Temperature dependent onset of shear thinning in supercooled glass-forming network liquids.

The onset of shear thinning and the transition from Newtonian to non-Newtonian behavior in the viscous flow of select chalcogenide and oxide network glass-forming liquids in the deeply supercooled regime and its temperature dependence are studied using parallel plate rheometry. In all cases, the onset occurs at a shear rate γ̇c that is several orders of magnitude lower than the shear relaxation rate τ0 -1 and the former increases with increasing temperature. These results are in good qualitative agreement with the predictions of the existing models of shear relaxation and shear thinning based on the nonlinear Langevin equation theory, random first order transition theory, and the free volume model. However, in contrast to the theoretical predictions, the reduced shear rate W0 (=τ0γ̇c) at the onset is found to range between 10-3 and 10-5 and decrease with increasing temperature. This temperature dependence becomes stronger with increasing fragility of the liquid. These results likely indicate that the shear thinning mechanism in network liquids could be fundamentally different from those in molecular, metallic, or polymeric glass-formers.

Rheological behavior of molecular vs network chalcogenide supercooled liquids.

The viscoelastic behavior of supercooled glass-forming liquids along the binary join As4S3-GeS2 with As4S3 contents varying from 81.25 to 9 mol. % and correspondingly with structures varying from predominantly molecular to a three-dimensional tetrahedral network is studied by small-amplitude oscillatory shear parallel plate rheometry. The storage shear modulus G' shows a scaling behavior of G'(ω) ∼ ωn in the terminal (low-frequency) regime, where n varies between 1 and 2 and shows an increasingly anomalous departure from the expected value of 2 (Maxwell scaling) with increasing molecule content. A concomitant departure from the Maxwell scaling is also observed for the loss modulus G″ at frequencies above the G'-G″ crossover. On the other hand, the variation in the phase angle δ with the complex modulus indicates that the molecular liquid does not display a purely viscous response even at the lowest frequencies. These results, combined with an analysis of the relaxation spectra of these liquids, suggest that the anomalous behavior of molecular liquids may be linked to their rather broad relaxation spectrum and the presence of slow relaxation processes associated with molecular clusters. Additionally, these liquids are also characterized by a wide high-frequency plateau in the relaxation spectral density that can be linked to the rotational dynamics of the constituent molecules. Such fundamental differences between the rheological behavior of molecular and network liquids may explain the significantly higher fragility of the former.

Communication: Observation of ultra-slow relaxation in supercooled selenium and related glass-forming liquids.

The rheological behavior of supercooled Se, As10Se90, and As20Se80 liquids is studied in the linear regime as a function of frequency, extending over nearly 11 orders of magnitude, using oscillatory parallel plate rheometry. While the viscoelastic response of the As20Se80 liquid is characterized by a single relaxation time scale, the Se and the As10Se90 liquids display two distinct relaxation processes, both of which are coupled to viscosity, although their time scales differ by nearly 3-5 orders of magnitude. The ultra-slow relaxation process appears to be related to the dynamics of -Se-Se-Se- chain segments in the structure of these liquids, with characteristic time scale and shear modulus that are dependent on the average chain length. The fast mode, on the other hand, is associated with the glassy modulus and is tentatively assigned to a Johari-Goldstein ß-process. These results, when taken together, are consistent with the presence of a hierarchical free energy landscape that characterizes the dynamics of the fragile Se and As10Se90 liquids.

Behavior of a supercooled chalcogenide liquid in the non-Newtonian regime under steady vs. oscillatory shear.

The steady and oscillatory shear rate dependence of viscosity of a supercooled chalcogenide liquid of composition As10Se90 is measured at Newtonian viscosities ranging between 103 and 107 Pa s using capillary and parallel plate rheometry. The liquid displays strong violation of the Cox-Merz rule in the non-Newtonian regime where the viscosity under steady shear is nearly an order of magnitude lower than that under oscillatory shear. This behavior is argued to be related to the emergence of unusually large (6-8 nm) cooperatively rearranging regions with long relaxation times in the liquid that result from significant structural rearrangements under steady shear.

Communication: Non-Newtonian rheology of inorganic glass-forming liquids: Universal patterns and outstanding questions.

All families of inorganic glass-forming liquids display non-Newtonian rheological behavior in the form of shear thinning at high shear rates. Experimental evidence is presented to demonstrate the existence of remarkable universality in this behavior, irrespective of chemical composition, structure, topology, and viscosity. However, contrary to intuition, in all cases the characteristic shear rates that mark the onset of shear thinning in these liquids are orders of magnitude slower than the global shear relaxation rates. Attempt is made to reconcile such differences within the framework of the cooperative structural relaxation model of glass-forming liquids.

Structure of glasses in the pseudobinary system Ga(2)Se(3)-GeSe(2): violation of chemical order and 8-N coordination rule.

Structure of glasses in the pseudobinary system Ga2Se3-GeSe2 with Ga2Se3 content ranging from 6.3 to 30 mol % is investigated using a combination of Raman and multinuclear ((71)Ga, (77)Se) solid state nuclear magnetic resonance (NMR) spectroscopy. The results indicate that the structure of these glasses consists primarily of a corner sharing network of (Ge/Ga)Se4 tetrahedra with some fraction of edge-sharing GeSe4 tetrahedra and of ethane-like (Se3)Ge-Ge(Se3) units, in which the Ga, Ge, and Se atoms adopt coordination numbers of 4, 4, and 2, respectively. As expected, the concentration of metal-metal bonds increases with addition of Ga2Se3 as the glass structure becomes too deficient in Se to satisfy the tetrahedral coordination of both Ga and Ge by Se atoms alone. These metal-metal bonds are mostly limited to Ge-Ge homopolar bonds, indicating a violation of chemical order. At relatively high degrees of Se-deficiency, however, spectroscopic evidence suggests the formation of triply coordinated Se atoms as an alternate mechanism to accommodate the tetrahedral coordination of Ga and Ge atoms. This observation indicates a violation of the 8-N coordination rule and is reminiscent of oxygen triclusters in isoelectronic Al2O3-SiO2 glasses. Compositional variation of physical properties such as density, molar volume, optical band gap, glass transition temperature, and fragility are shown to be consistent with the proposed structural model.

Hysteretically reversible phase transition in a molecular glass.

Pressure induced densification in a molecular arsenic sulfide glass is studied at ambient temperature using x-ray scattering, absorption and Raman spectroscopic techniques in situ in a diamond anvil cell. The relatively abrupt changes in the position of the first sharp diffraction peak, FSDP, and the pressure-volume equation of state near ∼2 GPa suggest a phase transition between low- and high-density amorphous phases characterized by different densification mechanisms and rates. Raman spectroscopic results provide clear evidence that the phase transition corresponds to a topological transformation between a low-density molecular structure and a high-density network structure via opening of the constituent As(4)S(3) cage molecules and bond switching. Pressure induced mode softening of the high density phase suggests a low dimensional nature of the network. The phase transformation is hysteretically reversible, and therefore, reminiscent of a first-order phase transition.

Molecular dynamics in supercooled P-Se liquids near the glass transition: results from 31P NMR spectroscopy.

The structure of phosphorus selenide glasses with compositions close to the P(4)Se(3) stoichiometry with and without doping with a few atom % Ge has been investigated with Raman and (31)P NMR spectroscopic techniques. The results indicate that the structure of these glasses consists predominantly of P(4)Se(3) cage molecules. However, in spite of this structural similarity, doping with Ge results in a remarkably large increase in T(g). The dynamical behavior of the constituent P(4)Se(3) molecules in the Ge-free composition is investigated with a (31)P NMR hole-burning technique in the supercooled liquid state. These molecules perform large angle rotational reorientations near and above the glass transition with time scales similar to those expected for shear relaxation. Such coupling between molecular rotation and shear relaxation processes near T(g) is reminiscent of the dynamical behavior of organic molecular glass-forming liquids. However, this behavior is in stark contrast with the large temporal decoupling between molecular rotation and shear relaxation previously reported for a Ge-doped arsenic sulfide liquid that contained similarly structured As(4)S(3) cage molecules.

Structure, topology and chemical order in Ge-As-Te glasses: a high-energy x-ray diffraction study.

High-energy x-ray diffraction is employed to study the atomic structure of bulk Ge(x)As(2x)Te(100-3x) glasses with compositions in the range 25 ≤ 3x ≤ 70. The coordination environments of Te atoms suggest significant violation of chemical order in these glasses. Analyses of the nearest-neighbor coordination environments and the parameters for the first sharp diffraction peak indicate that these telluride glasses are structurally and chemically more disordered as compared with their sulfide or selenide analogs. The compositional evolution of the structural parameters is shown to be consistent with the corresponding variation in molar volume and glass transition temperature.

Hierarchical dynamics of As2P2S8 quasi-molecular units in a supercooled liquid in the As-P-S system: a 31P NMR spectroscopic study.

The dynamics of As2P2S8 quasi-molecular units caged in an As-S network in the supercooled chalcogenide liquid of composition (As2S3)90(P2S5)10 have been studied near the glass transition region (Tg=468

A neutron scattering and nuclear magnetic resonance study of the structure of GeO2-P2O5 glasses.

Germanophosphate (GeO2-P2O5) glasses were studied with neutron diffraction, phosphorus, and oxygen nuclear magnetic resonance, calorimetry, viscosity measurements, and first-principles calculations. These data sets were combined to propose a structural model of GeO2-P2O5 glasses, which includes tetrahedrally coordinated phosphorus, formation of octahedrally coordinated germanium as P2O5 content increases, an absence of trigonally coordinated oxygen, and hence an absence of rutile-like GeO2 domains. The structural model was then used to propose explanations for both the observed composition dependence of the glass transition temperature and the fragility of the GeO2-P2O5 liquids.

Observation of a pressure-induced first-order polyamorphic transition in a chalcogenide glass at ambient temperature.

An apparently first-order polyamorphic transition has been observed with increasing pressure at ambient temperature in a molecular glass of composition Ge(2.5)As(51.25)S(46.25) Raman spectroscopic measurements on pressure-quenched samples and in situ x-ray diffraction measurements indicate that this transition corresponds to a collapse of the ambient-pressure molecular phase to a high-pressure network phase. The high-pressure phase first appears at a pressure of approximately 8-9 GPa and the transformation becomes complete at approximately 14-15 GPa. Calorimetric measurements indicate that the low- and high-pressure phases are thermodynamically distinct and that they coexist in the transition range.

Self-calibrating quantum efficiency measurement technique and application to Pr(3+)-doped sulfide glass.

A measurement technique is described in which the radiative quantum efficiency of certain transitions in rare-earth-doped glasses can be determined based only on relative fluorescence measurements. We calibrate the emission from the level of interest by measuring emission into that level from a higher excited level. Application of the technique to Pr(3+)-doped sulfide glasses yields quantum efficiencies for the (1)G(4) ? (3)H(5) transition as high as 60%, in good agreement with measurements using the integrating sphere technique. Calculated efficiency values based on the Judd-Ofelt technique are shown to be subject to inherent uncertainties.