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At least 73 records · Page 4
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

The structure of CaO–MgO–Al 2 O 3 –SiO 2 melts and glasses doped with FeO X –NiO

Neutron and x-ray diffraction measurements have been performed on CaO–MgO–Al 2 O 3 –SiO 2 (CMAS) glasses doped with NiO–Fe X O at room temperature, along with x-ray measurements on aerodynamically levitated liquids at ≥2000 K. The disordered structures have been modeled using empirical potential structure refinement to investigate the relation between the aluminosilicate network and the modifying cations. The SiO 4 and AlO 4 tetrahedra are found to have wider Si–O and Al–O bond distance distributions in the glass, and the first Ca–O n coordination shell is highly distorted, redistributing different populations of long and short bonds between the liquid and the glass. The addition of Fe and Ni at low aluminosilicate content increases the number of free oxygens not bonded to AlO 4 or SiO 4 . Mg–O and Fe–O are both found to be predominantly fourfold and fivefold in the liquid and glassy states. Despite these low coordination numbers, their bond angle distributions indicate that they are predominantly in nontetrahedral-type geometries, with ferrous and ferric iron possessing similar coordination environments. The Ca–O and Mg–O average coordination numbers and enthalpies of solution are consistent with their higher reactivity within relatively acidic aluminosilicate melts.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Rational sub-nanometer manipulation of polymer morphology for efficient chemical separations

The ability to control polymer morphology on the sub-nanometer length scale has broad implications for chemical separations. To achieve such control on easily processable systems, this proposal focuses on the synthesis and characterization of polymers containing appended labile moieties that are easily detached by thermolysis or UV irradiation deep within the glassy state. Once liberated, these moieties can diffuse from the polymer matrix as gaseous products, leaving behind templated pathways for selective diffusion and sorption of small molecules. With a specific target of creating polymeric membrane materials with unprecedented diffusion and (ad)sorption characteristics for chemical separations, synthesis of new materials will be complemented with advanced metrologies, simulations, and evaluation of thermodynamic and transport theory.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1974

Experiments leading to the production of new glasses in space

A number of oxide compositions were prepared as ceramic rods which were melted in a CO2 laser beam while spinning. The molten droplets which were spun off the rods were allowed to free-fall cool. Many of the compositions selected were obtained as glasses of never-before-reported composition. It can be concluded that it is possible to obtain spherules of glasses from oxide compositions that have never before been obtained in the 'glassy state.' These initial experiments encourage future attempts to prepare larger sized glass boules by containerless melting and cooling in space or in appropriately simulated space.

Happe, R. A.↗
NASA NTRS1976

The anomalous thermal properties of glasses at low temperatures

While experimentally there is great regularity below 1 deg K in the behavior of a particular thermal property for all amorphous dielectrics it is not understood why these properties should differ from those of crystalline dielectrics, since it would seem that at low temperatures long-wavelength elastic waves, similar in both cases, would determine the thermal properties. A model involving systems having very few levels is used in the present study, although the relation between the model's systems and the nature of the glassy state is not known. It is shown, among other effects, that: specific heat measurements above 0.1 K indicate a distribution of local modes independent of energy; ultrasonic velocity measurements give information about phonon-local mode coupling parameters; and thermal expansion and far infrared experiments indicate a phonon-assisted tunneling model.

Pohl, R. O.↗
NASA NTRS1977

Glass transitions in lubricants - Its relation to elastohydrodynamic lubrication /EHD/

A preliminary investigation into the possible role of glass transition and glassy state behavior of lubricants in EHD contacts is reported. Measurements of the glass transition of lubricants as a function of pressure by two methods are presented along with a discussion indicating possible implications of the results to EHD lubrication.

Alsaad, M.↗
NASA NTRS1978

The formation kinetics of lunar glasses

The kinetic treatment of crystallization and glass formation, involving the construction of time-temperature-transformation curves (TTT) corresponding to a given degree of crystallinity, is extended to permit the description of crystallization of a body initially cooled to a glassy state. The key assumption is that if at any time and temperature a crystallite is smaller than the critical size corresponding to that temperature, it will melt completely and can be ignored in any further calculations of the crystal distribution. This approach is used to predict the temperature of maximum crystallization rate for the matrix composition of lunar breccia 67975; results are shown to be in excellent agreement with experiment. Theoretical results obtained for anorthite indicate a barrier to nucleation in the range of 75 kT when the ratio of the undercooling to the liquidus temperature is 0.2. Measured nucleation barriers for the 67975 matrix composition are in the range of 42 to 45 kT.

Uhlmann, D. R.↗
NASA NTRS1981

Long-term influence of physical aging processes in epoxy matrix composites

Selected mechanical properties of (plus or minus 45 degree sub 4s) graphite/epoxy composites were found to be affected by sub T sub g annealing. Postcured specimens of Thornel 300 graphite/Narmco 5208 epoxy were sub T sub G annealed at 413 K (140 C) for ca. 10 to the first through 10 to the fifth powers min., with a prior quenching from above T sub g. The ultimate tensile strength, strain-to-break, and toughness of the composite were found to decrease as a function of sub T sub g annealing time. The time-dependent change in properties can be explained on the basis of physical aging which is related to free volume changes in the non-equilibrium glassy state of network epoxies. The results imply possible changes in composite properties with service time.

Kong, E. S. W.↗
NASA NTRS1981

Sub-T/g/ annealing studies of advanced epoxy-matrix graphite-fiber-reinforced composites

Annealing at temperatures below the glass transition temperature (sub-T/g/ annealing) in structural epoxy network glasses is found to affect long-term mechanical properties of symmetrically (+ or - 45 deg) reinforced 16-lamina graphite/epoxy composites. Post-cured specimens of Thornel 300 graphite/Narmco 5208 epoxy are sub-T(g) annealed at 140 C for about 10, 100, 1000, 10,000, and 100,000 min with a prior quenching above T(g). The ultimate tensile strength, strain-to-break, and static toughness of the composite materials are found to decrease as a function of sub-T(g) annealing time, while no weight loss is observed. Time-dependent changes in properties are explained by a physical aging concept based on free-volume decreases in the nonequilibrium glassy state of network epoxies, and results imply that changes in composite properties may occur with the service time.

Kong, E. S. W.↗
NASA NTRS1982

Crystal nucleation in Pd-Si alloys

A study of the crystal phase nucleation in undercooled droplets of Pd-Si alloys with composition near the Pd(84.5)Si(15.5) eutectic composition is reported. Molten droplets are released at the top of a drop tube and solidify (to either a crystalline or glassy state) during descent. This provides a containerless (and nearly gravity free) environment so that nucleation due to container walls or vibrations is eliminated. It is found that crystallization, due to homogeneous nucleation, is bypassed in droplets of 1 mm diameter when cooled at 760 K/sec. From this an upper limit of the homogeneous nucleation rate is estimated. Results are compared with a previously published study of nucleation in 0.06 mm to 0.33 mm diameter droplets, which indicated that nucleation results from heterogeneous surface nucleation and that the number of these nuclei is dependent on the atmosphere in the drop tube.

Drehman, A. J.↗
NASA NTRS1986

High-temperature oxidation of a rapidly solidified amorphous Ta-Ir alloy

The oxidation products formed at 500 and 700 C on an amorphous Ta-44.5 at. pct Ir alloy in an Ar-0.1 percent O2 gas mixture were characterized using SEM, XRD, EPMA, TEM, STEM, AES, and XPS. Initially, a thin (3-4 nm) layer of Ta2O5 formed at the surface of the alloy. Continued growth of the Ta2O5, which occurred very rapidly, involved diffusion of oxygen anions from the Ta2O5/gas interface to the alloy/Ta2O5 interface, where tantalum was selectively oxidized. Because the oxide grew more quickly than iridium could diffuse back into the alloy, the iridium coalesced into platelets of crystalline iridium-rich alloy that were oriented approximately parallel to the oxide/alloy interface, and which became embedded in a matrix of Ta2O5. The unoxidized core remained in the glassy state. The oxidation process and/or the dissolution of oxygen into the unoxidized alloy caused the alloy to become embrittled.

Cotell, Catherine M.↗
NASA NTRS1989

Superconducting ceramics in the Bi1.5SrCaCu2O sub x system by melt quenching technique

Bi sub 1.5 SrCaCu sub 2 O sub x has been prepared in the glassy state by rapid quenching of the melt. The kinetics of crystallization of various phases in the glass have been evaluated by a variable heating rate differential scanning calorimetry method. The formation various phases on thermal treatments of the glass has been investigated by powder X-ray diffraction and electrical resistivity measurements. Heating at 450 C formed Bi sub 2 Sr sub 2 CuO sub 6, which disappeared on further heating at 765 C, where Bi sub 2 Sr sub 2 CaCu sub 2 O sub 8 formed. Prolonged heating at 845 C resulted in the formation of a small amount of a phase with T sub c onset of approx. 108 K, believed to be Bi sub 2 Sr sub 2 Ca sub 2 Cu sub 3 O sub 10. This specimen showed zero resistivity at 54 K. The glass ceramic approach could offer several advantages in the fabrication of the high-T sub c superconductors in desired practical shapes such as continuous fibers, wires, tapes, etc.

Bansal, Narottam P.↗
NASA NTRS1990

Superconducting Bi(1.5)Pb(0.5)Sr2Ca2Cu3O(x) ceramics by rapid melt quenching and glass crystallization

The preparation of superconducting Bi(1.5)Pb(0.5)Sr2Ca2Cu3O(x) in the glassy state is described, and the results of a study of its crystallization kinetics are presented. The annealing parameters for transforming the glass into a superconductor containing a large fraction of the high-Tc phase were determined. It was found that prolonged annealing (longer than 10 days) in air at 840 C, followed by slow cooling, results in the Tc of 107.2 K and a sharp transition of 2 K.

Bansal, Narottam P.↗
NASA NTRS1992

Glass precursor approach to high-temperature superconductors

The available studies on the synthesis of high T sub c superconductors (HTS) via the glass precursor approach were reviewed. Melts of the Bi-Sr-Ca-Cu-O system as well as those doped with oxides of some other elements (Pb, Al, V, Te, Nb, etc.) could be quenched into glasses which, on further heat treatments under appropriate conditions, crystallized into the superconducting phase(s). The nature of the HTS phase(s) formed depends on the annealing temperature, time, atmosphere, and the cooling rate and also on the glass composition. Long term annealing was needed to obtain a large fraction of the 110 K phase. The high T sub c phase did not crystallize out directly from the glass matrix, but was preceded by the precipitation of other phases. The 110 K HTS was produced at high temperatures by reaction between the phases formed at lower temperatures resulting in multiphase material. The presence of a glass former such as B2O3 was necessary for the Y-Ba-Cu-O melt to form a glass on fast cooling. A discontinuous YBa2Cu3O(7-delta) HTS phase crystallized out on heat treatment of this glass. Attempts to prepare Tl-Ba-Ca-Cu-O system in the glassy state were not successful.

Bansal, Narottam P.↗
NASA NTRS1993

Polymer morphologh

All polymeric materials in their final application are aggregates of many molecules. For linear macromolecules, these aggregates are highly entangled and their macroscopic properties are affected in a little-known way by the interpenetration and entanglements of the molecules. Over the years, we have done occasional investigations of single molecule single crystals and found that there are many unsolved questions about their nucleation, growth, kinetically determined shape, and ultimate path to equilibrium morphology on annealing. This initial work could be extended by a study of the applicability of microgravity methods for the production and study of the formation of single molecule particles. The production of separated molecules of sufficient size to produce phase-like behavior would involve perhaps a spray of solutions containing single molecules, followed by evaporation of the volatiles, or precipitation out of dispersion droplets. Other methods may involve Langmuir films etc., as shown in our prior work. The microgravity environment should enhance the efficiency of any of these methods by avoiding the joining of growing particles by reduction of convection and settling due to density differences. Once produced, the single molecule droplets are to be quenched into the glassy state and analyzed morphologically and thermally. Their shape alone can be used for molecular mass determination (an old problem that suffered from the need to estimate the shape of collapsed (flat) droplets on a surface). Next would be the study of changes of properties as a function of time, temperature, and molecular mass (and distribution) on fusion to macroscopic single phases.

Wunderlich, Bernhard↗
NASA NTRS1996

Free Volume in Glassy Poly(arylene Ether Ketone)s

Amorphous polyarylene ether ketones were examined in the glassy state by positron annihilation lifetime spectroscopy ( PALS ) and in the melt by standard rheological techniques. Specimens were well-characterized fractions of two isomeric structures. PALS clearly shows that the polymer with meta linkages in its backbone contains larger voids (greater than 0.25 nm radius). Thus despite their similar bulk densities, the two materials must pack very differently on a local scale. On the other hand, the free volumes inferred from the WLF treatment of melt viscosity data are practically identical in both materials ca. 4% at T(sub g). The comparison between techniques sheds some light on the distribution of free volume.

Hinkley, J. A.↗
NASA NTRS1997

Structure-Property Relationships of Bismaleimides

The purpose of this research was to control and systematically vary the network topology of bismaleimides through cure temperature and chemistry (addition of various coreactants) and subsequently attempt to determine structure-mechanical property relationships. Characterization of the bismaleimide structures by dielectric, rheological, and thermal analyses, and density measurements was subsequently correlated with mechanical properties such as modulus, yield strength, fracture energy, and stress relaxation. The model material used in this investigation was 4,4'-BismaleiMidodIphenyl methane (BMI). BMI was coreacted with either 4,4'-Methylene Dianiline (MDA), o,o'-diallyl bisphenol A (DABA) from Ciba Geigy, or Diamino Diphenyl Sulfone (DDS). Three cure paths were employed: a low- temperature cure of 140 C where chain extension should predominate, a high-temperature cure of 220 C where both chain extension and crosslinking should occur simultaneously, and a low-temperature (140 C) cure followed immediately by a high-temperature (220 C) cure where the chain extension reaction or amine addition precedes BMI homopolymerization or crosslinking. Samples of cured and postcured PMR-15 were also tested to determine the effects of postcuring on the mechanical properties. The low-temperature cure condition of BMI/MDA exhibited the highest modulus values for a given mole fraction of BMI with the modulus decreasing with decreasing concentration of BMI. The higher elastic modulus is the result of steric hindrance by unreacted BMI molecules in the glassy state. The moduli values for the high- and low/high-temperature cure conditions of BMI/MDA decreased as the amount of diamine increased. All the moduli values mimic the yield strength and density trends. For the high-temperature cure condition, the room- temperature modulus remained constant with decreasing mole fraction of BMT for the BMI/DABA and BMI/DDS systems. Postcuring PMR-15 increases the modulus over that of the cured material even though density values of cured and postcured PMR were essentially the same. Preliminary results of a continuous and intermittent stress relaxation experiment for BMI:MDA in a 2:1 molar ratio indicate that crosslinking is occurring when the sample is in the undeformed state. Computer simulation of properties such as density, glass transition temperature, and modulus for the low- temperature cure conditions of BMI/MDA and BMI/DABA were completed. The computer modeling was used to help further understand and confirm the structure characterization results. The simulations correctly predicted the trends of these properties versus mole fraction BMI and were extended to other BMI/diamine systems.

Tenteris-Noebe, Anita D.↗
NASA NTRS1995

Determination of Quantum Chemistry Based Force Fields for Molecular Dynamics Simulations of Aromatic Polymers

Ab initio quantum chemistry calculations for model molecules can be used to parameterize force fields for molecular dynamics simulations of polymers. Emphasis in our research group is on using quantum chemistry-based force fields for molecular dynamics simulations of organic polymers in the melt and glassy states, but the methodology is applicable to simulations of small molecules, multicomponent systems and solutions. Special attention is paid to deriving reliable descriptions of the non-bonded and electrostatic interactions. Several procedures have been developed for deriving and calibrating these parameters. Our force fields for aromatic polyimide simulations will be described. In this application, the intermolecular interactions are the critical factor in determining many properties of the polymer (including its color).

Jaffe, Richard↗
DOE OSTI2020

Permeation of CO 2 and N 2 through glassy poly(dimethyl phenylene) oxide under steady- and presteady-state conditions

Glassy polymers are often used for gas separations because of their high selectivity. Although the dual-mode permeation model correctly fits their sorption and permeation isotherms, its physical interpretation is disputed, and it does not describe permeation far from steady state, a condition expected when separations involve intermittent renewable energy sources. To develop a more comprehensive permeation model, we combine experiment, molecular dynamics, and multiscale reaction–diffusion modeling to characterize the time-dependent permeation of N 2 and CO 2 through a glassy poly(dimethyl phenylene oxide) membrane, a model system. Simulations of experimental time-dependent permeation data for both gases in the presteady-state and steady-state regimes show that both single- and dual-mode reaction–diffusion models reproduce the experimental observations, and that sorbed gas concentrations lag the external pressure rise. The results point to environment-sensitive diffusion coefficients as a vital characteristic of transport in glassy polymers.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗