An official website of the United States government
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
Isothermal crystallization and time-temperature-transformation diagram of the organic semiconductor 5,11-bis(triethylsilylethynyl)anthradithiophene
Thermal annealing of organic semiconductors is critical for optimization of their electronic properties. The selection of the optimal annealing temperature –often done on a trial-and-error basis– is essential for achieving the most desired micro/nanostructure. While classical materials science relies on time-temperature-transformation (TTT) diagrams to predict such processing-structure relationships, this type of approach is yet to find widespread application in the field of organic electronics. In this work, we constructed a TTT diagram for crystallization of the widely studied organic semiconductor 5,11-bis(triethylsilylethynyl)anthradithiophene (TES-ADT) from its melt. Thermal analysis in the form of isothermal crystallization experiments showed distinctly different types of behaviour depending on the annealing temperature, in agreement with classical crystal nucleation and growth theory. Hence, the TTT diagram correlates with the observed variation in the number of crystal domains, the crystal coverage and film texture as well as the obtained polymorph. As a result, we are able to rationalize the influence of the annealing temperature on the charge-carrier mobility extracted from field-effect transistor (FET) measurements. Evidently, the use of TTT diagrams is a powerful tool to describe structure formation of organic semiconductors and can be used to predict processing protocols that lead to optimal device performance.
more »
« less
- Award ID(s):
- 1810273
- PAR ID:
- 10281237
- Date Published:
- Journal Name:
- Journal of Materials Chemistry C
- ISSN:
- 2050-7526
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
-
Abstract Post deposition thermal annealing of amorphous coatings improves optical properties of dielectric mirrors. However, excessive temperatures cause crystallization, resulting in a degradation of mechanical and optical properties. Therefore, annealing is limited to temperatures ‘below’ the crystallization threshold. The threshold is determined by x-ray diffraction (XRD) measurement which requires a significant amount of crystallized material for detection, yet it has been shown that a population of crystallites may exist in otherwise amorphous coatings below the threshold temperature. In this study XRD measurements show crystallites that grow during annealing within amorphous oxide coatings to a limited and predictable size predicated on the difference in density between the crystal and the surrounding amorphous phase and the average material’s Young’s modulus. These crystallites may be the point-like, extremely weak scatterers revealed in the LIGO test masses when imaged off-axis.more » « less
-
The use of flashlamp annealing as a low-temperature alternative or supplement to thermal annealing is investigated. Flashlamp annealing and thermal annealing were conducted on 100 nm thick indium tin oxide (ITO) films deposited on glass to compare the properties of films under different annealing methods. The ITO samples had an average initial sheet resistance of 50 Ω/sq. After flashlamp annealing, the sheet resistance was reduced to 33 Ω/sq only, while by thermal annealing at 210 °C for 30 min, a sheet resistance of 29 Ω/sq was achieved. Using a combination of flashlamp annealing and thermal annealing at 155 °C for 5 min, a sheet resistance of 29 Ω/sq was achieved. X-ray diffraction analysis confirmed that flashlamp annealing can be used to crystallize ITO. Flashlamp annealing allows for low-temperature crystallization of ITO on a time scale of 1–3 min. Through electrical and optical characterizations, it was determined that flashlamp annealing can achieve similar electrical and optical properties as thermal annealing. Flashlamp offers the method of low-temperature annealing, which is particularly suitable for temperature sensitive substrates.more » « less
-
Heng, Jerry (Ed.)The morphological evolution of organic crystals during crystallization depends on the face-specific growth rates. Classical growth rate models relate the face-specific growth rates to the crystal lattice, energy of stable facets, growth mechanism, and supersaturation. The complexities of these models have increased over time to account accurately for solution conditions, the structure of growth units, and their attachment rates. Such advanced growth rate models require several layers of computations to obtain attachment energies of facets, nucleation rates, kink density, and attachment rates. Among these, the most intensive and time-consuming computation is for attachment rates, which require molecular dynamic simulations. This substantially increases the overall computation time to predict the absolute growth rate for even one crystallization condition. Since it is nearly impossible to iterate such a growth rate model, optimization schemes cannot be implemented to identify solution conditions that favor specific crystal growth. To reduce the computational time for attachment rate calculations, we implement a group contribution method (GCM) that relates the properties of functional groups in a molecule to their attachment rates to the crystal lattice, thereby rapidly estimating the growth rates of organic crystals. The process of molecular attachment involves partial desolvation of a solvated molecule, referred to as a transition state, followed by total desolvation via spontaneous attachment to a crystal facet. The first step in GCM is to identify the equilibrium states of fully solvated and partially desolvated solute molecules. The degree of supersaturation dictates the extent of this equilibrium and, thereby, the activation barrier for the growth of crystals, according to transition state theory. Identifying this equilibrium phenomenon allows for capturing the functional-group-specific interactions that depend on molecular motion, which could be related to operating conditions such as temperature and pressure. The stochastic optimization technique with Monte-Carlo sampling allows an efficient optimization problem solution to obtain the group interaction parameters. The GCM approach is first validated for the estimation of growth rates of glutamic acid and L-histidine, and then extended to predict growth rates of alanine and glycine rapidly. The optimized parameters and GCM scheme can be used to estimate growth rates in other crystallization systems.more » « less
-
Abstract The processing–structure–property relationship using poly(lactic acid) (PLA) and poly(ethylene terephthalate) (PET) is explored. Specifically, both pre‐extension and preshear of amorphous PLA and PET above their glass transition temperaturesTg, carried out in the affine deformation limit, can induce a specific type of cold crystallization during annealing, i.e., nanoconfined crystallization (NCC) where crystal sizes are limited to a nanoscopic scale in all dimensions so as to render the processed PLA and PET optically transparent. The new polymer structure after premelt deformation can show considerably enhanced mechanical properties. For example, premelt stretching produces geometric condensation of the chain network. This structural alternation can profoundly change the mechanical characteristics, e.g., turning brittle PLA ductile. In contrast, after preshear of amorphous PLA aboveTg, the NCC containing PLA remains brittle, showing the importance to have geometric condensation from processing. Both AFM imaging and SAXS measurements are performed to verify that premelt deformation of PLA and PET indeed results in NCC from annealing that permits the strain‐induced cold crystallization to take place on the length scale of the mesh size of the deformed chain network.more » « less
- Free Publicly Accessible Full Text
-
Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1039/D1TC01482J
