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At least 253 records · Page 14
All sourcesNASA NTRSDOE OSTI
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 OSTI2025

Revisiting the Role of Mobile Ion Size for the Activation Barrier of Charge Transport in Single Ion Conducting Polymers

The development of polymer electrolytes for energy storage and conversion technologies requires a fundamental understanding of the material parameters controlling the energy barriers for ion transport. In glassy polymers, these activation barriers are usually extracted by using Arrhenius procedures. However, our recent studies of single ion conducting polymers reveal that this traditional Arrhenius description provides anomalously small prefactors, an issue that is widely disregarded in the literature. Here, to address it, an alternative approach was introduced for extracting the effective activation barrier E by imposing a physically valid limit (∼10 –13 s) for the ion hopping attempt time. Two consequences of this recent approach are that in polymer electrolytes (i) E is significantly (∼30–40%) lower than the barrier estimated using traditional Arrhenius fits and (ii) E displays significant temperature dependence even in the glassy state. Under these circumstances, we are revisiting the role of ion size, glass transition temperature T g , and dielectric and elastic constants of the polymer matrix on the effective activation barriers for ion transport as extracted using the recently proposed approach and highlight the differences from the picture that previously emerged based on simplistic apparent Arrhenius analysis. To this end, we investigate cation transport in three families of single ion conducting trifluoromethane sulfonimide-based polyanions with varied T g . Our results indicate that E decreases with mobile cation size and is highly sensitive to changes in the dielectric permittivity of the matrix, even for large cations. These insights call for revisions of many earlier results based on apparent Arrhenius fits as the proposed approach can provide more accurate guidance for the design of polymer electrolytes with enhanced ionic conductivity.

energy barrier↗
NASA NTRS1990

Tough, Microcracking-Resistant, High-Temperature Polymer

Simultaneous synthesis from thermosetting and thermoplastic components yields polyimide with outstanding properties. Involves process in which one polymer cross-linked in immediate presence of other, undergoing simultaneous linear chain extension. New material, LaRC-RP40 synthesized from high-temperature thermosetting imide prepolymer and from thermoplastic monomer. Three significantly improved properties: toughness, resistance to microcracking, and glass-transition temperature. Shows promise as high-temperature matrix resin for variety of components of aircraft engines and for use in other aerospace structures.

Pater, Ruth H.↗
NASA NTRS1990

Process for crosslinking methylene-containing aromatic polymers with ionizing radiation

A process for crosslinking aromatic polymers containing radiation-sensitive methylene groups (-CH2-) by exposing the polymers to ionizing radiation thereby causing crosslinking of the polymers through the methylene groups is described. Crosslinked polymers are resistant to most organic solvents such as acetone, alcohols, hydrocarbons, methylene, chloride, chloroform, and other halogenated hydrocarbons, to common fuels and to hydraulic fluids in contrast to readily soluble uncrosslinked polymers. In addition, the degree of crosslinking of the polymers depends upon the percentage of the connecting groups which are methylene which ranges from 5 to 50 pct and preferably from 25 to 50 pct of the connecting groups, and is also controlled by the level of irradiation which ranges from 25 to 1000 Mrads and preferably from 25 to 250 Mrads. The temperature of the reaction conditions ranges from 25 to 200 C and preferably at or slightly above the glass transition temperature of the polymer. The crosslinked polymers are generally more resistant to degradation at elevated temperatures such as greater than 150 C, have a reduced tendency to creep under load, and show no significant embrittlement of parts fabricated from the polymers.

Bell, Vernon L.↗
NASA NTRS1993

Polyimides containing the cyclobutene-3,4-dione moiety

In the present invention, linear aromatic polyimides containing the cyclobutene-3,4-dione moiety were produced from the reaction of a substituted or unsubstituted 1,2-bis(4-aminoanilino) cyclobutene-3,4-dione (SQDA) with various aromatic dianhydrides. These polymers had high molecular weights and their glass transition temperatures (Tgs) were greater than 500 C. Despite the very high Tg, these polymers exhibited excellent adhesion to glass. In addition, the films of these polyimides increased in flexibility with increasing cure temperatures. The novelty of this invention lies in the linear aromatic polyimide containing the cyclobutene-3,4-dione moiety. The presence of this moiety causes such changes in properties as Tgs greater than 500 C, excellent adhesion to glass, and increased flexibility with increasing cure temperatures.

St.clair, Terry L.↗
NASA NTRS1992

Sol-gel synthesis and densification of aluminoborosilicate powders. Part 2: Densification

Aluminoborosilicate (ABS) powders, high in alumina content, were synthesized by the sol-gel process utilizing four different methods of synthesis. The effect of these methods on the densification behavior of ABS powder compacts was studied. Five regions of shrinkage in the temperature range 25-1184 C were identified. In these regions, the greatest shrinkage occurred between the gel-to-glass transition temperature (T sub g approximately equal to 835 C) and the crystallization transformation temperature (T sub t approximately equal 900 C). The dominant mechanism of densification in this range was found to be viscous sintering. ABS powders were amorphous to x-rays up to T sub t at which a multiphasic structure crystallized. No 2Al2O3.B2O3 was found in these powders as predicted in the phase diagram. Above T sub t, densification was the result of competing mechanisms including grain growth and boria fluxed viscous sintering. Apparent activation energies for densification in each region varied according to the method of synthesis.

Bull, Jeffrey↗
NASA NTRS1990

Dynamic mechanical analysis of polymeric materials

Polymeric materials exhibit mechanical behavior which is dependent on temperature. Dynamic mechanical analysis measures the mechanical damping and resonant frequency of a material over a temperature range. Values of the dynamic loss modulus, storage modulus, and loss tangent can be calculated from these data. The glass transition temperature and onset temperature are obtained from curves of the dynamic moduli versus temperature.

Kern, Kristen T.↗
DOE OSTI2021

Bulk Glassy GeTe 2 : A Missing Member of the Tetrahedral GeX 2 Family and a Precursor for the Next Generation of Phase-Change Materials

Vitreous germanium disulfide GeS 2 and diselenide GeSe 2 belong to canonical chalcogenide glasses extensively studied over the past half century. Their high-temperature orthorhombic polymorphs are congruently melting compounds, and the tetrahedral crystal and glass structure is largely preserved in the melt. In contrast, the ditelluride counterpart is absent in the Ge-Te phase diagram, which shows only a single compound, monotelluride GeTe. Phase-change materials based on GeTe have become a technologically important class of solids, and their structure and properties are also widely studied. Surprisingly, very scarce information is available for alloys having GeTe 2 stoichiometry. Using a fast quenching procedure in silica capillaries, high-energy X-ray diffraction, and Raman spectroscopy supported by first-principles simulations, we show that bulk glassy GeTe 2 differs substantially from the lighter GeX 2 members, revealing 46% of trigonal germanium, 31% of three-fold coordinated tellurium, and only 20% of edge-sharing tetrahedra or pyramids. The fraction of homopolar Ge-Ge bonds is low; however, the population of dominant Te-Te dimers and Te n oligomers, n <= 10, appears to be significant. The complex structural and chemical topology of g-GeTe 2 is directly related to the thermodynamic metastability of germanium ditelluride, schematically represented by the following reaction: GeTe 2 $\rightleftarrows$ GeTe + Te. Disproportionation is complete above liquidus in the temperature range of semiconductor-metal transition, and the dense metallic GeTe 2 liquid, mostly consisting of five-fold coordinated Ge species, exhibits high fluidity, strong fragility (m = 99 ± 5), and presumably a fast structural transformation rate combined with low atomic mobility in the vicinity of the glass transition temperature, favorable for reliable long-term data retention in nonvolatile memories. The observed and predicted characteristic features make GeTe 2 a promising precursor for the next generation of phase-change materials, especially coupled with additional metal doping, depolymerizing the tetrahedral interconnected glass network and accelerating (sub)nanosecond crystallization.

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

Generic Behavior of Ultrastability and Anisotropic Molecular Packing in Codeposited Organic Semiconductor Glass Mixtures

Vapor-deposited glass mixtures of organic semiconductors commonly serve as active layers in organic electronic devices, whose lifetime and performance are strongly influenced by the stability and structure of these mixed glasses. Here, we study the stability and anisotropic molecular packing of six co-deposited organic semiconductor glass mixtures with 50:50 weight ratio, by differential scanning calorimetry and spectroscopic ellipsometry. We also find that all six binary systems exhibit high kinetic stability and significantly reduced enthalpy relative to the corresponding liquid-cooled glassy mixtures (ultrastable behavior), even for systems where the glass transition temperatures of the components differ by more than 90 K. Furthermore, we demonstrate that the birefringence of a co-deposited glass mixture, a measure of its anisotropic packing, can be predicted from the birefringence of glasses of the two pure components. These results for stability and structure are expected to be applicable to other co-deposited organic semiconductor glass mixtures, so long as the two components mix well in the glass and individually can form ultrastable glasses. Therefore, our findings are significant for designing novel electronic devices with enhanced device lifetime and increased operational efficiency.

36 MATERIALS SCIENCE↗
NASA NTRS2003

Thermal Contributions to the Degradation of Ground Laboratory and Space Irradiated Teflon

The aluminized Teflon fluorinated ethylene propylene outer most layer of the multilayer insulation blankets on the Hubble Space Telescope has become embrittled resulting in severe on-orbit cracking. During the second servicing mission, a piece of aluminized fluorinated ethylene propylene was retrieved that had curled, exposing the back-surface aluminum to space. This extremely embrittled piece reached 200 C on-orbit, 150 C higher than the nominal temperature extreme. Therefore, experiments have been conducted to determine the effect of heating on the degradation of fluorinated ethylene propylene that has been irradiated in a ground laboratory facility or in space on Hubble Space Telescope. Samples of pristine, x-ray irradiated and Hubble Space Telescope retrieved fluorinated ethylene propylene were heat treated from 50 to 200 C at 25 C intervals in a high vacuum facility and tensile tested. Density measurements were also obtained. Results indicate that heating does not embrittle non-irradiated Teflon. However, there is a significant dependence of the embrittlement of irradiated Teflon on heating temperature, with near complete loss of elongation at 100 C and higher. Rate of degradation changes, which were consistent with the glass transition temperature for fluorinated ethylene propylene, were present in the data. The results support chain scission as the primary mechanism of degradation of fluorinated ethylene propylene on Hubble Space Telescope, and indicate the significance of the on-orbit temperature of fluorinated ethylene propylene with respect to its degradation in the space environment.

deGroh, Kim K.↗
DOE OSTI2022

Dynamic heterogeneity and nanophase separation in rubber-toughened amine-cured highly cross-linked polymer networks

Solid state nuclear magnetic resonance (NMR) spectroscopy and small-to wide-angle X-ray scattering (SWAXS) methods were used to characterize the heterogeneous dynamics and polymer domain structure in rubber modified thermoset materials containing the diglycidyl ether of bisphenol A (DGEBA) epoxy resin and a mixture of Jeffamine reactive rubber and 4,4-diaminodicyclohexylmethane (PACM) amine curing agent. The polymer chain dynamics and morphologies as a function of the PACM/Jeffamine ratio were determined. Using dipolar-filtered NMR experiments, the resulting networks are shown to be composed of mobile and rigid regions that are separated on nanometer length scales, along with a dynamically immobilized interface region. Proton NMR spin diffusion experiments measured the dimensions of the mobile phase to range between 9 and 66 nm and varied with the relative PACM concentration. Solid state 13 C magic angle spinning NMR experiments show that the highly mobile phase is composed entirely of the dynamically flexible polyether chains of the Jeffamine rubber, the immobilized interface region is a mixture of DGEBA, PACM, and the Jeffamine rubber, with the PACM cross-linked to DGEBA predominantly residing in the rigid phase. The SWAXS results showed compositional nanophase separation spanning the 11–77 nm range. These measurements of the nanoscale compositional and dynamic heterogeneity provide molecular level insight into the very broad and controllable glass transition temperature distributions observed for these highly cross-linked polymer networks.

36 MATERIALS SCIENCE↗
DOE OSTI2021

High-Temperature-Performance Cyanate Ester Composites with Carboranes

Cyanate ester (CE) is an important class of materials among high-temperature performance thermosets. It is used in aerospace launch vehicles, heat sinks, booms, and trusses of satellites etc. due to its high glass transition temperatures (>220°C), excellent thermal stability, and low flammability. Current approaches to improve the thermal stability of CE include incorporation of siloxanes or phosphorus- based flame retardants (PFRs). In this work, we have explored boron-based hydroxy (PD) and epoxy (EP) functionalized carborane additives to improve the thermal properties of CE. Carborane fillers were solvent blended at various mass loadings in the resin and cured to study their effect on thermal properties. PD and EP carboranes react with CE to form iminocarbonate and oxazolidinone linkages respectively. Cure kinetics studies at different wt% loadings explained that carboranes catalyze the curing reaction by reducing curing activation energy by about 54% and 26% for 10 wt% loadings of PD and EP carboranes respectively. In addition, carborane-filled cyanate ester (CE) nanocomposites demonstrate an exceptionally high thermal stability as compared to the pristine resin in air and inert environment. Our thermogravimetric analysis (TGA) experiments show that the ultimate char yield of the resin can be increased from 0% to as high as 76% and 82% with 30 wt% PD and EP carborane loading respectively at 1000 °C in air. The initial degradation temperature T d;5 of the composites decreased with increasing carborane loadings in both air and argon. For instance, T d;5 for CE was 465 and 471.6 °C in argon and air while that for P20 was 437.4 and 452.1 °C. Modulated TGA studies gave evidence of the effect of carboranes on degradation kinetics and the mechanism of the resin in air and inert environment. The effect of bonding between carboranes and CE at various loadings on the thermal expansion of the matrix was also studied using Thermomechanical Analyzer (TMA). PD carborane reduced the T g for P20 to about 225 °C while CE had T g >350 °C.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS2004

High Temperature Transfer Molding Resins: Preliminary Composite Properties of PETI-375

As part of an ongoing effort to develop materials for resin transfer molding (RTM) of high performance/high temperature composites, a new phenylethynyl containing imide designated as PETI-375 has been under evaluation. PETI-375 was prepared using 2,3,3 ,4 - biphenyltetracarboxylic dianhydride (a-BPDA), 1,3-bis(4-aminophenoxy)benzene and 2,2 - bis(trifluoromethyl)benzidine and endcapped with 4-phenylethynylphthalic anhydride. This material exhibited a stable melt viscosity of 0.1-0.4 Pa sec at 280 C. High quality, void-free laminates were fabricated by high temperature RTM using unsized T-650 carbon fabric and evaluated. After curing for 1 hour at 371 C, the laminates exhibited a glass transition temperature of approx. 375 C by thermomechanical analysis. The laminates were essentially void and microcrack free as evidenced by optical microscopic examination. The chemistry, physical, and composite properties of PETI-375 will be discussed.

Connell, J. W.↗
NASA NTRS2024

Dynamic Mechanical Analysis of Post-Cured Bismaleimide Resins for Composite-Overwrapped Combustion Chambers Cycled From Cryogenic to High Temperatures

In support of the Rapid Analysis and Manufacturing Propulsion Technology (RAMPT) project, samples made of polybismaleimide (BMI) resin were made and tested under cryogenic conditions. Neat resin samples were tested for multiple cycles, from high temperature (300°C) to cryogenic temperature (-150°C), to replicate the conditions a rocket engine assembly would experience in a test campaign and in operation. To increase the glass transition temperature (and thus mechanical stability), samples were exposed to different post-cure temperatures and were tested using a dynamic mechanical analysis (DMA) instrument. Consistent with expectations, the BMI samples post-cured at higher temperatures generally resulted in higher storage modulus under high temperature test conditions but at the expense of storage modulus values at low temperature test conditions.

Christopher Stelter↗
DOE OSTI2023

Neutron scattering study of fluctuating and static spin correlations in the anisotropic spin glass Fe 2 Ti O 5

The anisotropic spin-glass transition, in which spin freezing is observed only along the c axis in pseudobrookite Fe 2 TiO 5 , has long been perplexing because the Fe 3+ moments (d 5 ) are expected to be isotropic. Recently, neutron diffraction demonstrated that surfboard-shaped antiferromagnetic nanoregions coalesce above the glass transition temperature T g ≈55K, and a model was proposed in which the freezing of the surfboard magnetization fluctuations leads to the anisotropic spin-glass state. Given this model, we have carried out high-resolution inelastic neutron scattering measurements of the spin-spin correlations to understand the temperature dependence of the intrasurfboard spin dynamics on neutron (picosecond) timescales. Here, in this paper, we report on the temperature-dependence of the spin fluctuations measured from single-crystal Fe 2 TiO 5 . Strong quasi-elastic magnetic scattering, arising from intrasurfboard correlations, is observed well above T g . The spin fluctuations possess a steep energy–wave vector relation and are indicative of strong exchange interactions, consistent with the large Curie-Weiss temperature. As the temperature approaches T g from above, a shift in spectral weight from inelastic to elastic scattering is observed. At various temperatures between 4 and 300 K, a characteristic relaxation rate of the fluctuations is determined. Despite the freezing of most of the spin correlations, an inelastic contribution remains even at base temperature, signifying the presence of fluctuating intrasurfboard spin correlations to at least T/T g ≈0.1 , consistent with an energy landscape that is a hybrid between conventional and geometrically frustrated spin glasses.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
NASA NTRS1985

Bulk Formation of Metallic Glasses and Amorphous Silicon from the Melt

By using metallic glass compositions with a high relative glass transition temperature, such as Pd40Ni40P20, homogeneous nucleation also becomes negligible. Large (5g) masses of this alloys were obtained using a molten B2O3 flux. Presently, bulk glass formation in iron based glasses is being investigated. It is expected that if an undercooling of about 250K can be achieved in a Ge or Si melt, formation of the amorphous semiconductor phase (rather than the crystal) may be kinetically favored. The volumetric behavior of undercooled liquid Ga droplet dispersion is investigated by dilatometry. A theoretical model (both analytical and numerical) was developed for transient nucleation in glass forming melts. The model, originally designed for isothermal conditions, was extended to continuous quenching. It is being applied to glass formation in various metallic and oxide systems. A further refinement will be the inclusion of diffusion controlled interfacial rearrangements governing the growth of the crystal embryos.

Spaepen, F.↗
DOE OSTI2025

Medium-Range Order, Density Fluctuations, and Activated Relaxation in the Equilibrated Deep Glass Regime

A successful microscopic theory of activated relaxation in metastable supercooled liquids is extended to the equilibrated deep glass regime. Surprisingly, the predicted power-law scaling connections of the dynamic barrier with diverse scalar order parameters (medium-range order correlation length, dimensionless compressibility, shear modulus) remain unchanged up to astronomically long timescales, despite a fundamental crossover of equilibrium thermodynamics and structure near the laboratory kinetic vitrification point. Quantitative tests against experiments on aged to equilibrium glass-forming liquids up to nearly 20 decades in time scale reveal good agreement. This conflicts with the idea of a crossover from super-Arrhenius to literal Arrhenius relaxation around the laboratory glass transition temperature, and supports the robustness of the theoretical idea that ultraslow dynamics is causally related to medium-range structural order. Here, new avenues of experimental and theoretical research in the deep glass regime are suggested.

Amorphous materials↗
NASA NTRS1973

Characterization of Adhesives for Attaching Reusable Surface Insulation on Space Shuttle Vehicles

An extensive development and testing program on adhesive systems shows that: (1) A closed cell silicone rubber sponge bonded to substrates with thin bond lines of glass filled adhesive exhibits density and modulus values approximately one third that of solid silicone adhesives; (2) utilization of glass or phenolic microballoons as fillers in silicone adhesives reduces density but increases moduli of the vulcanized materials; (3) the silicone elastomer based adhesives appear to be complex systems rather than homogeneous, isotropic materials. Tensile, shear, and compression properties plotted versus temperature verify this conjecture; and (4) constant strain-stress relaxation tests on glass-filled adhesive show that stress relaxation is most pronounced near the glass transition temperature.

Owen, H. P.↗