with mixture’s parameters showed that the percolation time is most likely controlled by the frequency of Brownian collisions, distance between dispersed particles, and intensity of cohesion between cement particles. On the other hand, a higher rigidification rate can be secured by increasing the number of contact points per unit volume of paste, nucleation rate of cement hydrates, and intensity of inter-particle cohesion.

Numerical simulation of a new two-dimensional variable-order fractional percolation equation in non-homogeneous porous media

Percolation flow problems are discussed in many research fields, such as seepage hydraulics, groundwater hydraulics, groundwater dynamics and fluid dynamics in porous media. Many physical processes appear to exhibit fractional-order behavior that may vary with time, or space, or space and time. The theory of pseudodifferential operators and equations has been used to deal with this situation. In this paper we use a fractional Darcys law with variable order Riemann-Liouville fractional derivatives, this leads to a new variable-order fractional percolation equation. In this paper, a new two-dimensional variable-order fractional percolation equation is considered. A new implicit numerical method and an alternating direct method for the two-dimensional variable-order fractional model is proposed. Consistency, stability and convergence of the implicit finite difference method are established. Finally, some numerical examples are given. The numerical results demonstrate the effectiveness of the methods. This technique can be used to simulate a three-dimensional variable-order fractional percolation equation.

Improved estimates of percolation and anisotropic permeability from 3-D X-ray microtomography using stochastic analyses and visualization

X-ray microtomography (micro-CT) with micron resolution enables new ways of characterizing microstructures and opens pathways for forward calculations of multiscale rock properties. A quantitative characterization of the microstructure is the first step in this challenge. We developed a new approach to extract scale-dependent characteristics of porosity, percolation, and anisotropic permeability from 3-D microstructural models of rocks. The Hoshen-Kopelman algorithm of percolation theory is employed for a standard percolation analysis. The anisotropy of permeability is calculated by means of the star volume distribution approach. The local porosity distribution and local percolation probability are obtained by using the local porosity theory. Additionally, the local anisotropy distribution is defined and analyzed through two empirical probability density functions, the isotropy index and the elongation index. For such a high-resolution data set, the typical data sizes of the CT images are on the order of gigabytes to tens of gigabytes; thus an extremely large number of calculations are required. To resolve this large memory problem parallelization in OpenMP was used to optimally harness the shared memory infrastructure on cache coherent Non-Uniform Memory Access architecture machines such as the iVEC SGI Altix 3700Bx2 Supercomputer. We see adequate visualization of the results as an important element in this first pioneering study.

Continuum percolation with discs having a distribution of radii

It is shown that for continuum percolation with overlapping discs having a distribution of radii, the net areal density of discs at percolation threshold depends non-trivially on the distribution, and is not bounded by any finite constant. Results of a Monte Carlo simulation supporting the argument are presented.

Understanding Protein Structure from a Percolation Perspective

Underlying the unique structures and diverse functions of proteins area vast range of amino-acid sequences and a highly limited number of folds taken up by the polypeptide backbone. By investigating the role of noncovalent connections at the backbone level and at the detailed side-chain level, we show that these unique structures emerge from interplay between random and selected features. Primarily, the protein structure network formed by these connections shows simple (bond) and higher order (clique) percolation behavior distinctly reminiscent of random network models. However, the clique percolation specific to the side-chain interaction network bears signatures unique to proteins characterized by a larger degree of connectivity than in random networks. These studies reflect some salient features of the manner in which amino acid sequences select the unique structure of proteins from the pool of a limited number of available folds.

Electrical Percolation studies of Polystyrene-multi wall carbon nanotubes Composites

Composites of Polystyrene-multi wall carbon nanotubes (PS-MWNTs) were prepared with loading up to 7 wt% of MWNTs by simple solvent mixing and drying technique. MWNTs with high aspect ratio similar to 4000 were used to make the polymer composites. A very high degree of dispersion of MWNTs was achieved by ultrasonication technique. As a result of high dispersion and high aspect ratio of the MWNTs electrical percolation was observed at rather low weight fraction similar to 0.0021. Characterization of the as prepared PS-MWNTs composites was done by Electron microscopy (EM), X-ray diffraction technique (XRD) and Thermogravimetery analysis (TGA).

Unusual metallic-like transport near the percolation threshold

In multiwall carbon nanotube (MWNT)-polystyrene (PS) composites, a weak temperature dependence of conductivity has been observed at a percolation threshold of 0.4 wt %. The power law [sigma(T)proportional to T-0.3] behavior indicates metallic-like behavior, unlike the usual activated transport for systems near the percolation threshold. The low field positive magnetoconductance follows H-2 dependence, due to the weak localization in disordered metallic systems. The marginal metallic nature of MWNT-PS at percolation threshold is further verified from the negligible frequency dependence of conductivity, in the temperature range of 300 to 5 K. (C) 2010 American Institute of Physics. [doi: 10.1063/1.3455895]

Ordering near the percolation threshold in models of two-dimensional interacting bosons with quenched dilution

Randomly diluted quantum boson and spin models in two dimensions combine the physics of classical percolation with the well-known dimensionality dependence of ordering in quantum lattice models. This combination is rather subtle for models that order in two dimensions but have no true order in one dimension, as the percolation cluster near threshold is a fractal of dimension between 1 and 2: two experimentally relevant examples are the O(2) quantum rotor and the Heisenberg antiferromagnet. We study two analytic descriptions of the O(2) quantum rotor near the percolation threshold. First a spin-wave expansion is shown to predict long-ranged order, but there are statistically rare points on the cluster that violate the standard assumptions of spin-wave theory. A real-space renormalization group (RSRG) approach is then used to understand how these rare points modify ordering of the O(2) rotor. A new class of fixed points of the RSRG equations for disordered one-dimensional bosons is identified and shown to support the existence of long-range order on the percolation backbone in two dimensions. These results are relevant to experiments on bosons in optical lattices and superconducting arrays, and also (qualitatively) for the diluted Heisenberg antiferromagnet La-2(Zn,Mg)(x)Cu1-xO4.

Characterization, electrical percolation and magnetization studies of polystyrene/multiwall carbon nanotube composite films

Polystyrene/multiwall carbon nanotube composite films are prepared with loading up to 7 weight percent (wt%) of multiwall carbon nanotubes by solution processing and casting technique. In the formation of these composite films, iron filled carbon nanotubes with high aspect ratio (similar to 4000) were used. Scanning electron microscopy study shows that the nanotubes are uniformly dispersed within the polymer matrix. At high magnification, bending of carbon nanotubes is noticed which can be attributed to their elastic properties. The electrical conductivity measurements show that the percolation threshold is rather low at 0.21 wt%. Hysteresis loop measurements on the bulk multiwall carbon nanotube and composite samples are done at 10, 150 and 300 K and the coercivity values are found to be largest at all the temperatures, for 1 wt% composite sample. (C) 2010 Elsevier B.V. All rights reserved.

Real-time multipurpose reservoir operation: a case study / Exploitation en temps reacuteel d'un reservoir agrave buts multiples: eacutetude d'un cas

A real-time operational methodology has been developed for multipurpose reservoir operation for irrigation and hydropower generation with application to the Bhadra reservoir system in the state of Karnataka, India. The methodology consists of three phases of computer modelling. In the first phase, the optimal release policy for a given initial storage and inflow is determined using a stochastic dynamic programming (SDP) model. Streamflow forecasting using an adaptive AutoRegressive Integrated Moving Average (ARIMA) model constitutes the second phase. A real-time simulation model is developed in the third phase using the forecast inflows of phase 2 and the operating policy of phase 1. A comparison of the optimal monthly real-time operation with the historical operation demonstrates the relevance, applicability and the relative advantage of the proposed methodology.

Percolation and Connectivity in AB Random Geometric Graphs

Given two independent Poisson point processes ©(1);©(2) in Rd, the AB Poisson Boolean model is the graph with points of ©(1) as vertices and with edges between any pair of points for which the intersection of balls of radius 2r centred at these points contains at least one point of ©(2). This is a generalization of the AB percolation model on discrete lattices. We show the existence of percolation for all d ¸ 2 and derive bounds for a critical intensity. We also provide a characterization for this critical intensity when d = 2. To study the connectivity problem, we consider independent Poisson point processes of intensities n and cn in the unit cube. The AB random geometric graph is de¯ned as above but with balls of radius r. We derive a weak law result for the largest nearest neighbour distance and almost sure asymptotic bounds for the connectivity threshold.

Signature of a silver phase percolation threshold in microscopically phase separated ternary Ge0.15Se0.85-xAgx (0≤x≤0.20) glasses

Temperature modulated alternating differential scanning calorimetric studies show that Se rich Ge0.15Se0.85−xAgx (0 x 0.20) glasses are microscopically phase separated, containing Ag2Se phases embedded in a Ge0.15Se0.85 backbone. With increasing silver concentration, Ag2Se phase percolates in the Ge–Se matrix, with a well-defined percolation threshold at x = 0.10. A signature of this percolation transition is shown up in the thermal behavior, as the appearance of two exothermic crystallization peaks. Density, molar volume, and microhardness measurements, undertaken in the present study, also strongly support this view of percolation transition. The superionic conduction observed earlier in these glasses at higher silver proportions is likely to be connected with the silver phase percolation.