Radiative Cooling Properties of Portlandite and Tobermorite: Two Cementitious Minerals of Great Relevance in Concrete Science and Technology.

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.

Electrical Conductive Properties of 3D-PrintedConcrete Composite with Carbon Nanofibers.

Electrical conductive properties in cement-based materials have received attention in recent years due to their key role in many innovative application (i.e., energy harvesting, deicing systems, electromagnetic shielding, and self-health monitoring). In this work, we explore the use 3D printing as an alternative method for the preparation of electrical conductive concretes. With this aim, the conductive performance of cement composites with carbon nanofibers (0, 1, 2.5, and 4 wt%) was explored by means of a combination of thermogravimetric analysis (TGA) and dielectric spectroscopy (DS) and compared with that of specimens prepared with the traditional mold method. The combination of TGA and DS gave us a unique insight into the electrical conductive properties, measuring the specimens' performance while monitoring the amount in water confined in the porous network. Experimental evidence of an additional contribution to the electrical conductivity due to sample preparation is provided. In particular, in this work, a strong correlation between water molecules in interconnected pores and the σ(ω) values is shown, originating, mainly, from the use of the 3D printing technique.

Thermal Energy Storage (TES) Prototype Based on Geopolymer Concrete for High-Temperature Applications.

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.

A multi-scale approach for percolation transition and its application to cement setting.

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 variables like the water-to-cement ratio and the presence of large quantities of nonreactive fillers. These counter-intuitive predictions were verified by ex-professo experiments that we have carried out to check the validity of our model.

Ultra-Fast Supercritical Hydrothermal Synthesis of Tobermorite under Thermodynamically Metastable Conditions.

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.

Effect of chemical environment on the dynamics of water confined in calcium silicate minerals: natural and synthetic tobermorite.

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.

Effect of addition of silica- and amine functionalized silica-nanoparticles on the microstructure of calcium silicate hydrate (C-S-H) gel.

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 (29)Si 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, (13)C 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.

Cause of the fragile-to-strong transition observed in water confined in C-S-H gel.

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)-10(8) 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.

Effect of hydration on the dielectric properties of C-S-H gel.

The behavior of water dynamics confined in hydrated calcium silicate hydrate (C-S-H) gel has been investigated using broadband dielectric spectroscopy (BDS; 10(-2)-10(6) Hz) in the low-temperature range (110-250 K). Different water contents in C-S-H gel were explored (from 6 to 15 wt%) where water remains amorphous for all the studied temperatures. Three relaxation processes were found by BDS (labeled 1 to 3 from the fastest to the slowest), two of them reported here for the first time. We show that a strong change in the dielectric relaxation of C-S-H gel occurs with increasing hydration, especially at a hydration level in which a monolayer of water around the basic units of cement materials is predicted by different structural models. Below this hydration level both processes 2 and 3 have an Arrhenius temperature dependence. However, at higher hydration level, a non-Arrhenius behavior temperature dependence for process 3 over the whole accessible temperature range and, a crossover from low-temperature Arrhenius to high-temperature non-Arrhenius behavior for process 2 are observed. Characteristics of these processes will be discussed in this work.