Abstract The (de)hydrogenation properties of a TiFe intermetallic compound (IMC) alloy activated by cold rolling inside a glovebox at ambient temperature were investigated by kinetic measurements, x-ray powder diffraction (XRD), and transmission electron microscopy (TEM). Rate-limiting steps were identified by testing kinetic models on hydrogen absorption and desorption curves. To prevent surface poisoning during air exposure, the TiFe IMC was also cold rolled with polytetrafluoroethylene (PTFE) and ultra-high molecular weight polyethylene (UHMWPE). The addition of either PTFE or UHMWPE to nanostructured TiFe by cold rolling did not produce a polymer-metal composite with O2 poisoning resistance, regardless of the polymer-mixing way adopted. This occurred because large surfaces of the particles were not adequately coated with polymer. The results identify challenges to the TiFe IMC polymer-covered material that must be overcome before a methodology can significantly contribute to the formation of nanostructured TiFe-polymer composites with enhanced hydrogen storage properties. The diffusion-controlled reactions in the cold-rolled TiFe IMC without polymer were prevalent in all cases, as predicted by the Jander three-dimensional diffusion model. The main contribution of this work regards estimation of the amount of hydrogen released, which was 0.60% after 6 min and reproducible for the three subsequent cycles.

This paper presents the results of Molecular Dynamics (MD) simulations of Cu60.0Zr32.5Ti7.5 alloy through the open source code LAMMPS. Amorphous samples were produced by quenching the molten metal from 2300 to 300 K. The pair distribution functions of the liquid and solid were calculated. Moreover, the atomic short-range order at 800, 700 and 300 K was obtained by using the Voronoi tesselation method. Cu-centered icosahedral clusters were the prevailing configuration. The tensile stress-strain curve showed that the material present plastic deformation, however, shear bands were not observed in the MD simulation. The evolution of viscosity in temperatures higher than its glass transition temperature was also determined. Furthermore, the fragility of the alloy at glass temperature was evaluated.

Coatings of amorphous metallic alloys can be obtained using different thermal spraying processes, such as HVOF, plasma spraying, cold spraying and others. Although many studies focused on investigating scientific issues concerning apply amorphous metallic coatings using thermal spraying, less attention have been paid to evaluate how research institutes and companies are collaborating and influencing each other to promote new technologies. In this paper, we assessed the collaboration of organizations and the knowledge flow on this relatively new field using bibliometrics and science mapping. The method relies on scientific publications indexed in Web of Science and clustered into research areas using the CWTS Publication-level Classification System. These results provide useful insights about how players are organized and may be used in the context of R&D management, science policy and decision making.

Magnesium (Mg) is a light metal with relatively low cost. Its hydride (MgH2) is interesting for the safe hydrogen storage in solid state and has a high gravimetric capacity of 7.6%. Practical application of Mg is still hampered by high reaction temperatures and slow kinetics. In order to improve it and focus on more viable industrial processing conditions, Mg plates, with or without iron (Fe) addition, in the form of wires and powders, were submitted to severe plastic deformation (SPD) in air, starting with extensive cold rolling (ECR), followed by repetitive rolling (ARB). The samples were characterized by X-ray diffraction (XRD), optical microscopy (OM), scanning (SEM) and transmission electron microscopy (TEM). H2 storage properties were evaluated by differential scanning calorimetry (DSC) and Sievert's volumetric method. Mg processed by ECR+ARB resulted in larger grain refinement and densities of cracks than ECR. In addition, Fe in the form of continuous wires was fragmented and resulted in a better distribution of particles than powders, which agglomerated. Thus, finally, the synergetic effect of microstructural features and Fe as catalyst and its distribution improved activation, kinetics and hydrogen storage capacity.

Thermal spraying processes allows high cooling rates and can favor the formation of amorphous microstructures. Amorphous metallic coatings can result in superior mechanical and functional properties. To follow new technological development and innovation paths, indicators based on patent data can be assembled to support technological forecasting assessments and decision making. This study mapped the technological development on amorphous alloys processed by thermal spraying using patent indicators from documents indexed in the Derwent Innovations Index database between the years 1997 and 2014. We evaluate the patent activity, the role of countries, the main technological subdomains and markets of interest, as well as the main metallic alloys explored as coating. We conclude that new technological developments should be expected in near future and these advances both in amorphous alloys and thermal spraying shall be constantly monitored in the coming years.

In this study, we have investigated the synthesis, microstructure and hydrogen storage properties of Mg-based nanocomposites containing different concentrations of TiCrV and TiCr1.2V0.8 alloys. The Mg-based nanocomposites of Mg containing Ti-Cr-V additives were prepared by reactive milling (RM) under hydrogen atmosphere. The structural characterization revealed the presence of the β-MgH2, γ-MgH2 and BCC phases in the powders samples after RM. In addition, a very refined and homogenous microstructure with average MgH2 crystallite size of around 10-12 nm was observed, including a nanometric dispersion of the additives in the magnesium hydride matrix. The doping with TiCrV and TiCr1,2V0,8 greatly improves the hydrogen desorption behavior of Mg in comparison with the sample without additive, resulting in the lowest onset temperature (240 ºC) for the sample containing 5%mol. of TiCrV. Very fast absorption and desorption kinetics at 275 ºC and 300 ºC (7 minutes and 5 minutes for full desorption and absorption, respectively) were observed in the samples containing TiCrV and TiCr1,2V0,8 without any notable difference between the type of additive used in comparison with the pure sample. However, a slight reduction in hydrogen capacity is observed in the mixtures than for the pure sample (6.7 wt.% against 7.3 wt.%).

A structural and mechanical characterization of pure aluminum and 2124 T6 aluminum alloy reinforced with quasicrystalline phases of composition Al65Cu20Fe15 and Al70.5Pd21Mn8.5 (%at.) were performed. The quasicrystalline phases were synthesized by arc melting and then milled to produce powder of the alloys, which were then mechanical mixed with the starting powders of aluminum and 2124 aluminum alloy. The composites were produced by hot extrusion of a mechanical mixture containing 20% (%wt.) of the reinforcing phases on the metallic matrix. The structural characterization of the composites was carried out by X-ray diffraction, scanning electron microscopy and transmission electron microscopy. Mechanical characterization was carried out by Vickers hardness measurements and torsion tests at room temperature. The pure aluminum/quasicrystal composite showed the presence of the same phases from the starting powder mixture while for the 2124 aluminum alloy/Al65Cu20Fe15 the quasicrystalline phase transformed to the tetragonal ω-Al7Cu2Fe during the solution heat treatment. Mechanical strength of the composites presented a substantial increase in comparison to the original matrix metal. While the equivalent ultimate tensile strength of the Al/quasicrystal composites reached values up to 215MPa and Vickers hardness up to 60HV, the 2124/quasicrystal composites reached values up to 670MPa and Vickers hardness up to 190HV.

Selective laser melting (SLM) is an additive manufacturing process used to produce parts with complex geometries layer by layer. This rapid solidification method allows fabricating samples in a non-equilibrium state and with refined microstructure. In this work, this method is used to fabricate 3 mm diameter rods of a Cu-based shape memory alloy. The phase formation, thermal stability and mechanical properties were investigated and correlated. Samples with a relative density higher than 92% and without cracks were obtained. A single monoclinic martensitic phase was formed with average grain size ranging between 28 to 36 μm. The samples exhibit a reverse martensitic transformation temperature around 106 ± 2 °C and a large plasticity in compression (around 15±1%) with a typical “double-yielding” behaviour.

Consolidation of amorphous powders, which take advantage of the supercooled liquid region, is an alternative way to overcome the size limitation in marginal metallic glasses. Cu36Ti34Zr22Ni8based amorphous powders were obtained during high energy ball-milling. The analyses revealed that amorphous structures of powders and ribbons are quite different and this led to a different thermal behavior being the powders more thermally stable than the ribbons. Extrusion was initially proposed as a consolidation process; however, the decrease in viscosity in remainder amorphous matrix was not sufficient for that process, but certainly sufficient for sintering the sample during hot consolidation. An amorphous/nanocrystalline microstructure known for enhancing the mechanical properties of their fully amorphous counterparts was obtained. Evaluation of mechanical properties by microhardness revealed the relatively high hardness of HV 768. From these results, consolidation by sintering seems a promising route to produce bulk metallic glasses nanocomposites.

In this paper we address some aspects of the kinetics of hydrogen absorption and desorption of Mg2FeH6 nanocomposite powder. The Mg2FeH6 material was prepared from a 2Mg-Fe composition by reactive milling under H2 pressure at room temperature. After mechano-chemical processing, the material was mainly constituted of Mg2FeH6 having a hydrogen gravimetric capacity corresponding to 94% of the theoretical capacity. The kinetics of hydrogen absorption at constant temperature and the transformation of phases during this process were studied. The kinetics of hydrogen absorption presented a two-step behaviour. First, β-MgH2 was formed with faster kinetics than Mg2FeH6 under constant temperature and H2 pressure. Then, β-MgH2 reacted with α-Fe forming Mg2FeH6 in a much slower reaction. Unexpectedly, reaction of hydrogen desorption showed an one-step kinetics, even if Mg2FeH6 and β-MgH2 phases were previously present in the powder.

MgH2 was processed by short time high-energy ball milling (BM) and cold rolling (CR). A new alternative processing route (CR + BM) using the combination of CR followed by short time BM step was also applied. The effects on the final morphology, crystalline structure and H-sorption properties were evaluated. The CR + BM processing (compared to BM and CR process) resulted in an inhomogeneous particle size distribution and the biggest crystallite size of MgH2, showing that there is a clear dependence between the size/shape of the particles which compose the starting material and the efficiency of crystallite size reduction during the BM process. On the other hand, we observed that a short BM step improved the kinetic properties of the cold rolled material. It shows that the particle size reduction of MgH2 obtained by CR combined with the increase in specific surface area attained by short BM step could be key factors to allow the use of the CR + BM route.

A mechanical spectroscopy study of Cu-Zr-Al bulk metallic glasses, was performed with two types of equipment: a Kê-type inverted torsion pendulum and an acoustic elastometer, working in the frequency ranges of Hz and kHz, respectively, with a heating rate of 1 K/min. The analysis of the anelastic relaxation shows similar spectra for both types of equipment resulting in internal friction patterns that vary with temperature and are not reproducible at each thermal cycle. The normalized of the square of the frequency changes from the first to later measurement cycles. These results indicate that the specimens of Cu-Zr-Al alloys were changing by mechanical relaxation, owing to the motion of atoms or clusters in the glassy state and possible "defects" produced during the processing of alloys.

Recently, intermetallic compounds have attracted much attention due to their potential technological applications as high-temperature materials. In particular the intermetallic compounds, associated with the Al-Ni binary system stand out as promising candidates for high-temperature materials for the use in harsh environments. It is expected that a bulk Al-Ni alloy may exceed the strength of many commercial materials. The great challenge in developing these alloys is to manipulate the solidification thermal parameters in order to obtain the desired microstructural features. One of the indicated routes to obtain very refined intermetallic phases dispersed in the microstructure is the spray forming process. The dendritic and eutectic growth dependences on cooling rate are already known for directionally solidified (DS) hypoeutectic Al-Ni alloys. In the case of rapidly solidified (RS) samples, extrapolations of such experimental laws are needed, which can be very helpful to estimate realistic values of high cooling rates imposed during the spray forming process. The present study aims to compare directionally solidified and spray-formed Al-5wt. (%)Ni alloy samples with a view to providing a basis for understanding how to control solidification parameters and the as-cast microstructure. The Al-5.0wt. (%)Ni alloy was shown to have a cellular morphology for the overspray powder size range examined (up to 500 µm). The mean cell spacing decreased from 5.0 to 1.1 µm with the decrease in the powder average diameter. It was found that the experimental cooling rates imposed during the atomization step of the overspray powder solidification varied from 10³ to 2.10(4) K/s. The DSC trace depicted a crystallization peak of an amorphous structure fraction in the smallest Al-5.0wt. (%)Ni alloy powder size range (<32 µm) estimating a 15 µm critical diameter of amorphous powder in the binary Al97.5Ni2.5 (at%) alloy.

In order to obtain quasicrystalline (QC) phase by mechanical alloying (MA) in the Al-Cu-Fe system, mixtures of elementary Al, Cu and Fe in the proportion of 65-20-15 (at. %) were produced by high energy ball milling (HEBM). A very high energy type mill (spex) and short milling times (up to 5 hours) were employed. The resulting powders were characterized by X-ray diffraction (XRD), differential scanning calorimetry (DSC) and scanning electron microscopy (SEM). QC phase was not directly formed by milling under the conditions employed in this work. However, phase transformations identified by DSC analysis reveals that annealing after HEBM possibly results in the formation of the ψ QC phase.

The amorphous Cu46Zr42Al7Y5 alloy presents large supercooled liquid region (ΔT X = 100 K), with a viscosity of about 10(6) N.s/m² where the material can flow as a liquid, making it possible an easy deformation in this temperature region. The aim of this work was to analyze processing routes to produce bulks of metallic glasses. Two kinds of materials were used: amorphous powders and ribbons, both were consolidated by hot extrusion in temperatures inside the range between Tg and Tx, with a ram speed of 1 mm/min and extrusion ratio of 3 : 1. Analysis of X-Ray Diffratometry (XRD), Differential Scanning Calorimetry (DSC) and Scanning Electron Microscopy (SEM), revealed that the proposed consolidation routes were effective to produce large bulks of amorphous materials, even with the strong decreasing of ΔT X observed after deformation by milling and during extrusion.