Rouzbeh Shahsavari

A realistic molecular model of cement hydrates

Despite decades of studies of calcium-silicate-hydrate (C-S-H), the structurally complex binder phase of concrete, the interplay between chemical composition and density remains essentially unexplored. Together these characteristics of C-S-H define and modulate the physical and mechanical properties of this “liquid stone” gel phase. With the recent determination of the calcium/silicon (C/S = 1.7) ratio and the density of the C-S-H particle (2.6 g/cm3) by neutron scattering measurements, there is new urgency to the challenge of explaining these essential properties. Here we propose a molecular model of C-S-H based on a bottom-up atomistic simulation approach that considers only the chemical specificity of the system as the overriding constraint. By allowing for short silica chains distributed as monomers, dimers, and pentamers, this C-S-H archetype of a molecular description of interacting CaO, SiO2, and H2O units provides not only realistic values of the C/S ratio and the density computed by grand canonical Monte Carlo simulation of water adsorption at 300 K. The model, with a chemical composition of (CaO)1.65(SiO2)(H2O)1.75, also predicts other essential structural features and fundamental physical properties amenable to experimental validation, which suggest that the C-S-H gel structure includes both glass-like short-range order and crystalline features of the mineral tobermorite. Additionally, we probe the mechanical stiffness, strength, and hydrolytic shear response of our molecular model, as compared to experimentally measured properties of C-S-H. The latter results illustrate the prospect of treating cement on equal footing with metals and ceramics in the current application of mechanism-based models and multiscale simulations to study inelastic deformation and cracking.

Combinatorial molecular optimization of cement hydrates.

Despite its ubiquitous presence in the built environment, concrete’s molecular-level properties are only recently being explored using experimental and simulation studies. Increasing societal concerns about concrete’s environmental footprint have provided strong motivation to develop new concrete with greater specific stiffness or strength (for structures with less material). Herein, a combinatorial approach is described to optimize properties of cement hydrates. The method entails screening a computationally generated database of atomic structures of calcium-silicate-hydrate, the binding phase of concrete, against a set of three defect attributes: calcium-to-silicon ratio as compositional index and two correlation distances describing medium-range silicon-oxygen and calcium-oxygen environments. Although structural and mechanical properties correlate well with calcium-to-silicon ratio, the cross-correlation between all three defect attributes reveals an indentation modulus-to-hardness ratio extremum, analogous to identifying optimum network connectivity in glass rheology. We also comment on implications of the present findings for a novel route to optimize the nanoscale mechanical properties of cement hydrate.

Universal composition–structure–property maps for natural and biomimetic platelet–matrix composites and stacked heterostructures

Many natural and biomimetic platelet-matrix composites--such as nacre, silk, and clay-polymer-exhibit a remarkable balance of strength, toughness and/or stiffness, which call for a universal measure to quantify this outstanding feature given the structure and material characteristics of the constituents. Analogously, there is an urgent need to quantify the mechanics of emerging electronic and photonic systems such as stacked heterostructures. Here we report the development of a unified framework to construct universal composition-structure-property diagrams that decode the interplay between various geometries and inherent material features in both platelet-matrix composites and stacked heterostructures. We study the effects of elastic and elastic-perfectly plastic matrices, overlap offset ratio and the competing mechanisms of platelet versus matrix failures. Validated by several 3D-printed specimens and a wide range of natural and synthetic materials across scales, the proposed universally valid diagrams have important implications for science-based engineering of numerous platelet-matrix composites and stacked heterostructures.

Toughness governs the rupture of the interfacial H-bond assemblies at a critical length scale in hybrid materials.

The geometry and material property mismatch across the interface of hybrid materials with dissimilar building blocks make it extremely difficult to fully understand the lateral chemical bonding processes and design nanocomposites with optimal performance. Here, we report a combined first-principles study, molecular dynamics modeling, and theoretical derivations to unravel the detailed mechanisms of H-bonding, deformation, load transfer, and failure at the interface of polyvinyl alcohol (PVA) and silicates, as an example of hybrid materials with geometry and property mismatch across the interface. We identify contributing H-bonds that are key to adhesion and demonstrate a specific periodic pattern of interfacial H-bond network dictated by the interface mismatch and intramolecular H-bonding. We find that the maximum toughness, incorporating both intra- and interlayer strain energy contributions, govern the existence of optimum overlap length and thus the rupture of interfacial (interlayer) H-bond assemblies in natural and synthetic hybrid materials. This universally valid result is in contrast to the previous reports that correlate shear strength with rupture of H-bonds assemblies at a finite overlap length. Overall, this work establishes a unified understanding to explain the interplay between geometric constraints, interfacial H-bonding, materials characteristics, and optimal mechanical properties in hybrid organic-inorganic materials.

Molecular mechanistic origin of nanoscale contact, friction, and scratch in complex particulate systems.

Nanoscale contact mechanisms, such as friction, scratch, and wear, have a profound impact on physics of technologically important particulate systems. Determining the key underlying interparticle interactions that govern the properties of the particulate systems has been long an engineering challenge. Here, we focus on particulate calcium-silicate-hydrate (C-S-H) as a model system and use atomistic simulations to decode the interplay between crystallographic directions, structural defects, and atomic species on normal and frictional forces. By exhibiting high material inhomogeneity and low structural symmetry, C-S-H provides an excellent system to explore various contact-induced nanoscale deformation mechanisms in complex particulate systems. Our findings provide a deep fundamental understanding of the role of inherent material features, such as van der Waals versus Coulombic interactions and the role of atomic species, in controlling the nanoscale normal contact, friction, and scratch mechanisms, thereby providing de novo insight and strategies for intelligent modulation of the physics of the particulate systems. This work is the first report on atomic-scale investigation of the contact-induced nanoscale mechanisms in structurally complex C-S-H materials and can potentially open new opportunities for knowledge-based engineering of several other particulate systems such as ceramics, sands, and powders and self-assembly of colloidal systems in general.

Screw dislocations in complex, low symmetry oxides: core structures, energetics, and impact on crystal growth.

Determining the atomic structure and the influence of defects on properties of low symmetry oxides have long been an engineering pursuit. Here, we focus on five thermodynamically reversible monoclinic and orthorhombic polymorphs of dicalcium silicates (Ca2SiO3)-a key cement constituent-as a model system and use atomistic simulations to unravel the interplay between the screw dislocation core energies, nonplanar core structures, and Peierls stresses along different crystallographic planes. Among different polymorphs, we found that the α polymorphs (α-C2S) has the largest Peierls stress, corresponding to the most brittle polymorph, which make it attractive for grinding processes. Interestingly, our analyses indicate that this polymorphs has the lowest dislocation core energy, making it ideal for reactivity and crystal growth. Generally, we identified the following order in terms of grinding efficiency based on screw dislocation analysis, α-C2S > αH-C2S > αL-C2S > β-C2S > γ-C2S, and the following order in term of reactivity, α -C2S > αL-C2S > γ-C2S > αH-C2S > β-C2S. This information, combined with other deformation-based mechanisms, such as twinning and edge dislocation, can provide crucial insights and guiding hypotheses for experimentalists to tune the cement grinding mechanisms and reactivity processes for an overall optimum solution with regard to both energy consumption and performance. Our findings significantly broaden the spectrum of strategies for leveraging both crystallographic directions and crystal symmetry to concurrently modulate mechanics and crystal growth processes within an identical chemical composition.

Dimensional Crossover of Thermal Transport in Hybrid Boron Nitride Nanostructures.

Although boron nitride nanotubes (BNNT) and hexagonal-BN (hBN) are superb one-dimensional (1D) and 2D thermal conductors respectively, bringing this quality into 3D remains elusive. Here, we focus on pillared boron nitride (PBN) as a class of 3D BN allotropes and demonstrate how the junctions, pillar length and pillar distance control phonon scattering in PBN and impart tailorable thermal conductivity in 3D. Using reverse nonequilibrium molecular dynamics simulations, our results indicate that although a clear phonon scattering at the junctions accounts for the lower thermal conductivity of PBN compared to its parent BNNT and hBN allotropes, it acts as an effective design tool and provides 3D thermo-mutable features that are absent in the parent structures. Propelled by the junction spacing, while one geometrical parameter, e.g., pillar length, controls the thermal transport along the out-of-plane direction of PBN, the other parameter, e.g., pillar distance, dictates the gross cross-sectional area, which is key for design of 3D thermal management systems. Furthermore, the junctions have a more pronounced effect in creating a Kapitza effect in the out-of-plane direction, due to the change in dimensionality of the phonon transport. This work is the first report on thermo-mutable properties of hybrid BN allotropes and can potentially impact thermal management of other hybrid 3D BN architectures.

Microwave Heating of Functionalized Graphene Nanoribbons in Thermoset Polymers for Wellbore Reinforcement.

Here, we introduce a systematic strategy to prepare composite materials for wellbore reinforcement using graphene nanoribbons (GNRs) in a thermoset polymer irradiated by microwaves. We show that microwave absorption by GNRs functionalized with poly(propylene oxide) (PPO-GNRs) cured the composite by reaching 200 °C under 30 W of microwave power. Nanoscale PPO-GNRs diffuse deep inside porous sandstone and dramatically enhance the mechanics of the entire structure via effective reinforcement. The bulk and the local mechanical properties measured by compression and nanoindentation mechanical tests, respectively, reveal that microwave heating of PPO-GNRs and direct polymeric curing are major reasons for this significant reinforcement effect.

Cements in the 21st Century: Challenges, Perspectives, and Opportunities

In a book published in 1906, Richard Meade outlined the history of portland cement up to that point1. Since then there has been great progress in portland cement-based construction materials technologies brought about by advances in the materials science of composites and the development of chemical additives (admixtures) for applications. The resulting functionalities, together with its economy and the sheer abundance of its raw materials, have elevated ordinary portland cement (OPC) concrete to the status of most used synthetic material on Earth. While the 20th century was characterized by the emergence of computer technology, computational science and engineering, and instrumental analysis, the fundamental composition of portland cement has remained surprisingly constant. And, although our understanding of ordinary portland cement (OPC) chemistry has grown tremendously, the intermediate steps in hydration and the nature of calcium silicate hydrate (C-S-H), the major product of OPC hydration, remain clouded in uncertainty. Nonetheless, the century also witnessed great advances in the materials technology of cement despite the uncertain understanding of its most fundamental components. Unfortunately, OPC also has a tremendous consumption-based environmental impact, and concrete made from OPC has a poor strength-to-weight ratio. If these challenges are not addressed, the dominance of OPC could wane over the next 100 years. With this in mind, this paper envisions what the 21st century holds in store for OPC in terms of the driving forces that will shape our continued use of this material. Will a new material replace OPC, and concrete as we know it today, as the preeminent infrastructure construction material?

Screw-Dislocation-Induced Strengthening–Toughening Mechanisms in Complex Layered Materials: The Case Study of Tobermorite

Nanoscale defects such as dislocations have a profound impact on the physics of crystalline materials. Understanding and characterizing the motion of screw dislocation and its corresponding effects on the mechanical properties of complex low-symmetry materials has long been a challenge. Herein, we focus on triclinic tobermorite, as a model system and a crystalline analogue of layered hydrated cement, and report for the first time how the motion of screw dislocation can influence the strengthening-toughening relationship, imparting brittle-to-ductile transitions. By applying shear loading in tobermorite systems with single and dipole screw dislocations, we observe dislocation jogs around the dislocation core, which increases the yield shear stress and the work-of-fracture when the dislocation lines are along the [100] and [010] directions. Our results demonstrate that the dislocation core acts as a bottleneck for the initial straight gliding to induce intralaminar gliding, which consequently leads to a significant improvement in the mechanical properties. Together, the fundamental knowledge gained in this work on the role of the motion of the dislocation core on the mechanical properties provides an improved understanding of deformation mechanisms in cementitious materials and other complex layered systems, providing new hypotheses and design guidelines for the development of strong, ductile, and tough materials.