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At least 955 records · Page 53
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

The role of collective elasticity on activated structural relaxation, yielding, and steady state flow in hard sphere fluids and colloidal suspensions under strong deformation

In this work, we theoretically study the effect of external deformation on activated structural relaxation and aspects of the nonlinear mechanical response of glassy hard sphere fluids in the context of elastically collective nonlinear Langevin equation theory. This microscopic force-based approach describes activated relaxation as a coupled local–nonlocal event involving caging and longer range collective elasticity, with the latter becoming more important and ultimately dominant with increasing packing fraction under equilibrium conditions. The central new question we address is how this physical picture of activated relaxation, and the relative importance of local caging vs collective elasticity physics, depends on external deformation. Theoretical predictions are presented for deformation-induced enhancement of mobility, the onset of relaxation speed up at remarkably low values of stress, strain, or shear rate, apparent power law thinning of the steady state structural relaxation time and viscosity, a non-vanishing activation barrier in the shear thinning regime, an apparent Herschel–Bulkley form of the rate dependence of the steady state shear stress, exponential growth of different measures of a dynamic yield or flow stress with the packing fraction, and reduced fragility and dynamic heterogeneity under deformation. The results are contrasted with experiments and simulations, and qualitative or better agreement is found. An overarching conclusion is that deformation strongly reduces the importance of longer range collective elastic effects relative to the local caging aspect for most, but not all, physical questions, with deformation-dependent fragility and dynamic heterogeneity phenomena being qualitatively sensitive to collective elasticity. Overall, nonlinear rheology is predicted to be a more local problem than quiescent structural relaxation, albeit with deformation-modified activated processes still important.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Synthesis and characterization of amorphous Fe2.75Dy-oxide thin films demonstrating room-temperature semiconductor, magnetism, and optical transparency

Recently, amorphous/disordered oxide thin films made from Fe and lanthanides like Dy and Tb have been reported to have a rich set of magnetic, optical, and electronic properties, as well as room-temperature magneto-electric coupling with multiferroics [A. Malasi et al., Sci. Rep. 5, 18157 (2015); H. Taz et al., Sci. Rep. 6, 27869 (2016); and H. Taz et al., Sci. Rep. 10, 1–10 (2020)]. Here, we report the synthesis and detailed characterization of Fe2.75Dy-oxide thin films prepared on various substrates using electron beam co-evaporation. The structure, chemistry, electric, magnetic, and optical properties were studied for the as-prepared and annealed (373 K, in air, 1 h) films of thickness 40 nm. High resolution transmission electron microscopy and electron diffraction study showed that the films were amorphous in both the as-prepared and annealed states. The electron energy-loss spectroscopy studies quantified that metal oxygen stoichiometry changed from Fe2.75Dy-O1.5 to Fe2.75Dy-O1.7 upon annealing. Synchrotron-based x-ray absorption spectroscopy investigation confirmed that the as-prepared films were highly disordered with predominantly metallic Fe and Dy states that became slightly oxidized with annealing in air. The as-prepared amorphous films demonstrated significantly high value of ordinary (∼10 cm2/V s) and anomalous (∼102 cm2/V s) Hall mobility and high electrical conductivity of ∼103 S/cm at room temperature. The cryogenic magnetic property measurement shows two-step magnetization below 200 K, suggesting exchange-spring magnetic interaction. The nature of the field cooled and zero-field cooled curves suggested a spin-glass like transition between 78 K and 80 K, with a characteristic broad peak. The Tauc plot analysis from optical transmission spectra confirms the existence of an optical bandgap of ∼2.42 eV that increased slightly to ∼2.48 eV upon annealing. This rich set of transport, optical, and magnetic properties in these thin films is very exciting and points to potential applicability in low-cost multifunctional devices requiring a combination of transparent, semiconducting, and magnetic responses, such as in spintronics.

Prasad Koirala, Krishna (ORCID:000000029137917X)↗
DOE OSTI2021

Ice, glass, and solid phases in artificial spin systems with quenched disorder

We present a numerical study on a disordered artificial spin-ice system, which interpolates between the long-range ordered square ice and the fully degenerate shakti ice. Starting from the square-ice geometry, disorder is implemented by adding vertical/horizontal magnetic islands to the center of some randomly chosen square plaquettes of the array at different densities. When no island is added, we have ordered square ice. When all square plaquettes have been modified, we obtain shakti ice, which is disordered yet in a topological phase corresponding to the Rys F-model. In between, geometrical frustration due to these additional center spins disrupts the long-range Ising order of square ice, giving rise to a spin-glass regime at low temperatures. The artificial spin system proposed in our work provides an experimental platform to study the interplay between quenched disorder and geometrical frustration.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2022

Intermolecular correlations of liquid and glassy CS 2 studied by synchrotron radiation x-ray diffraction

How is the orientation of molecular liquids ordered on cooling? What are the basic structures of molecular glasses, e.g., close to the crystalline structure or some special structures such as icosahedral cluster? These are long-standing questions in liquid and glass physics. Here, we have constructed a novel cryostat to prepare simple molecular glasses by vapor deposition and performed in situ synchrotron radiation x-ray diffraction experiments. The glassy state of a simple molecule CS 2 , which cannot be vitrified by normal liquid quenching, was successfully prepared with this instrument, and its diffraction data were collected in a wide Q-range of 0.16–25.7 Å -1 with a high-energy diffractometer at BL04B2, SPring-8. The diffraction data of liquid CS 2 were also recorded in a wide temperature range of 160–300 K. These diffraction data were analyzed with molecular dynamics simulations and reverse Monte Carlo modelings to investigate orientational correlation. From the obtained 3D structure models, the orientational correlation between neighboring CS 2 molecules was investigated quantitatively as a function of temperature. At room temperature, the parallel and T-shaped arrangements are preferred for the nearest neighbor correlation. On cooling, these arrangements are developed gradually, and its rate became prominent below the melting temperature (162 K). In the glassy state, the slipped-parallel arrangement is dominant as well as the T-shaped arrangement. Both arrangements appear in the CS 2 crystal, indicating that the structure of glassy CS 2 is close to that of crystalline CS 2 .

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Vapor deposition rate modifies anisotropic glassy structure of an anthracene-based organic semiconductor

We control the anisotropic molecular packing of vapor-deposited glasses of ABH113, a deuterated anthracene derivative with promise for future organic light emitting diode materials, by changing the deposition rate and substrate temperature at which they are prepared. We find that at substrate temperatures from 0.65 T g to 0.92 T g , the deposition rate significantly modifies the orientational order in the vapor-deposited glasses as characterized by x-ray scattering and birefringence. Both measures of anisotropic order can be described by a single deposition rate–substrate temperature superposition (RTS). This supports the applicability of the surface equilibration mechanism and generalizes the RTS principle from previous model systems with liquid crystalline order to non-mesogenic organic semiconductors. We find that vapordeposited glasses of ABH113 have significantly enhanced density and thermal stability compared to their counterparts prepared by liquidcooling. For organic semiconductors, the results of this study provide an efficient guide for using the deposition rate to prepare stable glasses with controlled molecular packing.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Effect of chemical substituents attached to the zwitterion cation on dielectric constant

Materials with high dielectric constant, ε s , are desirable in a wide range of applications including energy storage and actuators. Recently, zwitterionic liquids have been reported to have the largest ε s of any liquid and, thus, have the potential to replace inorganic fillers to modulate the material ε s . Although the large ε s for zwitterionic liquids is attributed to their large molecular dipole, the role of chemical substituents attached to the zwitterion cation on ε s is not fully understood, which is necessary to enhance the performance of soft energy materials. Here, we report the impact of zwitterionic liquid cation chemical substituents on ε s (50 < ε s < 300 at room temperature). Dielectric relaxation spectroscopy reveals that molecular reorientation is the main contributor to the high ε s . The low Kirkwood factor g calculated for zwitterionic liquids (e.g., 0.1–0.2) suggests the tendency for the antiparallel zwitterion dipole alignment expected from the strong electrostatic intermolecular interactions. With octyl cation substituents, the g is decreased due to the formation of hydrophobic-rich domains that restrict molecular reorientation under applied electric fields. In contrast, when zwitterion cations are functionalized with ethylene oxide (EO) segments, g increases due to the EO segments interacting with the cations, allowing more zwitterion rotation in response to the applied field. The reported results suggest that high ε s zwitterionic liquids require a large molecular dipole, compositionally homogeneous liquids (e.g., no aggregation), a maximized zwitterion number density, and a high g, which is achievable by incorporating polar chemical substituents onto the zwitterion cations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Memory in aging colloidal gels with time-varying attraction

Here, we report a combined rheology, x-ray photon correlation spectroscopy, and modeling study of gel formation and aging in suspensions of nanocolloidal spheres with volume fractions of 0.20 and 0.43 and with a short-range attraction whose strength is tuned by changing temperature. Following a quench from high temperature, where the colloids are essentially hard spheres, to a temperature below the gel point, the suspensions form gels that undergo aging characterized by a steadily increasing elastic shear modulus and slowing, increasingly constrained microscopic dynamics. The aging proceeds at a faster rate for stronger attraction strength. When the attraction strength is suddenly lowered during aging, the gel properties evolve non-monotonically in a manner resembling the Kovacs effect in glasses, in which the modulus decreases and the microscopic dynamics become less constrained for a period before more conventional aging resumes. Eventually, the properties of the gel following the decrease in attraction strength converge to those of a gel that has undergone aging at the lower attraction strength throughout. The time scale of this convergence increases as a power law with the age at which the attraction strength is decreased and decreases exponentially with the magnitude of the change in attraction. A model for gel aging in which particles attach and detach from the gel at rates that depend on their contact number reproduces these trends and reveals that the non-monotonic behavior results from the dispersion in the rates that the populations of particles with different contact number adjust to the new attraction strength.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Acoustic properties, elasticity, and equation of state of glycerol under pressure

Herein we employed high-pressure Brillouin scattering to study the pressure dependencies of acoustic modes of glycerol up to 14 GPa at 300 K. We observed longitudinal acoustic velocities and transverse acoustic velocities for the first time from 5 to 14 GPa. The results allow the determination of a complete set of elastic properties and an accurate determination of the pressure–volume (P–V) equation of state (EOS). EOS parameters, K 0 = 14.9 ± 1.8 GPa and K' 0 = 5.6 ± 0.5, were determined from fits to the data from ambient pressure to 14 GPa. Direct volume measurements of the P–V EOS are consistent with those determined by Brillouin scattering. A deviation from a Cauchy-like relationship for elastic properties was observed, and the pressure dependencies of the photoelastic constants and relaxation times were documented from 5 to 14 GPa. These results have broad implications for glass-forming liquids, viscoelastic theory, and mode coupling theory.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Mesoscopic two-point collective dynamics of glass-forming liquids

The collective density–density and hydrostatic pressure–pressure correlations of glass-forming liquids are spatiotemporally mapped out using molecular dynamics simulations. It is shown that the sharp rise of structural relaxation time below the Arrhenius temperature coincides with the emergence of slow, nonhydrodynamic collective dynamics on mesoscopic scales. The observed long-range, nonhydrodynamic mode is independent of wave numbers and closely coupled to the local structural dynamics. Below the Arrhenius temperature, it dominates the slow collective dynamics on length scales immediately beyond the first structural peak in contrast to the well-known behavior at high temperatures. Furthermore, these results highlight a key connection between the qualitative change in mesoscopic two-point collective dynamics and the dynamic crossover phenomenon.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Measuring the density, viscosity, and surface tension of molten titanates using electrostatic levitation in microgravity

Rare earth and barium titanates are useful as ferroelectric, dielectric, and optical materials. Measurements of their thermophysical properties in the liquid state can help guide melt processing technologies for their manufacture and advance understanding of fragile liquids' behavior and glass formation. Here, we report the density, thermal expansion, viscosity, and surface tension of molten BaTi 2 O 5 , BaTi 4 O 9 , and 83TiO 2 -17RE 2 O 3 (RE = La or Nd). Measurements were made using electrostatic levitation and droplet oscillation techniques in microgravity, which provide access to quiescent liquid droplets and deep supercooling of 510–815 K below the equilibrium melting points. Densities were measured over 900–2400 K. Viscosities were similar for all four compositions, increasing from ~10 mPa s near 2100 K to ~30 mPa s near 1750 K. Surface tensions were 450–490 dyn cm -1 for the rare earth titanates and 383–395 dyn cm -1 for the barium titanates; surface tensions of all compositions had small or negligible temperature dependence over 1700–2200 K. In conclusion, for solids recovered after melt quenching, x-ray microtomography revealed the fracture mechanics in crystalline products and minimal internal porosity in glass products, likely arising from entrapped gas bubbles. Internal microstructures were generally similar for products processed either in microgravity or in a terrestrial aerodynamic levitator.

42 ENGINEERING↗
DOE OSTI2024

Unusual dynamics of tetrahedral liquids caused by the competition between dynamic heterogeneity and structural heterogeneity

Tetrahedral liquids exhibit intriguing thermodynamic and transport properties because of the various ways tetrahedra can be packed and connected. Recently, an unusual temperature dependence of the stretching exponent β in a model tetrahedral liquid ZnCl 2 from T m + 85 K to T m + 35 K has been reported using neutron-spin echo spectroscopy. This discovery stands in sharp contrast to other glass-forming liquids. In this study, we conducted neural network force field driven molecular dynamic simulations of ZnCl 2 . We found a non-monotonic temperature dependence of β from liquid to supercooled liquid temperatures. Further structural decomposition and dynamic analysis suggest that this unusual dynamic behavior is a result of the competition between the decrease in the diversity of tetrahedra motifs (structural heterogeneity) and the increase in glassy dynamic heterogeneity. Furthermore, this result may contribute to new understandings of the structural relaxation of other network liquids.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Density of molten oxides measured in an aero-acoustic levitator

Knowing the thermophysical properties of high-temperature melts can aid the design of melt processes and validate atomic structural models, such as those used in studying glass formation. Property measurements on such melts are challenging, however, due to container-related contamination and heterogeneous nucleation. Containerless processing techniques that employ levitation can be used to avoid these obstacles. In that context, we demonstrate here the application of silhouette imaging to measure the density of molten oxides in an aero-acoustic levitation instrument (AAL). The AAL combines gas jet levitation with actively controlled acoustic positioning to enable full optical access to samples ca. 2–4 mm in diameter, which are laser beam heated and melted. The cross sections of molten drops are imaged using a monochromatic light source and narrowband-filtered camera. Melt volume is calculated from the cross sections and used to find density at several temperatures ranging 1530–1920 K, including up to 350 K of supercooling. We report densities for CaAl 2 O 4 , Ca 12 Al 14 O 33 , CaSiO 3 , their Fe 2 O 3 -bearing analogs, and 83TiO 2 -17RE 2 O 3 (RE = La or Nd). These provide important benchmarks of the capabilities, measurement uncertainties, and future outlook for this technique.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Structure of molten ytterbium aluminum garnet

Rare earth aluminum garnets are important materials in optical, dielectric, and thermal barrier applications. To advance the understanding of their melt processing and glass forming ability, we report the atomic structure of molten Yb 3 Al 5 O 12 over 1770–2630 K, which spans the equilibrium and supercooled liquid regimes. The melt density at T m = 2283 K is 5.50 g cm –3 , measured via silhouette imaging of electrostatically levitated drops over 1010–2420 K. Four separate structure measurements were made with aerodynamically levitated melts using x-ray and neutron diffraction with isotope substitution of Yb ( 172 Yb, 174 Yb, or nat Yb). Empirical potential structure refinement models were developed, which are in excellent agreement with the experiments. Coordination environments for Al–O are predominantly 4- and 5-coordinate, with a mean coordination of n AlO = 4.43(8), while Yb–O environments mostly range from 5- to 8-coordinate, with n YbO = 6.26(8). The cation–oxygen polyhedra are connected primarily by corner-sharing, with edge-sharing constituting up to ~1/3 of the connectivity among polyhedra with Yb or higher-coordinated Al–O. Structurally, the –Al–O– network in molten Yb 3 Al 5 O 12 appears conducive to glass formation: n OAl = 1.85(3), there are 1.86 AlO x –AlO x connections per Al atom (e.g., a mixture of Q 3 and Q 4 units), and the modal ring size is six cations. These characterize a network that is somewhat less constrained compared to SiO 2 glass, yet Yb 3 Al 5 O 12 cannot be quenched into crystal-free glass. Here, aluminum garnet compositions with larger rare earth cations do form glass, so these characterizations help reveal the structural characteristics corresponding to the limit of glass forming ability in rare earth aluminates.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Alpha-relaxation by scattering and medium-range atomic correlation in simple liquids

The relaxation dynamics of liquid and glass can be studied by inelastic x-ray or neutron scattering through the intermediate scattering function F(Q, t), where Q is the momentum transfer of scattering. Because of the time-consuming nature of these measurements, F(Q, t) is usually measured only at the first peak of the structure function S(Q), and its principal decay time is referred to as the α-relaxation time τ α . τ α is generally considered to describe the relaxation time of the bulk, which is related to viscosity and is controlled by the atomic cage around an atom. Here, through simulations on metallic liquids, we show that the α-relaxation time determined by scattering experiments does not purely reflect viscosity but is influenced by changes in spatial cooperativity. We also demonstrate that atomic caging is not exerted by the nearest neighbors but involves more cooperative atomic dynamics of the atomic medium-range order.

Glass transitions↗
DOE OSTI2021

Experimental test of a predicted dynamics–structure–thermodynamics connection in molecularly complex glass-forming liquids

Significance The physical origin of cooperative activated relaxation in glass-forming liquids, which underlies the huge growth of viscosity and suppression of diffusion with cooling, remains elusive. Understanding this problem is of fundamental scientific interest and can assist in the design of new materials. We combine experimental relaxation time and equation-of-state data of molecular liquids to provide strong evidence for the recent theoretical prediction that activated relaxation, though causally driven by dynamically coupled cage-scale hopping and nonlocal collective elasticity quantified by local structural correlations, is well captured based on a thermodynamic description with dimensionless compressibility as the key variable. A mechanistic deduction is the crossover from fragile to strong (e.g., inorganic networks) relaxation behavior arises from the irrelevance of long-range elasticity effects.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Evolution of magnetic surfboards and spin glass behavior in (Fe 1- p Ga p ) 2 TiO 5

The unusual anisotropy of the spin glass (SG) transition in the pseudobrookite system Fe 2 TiO 5 has been interpreted as arising from an induced, van der Waals-like, interaction among magnetic clusters. Here we present susceptibility ($\chi$) and specific heat data ($C$) for Fe 2 TiO 5 diluted with non-magnetic Ga, (Fe 1- p Ga p ) 2 TiO 5 , for disorder parameter $p$ = 0, 0.11, and 0.42, and elastic neutron scattering data for $p$ = 0.20. A uniform suppression of ${T_g}$ is observed upon increasing $p$, along with a value of $\chi \left( {{T_g}} \right)$ that increases as $T_g$ decreases, i.e. $d\chi ({T_g})/d{T_g} < 0$ We also observe $C\left( T \right) \propto {T^2}$ in the low temperature limit. In conclusion, the observed behavior places (Fe 1- p Ga p ) 2 TiO 5 in the category of a strongly geometrically frustrated SG.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2024

Chain dynamics of alternating polymers P(C n EG 4 )

Alternating or sequence defined polymers attract the attention of an increasing number of researchers recently. Due to their different blocks, they are very customizable and material properties can be tuned. In this publication, we present dynamical studies with focus on polymer dynamics, investigated by rheology and fast field cycling (FFC) NMR. The molecular weight dependencies of the relaxation time and zero-shear viscosity could hint to entanglement effects; however, the spectral shape of the viscoelastic data resembles the polymer dynamics of unentangled melts. Furthermore, taking both techniques into account, i.e. rheology and FFC NMR leads to the conclusion that the relaxation spectra of the alternating polymer are similar to those of linear polymers.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Sound velocities in shock-compressed soda lime glass: Melting and liquid-state response

Longitudinal sound velocities (and elastic moduli) were determined in soda lime glass (SLG) at peak shock stresses ranging between 40 and 90 GPa. Laser interferometry was used to obtain particle velocity histories and sound velocities by impacting SLG samples on lithium fluoride (LiF) optical windows. In all experiments, the SLG response consists of a sharp jump to a constant state followed by a release wave. The measured longitudinal sound velocities and moduli showed a marked decrease between 52 and 58 GPa, providing experimental evidence for the transformation from an amorphous solid to a liquid in shock-compressed SLG. Furthermore, the stress threshold (~55 GPa) for melting in SLG is considerably lower than the threshold reported in shock-compressed fused silica (~72 GPa), showing the effect of network-modifying cations on the onset of melting. The relative values of sound velocities, shock velocities, and the Hugoniot slopes—between 58 and 90 GPa—are fully consistent with the thermodynamic response of a shock-compressed liquid. Using the experimental results, the Grüneisen parameter (Γ) values were determined for liquid SLG to 90 GPa and then used to provide the Mie-Grüneisen equation of state for liquid SLG.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗