Impact of Superplasticizers on the Performance of Low-Grade Limestone-Based Cement Mixes.

Low-grade limestone (LGL) is not used to produce cement clinker, but this leftover material in cement quarries increases the water demand when used as a filler in concrete production. In this study, the effect of six commercial superplasticizers on the performance of cement mixes containing 35% LGL and 2% gypsum was investigated. The optimal doses of these superplasticizers were found in a range of different water/binder (w/b) ratios by conducting several Marsh cone and mini-slump tests. The addition of a superplasticizer with a higher active solid content produced a maximum cement flow, regardless of the w/b ratios. The LGL-based mortar samples admixed with this superplasticizer obtained a maximum compressive strength of about 36 MPa at the end of 28 days. SEM and XRD results showed the formation of a new calcium-rich mineral in their microstructure. These findings highlight the impact of the type and properties of superplasticizers on the performance of concrete mixes containing LGL as a supplementary cementitious material.

Mathematical Modeling of Initial Exothermic Behavior and Thixotropic Properties in Nanoclay-Enhanced Cementitious Materials.

In the realm of cementitious materials, integrating nanoclay shows promise in enhancing properties relevant to additive manufacturing. This paper presents a novel mathematical model that combines simple empirical dissolution/nucleation Avrami-like kinetics with a thixotropic kinetics equation. To analyze the initial exothermic peak, two sets of the calculation parameter function are built to describe the exothermic rate as a function of time, following an exponential pattern. This allows for the prediction of the changes in cumulative heat and heat rate during hydration, considering different concentrations of nanoclay. In the rheological aspect, the relationship between shear stress, shear rate, and time is modeled as a combination of exponential dependencies. This enables the prediction of the variations in shear stress with one variable while holding the other constant (either time or shear rate). By integrating these aspects, this model effectively describes both the first exothermal peak and the rheological behavior during cement hydration with the inclusion of nanoclay. Validated against experimental results, these models demonstrate good accuracy (overall below 3% error), reliability, and applicability. The findings offer valuable insights into the thermal and rheological aspects of concrete printing, enabling informed design decisions for both scientific and industrial applications.

Unveiling the Remarkable Potential of Geopolymer-Based Materials by Harnessing Manganese Dioxide Incorporation.

Thermoelectric (TE) building materials have the potential to revolutionize sustainable architecture by converting temperature differences into electrical energy. This study introduces geopolymeric TE materials enhanced with manganese dioxide (MnO2 ) as a modifying agent. Calorimetric experiments examine the impact of MnO2 on geopolymerization. Mechanical tests show that adding MnO2 (up to 5% by weight) improves the geopolymer composite's strength, achieving a peak compressive strength of 36.8 MPa. The Seebeck effect of the MnO2 -modified geopolymeric composite is also studied. The inclusion of MnO2 boosts the Seebeck coefficient of the geopolymer, reaching a notable 4273 µV C-1 at a 5% MnO2 dosage. This enhancement is attributed to an increase in the density of states (DOS) and a reduction in relaxation time. However, excessive MnO2 or high alkali levels may adversely affect the Seebeck coefficient by lengthening the relaxation time.

Silicate Dissolution Mechanism from Metakaolinite Using Density Functional Theory.

Metakaolin (MK) is a high-quality, reactive nanomaterial that holds promising potential for large-scale use in improving the sustainability of cement and concrete production. It can replace cement due to its pozzolanic reaction with calcium hydroxide and water to form cementitious compounds. Therefore, understanding the dissolution mechanism is crucial to fully comprehending its pozzolanic reactivity. In this study, we present an approach for computing the activation energies required for the dissolution of metakaolin (MK) silicate units at far-from-equilibrium conditions using the improved dimer method (IDM) and the transition-state theory (TST) within density functional theory (DFT). Four different models were prepared to calculate the activation energies required for breaking oxo-bridging bonds between silicate or aluminate units. Our results showed that the activation energy for breaking the oxo-bridging bond to a silicate neighbor is higher than that to an aluminate neighbor due to the ionic interaction. However, for complete silicate tetrahedra dissolution, a higher activation energy is required for breaking the oxo-bridging bond to the aluminate neighbor compared to the silicate neighbor. The findings provide methodology for missing input data to predict the mesoscopic dissolution rate, e.g., by the atomistic kinetic Monte Carlo (KMC) upscaling approach.

3D Off-Lattice Coarse-Grained Monte Carlo Simulations for Nucleation of Alkaline Aluminosilicate Gels.

This work presents a 3D off-lattice coarse-grained Monte Carlo (CGMC) approach to simulate the nucleation of alkaline aluminosilicate gels, their nanostructure particle size, and their pore size distribution. In this model, four monomer species are coarse-grained with different particle sizes. The novelty is extending the previous on-lattice approach from White et al. (2012 and 2020) by implementing a full off-lattice numerical implementation to consider tetrahedral geometrical constraints when aggregating the particles into clusters. Aggregation of the dissolved silicate and aluminate monomers was simulated until reaching the equilibrium condition of 16.46% and 17.04% in particle number, respectively. The cluster size formation was analyzed as a function of iteration step evolution. The obtained equilibrated nano-structure was digitized to obtain the pore size distribution and this was compared with the on-lattice CGMC and measurement results from White et al. The observed difference highlighted the importance of the developed off-lattice CGMC approach to better describe the nanostructure of aluminosilicate gels.

Coarse-Grained Monte Carlo Simulations with Octree Cells for Geopolymer Nucleation at Different pH Values.

Geopolymers offer a potential alternative to ordinary Portland cement owing to their performance in mechanical and thermal properties, as well as environmental benefits stemming from a reduced carbon footprint. This paper endeavors to build upon prior atomistic computational work delving deeper into the intricate relationship between pH levels and the resulting material's properties, including pore size distribution, geopolymer nucleate cluster dimensions, total system energy, and monomer poly-condensation behavior. Coarse-grained Monte Carlo (CGMC) simulation inputs include tetrahedral geometry and binding energy parameters derived from DFT simulations for aluminate and silicate monomers. Elevated pH values may can alter reactivity and phase stability, or, in the structural concrete application, may passivate the embedded steel reinforcement. Thus, we examine the effects of pH values set at 11, 12, and 13 (based on silicate speciation chemistry), investigating their respective contributions to the nucleation of geopolymers. To simulate a larger system to obtain representative results, we propose the numerical implementation of an Octree cell. Finally, we further digitize the resulting expanded structure to ascertain pore size distribution, facilitating a comparative analysis. The novelty of this study is underscored by its expansion in both system size, more accurate monomer representation, and pH range when compared to previous CGMC simulation approaches. The results unveil a discernible correlation between the number of clusters and pores under specific pH levels. This links geopolymerization mechanisms under varying pH conditions to the resulting chemical properties and final structural state.

Thermodynamic Modeling and Experimental Validation of Acetic Acid Attack on Hardened Cement Paste: Effect of Silica Fume.

Concrete structures are increasingly becoming exposed to organic acid attack conditions, such as those found in agriculture and food-related industries. This paper aims to experimentally verify the thermodynamic modeling of cement pastes under acetic acid attack. For this, a modeling approach implemented in IPHREEQC via Matlab is described, and results are compared with measured pH and compositions of equilibrated solutions (MP-AES) as well as unreacted/precipitated solids (XRF, XRD and STA) for a wide range of acid concentrations. The 11% replacement of cement by silica fume (SF) led to a 60 or 70% reduction (measured or modeled, respectively) of Portlandite content in the hardened cement paste due to the pozzolanic reaction resulting in higher content of CSH phases, which has effects on the progression of dissolution processes and a resulting pH with increased acid concentrations. Considering that no fitting parameter was used, the model predictions showed good agreement with measured values of pH, dissolved ion concentrations and composition of the remaining (degraded) solids overall. The discrepancies here were more pronounced at very high acid concentrations (equilibrium pH < ~4), i.e., after the full dissolution of hydrate phases due to limitations in the model used to describe Al-, Si- and Fe-gel phases and/or identified experimental challenges in precipitation of calcium and aluminum acetate hydrates.

Dissolution of ß-C2S Cement Clinker: Part 2 Atomistic Kinetic Monte Carlo (KMC) Upscaling Approach.

Cement clinkers containing mainly belite (ß-C2S as a model crystal), replacing alite, offer a promising solution for the development of environmentally friendly solutions to reduce the high level of CO2 emissions in the production of Portland cement. However, the much lower reactivity of belite compared to alite limits the widespread use of belite cements. Therefore, this work presents a fundamental atomistic computational approach for comprehending and quantifying the mesoscopic forward dissolution rate of ß-C2S, applied to two reactive crystal facets of (100) and (1¯00). For this, an atomistic kinetic Monte Carlo (KMC) upscaling approach for cement clinker was developed. It was based on the calculated activation energies (ΔG*) under far-from-equilibrium conditions obtained by a molecular dynamic simulation using the combined approach of ReaxFF and metadynamics, as described in the Part 1 paper in this Special Issue. Thus, the individual atomistic dissolution rates were used as input parameters for implementing the KMC upscaling approach coded in MATLAB to study the dissolution time and morphology changes at the mesoscopic scale. Four different cases and 21 event scenarios were considered for the dissolution of calcium atoms (Ca) and silicate monomers. For this purpose, the (100) and (1¯00) facets of a ß-C2S crystal were considered using periodic boundary conditions (PBCs). In order to demonstrate the statistical nature of the KMC approach, 40 numerical realizations were presented. The major findings showed a striking layer-by-layer dissolution mechanism in the case of an ideal crystal, where the total dissolution rate was limited by the much slower dissolution of the silicate monomer compared to Ca. The introduction of crystal defects, namely cutting the edges at two crystal boundaries, increased the overall average dissolution rate by a factor of 519.

Dissolution of ß-C2S Cement Clinker: Part 1 Molecular Dynamics (MD) Approach for Different Crystal Facets.

A major concern in the modern cement industry is considering how to minimize the CO2 footprint. Thus, cements based on belite, an impure clinker mineral (CaO)2SiO2 (C2S in cement chemistry notation), which forms at lower temperatures, is a promising solution to develop eco-efficient and sustainable cement-based materials, used in enormous quantities. The slow reactivity of belite plays a critical role, but the dissolution mechanisms and kinetic rates at the atomistic scale are not known completely yet. This work aims to understand the dissolution behavior of different facets of ß-C2S providing missing input data and an upscaling modeling approach to connect the atomistic scale to the sub-micro scale. First, a combined ReaxFF and metadynamics-based molecular dynamic approach are applied to compute the atomistic forward reaction rates (RD) of calcium (Ca) and silicate species of (100) facet of ß-C2S considering the influence of crystal facets and crystal defects. To minimize the huge number of atomistic events possibilities, a generalized approach is proposed, based on the systematic removal of nearest neighbors' crystal sites. This enables us to tabulate data on the forward reaction rates of most important atomistic scenarios, which are needed as input parameters to implement the Kinetic Monte Carlo (KMC) computational upscaling approach. The reason for the higher reactivity of the (100) facet compared to the (010) is explained.

Bond Behavior of a Bio-Aggregate Embedded in Cement-Based Matrix.

This paper investigates the bond behavior between a bio-aggregate and a cement-based matrix. The experimental evaluation comprised physical, chemical, image, and mechanical characterization of the bio-aggregate. The image analyses about the bio-aggregate's outer structure provided first insights to understand the particularities of this newly proposed bio-aggregate for use in cementitious materials. A mineral aggregate (granitic rock), largely used as coarse aggregate in the Brazilian civil construction industry, was used as reference. The bond behavior of both aggregates was evaluated via pull-out tests. The results indicated that both aggregates presented a similar linear elastic branch up to each respective peak loads. The peak load magnitude of the mineral aggregate indicated a better chemical adhesion when compared to the bio-aggregate's. The post-peak behavior, however, indicated a smoother softening branch for the bio-aggregate, corroborated by the microscopy image analyses. Although further investigation is required, the macaúba crushed endocarp was found to be a thriving bio-material to be used as bio-aggregate.

Dissolution of Portlandite in Pure Water: Part 1 Molecular Dynamics (MD) Approach.

The current contribution proposes a multi-scale bridging modeling approach for the dissolution of crystals to connect the atomistic scale to the (sub-) micro-scale. This is demonstrated in the example of dissolution of portlandite, as a relatively simple benchmarking example for cementitious materials. Moreover, dissolution kinetics is also important for other industrial processes, e.g., acid gas absorption and pH control. In this work, the biased molecular dynamics (metadynamics) coupled with reactive force field is employed to calculate the reaction path as a free energy surface of calcium dissolution at 298 K in water from the different crystal facets of portlandite. It is also explained why the reactivity of the (010), (100), and (11¯0) crystal facet is higher compared to the (001) facet. In addition, the influence of neighboring Ca crystal sites arrangements on the atomistic dissolution rates is explained as necessary scenarios for the upscaling. The calculated rate constants of all atomistic reaction scenarios provided an input catalog ready to be used in an upscaling kinetic Monte Carlo (KMC) approach.

Dissolution of Portlandite in Pure Water: Part 2 Atomistic Kinetic Monte Carlo (KMC) Approach.

Portlandite, as a most soluble cement hydration reaction product, affects mechanical and durability properties of cementitious materials. In the present work, an atomistic kinetic Monte Carlo (KMC) upscaling approach is implemented in MATLAB code in order to investigate the dissolution time and morphology changes of a hexagonal platelet portlandite crystal. First, the atomistic rate constants of individual Ca dissolution events are computed by a transition state theory equation based on inputs of the computed activation energies (ΔG*) obtained through the metadynamics computational method (Part 1 of paper). Four different facets (100 or 1¯00, 010 or 01¯0, 1¯10 or 11¯0, and 001 or 001¯) are considered, resulting in a total of 16 different atomistic event scenarios. Results of the upscaled KMC simulations demonstrate that dissolution process initially takes place from edges, sides, and facets of 010 or 01¯0 of the crystal morphology. The steady-state dissolution rate for the most reactive facets (010 or 01¯0) was computed to be 1.0443 mol/(s cm2); however, 0.0032 mol/(s cm2) for 1¯10 or 11¯0, 2.672 × 10-7 mol/(s cm2) for 001 or 001¯, and 0.31 × 10-16 mol/(s cm2) for 100 or 1¯00 were represented in a decreasing order for less reactive facets. Obtained upscaled dissolution rates between each facet resulted in a huge (16 orders of magnitude) difference, reflecting the importance of crystallographic orientation of the exposed facets.

Enhanced Metakaolin Reactivity in Blended Cement with Additional Calcium Hydroxide.

This study aims to increase the pozzolanic reactivity of metakaolin (MK) in Portland cement (PC) blends by adding additional calcium hydroxide (CH_add) to the initial mixture. Cement paste samples were prepared with PC, MK and water with a water-to-binder ratio of 0.6. Cement replacement ratios were chosen from 5 to 40 wt.% MK. For higher replacement ratios, i.e., 20, 30 and 40 wt.% MK, CH_add was included in the mixture. CH_add-to-MK ratios of 0.1, 0.25 and 0.5 were investigated. Thermogravimetric analysis (TGA) was carried out to study the pozzolanic reactivity after 1, 7, 28 and 56 days of hydration. A modified mass balance approach was used to normalize thermogravimetric data and to calculate the calcium hydroxide (CH) consumption of samples with CH_add. Results showed that, without CH_add, a replacement ratio of 30 wt.% or higher results in the complete consumption of CH after 28 days at the latest. In these samples, the pozzolanic reaction of MK turned out to be restricted by the amount of CH available from the cement hydration. The increased amount of CH in the samples with CH_add resulted in an enhanced pozzolanic reaction of MK as confirmed by CH consumption measurements from TGA.

Conductive Geopolymers as Low-Cost Electrode Materials for Microbial Fuel Cells.

Geopolymer (GP) inorganic binders have a superior acid resistance compared to conventional cement (e.g., Portland cement, PC) binders, have better microbial compatibility, and are suitable for introducing electrically conductive additives to improve electron and ion transfer properties. In this study, GP-graphite (GPG) composites and PC-graphite (PCG) composites with a graphite content of 1-10 vol % were prepared and characterized. The electrical conductivity percolation threshold of the GPG and PCG composites was around 7 and 8 vol %, respectively. GPG and PCG composites with a graphite content of 8 to 10 vol % were selected as anode electrodes for the electrochemical analysis in two-chamber polarized microbial fuel cells (MFCs). Graphite electrodes were used as the positive control reference material. Geobacter sulfurreducens was used as a biofilm-forming and electroactive model organism for MFC experiments. Compared to the conventional graphite anodes, the anode-respiring biofilms resulted in equal current production on GPG composite anodes, whereas the PCG composites showed a very poor performance. The largest mean value of the measured current densities of a GPG composite used as anodes in MFCs was 380.4 µA cm-2 with a standard deviation of 129.5 µA cm-2. Overall, the best results were obtained with electrodes having a relatively low Ohmic resistance, that is, GPG composites and graphite. The very first approach employing sustainable GPs as a low-cost electrode binder material in an MFC showed promising results with the potential to greatly reduce the production costs of MFCs, which would also increase the feasibility of MFC large-scale applications.

A Mass Balance Approach for Thermogravimetric Analysis in Pozzolanic Reactivity R3 Test and Effect of Drying Methods.

The reactivity of supplementary cementitious materials (SCMs) is a key issue in the sustainability of cement-based materials. In this study, the effect of drying with isopropanol and acetone as well as the interpretation of thermogravimetric data on the results of an R3 test for evaluation of the SCM pozzolanic reaction were investigated. R3 samples consisting of calcium hydroxide, potassium hydroxide, potassium sulphate, water, and SCM were prepared. Besides silica fume, three different types of calcined clays were investigated as SCMs. These were a relatively pure metakaolin, a quartz-rich metakaolin, and a mixed calcined clay, where the amount of other types of clays was two times higher than the kaolinite content. Thermogravimetric analysis (TGA) was carried out on seven-day-old samples dried with isopropanol and acetone to stop the reaction processes. Additional calorimetric measurement of the R3 samples was carried out for evaluation of the reaction kinetics. Results show that drying with isopropanol is more suitable for analysis of R3 samples compared to acetone. The use of acetone results in increased carbonation and TGA mass losses until 40 (isothermal drying for 30 min) and 105 °C (ramp heating), indicating that parts of the acetone remain in the sample, causing problems in the interpretation of TGA data. A mass balance approach was proposed to calculate calcium hydroxide consumption from TGA data, while also considering the amount of carbonates in the sample and TGA data corrections of original SCMs. With this approach, an improvement of the linear correlation of TGA results and heat release from calorimetric measurement was achieved.

Effect of Silica Fume on Metakaolin Geopolymers' Sulfuric Acid Resistance.

To demonstrate the importance of the Si/Al ratio in terms of geopolymer mix designs for acid resistance, a metakaolin-based geopolymer was modified by replacing the aforementioned precursor with different percentages of silica fume. Durability tests were performed by exposing geopolymers with varying amounts of silica fume (up to 9%) to sulfuric acid solution (pH 1) over a period of 84 days. Geopolymer samples were analyzed by X-ray diffraction (XRD), Fourier-transform infrared spectroscopy (FTIR) and scanning electron microscopy with energy-dispersive X-ray spectroscopy (SEM-EDX) before and after 7, 14, 28, 56 and 84 days of exposure. To show the time-dependent change of the elemental composition in the corroded layer after sulfuric acid attack, SEM-EDX elemental mappings were conducted and divided into 100 µm segments to generate element-specific depth profiles. The results show that above a critical silica fume content, the erosion of the sample surface by complete dissolution can be prevented and higher amounts of silica fume lead to a significant densification of large (protective) areas of the corroded layer, which delays the progress of corrosion.

Simple Model for Alkali Leaching from Geopolymers: Effects of Raw Materials and Acetic Acid Concentration on Apparent Diffusion Coefficient.

This paper investigates alkali leaching from geopolymers under various concentrations of acetic acid solutions. The effects of the raw metakaolin purity as well as fly ash-based geopolymer mortars and pastes are considered. A new methodology for (acetic) acid attack is proposed, adapting standard approaches, where the concentration of the leached alkali in the exposure solution is measured over time. The applicability of a simple diffusion-based mathematical model to determine the apparent diffusion coefficient (Dapp) for geopolymer pastes and mortars was validated. At the end of the paste tests, microstructural alterations of the specimens' cross-sections were analyzed microscopically, revealing occurrence of degradation across the outermost surface parts and, especially under acid attack, the formation of long cracks that connect the surface with the intact inner zone. Drastically different Dapp are discussed in terms of the differences in the mix designs, principally resulting in different alkali-binding capacities of the geopolymers, while the acid promoted dissolution and increased porosity. As a result of this interpretation, it was concluded that Dapp is governed mainly by the chemistry of the alkali release from the gel, as it overruled the effects of porosity and cracks.

Effect of Wood Biomass Ash Storage on the Properties of Cement Composites.

Since ash from wood biomass mostly ends up in landfills, recent research has focused on finding its economic and environmental added value as a potential new raw material in the construction industry. However, for wood ash to be used on an industrial scale in construction, a strategy for its proper storage must be defined. Proper storage of WBA is important to ensure quality control for applications in cementitious composites. This work investigated the aging of wood biomass ash (WBA) collected from five different power plants in Croatia and its influence on the performance of cementitious composites. WBA and cement pastes were investigated at different aging times (up to one year) using thermogravimetric analysis (TGA), powder X-ray diffraction (XRD), isothermal calorimetry and initial and final setting times. The results showed that storage of WBA in closed and open containers resulted in carbonation and hydration of mainly free lime and periclase, respectively, which affected the reactivity and setting times of WBA cement pastes.

Evaluation of Sulfuric Acid-Induced Degradation of Potassium Silicate Activated Metakaolin Geopolymers by Semi-Quantitative SEM-EDX Analysis.

Geopolymers are synthesized by mixing powdery solids, rich in amorphous silicon and aluminum species, with an alkaline solution, which leads to the formation of an inorganic alumosilicate network. Their acid resistance is affected by the composition, the porosity, and pore size distribution of the hardened binder as well as the type and concentration of the acidic solution. In the present study, two geopolymer mixtures with varying liquid-to-solid ratios and Si/Al ratios were exposed to a sulfuric acid solution (pH = 1) and analyzed after different durations of exposure (7, 14, 28, 56, and 70 days) by using a light microscope and scanning electron microscopy with energy-dispersive X-ray spectroscopy (SEM-EDX). SEM-EDX elemental mapping was used to evaluate the degradation from depth profiles of silicon (Si), aluminum (Al), and potassium (K) leaching. The results clearly show the leaching kinetics of potassium and the dealumination of the network. The separate consideration of specific reaction steps in the course of degradation, namely the depth of erosion (DE), the depth of deterioration (DD), and the depth of reaction for certain elements (DR(e)), indicate a combination of chemical and diffusion controlled degradation mechanisms.

Influence of Micro-Pore Connectivity and Micro-Fractures on Calcium Leaching of Cement Pastes-A Coupled Simulation Approach.

A coupled numerical approach is used to evaluate the influence of pore connectivity and microcracks on leaching kinetics in fully saturated cement paste. The unique advantage of the numerical model is the ability to construct and evaluate a material with controlled properties, which is very difficult under experimental conditions. Our analysis is based on two virtual microstructures, which are different in terms of pore connectivity but the same in terms of porosity and the amount of solid phases. Numerical fracturing was performed on these microstructures. The non-fractured and fractured microstructures were both subjected to chemical leaching. Results show that despite very different material physical properties, for example, pore connectivity and effective diffusivity, the leaching kinetics remain the same as long as the amount of soluble phases, i.e., buffering capacity, is the same. The leaching kinetics also remains the same in the presence of microcracks.