Effect of transition metals on energy absorption during strain-controlled fatigue of an aluminum alloy

Tensile and low cyclic fatigue tests were used to assess the influence of micro-additions of Ti/V/Zr on the performance of Al–7Si–1Cu–0.5Mg (wt.%) alloys in the as-cast and T6 heat-treated conditions and their improvement was compared to the base alloy. The microstructure of the as-cast Al–7Si–1Cu–0.5Mg (wt.%) base and modified alloys consisted of α-Al, eutectic Si, and Cu, the Mg- and Fe-based phases Al_2.1Cu, Al_8.5Si_2.4Cu, Al_7.2Si_8.3Cu₂Mg_6.9 and Al₁₄Si_7.1FeMg_3.3. In addition, the micro-sized Ti/V/Zr-rich phases Al_6.8Si_1.4Ti, Al_21.4Si_4.1Ti_3.5VZr_3.9, Al_6.7Si_1.2TiZr_1.8, Al_2.8Si_3.8V_1.6Zr and Al_5.1Si_35.4Ti_1.6Zr_5.7Fe were identified in the modified alloys. It was also noticed that increasing the content of Ti–V–Zr changed the morphology of Ti/V/Zr-rich phase. The tensile test results showed that the T6 heat-treated alloy modified with the addition of a higher content of Ti–V–Zr achieved the highest tensile strength of 343 MPa over the base alloy and alloys modified with additions of Ti, Ti–Zr and lower contents of Ti–V–Zr. The plastic strain energy density coefficient of the alloy modified with the addition of a higher content of Ti–V–Zr in the T6 temper condition was higher than the other studied alloys and reached 162 MJ m⁻³. The fatigue life of the same alloy was considerably longer than that of the other studied alloys, including the base alloy. The fractography revealed that all the studied alloys showed similar fracture behavior. The tensile cracks propagated through the eutectic Si and primary phases, exhibiting intergranular fracture along with some cleavage-like features of the plate-shaped Zr–Ti–V-rich intermetallics with the presence of fatigue striations on the latter, indicating their ductile nature. It is believed that the morphological changes of intermetallic precipitates containing Zr, Ti and V enhance the fatigue life of the alloy modified with additions of larger amounts of Ti–V–Zr in the T6 condition.     

Characterization of phase development in non-isothermally annealed mould-cast and heat-treated Al–Mn–Sc–Zr alloys

The effect of Mn addition on microstructure and mechanical properties during isochronal annealing in the temperature range of 20 °C–570 °C of the mould-cast and heat-treated Al–Sc–Zr alloys with a various content of Mn and Zr was studied. The electrical resistometry together with the microhardness (HV0.3) measurements were compared to microstructure development. The microstructure development was examined by scanning electron microscopy, transmission electron microscopy and electron diffraction. Relative resistivity changes and the microhardness of the mould-cast and heat-treated Al–Mn–Sc–Zr alloys exhibit similar dependence on annealing temperature. Precipitation of the Al₃Sc particles is responsible for the peak microhardness in all these alloys. The microhardness decrease is slightly delayed during the isochronal annealing and during the high temperature heat treatment in the mould-cast alloy with the higher Zr-content due to a higher oversaturation of Zr. The decomposition sequence of the oversaturated solid solution of the studied Al–Mn–Sc–Zr alloys is compatible with the recently published decomposition sequence of the Al–Sc–Zr system and also with the formation of Mn,Fe-containing particles. It seems very probable that the addition of Mn does not influence the decomposition of solid solution of the ternary Al–Sc–Zr system.     

Microstructural investigations on as-cast and annealed Al–Sc and Al–Sc–Zr alloys

Al–Sc and Al–Sc–Zr alloys containing 0.05, 0.1 and 0.5 wt.% Sc and 0.15 wt.% Zr were investigated using optical microscopy, electron microscopy and X-ray diffraction. The phase composition of the alloys and the morphology of precipitates that developed during solidification in the sand casting process and subsequent thermal treatment of the samples were studied. XRD analysis shows that the weight percentage of the Al₃Sc/Al₃(Sc, Zr) precipitates was significantly below 1% in all alloys except for the virgin Al0.5Sc0.15Zr alloy. In this alloy the precipitates were observed as primary dendritic particles. In the binary Al–Sc alloys, ageing at 470 °C for 24 h produced precipitates associated with dislocation networks, whereas the precipitates in the annealed Al–Sc–Zr alloys were free of interfacial dislocations except at the lowest content of Sc. Development of large incoherent precipitates during precipitation heat treatment reduced hardness of all the alloys studied. Growth of the Al₃Sc/Al₃(Sc, Zr) precipitates after heat treatment was less at low Sc content and in the presence of Zr. Increase in hardness was observed after heat treatment at 300 °C in all alloys. There is a small difference in hardness between binary and ternary alloys slow cooled after sand casting.     

Mechanical properties of Cu–Cr system alloys with and without Zr and Ag

The effects of addition of Zr and Ag on the mechanical properties of a Cu–0.5 wt%Cr alloy have been investigated. The addition of 0.15 wt%Zr enhances the strength and resistance to stress relaxation of the Cu–Cr alloy. The increase in strength is caused by both the decrease in inter-precipitate spacing of Cr precipitates and the precipitation of Cu₅Zr phase. The stress relaxation resistance is improved by the preferentially forming Cu₅Zr precipitates on dislocations, in addition to Cr precipitates on dislocations. The addition of 0.1 wt%Ag to the Cu–Cr and Cu–Cr–Zr alloys improves the strength, stress relaxation resistance and bend formability of these alloys. The increase in strength and stress relaxation resistance is ascribed to the decrease in inter-precipitate spacing of Cr precipitates and the suppression of recovery during aging, and to the Ag-atom-drag effect on dislocation motion. The better bend formability of the Ag-added alloys is explained in terms of the larger post-uniform elongation of the alloys.     

The synergic effects of Sc and Zr on the microstructure and mechanical properties of Al–Si–Mg alloy

In order to clarify the possibility of Zr substitution for Sc on the modification of Al-Si casting alloys, the microstructural evolution and tensile properties of Al-Si-Mg based alloys with different combinations of Sc and Zr contents (Sc + Zr = 0.5 wt.%) were systematically investigated. It was found that 0.5 wt.% Sc addition could refine the microstructure significantly and modify the eutectic Si from plate-like morphology to fiber, which promotes the spheroidization of eutectic Si during heat treatment. When Zr was added to partly replace Sc, the microstructure was first further refined, but was then slightly coarsened with increasing Zr content. Moreover, high Zr content was found to decrease its modification on eutectic Si. It was observed that Zr can also concomitantly improve strength and ductility compared with the alloy modified by Sc only. The improvement of mechanical properties was attributed to microstructural refinement, particularly the modification of eutectic Si and precipitation of secondary nano-scale Al₃(Sc_1 − xZr_x) dispersoids.     

Experimental investigation and thermodynamic description of the Mg–Y–Zr system

The Mg–Y–Zr system was studied via experimental investigation and thermodynamic modeling. Four diffusion couples and four key alloys of the Mg–Y–Zr system at 500 °C were prepared. The phase relations of the Mg–Y–Zr system were investigated by means of X-ray diffraction, scanning electron microscopy, and electron probe microanalysis. No ternary compound was found at 500 °C. The solubility of (αZr) in the Mg–Y intermetallics, i.e., Mg₂₄Y₅, Mg₂Y and MgY, was determined to be negligible. The differential scanning calorimetry measurement was performed on the Mg–Y–Zr alloys to obtain the phase transition temperature. The present thermodynamic calculations of the Mg–Y–Zr system matched well with the experimental data. The presently established Mg–Y–Zr phase diagram can offer a better understanding of the recent processing technique of creep-resistant magnesium alloys.     

Thermal stability and mechanical properties of nanocrystalline Fe–Ni–Zr alloys prepared by mechanical alloying

The thermal stability of nanostructured Fe_100?x?y Ni _x Zr _y alloys with Zr additions up to 4 at.% was investigated. This expands upon our previous results for Fe–Ni base alloys that were limited to 1 at.% Zr addition. Emphasis was placed on understanding the effects of composition and microstructural evolution on grain growth and mechanical properties after annealing at temperatures near and above the bcc-to-fcc transformation. Results reveal that microstructural stability can be lost due to the bcc-to-fcc transformation (occurring at 700 °C) by the sudden appearance of abnormally grown fcc grains. However, it was determined that grain growth can be suppressed kinetically at higher temperatures for high Zr content alloys due to the precipitation of intermetallic compounds. Eventually, at higher temperatures and regardless of composition, the retention of nanocrystallinity was lost, leaving behind fine micron grains filled with nanoscale intermetallic precipitates. Despite the increase in grain size, the in situ formed precipitates were found to induce an Orowan hardening effect rivaling that predicted by Hall–Petch hardening for the smallest grain sizes. The transition from grain size strengthening to precipitation strengthening is reported for these alloys. The large grain size and high precipitation hardening result in a material that exhibits high strength and significant plastic straining capacity.     

Transformation behavior and thermal stability of Al-based systems prepared by ball milling

Transmission electron microscopy, X-ray diffraction, scanning electron microscopy, differential thermal analysis, and differential scanning calorimetry were used to investigate the transformation behavior of (Al_0.88Ni_0.08Co_0.04)_100−x,Zr_x, (wherex = 0 to 5 at. %) alloys during ball milling, and the thermal stability during the reverse process of return to equilibrium. The results have shown that the crystalline to amorphous transformation occurs only in compositions containing Zr. Mechanical grinding is shown to easily amorphize the Al₃Zr compound which enters in equilibrium with the fcc-Al and (Co, Ni)₂Al₉ phases for the compositions studied. The formation of an amorphous phase at the fcc-Al and Co₂Al₉ grain boundaries leads to a wetting transition, and with decreasing grain size the initially nanostructured Al₈₈Ni₈Co₄ alloy was found to progressively transform to an amorphous alloy. The crystallization temperature, the activation energy, and the crystallization enthalpy increase, while the melting temperature of the quaternary alloys decrease with increasing Zr substitution up to 5 at. %.     

Microstructure,corrosion behavior and cytotoxicity of Zr–Nb alloys for biomedical application

In this work, the effects of Nb content on microstructure and corrosion behaviors of biomedical Zr–Nb alloys were systematically studied. The results of XRD analysis and optical microscopy indicated that the experimental Zr–Nb alloys had a duplex structure of α and β phases, and the content of β phase increased with the increase of Nb content. The electrochemical impedance spectroscopy (EIS) studies showed an improvement on the resistance of the spontaneous oxide film with increasing Nb content. The EIS data, fitted by R_s(Q_pR_p) model, suggested a single passive film formed on the experimental material surfaces. Polarization tests in Hank's solution revealed a nobler electrochemical behavior of the Zr–Nb alloys after alloying Nb to pure Zr. The corrosion resistance increased with increasing Nb content, as indicated by lower corrosion current densities and passive current densities and higher pitting potentials. The major components on the surfaces of the corroded Zr–Nb alloy samples detected by XPS were ZrO₂ and Nb₂O₅. The biocompatibility of Zr–Nb alloys was primarily evaluated by culturing L-929 cells in the extraction media of Zr–Nb alloy samples and excellent results were obtained. All of these above results suggested that the Zr–22Nb alloy, among the experimental alloys, showed a promising potential for biomedical applications.     

Reactions of Hf-Ag and Zr-Ag alloys with Al2O3 at elevated temperatures

We are studying reactions of Ti, V, Zr, and Hf with ceramics as part of a program to understand fundamental reaction and bonding mechanisms in active metal brazing of ceramics. In this paper we present results of experiments with model systems comprising Ag alloys that contain different amounts of Hf or Zr that were reacted with sapphire or 99.6% alumina for different times and temperatures in a controlled atmosphere furnace. In these alloys the Ag functions as an inert solvent, which allowed us systematically to determine the effects of changes in concentration of the active element. We observed qualitative wetting and spreading tendencies of the alloys during heating and examined cross sections after cooling using electron analytical techniques. For all reaction times studied, the Hf/Ag alloys formed a discontinuous reaction layer, which was consistent with earlier high-resolution electron microscopy that showed sub-micrometer HfO₂ particles embedded in the surfaces of the Al₂O₃ grains. By contrast, initial reaction of the Zr/Ag alloys with Al₂O₃ produced a continuous interface layer. With longer reaction times, the ZrO₂ reaction product became much thicker and exhibited three distinct zones at the interface. The results suggest that the rate limiting step in the Zr/Ag reaction is the chemical reaction at the interface, whereas with Hf/Ag reaction diffusion of products away from the interface is rate limiting.     

Influence of zirconium on grain refining efficiency of Al–Ti–C master alloys

The influence of Zirconium on the grain refinement performance of Al–Ti–C master alloys and the effect mechanism has been studied in this paper. The experimental results show that Zr not only results in poisoning the Al–Ti–B master alloy, but also poisons the Al–Ti–C master alloys. The poisoning effect is more obvious at higher melting temperature. When 0.12%Zr is added into the melt, the grain refinement performance of Al–5Ti–0.4C refiner with 0.2% addition level absolutely disappears at 800 °C. The experimental results also show that it is difficult to refine the commercial purity Al containing 0.15%Zr by Al–5Ti–0.4C master alloy. Further experiments show that the Zr element can interact with both TiAl₃ and TiC phases. If both of them are present, Zr preferentially reacts with TiAl₃ phase.     

Effects of trace zirconium on the initiation and propagation behavior of fatigue cracks in Cu–6Ni–2Mn–2Sn–2Al alloy

The effects of trace Zr on the fatigue behavior of Cu–6Ni–2Mn–2Sn–2Al alloy were studied through the initiation and growth behavior of a major crack. When stress amplitude was less than σ_a = 350 MPa, the fatigue life of Zr-containing alloys was about 2 times larger than that of alloy without Zr. When σ_a = 400 MPa, the effects of Zr addition on fatigue life disappeared. Increased fatigue life due to Zr addition resulted from an increase in crack initiation life and microcrack growth life. Zr addition generated strengthened grain boundaries (GBs) that developed from the precipitation of SnZr compounds. Strengthened GBs contributed to the increase in crack initiation life. The effects of Zr addition on fatigue behavior were discussed with relation to the behavior of microcracks.     

Microstructure and mechanical properties of Mg–Gd–Zr alloys with low gadolinium contents

Mg–xGd–0.6Zr (x = 2, 4, and 6% mass fraction) alloys were synthesized by semi-continuous casting process. The effects of gadolinium content and aging time on microstructures and mechanical properties of the Mg–xGd–0.6Zr alloys were investigated. The results show that the microstructures of the as-cast GKx (x = 2, 4, and 6%) alloys are typical grain structures and no Gd dendritic segregation. In as-cast Mg–6Gd–0.6Zr alloy, the second phases Mg_5.05Gd, Mg₂Gd, and Mg₃Gd will form due to non-equilibrium solidification during the casting process, and these second phases will disappear after hot-extrusion. The residual compressive stress exists in alloys after extrusion and increases with increasing Gd content. The existence of residual compressive stress contributes to the tensile strength. The elongation of all extruded alloys is over 30%, and the ultimate and yield tensile strength of the Mg–6Gd–0.6Zr alloy are 237 and 168 MPa, respectively. After isothermal aging for 10 h, the strength of extruded Mg–6Gd–0.6Zr alloys increases slightly, however, the elongation of alloys rarely decreases. The fracture mechanism of all studied alloys is ductile fracture.     

Effects of Sc(Zr) on the microstructure and mechanical properties of as-cast Al–Mg alloys

Both the addition of 0.6% Sc and simultaneous addition of 0.2% Sc and 0.1% Zr exerted a remarkable effect on grain refinement of as-cast Al–Mg alloys, changing typical dendritic microstructure into fine equiaxed grains. Such effect was found to be related to the formation of primary particles, which acted as heterogeneous nucleation sites for α-Al matrix during solidification. Primary particles formed in Al–Mg–Sc–Zr alloy could be identified as the eutectic structure consisting of multilayer of ‘Al₃(Sc,Zr)?+?α-Al?+?Al₃(Sc,Zr)’, with a ‘cellular-dendritic’ mode of growth. In addition, an attractive comprehensive property of as-cast Al–5Mg alloy due to the addition of 0.2% Sc and 0.1% Zr was obtained.     

Microstructure and bond strength of Ni–Cr steel/Al2O3 joints brazed with Ag–Cu–Zr alloys containing Sn or Al

Abstract

Sintered Al₂O₃ was joined to Ni–Cr steel by the active metal brazing route with Ag–Cu–Zr brazing alloys containing Sn or Al. A single ZrO₂ layer with a monoclinic structure was formed at the Al₂O₃ /brazement interface by the migration of Zr in the molten brazing alloy to the Al₂O₃ surface, followed by a redox reaction between the Al₂O₃ and Zr. The remainder of the brazement formed a Cu–Ag eutectic alloy. Precipitates CuZr₂ and Cu–Zr–Al were formed in the brazements of the Ni–Cr steel/ Al₂O₃ joints brazed with Ag–Cu–Zr alloys and Al containing Ag–Cu–Zr alloys, respectively. On the other hand, no precipitates were formed in the brazement of the Ni–Cr steel/Al₂O₃ joints brazed with Sn containing Ag–Cu–Zr alloys. The Ni–Cr steel/ Al₂O₃ joints brazed with Sn containing Ag–Cu–Zr alloys showed much higher fracture shear strengths than those brazed with Ag–Cu–Zr alloys or Al containing Ag–Cu–Zr alloys.     

Mn和Zr对Al-Zn-Mg-Cu铝合金各向异性的影响

采用光学显微镜(OM)、扫描电子显微镜(SEM)、透射电子显微镜(TEM)以及室温拉伸、剥落腐蚀、晶间腐蚀等测试方法,研究了微量的Mn和Zr对Al-Zn-Mg-Cu铝合金的组织和性能各向异性的影响。结果表明,在Al-Zn-Mg-Cu-Ti合金中,分别添加微量的Mn和Zr,合金中对应析出细小弥散的Al6Mn和Al3Zr相,这两相均能抑制基体再结晶,促使合金的晶粒纵横比增大。合金的力学性能、抗晶间腐蚀和剥落腐蚀性能提高,但性能各向异性增大。同时,结果显示Zr对合金的组织和性能各向异性的影响显著大于Mn。     

Effects of samarium content on microstructure and mechanical properties of Mg–0.5Zn–0.5Zr alloy

Effects of samarium (Sm) content (0, 2.0, 3.5, 5.0, 6.5 wt%) on microstructure and mechanical properties of Mg–0.5Zn–0.5 Zr alloy under as-cast and as-extruded states were thoroughly investigated. Results indicate that grains of the as-cast alloys are gradually refined as Sm content increases. The dominant intermetallic phase changes from Mg₃Sm to Mg₄₁Sm₅ till Sm content exceeds 5.0 wt%. The dynamically precipitated intermetallic phase during hot-extrusion in all Sm-containing alloys is Mg₃Sm. The intermetallic particles induced by Sm addition could act as heterogeneous nucleation sites for dynamic recrystallization during hot extrusion. They promoted dynamic recrystallization via the particle stimulated nucleation mechanism, and resulted in weakening the basal texture in the as-extruded alloys. Sm addition can significantly enhance the strength of the as-extruded Mg–0.5Zn–0.5 Zr alloy at room temperature, with the optimal dosage of 3.5 wt%. The optimal yield strength (YS) and ultimate tensile strength (UTS) are 368 MPa and 383 MPa, which were enhanced by approximately 23.1% and 20.8% compared with the Sm-free alloy, respectively. Based on microstructural analysis, the dominant strengthening mechanisms are revealed to be grain boundary strengthening and dispersion strengthening.     

The influence of reactive element additions to β-NiAlCr alloys on the morphology of thermally grown oxides

Abstract

The effect of the reactive elements (REs), Y and Zr, on oxidation of β-NiCrAl alloy at 1373 K in a gas mixture of argon with 20 vol.% oxygen at atmospheric pressure was evaluated using X-ray diffractometry, scanning electron microscopy, electron probe X-ray microanalysis and secondary ion mass spectroscopy. The oxide surfaces and interface morphologies, compositions and growth kinetics were studied for alloys with 0.32 at.% Zr and 0.24 at.% Y additions and for an undoped alloy. The oxide layer produced on the three different alloys contains mainly α-alumina and some intermediate alumina modification, Cr₂O₃ and RE-oxides. A needle-like morphology was seen on top of the oxide layer for the undoped and Zr alloy. Needle formation on the Y alloy was suppressed by the formation of a thin Y₂O₃ layer during the initial stage of oxidation. Needles were maintained to long oxidation times for the undoped alloy, but disappeared on the doped alloys indicating that some cation diffusion is possible when REs are present. Fewer intermediate alumina modifications are seen for the oxide layers on the RE alloys showing that the REs promote the formation of the α-alumina phase. Oxide layer growth occurs in two stages for all alloys. Initially, oxide growth is rapid with outward diffusion of aluminium. The second stage of oxidation is slow and is initiated by the formation of a closed α-alumina layer limiting further oxidation to inward oxygen diffusion. This stage is characterised by parabolic growth kinetics associated with a constant aluminium interface concentration. The oxide layer is thinnest for the Y alloy due the fine Y₂O₃ layer acting as a diffusion barrier. The oxide/alloy interface for the undoped alloy is flat and shows many voids, whereas voids are not seen for the RE alloys. This is due to the promotion of a closed α-alumina layer giving predominantly inward growth early in the oxidation process. Oxide pegs of the RE are also seen growing into the alloys. The lack of voids and the oxide pegs are advantageous for oxide layer adhesion to the doped alloys.     

Interaction of ZrFe<Subscript>2</Subscript> doped with Ti and Al with hydrogen

The influence of doping with Ti and Al on the structure and hydrogen sorption properties of ZrFe₂ was studied by XRD, XRSMA, and measurement of hydrogen absorption and desorption isotherms at pressure up to 300 MPa. The hydrogen capacity and equilibrium desorption pressures of hydrides decrease with increasing Al content at a constant ratio of Ti and Zr. The increase in the Ti content at a constant content of Al in alloys also leads to a decrease in hydrogen capacity; however, the equilibrium desorption pressures of hydrides increase considerably. Zr_1−x Ti _x (Fe_1−y Al _y )₂ (x= 0.2–0.8; y = 0.05–0.4) alloys were investigated.     

Precipitation hardening of Cu – Ti – Zr alloys

Abstract

The influence of age hardening temperature and time on the hardness, tensile properties, electrical conductivity, and microstructure of Cu – 4Ti – 0.1Zr and Cu – 3Ti – 0.1Zr alloys has been investigated. The resulting microstructure of these alloys suggests that zirconium addition prohibited the formation of compositional modulations in the solution treated condition. These alloys exhibited maximum hardness and strength on peak aging at 450°C for 24 h by the formation of a coherent and metastable Cu₄Ti phase (β') in modulated structure while overaging occurred by the formation of equilibrium phase β-Cu₃Ti. The electrical conductivity of both the alloys increased moderately on aging. Unlike in an earlier study of binary Cu – Ti and some ternary Cu – Ti – X alloys, overaging did not cause any discontinuous precipitation in the Cu – Ti – Zr alloys investigated. Modulated structure formed on peak aging persisted on prolonged aging at 450°C for 80 h or at 500°C for 8 h.