Lina Hu

Thermodynamic anomaly of the sub-Tg relaxation in hyperquenched metallic glasses

Recently, we observed an unusual non-monotonic glass relaxation phenomenon, i.e., the three-step sub-T(g) relaxation in hyperquenched CuZrAl glass ribbons [L. N. Hu and Y. Z. Yue, Appl. Phys. Lett. 98, 081904 (2011)]. In the present work, we reveal the origin of this abnormal behavior by studying the cooling rate dependence of the sub-T(g) enthalpy relaxation in two metallic glasses. For the Cu46Zr46Al8 glass ribbons the sub-T(g) enthalpy relaxation pattern exhibits a three-step trend with the annealing temperature only when the ribbons are fabricated below a critical cooling rate. For the La55Al25Ni20 glass ribbons the activation energy for the onset of the sub-T(g) enthalpy relaxation also varies non-monotonically with the cooling rate of fabrication. These abnormal relaxation phenomena are explained in terms of the competition between the low and the high temperature clusters during the fragile-to-strong transition. By comparisons of chemical heterogeneity between Cu46Zr46Al8 and La55Al25Ni20, we predict that the abnormal relaxation behavior could be a general feature for the HQ metallic glasses.

Abnormal sub-Tg enthalpy relaxation in the CuZrAl metallic glasses far from equilibrium

The sub-Tg enthalpy relaxation in glasses far from equilibrium (i.e., hyperquenched glasses) is usually manifested as a monotonic increase in both the onset temperature and the extent of enthalpy recovery with increasing the annealing temperature. Here we report an abnormal three-steplike relaxation pattern in hyperquenched Cu45Zr45Al10 and Cu48Zr48Al4 glasses below Tg, i.e., the usual monotonic increase is inverted when the annealing temperature increases to a critical value. This abnormal relaxation pattern could be attributed to the high extent of chemical heterogeneity in the CuZrAl supercooled liquids, and present a thermodynamic evidence for the dynamic fragile-to-strong transition in metallic glass-forming liquids.

Structural evolution during the sub-Tg relaxation of hyperquenched metallic glasses

We report the structural characteristics during the sub-Tg relaxation in hyperquenched La55Al25Ni20 glasses. The sub-Tg relaxation is associated with the structural change in intermediate range order, as manifested by the appearance of a prepeak in the x-ray diffraction spectrum. Such structural change could be the source of the Johari–Goldstein relaxation in metallic glasses. The mechanism governing the evolution of the prepeak is different between the glasses with the fictive temperature below 604 K and those above 604 K. Cooperative motion of atoms in La-centered clusters was further discussed in terms of the atomic bond deficiency model.

A Direct Link between the Fragile-to-Strong Transition and Relaxation in Supercooled Liquids

It is known that both the fragile-to-strong (F-S) transition and relaxation processes occur in numerous supercooled liquids upon cooling toward the glass transition temperature. The key question is whether and how these two dynamic processes are correlated. Here, we show a direct link between the two processes for both metallic glass-forming liquids (MGFLs) with different fragilities and also for nonmetallic glass-forming liquids. By comparing the F-S transition extent parameter f with the parameter r that characterizes the competition between the α and the slow β relaxations, we have discovered a negative exponential connection between the two parameters of supercooled liquids. The finding indicates that the slow β relaxation plays a dominant role in the F-S transition. This work provides new insight into the microscopic mechanism of the F-S transition and creates a strong basis for predicting whether and to what extent the F-S transition occurs in supercooled liquids.

Indication of liquid-liquid phase transition in CuZr-based melts

We study the dynamic behavior of CuZr-based melts well above the liquidus temperature. The results show a discontinuous change in viscosity during cooling, which is attributed to an underlying liquid-liquid phase transition (LLPT) in these melts. The LLPT is further verified by thermodynamic response in the same temperature region. We find that the LLPT in the Cu46Zr46Al8 melt is reversible above 1350 K upon repeated heating and cooling. Based on the concept of fluid cluster in metallic melts, the reversible LLPT is attributed to the structural transition from the strongly ordered high-density liquids to the weak-local low-density liquids upon cooling.

Structural evolution during fragile-to-strong transition in CuZr(Al) glass-forming liquids

In the present work, we show experimental evidence for the dynamic fragile-to-strong (F-S) transition in a series of CuZr(Al) glass-forming liquids (GFLs). A detailed analysis of the dynamics of 98 glass-forming liquids indicates that the F-S transition occurs around Tf-s ≈ 1.36 Tg. Using the hyperquenching-annealing-x-ray scattering approach, we have observed a three-stage evolution pattern of medium-range ordering (MRO) structures during the F-S transition, indicating a dramatic change of the MRO clusters around Tf-s upon cooling. The F-S transition in CuZr(Al) GFLs is attributed to the competition among the MRO clusters composed of different locally ordering configurations. A phenomenological scenario has been proposed to explain the structural evolution from the fragile to the strong phase in the CuZr(Al) GFLs.

Glass transition temperature of bulk metallic glasses: A linear connection with the mixing enthalpy

A linear relationship is found between the glass transition temperature Tg and the absolute value of the mixing enthalpy, |ΔHchem|, for bulk metallic glass systems. The increasing (or lowering) of Tg with an admixture of metals or other elements manifests itself in the larger (or smaller) of |ΔHchem| in a given system. The results indicate that the composition dependence of Tg results from the change of excess entropy (Sex) during thermal excitation. The |ΔHchem|, which relates to the strength of interaction among different atoms, corresponds to part of the Sex at Tg [Sex(Tg)]. The glass transition temperatures for Cu-Zr (Hf)-, Zr-Cu-, and La-Al-based glassy alloys are correlated with the interaction intensity between their based binary eutectic compositions, respectively.

Sub-Tg relaxation patterns in Cu-based metallic glasses far from equilibrium

We investigate the sub-T(g) relaxation patterns (RPs) in binary and quaternary Cu-based glass ribbons (GRs) by using the hyperquenching-sub-T(g) annealing-calorimetric approach. This study contributes to revealing the structural or dynamic evolution in liquids related to the observed three-stage sub-T(g) relaxation processes in GRs. In this work, we have achieved the following three findings. First, the abnormal three-stage relaxation behavior is not a general phenomenon for Cu-based metallic glasses and could not be simply predicted by the large difference in the enthalpy of mixing between different elements in alloys. Second, the abnormal three-stage RP is associated with the non-monotonic change of cluster size with medium range order in supercooled liquids. Third, the existence of the liquid-liquid phase transition depicted by anomalous viscosity drop during cooling in superheated liquids could be a signature of the unusual structural change causing the abnormal three-step sub-T(g) RP in the GRs. This work helps to better understand the complex structural evolution from superheated to supercooled liquids approaching T(g).

Energy state of Nd3+ doped in barium sodium niobate crystals

Nd-doped barium sodium niobate (Ba2Na)1−xNdxNb5O15 (BNN:Nd), with x=0.025 and a Curie temperature of 537±2 °C, crystallizes with a filled tungsten bronze-type structure in the tetragonal system. The lattice constants are a=b=1.2446(1) and c=0.3991(1) nm at room temperature. There are two formulas per unit cell. The five typical deep energy levels, formed by the Nd3+ ions doped in the A1 and A2 sites, are 2.36, 2.12, 1.68, 1.55, and 1.43 eV. Investigating the green and yellow second-harmonic generation shows that the BNN:Nd crystal can be expected as a useful material for the green, especially for the yellow laser radiation at room temperature.

Anomalous Crystallization as a Signature of the Fragile-to-Strong Transition in Metallic Glass-Forming Liquids

We study the fragile-to-strong (F-S) transition of metallic glass-forming liquids (MGFLs) by measuring the thermal response during annealing and dynamic heating of La55Al25Ni5Cu15 glass ribbons fabricated at different cooling rates. We find that the glasses fabricated in the intermediate regime of cooling rates (15-25 m/s) exhibit an anomalous crystallization behavior upon reheating as compared to the glasses formed at other cooling rates. This anomalous crystallization behavior implies the existence of a thermodynamic F-S transition, could be used as an alternative method for detecting the F-S transition in MGFLs, and sheds light on the structure origin of the F-S transition. This work also contributes to obtaining a general thermodynamic picture of the F-S transition in supercooled liquids.