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At least 271 records · Page 15
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Ruthenium solubility and its impact on the crystallization behavior and electrical conductivity of MoO 3 -containing borosilicate-based model high-level nuclear waste glasses

The present study focuses on investigating the solubility of RuO 2 in a borosilicate-based model high-level waste glass and understanding its impact on the crystallization behavior and electrical conductivity of the resulting vitrified waste forms. The solubility limit of RuO 2 in the investigated glass composition has been determined to be 460 ppm by weight. The higher concentration of RuO 2 results in sub-micron sized Ru-rich inclusions in the glassy matrix, which eventually agglomerate to form needle-like and polyhedral RuO 2 crystals. It is observed that RuO 2 selectively promotes the crystallization of the rare-earth apatite phase over the powellite phase. The as-synthesized RuO 2 -containing glasses exhibit semiconducting behavior with a similar level of electrical conductivity below the glass transition. Here, the percolation of non-uniformly distributed RuO 2 inclusions may result in a formation of short-range low-resistive conduction pathways in the host glass matrix leading to an apparent metallic-like behavior of selected thin samples with the highest ruthenium content.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Plasmonic Ag nanocomposite phosphate glasses produced via γ-ray irradiation as reduction route

This paper reports on the impact of γ-ray irradiation (10, 100 kGy) on melt-quenched Ag + -doped phosphate glass and the effects of subsequent thermal processing leading to the production of plasmonic Ag nanocomposites. The γ-irradiated glasses were characterized alongside the pristine by differential scanning calorimetry (DSC), Raman spectroscopy, electron paramagnetic resonance (EPR) spectroscopy, optical absorption, and photoluminescence (PL) spectroscopy. DSC characterization showed consistent glass transition temperatures (T g ) before and after γ-irradiation whereas the crystallization temperatures tended to decrease with increasing γ-ray dose. However, a lack of alteration of the glass network structure was supported by Raman spectroscopy. Room temperature EPR spectra clearly showed the formation of phosphorus oxygen hole center (POHC) defects in the undoped host, in addition to another doublet likely associated with a P 3 defect. The presence of paramagnetic silver species encompassing Ag 2+ and 107/109 Ag 0 atoms was also indicated in the silver-activated glass together with POHC defects. Optical absorption spectra were also consistent with the presence of various radiation-induced centers. Further analyzing the glass absorption edge via Tauc plots suggested the formation of electron center (EC) defects in γ-irradiated samples wherein the silver-doped glass exhibited decreasing band gap energies with increasing γ-ray dose. The PL characterization showed the silver-related radio-PL effect was induced exhibiting broad band emission with two maxima around 500 and 625 nm stemming from various molecular Ag$^{x+}_{n}$ clusters. Emission decay analyses revealed that the longer wavelength emission exhibited slower decay. The highest radiation dose of 100 kGy however resulted in weaker emission and faster decay kinetics attributed to energy transfer between the luminescent silver species and POHC defects. Finally subjecting the γ-irradiated Ag-doped glasses to heat treatment near the T g at 490 °C led to the development of the surface plasmon resonance of Ag nanoparticles (NPs) and the vanishing of the Ag$^{x+}_{n}$ clusters luminescence. In conclusion, the presence of the matrix-related EC defects was deemed accountable for the thermally induced reduction and consequent precipitation of Ag NPs making the plasmonic glasses attractive for photonic applications such as nonlinear optics.

36 MATERIALS SCIENCE↗
NASA NTRS1980

On the barrier to crystal nucleation in lunar glasses

The paper describes an analytical method for calculating in detail the size distributions of small crystallites and nuclei in supercooled liquids as they are being quenched to form a glass and subsequently reheated above the glass transition to produce crystallization. This method is applied to experiments performed using differential thermal analysis (DTA) to estimate the barriers to crystal nucleation and the cooling rates required to form glasses or bodies with various degrees of crystallinity. DTA data and derived nucleation barriers are reported for anorthite and for the following lunar compositions: 15498, 15418, matrix and intrusion compositions of breccia 15286, Apollo 15 green glass, Luna 24 highland basalt, and 65016.

Yinnon, H.↗
NASA NTRS2024

On the Role of Friction and Particle Size Distribution in Granular Packings

Packing of particles in a disordered arrangement has tremendous significance in both condensed matter physics and engineering applications. The last three decades have seen remarkable progress in our understanding of the physics of granular packings that has been largely facilitated by a rapid growth in the power of modern computers. Although granular packings are ubiquitous in diverse natural settings, from clogging of powders in hoppers to the crowding of living cells, a significant motivation for modeling granular packings has emerged from a proposal that the transition from a fluid-like state to a solid-like state of a granular material upon increasing volume fraction, called jamming, is intimately related to the origins of glass transition in thermal systems. As such, a majority of modeling efforts have focused on the jamming behavior of an idealized granular material: frictionless, monodisperse sphere. While such studies have illuminated the rich physics of jamming, granular materials in nature and engineering practice are rarely frictionless or monodisperse. The analogous research on the packing of these ‘real-world’ granular materials is still not fully developed. Besides requiring the exploration of a huge parameter space, three key computational considerations have inhibited their modeling: (i) traditional computational methods are not adept at simulating mechanically-stable packings of frictional particles near the jamming transition; (ii) standard algorithms of contact detection in discrete element methods are impractical to simulate granular packings with a wide distribution of particle sizes; (iii) a lack of well-established contact mechanics models of friction that can accurately reproduce experimental data. This chapter will review the latest computational advances to simulate the jamming of size-dispersed frictional particles, and describe the rich microstructural diversity that emerges in their packings.

granular↗
NASA NTRS1990

Absorption Of Gases By Glassy Polymers

Report discusses solubility of gas in glassy polymer, both above and below glass-transition temperature (Tg). Thermodynamic arguments brought to bear on previously-developed mathematical models, result being new model that enables calculation of infinite-dilution partial molar volume of solvent in glass or liquid solvent from data on pressure, volume, and temperature of solute in equilibrium with solvent.

Fedors, Robert F.↗
NASA NTRS2003

Nucleation and Crystallization as Induced by Bending Stress in Lithium Silicate Glass Fibers

Glass Fibers of Li2O.2SiO2 (LS2) and Li2O.1.6SiO2 (LS1.6) compositions were heated near, but below, the glass transition temperature for different times while subjected to a constant bending stress of about 1.2 GPa. The nucleation density and the crystallization tendency estimated by differential thermal analysis (DTA) of a glass sample in the vicinity of the maximum of the bending stress increased relative to that of stress-free glass fibers. LS2 glass fibers were found more resistant to nucleation and crystallization than the Ls1.6 glass fibers. These results are discussed in regards to shear thinning effects on glass stability.

Reis, Signo T.↗
DOE OSTI2023

Vapor-to-glass preparation of biaxially aligned organic semiconductors

Physical vapor deposition (PVD) provides a route to prepare highly stable and anisotropic organic glasses that are utilized in multi-layer structures such as organic light-emitting devices. While previous work has demonstrated that anisotropic glasses with uniaxial symmetry can be prepared by PVD, here, we prepare biaxially aligned glasses in which molecular orientation has a preferred in-plane direction. With the collective effect of the surface equilibration mechanism and template growth on an aligned substrate, macroscopic biaxial alignment is achieved in depositions as much as 180 K below the clearing point TLC−iso (and 50 K below the glass transition temperature Tg) with single-component disk-like (phenanthroperylene ester) and rod-like (itraconazole) mesogens. The preparation of biaxially aligned organic semiconductors adds a new dimension of structural control for vapor-deposited glasses and may enable polarized emission and in-plane control of charge mobility.

Chemistry↗
NASA NTRS1991

Crystallization and properties of Sr-Ba aluminosilicate glass-ceramic matrices

Powders of roller quenched (Sr,Ba)O-Al2O3-2SiO2 glasses of various compositions were uniaxially pressed into bars and hot isostatically pressed at 1350 C for 4 hours or cold isostatically pressed and sintered at different temperatures between 800 to 1500 C for 10 or 20 hours. Densities, flexural strengths, and linear thermal expansion were measured for three compositions. The glass transition and crystallization temperatures were determined by Differential Scanning Calorimetry (DSC). The liquidus and crystallization temperature from the melt were measured using high temperature Differential Thermal Analysis (DTA). Crystalline phases formed on heat treatment of the glasses were identified by powder X ray diffraction. In Sr containing glasses, the monoclinic celsian phase always crystallized at temperatures above 1000 C. At lower temperatures, the hexagonal analog formed. The temperature for orthorhombic to hexagonal structural transformation increased monotonically with SrO content, from 327 C for BaO-Al2O3-2SiO2 to 758 C for SrO-Al2O3-2SiO2. These glass powders can be sintered to almost full densities and monoclinic celsian phase at a relatively low temperature of 1100 C.

Bansal, Narottam P.↗
DOE OSTI2020

Viscosity-temperature relation based on the evolution of medium-range structures of silica

The viscosity of glass is the most important technological property to glass manufactures and various applications. Practically, finding an accurate equation to express the glass viscosity behavior in the entire glass transition temperature range is tremendously challenge because it spans more than ten orders of magnitude. After a brief review of existing empirical viscosity equations, this work focuses on the correlating silica viscosity behavior with the evolution of glass medium-range structure, based on the recently proposed nanoflake model. From this new model, a new equation is constructed, which correctly describes the Arrhenius-type behavior of silica viscosity η above the melting temperature Tm, and non-Arrhenius-type behavior from Tm to a critical temperature Tc. At temperature lower than Tc, the equation predicts Arrhenius-type behavior again for the viscous flow with increased activation energy. The new equation agrees with experimental data in the entire temperature spanned from extremely high to extremely low. Furthermore, the application of the new equation is shown to extend to sodium silicate glasses as well.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Transient nature of fast relaxation in metallic glass

Metallic glasses exhibit fast mechanical relaxations at temperatures well below the glass transition, one of which shows little variation with temperature known as nearly constant loss (NCL). Despite the important implications of this phenomenon to deformation, the origin of the relaxation is unclear. Through molecular dynamics simulations of a model metallic glass, Cu 64.5 Zr 35.5 , we implement molecular dynamics dynamical mechanical spectroscopy (MD-DMS) with system stress decomposed into atomic-level stresses to identify the group of atoms responsible for NCL. This work demonstrates that NCL relaxation is due to transient groups of atoms that revert to the typical atomic-level viscoelastic behavior over picosecond timescales. They are homogenously distributed throughout the glass and have no outstanding features, rather than having defect-like local structure as previously reported.

36 MATERIALS SCIENCE↗
NASA NTRS1983

Cooling rates for glass containing lunar compositions

Cooling rates required to form glassy or partly-crystalline bodies of 14 lunar compositions have been estimated using a previously introduced, simplified model. The calculated cooling rates are found to be in good agreement with cooling rates measured for the same compositions. Measurements are also reported of the liquidus temperature and glass transition temperature for each composition. Inferred cooling rates are combined with heat flow analyses to obtain insight into the thermal histories of samples 15422, 14162, 15025, 74220, 74241, 10084, 15425, and 15427. The critical cooling rates required to form glasses of 24 lunar compositions, including the 14 compositions of the present study, are suggested to increase systematically with increasing ratio of total network modifiers/total network formers in the compositions. This reflects the importance of melt viscosity in affecting glass formation.

Fang, C. Y.↗
NASA NTRS2006

Automated Low-Gravitation Facility Would Make Optical Fibers

A report describes a proposed automated facility that would be operated in outer space to produce high-quality optical fibers from fluoride-based glasses, free of light-scattering crystallites that form during production in normal Earth gravitation. Before launch, glass preforms would be loaded into a mechanism that would later dispense them. A dispensed preform would be melted, cooled to its glass-transition temperature rapidly enough to prevent crystallization, cooled to ambient temperature, then pushed into a preform tip heater, wherein it would be reheated to the softening temperature. A robotic manipulator would touch a fused silica rod to the softened glass to initiate pulling of a fiber. The robot would pull the fiber to an attachment on a take-up spool, which would thereafter be turned to pull the fiber. The diameter of the fiber would depend on the pulling speed and the viscosity of the glass at the preform tip. Upon depletion of a preform, the robot would place the filled spool in storage and position an empty spool to pull a fiber from a new preform. Pulling would be remotely monitored by a video camera and restarted by remote command if a break in the fiber were observed.

Tucker, Dennis S.↗
NASA NTRS1992

Phase transformations in SrAl2Si2O8 glass

Bulk glass of SrAl2Si2O8 composition crystallized at temperatures below 1000 C into hexacelsian, a hexagonal phase which undergoes a reversible, rapid transformation to an orthorhombic phase at 758 C, and at higher temperatures crystallized as celsian, a monoclinic phase. The glass transition temperature and crystallization onset temperature were determined to be 883 C and 1086 C, respectively, from DSC at a heating rate of 20 C/min. Thermal expansion of the various phases and density and bend strengths of cold isostatically pressed glass powder bars, sintered at various temperatures, were measured. The kinetics of the hexacelsian-to-celsian transformation for SrAl2Si2O8 were studied. Hexacelsian flakes were isothermally heat treated at temperatures from 1025-1200 C for various times. Avrami plots were determined by quantitatively measuring the amount of monoclinic celsian formed at various times using x ray diffraction. The Avrami constant was determined to be 1.1, suggesting a diffusionless, one dimensional transformation mechanism. The activation energy was determined from an Arrhenius plot of 1n k vs. 1/T to be 125 kilocal/mole. This value is consistent with a mechanism which transforms the layered hexacelsian structure to a three dimensional framework celsian structure and involves the breaking of Si-O bonds.

Drummond, Charles H., III↗
DOE OSTI2022

Redesigned Hybrid Nylons with Optical Clarity and Chemical Recyclability

Aliphatic polyamides, or nylons, are typically highly crystalline and thermally robust polymers used in high-performance applications. Nylon 6, a high-ceiling-temperature (HCT) polyamide from e-caprolactam, lacks expedient chemical recyclability, while low-ceiling temperature (LCT) nylon 4 from pyrrolidone exhibits complete chemical recyclability, but it is thermally unstable and not melt-processable. Here, we introduce a hybrid nylon, nylon 4/6, based on a bicyclic lactam composed of both HCT ..epsilon..-caprolactam and LCT pyrrolidone motifs in a hybridized offspring structure. Hybrid nylon 4/6 overcomes trade-offs in (de)polymerizability and performance properties of the parent nylons, exhibiting both excellent polymerization and facile depolymerization characteristics. This stereoregular polyamide forms nanocrystalline domains, allowing optical clarity and high thermal stability, however, without displaying a melting transition before decomposition. Of a series of statistical copolymers comprising nylon 4/6 and nylon 4, a 50/50 copolymer achieves the greatest synergy in both reactivity and polymer properties of each homopolymer, offering an amorphous nylon with favorable properties, including optical clarity, a high glass transition temperature, melt processability, and full chemical recyclability.

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

Q-dependent collective relaxation dynamics of glass-forming liquid Ca0.4K0.6(NO3)1.4 investigated by wide-angle neutron spin-echo

Abstract The relaxation behavior of glass formers exhibits spatial heterogeneity and dramatically changes upon cooling towards the glass transition. However, the underlying mechanisms of the dynamics at different microscopic length scales are not fully understood. Employing the recently developed wide-angle neutron spin-echo spectroscopy technique, we measured the Q -dependent coherent intermediate scattering function of a prototypical ionic glass former Ca 0.4 K 0.6 (NO 3 ) 1.4 , in the highly viscous liquid state. In contrast to the structure modulated dynamics for Q < 2.4 Å −1 , i.e., at and below the structure factor main peak, for Q > 2.4 Å −1 , beyond the first minimum above the structure factor main peak, the stretching exponent exhibits no temperature dependence and concomitantly the relaxation time shows smaller deviations from Arrhenius behavior. This finding indicates a change in the dominant relaxation mechanisms around a characteristic length of 2π/(2.4 Å −1 ) ≈ 2.6 Å, below which the relaxation process exhibits a temperature independent distribution and more Arrhenius-like behavior.

42 ENGINEERING↗
DOE OSTI2024

Effects of Al Substitution for Fe in Na₅FeSi₄O₁₂ (5.1.8) Glasses: Structure and Crystallization

In this study, the effects of substituting Al for Fe in 5Na2O∙(Al2O3)x∙(Fe2O3)1-x∙8SiO2 glass, x=0 to 1, and Na5AlxFe1-xSi4O12 (5.1.8) crystal, were investigated using thermal analysis, Fe K-edge X-ray absorption, X-ray diffraction, Raman spectroscopy, and Electron Probe Microanalysis. In both glass and crystallized glass, nearly all the Fe was tetrahedrally coordinated Fe3+, as expected from the high concentration of Na2O. The substitution of Al for Fe in the glasses caused the glass transition temperature to increase as polymerization increased, as evidenced by Raman, likely due to both field strength differences of Al vs Fe and a small amount of Fe2+ network modifier present with Fe. After heat treatment at 700 °C for 24 hours, the glasses had crystallized, forming Na2SiO3 and NaAlSiO4 in compositions with high Al concentrations and the 5.1.8 crystal in compositions with high Fe concentrations. Through electron microprobe, it was determined that <0.04 formula unit Al incorporated into the 5.1.8 crystal, i.e. Na5Fe0.96Al0.04Si4O12. The 5.1.8 crystal only formed when Fe concentration was higher than Al in the starting glass.

Antonio, Raine (ORCID:0009000634297975)↗
NASA NTRS1991

Dynamic mechanical properties of N-phenylnadimide modified PMR polyimide composites

Temperature-frequency dependence of alpha, beta, and gamma transitions was determined using a Rheometrics dynamic spectrometer on a series of unidirectional Celion 6000/N-phenylnadimide (PN) modified PMR polyimide composites. The objective was to see if any correlations exist between crosslinked network structure and dynamic mechanical properties. Variation in crosslinked network structures was achieved by altering the polyimide formulation through addition of various quantities of PN into the standard PMR-15 composition. As a control, PMR-15 composite system exhibited well-defined alpha, beta, and gamma transitions in the regions of 360, 100, and -120 C, respectively. Their activation energies were estimated to be 232, 60, and 14 kcal/mole, respectively. Increasing the amount of PN concentration caused lowering of the activation energies of the three relaxations, a decrease of the glass transition temperature, and increasing intensities of the three damping peaks, compared to the control PMR-15 counterpart. These dynamic mechanical responses were in agreement with formation of a more flexible copolymer from PN and PMR-15 prepolymer.

Pater, Ruth H.↗
DOE OSTI2024

Infinitely rugged intra-cage potential energy landscape in metallic glasses caused by many-body interaction

The absence of translational symmetry in glassy materials poses a significant challenge in establishing effective structure-property relationships in real space. Consequently, the potential energy landscape (PEL) in phase space is widely utilized to comprehend the complex phenomena in glasses. The classical PEL features a two-scale profile comprising mega-basins and sub-basins, corresponding to α-relaxations (e.g. glass transition) and β-relaxations (e.g. local cage-breaking atomic rearrangements), respectively. Recent studies, however, reveal that sub-basins are not smooth and contain finer structures, the origins of which remain elusive. Here we probe the smoothness of sub-basin bottoms in glasses' PEL by introducing small intra-cage cyclic loading and then measuring the net changes in atomic-level stresses. Compared to glasses with pair interaction, glasses with many-body interaction exhibit orders-of-magnitude larger and loading-dependent stress changes even before the first cage-breaking event takes place, which reflect much more feature-rich sub-basins. We further demonstrate this stark contrast stems from the spatial distribution of individual atom's constraining force field. Specifically, at vanishing perturbations, many-body interactions disrupt the positive-definite synchrony in energy variations of the perturbed atom and the whole system, causing inherently less confined atomic responses and infinitely rugged sub-basins. The implications of these findings for the selective addition or removal of fine structures in the PEL and the subsequent tuning of glassy materials' responses to external stimuli are also explored.

36 MATERIALS SCIENCE↗