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At least 235 records · Page 13

Glass-rich chondrules in ordinary chondrites

There are two types of glass-rich chondrules in unequilibrated ordinary chondrites (OC): (1) porphyritic chondrules containing 55-85 vol% glass or microcrystalline mesostasis and (2) nonporphyritic chondrules, containing 90-99 vol% glass. These two types are similar in mineralogy and bulk composition to previously described Al-rich chondrules in OC. In addition to Si-, Al- and Na-rich glass or Ca-Al-rich microcrystalline mesostasis, glass-rich chondrules contain dendritic and skeletal crystals of olivine, Al2O3-rich low-Ca pyroxene and fassaite. Some chondrules contain relict grains of forsterite +/- Mg-Al spinel. We suggest that glass-rich chondrules were formed early in nebular history by melting fine-grained precursor materials rich in refractory (Ca, Al, Ti) an moderately volatite (Na, K) components (possibly related to Ca-Al-rich inclusions) admixed with coarse relict forsterite and spinel grains derived from previously disrupted type-I chondrules.

Krot, Alexander N.↗

Raman and Photoluminescence Spectroscopy of Er(3+) Doped Heavy Metal Oxide Glasses

The potential applications of rare-earth ion doped materials include fiber lasers which can be pumped conveniently by infrared semiconductor laser diodes. The host material systems most widely studied are fluoride crystals and glasses because fluorides have low nonradiative relaxation rates due to their lower phonon energies. However, the mechanical strength, chemical durability and temperature stability of the oxide glasses are generally much better than fluoride glasses. The objective of this research was to investigate the optical and spectroscopic properties of Er(3+)-doped lead-germanate and lead-tellurium-germanate glasses. The maximum vibrational energy of lead-tellurium-germanate glasses are in the range of 740-820/cm, intermediate between those of silicate (1150/cm) and fluoride (530/cm) glasses.

Dyer, Keith↗

Lifetime Predictions of a Titanium Silicate Glass with Machined Flaws

A dynamic fatigue study was performed on a Titanium Silicate glass to assess its susceptibility to delayed failure and to compare the results with those of a previous study. Fracture mechanics techniques were used to analyze the results for the purpose of making lifetime predictions. The material strength and lifetime was seen to increase due to the removal of residual stress through grinding and polishing. Influence on time-to-failure is addressed for the case with and without residual stress present. Titanium silicate glass otherwise known as ultra-low expansion (ULE)* glass is a candidate for use in applications requiring low thermal expansion characteristics such as telescope mirrors. The Hubble Space Telescope s primary mirror was manufactured from ULE glass. ULE contains 7.5% titanium dioxide which in combination with silica results in a homogenous glass with a linear expansion coefficient near zero. delayed failure . This previous study was based on a 230/270 grit surface. The grinding and polishing process reduces the surface flaw size and subsurface damage, and relieves residual stress by removing the material with successively smaller grinding media. This results in an increase in strength of the optic during the grinding and polishing sequence. Thus, a second study was undertaken using samples with a surface finish typically achieved for mirror elements, to observe the effects of surface finishing on the time-to-failure predictions. An allowable stress can be calculated for this material based upon modulus of rupture data; however, this does not take into account the problem of delayed failure, most likely due to stress corrosion, which can significantly shorten lifetime. Fortunately, a theory based on fracture mechanics has been developed enabling lifetime predictions to be made for brittle materials susceptible to delayed failure. Knowledge of the factors governing the rate of subcritical flaw growth in a given environment enables the development of relations between lifetime, applied stress and failure probability for the material under study. Dynamic fatigue is one method of obtaining the necessary information to develop these relationships. In this study, the dynamic fatigue method was used to construct a time-to-failure diagram for polished ULE glass.

Tucker, Dennis S.↗

Proof Test Diagrams for a Lithia-Alumina-Silica Glass-Ceramic

The glass-ceramic (Zerodur, Schott Glaswerke, Mainz, Germany) contains 70% to 78% by weight crystalline phase of high-quartz structure with a mean crystal size of 50-55 nm. The vitreous phase has a positive thermal expansion coefficient which is practically balanced by the negative coefficient of the crystalline phase. This results in a material which can maintain longitudinal stability during thermal cycling. This was one of the reasons for its choice as the material for the grazing incidence mirrors for the Chandra X-Ray Facility. Brittle materials such as glass and glass-ceramics which exhibit slow crack growth and subsequent fast fracture to failure exhibit a time dependence in strength. The decrease in strength for a constant applied load is known as static fatigue. In many cases, environment plays a major role in the material lifetime. It has been shown for silicate glasses that crack velocity will increase as the amount of water vapor in the environment surface finish and rate of loading. A rough surface finish leads to a lower tensile strength than for an optically polished surface. The strength of glass is observed in general to increase with increasing load rate. This phenomena is known as dynamic fatigue. This was observed for Zerodur by Tucker and Gent and Tucker in previous dynamic fatigue studies, in which lifetimes were obtained. All of the above named factors need to be considered when glass is to be used in load bearing applications.

Tucker, Dennis S.↗

Method of Estimating Continuous Cooling Transformation Curves of Glasses

A method is proposed for estimating the critical cooling rate and continuous cooling transformation (CCT) curve from isothermal TTT data of glasses. The critical cooling rates and CCT curves for a group of lithium disilicate glasses containing different amounts of Pt as nucleating agent estimated through this method are compared with the experimentally measured values. By analysis of the experimental and calculated data of the lithium disilicate glasses, a simple relationship between the crystallized amount in the glasses during continuous cooling, X, and the temperature of undercooling, (Delta)T, was found to be X = AR(sup-4)exp(B (Delta)T), where (Delta)T is the temperature difference between the theoretical melting point of the glass composition and the temperature in discussion, R is the cooling rate, and A and B are constants. The relation between the amount of crystallisation during continuous cooling and isothermal hold can be expressed as (X(sub cT)/X(sub iT) = (4/B)(sup 4) (Delta)T(sup -4), where X(sub cT) stands for the crystallised amount in a glass during continuous cooling for a time t when the temperature comes to T, and X(sub iT) is the crystallised amount during isothermal hold at temperature T for a time t.

Zhu, Dongmei↗

Computer Modeling of Thermal Convection in Melts to Explain Glass Formation in Low Gravity and on Earth

Experiments conducted up to this time on glass forming melts in the low gravity environment of space show that glasses prepared in low-g are more chemically homogeneous and more resistant to crystallization than the comparable glasses prepared at 1-g on Earth. This result is somewhat surprising and opposite to the accepted concept on glass formation for a melt. A hypothesis based on "shear thinning" of a melt, a decrease in viscosity with increasing shear stress, is proposed as an explanation for the observed low-gravity results. This paper describes detailed simulation procedures to test the role of thermal convection in introducing shear stress in glass forming melts, using a lithium disilcate melt as a model. The simulation system in its idealized version consists of a cylinder that is heated at one end and cooled at the other with gravity acting in a transverse direction to the thermal gradient. The side wall of the cylinder is assumed to be insulating. The governing equations of motion and energy are solved using variable properties for viscosity (Arrehenius and non-Arrehenius behaviors) and density (constant and temperature dependent). Other parametric variables in the calculations include gravity level and gravity vector orientation. The shear stress in the system are then computed as a function of gravity from the calculated values of maximum melt velocity, and its effect on melt viscosity (shear thinning) is predicted. Also included and discussed are the modeling efforts related to other potential convective processes in glass forming melts and their possible effects on melt viscosity.

Ray, Chandra S.↗

Experimental Constraints on the Partitioning and Valence of V and Cr in Garnet and Coexisting Glass

A series of experiments with garnet and coexisting melt have been carried out across a range of oxygen fugacities (near hematite-magnetite (HM) to below the iron-wustite (IW) buffers) at 1.7 GPa to study the partitioning and valence of Cr and V in both phases. Experiments were carried out in a non end loaded piston cylinder apparatus, and the run products were analyzed with electron microprobe and xray absorption near edge structure (XANES) analysis at beamline 13-ID at the Advanced Photon Source of Argonne National Lab. The valence of vanadium and chromium were determined using the position and intensity of the Ka pre-edge peaks, calibrated on a series of Cr and Vbearing standard glasses. This technique has been applied to V and Cr in glasses and V in spinels previously, and in these isotropic phases there are no orientational effects on the XANES spectra (Righter et al., 2006, Amer. Mineral. 91, 1643-1656). We also now demonstrate this to be true for V and Cr in garnet. Also, previous work has shown that V has a higher valence in the glass (or melt) than in the coexisting spinel. This is also true for V in garnet-glass pairs in this study. Vanadium valence in garnets varies from 2.7 below the IW buffer to 3.7 near HM, and for coexisting glass it varies from 3.2 to 4.3. Vanadium valence measured in some natural garnets from mantle localities indicates V in the more reduced range at 2.5. Comparisons will be made between fO2 estimated from V valence and other methods for garnet-bearing mantle samples. In contrast, Cr valence measured in garnet and coexisting glass for all experimental and natural samples is 2.9- 3.0, suggesting that the valence of Cr does not vary within either phase across a large fO2 range. These results demonstrate that while V varies from 2+ to 3+ to 4+ in garnet-melt systems, Cr does not, and this will ultimately affect the partitioning behavior of these two elements in natural systems. Garnet/melt D(Cr) are between 12 and 17 across this range of fO2, whereas D(V) has the highest partition coefficient approx.3, near the IW buffer where the valence of V is almost entirely 3+.

Righter, K.↗

Sulfur Isotopes in Gas-rich Impact-Melt Glasses in Shergottites

Large impact melt glasses in some shergottites contain huge amounts of Martian atmospheric gases and they are known as gas-rich impact-melt (GRIM) glasses. By studying the neutron-induced isotopic deficits and excesses in Sm-149 and Sm-150 isotopes resulting from Sm-149 (n,gamma) 150Sm reaction and 80Kr excesses produced by Br-79 (n,gamma) Kr-80 reaction in the GRIM glasses using mass-spectrometric techniques, it was shown that these glasses in shergottites EET79001 and Shergotty contain regolith materials irradiated by a thermal neutron fluence of approx.10(exp 15) n/sq cm near Martian surface. Also, it was shown that these glasses contain varying amounts of sulfates and sulfides based on the release patterns of SO2 (sulfate) and H2S (sulfide) using stepwise-heating mass-spectrometric techniques. Furthermore, EMPA and FE-SEM studies in basaltic-shergottite GRIM glasses EET79001, LithB (,507& ,69), Shergotty (DBS I &II), Zagami (,992 & ,994) showed positive correlation between FeO and "SO3" (sulfide + sulfate), whereas those belonging to olivine-phyric shergottites EET79001, LithA (,506, & ,77) showed positive correlation between CaO/Al2O3 and "SO3".

Rao, M. N.↗

Volcanic Coatings on Picritic Apollo 17 Glasses; Submicrometer-Deposits of Fe-CR-Metal

The purposes of our ongoing investigations of Apollo 15 green and Apollo 17 orange and black volcanic glasses are threefold: first, to increase our understanding of the volcanic origin of the glasses; second, to determine the nature of the coating materials deposited on the glasses during their cooling in the volcanic environment; and, third, to help determine the nature of the gases involved in the volcanic fire-fountaining that occurred at approximately 3.5 Ga on the moon. We are continuing studies of coatings on volcanic glasses using analytical techniques not available when these glasses were originally studied; these include high-resolution FE-TEM and X-ray mapping, along with other highly detailed methods including TEM electron diffraction analysis. Initial studies of Apollo 15 green volcanic glasses using the techniques described above revealed for the first time the presence of areas containing distinct layering of volcanic surface deposits. S was associated with some of the inner layer of metallic Fe but was absent from the outer layer. Zn was associated with S in some places in the inner layer. An example of a typical spherule used for this study is shown in Fig. 1. It is a black (quench-crystallized) bead from near the bottom of the 74001/2 double drive tube; black beads such as this one are essentially identical in composition to the orange (uncrystallized) beads of the 74001/2 core.

McKay, David S.↗

Precipitation of Secondary Phases from the Dissolution of Silicate Glasses

Basaltic and anorthositic glasses were subjected to aqueous weathering conditions in the laboratory where the variables were pH, temperature, glass composition, solution composition, and time. Leached layers formed at the surfaces of glasses followed by the precipitation of X-ray amorphous iron and titanium oxides in acidic and neutral solutions at 25 C over time. Glass under oxidative hydrothermal treatments at 150 C yielded a three-layered surface; which included an outer smectite layer, a Fe-Ti oxide layer and an innermost thin leached layer. The introduction of Mg into solutions facilitated the formation of phyllosilicates. Aqueous hydrothermal treatment of anorthositic glasses (high Ca, low Ti) at 200 C readily formed smectite, whereas, the basaltic glasses (high Ti) were more resistant to alteration and smectite was not observed. Alkaline hydrothermal treatment at 2000e produced zeolites and smectites; only smectites formed at 200 C in neutral solutions. These mineralogical changes, although observed under controlled conditions, have direct applications in interpreting planetary (e.g., meteorite parent bodies) and terrestrial aqueous alteration processes.

Ming, Douglas W.↗

Widespread Weathered Glass on the Surface of Mars

Low albedo sediments cover >10(exp 7) sq km in the northern lowlands of Mars, but the composition and origin of these widespread deposits have remained ambiguous despite many previous investigations. Here we use near-infrared spectra acquired by the Mars Express OMEGA (Observatoire pour la Mineralogie, l'Eau, les Glaces, et l'Activite') imaging spectrometer to show that these sediments exhibit spectral characteristics that are consistent with both high abundances of iron-bearing glass and silica-enriched leached rinds on glass. This interpretation is supported by observations of low-albedo soil grains with possible rinds at the Phoenix Mars Lander landing site in the northern lowlands. By comparison with the extensive glass-rich dune fields and sand sheets of Iceland, we propose an explosive volcanic origin for these glass-rich sediments. We also propose that the glassy remnant rinds on the sediments are the result of post-depositional alteration, as these rinds are commonly formed in arid terrestrial volcanic environments during water-limited, moderately acidic leaching. These weathered, glass-rich deposits in the northern lowlands are also colocated with the strongest concentrations of a major global compositional surface type previously identified in mid-infrared spectra, suggesting that they may be representative of global processes. Our results provide potential confirmation of models suggesting that explosive volcanism has been widespread on Mars, and also raise the possibilities that glass-rich volcaniclastics are a major source of eolian sand on Mars and that widespread surficial aqueous alteration has occurred under Amazonian climatic conditions.

Horgan, Briony↗

High Resolution Imaging and Analysis of Terrestrial Impact Glass: Amorphous Materials, Phyllosilicates and Everything in Between

Introduction: Impact cratering is one of the most ubiquitous geologic processes shaping the surface of all solid bodies in our solar system. Impacts are also a major source of clay minerals, poorly crystalline clay-like phases and amorphous (i.e., lacking long-range atomic order) materials on Earth and Mars. Phyllosilicates and amorphous materials have consistently formed a major component (~20-70 wt%) of every single drilled rock and soil sample in Gale Crater on Mars, as determined by the CheMin instrument on Curiosity. The origin of the amorphous component is speculative, but could be primary impact or volcanic-produced glass(es) deposited via aeolian or fluvial processes, secondary aqueous alteration products or chemical precipitates; it is likely to be a combination of all three possibilities. Efforts to determine the composition of these materials across the rover’s traverse through Gale Crater are ongoing. Naturally occurring amorphous phases are found in a variety of environments on Earth, and terrestrial analogue studies may help shed light on how they may have formed on Mars. Primary and altered impact glass are likely widespread on Mars and may have contributed to the amorphous component found throughout Gale Crater. In its pristine, unaltered state, impact glass (i.e., melt glass) is considered amorphous. However, truly unaltered glass is rarely preserved in crater fill impactites as it quickly alters in the post-impact environ-ment, commonly forming a mixture of hydrated aluminosilicate phases whose structures are not always discernable at the microscale (i.e., they may be amorphous or contain short-range order). These phases are part of an incredibly complex group of materials; differences in their composition and crystalline structure (or lack thereof) and genetic relationship to the more well-crystalline clay minerals are often only discernable at the nanoscale, beyond the resolution of traditional X-ray diffractometers (XRD) and scanning electron microscopes/microprobes (SEM/EPMA) alone. In this contribution, we summarize recent results from ongoing characterization of clay minerals, poorly crystalline clay-like phases, and amorphous materials preserved in altered terrestrial impact glass from the Chicxulub (~66 Ma) and Ries (~15 Ma) impact structures. This work has been performed using a combination of high-resolution transmission electron microscopy (HR-TEM), SEM, microprobe/EPMA, Raman spectroscopy and XRD.

Impact crater↗

The structure of high-Mg alkali-bearing aluminosilicate glasses investigated in situ at ambient and high pressure by multi-angle energy dispersive X-ray diffraction and infrared microspectroscopy

The structural properties of synthetic high-Mg alkali-bearing aluminosilicate glasses analogues of natural picritic-to-komatiitic magmas were investigated in situ by multiangle energy dispersive X-ray diffraction at 2.1 GPa and ambient pressure and by Fourier Transform infrared spectroscopy up to 5.4 GPa in a cycle of compression and decompression experiments. Our results show that the intermediate range ordering of the glass structure at 2.1 GPa is 3.14 Å, increasing to 3.19 Å when decompressed. The local structure shows T-O lengths of 1.66 Å (2.1 GPa) and 1.65 Å (ambient pressure), T-T distances of 3.19 Å at high pressure, which lengthen to 3.21 Å at ambient pressure, causing the T-O-T angle of 147° determined at 2.1 GPa to widen to 154° upon decompression. The deconvoluted infrared spectra result in the presence of Q 1 , Q 2 , Q 3 populations in the aluminosilicate spectral region, whose proportions remain relatively unchanged up to 5.4 GPa. The structural response of the investigated glasses to cold-compression does not involve changes in polymerization, but rather a shrinking and compaction of the structure as evidenced by the Qn species shifting to higher wavenumbers as a function of pressure. The structural properties determined from X-ray diffraction for this glass composition are discussed together with those of glasses emerging from previous studies to highlight a compositional dependence mainly dictated by the amount of SiO 2 and Al 2 O 3 .

glass structure↗

Impact of Crystalline Phases on Low-Activity Waste Glass Durability: Insights from PCT and VHT

During vitrification of nuclear wastes, slow cooling along the container centerline promotes crystalline phase formation, which can alter residual glass composition and reduce chemical durability. This study investigates the effects of crystalline phases on the chemical durability of low-activity waste (LAW) borosilicate glasses using the product consistency test (PCT) and vapor hydration test (VHT) on container centerline cooled (CCC) samples. A preliminary model (R2 = 0.88) was developed to predict CCC PCT responses based on glass composition, PCT data from quenched glasses, and measured crystal fractions. Using the latest LAW glass dataset, the feasibility of predictive modeling is evaluated, limitations in current data and methods are identified, and challenges for improving model accuracy are discussed to guide future data collection and model development.

borosilicate glass↗

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↗

Atom Probe Tomography Investigation of Clustering in Model P 2 O 5 -Doped Borosilicate Glasses for Nuclear Waste Vitrification

Atom probe tomography (APT) has been utilized to investigate the microstructure of two model borosilicate glasses designed to understand the solubility limits of phosphorous pentoxide (P 2 O 5 ). This component is found in certain high-level radioactive defence wastes destined for vitrification, where phase separation can potentially lead to a number of issues relating to the processing of the glass and its long-term chemical and structural stability. The development of suitable focused ion beam (FIB)-preparation routes and APT analysis conditions were initially determined for the model glasses, before examining their detailed microstructures. In a 3.0 mol% P 2 O 5 -doped glass, both visual inspection and sensitive statistical analysis of the APT data show homogeneous microstructures, while raising the content to 4.0 mol% initiates the formation of phosphorus-enriched nanoscale precipitates. This study confirms the expected inhomogeneities and phase separation of these glasses and offers routes to characterizing these at near-atomic scale resolution using APT.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Electronic 1/f noise as a probe of dimensional effects on spin-glass dynamics

Over the past decade, spin-glass simulations have improved to the point that they now access time- and length-scales comparable to experiments at the mesoscale. A recent series of thin-film field-cooled/zero-field-cooled magnetization (FC/ZFC) experiments demonstrated activated spin dynamics, with a temperature-independent activation energy proportional to the logarithm of the film thickness and with coefficients in remarkable agreement with the simulation. These measurements require the application of small magnetic fields, which has been shown to affect the spin-glass energy landscape. Measurements of the 1/f noise in metallic spin-glasses have been previously shown to be a sensitive probe of the spin dynamics, and the measurements can be made without applying a magnetic field. In this mini-review, we review these techniques and discuss how transport measurements can fit into the current landscape of spin-glass measurements. We compare previous measurements to more recent measurements on similar films, made with ostensibly different cooling protocols, and compare both the previous and recent measurements to the magnetometry. The transport measurements—taken over a wider range of temperature than magnetometry—suggest that the maximum spin-glass energy barrier height is temperature-dependent, not fixed, possibly due to two-dimensional dynamics. We discuss this possibility, along with future measurements, which may be able to resolve this mystery.

1/f noise↗

Role of water in fracture of modified silicate glasses

Decarbonizing the glass industry requires alternative melting technology, as current industrial melting practices rely heavily on fossil fuels. Hydrogen has been proposed as an alternative to carbon-based fuels, but the ensuing consequences on the mechanical behavior of the glass remain to be clarified. A critical distinction between hydrogen and carbon-based fuels is the increased generation of water during combustion, which raises the equilibrium solubility of water in the melt and alters the behavior of the resulting glass. A series of five silicate glasses with 80% silica and variable [Na 2 O]/([H 2 O] + [Na 2 O]) ratios were simulated using molecular dynamics to elucidate the effects of water on fracture. Several fracture toughness calculation methods were used in combination with atomistic fracture simulations to examine the effects of hydroxyl content on fracture behavior. Here, this study reveals that the crack propagation pathway is a key metric to understanding fracture toughness. Notably, the fracture propagation path favors hydrogen sites over sodium sites, offering a possible explanation of the experimentally observed effects of water on fracture properties.

36 MATERIALS SCIENCE↗