Theory of Sorption Hysteresis in Nanoporous Solids: II. Molecular condensation

Motivated by the puzzle of sorption hysteresis in Portland cement concrete or cement paste, we develop in Part II of this study a general theory of vapor sorption and desorption from nanoporous solids, which attributes hysteresis to hindered molecular condensation with attractive lateral interactions. The classical mean-field theory of van der Waals is applied to predict the dependence of hysteresis on temperature and pore size, using the regular solution model and gradient energy of Cahn and Hilliard. A simple "hierarchical wetting" model for thin nanopores is developed to describe the case of strong wetting by the first monolayer, followed by condensation of nanodroplets and nanobubbles in the bulk. The model predicts a larger hysteresis critical temperature and enhanced hysteresis for molecular condensation across nanopores at high vapor pressure than within monolayers at low vapor pressure. For heterogeneous pores, the theory predicts sorption/desorption sequences similar to those seen in molecular dynamics simulations, where the interfacial energy (or gradient penalty) at nanopore junctions acts as a free energy barrier for snap-through instabilities. The model helps to quantitatively understand recent experimental data for concrete or cement paste wetting and drying cycles and suggests new experiments at different temperatures and humidity sweep rates.Comment: 26 pages, 10 fig

Model B4 : multi-decade creep and shrinkage prediction of traditional and modern concretes

To improve the sustainability of concrete infrastructure, engineers face the challenge of incorporating new concrete materials while pushing the expected design life beyond 100 years. The time-dependent creep and shrinkage response of concrete governs the serviceability and durability in this multi-decade time frame. It has been shown that current prediction equations for creep and shrinkage underestimate material deformations observed in structures outside of a laboratory environment. A new prediction model for creep and shrinkage is presented that can overcome some of the shortcomings of the current equations. The model represents an extension and systematic recalibration of model B3, a 1995 RILEM Recommendation, which derives its functional form from the phenomena of diffusion, chemical hydration, moisture sorption, and the evolution of micro-stresses in the cement structure. The model is calibrated through a joint optimization of a new enlarged laboratory test database and a new database of bridge deflection records to overcome the bias towards short-term behavior. A framework for considering effects of aggregates, admixtures, additives, and higher temperatures is also incorporated

Attractive forces in microporous carbon electrodes for capacitive deionization

The recently developed modified Donnan (mD) model provides a simple and useful description of the electrical double layer in microporous carbon electrodes, suitable for incorporation in porous electrode theory. By postulating an attractive excess chemical potential for each ion in the micropores that is inversely proportional to the total ion concentration, we show that experimental data for capacitive deionization (CDI) can be accurately predicted over a wide range of applied voltages and salt concentrations. Since the ion spacing and Bjerrum length are each comparable to the micropore size (few nm), we postulate that the attraction results from fluctuating bare Coulomb interactions between individual ions and the metallic pore surfaces (image forces) that are not captured by meanfield theories, such as the Poisson-Boltzmann-Stern model or its mathematical limit for overlapping double layers, the Donnan model. Using reasonable estimates of the micropore permittivity and mean size (and no other fitting parameters), we propose a simple theory that predicts the attractive chemical potential inferred from experiments. As additional evidence for attractive forces, we present data for salt adsorption in uncharged microporous carbons, also predicted by the theory.Comment: 19 page

Analysis of ionic conductance of carbon nanotubes

We use space-charge (SC) theory (also called the capillary pore model) to describe the ionic conductance, G, of charged carbon nanotubes (CNTs). Based on the reversible adsorption of hydroxyl ions to CNT pore walls, we use a Langmuir isotherm for surface ionization and make calculations as a function of pore size, salt concentration c, and pH. Using realistic values for surface site density and pK, SC theory well describes published experimental data on the conductance of CNTs. At extremely low salt concentration, when the electric potential becomes uniform across the pore, and surface ionization is low, we derive the scaling G∝sqrt[c], while for realistic salt concentrations, SC theory does not lead to a simple power law for G(c)

Size scaling of strength in thin film delamination

We investigate by numerical simulation the system size dependence of the shear delamination strength of thin elastic films. The films are connected to a rigid substrate by a disordered interface containing a pre-existing crack. The size dependence of the strength of this system is found to depend crucially on the crack shape. For circular cracks, we observe a crossover between a size-independent regime at large crack radii which is controlled by propagation of the pre-existing crack, and a size-dependent regime at small radii which is dominated by nucleation of new cracks in other locations. For cracks of finite width that span the system transversally, we observe for all values of the crack length a logarithmic system size dependence of the failure stress. The results are interpreted in terms of extreme value statistics.Comment: 10 pages, 4 figure

Diffusion-Limited Aggregation on Curved Surfaces

We develop a general theory of transport-limited aggregation phenomena occurring on curved surfaces, based on stochastic iterated conformal maps and conformal projections to the complex plane. To illustrate the theory, we use stereographic projections to simulate diffusion-limited-aggregation (DLA) on surfaces of constant Gaussian curvature, including the sphere ($K>0$) and pseudo-sphere ($K<0$), which approximate "bumps" and "saddles" in smooth surfaces, respectively. Although curvature affects the global morphology of the aggregates, the fractal dimension (in the curved metric) is remarkably insensitive to curvature, as long as the particle size is much smaller than the radius of curvature. We conjecture that all aggregates grown by conformally invariant transport on curved surfaces have the same fractal dimension as DLA in the plane. Our simulations suggest, however, that the multifractal dimensions increase from hyperbolic ($K0$) geometry, which we attribute to curvature-dependent screening of tip branching.Comment: 4 pages, 3 fig

Crack stability in the fracture of cementitious materials

The aim of the present study is to investigate the stability of crack propagation in cementitious materials. Tests were conducted on bend specimens in three-point and four-point loading conditions. Three-point bend specimens showed stable crack growth for mortar, normal strength and high strength concrete specimens. Alternatively, four-point bend specimens showed catastrophic failure for mortar and quasi-catastrophic failure for normal strength and high strength concrete specimens. Results will be discussed in relation to brittleness number model and specific microstructural features including the interfacial transition zone between the cement paste and the aggregate and the attendant toughening mechanisms

Nucleation of cracks in a brittle sheet

We use molecular dynamics to study the nucleation of cracks in a two dimensional material without pre-existing cracks. We study models with zero and non-zero shear modulus. In both situations the time required for crack formation obeys an Arrhenius law, from which the energy barrier and pre-factor are extracted for different system sizes. For large systems, the characteristic time of rupture is found to decrease with system size, in agreement with classical Weibull theory. In the case of zero shear modulus, the energy opposing rupture is identified with the breakage of a single atomic layer. In the case of non-zero shear modulus, thermally activated fracture can only be studied within a reasonable time at very high strains. In this case the energy barrier involves the stretching of bonds within several layers, accounting for a much higher barrier compared to the zero shear modulus case. This barrier is understood within adiabatic simulations

Crackling noise in three-point bending of heterogeneous materials

We study the crackling noise emerging during single crack propagation in a specimen under three-point bending conditions. Computer simulations are carried out in the framework of a discrete element model where the specimen is discretized in terms of convex polygons and cohesive elements are represented by beams. Computer simulations revealed that fracture proceeds in bursts whose size and waiting time distributions have a power law functional form with an exponential cutoff. Controlling the degree of brittleness of the sample by the amount of disorder, we obtain a scaling form for the characteristic quantities of crackling noise of quasi-brittle materials. Analyzing the spatial structure of damage we show that ahead of the crack tip a process zone is formed as a random sequence of broken and intact mesoscopic elements. We characterize the statistics of the shrinking and expanding steps of the process zone and determine the damage profile in the vicinity of the crack tip.Comment: 11 pages, 15 figure