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Addition of different types of phase change materials (PCMs) to cement-based materials for thermal energy storage has been broadly investigated in the literature. Many studies have researched the addition of organic PCMs and the thermal performance of the PCM-cement system. However, drawbacks such as leakage and poor thermal conductivity of the PCMs have stimulated studies to improve thermal properties within the PCM-cement system. Among the different solutions, addition of carbonous materials (such as graphite and carbon nanotubes) to improve thermal conductivity of the PCMs have been investigated. In the current work, an innovative system that contains microencapsulated PCMs (MPCMs) and purposely synthesized reduced graphene oxide (rGO) has been designed and assessed. The addition of rGO has two aims. The first one is to speed up the heat storage/release velocity by improving the thermal conductivity of the whole system. The second one is to improve the electrical conductivity of the system in order to actively (by applying voltage) be able to turn on the thermal storage/release feature. Up to the authors' knowledge, this is a novel approach for the development of active PCM-cement based thermal energy storage systems. Furthermore, in the present study, the use of paraffinic PCMs was compared with that of biobased PCMs in order to provide a more sustainable solution to the design of cement-based elements for buildings applications. A comprehensive thermal characterization (heat storage capacity, thermal conductivity and diffusivity) has been carried out as well as microstructural characterization. Moreover, broadband dielectric spectroscopy was used to characterize the electrical conductivity of the novel MPCM-rGO-cement system.

Although concrete and cement-based materials are the most engineered materials employed by mankind, their potential for use in daytime radiative cooling applications has yet to be fully explored. Due to its complex structure, which is composed of multiple phases and textural details, fine-tuning of concrete is impossible without first analyzing its most important ingredients. Here, the radiative cooling properties of Portlandite (Ca(OH)2) and Tobermorite (Ca5Si6O16(OH)2·4H2O) are studied due to their crucial relevance in cement and concrete science and technology. Our findings demonstrate that, in contrast to concrete (which is a strong infrared emitter but a poor sun reflector), both Portlandite and Tobermorite exhibit good radiative cooling capabilities. These results provide solid evidence that, with the correct optimization of composition and porosity, concrete can be transformed into a material suitable for daytime radiative cooling.

Geopolymer (GEO) concrete emerges as a potential high-temperature thermal energy storage (TES) material, offering a remarkable thermal storage capacity, approximately 3.5 times higher than regular Portland cement (OPC) concrete, without compromising its environmentally benign nature., This research dissects the application of GEO concrete as a high-temperature TES material, primarily focusing on its optimization and scalability. The introductory part of the study involves the development and validation of a three-dimensional numerical model using computational fluid dynamics (CFD). The model demonstrated an average accuracy rate of 5 %, as justified by empirical data. Later, a two-tiered investigation to determine the optimal design for GEO concrete TES systems was investigated. Three different geometries plus the impact of crucial parameters such as air velocity, tube diameter, and module size on the thermal storage capacity (Q) studied. It further extends into a parametric examination, exploring a variety of tube sizes, arrangements, and configurations. It is found that air velocity primarily influences Q., A subsequent phase provides an analysis of the thermodynamic effects brought by the inclusion of tubes within TES modules through an equivalent parametric study. It exposes the thermal resistance resulting from tube insertion. The study reinforces the superior thermal performance of tubeless GEO concrete TES configurations, as signified by overall heat transfer rate (Q̇). The study also signals the significant roles of key parameters in determining the temperature (T) and Q within TES unit using Pearson's correlation coefficient equation., As a final observation, this work emphasizes the sustained significance of on-site evaluations to consistently monitor the interplay between TES materials and high-temperature fluids (HTFs) over extended periods for viability analysis purposes.

The last generation of cement hydration accelerators relies on the seeding effect induced by amorphous calcium silicate hydrate particles. However, little is known about the effect of variables, such as the degree of crystallinity and morphology, on their performance. In this work, particles with a Ca/(Si+Al) molar ratio of 0.83 and different proportions of aluminum substitution for silicon were synthesized under hydrothermal conditions. X-ray diffractograms, nuclear magnetic resonance spectra, and scanning electron microscopy images showed that this altered the degree of crystallinity, structure, and morphology of the particles. Nevertheless, the addition of the synthesis products to cement pastes and their subsequent study by isothermal calorimetry and mechanical tests showed that the variables with the largest impact on cement hydration are the dosage and the proper dispersion of the particles. In fact, the use of a dispersing agent is highly recommended while drying of the particles should be avoided to prevent irreversible agglomeration processes from taking place.

Thermal energy storage (TES) systems are dependent on materials capable of operating at elevated temperatures for their performance and for prevailing as an integral part of industries. High-temperature TES assists in increasing the dispatchability of present power plants as well as increasing the efficiency in heat industry applications. Ordinary Portland cement (OPC)-based concretes are widely used as a sensible TES material in different applications. However, their performance is limited to operation temperatures below 400 °C due to the thermal degradation processes in its structure. In the present work, the performance and heat storage capacity of geopolymer-based concrete (GEO) have been studied experimentally and a comparison was carried out with OPC-based materials. Two thermal scenarios were examined, and results indicate that GEO withstand high running temperatures, higher than 500 °C, revealing higher thermal storage capacity than OPC-based materials. The high thermal energy storage, along with the high thermal diffusion coefficient at high temperatures, makes GEO a potential material that has good competitive properties compared with OPC-based TES. Experiments show the ability of geopolymer-based concrete for thermal energy storage applications, especially in industries that require feasible material for operation at high temperatures.

KIMERA is a scientific tool for the study of mineral dissolution. It implements a reversible Kinetic Monte Carlo (KMC) method to study the time evolution of a dissolving system, obtaining the dissolution rate and information about the atomic scale dissolution mechanisms. KIMERA allows to define the dissolution process in multiple ways, using a wide diversity of event types to mimic the dissolution reactions, and define the mineral structure in great detail, including topographic defects, dislocations, and point defects. Therefore, KIMERA ensures to perform numerous studies with great versatility. In addition, it offers a good performance thanks to its parallelization and efficient algorithms within the KMC method. In this manuscript, we present the code features and show some examples of its capabilities. KIMERA is controllable via user commands, it is written in object-oriented C++, and it is distributed as open-source software.

The development of self-healing high performance concretes (HPC) is mainly based on the necessity to guarantee durable concrete structures under extreme environmental and/or operating conditions. The implementation of self-healing HPC can be an efficient solution to these special situations avoiding or reducing future rehabilitations. These special concretes can significantly reduce the maintenance costs although the initial cost of the concrete infrastructure is expected to increase. Due to their special composition, HPC have certain self-healing capacity but it must be improved by using engineered additions in order to heal wider cracks or to have a faster response. However, although the use of nanoparticles is significantly increasing in the construction industry, only few works can be found in the literature focused on the exploitation of nanoparticles for improving the self-healing performance of HPC. In the present chapter, the main publications related to this issue are described, as well as the modifications that the inclusion of these self-healing systems based on nanoparticles causes in the microstructural, physico-mechanical, and durable performance of the corresponding HPC. Additionally, an overall idea concerning the modifications promoted in certain properties by self-healing systems not based on nanoparticles in HPC is also given.

Shortly after mixing cement grains with water, a cementitious fluid paste is formed that immediately transforms into a solid form by a phenomenon known as setting. Setting actually corresponds to the percolation of emergent network structures consisting of dissolving cement grains glued together by nanoscale hydration products, mainly calcium-silicate-hydrates. As happens in many percolation phenomena problems, the theoretical identification of the percolation threshold (i.e. the cement setting) is still challenging, since the length scale where percolation becomes apparent (typically the length of the cement grains, microns) is many times larger than the nanoscale hydrates forming the growing spanning network. Up to now, the long-lasting gap of knowledge on the establishment of a seamless handshake between both scales has been an unsurmountable obstacle for the development of a predictive theory of setting. Herein we present a true multi-scale model which concurrently provides information at the scale of cement grains (microns) and at the scale of the nano-hydrates that emerge during cement hydration. A key feature of the model is the recognition of cement setting as an off-lattice bond percolation process between cement grains. Inasmuch as this is so, the macroscopic probability of forming bonds between cement grains can be statistically analysed in smaller local observation windows containing fewer cement grains, where the nucleation and growth of the nano-hydrates can be explicitly described using a kinetic Monte Carlo Nucleation and Growth model. The most striking result of the model is the finding that only a few links (~12%) between cement grains are needed to reach setting. This directly unveils the importance of explicitly including nano-texture on the description of setting and explains why so low amount of nano-hydrates is needed for forming a spanning network. From the simulations, it becomes evident that this low amount is least affected by processin, Materials and Environment

Shortly after mixing cement grains with water, a cementitious fluid paste is formed that immediately transforms into a solid form by a phenomenon known as setting. Setting actually corresponds to the percolation of emergent network structures consisting of dissolving cement grains glued together by nanoscale hydration products, mainly calcium-silicate-hydrates. As happens in many percolation phenomena problems, the theoretical identification of the percolation threshold (i.e. the cement setting) is still challenging, since the length scale where percolation becomes apparent (typically the length of the cement grains, microns) is many times larger than the nanoscale hydrates forming the growing spanning network. Up to now, the long-lasting gap of knowledge on the establishment of a seamless handshake between both scales has been an unsurmountable obstacle for the development of a predictive theory of setting. Herein we present a true multi-scale model which concurrently provides information at the scale of cement grains (microns) and at the scale of the nano-hydrates that emerge during cement hydration. A key feature of the model is the recognition of cement setting as an off-lattice bond percolation process between cement grains. Inasmuch as this is so, the macroscopic probability of forming bonds between cement grains can be statistically analysed in smaller local observation windows containing fewer cement grains, where the nucleation and growth of the nano-hydrates can be explicitly described using a kinetic Monte Carlo Nucleation and Growth model. The most striking result of the model is the finding that only a few links (~12%) between cement grains are needed to reach setting. This directly unveils the importance of explicitly including nano-texture on the description of setting and explains why so low amount of nano-hydrates is needed for forming a spanning network. From the simulations, it becomes evident that this low amount is least affected by processing v

Tobermorite is a fibrillar mineral of the family of calcium silicates. In spite of not being abundant in nature, its structure and properties are reasonably well known because of its interest in the construction industry. Currently, tobermorite is synthesized by hydrothermal methods at mild temperatures. The problem is that such processes are very slow (>5 h) and temperature cannot be increased to speed them up because tobermorite is metastable over 130 °C. Furthermore the product obtained is generally foil-like and not very crystalline. Herein we propose an alternative synthesis method based on the use of a continuous flow reactor and supercritical water. In spite of the high temperature, the transformation of tobermorite to more stable phases can be prevented by accurately controlling the reaction time. As a result, highly crystalline fibrillar tobermorite can be obtained in just a few seconds under thermodynamically metastable conditions.

In this work we study the influence of adding nano-silica (SiO2, Nyasil™) and aminopropyl (-(CH2)3-NH2,) functionalized silica nanoparticles (Stoga) during the synthesis of calcium-silicate-hydrate (C-S-H gel). Characterization by solid state 29Si NMR and ATR-FTIR spectroscopy showed that the addition of both particle types increases the average length of the silicate chains in C-S-H gel being this effect slightly more important in the case of Stoga particles. In addition, 13C NMR and XPS confirmed that the aminopropyl chain remains in the final product cleaved to silicon atoms at the end of the silicate chain of C-S-H gel whereas XRD measurements showed that this result in an increment in the basal distance compared with ordinary CSH. In addition, the dynamics of water within the pores of C-S-H gel was analyzed by broadband dielectric spectroscopy. We observed that water confined in C-S-H formed with the addition of nanoparticles is faster than that in plain C-S-H which can be related to a different porous structure in these materials.

Confined water in the slit mesopores of the mineral tobermorite provides an excellent model system for analyzing the dynamic properties of water confined in cement-like materials. In this work, we use broadband dielectric spectroscopy (BDS) to analyze the dynamic of water entrapped in this crystalline material. Two samples, one natural and one synthetic, were analyzed, and despite their similar structure, the motion of confined water in their zeolitic cavity displays considerably different behavior. The water dynamics splits into two different behaviors depending on the chemical nature of the otherwise identical structural environment: water molecules located in areas where the primary building units are SiO4 relax slowly compared to water molecules located in cavities built with both AlO4 and SiO4. Compared to water confined in regular porous systems, water restricted in tobermorite is slower, indicating that the mesopore structure induces high disorder in the water structure. A comparison with water confined in the C–S–H gel is also discussed in this work. The strong dynamical changes in water due to the presence of aluminum might have important implications in the chemical transport of ions within hydrated calcium silicates, a process that governs the leaching and chemical degradation of cement.

[EN]: Calcium leaching is a degradation process consisting in progressive dissolution of the cement paste by migration of calcium atoms to the aggressive solution. It is therefore, a complex phenomenon involving several phases and dissolution and diffusion processes simultaneously. Along this work, a new computational scheme for the simulation of the degradation process in three dimensions was developed and tested. The toolkit was used to simulate accelerated calcium leaching by a 6M ammonium nitrate solution in cement matrices. The obtained outputs were the three dimensional representation of the matrix and the physicochemical properties of individual phases as a consequence of the degradation process. This not only makes it possible to study the evolution of such properties as a function of time but also as a function of the position within the matrix. The obtained results are in good agreement with experimental values of the elastic modulus in degraded and undegraded samples., [ES]: El lixiviado de calcio es un proceso de degradación consistente en la disolución progresiva de la pasta de cemento por la migración de los átomos de calcio a la disolución agresiva. Se trata por tanto de un fenómeno complejo que involucra simultáneamente diferentes fases y procesos de disolución y difusión. En este trabajo se desarrolló y probó una nueva herramienta computacional para la simulación del proceso de degradación en tres dimensiones. Para ello se simuló el lixiviado de calcio acelerado provocado por una disolución de nitrato amónico 6M en matrices de cemento. Como resultado se obtuvieron la representación tridimensional de la matriz y las propiedades físico-químicas sus fases a lo largo del tiempo. Esto permitió estudiar la evolución de dichas propiedades a lo largo del proceso de degradación así como en función de su posición dentro de la matriz. Los resultados obtenidos coinciden con los valores experimentales del módulo elástico tanto de muestras degradadas como intactas.

The structure of the C-S-H gel in hydrated cement samples prepared with and without the addition of silica nanoparticles is studied in this work through the deconvolution of 29Si MAS-NMR spectra. X-ray diffraction and energy dispersive X-ray microanalysis are also considered for the analysis. A method with improved sensitivity and reliability is proposed for the deconvolution of the spectra into elementary components involving a good fitting of both the spectral curve and its second derivative. The increased sensitivity of the deconvolution proves to be especially interesting for the characterization of low concentration components in the NMR spectra, and the high reliability allows properly defining the effect of nanosilica addition on the C-S-H gel nanostructure. In fact, the addition of nanosilica is found to produce a pozzolanic reaction that results in an increase of the mean silicate chain length and an enhancement of the aluminum incorporation into the C-S-H gel phase.

This research work deals with durability aspects of ternary cements containing 79 wt.% ordinary Portland cement (CEM I), 10.5 wt.% coal fly ash and 10.5 wt.% thermally activated paper sludge. Aging tests were performed to study the resistance of the new ternary cement matrixes to the following aggressive exposure conditions: accelerated freeze/thaw cycles, marine environment and Spanish plateau climate conditions. Ternary cements revealed a high resistance to accelerated freeze/thaw cycles. In addition, after 18 months of exposure, they exhibited enhanced performance under marine conditions and similar resistance to Spanish plateau’s climate, compared to ordinary Portland cement.

In this study, the rotational dynamics of hydration water confined in calcium-silicate-hydrate (C-S-H) gel with a water content of 22 wt.% was studied by broadband dielectric spectroscopy in broad temperature (110-300 K) and frequency (10-1-108 Hz) ranges. The C-S-H gel was used as a 3D confining system for investigating the possible existence of a fragile-to-strong transition for water around 220 K. Such transition was observed at 220 K in a previous study [Y. Zhang, M. Lagi, F. Ridi, E. Fratini, P. Baglioni, E. Mamontov and S. H. Chen, J. Phys.: Condens. Matter 20, 502101 (2008)] on a similar system, and it was there associated with a hidden critical point of bulk water. However, based on the experimental results presented here, there is no sign of a fragile-to-strong transition for water confined in C-S-H gel. Instead, the fragile-to-strong transition can be explained by a merging of two different relaxation processes at about 220 K. © 2013 AIP Publishing LLC.

Calcium leaching is a degradation process that consists in the progressive dissolution of the cement paste as a consequence of the migration of the calcium ions to the aggressive solution. Although it is a well known phenomenon, a way of reducing it has not been found yet. The aim of this work is to prove how the addition of small amounts of silica nanoparticles to the cement paste can induce such reduction. The experimental results obtained have shown that nanosilica increases the strength of the cement paste about a 30% in cured samples and more than a 100% in the asymptotically leached ones. At the level of the structure of the C–S–H gel, silica nanoparticles increase the average length of the silicate chains and reduce their polymerization as calcium dissolves. An important decrease of the degradation in terms of porosity and amount of calcium lost has also been observed.

The high strength steels employed as reinforcement in pre-stressed concrete structures are drawn wire steels of eutectoid composition with a pearlitic microstructure. This work is focused on the study, by atomic force microscopy, of the early stages of the corrosion of such steels as a consequence of their exposition to a sodium chloride solution. The obtained images show the pearlitic microstructure of the steel, with a preferential attack of the ferrite phase and the cementite acting as a cathode. The corrosion rate was determined by calculating the amount of material lost from a roughness analysis. The obtained results are in good agreement with the predictions of Galvelel’s theory, according to which the corrosion rate slows down as the pit depth increases.