The aim of this review article on recent developments of mechanochemistry (nowadays established as a part of chemistry) is to provide a comprehensive overview of advances achieved in the field of atomistic processes, phase transformations, simple and multicomponent nanosystems and peculiarities of mechanochemical reactions. Industrial aspects with successful penetration into fields like materials engineering, heterogeneous catalysis and extractive metallurgy are also reviewed. The hallmarks of mechanochemistry include influencing reactivity of solids by the presence of solid-state defects, interphases and relaxation phenomena, enabling processes to take place under non-equilibrium conditions, creating a well-crystallized core of nanoparticles with disordered near-surface shell regions and performing simple dry time-convenient one-step syntheses. Underlying these hallmarks are technological consequences like preparing new nanomaterials with the desired properties or producing these materials in a reproducible way with high yield and under simple and easy operating conditions. The last but not least hallmark is enabling work under environmentally friendly and essentially waste-free conditions (822 references).

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Hallmarks of mechanochemistry: From nanoparticles to technology

An overview of thermal energy storage systems

A concentrating solar power (CSP) system converts sunlight into a heat source which can be used to drive a conventional power plant. Thermal energy storage (TES) improves the dispatchability of a CSP plant. Heat can be stored in either sensible, latent or thermochemical storage. Commercial deployment of CSP systems have been achieved in recent years with the two-tank sensible storage system using molten salt as the storage medium. Considerable research effort has been conducted to improve the efficiency of the CSP system and make the cost of electricity comparable to that of the conventional fossil-fuel power plant. This paper provides a comprehensive summary of CSP plants both in operation and under construction. It covers the available technologies for the receiver, thermal storage, power block and heat transfer fluid. This paper also reviews developments in high temperature TES over the past decade with a focus on sensible and latent heat storage. High temperature corrosion and economic aspects of these systems are also discussed.

Review on concentrating solar power plants and new developments in high temperature thermal energy storage technologies

Solar thermal energy, especially concentrated solar power (CSP), represents an increasingly attractive renewable energy source. However, one of the key factors that determine the development of this technology is the integration of efficient and cost effective thermal energy storage (TES) systems, so as to overcome CSP's intermittent character and to be more economically competitive. This paper presents a review on thermal energy storage systems installed in CSP plants. Various aspects are discussed including the state-of-the-art on CSP plants all over the world and the trend of development, different technologies of TES systems for high temperature applications (200–1000°C) with a focus on thermochemical heat storage, and storage concepts for their integration in CSP plants. TES systems are necessary options for more than 70% of new CSP plants. Sensible heat storage technology is the most used in CSP plants in operation, for their reliability, low cost, easy to implement and large experimental feedback available. Latent and thermochemical storage technologies have much higher energy density thus may have a bright foreground. New concepts for TES integration are also proposed, especially coupled technology for higher operating temperature and cascade TES of modularized storage units for intelligent temperature control. The key contributions of this review paper consist of a comprehensive survey of CSP plants, their TES systems, the ways to enhance the heat and/or mass transfers and different new concepts for the integration of TES systems.

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Thermal energy storage systems for concentrated solar power plants

The effects of the hydrostatic and shear-inducing pressure on the physicochemical properties of solids are analysed. The mechanochemical reactions and mechanical activation are illustrated with various types of chemical transformations ranging from polymorph transitions to solid-state reactions. The prospects for the use of mechanochemistry for the solution of applied problems are discussed.

https://iopscience.iop.org/article/10.1070/RC2006v075n03ABEH001205/pdf

Mechanochemistry and mechanical activation of solids

The effect of the mechanical activation of the reactants on the self-propagating high-temperature synthesis (SHS) of niobium silicides was investigated. SHS experiments were performed on reactant powder blends of composition Nb:Si = 1:2 and Nb:Si = 5:3 pretreated for selected milling times. A self-sustaining reaction could be initiated when a sufficiently long milling time was employed. At short milling times, the reactions self-extinguished or propagated in an unsteady mode. Combustion peak temperature, wave velocity, and product composition were markedly influenced by the length of the milling treatment. Single-phase products could be obtained for sufficiently long milling times. Observation of microstructural evolution in quenched reactions together with isothermal experiments allowed clarification of the mechanism of the combustion process and the role played by the mechanical activation of the reactants.

https://www.cambridge.org/core/services/aop-cambridge-core/content/view/S0884291400066607

Combustion synthesis of mechanically activated powders in the Nb-Si system

The influence of mechanical activation on the characteristics and mechanism of ignition of self-propagating high-temperature synthesis processes of different silicides in the systems Me–Si (Me =Ti, Nb, Mo) was investigated. The results show that mechanical activation does not alter the mechanism involved but influences significantly the ignition characteristics. The influence, however, strongly depends on the stoichiometry of the mixtures. The composition Ti:Si = 1:2 shows the largest influence, with the ignition temperatures decreasing from 1400 °C for unmilled powders to about 600 °C for powders milled for several hours. The compositionsTi:Si = 5:3, Nb:Si = 1:2 show less pronounced decreases, while the compositionMo:Si = 1:2 shows no decrease. These differences are discussed in terms of the role of microstructure in the reaction mechanism and the different response of the systems to contamination, particularly from oxygen. The results suggest that for these systems self-ignition processes during milling cannot be explained only on the basis of the decrease in the ignition temperature.

https://www.cambridge.org/core/services/aop-cambridge-core/content/view/S0884291400088877

Ignition mechanism of mechanically activated Me–Si(Me = Ti, Nb, Mo) mixtures

In this work, we report on the self-propagating reaction in Ti–Si blends, observed by SHS and MASHS (mechanical activated SHS) techniques. In spite of the differences between the two reacting methods, correlations were found between the key parameters of the two modes of activation. Moreover, this comparative study enabled us to gain some hints on the reaction mechanism. The combustive behavior of powder mixtures with stoichiometries corresponding to the intermetallics present in the Ti–Si phase diagram (TiSi2, TiSi, Ti5Si4, and Ti5Si3) was studied. The SHS characteristics, such as combustion temperature, propagation rate, and ignition temperature was strongly dependent on both the initial stoichiometry and milling time. Particular attention was paid to the influence of the initial stoichiometry and milling conditions on the reaction mechanism. A single-step dissolution-precipitation mechanism was found for the composition Ti : Si = 5 : 3. On the other hand, at the composition Ti : Si = 1 : 2, the mechanism shows two steps, the first, active at the leading front of the combustion front, involving only solid phases, and the second, active in the afterburn region, involving solid–liquid interaction.

Self-Propagating Reactions in the Ti–Si System: A SHS-MASHS Comparative Study

The eutectic Mg49–Zn51 (mass%) alloy has been identified as a suitable material for latent heat thermal energy storage. Within this scope, the exhibited solid–solid and solid–liquid phase transitions have been carefully characterized. A detailed thermodynamic study focused on the specific heat of the investigated alloy is also provided. The Cp behaviour, very important in the thermal energy storage frame, is theoretically modelled and experimentally validated by quasi-isothermal modulated differential scanning calorimetry measurements. Different intermetallic phases of the Mg–Zn binary system have also been successfully described within this approach in the complete temperature range.

Stefania Doppiu

Papers

Combustion synthesis of mechanically activated powders in the Nb-Si system

Ignition mechanism of mechanically activated Me–Si(Me = Ti, Nb, Mo) mixtures

Self-Propagating Reactions in the Ti–Si System: A SHS-MASHS Comparative Study

Thermodynamic study of the eutectic Mg49–Zn51 alloy used for thermal energy storage

Experimental investigation of Mg-Zn-Al metal alloys for latent heat storage application