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Studies on Cement Pastes Exposed to Water and Solutions of Biological Waste
The paper presents studies on the early stages of biological corrosion of ordinary Portland cements (OPC) subjected to the reactive media from the agricultural industry. For ten months, cement pastes of CEM I type with various chemical compositions were exposed to pig slurry, and water was used as a reference. The phase composition and structure of hydrating cement pastes were characterized by X-ray diffraction (XRD), thermal analysis (DTA/TG/DTG/EGA), and infrared spectroscopy (FT-IR). The mechanical strength of the cement pastes was examined. A 10 to 16% decrease in the mechanical strength of the samples subjected to pig slurry was observed. The results indicated the presence of thaumasite (C3S·CO2·SO3·15H2O) as a biological corrosion product, likely formed by the reaction of cement components with living matter resulting from the presence of bacteria in pig slurry. Apart from thaumasite, portlandite (Ca(OH)2)—the product of hydration—as well as ettringite (C3A·3CaSO4·32H2O) were also observed. The study showed the increase in the calcium carbonate (CaCO3) phase. The occurrence of unreacted phases of cement clinker, i.e., dicalcium silicate (C2S) and tricalcium aluminate (C3A), in the samples was confirmed. The presence of thaumasite phase and the exposure condition-dependent disappearance of CSH phase (calcium silicate hydrate), resulting from the hydration of the cements, were demonstrated.
Physicochemical properties of Mn1.45Co1.45Cu0.1O4 spinel coating deposited on the Crofer 22 H ferritic steel and exposed to high-temperature oxidation under thermal cycling conditions
AbstractThe Crofer 22 H ferritic steel substrate was coated with an Mn1.45Co1.45Cu0.1O4 spinel by means of electrophoresis. After high-temperature oxidation under thermal cycling conditions, the physicochemical properties of the obtained system were evaluated. During 48-h cycles that involved heating the samples up to temperatures of either 750 or 800 °C, the oxidation kinetics of both coated and unmodified steel approximately obeyed the parabolic rate law. The unmodified steel was oxidized at a higher rate than the system consisting of the substrate and the coating. In its bulk form, the spinel consisted entirely of the cubic phase and it exhibited high electrical conductivity. The Mn1.45Co1.45Cu0.1O4 coating, on the other hand, was compact and consisted of two phases—the cubic and the tetragonal one—and it was characterized by good adhesion to the metallic substrate. After cyclic oxidation studies conducted for the two investigated temperatures (750 or 800 °C), the coating was determined to provide a considerable improvement in the electrical properties of the Crofer 22 H ferritic steel, as demonstrated by the area-specific resistance values measured for the steel/coating system. The evaporation rate of chromium measured for these samples likewise indicates that the coating is capable of acting as an effective barrier against the formation of volatile compounds of chromium. The Mn1.45Co1.45Cu0.1O4 spinel can therefore be considered a suitable material for a coating on the Crofer 22 H ferritic steel, with intermediate-temperature solid oxide electrolyzer cells as the target application.
Correction: Durczak et al. Modern Methods of Asbestos Waste Management as Innovative Solutions for Recycling and Sustainable Cement Production. Sustainability 2024, 16, 8798
The authors would like to make the following corrections to the published paper [...]
Effect of Variable Synthesis Conditions on the Formation of Ye’elimite-Aluminate-Calcium (YAC) Cement and Its Hydration in the Presence of Portland Cement (OPC) and Several Accessory Additives
In the presented study, ye’elimite-aluminate-calcium (YAC) cement was synthesized. Complete synthesis of crystalline phases was achieved at a temperature of 1300 °C, which is 150 °C lower than the temperature standardly used in the processes of obtaining calcium aluminate cements (CAC). The greatest amount of ye’elimite phase (Klein complex), roughly 87% by mass, was acquired utilizing a sulphur ion transporter derived from artificial dihydrate gypsum obtained in the flue gas desulphurization process (variation I). In the case of anhydrite, the amount of synthesized crystalline ye’elimite in the clinker was 67% by weight (variant II). Depending on the synthesis conditions in the clinkers, the quantity of obtained calcium aluminates (C12A7, CA, and CA2) ranged from 20 to 40% by weight. Studies on the hydration process of YAC cement samples showed that the main products are hydrated calcium aluminates and dodecahydrate calcium alumino-sulphate. In sinters of YAC and OPC, no crystalline ettringite was observed. Hydration analysis of Chinese cement revealed the presence of crystalline ettringite and dodecahydrate calcium alumino-sulphate, as well as hydrated calcium silicates of the CSH type accompanied with pseudo-crystalline Al(OH)3. The obtained clinkers from variants I and II constitute a special binder, which, due to its phase composition after hydration, can be used in the construction of reactors for biogas production in eco-energy applications.
Modern Methods of Asbestos Waste Management as Innovative Solutions for Recycling and Sustainable Cement Production
Managing asbestos waste presents a significant challenge due to the widespread industrial use of this material, and the serious health and environmental risks it poses. Despite its unique properties, such as resistance to high temperatures and substantial mechanical strength, asbestos is a material with well-documented toxicity and carcinogenicity. Ensuring the safe removal and disposal of asbestos-containing materials (ACM) is crucial for protecting public health, the environment, and for reducing CO2 emissions resulting from inefficient waste disposal methods. Traditional landfill disposal methods have proven inadequate, while modern approaches—including thermal, chemical, biotechnological, and mechanochemical methods—offer potential benefits but also come with limitations. In particular, thermal techniques that allow for asbestos degradation can significantly reduce environmental impact, while also providing the opportunity to repurpose disposal products into materials useful for cement production. Cement, a key component of concrete, can serve as a sustainable alternative, minimizing CO2 emissions and reducing the need for primary raw materials. This work provides insights into research on asbestos waste management, offering a deeper understanding of key initiatives related to asbestos removal. It presents a comprehensive review of best practices, innovative technologies, and safe asbestos management strategies, with particular emphasis on their impact on sustainable development and CO2 emission reduction. Additionally, it discusses public health hazards related to exposure to asbestos fibers, and worker protection during the asbestos disposal process. As highlighted in the review, one promising method is the currently available thermal degradation of asbestos. This method offers real opportunities for repurposing asbestos disposal products for cement production; thereby reducing CO2 emissions, minimizing waste, and supporting sustainable construction.
The Effect of Biological Corrosion on the Hydration Processes of Synthetic Tricalcium Aluminate (C3A)
This paper presents a study related to the biological degradation of a tricalcium aluminate (C3A) phase treated with reactive media from the agricultural industry. During one month of setting and hardening, synthetic C3A was subjected to corrosion in corn silage, pig slurry and chicken manure. The hardening process of the C3A phase in water was used as a reference sample. The phase composition and microstructure of the hydrating tricalcium aluminate slurries were characterised by X-ray diffraction (XRD), thermal analysis (DTA/TG/DTG/EGA), scanning microscopy (SEM, EDS) and infrared spectroscopy (FT-IR). In the samples studied, it was observed that the qualitative and quantitative phase composition of the synthetic tricalcium aluminate preparations changed depending on the corrosion exposure conditions. The main crystalline phases formed by the hydration of the examined samples in water as well as in corrosive media were the catoite (Ca3Al2(OH)12) and hydrocalumite (Ca2Al(OH)7·3H2O) phases. Detailed analysis showed the occurrence of secondary crystallisation in hydrating samples and the phases were mainly calcium carbonates (CaCO3) with different crystallite sizes. In the phase composition of the C3A pastes, varying amounts of aluminium hydroxides (Al(OH)3) were also present. The crystalline phases formed as a result of secondary crystallisation represented biological corrosion products, probably resulting from the reaction of hydrates with secondary products resulting from the metabolic processes of anaerobic bacterial respiration (from living matter) associated with the presence of bacteria in the reaction medium. The results obtained contribute towards the development of fast-acting and bio-corrosion-resistant special cements for use in bioenergetics.
Synthesis and Investigation of the Hydration Degree of CA2 Phase Modified with Boron and Fluorine Compounds
This study investigated the effect of fluoride and boron compound additives on the synthesis and hydration process of calcium aluminate (CA2). The analysis showed that the temperature of the full synthesis of CA2 without mineralizing additives was 1500 °C. However, the addition of fluorine and boron compounds at 1% and 3% significantly reduced the synthesis temperature to a range of 1100–1300 °C. The addition of fluoride compounds did not result in the formation of fluoride compounds from CaO and Al2O3, except for the calcium borate phase (Ca3(BO3)2) under certain conditions. In addition, the cellular parameters of the synthesized calcium aluminate phases were not affected by the use of these additives. Hydration studies showed that fluoride additives accelerate the hydration process, potentially improving mechanical properties, while boron additives slow down the reaction with water. These results highlight the relevance of fluoride and boron additives to the synthesis process and hydration kinetics of calcium aluminate, suggesting the need for further research to optimize their application in practice. TG studies confirmed the presence of convergence with respect to X-ray determinations made. SEM, EDS and elemental concentration maps confirmed the presence of a higher Al/Ca ratio in the samples and also showed the presence of hexagonal and regular hydration products.
Changes in the Phase Composition of Calcium Aluminoferrites Based on the Synthesis Condition and Al2O3/Fe2O3 Molar Ratio
The presented work concerns the study of the changes in the phase composition of calcium aluminoferrites which depend on the synthesis conditions and the selection of the Al2O3/Fe2O3 molar ratio (A/F). The A/F molar ratio extends beyond the limiting composition of C6A2F (6CaO·2Al2O3·Fe2O) towards phases richer in Al2O3. An increase in the A/F ratio above unity favours the formation of other crystalline phases such as C12A7 and C3A, in addition to calcium aluminoferrite. Slow cooling of melts characterised by an A/F ratio below 0.58, results in the formation of a single calcium aluminoferrite phase. Above this ratio, the presence of varying contents of C12A7 and C3A phases was found. The process of rapid cooling of the melts with an A/F molar ratio approaching the value of four favours the formation of a single phase with variable chemical composition. Generally, an increase in the A/F ratio above the value of four generates the formation of a calcium aluminoferrite amorphous phase. The rapidly cooled samples with compositions of C22.19A10.94F and C14.61A6.29F were fully amorphous. Additionally, this study shows that as the A/F molar ratio of the melts decreases, the elemental cell volume of the calcium aluminoferrites decreases.