Density change upon crystallization of amorphous Zr–Cu–Al thin films

Systematic deflection measurements with micro-cantilevers and a combinatorial-deposition method have been used to investigate the density change upon crystallization of amorphous Zr–Cu–Al thin films. It is found that, in general, the density change decreases from Cu-/Al-rich compositions to Zr-rich compositions, and the previously reported good glass-forming compositions are found to correspond to global minima of the density change inside respective local eutectic systems. Furthermore, we propose that the general trend of density change as a function of alloy compositions discovered in this work may have implications for the macroscopic plasticity of metallic glasses.     

Evaluation of elastic modulus and hardness of Fe–Al base intermetallics by nano-indentation techniques

Nanoindentation has been used to study Young's modulus and hardness of Fe–Al alloys with Al contents from 22 to 47 at%, and the influence of Cr additions to near Fe₃Al alloys. Materials are examined in the quenched state and the well-annealed state with, respectively, relatively poor order with retained thermal vacancies, and good order with few vacancies. Significant changes occur in both modulus and hardness, affected by Al content, Cr addition and heat treatment. These changes are discussed in terms of state of order, possible role of magnetisation, and vacancies.     

Crystallization process and shape memory properties of Ti–Ni–Zr thin films

The crystallization process of as-deposited Ti–Ni–(10.8–29.5)Zr amorphous thin films was investigated. The Ti–Ni–Zr as-deposited films with a low Zr content exhibited a single exothermic peak due to the crystallization of (Ti,Zr)Ni with a B2 structure. In contrast, a two-step crystallization process was observed in the Ti–Ni–Zr thin films with a high Zr content. Shape memory behavior of Ti–Ni–Zr thin films heat treated at 873–1073 K was investigated by thermal cycling tests under various stresses. The martensitic transformation start temperature increased with increasing Zr content until reaching the maximum value, then decreased with further increasing Zr content. The inverse dependence of transformation temperature on Zr content in the thin films with a high Zr content is due to the formation of a NiZr phase during the crystallization heat treatment. The formation of the NiZr phase increased the critical stress for slip but decreased the recovery strain.     

Microstructure and mechanical properties of Ti–Nb–Fe–Zr alloys with high strength and low elastic modulus

Zr was added to Ti–Nb–Fe alloys to develop low elastic modulus and high strength β-Ti alloys for biomedical applications. Ingots of Ti–12Nb–2Fe–(2, 4, 6, 8, 10)Zr (at.%) were prepared by arc melting and then subjected to homogenization, cold rolling, and solution treatments. The phases and microstructures of the alloys were analyzed by optical microscopy, X-ray diffraction, and transmission electron microscopy. The mechanical properties were measured by tensile tests. The results indicate that Zr and Fe cause a remarkable solid-solution strengthening effect on the alloys; thus, all the alloys show yield and ultimate tensile strengths higher than 510 MPa and 730 MPa, respectively. Zr plays a weak role in the deformation mechanism. Further, twinning occurs in all the deformed alloys and is beneficial to both strength and plasticity. Ti–12Nb–2Fe–(8, 10)Zr alloys with metastable β phases show low elastic modulus, high tensile strength, and good plasticity and are suitable candidate materials for biomedical implants.     

On some special features of the structure and properties of metallic “thin” films

Conclusions  

Machining of a Zr–Ti–Al–Cu–Ni metallic glass

Zr_52.5Ti₅Cu_17.9Ni_14.6Al₁₀ metallic glass machining chips were characterized using SEM, X-ray diffraction and nano-indentation. Above a threshold cutting speed, oxidation of the Zr produces high flash temperatures and causes crystallization. The chip morphology was unique and showed the presence of shear bands, void formation and viscous flow.     

Correlation between mechanical behavior and glass forming ability of Zr–Cu metallic glasses

A series of Zr–Cu glassy ribbons were fabricated, and the compositional dependence of microhardness in the as-quenched and annealed state was systematically investigated. The as-quenched microhardness exhibits a positive deviation from linearity at the compositions which correspond to local maximum in glass forming ability (GFA). Upon annealing, the microhardness change is relatively smaller for the high GFA compositions. High atomic packing density at the special compositions should be responsible for the microhardness behavior.     

On the formation of faceted Al3Zr (β′) precipitates in Al–Li–Cu–Mg–Zr alloys

Trace additions of Zr to Al alloys inhibit recrystallization through the formation of spherical and coherent Al₃Zr (β′) precipitates. Recently, observations have been made of faceted β′ precipitates in several hot deformed Al alloys, although no systematic experimental study of either the causes of the formation of such precipitates or their orientation relationships with the Al matrix has so far been reported. A detailed examination of the orientation relationships shows that the cube-on-cube orientation relationship existing between spherical, coherent β′ precipitates and the Al matrix does not hold good for the faceted β′ particles and that the faceted β′ particles are twin-related with the matrix. It is shown that the twin-related β′ particles are not incoherent, but bound by large facets fully coherent with the matrix, and that such particles are associated with fairly significant coherency strains. A probable shape of the faceted β′ is also described.     

Composition dependence of the microstructure and mechanical behavior of Ti–Zr–Cu–Pd–Sn–Nb bulk metallic glass composites

Ti-based bulk metallic glass composite alloys Ti₅₆Zr₆Cu_19.8Pd_8.4Sn_1.8Nb₈, Ti₆₄Zr₄Cu_13.2Pd_5.6Sn_1.2Nb₁₂ and Ti₆₈Cu_13.2Pd_5.6Sn_1.2Nb₁₂ were designed to obtain the microstructure composing of β-Ti dendrites and glassy matrix. The compressive and three-point bending properties were investigated. It was found that the actual microstructure of the Nb-added alloys consisted of primarily precipitated β-Ti dendrites, network-like glassy matrix, and extra island-like Ti₂Cu intermetallic phase with different volume fractions. Under compressive loading, all the Nb-added alloys presented higher yield strength combined with remarkably increased plasticity. Under bending condition, however, the alloys Ti₅₆Zr₆Cu_19.8Pd_8.4Sn_1.8Nb₈ and Ti₆₄Zr₄Cu_13.2Pd_5.6Sn_1.2Nb₁₂ with higher Ti₂Cu volume fractions became completely brittle. The alloy Ti₆₈Cu_13.2Pd_5.6Sn_1.2Nb₁₂ could keep its plastic deformability due to the decreased Ti₂Cu volume fraction. Compressive deforming behavior of the Nb-added alloys was determined by the ductile β-Ti phase and glassy matrix, nevertheless, bending deforming behavior of the alloys was determined by the volume fraction and distribution of the brittle intermetallics.     

Influence of Al on the microstructure and mechanical properties of Cr–Zr–(Al–)N coatings with low and high Zr content

Low Zr (S1) and high Zr (S2) quaternary Cr–Zr–(Al–)N coatings with increasing Al content were deposited by d.c. reactive magnetron sputtering. The structure, fracture cross-section morphology and mechanical properties of the coatings were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), nanoindentation, scratch testing and Vickers micro-indentation testing. All the coatings present an fcc NaCl-type B1 structure; in the low Zr content coatings, the diffraction peaks shift towards higher angles as the Al content increases. The grain size is approximately constant in a range from 6 to 8 nm, except for high Zr content films where a significant decrease in crystalline order is observed (grain size ~ 2.5 nm). In both series, the microstructure changed from equiaxed to columnar with increasing Al content. The highest hardness and strongest adhesion values were achieved in coatings with lower Zr and Al content. Conversely, the coatings with high Zr and the highest Al content exhibited an abrupt decrease in hardness, adhesion strength and toughness.     

Internal structures and shape memory properties of sputter-deposited thin films of a Ti–Ni–Cu alloy

Low-temperature heat treatments of the sputter-deposited amorphous films, which were previously proved to be a new method to produce very good shape memory properties for Ti-rich Ti–Ni alloys, have been applied to a ternary Ti–43.0Ni–6.2Cu alloy (at.%). The basically same nanometric structures as in the binary alloy are formed, i.e. the nanometric structures consist of extremely thin plate precipitates of bct structure, which are formed on {100} planes of the parent B2 structure and have the c-axis normal to the habit planes. High-shape recovery stresses of about 500 MPa with recoverable shape strains of 5% are obtained without accompanying any permanent strains. A shape recovery stress of more than 870 MPa is attained if it is allowed to involve about 1% permanent strain. Although these bct precipitates have large tetragonalities, they are perfectly coherent with the parent bcc lattice. The maximum shape recovery stress is nearly twice that of the Ti-rich Ti–Ni binary alloy having a similar nanometric structure. It is suggested that this remarkable increase in recovery stress may be attributed to the change in Burgers vector of dislocations caused by partial disordering in Ti–Ni–Cu alloys. It is emphasized that the shape recovery stress in this ternary alloy is four times that of the Ti₂Ni containing samples and 10 times that of a bulk Ti–45Ni–5Cu alloy.     

Structure of martensite in sputter-deposited (Ni,Cu)-rich Ti–Ni–Cu thin films containing Ti(Ni,Cu)2 precipitates

The martensite structure in sputter-deposited thin films of Ti_48.6Ni_35.9Cu_15.5 was studied. The Ti(Ni,Cu)₂ phase precipitates during the annealing process. Fine Ti(Ni,Cu)₂ precipitates can be deformed by the shear deformation of martensitic transformation, but they obstruct the movement of the twin boundaries to some extent. Coarse Ti(Ni,Cu)₂ precipitates seriously impede the growth of martensite plates and lead to a rectangular-cell-like structure of martensite in the film annealed at 873 K. The resistance of Ti(Ni,Cu)₂ precipitates to the growth of the martensite plates enhances with the coarsening of Ti(Ni,Cu)₂ precipitates, which is one of the reasons for the decrease in the maximum recoverable strain with increasing annealing temperature. B19′ martensite with (0 0 1) compound twinning is frequently observed near coarse Ti(Ni,Cu)₂ precipitates and grain boundaries in films annealed at 873 and 973 K. The local stress concentration should be responsible for the presence of B19′ martensite.     

Structural origins for the high plasticity of a Zr–Cu–Ni–Al bulk metallic glass

The structural origins for the high plasticity of a Zr₅₃Cu_18.7Ni₁₂Al_16.3 (at.%) bulk metallic glass are explored. Under plastic flow conditions, in situ synchrotron high-energy X-ray diffraction reveals that the atomic strain saturates to the closest packing in the longitudinal direction of the applied load while atoms yield in the transverse plane. Scanning electron microscopy investigation reveals that global plasticity benefits from abundant shear band multiplication and interactions. Atomic level flows are seen to accompany profuse shear bands. The plasticity enhancement of this metallic glass benefits from such atomic level flows. Atomic level flow facilitates the activation of shear transformation zones that further self-assemble to promote shear band multiplication. On the other hand, it also mitigates the shear band propagation that prevents catastrophic shear band extension.     

On the Ti2Ni precipitates and Guinier–Preston zones in Ti-rich Ti–Ni thin films

After heat treatment, there may exist different types of precipitates in Ti-rich thin films, i.e. spherical Ti₂Ni precipitates and plate-like Guinier–Preston (GP) zones. While the Ti₂Ni precipitates impede the shear deformation of martensitic transformation, the GP zones do not stop both the shear deformation of martensitic transformation and the twinning shear of (001) deformation twin in the martensite phase. An elastic deformation model of the GP zone during martensitic transformation and subsequent deformation in the martensite was built up. The model can explain the GP zones-related shape memory properties self-consistently. These results supply microstructural explanation for the previous results that Ti-rich Ti–Ni thin films with GP zones show a large transformation strain despite the presence of the GP zones, while thin films with Ti₂Ni precipitates show a relatively small transformation strain.     

Cyclic compression behavior of a Cu–Zr–Al–Ag bulk metallic glass

The cyclic compression behavior of a Cu₄₅Zr₄₅Al₅Ag₅BMG was investigated in order to elucidate the damage initiation and growth mechanisms. The present Cu₄₅Zr₄₅Al₅Ag₅ BMG was found to have a fatigue-endurance limit of 1418 MPa and fatigue ratio of 0.77. Fracture under cyclic compression occurred in a pure shear mode. The fracture surface forms an angle of 41° with respect to the loading axis. This angle was similar to the monotonic compressive fracture angle for the present BMG. The cyclic compression fracture surface displays a morphology nearly identical to the monotonic compression fracture surface. In addition to many shear bands and cracks, areas of “chipping” were commonly found on the outside surfaces of the fatigue specimens. An attempt was made to measure crack growth rates, and two types of crack growth behavior were found. With the first type, the growth rate decreased with cycles due to the decrease in the driving force for crack propagation. With the second type, the crack growth rate increased with cycles after chipped areas developed. The fatigue deformation process for BMGs under cyclic compression was carefully studied and rationalized.     

Influence of megaplastic deformation on the structure and hardness of Al–Cu–Mg alloy after aging

Methods of electron microscopy and X-ray diffraction have been used to investigate structural and phase transformations in the aluminum alloy of grade A2024 (Al–4.5 Cu–1.37 Mg–0.61 Mn–0.07 Si–0.27 Fe–0.02 Zn–0.02 Ti (wt %)) after aging and deformation by shear under high quasi-static pressure. It has been shown that the combination of two-stage aging with megaplastic deformation leads to the refinement of the structure to a nanolevel and to strengthening of the alloy (to an increase in the microhardness to 3000 MPa). The values of true deformation at which the deformation-induced dissolution of the particles of the strengthening S phase occurs have been determined.     

Phase transformations in Al–Cu thin films: precipitation and copper redistribution

The (micro-)structural changes occurring in thin Al–Cu films of about 500 nm thickness and containing up to 1 at% Cu have been investigated. In particular, the copper distribution and the precipitation behaviour have been studied in situ during thermal cycling between 323 and 773 K. After slow cooling, large second-phase particles are observed which are mostly located at grain boundary triple points; the shape and size depend on the copper concentration. The average distance between these particles is about 16 μm, which is larger than the average grain size of approximately 1 μm. No second-phase particles have been observed within the aluminium grains. After cooling, a relatively large amount of copper (about 0.2 at%) as compared with bulk Al–Cu (0.001 at%) is not contained in second-phase particles. Most likely, this copper has segregated at grain boundaries, interfaces and dislocations. The temperature at which Al₂Cu starts to form in the thin films is well below the copper solvus for bulk material.     

Structural and mechanical properties of Cr–Al–O–N thin films grown by cathodic arc deposition

Coatings of (Cr_xAl_1?x)_δ(O_1?yN_y)_ξ with 0.33 ? x ? 0.96, 0 ? y ? 1 and 0.63 ? δ/ξ ? 1.30 were deposited using cathodic arc evaporation in N₂/O₂ reactive gas mixtures on 50 V negatively biased WC–10 wt.% Co substrates from different Cr and Al alloys with three different Cr/Al compositional ratios. For N₂ < 63% of the total gas, ternary (Cr,Al)₂O₃ films containing <1 at.% of N forms; as determined by elastic recoil detection analysis. Increasing the N₂ fraction to 75% and above results in formation of quaternary oxynitride films. Phase analyses of the films by X-ray diffraction, transmission electron microscopy and X-ray photoelectron spectroscopy show the predominance of cubic Cr–Al–N and cubic-(Cr,Al)₂O₃ solid solutions and secondary hexagonal α-(Cr,Al)₂O₃ solid solution. High Cr and Al contents result in films with higher roughness, while high N and O contents result in smoother surfaces. Nanoindentation hardness measurements showed that Al-rich oxide or nitride films have hardness values of 24–28 GPa, whereas the oxynitride films have a hardness of ～30 GPa, regardless of the Cr and Al contents. Metal cutting performance tests showed that the good wear properties are mainly correlated to the oxygen-rich coatings, regardless of the cubic or corundum fractions.