Browsing by Subject "Physical aging"
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Item Carbon dioxide plasticization and conditioning of thin glassy polymer films monitored by gas permeability and optical methods(2012-05) Horn, Norman Randall; Paul, Donald R.; Freeman, Benny; Biewlawski, Chris; Ellison, Christopher J.; Sanchez, IsaacThis research project investigated physical aging and carbon dioxide plasticization behavior of glassy polymer films. Recent studies have shown that thin glassy polymer films undergo physical aging more rapidly than thick films. This suggests that thickness may also play a role in the plasticization and conditioning responses of thin glassy films in the presence of highly-sorbing penetrants such as CO₂. The effect of film thickness on CO₂ permeation and sorption was studied extensively through carefully defined and controlled methods that provide a basis for future study of plasticization behavior. Thin films are found to be more sensitive than thick films to CO₂ exposure, undergoing more extensive and rapid plasticization at any pressure. The response of glassy polymers films to CO₂ is not only dependent on thickness, but also on aging time, CO₂ pressure, exposure time, and prior history. Thin films experiencing constant CO₂ exposure for longer periods of time exhibit an initial large increase in CO₂ permeability, which eventually reaches a maximum, followed by a significant decrease in permeability for the duration of the experiment. Thick films, in contrast, do not seem to exhibit this trend for the range of conditions explored. For a series of different polymers, the extent of plasticization response tracks with CO₂ solubility. There is little data available for gas sorption in thin glassy polymer films. In this work, a novel method involving spectroscopic ellipsometry is used to obtain simultaneously the film thickness and CO₂ sorption capacity for thin glassy polymer films. This allows a more comprehensive look at CO₂ permeability, sorption, and diffusivity as a function of both CO₂ pressure and exposure time. Like the gas permeation data, these experiments suggest that thin film sorption behavior is substantially different than that of thick film counterparts. Dynamic ellipsometry experiments show that refractive index minima, fractional free volume maxima, and CO₂ diffusivity maxima correlate well with observed CO₂ permeability maxima observed for thin Matrimid® films. These experiments demonstrate that plasticization and physical aging are competing processes. Aging, however, dominates over long time scales. Over time, CO₂ diffusivity is most affected by these competing effects, and the evolution of CO₂ diffusivity is shown to be the main contributing factor to changes in CO₂ permeability at constant pressure.Item Effects of elevated temperature on the physical aging and gas transport of sub-micron polybenzimidazole gas separation membranes(2020-07-16) Merrick, Melanie Mae; Freeman, B. D. (Benny D.); Paul, Donald R; Sanchez, Isaac C; Riffle, Judy S; Lynd, Nathaniel AThe promising potential of polybenzimidazole (PBI) membranes for high temperature (~200 °C), hydrogen-selective gas separations has been reported for many membrane geometries (e.g., bulk, composite, and hollow fiber), but never for sub-micron, spin-cast membranes. Numerous studies have shown that the performance of spin-cast membranes, which simulate commercially relevant thicknesses, declines more quickly with time than that of thick membranes due to accelerated physical aging. However, because most existing membranes are used near ambient temperature, the physical aging of sub-micron, spin-cast membranes has never been studied at temperatures above 55 °C. Because physical aging is dependent on both thickness and temperature, emerging high temperature membrane applications make it both intellectually and practically imperative to characterize spin-cast membranes in this new temperature regime. For the first time, physical aging studies of spin-cast, sub-micron membranes have been extended to elevated temperatures. PBI membranes, cast from commercial-grade Celazole®, were aged in a high-temperature permeation system while the gas permeabilities were periodically measured over more than 1500 hours. When aging at 190 °C, membrane gas permeabilities decreased rapidly then plateaued after 300 hours of aging. The observation of a plateau (i.e., equilibration) had never before been seen for a membrane, nor, to our knowledge, for any polymer ~250 °C below its glass transition temperature. Decreases in membrane permeability were accompanied by increases in selectivity for H₂, which are traditionally represented by Robeson upper bound plots. These shifts were consistent with previous membrane physical aging studies and indicate membrane size-sieving ability improves with aging. Celazole®’s permeability reductions at lower aging temperatures (e.g., 175 °C) were qualitatively similar to those at 190 °C, but occurred over a longer time period. When graphed vs. the logarithm of aging time, the permeability reductions at various temperatures could be superimposed via time-temperature superposition, which is a hallmark of physical aging. A thorough review of physical aging studies in the polymer physics literature is presented to give context for this unexpectedly short equilibration time far below the glass transition. Comparisons are then made between the current study and previous aging studies in the polymer physics field. Overall, the observation of a plateau at short aging times for a polymer deep in the glassy state casts doubt on our understanding of physical aging’s temperature-dependence and our ability to predict membranes’ long-term stability in elevated temperature applications.Item Evaluation of transport and transport stability in glassy polymer membranes(2014-05) Czenkusch, Katrina Marie; Paul, Donald R.; Freeman, B. D. (Benny D.); Sanchez, Isaac C; Ellison, Christopher J; Li, WeiBoth novel membrane materials with better separation characteristics and a better fundamental understanding of membrane transport stability are needed to improve the competitiveness of commercial membrane separations. In this work, the effect of a novel moiety, hexafluoroalcohol, on the gas transport properties of an aromatic polyimide membrane are evaluated. The hexafluoroalcohol group increases the membrane’s fractional free volume, which increases the membrane’s permeability to all gases. Additionally, the HFA-containing polyimide shows resistance to plasticization by carbon dioxide. However, ideal selectivity for several gas pairs is unchanged by the inclusion of hexafluoroalcohol and the increase in the polymer’s fractional free volume. This lack of selectivity loss with increasing free volume is attributed to hydrogen bonding between the hexafluoroalcohol and imide groups, which reduces chain mobility. The ethanol dehydration characteristics of a so-called “TR” polymer are also evaluated in this work. TR polymers are heterocyclic, aromatic polymers synthesized by a solid-state, high temperature condensation from ortho-functional polyimides. Pervaporation studies on a representative TR polymer film demonstrate that the material has separation properties that exceed those of a commercial ethanol dehydration membrane. The transport properties of the TR film, combined with high thermal and chemical stability characteristic of these materials, make TR polymers promising materials for high-temperature, high-water content ethanol dehydration. Finally, the physical aging and plasticization of cellulose triacetate, the dominant natural gas purification membrane, is presented. Although this material has been used industrially for over 30 years, the physical aging and plasticization of the material, particularly in sub-micron films, has never been studied. Although cellulose triacetate does show physical aging behavior, as observed by permeability decreases over time, cellulose triacetate thin films do not show accelerated aging. Furthermore, the plasticization of thin cellulose triacetate films is reduced, rather than increased as seen in other polymers. The unusual transport stability of thin cellulose triacetate films may be due to their complex, semi-crystalline morphology, which, due to the thermal instability of the material, may not be thermally controlled.Item Physical aging of glassy polymers in confined environments(2012-12) Murphy, Thomas Matthew; Paul, Donald R.; Freeman, B. D. (Benny D.); Ellison, Christopher J; Vanden Bout, David A; Sanchez, Isaac CThis research project investigated the physical aging of glassy polymers in confined environments. Many recent studies of aging in glassy polymers have observed that aging behavior is often strongly affected by confinement. Understanding aging in confined environments (e.g., thin polymer films and nanocomposites) is vital for predicting long-term performance in applications that use confined glassy polymers, such as gas separation membranes and advanced nanocomposite materials. Aging in bulk and layered films produced via layer-multiplying co-extrusion was studied using gas permeability measurement and differential scanning calorimetry (DSC). The layered films consisted of polysulfone (PSF) and a rubbery co-layering material, with PSF layers ranging in thickness from ~185 nm to ~400 nm. Gas permeation aging studies at 35 °C revealed that the PSF layers in layered films aged in a manner that was similar to bulk PSF and independent of layer thickness. This finding differs from what was observed previously in freestanding PSF films, in which aging depended strongly on thickness and was accelerated relative to bulk. Isothermal aging studies at 170 °C and cooling rate studies were performed on both bulk and layered samples using DSC. The aging of the PSF layers was similar to aging in bulk PSF for films having PSF layer thicknesses of ~640 nm and ~260 nm, while the film with 185 nm PSF layers showed a slightly higher aging rate than that of bulk PSF. The results of the DSC studies generally support the conclusions of our gas permeation aging studies. The absence of strong thickness dependence in aging studies of layered films tends to support the idea that the effect of film thickness on physical aging stems from interfacial characteristics and not merely thickness per se. The physical aging of thin polystyrene (PS) films at 35 °C was also investigated using gas permeation techniques. PS films of 400 nm and 800 nm did not exhibit aging behavior that was highly accelerated relative to bulk or strongly dependent on film thickness. At the thicknesses and aging temperature considered, the aging of PS shows much weaker thickness dependence than that seen in polymers like PSF and Matrimid.Item Physical aging of thin and ultrathin glassy polymer films(2010-05) Rowe, Brandon William; Paul, Donald R.; Freeman, B. D. (Benny D.); Ganesan, Venkat; Eldridge, R B.; Kulkarni, SudhirThis research effort investigated the influence of confinement on the physical aging behavior of thin and ultrathin glassy polymer membranes. Membrane permeability changes with time due to physical aging, and for reasons not completely understood, the rate of permeability change can become orders of magnitude faster in films thinner than one micron. Special experimental techniques were developed to enable the study of free standing, ultrathin glassy polymer films using gas permeability measurements. The gas transport properties and physical aging behavior of free-standing glassy polysulfone (PSF) and Matrimid® films from 18-550 nm thick are presented. Physical aging persists in glassy films approaching the length scale of individual polymer coils. The membranes exhibited significant reductions in gas permeability and increases in selectivity with aging time. Additionally, the influence of physical aging on the free volume profile in thin PSF films was investigated using variable energy positron annihilation lifetimespectroscopy (PALS). The films exhibited decreasing o-Ps lifetime during physical aging, while o-Ps intensity remained constant. The o-Ps lifetime was reduced at lower implantation energies, indicating smaller free volume elements near the film surface. Thin films aged dramatically faster than bulk PSF and the PALS results agree favorably to behavior tracked by gas permeability measurements. The physical aging behavior of ultrathin films with different previous histories was also studied. The state of these materials was modulated by various conditioning treatments. Regardless of the previous history, the nature of the aging response was consistent with the aging behavior of an untreated film that was freshly quenched from above Tg, i.e., permeability decreased and pure gas selectivity increased with aging time. However, the extent of aging-induced changes in transport properties of these materials depended strongly on previous history. The properties of these ultrathin films deviate dramatically from bulk behavior, and the nature of these deviations is consistent with enhanced mobility and reduced Tg in ultrathin films, which allows them to reach a lower free volume state more quickly than bulk material. The Struik physical aging model was extended to account for the influence of film thickness on aging, and was shown to accurately describe the experimental data.