Material design and development: From classical thermodynamics to CALPHAD and ICME approaches

This paper presents an overview and examples of material design and development using (1) classical thermodynamics; (2) CALPHAD (calculation of phase diagrams) modeling; and (3) Integrated Computational Materials Engineering (ICME) approaches. Although the examples are given in lightweight aluminum and magnesium alloys for structural applications, the fundamental methodology and modeling principles are applicable to all materials and engineering applications. The examples in this paper have demonstrated the effectiveness and limitations of classical thermodynamics in solving specific problems (such as nucleation during solidification and solid-state precipitation in aluminum alloys). Computational thermodynamics and CALPHAD modeling, when combined with critical experimental validation, have been used to guide the selection and design of new magnesium alloys for elevated-temperature applications. The future of material design and development will be based on a holistic ICME approach. However, key challenges exist in many aspects of ICME framework, such as the lack of diffusion/mobility databases for many materials systems, limitation of current microstructural modeling capability and integration tools for simulation codes of different length scales.     

Third order optical nonlinearities characteristics of Disperse Red1 organic dye molecules inside of polymeric nanocapsules

Measuring nonlinear optical response of a specific material in a mixture, not only leads to investigate the behavior of a particular component in various circumstances, but also can be a way to select suitable combination and optimum concentration of additives and therefore obtaining the maximum nonlinear optical signals. In this work, by using dual-arm Z-scan technique, the nonlinear refractive index of Disperse Red1 (DR1) organic dye molecules inside the core of prepared polymeric nanocapsules was measured among various materials which prepared nanocapsules were made of them. Then the measured value was compared with nonlinear refractive index of DR1 solved in dichloromethane.     

Enhancement of optical and electrical properties of SILAR deposited ZnO thin films through fluorine doping and vacuum annealing for photovoltaic applications

Undoped and fluorine doped ZnO thin films were deposited onto glass substrates using successive ionic layer adsorption and reaction (SILAR) technique and then annealed at 350 °C in vacuum ambience. The F doping level was varied from 0 to 15 at% in steps of 5 at%. The XRD analysis showed that all the films are polycrystalline with hexagonal wurtzite structure and preferentially oriented along the (002) plane. Crystallite sizes were found to increase when 5 at% of F is doped and then decreased with further doping. It was seen from the SEM images that the doping causes remarkable changes in the surface morphology and the annealing treatment results in well-defined grains with an improvement in the grain size irrespective of doping level. All the films exhibit good transparency (>70%) after vacuum annealing. Electrical resistivity of the film was found to be minimum (1.32×10⁻³ Ω cm) when the fluorine doping level was 5 at%.     

Mishik A. Kazaryan (1948–2020) – One of the pioneers of Russian hydrogen energetics

In 2018, Mishik Airazatovich Kazaryan received the highest award of the International Association for Alternative Energy and Ecology - Order of Antoine de Saint-Exupéry “For Improving the Quality of Life on the Planet of People” (IAAEE) on nominating the Award Committee of the Editorial Board of the International Scientific Journal for Alternative Energy and Ecology (ISJAEE). The award was given for his outstanding contribution to development of alternative energetics and ecology. M.A. Kazaryan's prominent contribution to the development of alternative energetics and ecology is based on his pioneering works in the field of development of methods for producing hydrogen as environmentally friendly safe fuel, as well as works in the field of processing organic compounds by various physical methods. As a part of joint research with colleagues from Lebedev Physical Institute of RAS (LPI), M.A. Kazaryan participated in creation of new methods for producing hydrogen from various chemical compounds. The method of conversion of liquid-phase compounds in plasma discharges under the influence of intensive ultrasonic cavitation occupies a special place. In the course of these works, it is shown that low-temperature plasma initiated in liquid-phase media in discharge between electrodes is able to effectively decompose hydrogen-containing molecules of organic compounds and form gaseous products where the part of hydrogen is more than 90%. Estimations of energy efficiency calculated taking into account hydrogen combustion heat and initial substances, as well as electricity costs, showed an efficiency level of about 60–70% in depending on the composition of the starting mixture. Another notable contribution of M.A. Kazaryan to the development of alternative energetics was the work on the optimization and justification of technological and structural parameters of energy discharge devices based on high-voltage pulse-periodic discharge for creating a reactor for plasmachemical processing of polymer wastes into hydrogen and other valuable compounds.     

Facile growth of novel morphology correlated Ag/Co-doped ZnO nanowire/flake-like composites for superior photoelectrochemical water splitting activity

In this paper, novel morphology correlation between silver nanowires (AgNWs) and cobalt (Co)-doped ZnO (Co-ZnO) flake-like thin films (nanowire/flake-like) has been proposed for enhanced photoelectrochemical (PEC) water splitting activity. Here in, high-quality AgNWs/Co-ZnO heterostructures enabled superior visible light water splitting activity compared to the pure ZnO and AgNWs/ZnO. To address the strategic effect of AgNWs coupling and transition metal (Co-2?at%) doping into the ZnO host lattice, we have carried out the X-ray diffraction, field emission scanning microscopy, X-ray photoelectron spectroscopy, UV–Vis transmittance, water contact angle and PEC analyses. In this way, PEC water splitting activity was mainly examined by linear sweep voltammetry (I-V), amperometric I-t and photoconversion efficiency (η) studies. The experimental results provide clear evidence of morphology correlation between AgNWs and Co-ZnO flake-like structures for strong visible light absorption. Specifically, AgNWs/Co-ZnO composites exhibited significant enhancement in the photocurrent density (7.0?×?10^?4 A/cm²) than AgNWs/ZnO (3.2?×?10^?4 A/cm²) and pure ZnO (1.5?×?10^?6 A/cm²). As a result, detailed AgNWs/Co-ZnO geometry has great potential for photoconversion efficiency (0.73%). In a word, the merits of controllable AgNWs/Co-ZnO heterostructure are proposed to improve the visible light harvesting and charge carrier generation for energy conversion devices.     

Effect of stoichiometry and Cu-substitution on the phase structure and hydrogen storage properties of Ml-Mg-Ni-based alloys

To improve the electrochemical properties of rare-earth–Mg–Ni-based hydrogen storage alloys, the effects of stoichiometry and Cu-substitution on the phase structure and thermodynamic properties of the ...     

Influence of the Temperature on Coccolith-Containing Systems from Emiliania huxleyi Cultivations

Thermogravimetric analysis of a coccolith-containing biogenic broth showed a three-step degradation process. According to this system behavior, the biogenic broth was heated to specific temperatures and characterized in terms of its morphology, surface chemistry, and crystallinity. The elemental and organic composition of the treated samples was also evaluated and compared to the reference material. The presented results were acquired in an effort to exploit pretreatment scenarios for such a biogenic system that would improve and support a separation process.     

CuInS2/SiNWs/Si composite material for application as potential photoelectrode for photoelectrochemical hydrogen generation

This work aims at developing a new composite material based on nanosized semiconducting CuInS₂ (CIS) particles combined with silicon nanowires grown on a silicon substrate (SiNWs/Si) for photoelectrochemical (PEC)-splitting of water. The CIS particles were prepared via a colloidal method using N-methylimidazole (NMI) as the solvent and an annealing treatment. The SiNWs were obtained by chemical etching of silicon (100) substrates assisted by a metal. The CIS/SiNWs/Si composite material was obtained by deposition of an aliquot of a suspension of CIS particles onto the SiNWs/Si substrate, using spin coating followed by a drying step. The XRD pattern demonstrated that CuInS₂ grows in the tetragonal/chalcopyrite phase, while SiNWs/Si presents a cubic structure. The SEM images show semi-spherical particles (～10 nm) distributed on the surface of silicon nanowires (～10 μm). The EIS measurements reveal n-type conductivity for CIS, SiNWs/Si and CIS/SiNWs/Si materials, which could favour the oxidation reaction of water molecules.     

Distribution of carbon contamination in MgAl2O4 spinel occurring during spark-plasma-sintering (SPS) processing: I – Effect of heating rate and post-annealing

Carbon contamination from the carbon paper/dies during spark-plasma-sintering (SPS) processing was examined in the MgAl₂O₄ spinel. The carbon contamination sensitively changes with the heating rate during the SPS processing. At the high heating rate of 100 °C/min, the carbon contamination having organized structures occurred over almost the entire area from the surface to deep inside the SPSed spinel disk. In contrast, at the slow heating rate of 10 °C/min, the carbon contamination having disordered structures occurred only around the surface area. The carbon phases transform into high pressure CO/CO₂ gases by post-annealing in air and lead to pore formation along the grain junctions. The pore formation significantly occurs at the high heating rate due to the large amount of the contaminant carbon phases. This suggests that if once the carbon contamination was formed in the materials, it is very difficult to remove the carbon phases from the materials.