Calorimetric Studies and Thermodynamic Modeling of Ag-Mg-Ti Liquid Alloys.

Due to the absence of thermodynamic data concerning the Ag-Mg-Ti system in the existing literature, this study aims to fill this gap by offering the outcomes of calorimetric investigations conducted on ternary liquid solutions of these alloys. The measurements were performed using the drop calorimetry method at temperatures of 1294 K and 1297 K for the liquid solutions with the following constant mole fraction ratio: xAg/xMg = 9/1, 7/3, 1/1, 3/7 [(Ag0.9Mg0.1)1-xTix, (Ag0.7Mg0.3)1-xTix, (Ag0.5Mg0.5)1-xTix, (Ag0.3Mg0.7)1-xTix)], and xAg/xTi = 19/1 [(Ag0.95Ti0.05)1-xMgx]. The results show that the mixing enthalpy change is characterized by negative deviations from the ideal solutions and the observed minimal value equals -13.444 kJ/mol for the Ag0.95Ti0.05 alloy and xMg = 0.4182. Next, based on the thermodynamic properties of binary systems described by the Redlich-Kister model and the determined experimental data from the calorimetric measurements, the ternary optimized parameters for the Ag-Mg-Ti liquid phase were calculated by the Muggianu model. Homemade software (TerGexHm 1.0) was used to optimize the calorimetric data using the least squares method. Next, the partial and molar thermodynamic functions were calculated and are presented in the tables and figures. Moreover, this work presents, for comparative purposes, the values of the enthalpy of mixing of liquid Ag-Mg-Ti alloys, which were calculated using Toop's model. It was found that the best agreement between the modeled and experimental data was observed for the cross-sections xAg/xTi = 19/1 [(Ag0.95Ti0.05)1-xMgx] and xAg/xMg = 9/1 [(Ag0.9Mg0.1)1-xTix]. The results of the experiments presented in this paper are the first step in the investigation and future evaluation of the thermodynamics of phases and the calculation of the phase diagram of the silver-magnesium-titanium system.

Long-Term Stability of Light-Induced Ti3+ Defects in TiO2 Nanotubes for Amplified Photoelectrochemical Water Splitting.

This study shows that the simple approach of keeping anodic TiO2 nanotubes at 70 °C in ethanol for 1 h results in improved photoelectrochemical water splitting activity due to initiation of crystallization in the material amplified by the light-induced formation of a Ti3+ -Vo states under UV 365 nm illumination. For the first time, the light-induced Ti3+ -Vo states are generated when oxygen is present in the reaction solution and are stable when in contact with air (oxygen) for a long time (two months). We confirmed here that the amorphous or nearly amorphous structure of titania supports the survival of Ti3+ species in contact with oxygen. It is also shown that the ethanol treatment substantially improves the morphology of the titania nanotube arrays, specifically, less surface cracking and surface purification from C- and F-based contamination from the electrolyte used for anodizing.

On the Influence of Manufacturing Parameters on the Microstructure, Mechanical Properties and Corrosion Resistance of AISI 316L Steel Deposited by Laser Engineered Net Shaping (LENS®).

Samples of 316L SS were manufactured by Laser Engineered Net Shaping (LENS®) using different technological parameters. The deposited samples were investigated in terms of microstructure, mechanical properties, phase content and corrosion resistance (salt chamber and electrochemical corrosion). Parameters were chosen to obtain a proper sample built for layer thicknesses of 0.2, 0.4 and 0.7 mm by changing the laser feed rate while keeping the powder feed rate constant. After a comprehensive analysis of the results, it was found that the manufacturing parameters slightly affected the resulting microstructure and also had a minor impact (almost undetectable considering the uncertainty of the measurement) on the mechanical properties of samples. Decreases in resistance to electrochemical pitting corrosion and environmental corrosion with an increased feed rate and a decrease in layer thickness and grain size were observed; however, all additively manufactured samples were found to be less prone to corrosion than the reference material. In the investigated processing window, no influence of deposition parameters on the phase content of the final product was found-all the samples were found to possess austenitic microstructure with almost no detectable ferrite.

Mixing Enthalpies of Liquid Ag-Mg-Pb Alloys: Experiment vs. Thermodynamic Modeling.

A drop calorimetric method was used to measure liquid Ag-Mg-Pb alloys. The partial and integral mixing enthalpies of the investigated alloys were determined at a temperature of 1116 K. The experiments were performed for four separate series starting from binary alloys with a constant xMg/xPb ratio of 1/3, 1, 3 ((Mg0.25Pb0.75)1-xAgx, (Mg0.50Pb0.50)1-xAgx, (Mg0.75Pb0.25)1-xAgx) and xAg/xMg ratio of 1/3 (Ag0.25Mg0.75)1-xPbx. Next, the ternary interaction parameters were determined using the Muggianu model, the thermodynamic properties of binary systems in the form of the Redlich-Kister equations and the values of the mixing enthalpy changes, which were determined in this study. The partial mixing enthalpies of Ag, Mg, and Pb were calculated based on the binary and elaborated ternary interaction parameters for the same intersections in which the measurements were conducted. It was found that the ternary Ag-Mg-Pb liquid solutions are characterized by negative deviations from the ideal solutions, with a maximal value slightly lower than -13 kJ/mol for alloys with the ratio (Mg0.75Pb0.25) and xAg = 0.4166.

The Influence of Layer Thickness on the Microstructure and Mechanical Properties of M300 Maraging Steel Additively Manufactured by LENS® Technology.

This work investigates the effect of layer thickness on the microstructure and mechanical properties of M300 maraging steel produced by Laser Engineered Net Shaping (LENS®) technique. The microstructure was characterized using light microscopy (LM) and scanning electron microscopy (SEM). The mechanical properties were characterized by tensile tests and microhardness measurements. The porosity and mechanical properties were found to be highly dependent on the layer thickness. Increasing the layer thickness increased the porosity of the manufactured parts while degrading their mechanical properties. Moreover, etched samples revealed a fine cellular dendritic microstructure; decreasing the layer thickness caused the microstructure to become fine-grained. Tests showed that for samples manufactured with the chosen laser power, a layer thickness of more than 0.75 mm is too high to maintain the structural integrity of the deposited material.

Calorimetric Studies of Magnesium-Rich Mg-Pd Alloys.

Solution calorimetry with liquid aluminum as the bath was conducted to measure the enthalpy of a solution of magnesium and palladium as well as the standard formation enthalpies of selected magnesium-palladium alloys. These alloys were synthesized from pure elements, which were melted in a resistance furnace that was placed in a glove box containing high-purity argon and a very low concentration of impurities, such as oxygen and water vapor. A Setaram MHTC 96 Line evo drop calorimeter was used to determine the energetic effects of the solution. The enthalpies of the Mg and Pd solutions in liquid aluminum were measured at 1033 K, and they equaled -8.6 ± 1.1 and -186.8 ± 1.1 kJ/mol, respectively. The values of the standard formation enthalpy of the investigated alloys with concentrations close to the Mg6Pd, ε, Mg5Pd2, and Mg2Pd intermetallic phases were determined as follows: -28.0 ± 1.2 kJ/mol of atoms, -32.6 ± 1.6 kJ/mol of atoms, -46.8 ± 1.4 kJ/mol of atoms, and -56.0 ± 1.6 kJ/mol of atoms, respectively. The latter data were compared with existing experimental and theoretical data from the literature along with data calculated using the Miedema model.

Hydrogen Sorption Behavior of Cast Ag-Mg Alloys.

In this paper, the hydrogen sorption properties of casted Ag-Mg alloys were investigated. The obtained alloys were structurally analyzed by X-ray diffraction (XRD) and observed by scanning electron microscopy (SEM). The study was carried out for four alloys from the two-phase region (Mg) + γ' (AgMg4) with nominal concentrations of 5 wt. %, 10 wt. %, 15 wt. %, and 20 wt. % Ag, four alloys with nominal compositions equivalent to intermetallic phases: AgMg4, AgMg3, AgMg, and Ag3Mg, one alloy from the two-phase region AgMg + Ag3Mg (Ag60Mg40), and one alloy from the two-phase region AgMg + AgMg3 (Ag40Mg60). The hydrogenation process was performed using a Sievert-type sorption analyzer. The hydride decomposition temperature and kinetic properties of the synthesized hydrides were investigated by differential scanning calorimetry (DSC) coupled with thermogravimetric analysis (TGA). Samples with high magnesium content were found to readily absorb significant amounts of hydrogen, while hydrogen absorption was not observed for samples with silver concentrations higher than 50 at. % (AgMg intermetallic phase).

Magnesium-Based Materials for Hydrogen Storage-A Scope Review.

Magnesium hydride and selected magnesium-based ternary hydride (Mg2FeH6, Mg2NiH4, and Mg2CoH5) syntheses and modification methods, as well as the properties of the obtained materials, which are modified mostly by mechanical synthesis or milling, are reviewed in this work. The roles of selected additives (oxides, halides, and intermetallics), nanostructurization, polymorphic transformations, and cyclic stability are described. Despite the many years of investigations related to these hydrides and the significant number of different additives used, there are still many unknown factors that affect their hydrogen storage properties, reaction yield, and stability. The described compounds seem to be extremely interesting from a theoretical point of view. However, their practical application still remains debatable.

Direct Synthesis of Fe-Al Alloys from Elemental Powders using Laser Engineered Net Shaping.

The laser engineered net shaping (LENS®) process is shown here as an alternative to melting, casting, and powder metallurgy for manufacturingiron aluminides. This technique was found to allow for the production ofFeAl and Fe3Al phases from mixtures of elemental iron and aluminum powders. Theinsitusynthesis reduces the manufacturing cost and enhances the manufacturing efficiency due to the control of the chemical and phase composition of the deposited layers. The research was carried out on samples with different chemical compositionsthat were deposited on the intermetallic substrates that were produced by powder metallurgy. The obtained samples withthe desired phase composition illustrated that LENS® technology can be successfully applied to alloys synthesis.

Nanoconfined NaAlH4: prolific effects from increased surface area and pore volume.

Nanoconfinement is a promising technique to improve the properties of nanomaterials such as the kinetics for hydrogen release and uptake and the stability during cycling. Here we present a systematic study of nanoconfined NaAlH4 in nanoporous scaffolds with increasing surface area and pore volume and almost constant pore sizes in the range of 8 to 11 nm. A resorcinol formaldehyde carbon aerogel was CO2-activated under different conditions and provided aerogels with BET surface areas of 704, 1267 and 2246 m(2) g(-1) and total pore volumes of 0.91, 1.30 and 2.21 mL g(-1), respectively. Nanoconfinement of NaAlH4 was achieved by melt infiltration and (27)Al MAS NMR reveals that the respective scaffolds incorporate 68, 82 and 91 wt% NaAlH4, for the above-mentioned samples, while the remaining fraction decomposes to metallic Al indicating that increasing CO2-activation tends to facilitate the infiltration process. The frequencies for the (23)Na and (27)Al MAS NMR centerband resonances from NaAlH4 vary systematically for the infiltrated samples and are shifted towards higher frequency and become more narrow with increasing degree of CO2 activation of the scaffolds. This new effect is attributed to increasing interactions with conduction electrons from increasingly graphite-/graphene-like scaffolds. The bulk versus nanoconfined ratio of NaAlH4 was investigated using Rietveld refinement, revealing that the majority of added NaAlH4 is confined inside the nanopores. The hydrogen desorption kinetics decreased with increasing surface area and the hydrogen storage capacity is more stable and decreases less during continuous hydrogen release and uptake cycles. In fact, the available amount of hydrogen (2.7 wt% H2) was more than doubled compared to the nanoconfinement in the non-activated carbon aerogel (1.3 wt% H2). Furthermore, it was demonstrated that Ti-functionalization of the CO2-activated aerogels combines the high storage capacity with fast hydrogen release kinetics from NaAlH4 which fully decomposes into Na3AlH6 at T ≤ 100 °C.

Improved hydrogen storage kinetics of nanoconfined NaAlH4 catalyzed with TiCl3 nanoparticles.

Nanoparticles of NaAlH(4) have been infiltrated in nanoporous carbon aerogel with TiCl(3) nanoparticles in order to explore possible synergetic effects between nanoconfinement and a functionalized catalytic scaffold. Resorcinol formaldehyde carbon aerogels with an average pore size of 17 nm and total pore volume of 1.26 mL/g were infiltrated with TiCl(3) to obtain an aerogel doped with 3.0 wt % TiCl(3) nanoparticles. NaAlH(4) was melt-infiltrated into the functionalized carbon aerogel at 189 °C and p(H(2)) ∼ 186-199 bar. Energy-dispersive spectrometry (EDS) combined with focused ion beam (FIB) techniques revealed the presence of Na, Al, Ti, and Cl inside the aerogel scaffold material. The infiltrated NaAlH(4) was X-ray amorphous, whereas (27)Al magic-angle spinning (MAS) NMR spectroscopy confirmed the presence of nanoconfined NaAlH(4). Temperature-programmed desorption mass spectroscopy (TPD-MS) and Sieverts' measurements demonstrated significantly improved hydrogen desorption kinetics for this new nanoconfined NaAlH(4)-TiCl(3) material as compared to nanoconfined NaAlH(4) without the catalysts TiCl(3) and to bulk ball-milled samples of NaAlH(4)-TiCl(3). We find that the onset temperature for hydrogen release was close to room temperature (T(onset) = 33 °C), and the hydrogen release rate reached a maximum value at 125 °C, which demonstrates favorable synergetic effects between nanoconfinement and catalyst addition.