Two-phase quasi-equilibrium in ?-type Ti-based bulk metallic glass composites.
ABSTRACT: The microstructural evolution of cast Ti/Zr-based bulk metallic glass composites (BMGCs) containing ?-Ti still remains ambiguous. This is why to date the strategies and alloys suitable for producing such BMGCs with precisely controllable volume fractions and crystallite sizes are still rather limited. In this work, a Ti-based BMGC containing ?-Ti was developed in the Ti-Zr-Cu-Co-Be system. The glassy matrix of this BMGC possesses an exceptional glass-forming ability and as a consequence, the volume fractions as well as the composition of the ?-Ti dendrites remain constant over a wide range of cooling rates. This finding can be explained in terms of a two-phase quasi-equilibrium between the supercooled liquid and ?-Ti, which the system attains on cooling. The two-phase quasi-equilibrium allows predicting the crystalline and glassy volume fractions by means of the lever rule and we succeeded in reproducing these values by slight variations in the alloy composition at a fixed cooling rate. The two-phase quasi-equilibrium could be of critical importance for understanding and designing the microstructures of BMGCs containing the ?-phase. Its implications on the nucleation and growth of the crystalline phase are elaborated.
Project description:Multi-principal-element alloys share a set of thermodynamic and structural parameters that, in their range of adopted values, correlate to the tendency of the alloys to assume a solid solution, whether as a crystalline or an amorphous phase. Based on empirical correlations, this work presents a computational method for the prediction of possible glass-forming compositions for a chosen alloys system as well as the calculation of their critical cooling rates. The obtained results compare well to experimental data for Pd-Ni-P, micro-alloyed Pd-Ni-P, Cu-Mg-Ca, and Cu-Zr-Ti. Furthermore, a random-number-generator-based algorithm is employed to explore glass-forming candidate alloys with a minimum critical cooling rate, reducing the number of datapoints necessary to find suitable glass-forming compositions. A comparison with experimental results for the quaternary Ti-Zr-Cu-Ni system shows a promising overlap of calculation and experiment, implying that it is a reasonable method to find candidates for glass-forming alloys with a sufficiently low critical cooling rate to allow the formation of bulk metallic glasses.
Project description:Bulk metallic glass matrix composites (BMGMCs) are a new class of metal alloys which have significantly increased ductility and impact toughness, resulting from the ductile crystalline phases distributed uniformly within the amorphous matrix. However, the 3D structures and their morphologies of such composite at nano and micrometre scale have never been reported before. We have used high density electric currents to thermally shock a Zr-Ti based BMGMC to different temperatures, and used X-ray microtomography, FIB-SEM nanotomography and neutron diffraction to reveal the morphologies, compositions, volume fractions and thermal stabilities of the nano and microstructures. Understanding of these is essential for optimizing the design of BMGMCs and developing viable manufacturing methods.
Project description:Martensitic transformations originate from a rigidity instability, which causes a crystal to change its lattice in a displacive manner. Here, we report that the martensitic transformation on cooling in Ti-Zr-Cu-Fe alloys yields an amorphous phase instead. Metastable ?-Ti partially transforms into an intragranular amorphous phase due to local lattice shear and distortion. The lenticular amorphous plates, which very much resemble ?'/?? martensite in conventional Ti alloys, have a well-defined orientation relationship with the surrounding ?-Ti crystal. The present solid-state amorphization process is reversible, largely cooling rate independent and constitutes a rare case of congruent inverse melting. The observed combination of elastic softening and local lattice shear, thus, is the unifying mechanism underlying both martensitic transformations and catastrophic (inverse) melting. Not only do we reveal an alternative mechanism for solid-state amorphization but also establish an explicit experimental link between martensitic transformations and catastrophic melting.
Project description:Ti alloys have attracted continuing research attention as promising biomaterials due to their superior corrosion resistance and biocompatibility and excellent mechanical properties. Metastable ?-type Ti alloys also provide several unique properties such as low Young's modulus, shape memory effect, and superelasticity. Such unique properties are predominantly attributed to the phase stability and reversible martensitic transformation. In this study, the effects of the Nb and Zr contents on phase constitution, transformation temperature, deformation behavior, and Young's modulus were investigated. Ti-Nb and Ti-Nb-Zr alloys over a wide composition range, i.e., Ti-(18-40)Nb, Ti-(15-40)Nb-4Zr, Ti-(16-40)Nb-8Zr, Ti-(15-40)Nb-12Zr, Ti-(12-17)Nb-18Zr, were fabricated and their properties were characterized. The phase boundary between the ? phase and the ?'' martensite phase was clarified. The lower limit content of Nb to suppress the martensitic transformation and to obtain a single ? phase at room temperature decreased with increasing Zr content. The Ti-25Nb, Ti-22Nb-4Zr, Ti-19Nb-8Zr, Ti-17Nb-12Zr and Ti-14Nb-18Zr alloys exhibit the lowest Young's modulus among Ti-Nb-Zr alloys with Zr content of 0, 4, 8, 12, and 18 at.%, respectively. Particularly, the Ti-14Nb-18Zr alloy exhibits a very low Young's modulus less than 40 GPa. Correlation among alloy composition, phase stability, and Young's modulus was discussed.
Project description:The suitability of Ti as a band gap modifier for ?-Ga<sub>2</sub>O<sub>3</sub> was investigated, taking advantage of the isostructural ? phases and high band gap difference between Ti<sub>2</sub>O<sub>3</sub> and Ga<sub>2</sub>O<sub>3</sub>. Films of (Ti,Ga)<sub>2</sub>O<sub>3</sub> were synthesized by atomic layer deposition on sapphire substrates, and characterized to determine how crystallinity and band gap vary with composition for this alloy. We report the deposition of high quality ?-(Ti<sub>x</sub>Ga<sub>1-x</sub>)<sub>2</sub>O<sub>3</sub> films with x = 3.7%. For greater compositions the crystalline quality of the films degrades rapidly, where the corundum phase is maintained in films up to x = 5.3%, and films containing greater Ti fractions being amorphous. Over the range of achieved corundum phase films, that is 0% ? x ? 5.3%, the band gap energy varies by ?270 meV. The ability to maintain a crystalline phase at low fractions of Ti, accompanied by a modification in band gap, shows promising prospects for band gap engineering and the development of wavelength specific solar-blind photodetectors based on ?-Ga<sub>2</sub>O<sub>3</sub>.
Project description:(Ti,Zr)C powder was sintered with WC-Co following an industrial process, including an isotherm at 1410 °C. A series of interrupted sintering trials was performed with the aim of studying the sintering behavior and the microstructural evolution during both solid-state and liquid-state sintering. Reference samples, using the same elemental compositions but with the starting components TiC and ZrC instead of (Ti,Zr)C, were also sintered. The microstructure was investigated using scanning electron microscopy and energy dispersive X-ray spectroscopy. It is found that the (Ti,Zr)C phase decomposes into Ti-rich and Zr-rich nano-scale lamellae before the liquid-state of the sintering initiates. The final microstructure consists of the binder and WC as well as two different γ phases, rich in either Ti (γ₁) or Zr (γ₂). The γ₂ phase grains have a core-shell structure with a (Ti,Zr)C core following the full sintering cycle. The major differences observed in (Ti,Zr)C with respect to the reference samples after the full sintering cycle were the referred core-shell structure and the carbide grain sizes; additionally, the microstructural evolution during sintering differs. The grain size of carbides (WC, γ₁, and γ₂) is about 10% smaller in WC-(Ti,Zr)C-Co than WC-TiC-ZrC-Co. The shrinkage behavior and hardness of both composites are reported and discussed.
Project description:Metallic glasses are lucrative engineering materials owing to their superior mechanical properties such as high strength and great elastic strain. However, the Achilles' heel of metallic amorphous materials - low plasticity caused by instantaneous catastrophic shear banding, significantly undercut their structural applications. Here, the nanolayered crystalline Cu/amorphous Cu-Zr micropillars with equal layer thickness spanning from 20-100 nm are uniaxially compressed and it is found that the Cu/Cu-Zr micropillars exhibit superhigh homogeneous deformation (≥ 30% strain) rather than localized shear banding at room temperature. This extraordinary plasticity is aided by the deformation-induced devitrification via absorption/annihilation of abundant dislocations, triggering the cooperative shearing of shear transformation zones in glassy layers, which simultaneously renders the work-softening. The synthesis of such heterogeneous nanolayered structure not only hampers shear band generation but also provides a viable route to enhance the controllability of plastic deformation in metallic glassy composites via deformation-induced devitrification mechanism.
Project description:This work aims to achieve deep insight into the phenomenon of phase transformation upon rapid cooling in metal systems and reveal the physical meaning of scatter in the time taken to reach crystallization. The total number of pure metals considered in this work accounts for 14. Taking pure copper as an example, the correlation between phase selection of crystal or glass and cooling rate was investigated using molecular dynamic simulations. The obtained results demonstrate that there exists a cooling rate region of 6.3?×?10(11)-16.6?×?10(11)?K/s, in which crystalline fractions largely fluctuate along with cooling rates. Glass transformation in this cooling rate region is determined by atomic structure fluctuation, which is controlled by thermodynamic factors. According to the feature of bond-orientation order at different cooling rates, we propose two mechanisms of glass formation: (i) kinetic retardation of atom rearrangement or structural relaxation at a high cooling rate; and (ii) competition of icosahedral order against crystal order near the critical cooling rate.
Project description:Through high-energy x-ray diffraction and atomic pair density function analysis we find that Zr-based metallic alloy, heated to the supercooled liquid state under hydrostatic pressure and then quenched to room temperature, exhibits a distinct glassy structure. The PDF indicates that the Zr-Zr distances in this glass are significantly reduced compared to those quenched without pressure. Annealing at the glass transition temperature at ambient pressure reverses structural changes and the initial glassy state is recovered. This result suggests that pressure causes a liquid-to-liquid phase transition in this metallic alloy supercooled melt. Such a pressure induced transition is known for covalent liquids, but has not been observed for metallic liquids. The High Pressure Quenched glasses are stable in ambient conditions after decompression.
Project description:The data presented here is complementary to the publication entitled "High temperature, low neutron cross-section high-entropy alloys in the Nb-Ti-V-Zr system" . A homogenization methodology with slower cooling rate (∼2 °C/min) was performed. X-ray diffraction and scanning electron microscopy (backscattered electron and energy dispersive spectroscopy) data pertaining to annealed high-entropy alloy composition NbTiVZr is presented.