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.

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.

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.

A Review on Cementitious Self-Healing and the Potential of Phase-Field Methods for Modeling Crack-Closing and Fracture Recovery.

Improving the durability and sustainability of concrete structures has been driving the enormous number of research papers on self-healing mechanisms that have been published in the past decades. The vast developments of computer science significantly contributed to this and enhanced the various possibilities numerical simulations can offer to predict the entire service life, with emphasis on crack development and cementitious self-healing. The aim of this paper is to review the currently available literature on numerical methods for cementitious self-healing and fracture development using Phase-Field (PF) methods. The PF method is a computational method that has been frequently used for modeling and predicting the evolution of meso- and microstructural morphology of cementitious materials. It uses a set of conservative and non-conservative field variables to describe the phase evolutions. Unlike traditional sharp interface models, these field variables are continuous in the interfacial region, which is typical for PF methods. The present study first summarizes the various principles of self-healing mechanisms for cementitious materials, followed by the application of PF methods for simulating microscopic phase transformations. Then, a review on the various PF approaches for precipitation reaction and fracture mechanisms is reported, where the final section addresses potential key issues that may be considered in future developments of self-healing models. This also includes unified, combined and coupled multi-field models, which allow a comprehensive simulation of self-healing processes in cementitious materials.

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.

Modeling SAOS Yield Stress of Cement Suspensions: Microstructure-Based Computational Approach.

Two static yield stress models, one known as YODEL and the newly proposed BreakPro, based on inter-particle bond breaking probability, were employed to comparatively simulate the yield stress of cement suspensions, induced by oscillatory rheological tests with small amplitude oscillatory shear (SAOS). This yield stress occurs at a critical strain in the order of 0.01%, and is commonly attributed to the limit of the linear viscoelastic domain, where attractive forces bridge the cement particles and form a flocculated particle network. YODEL is based on van der Waals (vdW) interaction forces to describe the yield stress for flow onset at a critical strain of a few percent, developed for simple non-reactive particulate suspensions. However, due to the high pH and reactivity of cementitious suspensions, their particle interaction forces are much higher than vdW. Therefore, until now, the YODEL adaptations to cementitious suspensions did not explicitly consider the microstructural-based salient feature of the original model, but used it as an implicit fitting parameter to scale the average attractive force. In this paper, the force is inversely estimated using the full power of the two microstructural-based models, presenting a new mathematical tool for investigating the fragility of the rigid percolated structure of cement suspensions. The model parameters were calibrated on measured yield stresses obtained by SAOS measurements in a high-sensitivity rheometer. The estimated forces were found to be 5.57 (BreakPro) and 1.43 (YODEL) times higher than typical van der Waals forces. The YODEL percolation threshold of 21% turned out to be significantly lower than the one found by the BreakPro model (37%). This indicated that BreakPro modeling assumptions are better suited for the description of yield stress at SAOS critical strain than the YODEL model.

A Comparative Study on the Thermal Energy Storage Performance of Bio-Based and Paraffin-Based PCMs Using DSC Procedures.

Thermal-Energy Storage (TES) properties of organic phase change materials have been experimentally investigated and reported in this paper. Three paraffin-based Phase Change Materials (PCMs) and one bio-based PCM are considered with melting temperatures of 24 °C, 25 °C and 26 °C. Sensible heat storage capacities, melting characteristics and latent heat enthalpies of the studied PCMs are investigated through Differential Scanning Calorimetry (DSC) measurements. Two alternative methods, namely the classical dynamic DSC and a stepwise approach, are performed and compared with the aim to eliminate and/or overcome possible measurement errors. In particular, for DSC measurements this could be related to the size of the samples and its representativity, heating rate effects and low thermal conductivity of the PCMs, which may affect the results and possibly cause a loss of objectivity of the measurements. Based on results achieved from this study, clear information can be figured out on how to conduct and characterize paraffin and bio-based PCMs, and how to apply them in TES calculations for building applications and/or simulations. It is observed that both paraffinic and bio-based PCMs possess a comparable TES capacity within the selected phase transition temperature, being representative for the human thermal comfort zone. The phase change of bio-based PCMs occurred over a much narrower temperature range when compared to the wider windows characterizing the paraffin-based materials. Bio-based PCMs turned out to be very suitable for building applications and can be an environmentally friendly substitute for petroleum-based PCMs.

Modelling the Thermal Energy Storage of Cementitious Mortars Made with PCM-Recycled Brick Aggregates.

This paper reports a numerical approach for modelling the thermal behavior and heat accumulation/liberation of sustainable cementitious composites made with Recycled Brick Aggregates (RBAs) employed as carriers for Phase-Change Materials (PCMs). In the framework of the further development of the fixed grid modelling method, classically employed for solving the well-known Stefan problem, an enthalpy-based approach and an apparent calorific capacity method have been proposed and validated. More specifically, the results of an experimental program, following an advanced incorporation and immobilization technique, developed at the Institut für Werkstoffe im Bauwesen for investigating the thermal responses of various combinations of PCM-RBAs, have been considered as the benchmark to calibrate/validate the numerical results. Promising numerical results have been obtained, and temperature simulations showed good agreement with the experimental data of the analyzed mixtures.

Reactivity and Microstructure of Metakaolin Based Geopolymers: Effect of Fly Ash and Liquid/Solid Contents.

Geopolymers are inorganic binders based on mixtures of an aluminosilicate powder with an alkali-silicate solution. Properties of geopolymers are strongly determined by the type of reactive solid, the liquid/solid ratio of paste and, amongst others, the Si/Al ratio of the formed geopolymer network. In this study, fly ash blended metakaolin based geopolymers with varying liquid/solid ratios (l/s), activated by potassium silicate solution, are investigated. Reactivity of metakaolin and fly ash was investigated by powder X-ray diffraction (XRD) and dissolution tests. Reactivity, mechanical properties and microstructure of hardened pastes were analyzed by setting and compressive strength tests, mercury intrusion porosimetry (MIP), capillary water absorption tests, thermogravimetric analysis-differential scanning calorimeter (TGA-DSC), isothermal calorimetry and scanning electron microscopy with energy dispersive spectroscopy (SEM-EDS). The results show that substitution of metakaolin by fly ash as well as variation of l/s brings advantages up to a certain degree, but also has a considerable influence on the pore size distribution, mechanical properties, Si/Al ratio of the geopolymer network and the content of bound water.

Relating Ettringite Formation and Rheological Changes during the Initial Cement Hydration: A Comparative Study Applying XRD Analysis, Rheological Measurements and Modeling.

In order to gain a deeper understanding of the rheological development of hydrating ordinary Portland cement (OPC) pastes at initial state, and to better understand their underlying processes, quantitative X-ray diffraction (XRD) analysis and rheological measurements were conducted and their results combined. The time-dependent relation between phase development and flow behavior of cement paste was investigated at two different temperatures (20 and 30 °C), over a period of two hours. Regarding the phase development during hydration, ettringite precipitation was identified as the dominant reaction in the first two hours. For both temperatures, the increasing ettringite content turned out to correlate very well with the loss of workability of the reacting cement paste. An exponential relationship between ettringite growth and flow behavior was observed that could be explained by applying the Krieger-Dougherty equation, which describes the influence of solid fraction on the viscosity of a suspension.

Geopolymer, Calcium Aluminate, and Portland Cement-Based Mortars: Comparing Degradation Using Acetic Acid.

In this paper, we comparitvley studied acetic acid attacks on geopolymer (GP-M), calcium aluminate (CAC-M), and Portland cement (PC-M)-based mortars. Consequent formations of deteriorated or transition layers surrounding the unaltered core material was classified in these three mortars, according to different degradation levels depending on what binder type was involved. Apart from mass loss, hardness, and deterioration depth, their microstructural alterations were analyzed using test methods such as scanning electron microscopy with energy dispersive spectroscopy (SEM-EDS), mercury intrusion porosimetry (MIP), powder X-ray diffraction (XRD), and thermogravimetric analysis-differential scanning calorimeter (TGA-DSC), which showed the different mechanisms for each binder type. Elemental maps revealed the decalcification (PC-M and CAC-M) and depolymerization (GP-M) that occurred across the mortar sections. The mass loss, hardness, and porosity were the least affected for GP-M, followed by CAC-M. These results points out that geopolymer-based mortars have improved acid resistance, which can be used as a potential alternative to conventional cement concretes that have been exposed to agro-industrial environments.