Building materials generally perform poorly in a high temperature environment. Residential fires and fires in road tunnels are common occurrences. Furthermore, some factories have no option besides exposing their infrastructure to very high temperatures due to the nature of their operation logistics. Therefore, there is a clear need for developing structural materials that can withstand high temperatures ensuring safety during such events. The present thesis deals with thermal shock damage in construction materials. Specifically, the first half of the thesis focuses on the development of an structural material that would fare well on severe cyclic thermal shock conditions found in a steel factory. The second half aims to improve the capacity of engineers and scientists to predict whether a concrete of a given mixture would suffer from spalling under certain heating conditions. Initially, a review of the main effects and chemical changes caused by high temperature was performed on the conventional building materials, followed by some novel materials being currently explored by the civil engineering scientific community. This aided in the pre-selection of material to be tested at later stages. Further, existing theories concerning high temperature spalling, the causes and the main methods of mitigation were reviewed. @en

Spalling is the main problem concerning safety in concrete structures under rapid heating. Despite being studied for nearly a century, its prediction remains a challenge. In addition, the main recommendations for its prevention are merely the addition of a fixed amount of polypropylene fibres, without accounting for mix design. This paper presents an experimental study focusing on the thermo-hygral mechanism contribution to spalling. The use of mercury intrusion porosimetry and X-ray microtomography for the determination of pore connectivity is considered a key parameter. The results of the experiment are used for the development and calibration of an analytical equation capable of predicting spalling in concrete samples. The equation is then validated using over 100 examples extracted from literature, achieving an accuracy of 91.2%. Based on the validation, the proposed equation is a step forward in the prediction of concrete spalling based on the mix design parameters.

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Municipal solid waste incineration (MSWI) bottom ash, due to its high mineral content, presents great potential as supplementary cementitious material (SCM). Weathering, also known as aging, is a treatment process commonly employed in waste management to minimize the risk of heavy metal leaching from MSWI bottom ash. Using weathered MSWI bottom ash to produce blended cement pastes is considered as a high-value-added and sustainable waste disposal solution. However, a critical challenge arises from the metallic aluminum (Al) in weathered MSWI bottom ash, which is known to induce detrimental effects such as volume expansion and strength loss of blended cement pastes. While most metallic Al in weathered MSWI bottom ash can be removed with eddy current separators in metal recovery plants, the residual metallic Al, owing to its small particle size, cannot be removed with the same technique. This study is dedicated to addressing this issue. An in-depth analysis was conducted on residual metallic Al embedded in weathered MSWI bottom ash particles, aiming to guide the removal of this metal. This analysis revealed that mechanical removal was the most suitable method for extracting metallic Al. The specific processes and mechanisms underlying this method were elucidated. After reducing metallic Al content in weathered MSWI bottom ash by 77 %, a significant improvement in the quality of blended cement pastes was observed. This work contributes to the broader adoption of mechanical treatments for removing residual metallic Al from weathered MSWI bottom ash and facilitates the application of treated ash as SCM.

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The utilization of locally available concrete waste for producing recycled concrete aggregates is recognized as one of the most sustainable ways of satisfying the growing demand for concrete production. However, the quality of concrete waste depends on its origin and it may significantly differ from one concrete structure to another. Knowing the chemical composition of the parent concrete is crucial for determining or verifying the origin of the raw materials. For this reason, pre-demolition concrete waste streams need to be characterized and classified. Therefore, a new non-destructive method for determining the cement and aggregate type in hardened concrete using handheld X-ray fluorescence (hXRF) analyser is presented in this paper. The method was tested on different raw powders and on concretes containing different types of cements including CEM I 42.5 N (Portland cement), CEM II/B-V 42.5 N (Portland-fly ash cement), CEM III/B 42.5 N (GGBFS cement). Combined desktop XRF and Energy-dispersive X-ray Spectroscopy (EDS) measurements were used for the purpose of validation. The results revealed that the curing of concrete affects the results: a dried concrete surface condition was optimal for measurements since it limits the impact of the concrete surface moisture and efflorescence on characteristic element oxides, such as CaO. The effective measurement duration was 30 s. A CEM III/B 42.5 N (GGBFS)-based concrete surface was distinguished from other concretes using Al2O3, MgO and Fe2O3 as characteristic oxides. The inner layers of concrete were rich in SiO2, the oxide characteristic for the aggregate composition tested in this study. This shows that hXRF is suitable for use in concrete, provided that the concrete surface is dried and the characteristic elements are defined to ensure a distinction between different cement and aggregate types. Direct adoption of such characterization, however, requires field testing across a wide range of concrete compositions and in situ conditions.@en

Industries such as metal, ceramics and petrochemicals suffer from high temperature spills. Such events exert a unique form of loading in concrete structures that cannot be accurately simulated by heating of samples in an oven. Calcium aluminate cement (CAC) based concrete is the industry standard for such environment, and while much is known regarding its heating, literature considering hot spills on concrete surfaces is scarce. In this paper, slag is heated up to the same temperature as in a steel factory and then poured on top of cement paste samples with W/C ratios of 0.20 and 0.40. A combination of FEM, TGA, XRD and SEM/EDS was used to investigate the effects of hot spill on the samples. The rapid expansion caused by the thermal shock generated cracks in only some of the samples, while the high temperature environment and unidirectional escape of water caused chemical changes in all samples.@en

Concrete structures perform poorly when withstanding thermal shock events, usually requiring repair or replacement after one single instance. In certain industries (such as petrol, metallurgic and ceramics), these events are not only likely but frequent, which represents a considerable financial burden. One option to solve this issue would be to decrease the heating rate imposed onto the concrete material through the use of a protective surface layer. In this work, the suitability of dunite and microgabbro as protective materials is explored through X-ray diffraction, thermal dilation, optical microscopy, X-ray microtomography, thermo-gravimetric analysis and a compressive test. Further, the thermal dilation was used as an input to simulate a composite concrete-rock wall and the respective stresses caused by a thermal shock event. The dehydration of chrysotile in dunite and the decomposition of analcime, chamosite and pumpellyite in microgabbro were both favourable for the performance of the stones in the desired application. The thermal stability and deformation were found in the range of what can be applied directly on concrete; however, it was clear that pre-heating treatment results in a far more durable system in a cyclic thermal load situation.@en

Remarkable attention from both academia and industry has been attracted to extrusion-based 3D concrete printing (3DCP) during the last decade. Many companies in the Netherlands, e.g., Royal BAM Group, CyBe, Twente Additive Manufacturing, and Bruil, are attempting to implement this technology in practice. 3DCP is the focused digital concrete manufacturing technique in this study. The development of printable cementitious composites is possibly the most critical aspect in 3DCP. Compared to mold-cast concrete process, several essential material parameters need to be controlled in 3DCP process, i.e., pumpability, extrudability, buildability, and others. Conventional materials technology appears to have limited resources to offer for further enhancing the capabilities of 3D printing. Therefore, there is a dire need for adopting non-conventional materials solutions for which nanomaterials can play a vital role. Controlling the rheology is the key to successful 3DCP, as achieving dimensional stability and the minimum required mechanical properties in green state are the main challenges. Furthermore, achieving a required strength development rate and enabling smart monitoring of the 3DCP are the other goals that are desired in designing such materials. Recent research shows that successful modification of cementitious materials can be achieved by incorporating nanomaterials in the materials design for the enhanced fresh and hardened state properties. In this chapter, a summary of these developments is compiled in the light of potential applications, safety issues, and technological challenges.

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For many 3D printed cementitious materials, air voids may play a dominant role in the interlayer bond strength. However, to date, far too little attention has been paid to reveal the air void characteristics in 3D printed cementitious materials. Therefore, to fill this gap, this study attempts to provide an example of systematically characterizing the typical air void system of 3D printed cementitious materials via different image acquisition and analysis techniques. Two printable limestone and calcined clay-based mixtures were employed to prepare the printed samples. The micrographs were acquired by using optical image scanning and X-ray computed tomography. Afterwards, air void metrics in printed cementitious materials were determined, i.e., content, distribution, size, and shape. The results revealed that most of the air voids with the diameter in the range of 10–1000 μm were distributed evenly in the layer region of printed samples. Large air voids (1000–6000 μm) were enclosed mainly between the printed filaments (interface region), which resulted in the relatively higher local porosity than that of layer region. Additionally, the majority of air voids displayed irregular and elongated shapes, which could be attributed to the extrusion and layer-wise manufacturing processes in 3D printing. Finally, a comparison between optical image scanning and X-ray computed tomography was given.@en

The investigation of new compositions is crucial for the expansion of possible applications of glass, from the typical applications for building engineering, in the form of cast blocks or float glass, to more advanced technologies, such as 3D-printed glass or glass-to-metal connections. Since high melting temperatures and brittleness are two important drawbacks of glass, this work aims to improve both properties. Characterisation techniques, such as thermal analysis, nano-indentation, and UV/VIS spectroscopy, are used to evaluate the properties of the samples. The modification of the properties is achieved via changes in the composition of the glass, using compounds such as phosphorus pentoxide, aluminium oxide and boron oxide. Then, the choice of different glass formers and modifiers contributes to the development of compositions with lower melting and glass transition temperatures. The reduction of the melting temperature allows a saving of energy during the manufacturing. The structures of the glasses differ from the standard soda–lime–silica and borosilicate glasses, leading to a different mechanical behaviour. Furthermore, these new compositions incorporate up to 35% of fly ash in their formulas. The valorisation of these by-products reduces costs and gas emission.@en

X-ray computer scanning tomography (CT scan) is an increasingly more available technique, which has been applied to material sciences for years. Although most of its use is qualitative for gaining insights on material behavior, quantitative analysis for estimations of deterioration rates is possible. This paper describes an unbiased, straightforward method to determine the amount of reinforcement lost to corrosion through the use of X-ray tomography without the need to remove the concrete cover. Other methods of assessment such as gravimetric analysis, half-cell potential, resistivity of mortar cover, corrosion current, and scanning electron microscopy (SEM) are used in the same samples for comparison. While the electrical and electrochemical tests are valuable to describe the state of the samples, those demonstrated poor capacity of determining the stage of corrosion of the reinforcement in terms of amount of material lost. Electron microscopy could determine how much of the reinforcement corroded with high accuracy; however, these results are deficient in representativity, being based on a single plane of the steel. X-ray tomography, while suffering from sample size limitation, could provide quantitative information on the total volume of material lost for each sample with far higher accuracy than indirect techniques, which is significant for the forensic determination of remaining life service of structures.

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Superabsorbent Polymers (SAP) have been recently subject of investigation as smart admixtures for cement-based materials. The properties of these polymers enable their use for internal curing, increasing freeze/thaw resistance, boosting autogenous self-healing and providing a crack self-sealing effect in cementitious composites. Except for the earliest application, the functioning of these beneficial effects invloves the absorption by the polymers of ingress water in the hardened cementitious matrix and later release, as well as their capacity to complete multiple absorption/desorption cycles. In this work, the absorption of water in mortar with superabsorbent polymers is monitored during the first 60 min of absorption through micro-CT. The experimental series included the presence of cracks. The registration and differentiation of sub-minute (18 s) scans enabled the individuation of bulk water content distribution in the mortar with a resolution of 55 μm. The swollen volume of SAP could also be quantified and studied in time. The results point out that although embedded SAP absorb water from the matrix, this absorption is slow and reduced with respect to water absorption during mixing for the used SAP. Same effect is observed for SAP in the cracks.

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Recent studies have shown that concrete containing Phase Change Materials (PCM) with low transition temperatures may reduce the number of freeze/thaw cycles suffered by the cementitious composite in temperate climates. Nevertheless, the positive influence of such admixtures on the frost resistance of cement-based materials has not been directly shown, nor the negative. In this study, mortars with different contents of microencapsulated PCM by volume of cement paste were studied with regard to the progression of their internal and salt scaling damages during freeze/thaw cycles. X-ray micro tomography was used to monitor damage development and spatial distribution in the mortars. Furthermore, the pore system and microstructure of the PCM-modified mortars were characterized to unveil the causes of the observed macroscopic behavior during frost weathering. The results show that limited amounts of PCM in mortar, namely 10% by volume of cement paste, results beneficial for the frost and scaling resistance of the composite. Whereas, for larger PCM additions, like 30% by volume of paste, the changes in microstructure, porosity and mechanical strength brought in by these admixtures resulted in worsened performance against freeze/thawing cycles.

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In this study, the interface between different types of bacteria-embedded self-healing polylactic acid capsules (PLA) and cement paste is investigated. Particularly, the changes in microstructure and mechanical properties of the interface with respect to bulk cement paste were studied. First, nanoindentation was performed to obtain maps of hardness and elastic modulus in the interfaces. Lattice modeling of uniaxial tensile test on the mapped locations was performed then to obtain the overall tensile strength and stiffness of the interface. Moreover, hydrates assemblage and chemical composition around the PLA particles were studied through Backscattering Electron images and Energy Dispersive X-ray Spectroscopy. The ratios between resulting tensile strength and elastic modulus of the interface with respect to bulk paste were obtained for each PLA type. The results suggest that PLA can be tailored to optimize the physico-mechanical properties of the interface and hence, the mechanical behavior and triggering efficiency of the self-healing system.@en

Calcium aluminate cements (CAC) are widely used for the production of refractory concretes that are able to withstand extreme temperatures. During exposure to such temperatures, the main hydration phases revert to mayenite, calcium aluminate and calcium dialuminate. Many investigations focused on the description of this mechanism and how it affects the remaining mechanical properties of the concrete. However, subsequent contact with air humidity after high temperature exposure further modifies the composition of the cement paste. The effects of re-hydration on the pore network and mechanical properties of concrete are critical to the design of durable systems under repeated exposure to high temperatures, as well as assessing the remaining quality of damaged structures. Yet such effects remain poorly understood. This research focuses on the use of CAC as a compatible protection layer to concrete made with ordinary Portland cement (OPC) in order to sustain infrastructure in industries which may have occasional or even constant high temperature spills (such as steel, aluminum, petro-chemicals and others). To achieve such goal, slabs with one layer composed of CAC mortar and a second layer made of OPC mortar will be subjected to contact with molten glass at 1530°C followed by exposure to ambient moisture in a fog room. The microstructure of these samples will then be studied and compared. @en

The potential of using phase change materials (PCM) in cementitious materials to mitigate damage due to thermal loadings has been recently focus of intensive research. In the case of PCM with transition temperatures near to the freezing point of water, their potential to delay frost in a cementitious matrix has been largely investigated through the monitoring of internal temperature changes when exposed to repeated cycles of subzero and ambient temperature. Yet, the effect of these admixtures to prevent damage in cement-based materials has not been directly studied. In this paper,mortars cylinders of two different sizes and containing 0, 10 and 30%of PCM replacement by volume of aggregates were subjected to frost salt scaling during freeze and thaw cycles. Prior to the start of the weathering and after cycles 1, 3, 7 and 15 the cylindrical specimens were subjected to X-ray microtomography to monitor morphological changes due to frost action, such as chipping and cracks. Compressive and flexural strength, coefficient of thermal expansion and apparent porosity of the undamaged composites were also investigated. Results suggest that the improvement of frost scaling resistance of the mortars with incorporated PCM is a trade-off between resulting mechanical proper-ties, thermal volume stability and porosity of the composite, as evinced from the better performance of mortars with 10%of PCM replacement.@en

In this article a trip is taken to characterize concrete through its hardened cement paste based on its microstructure. Optical microscopy is coupled to advanced image analysis, as well as statistical data analysis to characterize heterogeneous concrete material. The article takes a closer look at the determination of the w/c ratio through the analysis of capillary porosity by using image analysis. It is shown that accurate analysis does not shown identical results in the w/c ratio even for standard reference samples with known w/c ratio. In the article it is shown that this is not because the techniques we use to determine the w/c ratios are not accurate enough, but much more because of the local variation in the microstructure. The attention shifts with this article from the analysis technique to what we actually observe in the microstructure. Hopefully this will change our thinking about the distribution in local microstructure variation and will help to set off more research towards the capturing and modelling of these local microstructure variation into consequences at a more structural level.@en

In the past two decades, much research has been devoted to overcoming the inherent brittleness of cementitious materials. To that end, several solutions have been proposed, mainly utilizing fibres. One of the most promising classes of materials is strain hardening cementitious composite (SHCC). It utilizes PVA fibres, and it relatively costly compared to regular concrete, so it is commonly used only in surface layers. This paper presents a multi-functional ductile cementitious composite based on SHCC. It uses microencapsulated phase change materials (PCMs), capable of reducing temperature fluctuations in the material due to their high heat of fusion. It is shown that, although addition of microencapsulated PCMs are detrimental to compressive strength, they have very little effect on the flexural strength and deflection capacity. This material has potential to reduce temperature effects on concrete surfaces, while at the same time being extremely ductile.

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Abstract In the past two decades, much research has been devoted to overcoming the inherent brittleness of cementitious materials. To that end, several solutions have been proposed, mainly utilizing fibres. One of the most promising classes of materials is strain hardening cementitious composite (SHCC). It utilizes PVA fibres, and it is relatively costly compared to regular concrete, so it is commonly used only in surface layers. In this paper, a multi-functional ductile cementitious composite based on SHCC has been developed. It uses microencapsulated phase change materials (PCMs), capable of reducing temperature fluctuations in the material due to their high heat of fusion. It is shown that, although addition of microencapsulated PCMs are detrimental to compressive strength, they have very little effect on the flexural strength and deflection capacity. In the future work, mixtures with higher PCM contents will be developed in order to exploit their heat storage capability better. This material has potential to reduce temperature effects on concrete surfaces, while at the same time being extremely ductile. @en