Strength and Microstructure Assessment of Partially Replaced Ordinary Portland Cement and Calcium Sulfoaluminate Cement with Pozzolans and Spent Coffee Grounds.

Supplementary cementitious materials are considered a viable and affordable way to reduce CO2 emissions from the cement industry's perspective since they can partially or nearly entirely replace ordinary Portland cement (OPC). This study compared the impact of adding spent coffee grounds (SCGs), fly ash (FA), and volcanic ash (VA) to two types of cement: OPC and calcium sulfoaluminate cement (CSA). Cement samples were characterized using compressive strength measurements (up to 210 days of curing), scanning electron microscopy with energy dispersive X-ray spectroscopy (SEM-EDS), X-ray diffraction (XRD), attenuated total reflection infrared spectroscopy, and hydration temperature measurements. In all the studied systems, the presence of SCGs reduced compressive strength and delayed the hydration process. CSA composite cement containing 3.5% SCGs, 30% FA, and 30% VA showed compressive strength values of 20.4 MPa and 20.3 MPa, respectively, meeting the minimum requirement for non-structural applications. Additionally, the results indicate a formation of cementitious gel, calcium silicate hydrate (C-S-H) in the OPC-based composite cements, and calcium alumino-silicate hydrate (C-A-S-H) as well as ettringite in the CSA-based composite cements.

New insights into the atomic structure of amorphous TiO2 using tight-binding molecular dynamics.

Amorphous TiO2 (a-TiO2) could offer an attractive alternative to conventional crystalline TiO2 phases for photocatalytic applications. However, the atomic structure of a-TiO2 remains poorly understood with respect to that of its crystalline counterparts. Here, we conduct some classical molecular dynamics simulations of a-TiO2 based on a selection of empirical potentials. We show that, on account of its ability to dynamically assign the charge of each atom based on its local environment, the second-moment tight-binding charge equilibration potential yields an unprecedented agreement with available experimental data. Based on these simulations, we investigate the degree of order and disorder in a-TiO2. Overall, the results suggest that a-TiO2 features a large flexibility in its local topology, which may explain the high sensitivity of its structure to the synthesis method being used.

Anomalous variations in the viscous activation energy of suspensions induced by fractal structuring.

HYPOTHESIS: In suspensions, the activation energy of viscous flow is an important property that controls the temperature dependence of the viscosity. However, the differentiated roles of the properties of the liquid phase and the structure of the solid particles in controlling the activation energy remain unclear. We propose here that particle fractal structuring yields an anomalous behavior in the activation energy of viscous flow. EXPERIMENTS: The rheology of two series of suspensions consisting of glass beads suspended in poly(1-decene) was investigated over a wide range of solid volume fractions (0.00 ≤ φ ≤ 0.55). These suspensions were characterized by their viscosity (η, Pa∙s) via shear rate sweeps and by their yield stress (Pa) via oscillatory amplitude sweeps. FINDINGS: Interestingly, for suspensions consisting of nominally smaller particles (d50 ≈ 5 µm), we observe an anomalous decrease in the activation energy (Ea, kJ/mol) of viscous flow with increasing solid fraction. Based on oscillatory rheology analyses, it is suggested that such anomalous behavior arises due to entropic effects that result from the formation of fractally-architected cooperatively rearranging regions (i.e., agglomerates) in the suspension.

Direct observation of pitting corrosion evolutions on carbon steel surfaces at the nano-to-micro- scales.

The Cl--induced corrosion of metals and alloys is of relevance to a wide range of engineered materials, structures, and systems. Because of the challenges in studying pitting corrosion in a quantitative and statistically significant manner, its kinetics remain poorly understood. Herein, by direct, nano- to micro-scale observations using vertical scanning interferometry (VSI), we examine the temporal evolution of pitting corrosion on AISI 1045 carbon steel over large surface areas in Cl--free, and Cl--enriched solutions. Special focus is paid to examine the nucleation and growth of pits, and the associated formation of roughened regions on steel surfaces. By statistical analysis of hundreds of individual pits, three stages of pitting corrosion, namely, induction, propagation, and saturation, are quantitatively distinguished. By quantifying the kinetics of these processes, we contextualize our current understanding of electrochemical corrosion within a framework that considers spatial dynamics and morphology evolutions. In the presence of Cl- ions, corrosion is highly accelerated due to multiple autocatalytic factors including destabilization of protective surface oxide films and preservation of aggressive microenvironments within the pits, both of which promote continued pit nucleation and growth. These findings offer new insights into predicting and modeling steel corrosion processes in mid-pH aqueous environments.

A thermodynamics-based approach for examining the suitability of cementitious formulations for solidifying and stabilizing coal-combustion wastes.

Cementitious binders are often used to immobilize industrial wastes such as residues of coal combustion. Such immobilization stabilizes wastes that contain contaminants by chemical containment, i.e., by uptake of contaminants into the cementitious reaction products. Expectedly, the release ("leachability") of contaminants is linked to: (i) the stability of the matrix (i.e., its resistance to decomposition on exposure to water), and, (ii) its porosity, which offers a pathway for the intrusion of water and egress of contaminant species. To examine the effects of the matrix chemistry on its suitability for immobilization, an equilibrium thermodynamics-based approach is demonstrated for cementitious formulations based on: ordinary portland cement (OPC), calcium aluminate cement (CAC) and alkali activated fly ash (AFA) binding agents. First, special focus is placed on computing the equilibrium phase assemblages using the bulk reactant compositions as an input. Second, the matrix's stability is assessed by simulating leaching that is controlled by progressive dissolution and precipitation of solids across a range of liquid (leachant)-to-(reaction product) solid (l/s) ratios and leachant pH's; e.g., following the LEAF 1313 and 1316 protocols. The performance of each binding formulation is evaluated based on the: (i) relative ability of the reaction products to chemically bind the contaminant(s), (ii) porosity of the matrix which correlates to its hydraulic conductivity, and, (iii) the extent of matrix degradation that follows leaching and which impact the rate and extent of release of potential contaminants. In this manner, the approach enables rapid, parametric assessment of a wide-range of stabilization solutions with due consideration of the matrix's mineralogy, porosity, and the leaching (exposure) conditions.

Anion Capture and Exchange by Functional Coatings: New Routes to Mitigate Steel Corrosion in Concrete Infrastructure.

Chloride-induced corrosion is a major cause of degradation of reinforced concrete infrastructure. While the binding of chloride ions (Cl-) by cementitious phases is known to delay corrosion, this approach has not been systematically exploited as a mechanism to increase structural service life. Recently, Falzone et al. [Cement and Concrete Research72, 54-68 (2015)] proposed calcium aluminate cement (CAC) formulations containing NO3-AFm to serve as anion exchange coatings that are capable of binding large quantities of Cl- ions, while simultaneously releasing corrosion-inhibiting NO3- species. To examine the viability of this concept, Cl- binding isotherms and ion-diffusion coefficients of a series of hydrated CAC formulations containing admixed Ca(NO3)2 (CN) are quantified. This data is input into a multi-species Nernst-Planck (NP) formulation, which is solved for a typical bridge-deck geometry using the finite element method (FEM). For exposure conditions corresponding to seawater, the results indicate that Cl- scavenging CAC coatings (i.e., top-layers) can significantly delay the time to corrosion (e.g., 5 ≤ df ≤ 10, where df is the steel corrosion initiation delay factor [unitless]) as compared to traditional OPC-based systems for the same cover thickness; as identified by thresholds of Cl-/OH- or Cl-/NO3- (molar) ratios in solution. The roles of hindered ionic diffusion, and the passivation of the reinforcing steel rendered by NO3- are also discussed.

Cooling rate effects in sodium silicate glasses: Bridging the gap between molecular dynamics simulations and experiments.

Although molecular dynamics (MD) simulations are commonly used to predict the structure and properties of glasses, they are intrinsically limited to short time scales, necessitating the use of fast cooling rates. It is therefore challenging to compare results from MD simulations to experimental results for glasses cooled on typical laboratory time scales. Based on MD simulations of a sodium silicate glass with varying cooling rate (from 0.01 to 100 K/ps), here we show that thermal history primarily affects the medium-range order structure, while the short-range order is largely unaffected over the range of cooling rates simulated. This results in a decoupling between the enthalpy and volume relaxation functions, where the enthalpy quickly plateaus as the cooling rate decreases, whereas density exhibits a slower relaxation. Finally, we show that, using the proper extrapolation method, the outcomes of MD simulations can be meaningfully compared to experimental values when extrapolated to slower cooling rates.

Vertical scanning interferometry: A new method to quantify re-/de-mineralization dynamics of dental enamel.

OBJECTIVE: Remineralization and demineralization are processes that compete in the oral environment. At this time, numerous therapeutic agents are being developed to promote remineralization (precipitation) or suppress demineralization (dissolution). To evaluate the relative efficacy of such treatments, there is a need for non-invasive, real-time, high-resolution quantifications of topographical changes occurring during demineralization and remineralization. METHODS: Vertical scanning interferometry (VSI) is demonstrated to be a quantitative method to assess reactions, and topographical changes occurring on enamel surfaces following exposure to demineralizing, and remineralizing liquids. RESULTS: First, the dissolution rate of enamel was compared to that of synthetic hydroxyapatite (HAP) under acidic conditions (pH=4). Second, VSI was used to compare the remineralization effects of F(-)-based and CCP-ACP agents. The former produced a remineralization rate of ≈349nm/h, similar to simulated body fluid (SBF; concentration 4.6×) while the latter produced a remineralization rate of ≈55nm/h, corresponding to 1.7× SBF. However, the precipitates formed by the CCP-ACP agent are found to demineralize 2.7× slower than that produced by its F(-)-counterpart. SIGNIFICANCE: Based on this new VSI-based data, a remineralization factor (RF) and demineralization (DF) factor benchmarked, respectively, to 1× SBF and the demineralization rate of human enamel are suggested as figures of merit of therapeutic performance of dental treatments. Taken together, the outcomes offer new insights that can inform clinicians and researchers on the selection of remineralization strategies.