Thermodynamics and reaction pathways of hydrogen sorption in Mg6(Pd,TM) (TM = Ag,Cu and Ni) pseudo-binary compounds

Mg₆(Pd,TM) (TM = Ag, Cu and Ni) pseudo-binary compounds have been synthesized at the TM solubility limit to determine the influence of TM on the thermodynamics and reaction pathways of the Mg₆Pd–H system. All compounds exhibit a two-plateau pressure behaviour, being the value of the high plateau pressure well above that of the Mg/MgH₂ system. Such destabilization is explained by the formation of different Mg–(Pd,TM) intermetallics and/or Mg₂NiH₄ hydride phases during the hydrogenation reaction. The formation of these phases not only increases the enthalpy of hydrogenation but also enhances disorder leading to a limited destabilization of the hydrogenated state. This compensation effect is characterized by a linear correlation between enthalpy and entropy terms. In addition, this work also provides the assessment at 623 K of the ternary Mg–Pd–Cu phase diagram in the Mg-rich corner.     

Oxidation Behavior of a PVD-Processed Mg–10.6Zr Alloy

The oxidation behavior in air of a physical vapor-deposited (PVD) Mg–10.6Zr (wt. %) alloy was studied in the 325–450°C temperature range. The oxidation rate of this alloy remains low at temperatures below 375°C. However, at higher temperatures, the alloy experienced extremely high oxidation rates, which can even lead to disintegration of the sample. Oxidation is controlled by fast inward oxygen transport along the open boundaries of the alloy, leading to the formation of cracks throughout the sample, and subsequent formation of a thin MgO at crack interfaces. The MgO layer remains protective while coarsening of zirconium precipitates at the open boundaries does not take place. Thickening of Zr precipitates over a critical size induces impairment of the MgO layer at crack interfaces, facilitating inward oxygen diffusion. The volume increase resulting from the formation of new oxide at open boundaries favors decohesion of open boundaries, leading to accelerated oxidation.     

Oxidation behaviour of Al-alloyed ZrSi2 at 700°C

The oxidation resistance of ZrSi₂-4 at.% Al prepared by reaction sintering was evaluated in air at 700°C. Two different stages were distinguished. In the first regime the oxidation rate remains high whereas the second one is characterised by a marked decrease on the oxidation rate. Passage from the first to the second stage, associated with a transition stage, is determined by the formation of a continuous protective alumina-rich layer at the scale/alloy interface. An oxidation mechanism is proposed to explain the different stages occurring through the oxidation. Grain boundaries contribute to the fast inward oxygen transport into the alloy, leading to internal oxidation of non-reacted silicon and aluminium during the reactive sintering stage of the processing. Oxidation resistance could be improved by increasing the grain size of the alloy and by using an appropriated processing method addressed to minimise or suppress the presence of silicon and aluminium particles at ZrSi₂ grain boundaries.     

Effect of Extrusion Temperature on the Plastic Deformation of an Mg-Y-Zn Alloy Containing LPSO Phase Using <Emphasis Type="Italic">In Situ</Emphasis> Neutron Diffraction

The evolution of the internal strains during in situ tension and compression tests has been measured in an MgY₂Zn₁ alloy containing long-period stacking ordered (LPSO) phase using neutron diffraction. The alloy was extruded at two different temperatures to study the influence of the microstructure and texture of the magnesium and the LPSO phases on the deformation mechanisms. The alloy extruded at 623 K (350 °C) exhibits a strong fiber texture with the basal plane parallel to the extrusion direction due to the presence of areas of coarse non-recrystallised grains. However, at 723 K (450 °C), the magnesium phase is fully recrystallised with grains randomly oriented. On the other hand, at the two extrusion temperatures, the LPSO phase orients their basal plane parallel to the extrusion direction. Yield stress is always slightly higher in compression than in tension. Independently on the stress sign and the extrusion temperature, the beginning of plasticity is controlled by the activation of the basal slip system in the dynamic recrystallized grains. Therefore, the elongated fiber-shaped LPSO phase which behaves as the reinforcement in a metal matrix composite is responsible for this tension–compression asymmetry.     

Estimation of anisotropy of mechanical properties in Mg alloys by means of compressive creep tests

A detailed knowledge of dependence of mechanical properties on orientation in materials prepared by directional processes may present an important factor influencing the design of construction parts. Toward this end, the compressive creep testing of short specimens may be useful. Three different magnesium-based materials were subjected to this testing: (i) pure magnesium, (ii) magnesium matrix composite reinforced with 10 vol.% of titanium, and (iii) magnesium alloy WE54. All three materials were prepared through a powder metallurgical route with final hot extrusion. The specimens for creep tests were cut in such a way that their longitudinal axis (i.e., the direction of compressive creep stress) and the axis of extruded bar contained a predestined angle. Two extreme cases can be observed: In pure Mg and in Mg-Ti composites, the dependence of the creep rate is very sensitive to the orientation especially at small inclinations from extrusion axis. The greatest creep resistance is observed in specimens with stress axis parallel to the extrusion axis, the lowest at declinations from 45 to 90°. On the other hand, in WE54 no orientation dependence was observed. Possible explanations of the behavior based on microstructural observations are discussed. __________ Translated from Problemy Prochnosti, No. 1, pp. 125–128, January–February, 2008.     

Indentation creep of lead and lead-copper alloys

Stress exponent values have been determined in Pb and Pb-Cu alloys with small Sn, Se and Pd additions by indentation methods (long time hardness tests) to evaluate their applicability as compared with tensile tests. Homogeneous, fine grained alloys were obtained by induction melting and thermo-mechanical treatments. Grain size was 38–60 m in alloys and 183 m in pure lead. Stress exponent values, i.e. of 11–12 agree between different methods of derivation and, in fine grained material, with tensile methods. The largest differences in pure lead, i.e. 10–11 versus 7–8 are attributed to high strain rates when indentation size is comparable to grain size. In all cases indentation and tensile tests indicate the same deformation mechanism, namely slip creep. The indentation test is thus considered useful, within limits, to acquire information on the deformation mechanism.     

Improvement of Oxidation Behavior of a Ti–48Al–2Cr Alloy by a Nitridation Treatment

The effect of a nitridation treatment for 10 hr at 800°C on the oxidation resistance of a Ti–48Al–2Cr (at.%) alloy in air at 800°C was evaluated. Results prove that nitridation decreases by about 40% the total mass gain of nonnitrided material, although the oxidation mechanism is the same for both materials. The oxidation can be divided into two stages. The formation of a nonprotective mixed alumina–rutile scale during the transient stage results in a high oxidation rate. A further decrease in the oxidation rate arises from the establishment of an external alumina-rich layer during the steady stage. The main difference between the scale developed on both materials is the continuous nature of the nitride layer present in the nitrided material during the entire exposure. The thin continuous nitride layer formed during the nitridation treatment acts beneficially as a diffusion barrier, preventing oxygen dissolution in the ₂-Ti₃Al phase during the transient stage. Furthermore, the oxygen gradient through the oxide scale is kept low, because no oxygen is removed at the scale–alloy interface.     

Evolution of internal strain during plastic deformation in magnesium matrix composites

Synchrotron radiation diffraction during in situ tensile tests has been used to evaluate the internal elastic strains within the grains of magnesium alloy, AZ31, unreinforced and reinforced with 5 and 10% volume of SiC particles. Composites present initial thermal residual stresses, which are positive (tensile) in the matrix and negative (compressive) in the reinforcing particles. Internal elastic strains evolve in a similar behaviour in the unreinforced AZ31 and in both composites. However, the accumulated elastic strains are reduced in the case of the composite because a part of the applied load is borne by the ceramic particles.     

Influence of Powder Particle Size on the Oxidation Behavior of a PM Ni3Al Alloy

The influence of particle size on the oxidationbehavior of Ni₃Al prepared by powdermetallurgy (PM) was investigated in the temperaturerange of 535 to 1020°C for exposures up to 200 hr.Four alloys were obtained, each one processed with a differentpowder particle size fraction (<25, 25-50, 50-100,and 100-200 m). For temperatures below 730°C,the scale consists of an outer NiO layer, a thindiscontinuous intermediate nickel layer, and an internaloxidation zone. The lowest oxidation rate corresponds tothe material with the smallest particle size. Thisresults from its higher grain-boundary density; the boundaries act as easy-diffusion paths foraluminum leading to the rapid formation of a continuousinner alumina layer. At temperatures above 730°C, athree layered scale is observed consisting of an outer NiO layer, an intermediate layer that,depending on temperature, consisted of a mixture ofnickel and aluminum oxides orNiAl₂O₄, and an inner layer ofAl₂O₃, which accounts for thehigher oxidation resistance. The oxidation attack is characterized byintrusions of the scale into the alloy, the intrusionnumber increasing as the particle size decreases. It isassumed that oxide particles and impurities present at the original particle boundaries facilitatealumina growth along these regions. Thus, the lowestoxidation rate for the highest temperature rangecorresponds to the largest particle-sizematerial.