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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.
Glass Fibers of Li2O.2SiO2 (LS2) and Li2O.1.6SiO2 (LS1.6) compositions were heated near, but below, the glass transition temperature for different times while subjected to a constant bending stress of about 1.2 GPa. The nucleation density and the crystallization tendency estimated by differential thermal analysis (DTA) of a glass sample in the vicinity of the maximum of the bending stress increased relative to that of stress-free glass fibers. LS2 glass fibers were found more resistant to nucleation and crystallization than the Ls1.6 glass fibers. These results are discussed in regards to shear thinning effects on glass stability.
As part of an ongoing effort to develop materials for resin transfer molding (RTM) processes to fabricate high performance/high temperature composite structures, phenylethynyl containing imides have been under investigation. New phenylethynyl containing imide compositions were prepared using 2,3,3',4'-biphenyltetracarboxylic dianhydride (a-BPDA) and evaluated for cured glass transition temperature (Tg), melt flow behavior, and for processability into flat composite panels via RTM. The a-BPDA imparts a unique combination of properties that are desirable for high temperature transfer molding resins. In comparison to its symmetrical counterpart (i.e. 3,3',4,4'-biphenyltetracarboxylic dianhydride), a-BPDA affords oligomers with lower melt viscosities and when cured, higher Tgs. Several candidates exhibited the appropriate combination of properties such as a low and stable melt viscosity required for RTM processes, high cured Tg, and moderate toughness. The chemistry, physical, and composite properties of select resins will be discussed.
We generalize a microscopic statistical mechanical theory of the activated dynamics of dilute spherical penetrants in glass-forming liquids to study the influence of crosslinking in polymer networks on the penetrant relaxation time and diffusivity over a wide range of temperature and crosslink fraction (f n ). Our calculations are relevant to recent experimental studies of a nm-sized molecule diffusing in poly-(n-butyl methacrylate) networks. The theory predicts the penetrant relaxation time increases exponentially with the glass transition temperature, T g (f n ), which grows roughly linearly with the square root of fn due to the coupling of local hopping to longer-range collective elasticity. Moreover, T g is also found to be proportional to a geometric confinement parameter defined as the ratio of the penetrant diameter to the mean network mesh size. The decoupling ratio of the penetrant and Kuhn segment alpha times displays a complex non-monotonic dependence on f n and temperature that is well collapsed based on the variable T g (f n )/T. A model for the penetrant diffusion constant that combines activated relaxation and entropic mesh confinement is proposed, which results in a significantly stronger suppression of mass transport with degree of effective supercooling than predicted for the penetrant alpha time. Furthermore, this behavior corresponds to a new network-based type of “decoupling” of diffusion and relaxation. In contrast to the diffusion of larger nanoparticles in high temperature rubbery networks, our analysis in the supercooled regime suggests that for the penetrants studied the mesh confinement effects are of secondary importance relative to the consequences of crosslink-induced slowing down of activated hopping of glassy physics origin.
Eutectogels (ETGs) prepared from deep eutectic solvents (DESs), a gelator, and water have many uses in separations, catalysis, and energy storage systems. In these applications, temperature-dependent molecular diffusional properties and intermolecular interactions play a critical role in their function. Diffusional properties of Alexa Fluor 633 and ATTO 647N were measured across a range of temperatures in choline chloride:2glycerol DESs comprised of one molar equivalent of choline chloride and two molar equivalents of glycerol (also known as glyceline) as well as ETGs made from this DES, a xanthan gum gelator, and 10% w/w water or 20% w/w water. Fluorescence recovery after photobleaching (FRAP) was employed to evaluate potential changes in molecular diffusion within DESs and ETGs from 20 to 100 °C. Surprisingly, the ETGs have a larger sample viscosity but also exhibit faster molecular diffusion when compared to the dry DES. This is attributed to macroscopic properties of the ETGs (e.g., pores, three-dimensional structure). The FRAP data also show an irreversible temperature-dependent decrease in the diffusion coefficient of both fluorophores in the ETGs. This is consistent with differential scanning calorimetry data of the ETG, which shows a shift to a more negative glass transition temperature (−36 °C to −47 °C) after the first cooling/heating cycle. Raman data reveal no detectable changes in the intermolecular interactions in either the DESs or ETGs as a function of temperature or water content. Finally, the findings on temperature- and water-dependent diffusional properties of DESs and ETGs provide a foundation for optimizing the use of these materials across various applications, particularly where repeated heating/cooling cycles may be used.
Nanomechanics of individual carbon and boron-nitride nanotubes and their application as reinforcing fibers in polymer composites has been reviewed with interplay of theoretical modeling, computer simulations and experimental observations. The emphasis in this work is on elucidating the multi-length scales of the problems involved, and of different simulation techniques that are needed to address specific characteristics of individual nanotubes and nanotube polymer-matrix interfaces. Classical molecular dynamics simulations are shown to be sufficient to describe the generic behavior such as strength and stiffness modulus but are inadequate to describe elastic limit and nature of plastic buckling at large strength. Quantum molecular dynamics simulations are shown to bring out explicit atomic nature dependent behavior of these nanoscale materials objects that are not accessible either via continuum mechanics based descriptions or through classical molecular dynamics based simulations. As examples, we discus local plastic collapse of carbon nanotubes under axial compression and anisotropic plastic buckling of boron-nitride nanotubes. Dependence of the yield strain on the strain rate is addressed through temperature dependent simulations, a transition-state-theory based model of the strain as a function of strain rate and simulation temperature is presented, and in all cases extensive comparisons are made with experimental observations. Mechanical properties of nanotube-polymer composite materials are simulated with diverse nanotube-polymer interface structures (with van der Waals interaction). The atomistic mechanisms of the interface toughening for optimal load transfer through recycling, high-thermal expansion and diffusion coefficient composite formation above glass transition temperature, and enhancement of Young's modulus on addition of nanotubes to polymer are discussed and compared with experimental observations.
Samples of poly(etheretherketone) (PEEK) neat resin and APC-2 carbon fiber composite were subjected to various heat treatments, and the effect of quenching and annealing treatments was studied by wide-angle X-ray scattering. It is found that high-temperature treatments may introduce disorder into neat resin and composite PEEK when followed by rapid cooling. The disorder is metastable and can revert to ordered state when the material is heated above its glass transition temperature and then cooled slowly. The disorder may result from residual thermal stresses.
The effects of simulated space environmental parameters on microdamage induced by the environment in a series of commercially available graphite-fiber-reinforced composite materials were determined. Composites with both thermoset and thermoplastic resin systems were studied. Low-Earth-Orbit (LEO) exposures were simulated by thermal cycling; geosynchronous-orbit (GEO) exposures were simulated by electron irradiation plus thermal cycling. The thermal cycling temperature range was -250 F to either 200 F or 150 F. The upper limits of the thermal cycles were different to ensure that an individual composite material was not cycled above its glass transition temperature. Material response was characterized through assessment of the induced microcracking and its influence on mechanical property changes at both room temperature and -250 F. Microdamage was induced in both thermoset and thermoplastic advanced composite materials exposed to the simulated LEO environment. However, a 350 F cure single-phase toughened epoxy composite was not damaged during exposure to the LEO environment. The simuated GEO environment produced microdamage in all materials tested.
New polyimides synthesized from reactions of aromatic hexafluoroisopropyl dianhydrides with asymmetric amide diamines. Soluble to extent of at least 10 percent by weight at temperature of about 25 degrees C in common amide solvents such as N-methylpyrrolidone, N,N-dimethylacetamide, and N,N-dimethylformamide. Polyimides form tough, flexible films, coatings, and moldings. Glass-transition temperatures ranged from 300 to 365 degrees C, and crystalline melting temperatures observed between 543 and 603 degrees C. Display excellent physical, chemical, and electrical properties. Useful as adhesives, laminating resins, fibers, coatings for electrical and decorative purposes, films, wire enamels, and molding compounds.
In setting forth its strategic plan, NASA has indicated that low-cost access to space is the key to unleashing the commercial potential of space and greatly expanding space research and exploration. The development of advanced materials will be an enabling technology for this quest for low-cost space access. In this research program, we are attempting to address the need for new advanced materials by developing high-performance nanodispersed inorganic/organic and organic/organic polyimide composites utilizing specific interactions. Our goal is to systematically manipulate these interactions and investigate the resulting processing morphology-property relationships. Specifically, we will investigate three main parameters on these relationships. These include (1) the type of polyimide; (2) the structure of the inorganic nanoparticle being used; and (3) manipulation of the interfacial energy. During the first year of this effort, we have demonstrated the successful synthesis of PMR-15/layered silicate nanocomposites. Morphological studies indicate that exfoliated structures were obtained in most instances, with a mixture of exfoliated and intercalated structures being observed also. Significant enhancements of the onset of decomposition were obtained by varying the strength of the interaction between the nanoparticle and the polymer. Varying the amount of a specific nanoparticle also affected the decomposition temperatures. A slight catalytic effect of the nanoparticles on both the imidization and crosslinking reaction has been observed and will be presented. In addition, incorporation of the nanoparticles was found to increase the glass transition temperature and slightly broaden the breadth of this relaxation.
Two phenylethynyl terminated oligomers designated PETI-298 and PETI-330 were developed at the NASA Langley Research Center and have emerged as leading candidates for composite applications requiring high temperature performance (i.e. greater than or equal to 288 C for 1000 hours) combined with the ability to be readily processed into composites without the use of an autoclave or complex/lengthy cure or post-cure cycle. These high performance/high temperature composites are potentially useful on advanced aerospace vehicles in structural applications and as aircraft engine components such as inlet frames and compressor vanes. The number designation (i.e. 298, 330) refers to the glass transition temperature in degrees Celsius as determined on neat resin cured for 1 hour at 371 C. The resins are processable by non-autoclave techniques such as resin transfer molding (RTM), vacuum assisted RTM (VARTM) and resin infusion (RI). Both resins exhibit low complex melt viscosities (0.1-10 poise) at 280 C and are stable for greater than or equal to 2 hours at this temperature. Typically, the resins are melted, de-gassed and infused or injected at 280 C and subsequently cured at 371 C for 1-2 hours. Virtually no volatiles are evolved during the cure process. The resin synthesis is straightforward and has been scaled-up to 25 kg batches. The chemistry of PETI-298 and PETI-330 and the RTM AS-4 and T-650 carbon fabric laminate properties, and those of BMI-5270 for comparison, are presented.
Tests of weathering and aging behavior are being developed to characterize the degradation and predict the lifetimes of low-cost photovoltaic arrays. Environmental factors which affect array performance include UV radiation, thermal energy, water, oxygen (generally involved in synergistic effects with UV radiation or high temperatures), physical stress, pollutants (oxides of nitrogen, sulfur dioxide and ozone), abrasives and dirt. A survey of photovoltaic array testing has shown the need to establish quantitative correlations between certain measurable properties (carbonyl formation, glass transition temperature, and molecular weight change) and modes of degradation and failure.
One of the greatest obstacles with the fluorozirconate ZBLAN (ZrF4-BaF2-LaF3-AIF3-NaF) is the problem of devitrification. Fluoride glasses have a narrow working range and the viscosity is a strong function of temperature. Rates of nucleation and growth of crystals in the glass depend on the viscosity, making these glasses unstable and prone to crystallization. The viscosity of ZBLAN at the drawing temperature is low, usually between two to five poise, so it is difficult to obtain fibers from their preform melts without crystallization. The preforms usually contain heterogeneous nuclei which grow into microcrystallites above the glass transition temperature, T(g). Since microcrystallites in an optical fiber cause extrinsic light scattering losses of the optical signal, fiber drawing must be completed in a short time to minimize the generation of light scattering centers. To keep these losses to a minimum and to fabricate low scattering loss fibers and other optical components, this research deals with the possibility of minimizing crystallite formation by removing the gravitational influence of solutal segregation of the ZBLAN elements. This report reviews the early work on the KC-135 aircraft, the development of the ZBLAN Rocket Experiment, preparations at the White Sands Missile Range, analysis of the flight and ground test results, lessons learned and future experimentation.
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.
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As part of an effort on high temperature structural resins for aerospace applications, a new family of polyimides containing carbon and ether connecting groups between aromatic rings were prepared. Several of these polyimides were semicrystalline. One polyimide, designated LARC-CPI, with a glass transition temperature of 222 C and a crystalline melt temperature of 350 C, was evaluated in the form of an adhesive, film, and molding. Unoriented films exhibited excellent resistance to solvents and strong bases and high tensile properties. Compact tension specimens gave very high fracture toughness values. Titanium tensile shear specimens provided exceptional strength under a variety of test conditions. The chemistry and the physical and mechanical properties of LARC-CPI are discussed.
Studies were conducted with six different candidate high-temperature neat matrix resin specimens of varied geometric shapes to investigate the mechanisms involved in the thermal degradation of polyimides like PMR-15. The metrics for assessing the quality of these candidates were chosen to be glass transition temperature (T(sub g)), thermo-oxidative stability, dynamic mechanical properties, microstructural changes, and dimensional stability. The processing and mechanical properties were not investigated in the study reported herein. The dimensional changes and surface layer growth were measured and recorded. The data were in agreement with earlier published data. An initial weight increase reaction was observed to be dominating at the lower temperatures. However, at the more elevated temperatures, the weight loss reactions were prevalent and probably masked the weight gain reaction. These data confirmed the findings of the existence of an initial weight gain reaction previously reported. Surface- and core-dependent weight losses were shown to control the polymer degradation at the higher temperatures.
A report describes a proposed automated facility that would be operated in outer space to produce high-quality optical fibers from fluoride-based glasses, free of light-scattering crystallites that form during production in normal Earth gravitation. Before launch, glass preforms would be loaded into a mechanism that would later dispense them. A dispensed preform would be melted, cooled to its glass-transition temperature rapidly enough to prevent crystallization, cooled to ambient temperature, then pushed into a preform tip heater, wherein it would be reheated to the softening temperature. A robotic manipulator would touch a fused silica rod to the softened glass to initiate pulling of a fiber. The robot would pull the fiber to an attachment on a take-up spool, which would thereafter be turned to pull the fiber. The diameter of the fiber would depend on the pulling speed and the viscosity of the glass at the preform tip. Upon depletion of a preform, the robot would place the filled spool in storage and position an empty spool to pull a fiber from a new preform. Pulling would be remotely monitored by a video camera and restarted by remote command if a break in the fiber were observed.