RESUMEN
As the most popular liquid metal (LM), gallium (Ga) and its alloys are emerging as functional materials due to their unique combination of fluidic and metallic properties near room temperature. As an important branch of utilizing LMs, micro- and submicron-particles of Ga-based LM are widely employed in wearable electronics, catalysis, energy, and biomedicine. Meanwhile, the phase transition is crucial not only for the applications based on this reversible transformation process, but also for the solidification temperature at which fluid properties are lost. While Ga has several solid phases and exhibits unusual size-dependent phase behavior. This complex process makes the phase transition and undercooling of Ga uncontrollable, which considerably affects the application performance. In this work, extensive (nano-)calorimetry experiments are performed to investigate the polymorph selection mechanism during liquid Ga crystallization. It is surprisingly found that the crystallization temperature and crystallization pathway to either α -Ga or ß -Ga can be effectively engineered by thermal treatment and droplet size. The polymorph selection process is suggested to be highly relevant to the capability of forming covalent bonds in the equilibrium supercooled liquid. The observation of two different crystallization pathways depending on the annealing temperature may indicate that there exist two different liquid phases in Ga.
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The recent discovery of non-classical crystal nucleation pathways has revealed the role of fluctuations in the liquid structural order, not considered in classical nucleation theory. On the other hand, classical crystal growth theory states that crystal growth is independent of interfacial energy, but this is questionable. Here we elucidate the role of liquid structural ordering in crystal nucleation and growth using computer simulations of supercooled liquids. We find that suppressing the crystal-like structural order in the supercooled liquid through a new order-killing strategy can reduce the crystallisation rate by several orders of magnitude. This indicates that crystal-like liquid preordering and the associated interfacial energy reduction play an essential role in nucleation and growth processes, forcing critical modifications of the classical crystal growth theory. Furthermore, we evaluate the importance of this additional factor for different types of liquids. These findings shed new light on the fundamental understanding of crystal growth kinetics.
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The origin of glass formation is one of the most fundamental issues in glass science. The glass-forming ability (GFA) of multicomponent systems, such as metallic glasses and phase-change materials, can be enormously changed by slight modifications of the constituted elements and compositions. However, its physical origin remains mostly unknown. Here, by molecular dynamics simulations, we study three model metallic systems with distinct GFA. We find that they have a similar driving force of crystallization, but a different liquid-crystal interface tension, indicating that the latter dominates the GFA. Furthermore, we show that the interface tension is determined by nontrivial coupling between structural and compositional orderings and affects crystal growth. These facts indicate that the classical theories of crystallization need critical modifications by considering local ordering effects. Our findings provide fresh insight into the physical control of GFA of metallic alloys and the switching speed of phase-change materials without relying on experience.
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Marine tetrapods quickly diversified and were established as marine top predators after the end-Permian Mass extinction (EPME). Ichthyosaurs were the forerunner of this rapid radiation but the main drivers of the diversification are poorly understood. Cartorhynchus lenticarpus is a basal ichthyosauriform with the least degree of aquatic adaptation, holding a key to identifying such a driver. The unique specimen appeared edentulous based on what was exposed but a CT scanning revealed that the species indeed had rounded teeth that are nearly perpendicular to the jaw rami, and thus completely concealed in lateral view. There are three dental rows per jaw ramus, and the root lacks infoldings of the dentine typical of ichthyopterygians. The well-developed and worn molariform dentition with three tooth rows supports the previous inference that the specimen is not of a juvenile. The premaxilla and the corresponding part of the dentary are edentulous. Molariform dentition evolved three to five times independently within Ichthyosauriformes in the Early and Middle Triassic. Convergent exploitation of hard-shelled invertebrates by different subclades of ichthyosauriforms likely fueled the rapid taxonomic diversification of the group after EPME.
Asunto(s)
Evolución Biológica , Dentición , Extinción Biológica , Fósiles , Paleontología , Pleurodeles , Animales , Pleurodeles/anatomía & histología , Diente/anatomía & histología , Diente/diagnóstico por imagenRESUMEN
The Early Triassic Chaohu Fauna from Anhui Province, China, contains the oldest record of Mesozoic marine reptiles, such as Cartorhynchus and Sclerocormus. Most specimens from the fauna belong to the ichthyosauriform Chaohusaurus, more specifically resembling C. chaoxianensis. However, a wide range of morphological variation exists within about 40 skeletons that have been prepared, likely reflecting mixed signals from both sexual and taxonomic differences. We test whether the sexual and taxonomic signals are separable based on quantification, aided by the knowledge of sexual dimorphism in extant marine tetrapods. There are two different suites of dimorphism that divide the specimens differently from each other yet consistently within each suite, resulting in four morphotypes in combination, likely representing two sexes of two taxa. Presumed males have larger 'organ of prehension' sensu Darwin, specifically limbs in the present case, for a given body length. This sexing criterion is supported by the only specimen of a gravid female, which belongs to the morphotype with short limbs. Males also have larger skulls for the trunk length compared to females. This study demonstrates that sexual and taxonomic signals are separable in fossil reptiles, with a sufficient sample size and careful analyses.
Asunto(s)
Fósiles/anatomía & histología , Reptiles/anatomía & histología , Caracteres Sexuales , Animales , Evolución Biológica , Tamaño Corporal , Femenino , Masculino , Tamaño de los Órganos , Reptiles/clasificación , Reptiles/fisiologíaRESUMEN
The origin of dramatic slowing down of dynamics in metallic glass-forming liquids toward their glass transition temperatures is a fundamental but unresolved issue. Through extensive molecular dynamics simulations, here we show that, contrary to the previous beliefs, it is not local geometrical orderings extracted from instantaneous configurations but the intrinsic correlation between configurations that captures the structural origin governing slow dynamics. More significantly, it is demonstrated by scaling analyses that it is the correlation length extracted from configuration correlation rather than dynamic correlation lengths that is the key to determine the drastic slowdown of supercooled metallic liquids. The key role of the configuration correlation established here sheds important light on the structural origin of the mysterious glass transition and provides an essential piece of the puzzle for the development of a universal theoretical understanding of glass transition in glasses.
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Metallic glasses (MGs) have so far attracted considerable attention for their applications as bulk materials. However, new physics and applications often emerge by dimensional reduction from three dimensions (3D) to two dimensions (2D). Here, we study, by molecular dynamics simulations, how the liquid-to-glass transition of a binary Cu_{50}Zr_{50} MG is affected by spatial dimensionality. We find clear evidence that crystal-like structural ordering controls both dynamic heterogeneity and slow dynamics, and thus plays a crucial role in the formation of the 2DMG. Although the 2DMG reproduces the dynamical behaviors of its 3D counterpart by considering Mermin-Wagner-type fluctuations specific to 2D, this atomic-scale structural mechanism is essentially different from that for the 3DMG in which icosahedral clusters incompatible with crystallographic symmetry play a key role in glassy behaviors. Our finding provides a structural mechanism for the formation of 2DMGs, which cannot be inferred from the knowledge of 3DMGs. The results suggest a structural basis for the glass transition in 2DMG and provide possible explanations for some previous experimental observations in ultrathin film MGs.
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Although the structure and dynamics of metallic glass-forming liquids have been extensively investigated, studies of the pressure effects are rare. In the present study, the structural and dynamical properties of a ternary metallic liquid are systematically studied via extensive molecular dynamics simulations. Our results clearly show that, like isobaric cooling, isothermal compression could also slow down the dynamics of metallic liquid, leading to glass formation. However, the temperature- and pressure-induced glass transitions differ in the formation of local coordination structures and the variation of fragility. The increase of the kinetic fragility with increasing pressure is also accompanied by a monotonic structural fragility change. These findings may suggest a link between dynamics and structure. In addition, with increasing pressure, the dynamics becomes more heterogeneous, as revealed by the non-Gaussian parameter and dynamic correlation length. Here the length scales of both slow and fast domains are examined and discussed by analyzing the four-point dynamic structure factor associated with spatial correlations of atomic mobility. These correlation lengths coexist in the metallic liquids and grow comparatively in the considered temperature and pressure ranges. Finally, the scaling relation between the relaxation times and correlation lengths is discussed, which is found to be consistent with the spirit of Adam-Gibbs and random first-order transition theories.
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A multicomponent metallic glass (MG) with highly efficient and anomalous durability for catalyzing water splitting is reported. The outstanding performance of the MG catalyst contributed by self-optimized active sites originates from the intrinsic chemical heterogeneity and selective dealloying on the disordered surface; thus, a new mechanism for improving the durability of catalysts is uncovered.
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A ternary metallic glass-forming liquid is found to be not strongly correlating thermodynamically, but its average dynamics, dynamic heterogeneities including the high order dynamic correlation length, and static structure are still well described by thermodynamic scaling with the same scaling exponent γ. This may indicate that the metallic liquid could be treated as a single-parameter liquid. As an intrinsic material constant stemming from the fundamental interatomic interactions, γ is theoretically predicted from the thermodynamic fluctuations of the potential energy and the virial. Although γ is conventionally understood merely from the repulsive part of the inter-particle potentials, the strong correlation between γ and the Grüneisen parameter up to the accuracy of the Dulong-Petit approximation demonstrates the important roles of anharmonicity and attractive force of the interatomic potential in governing glass transition of metallic glassformers. These findings may shed light on how to understand metallic glass formation from the fundamental interatomic interactions.
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Contrary to the fast radiation of most metazoans after the end-Permian mass extinction, it is believed that early marine reptiles evolved slowly during the same time interval. However, emerging discoveries of Early Triassic marine reptiles are questioning this traditional view. Here we present an aberrant basal ichthyosauriform with a hitherto unknown body design that suggests a fast radiation of early marine reptiles. The new species is larger than coeval marine reptiles and has an extremely small head and a long tail without a fluke. Its heavily-built body bears flattened and overlapping gastral elements reminiscent of hupehsuchians. A phylogenetic analysis places the new species at the base of ichthyosauriforms, as the sister taxon of Cartorhynchus with which it shares a short snout with rostrally extended nasals. It now appears that ichthyosauriforms evolved rapidly within the first one million years of their evolution, in the Spathian (Early Triassic), and their true diversity has yet to be fully uncovered. Early ichthyosauromorphs quickly became extinct near the Early-Middle Triassic boundary, during the last large environmental perturbation after the end-Permian extinction involving redox fluctuations, sea level changes and volcanism. Marine reptile faunas shifted from ichthyosauromorph-dominated to sauropterygian-dominated composition after the perturbation.