Hydrides based on magnesium and intermetallic compounds provide a viable solution to the challenge of energy storage from renewable sources, thanks to their ability to absorb and desorb hydrogen in a reversible way with a proper tuning of pressure and temperature conditions. Therefore, they are expected to play an important role in the clean energy transition and in the deployment of hydrogen as an efficient energy vector. This review, by experts of Task 40 ‘Energy Storage and Conversion based on Hydrogen’ of the Hydrogen Technology Collaboration Programme of the International Energy Agency, reports on the latest activities of the working group ‘Magnesium- and Intermetallic alloys-based Hydrides for Energy Storage’. The following topics are covered by the review: multiscale modelling of hydrides and hydrogen sorption mechanisms; synthesis and processing techniques; catalysts for hydrogen sorption in Mg; Mg-based nanostructures and new compounds; hydrides based on intermetallic TiFe alloys, high entropy alloys, Laves phases, and Pd-containing alloys. Finally, an outlook is presented on current worldwide investments and future research directions for hydrogen-based energy storage.

Magnesium- and intermetallic alloys-based hydrides for energy storage: modelling, synthesis and properties

Abstract This paper studies the phase composition, microstructure, hardness and wear resistance of nickel-base plasma sprayed coatings, on two types of substrates, steel and cast iron. The processing method of metal and compound powders for plasma spraying is detailed, together with the characteristics of the powders before and after processing. It has been found that in as-coated condition, the surface layers have phase composition of crystalline γ-Ni solid solution and amorphous phases on steel substrate. On cast iron substrate, in addition to these, Ni3B, CrB, Cr23C6 have been identified. The effect of heat treatment of coatings on steel substrate at temperatures up to 1200 °C has been investigated. It has been found that the coatings have high values of hardness and wear resistance. There are changes in the phase compositions on the surface of the Ni-base coatings during wear testing upon the effect of friction heat, and the wear volume after 60 min for the coating on cast iron substrate is much lower than for those on steel substrate.

Nickel-base plasma sprayed coatings on steel and cast iron substrates

Providing a minimum of theory, this review focuses on practical aspects of analyzing the kinetics of nonisothermal crystallization as measured with differential scanning calorimetry (DSC). It is noted that kinetic analysis is dominated by approaches based on the Avrami and Arrhenius equations. Crystallization kinetics should not be considered synonymous with the Avrami model, whose nonisothermal applications are subject to very restrictive assumptions. The Arrhenius equation can serve only as a narrow temperature range approximation of the actual bell-shaped temperature dependence of the crystallization rate. Tests of the applicability of both equations are discussed. Most traditional kinetic methods tend to offer very unsophisticated treatments, limited only to either glass or melt crystallization. Differential or flexible integral isoconversional methods are applicable to both glass and melt crystallization because they can accurately approximate the temperature dependence of the crystallization rate with a series of the Arrhenius equations, each of which corresponds to its own narrow temperature interval. The resulting temperature dependence of the isoconversional activation energy can be parameterized in terms of the Turnbull–Fisher or Hoffman–Lauritzen theories, and the parameters obtained can be meaningfully interpreted and used for kinetic simulations.

/pdf/nonisothermal-crystallization-kinetics-by-dsc-practical-q7heakgm.pdf

Nonisothermal Crystallization Kinetics by DSC: Practical Overview

This study evaluated the thermal stability and process safety of tert-butyl peroxybenzoate (TBPB), tert-butyl peroxy-2-ethylhexanoate (TBPO), and their mixture. Thermogravimetric (TG) analysis, differential scanning calorimetry (DSC), and accelerated rate calorimetry were used to elucidate the thermal behavior and breakdown kinetics. The TG results indicated moderate to low breakdown temperatures for all samples, demonstrating their thermal stability. DSC revealed onset temperatures for exothermic disintegration between 66.66 °C and 104.23 °C. The mixture had two distinct exothermic peaks, signifying the thermal decomposition of the mixture was such that the characteristic temperature and heat of the reaction were between those of TBPB and TBPO. Using Heat–Wait–Search methodology, the study identified thermal runaway exothermically. Under pseudoadiabatic conditions, the mixture exhibited greater increases in temperature and pressure—of 115.06 °C and 28.77 bar, respectively—compared with the individual compounds. To elucidate the apparent activation energy (Ea) and reaction kinetics, the study applied models developed by Arrhenius, Flynn-Wall-Ozawa, Friedman, Kissinger, and Starink. The Ea values obtained based on the TG, DSC, and ARC experiments were approximately 50.47, 98.19, and 99.71 kJ/mol, respectively, and were lower than those of TBPB and TBPO pure substances. The self-accelerating decomposition temperature of TBPB/TBPO decreased from 34 to 32 °C as the packaging of TBPB/TBPO was increased from 25 to 100 kg and was more than 10 °C lower than that of the individual substance. These findings offer a framework for evaluating the thermal risks associated with TBPB and TBPO, particularly when mixed. They contribute to the safe transit, storage, and handling of industrial organic peroxides, enriching our collective understanding of the stability and safety of these compounds. 

Calorimetric and kinetic evaluation of thermal stability and process safety in tert-butyl peroxy-2-ethylhexanoate and tert-butyl peroxybenzoate

This study explores the significance of isoconversional methods in thermal analysis and their pivotal role in evaluating the quality of experimental data. The thermal degradation of polylactic acid tannin nanocomposite and the non isothermal crystallization of poly(ethylene 2,5-furandicarboxylate) carbon nanotubes nanocomposites were studied. Four commonly used methods were employed to calculate activation energy (Eα) and pre-exponential factor versus the degree of conversion. The examination of error bars further contributed to evaluating the precision of calculations. The discussion covered the impact of temperature changes on data quality and highlighted the significant sensitivity to these variations. The accuracy of these measurements depends not only on factors like temperature and material quality but also on the specific mathematical method used for baseline subtraction. Isoconversional methods exhibit distinct behaviors, emphasizing the significance of precise data and analysis techniques. Temperature changes not only affect Eα but also slightly alter the curve shapes. Error bars exhibit increased sensitivity to even minor temperature changes. Missteps in baseline subtraction can lead to inaccurate results and affect the estimation of Eα. The study's overall findings highlight the necessity of stringent quality control measures to guarantee reliable and accurate kinetic analysis. 

Isoconversional methods: A powerful tool for kinetic analysis and the identification of experimental data quality

Nonisothermal Crystallization Kinetics: Studying the Validity of Different Johnson–Mehl–Avrami–Erofeev–Kolmogorov (JMAEK) Based Equations

Carbon steel is one of the most commonly used metals in the construction and industrial sectors due to its very good mechanical properties [1]. However, it oxidizes quickly and easily, in elevated temperature and corrosive environments [2]. Nickel aluminum alloys are known to exhibit resistance to high temperature [3]. In this work Al-Ni coatings were developed by a combination of two processes. An initial Ni layer was electrochemically deposited on steel followed by aluminization by pack cementation. Al-Ni alloys were formed on the top of the coatings followed by a layer of pure Ni. At the same time Ni interdiffused in the ferrous substrate creating Ni-Fe compounds, increasing the coating adherence. The structure and phase identification were performed using X-ray diffraction, while the morphology and elemental analysis was examined by Scanning electron microscopy. Non-isothermal and isothermal thermogravimetric measurements were performed on the coated and uncoated samples in order to define the critical oxidation temperatures and evaluate the thermal resistance at long lasting exposures.

Synthesis of Al-Ni coatings by pack cementation and examination of their high temperature oxidation resistance

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Nonisothermal Crystallization Kinetics: Studying the Validity of Different Johnson–Mehl–Avrami–Erofeev–Kolmogorov (JMAEK) Based Equations

Synthesis of Al-Ni coatings by pack cementation and examination of their high temperature oxidation resistance