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At least 19 records
All sourcesNASA NTRSDOE OSTI
NASA NTRS2004

Deformation, Stress Relaxation, and Crystallization of Lithium Silicate Glass Fibers Below the Glass Transition Temperature

The deformation and crystallization of Li(sub 2)O (center dot) 2SiO2 and Li(sub 2)O (center dot) 1.6SiO2 glass fibers subjected to a bending stress were measured as a function of time over the temperature range -50 to -150 C below the glass transition temperature (Tg). The glass fibers can be permanently deformed at temperatures about 100 C below T (sub)g, and they crystallize significantly at temperatures close to, but below T,, about 150 C lower than the onset temperature for crystallization for these glasses in the no-stress condition. The crystallization was found to occur only on the surface of the glass fibers with no detectable difference in the extent of crystallization in tensile and compressive stress regions. The relaxation mechanism for fiber deformation can be best described by a stretched exponential (Kohlrausch-Williams-Watt (KWW) approximation), rather than a single exponential model.The activation energy for stress relaxation, Es, for the glass fibers ranges between 175 and 195 kJ/mol, which is considerably smaller than the activation energy for viscous flow, E, (about 400 kJ/mol) near T, for these glasses at normal, stress-free condition. It is suspected that a viscosity relaxation mechanism could be responsible for permanent deformation and crystallization of the glass fibers below T,

Ray, Chandra S.↗
DOE OSTI2020

Glassy polymers: Historical findings, membrane applications, and unresolved questions regarding physical aging

Polymers below their glass transition temperature (Tg) are non-equilibrium glasses because excess free volume “frozen” between kinetically-restricted polymer chains slowly relaxes over time towards equilibrium via local, segmental chain motion. This process, known as physical aging, is observed through time-dependent decreases in a polymer's specific volume, enthalpy, etc. This article focuses on the history of glassy polymers in membrane separation applications. Open questions regarding the influence of thickness (e.g., membrane geometry) and temperature on physical aging in glassy polymers are highlighted.

36 MATERIALS SCIENCE↗
NASA NTRS2002

Investigation of low glass transition temperature on COTS PEMs reliability

Many factors influence PEM component reliability.One of the factors that can affect PEM performance and reliability is the glass transition temperature (Tg) and the coefficient of thermal expansion (CTE) of the encapsulant or underfill. JPL/NASA is investigating how the Tg and CTE for PEMs affect device reliability under different temperature and aging conditions. Other issues with Tg are also being investigated. Some preliminary data will be presented on glass transition temperature test results conducted at JPL.

Glass transition temperature PEMs↗
NASA NTRS2004

Development of DMBZ-15 High-Glass-Transition-Temperature Polyimides as PMR-15 Replacements Given R&D 100 Award

PMR-15, a high-temperature polyimide developed in the mid-1970s at the NASA Lewis Research Center,1 offers the combination of low cost, easy processing, and good high-temperature performance and stability. It has been recognized as the leading polymer matrix resin for carbon-fiber-reinforced composites used in aircraft engine components. The state-of-the-art PMR-15 polyimide composite has a glass-transition temperature (Tg) of 348 C (658 F). Since composite materials must be used at temperatures well below their glass-transition temperature, the long-term use temperatures of PMR-15 composites can be no higher than 288 C (550 F). In addition, PMR-15 is made from methylene dianiline (MDA), a known liver toxin. Concerns about the safety of workers exposed to MDA during the fabrication of PMR-15 components and about the environmental impact of PMR-15 waste disposal have led to the industry-wide implementation of special handling procedures to minimize the health risks associated with this material. These procedures have increased manufacturing and maintenance costs significantly and have limited the use of PMR-15 in commercial aircraft engine components.

Chuang, Kathy↗
DOE OSTI2024

Time-Temperature-Transformation (TTT) Diagram for a Sludge Batch 9 Glass Composition Based on Coupled-Operation with the Salt Waste Processing Facility

The amorphous structure of a glass waste form has the potential to rearrange into crystalline phases at temperatures between the liquidus temperature and the glass transition temperature (Tg). Certain phases that can form will be detrimental to the durability of the glass and it is important to know the conditions that promote devitrification. The canister-centerline-cooling (CCC) profile is used to replicate the area within the center of the Defense Waste Processing Facility (DWPF) canister with the slowest cooling during the initial cool down after pouring, which has the greatest potential for crystallization. Other time-temperature conditions that cause significant changes in either phase structure or phase composition are identified by a time-temperature-transformation (TTT) study. The phase stability of a waste form must be determined as a part of the Waste Acceptance Product Specifications (WAPS) if it is to eventually be stored in a geologic repository. This requires the creation of a TTT diagram and analysis of the Tg, as defined by the Department of Energy (DOE). The previous TTT study for a DWPF glass waste form was completed in 2010 prior to coupled operation with the Salt Waste Processing Facility (SWPF). SWPF transfers two high activity waste streams to DWPF for vitrification: a cesium-containing strip effluent and a stream containing monosodium titanate/sludge solids. These SWPF streams were first transferred to DWPF for vitrification during Sludge Batch 9 (SB9) in 2021. The impact of these SWPF streams on crystallization behavior was not determined in previous studies and the need for data to satisfy WAPS Specification 1.4 for SB9 was identified.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
NASA NTRS2003

Polyimides by Photochemical Cyclopolymerization

The polyimides of this invention are derived from a Diels-Alder cyclopolymerization of a photochemically generated bisdiene with dienophiles, such as bismaleimides, trismaleimides and mixtures thereof with maleimide end-caps. Irradiation of one or more diketones produces two distinct hydroxy o-quinodimethane (photoenol) intermediates. These intermediates are trapped via a Diels-Alder cycloaddition with appropriate dienophiles, e.g., bismaleimide and/or trismaleimides to give the corresponding polyimides in quantitative yields. When bismaleimides, trismaleimides or mixtures thereof with maleimide end-caps are used as the dienophile, the resulting polyimides have glass transition temperatures (Tg) as high as 300 C. Polyimide films can be prepared by ultraviolet irradiation of high solids content varnishes of the monomers in a small amount of solvent, e.g., cyclohexanone, dimethyl formamide, N-methylpyrollidone and the like. These polyimides are characterized as having high glass transition temperatures, good mechanical properties and improved processing in the manufacture of adhesives, electronic materials and films.

Michael A Meador↗
NASA NTRS1991

Applying state diagrams to food processing and development

The physical state of food components affects their properties during processing, storage, and consumption. Removal of water by evaporation or by freezing often results in formation of an amorphous state (Parks et al., 1928; Troy and Sharp, 1930; Kauzmann, 1948; Bushill et al., 1965; White and Cakebread, 1966; Slade and Levine, 1991). Amorphous foods are also produced from carbohydrate melts by rapid cooling after extrusion or in the manufacturing of hard sugar candies and coatings (Herrington and Branfield, 1984). Formation of the amorphous state and its relation to equilibrium conditions are shown in Fig. 1 [see text]. The most important change, characteristic of the amorphous state, is noticed at the glass transition temperature (Tg), which involves transition from a solid "glassy" to a liquid-like "rubbery" state. The main consequence of glass transition is an increase of molecular mobility and free volume above Tg, which may result in physical and physico-chemical deteriorative changes (White and Cakebread, 1966; Slade and Levine, 1991). We have conducted studies on phase transitions of amorphous food materials and related Tg to composition, viscosity, stickiness, collapse, recrystallization, and ice formation. We have also proposed that some diffusion-limited deteriorative reactions are controlled by the physical state in the vicinity of Tg (Roos and Karel, 1990, 1991a, b, c). The results are summarized in this article, with state diagrams based on experimental and calculated data to characterize the relevant water content, temperature, and time-dependent phenomena of amorphous food components.

Non-NASA Center↗
NASA NTRS2005

Polyimides by Photochemical Cyclopolymerization

The novel polyimides of this invention are derived from Diels-Alder cyclopolymerization of photochemically generated bisdienes with dienophiles, such as bismaleimides, trismaleimides and mixtures thereof with maleimide endcaps. Irradiation of one or more diketones produces two distinct hydroxy o-quinodimethane (photoenol) intermediates. These intermediates are trapped via Diels-Alder cycloaddition with appropriate dienophiles, e.g., bismaleimide and/or trismaleimides to give the corresponding polyimides in quantitative yields. When bismaleimides, trismaleimides or mixtures thereof with maleimide end-caps are used as the dienophile, the resulting polyimides have glass transition temperatures (Tg) as high as 300 C. Polyimide films can be prepared by ultraviolet irradiation of high solids content varnishes of the monomers in a small amount of solvent, e.g., cyclohexanone, dimethyl formamide, N-methylpyrollidone and the like. These novel polyimides are characterized as having high glass transition temperatures, good mechanical properties and improved processing in the manufacture of adhesives, electronic materials and films.

Meador, Michael A.↗
NASA NTRS2005

Polyimides by photochemical cyclopolymerization

The novel polyimides of this invention are derived from Diels-Alder cyclopolymerization of photochemically generated bisdienes with dienophiles, such as bismaleimides, trismaleimides and mixtures thereof with maleimide end-caps. Irradiation of one or more diketones produces two distinct hydroxy o-quinodimethane (photoenol) intermediates. These intermediates are trapped via Diels-Alder cycloaddition with appropriate dienophiles, e.g., bismaleimide and/or trismaleimides to give the corresponding polyimides in quantitative yields. When bismaleimides, trismaleimides or mixtures thereof with maleimide end-caps are used as the dienophile, the resulting polyimides have glass transition temperatures (Tg) as high as 300? C. Polyimide films can be prepared by ultraviolet irradiation of high solids content varnishes of the monomers in a small amount of solvent, e.g., cyclohexanone, dimethyl formamide, N-methylpyrollidone and the like. These novel polyimides are characterized as having high glass transition temperatures, good mechanical properties and improved processing in the manufacture of adhesives, electronic materials and films.

Meador, Michael A.↗
NASA NTRS2002

Polyesters by Photochemical Cyclopolymerization

The polyesters of this invention are derived from a Diels-Alder cyclopolymerization of a photochemically generated bisdiene with dienophiles, such as di(acrylates), tri (acrylates), di(methacrylates), tri(methacrylates) and mixtures thereof with mono(methacrylates) or mono(acrylate) end-caps. Irradiation of one or more diketones produces two distinct hydroxy o-quinodimethane (photoenol) intermediates. These intermediates are trapped via a Diels-Alder cycloaddition with appropriate dienophiles, e.g., di(acrylates) to give the corresponding in polyesters quantitative yields. When di(acrylates), tri(acrylates) and di and tri(methacrylates) or mixtures thereof with monoacrylate end-caps are used as the dienophile, the resulting polyesters have glass transition temperatures (Tg) as high as 200 C. Polyesters films can be prepared by ultraviolet irradiation of high solids content varnishes of the monomers in a small amount of solvent, e.g., cyclohexanone, dimethyl formamide, N-methylpyrollidone and the like. These polyesters, i.e. polyesters are characterized as having high glass transition temperatures, good mechanical properties and improved processing in the manufacture of composites, adhesives, electronic materials and films.

Michael A Meador↗
DOE OSTI2020

A Deep Neural Network for Accurate and Robust Prediction of the Glass Transition Temperature of Polyhydroxyalkanoate Homo- and Copolymers

The purpose of this study was to develop a data-driven machine learning model to predict the performance properties of polyhydroxyalkanoates (PHAs), a group of biosourced polyesters featuring excellent performance, to guide future design and synthesis experiments. A deep neural network (DNN) machine learning model was built for predicting the glass transition temperature, Tg, of PHA homo- and copolymers. Molecular fingerprints were used to capture the structural and atomic information of PHA monomers. The other input variables included the molecular weight, the polydispersity index, and the percentage of each monomer in the homo- and copolymers. The results indicate that the DNN model achieves high accuracy in estimation of the glass transition temperature of PHAs. In addition, the symmetry of the DNN model is ensured by incorporating symmetry data in the training process. The DNN model achieved better performance than the support vector machine (SVD), a nonlinear ML model and least absolute shrinkage and selection operator (LASSO), a sparse linear regression model. The relative importance of factors affecting the DNN model prediction were analyzed. Sensitivity of the DNN model, including strategies to deal with missing data, were also investigated. Compared with commonly used machine learning models incorporating quantitative structure–property (QSPR) relationships, it does not require an explicit descriptor selection step but shows a comparable performance. The machine learning model framework can be readily extended to predict other properties.

quantitative structure–property relationship (QSPR↗
DOE OSTI2020

One-Dimensional Glassy Behavior of Ultraconfined Water Strings

Water is renowned for its anomalous behaviors, which can be linked to a distributed H-bond network in bulk water. Ultraconfinement of the water molecule can remove H-bonding, leaving only molecular water. In natural cordierite crystals, water is trapped in an orthorhombic channel with an average diameter of 5.7 Å, running through the center of the unit cell parallel to the c-axis. Calorimetric measurements reveal the existence of a one-dimensional (1D) glass linked to this water. In these channels, water molecules in truncated, sparse 1D strings interact only via dipole–dipole correlations. Here, a physical 1D glass is formed from these strings. This unusual state can be explained by a modified Ising model. This model predicts a dependence of the glass transition temperature, Tg, on the size of these domains. This is confirmed experimentally.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
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.↗
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 NTRS1986

Structure-to-property Relationships in Addition Cured Polymers 2: Resin Tg Composite Initial Mechanical Properties of Norbornenyl Cured Polyimide Resins

PRM (polymerization of monomeric reactants) methodology was used to prepare thirty different polyimide oligomeric resins. Monomeric composition as well as chain length between sites of crosslinks were varied to examine their effects on glass transition temperature (Tg) of the cured/postcured resins. An almost linear correlation of Tg versus molecular distance between the crosslinks was observed. An attempt was made to correlate Tg with initial mechanical properties (flexural strength and interlaminar shear strength) of unidirectional graphite fiber composites prepared with these resins. However, the scatter in mechanical strength data prevented obtaining as clear a correlation as was observed for the structural modification/crosslink distance versus Tg. Instead, only a range of composite mechanical properties was obtained at the test temperatures studied (room temperature, 288 and 316 C). Perhaps more importantly, what did become apparent during the attempted correlation study was: (1) that PMR methodology could be used to prepare composites from resins that contain a wide variety of monomer modifications, and (2) that these composites almost invariably provided satisfactory initial mechanical properties as long as the resins selected were melt processable.

Alston, W. B.↗
NASA NTRS1986

Structure-to-property relationships in addition cured polymers. II - Resin Tg and composite initial mechanical properties of norbornenyl cured polyimide resins

PRM (polymerization of monomeric reactants) methodology was used to prepare thirty different polyimide oligomeric resins. Monomeric composition as well as chain length between sites of crosslinks were varied to examine their effects on glass transition temperature (Tg) of the cured/postcured resins. An almost linear correlation of Tg versus molecular distance between the crosslinks was observed. An attempt was made to correlate Tg with initial mechanical properties (flexural strength and interlaminar shear strength) of unidirectional graphite fiber composites prepared with these resins. However, the scatter in mechanical strength data prevented obtaining as clear a correlation as was observed for the structural modification/crosslink distance versus Tg. Instead, only a range of composite mechanical properties was obtained at the test temperatures studied (room temperature, 288 and 316 C). Perhaps more importantly, what did become apparent during the attempted correlation study was: (1) that PMR methodology could be used to prepare composites from resins that contain a wide variety of monomer modifications, and (2) that these composites almost invariably provided satisfactory initial mechanical properties as long as the resins selected were melt processable.

Alston, William B.↗
DOE OSTI2023

Temperature-induced densification in compressed basaltic glass revealed by in-situ ultrasonic measurements

Abstract Acoustic velocities of a model basalt glass (64 mol% CaMgSi2O6 + 36 mol% CaAl2Si2O8) were measured along different pressure-temperature (P-T) paths. One set of experiments involved isothermal compression-decompression cycles, performed at temperatures of 300, 641, 823, and 1006 K and pressures up to 12.2 GPa. The other set of experiments involved constant-load heating-cooling cycles at temperatures up to 823 K and pressures up to 7.5 GPa. Both sets of experiments were performed in a multi-anvil apparatus using a synchrotron-based ultrasonic technique. Our results show that the glass compressed isothermally at 300 K (cold-compression) displays anomalously decreasing compressional (VP) and shear (VS) wave velocities with increasing pressure until ~8 GPa. Beyond 8 GPa, both VP and VS start to increase sharply with pressure and irreversible densification of the glass occurred, producing large hysteresis loops of velocities upon decompression. However, for the glass compressed isothermally at increasingly higher temperatures (hot-compression), the velocity minima gradually shift to lower pressures. At temperature close to the glass transition temperature Tg, the velocity minima disappear completely, displaying a monotonic increase of velocities during compression and higher VP and VS during decompression. In addition, constant-load heating-cooling experiments show that velocities generally decrease slightly with increasing temperature, but start to increase once heated above a threshold temperature (~650 K). During cooling the velocities increase almost linearly with decreasing temperature, resulting in higher velocities (~1.5–2.5% higher) when returned to 300 K. This implies that a temperature-induced densification may have occurred in the glass at high pressures. Raman spectra on recovered samples show that the hot-compressed and high-P heated glasses contain distinctly densified and depolymerized structural signatures compared to the initial glass and the cold-compressed glass below the velocity transition pressure PT (~8 GPa). Such densification may be attributed to the breaking of bridging oxygen bonds and compaction in the intermediate-range structure. Our results demonstrate that temperature can facilitate glass densification at high pressures and point out the importance of P-T history in understanding the elastic properties of silicate glasses. Comparison with melt velocity suggests that hot-compressed glasses may better resemble the pressure dependence of velocity of silicate melts than cold-compressed glasses, but still show significantly higher velocities than melts. If the abnormal acoustic behaviors of cold-compressed glasses were used to constrain melt fractions in the mantle low-velocity regions, the melt fractions needed to explain a given velocity reduction would be significantly underestimated at high pressures.

Geochemistry & Geophysics↗