skip to main content


This content will become publicly available on September 1, 2024

Title: Nanocrystallization of Cu46Zr33.5Hf13.5Al7 Metallic Glass
The recently discovered Cu46Zr33.5Hf13.5Al7 (at.%) bulk metallic glass (BMG) presents the highest glass-forming ability (GFA) among all known copper-based alloys, with a record-breaking critical casting thickness (or diameter) of 28.5 mm. At present, much remains to be explored about this new BMG that holds exceptional promise for engineering applications. Here, we report our study on the crystallization behavior of this new BMG, using isochronal and isothermal differential scanning calorimetry (DSC), X-ray diffraction (XRD), and transmission electron microscopy (TEM). With the calorimetric data, we determine the apparent activation energy of crystallization, the Avrami exponent, and the lower branch of the isothermal time–temperature–transformation (TTT) diagram. With XRD and TEM, we identify primary and secondary crystal phases utilizing samples crystallized to different degrees within the calorimeter. We also estimate the number density, nucleation rate, and growth rate of the primary crystals through TEM image analysis. Our results reveal that the crystallization in this BMG has a high activation energy of ≈360 kJ/mole and that the primary crystallization of this BMG produces a high number density (≈1021 m−3 at 475 °C) of slowly growing (growth rate < 0.5 nm/s at 475 °C) Cu10(Zr,Hf)7 nanocrystals dispersed in the glassy matrix, while the second crystallization event further produces a new phase, Cu(Zr,Hf)2. The results help us to understand the GFA and thermal stability of this new BMG and provide important guidance for its future engineering applications, including its usage as a precursor to glass–crystal composite or bulk nanocrystalline structures.  more » « less
Award ID(s):
1945520 2221854
NSF-PAR ID:
10503949
Author(s) / Creator(s):
; ; ; ; ;
Publisher / Repository:
MDPI
Date Published:
Journal Name:
Crystals
Volume:
13
Issue:
9
ISSN:
2073-4352
Page Range / eLocation ID:
1322
Subject(s) / Keyword(s):
metallic glass crystallization nucleation and growth Cu alloys nano-crystal amor- 32 phous alloys ImageJ supercooled liquid calorimetry
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. Hf0.5Zr0.5O2‐based materials have garnered significant attention for applications requiring ferroelectricity at the nanoscale. This behavior arises due to the stabilization of metastable phases at room temperature. However, the synthesis of phase pure Hf0.5Zr0.5O2remains a challenging problem in both thin films and nanoparticles. Herein, the crystallization of Hf0.5Zr0.5O2nanoparticles from an as‐synthesized amorphous phase is studied. By tailoring the aggregate nature of the intermediate amorphous nanoparticles via different drying processes, the crystallization pathway can be altered, resulting in significant differences in crystal structure, crystallite size, and crystallite morphology after calcination. X‐ray diffraction (XRD) and Rietveld refinement show the dominant crystallographic phase changes from a monoclinic structure to a cubic structure for samples with decreased aggregation. Samples prepared via freeze drying exhibit the most aggregation control and correspond with the observation of single‐crystalline particle aggregates and branching structures attributed to a crystallization by particle attachment mechanism. Herein, differing crystallization pathways lead to unique crystal morphologies that stabilize the traditionally high‐temperature phases of Hf0.5Zr0.5O2‐based materials that are necessary for functional applications.

     
    more » « less
  2. Abstract

    Modifiers are commonly used in natural, biological, and synthetic crystallization to tailor the growth of diverse materials. Here, we identify tautomers as a new class of modifiers where the dynamic interconversion between solute and its corresponding tautomer(s) produces native crystal growth inhibitors. The macroscopic and microscopic effects imposed by inhibitor-crystal interactions reveal dual mechanisms of inhibition where tautomer occlusion within crystals that leads to natural bending, tunes elastic modulus, and selectively alters the rate of crystal dissolution. Our study focuses on ammonium urate crystallization and shows that the keto-enol form of urate, which exists as a minor tautomer, is a potent inhibitor that nearly suppresses crystal growth at select solution alkalinity and supersaturation. The generalizability of this phenomenon is demonstrated for two additional tautomers with relevance to biological systems and pharmaceuticals. These findings offer potential routes in crystal engineering to strategically control the mechanical or physicochemical properties of tautomeric materials.

     
    more » « less
  3. The engineering thermoplastic poly(ether ether ketone) (PEEK) has a rigid backbone that crystallizes relatively slowly upon cooling the melt. In this study, fast scanning chip calorimetry (FSC) was used to analyze isothermal crystallization between 170 and 285 °C, a range from about 27 K above the glass transition temperature up to the melting temperature. Incorporation of carbon nanotubes (CNT) enhances nucleation at all crystallization temperatures, including low temperatures. FSC also was employed to study crystallization at cooling rates spanning 0.33 to 8000 K/s, important as PEEK is subject to these conditions during melt processing. The critical cooling rate to produce a vitrified sample was increased from 500 K/s in the neat PEEK to 4000 K/s in a 5% CNT/PEEK nanocomposite due to faster nucleation rate caused by heterogeneous nucleation. 
    more » « less
  4. Abstract

    Understanding the thermal stability of metallic glasses is critical to determining their safe temperatures of service. In this paper, the crystallization mechanism in spark plasma sintered Fe48Cr15Mo14Y2C15B6metallic glass is established by analyzing the crystal size distribution using x-ray diffraction, transmission electron microscopy andin-situsmall angle neutron scattering. Isothermal annealing at 700 °C and 725 °C for 100 min resulted in the formation of (Fe,Cr)23C6crystals, measured from transmission electron micrographs, to be from 10 to 30 nm. The small angle neutron scattering intensity measuredin-situ, over a Q-range of 0.02 to 0.3 Å−1, during isothermal annealing of the sintered samples, confirmed the presence of (Fe,Cr)23C6crystals. The measured scattering intensity, fitted by the maximum entropy model, over the Q-range of 0.02 to 0.06 Å−1, revealed that the crystals had radii ranging from 3 to 18 nm. The total volume fraction of crystals were estimated to be 0.13 and 0.22 upon isothermal annealing at 700 °C and 725 °C for 100 min respectively. The mechanism of crystallization in this spark plasma sintered iron based metallic glass was established to be from pre-existing nuclei as confirmed by Avrami exponents of 0.25 ± 0.01 and 0.39 ± 0.01 at the aforesaid temperatures.

     
    more » « less
  5. Zircon xenocrysts from alkali basalts in Ratanakiri Province, Cambodia represent a unique low-Hf zircon within a 12,000 km long Indo-Pacific megacryst zone. Colorless, yellow, brown, and red crystals ({100}, {101}, subordinate {211}, {1103}), with hopper growth and corrosion features range up to 20 cm in size. Zircon chemistry indicates juvenile, Zr-saturated, mantle-derived alkaline melt (Hf 0.6–0.7 wt %, Y <0.2 wt %, U + Th + REE (Rare-Earth Elements) < 600 ppm, Zr/Hf 66–92, Eu/Eu*N ~1, positive Ce/Ce*N, HREE (Heavy REE) enrichment). Incompatible element depletion with increasing Yb/SmN from core to rim at ~ constant Hf suggests single stage growth. Ti-in-zircon temperatures (~570–740 °C) are lower than predicted by crystal morphology (800–900 °C) and decrease from core to rim (ΔT = 10–50 °C). The δ18O values (4.88 to 5.01‰ VSMOW (Vienna Standard Mean Ocean Water)) are relatively low for xenocrysts from the zircon Indo-Pacific zone (ZIP). The 176Hf/177Hf values (+ εHf 4.5–10.2) give TDepleted Mantle model source ages of 260–462 Ma and TCrustal ages of 391–754 Ma. The source magmas reflect variably depleted lithospheric mantle with little supracrustal input. Zircon U-Pb (0.88–1.56 Ma) and (U-Th)/He (0.86–1.02 Ma) ages are older than host basalt ages (~0.7 Ma), which suggests limited residence before transport. Zircon genesis suggests Zr-saturated, Al-undersaturated, carbonatitic-influenced, low-degree partial melting (<1%) of peridotitic mantle at ~60 km beneath the Indochina terrane. 
    more » « less