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1.
Lili Cui  D.R. Paul  W.J. Koros 《Polymer》2011,52(24):5528-5537
Membranes made from glassy polymers have been of great interest in the past decade for CO2 removal from natural gas streams; however, strongly soluble gases, such as CO2, can cause “plasticization” of polymer membranes, which greatly reduces the separation efficiency. This work examines the response of several 6FDA-based polyimides thin film membranes with thicknesses around 200 nm to CO2 exposure and physical aging. DABA units are incorporated to create crosslinkable sites for such materials. Introducing DABA units to the 6FDA-DAM and 6FDA-mPDA polymers seems to result in materials even more prone to CO2 plasticization. A unique thermal annealing approach is used to crosslink the polyimides via decarboxylation of the DABA units; the resulting crosslinked polymers appear to be much more plasticization resistant at high CO2 pressures compared to their DABA containing counterparts prior to crosslinking. Prior thermal history plays a significant role in both the physical aging of the thin film membranes and their CO2 plasticization resistance particularly for chemical structures that tend to lead to high free volume and permeability.  相似文献   

2.
This work reports the gas separation performance of several 6FDA-based polyimides with different chemical structures, to correlate chemical structure with gas transport properties with a special focus on CO2 and CH4 transport and plasticization stability of the polyimides membranes relevant to natural gas purification. The consideration of the other gases (He, O2 and N2) provided additional insights regarding effects of backbone structure on detailed penetrant properties. The polyimides studied include 6FDA-DAM, 6FDA-mPDA, 6FDA-DABA, 6FDA-DAM:DABA (3:2), 6FDA-DAM:mPDA (3:2) and 6FDA-mPDA:DABA (3:2). Both pure and binary gas permeation were investigated. The packing density, which is tunable by adjusting monomer type and composition of the various samples, correlated with transport permeability and selectivity. The separation performance of the polyimides for various gas pairs were also plotted for comparison to the upper bound curves, and it was found that this family of materials shows attractive performance. The CO2 plasticization responses for the un-cross-linked polyimides showed good plasticization resistance to CO2/CH4 mixed gas with 10% CO2; however, only the cross-linked polyimides showed good plasticization resistance under aggressive gas feed conditions (CO2/CH4 mixed gas with 50% CO2 or pure CO2). For future work, asymmetric hollow fibers and carbon molecular sieve membranes based on the most attractive members of the family will be considered.  相似文献   

3.
Industrial gas separation membranes have selective dense layers with thicknesses around 100 nm. It has long been assumed that these thin layers have the same properties as thick (bulk) films. However, recent research has shown that thin films with such thickness experience accelerated physical aging relative to bulk films and, thus, their permeation properties can differ significantly from the bulk. Thin films made from Extem® XH 1015, a new commercial polyetherimide, have been investigated by monitoring their gas permeability. The permeability of the thin films is originally greater than the thick films but eventually decreases well below the permeability of the thick film. The CO2 plasticization of Extem thin films is explored using a series of exposure protocols that indicate CO2 plasticization is a function of film thickness, aging time, exposure time, pressure and prior history.  相似文献   

4.
Physical aging of both thick and thin films of “high free-volume” glassy perfluoropolymers was studied by monitoring changes in pure gas permeability of O2, N2 and CH4. All permeability measurements were done at a fixed temperature of 35 °C for more than 1000 h of aging. Two grades of perfluoropolymers, Teflon AF and Hyflon AD, having different comonomer structures but with similar comonomer ratios were studied to understand the effect of comonomer type and content on the aging behavior. The effect of casting process (solution vs. spin coating) and solvent type (vapor pressure and boiling point) had a significant effect on the absolute permeability of both thick and thin films; however, the aging rates were more affected by thickness and solvent type rather than the casting process for similar thicknesses. After 1000 h of aging, the relative permeability for thin films of Teflon AF 2400 was decreased by 27% compared to only 10% for thick films prepared from Novec 7500 solvent. Teflon AF, which has a higher fractional free volume (FFV) than Hyflon AD, is believed to undergo significant aging well before the initial permeability measurement could be made (after ∼ 1 h of aging) and, therefore, Teflon AF materials showed a lower decrease in relative permeability compared to Hyflon AD for the same aging time. The comonomer type and content has a significant effect on the permeability; the initial absolute oxygen permeability for AF 2400 was an order of magnitude higher compared to AD 60. The physical aging of thin films of the various glassy perfluoropolymers was also tracked by recording changes in the refractive index and thickness with time by ellipsometry. The ellipsometry data also confirmed higher aging rates in Hyflon AD compared to Teflon AF materials. The volumetric aging rate, obtained from the change in the refractive index using the Lorentz–Lorenz equation, and the permeability reduction rate from the (P1000h/P1h) ratio showed an excellent linear correlation. The (P1000h/P1h) ratio also showed a stronger correlation with (Tg−35) °C than with FFV.  相似文献   

5.
Thomas M. Murphy 《Polymer》2011,52(26):6117-6125
The physical aging of polymers in confined environments has been an area of intensive study in recent times. The rate of physical aging in thin films of many polymers used in gas separation membranes is dependent on film thickness and accelerated relative to bulk. In this study, the physical aging of polymer films with alternating glassy polysulfone and rubbery polyolefin layers was monitored by measuring the gas permeability of O2 and N2 as a function of aging time at 35 °C. The alternating layer structures were formed by a melt co-extrusion process. The polysulfone layers have thicknesses ranging from 185 to 400 nm, and the overall thicknesses of the films are on the order of 80-120 μm. The aging of freestanding thin films of polysulfone is rapid and exhibits clear thickness dependence, whereas the aging of multilayered films was observed to be similar to bulk and showed no dependence on layer thickness. At 1000 h of aging time, a 400 nm freestanding PSF film decreased in O2 permeability by 35%, whereas on average the bulk and multilayered films only experienced a decline of 10-15%. A slight increase in O2/N2 selectivity for the multilayered films was observed over the course of aging.  相似文献   

6.
Norman R. Horn 《Polymer》2011,52(7):1619-5594
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. In this paper, a carefully designed systematic study explores the effect of thickness on the CO2 plasticization and conditioning phenomena in Matrimid®, a polyimide commonly used in commercial gas separation membranes. 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. Finally, 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.  相似文献   

7.
Membrane-based separations play a key role in energy conservation and reducing greenhouse gas emissions by providing low energy routes for a wide variety of industrially-important separations. For reasons not completely understood, membrane permeability changes with time, due to physical aging, and the rate of permeability change can become orders of magnitude faster in films thinner than one micron. The gas transport properties and physical aging behavior of free-standing glassy polysulfone and Matrimid® films as thin as 18 nm are presented. Physical aging persists in glassy films approaching the length scale of individual polymer coils. The films studied ranged from 18–550 nm thick. They exhibited reductions in gas permeability, some more than 50%, after 1000 h of aging at 35 °C, and increases in selectivity. 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. The Struik physical aging model was extended to account for the influence of film thickness on aging rate, and it was shown to adequately describe the aging data.  相似文献   

8.
J.H. Kim  D.R. Paul 《Polymer》2006,47(9):3094-3103
The effect of molecular structure on the kinetics of physical aging of thin films (∼350 nm) formed from glassy 6FDA-based polyimides was investigated by tracking the changes in gas permeability (He, O2 and N2) at 35 °C for more than 2000 h. The structures studied included homopolymers of 6FDA with 6FpDA and with DAM plus copolymers where a portion of the latter two monomers was replaced with DABA to introduce carboxyl units into the structure for subsequent cross-linking studies. Over this period of aging, the oxygen permeability decreased by a factor of two for the polyimide containing the diamine 6FpDA and by a factor of five for the polyimide containing the diamine DAM. Introduction of DABA units accelerated the aging in the case of 6FpDA and slowed the aging in the case of DAM. Aging rate seems to correlate with the level of free volume of the polymer; the higher the free volume, the faster is the aging. Selectivity for all gas pairs increased upon aging but the rate is not simply explained by free volume alone because the difference in size of the two gas molecules is also reflected in the response to physical aging observed.  相似文献   

9.
Y. Huang 《Polymer》2004,45(25):8377-8393
The physical aging at 35 °C of three glassy polymers, polysulfone, a polyimide and poly(2,6-dimethyl-1,4-phenylene oxide), has been tracked by measurement of the permeation of three gases, O2, N2, and CH4, for over 200 days. Several techniques were used to accurately determine the thickness of films (∼400 nm-62 μm) in order to obtain absolute permeability coefficients and to study the effects of film thickness on the rate of physical aging. Each film was heated above the polymer Tg to set the aging clock to time zero; ellipsometry revealed that this procedure leads to isotropic films having initial characteristics independent of film thickness. A substantial pronounced aging response, attributed to a decrease in polymer free volume, was observed at temperatures more than 150 °C below Tg for thin films of each polymer compared to what is observed for the bulk polymers. The films with thicknesses of approximately 400 nm of the three polymers exhibit an oxygen permeability decrease by as much as two-fold or more and about 14-15% increase in O2/N2 selectivity at an aging time of 1000 h. The results obtained in this study were compared with prior work on thickness dependent aging. The effects of crystallinity on physical aging were examined briefly.  相似文献   

10.
J.H. Kim  D.R. Paul 《Polymer》2006,47(9):3104-3111
The change in refractive index with time for thin films (∼350 nm) formed from glassy 6FDA-based polyimides was monitored by ellipsometry to quantitatively track the physical aging process. The refractive index increased linearly, attributed to the densification of the glassy polyimide, with respect to aging time, on a logarithmic scale; this result is consistent with the decrease in gas permeability during physical aging reported in part I of this series. An excellent correlation was formed between the volumetric aging rate r, computed from the refractive index change by the Lorentz-Lorenz equation, and the permeability reduction rate, ; this relationship depends on the type of gas but appears to be the same for all polymer structures examined. The change in fractional free volume was examined from the refractive index data using parameters determined by group contribution methods. The free volume versus aging time results are well-described by the self-retarding relaxation model of Struik; however, this model does not explain the strong effect of thickness on aging rate. The change in free volume correlates well with the change in gas permeability of these thin films.  相似文献   

11.
Most studies using gas permeation to characterize physical aging in thin polymer films have focused on polymers of interest as membrane materials, such as polysulfone (PSF) and Matrimid. Many other physical aging studies, using techniques other than gas permeation, focus on polystyrene (PS). In this work, physical aging in bulk PS films and PDMS-coated thin PS films was studied using well-established gas permeation techniques. The ~400 nm PS films aged slightly faster than bulk PS. However, the difference between rates of aging in thin and thick films was much less than that reported in PSF and Matrimid films of similar thicknesses. The ~800 nm films aged in a manner generally similar to bulk PS. Comparison of the normalized oxygen permeability of ~400 nm films of PS, PSF, and Matrimid revealed that a ~400 nm PS film experiences a slower decline in relative permeability than a PSF or Matrimid film does. Unlike what has been observed previously in studies of PSF and Matrimid films, PS films do not appear to show aging behavior that is strongly dependent on film thickness or highly accelerated relative to bulk. Because it would be difficult to use the results of PS aging studies to predict the aging behavior of typical gas separation polymers, we suggest that PS is not a good model for the aging behavior of commercially useful gas separation membrane materials.  相似文献   

12.
Norman R. Horn 《Polymer》2011,52(24):5587-5594
We have demonstrated in previous studies that thin glassy polymer films exhibit complex responses to highly sorbing penetrants, such as CO2, relative to their thick film counterparts. In this paper, we apply similar experiments to two new polymers, including a polysulfone made from bisphenol A (PSF), and poly(2,6-dimethyl-1,4-phenylene oxide) (PPO), and compare their responses to Matrimid® to understand better CO2 plasticization behavior of these materials when in thin film form. As expected, the extent of plasticization response tracks with CO2 solubility; CO2 diffusivity may also be an important factor at shorter exposure times. Experiments at longer CO2 exposure times revealed that each polymer experiences the permeability maximum observed in our previous work as well. However, polymers that are not as highly sorbing to CO2, like polysulfone, may not at some conditions exhibit a distinct permeability maximum but will still decrease in permeability after a long period of CO2 exposure owing to physical aging.  相似文献   

13.
Brandon W. Rowe 《Polymer》2010,51(16):3784-6125
The physical aging behavior of thin glassy polysulfone (PSF) films (∼125 nm) with different previous histories was tracked using gas permeability measurements. The initial states of these materials were modulated by thermal annealing at fixed temperatures below the glass transition or by exposure to high pressure (800 psig (56.2 bara)) CO2 for various times. Regardless of the previous history, the nature of the aging response in these samples 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 aging behavior was described using Struik’s aging model by allowing the initial conditions to depend on each sample’s previous history.  相似文献   

14.
The influence of physical aging on the profile of free volume characteristics in thin polysulfone (PSF) films was investigated using variable energy positron annihilation lifetime spectroscopy. The PSF 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 (i.e., in the top ∼50 nm). These near-surface regions of the films age dramatically faster than bulk PSF. The accelerated aging is consistent with the notion of enhanced mobility near the film surface, which allows polymer near the surface to reach a lower free volume state more quickly than the bulk. No influence of the silicon wafer support on aging behavior was detected. Additionally, the impact of CO2 conditioning on physical aging was briefly examined. The results from these studies were compared to aging behavior of ultrathin PSF films tracked by gas permeability measurements, and favorable agreement was found.  相似文献   

15.
Novel polypyrrole (PPy)/polydimethylsiloxane (PDMS) composite membrane was prepared by interfacial polymerization to make a very effective gas separation membrane. We found that Polymerized PPy films as thin as ~200 nm could be chemically synthesized as freestanding membranes by using the interfacial polymerization technique. Additionally, we show that difference morphology of PPys films was obtained by controlling polymerization rate and more dense films were formed at low polymerization rate. Wide X-ray diffraction study showed the d spacing value of the PPy film decreased from 4.89 å to 3.67 å by the rate of polymerization decreases. According to d spacing value decrease, selectivity of a PPy composite membrane was increased dramatically and permeability was reduced gradually. This high selectivity was derived from d spacing closed to the kinetic diameter of nitrogen. These results indicated that the permeability is controlled by the diffusion coefficient, reflecting the packed structure of the PPy film. The highest selectivity value of composite membrane that was prepared by interfacial polymerization was O2/N2=17.2 and permeability for O2 was 40.2 barrer.  相似文献   

16.
Mixed-matrix membranes (MMMs), judiciously combining processability of polymer and remarkable separation performance of nanofillers, have been extensive pursuits for molecular separation process. Permeability matching between filler and polymer is one of the necessary requisites to desirable mixed-matrix effect. Considering the superior molecular sieving effect of UTSA-280 metal-organic frameworks on C2H4 and C2H6, here, we report two types of UTSA-280/6FDA-polyimide MMMs toward C2H4/C2H6 separation. The molecular sieving effect of UTSA-280 endowed 6FDA-DAM:DABA(3:2) membrane with simultaneous improvements in C2H4 permeability and C2H4/C2H6 selectivity. Optimally, when the filler reached 21.80 wt%, C2H4 permeability and C2H4/C2H6 selectivity was increased to 6.49 Barrer (by 15%) and 4.94 (by 32%), respectively. On the contrary, UTSA-280/6FDA-DAM MMMs showed undesirable mixed-matrix effect that C2H4 permeability decreased meanwhile C2H4/C2H6 selectivity nearly kept at polymeric pristine membrane level. It was found that permeability matching between two phases was responsible to these opposite mixed-matrix effects. More specifically, UTSA-280 had a relatively low gas permeability so that it required a less permeable polymeric matrix like 6FDA-DAM:DABA(3:2) to exert its molecular sieving effect. Furthermore, the optimal-matching 6FDA-matrix in permeability with UTSA-280 fillers was predicted by theoretical model. This work not only reports improving C2H4/C2H6 separation performance via mixed-matrix formulation, but also emphasizes the importance of permeability matching between polymer and filler to realize the mixed-matrix effect.  相似文献   

17.
This work reports two series of structurally different aromatic polyimides based on 4,4´-diaminodiphenylmethane (DPM) and 4,4´-diaminotriphenylmethane (TPM) and three commercial dianhydrides. All TPM-based polyimides formed membranes due to their high molecular weight (inherent viscosities ~0.93–1.14 dl/g), they exhibited high thermal stability (5 %: 490–544 °C), glass transition temperatures between 269 and 293 °C, and reasonable mechanical properties. The incorporation of pendant phenyl moieties in the TPM-based polyimides has a strong effect producing an improvement in solubility, thermal stability, density and gas permeability coefficient in comparison with DPM-based polyimides. The most interesting polyimide TPM-6FDA, containing phenyl and trifluoromethyl as bulky pendant groups, showed higher gas permeability coefficient for CO2 (23.73 Barrer) and the best ideal selectivity to the gas pair CO2/CH4 (α = 28.93).  相似文献   

18.
Dense and thin electrolyte films are desirable for solid oxide fuel cells (SOFCs) because of their low gas leakage and low ohmic resistances. This work aims at the preparation of thin dense Gd‐doped ceria (CGO) electrolyte films using a cost‐effective deposition method in ambient atmosphere–electrostatic spray deposition (ESD). The deposition parameters such as deposition temperature, concentration and flow rate of precursor solution were changed systematically to examine their effects on film morphology and hence electrochemical performance. While the film morphology was examined by a scanning electron microscope, the electrochemical performance was revealed by measuring open circuit voltages (OCVs) of NiO‐CGO/CGO/Ba0.5Sr0.5Co0.8Fe0.2O3‐δ (BSCF) cells in 500–700 °C with humidified hydrogen as fuel and air as oxidant. The results show that a CGO film of 25 μm thick obtained at a deposition temperature of 400 °C, a precursor solution flow rate of 6 ml h–1 and a precursor concentration of 0.3 M was dense with very few isolated pores and the OCV of the associated cell was 0.915 V at 500 °C. This implies that the CGO film has negligible gas leakage and ESD is a promising method for preparing thin dense electrolyte films for SOFCs.  相似文献   

19.
Recent studies of physical aging in confined polymer glasses have revealed that aging behavior in confinement often differs from bulk behavior. This study used DSC to characterize physical aging and structural relaxation in bulk polysulfone (PSF) and co-extruded multilayered films of PSF and an olefin block copolymer (OBC) that have average PSF layer thicknesses of 640 nm, 260 nm, and 185 nm. The films were aged isothermally at 170 °C, and the recovered enthalpy upon reheating was measured over time. The films with 640 nm and 260 nm PSF layers had aging rates very similar to that of bulk PSF, while the film with 185 nm PSF layers had an aging rate slightly greater than the bulk value. The cooling rate dependence of the limiting fictive temperature (Tf′) in multilayered and bulk PSF samples was also characterized. Values of Tf′ were similar for all films at each cooling rate. The results of this work are in general agreement with our previous gas permeation aging study of multilayered PSF films aged at 35 °C, in which the effect of layer thickness on aging behavior was minimal. This stands in contrast to studies with thin, freestanding PSF films, which exhibit accelerated aging relative to bulk and have aging rates that depend strongly on film thickness.  相似文献   

20.
An equation based on the segmental/chain mobility in free volume theory was derived to correlate the gas permeation coefficient and the aging time. An accelerated physical aging of a fluoropolyimide was observed and employed to validate this equation. A strong thickness‐dependent aging process was found by employing pure O2 and N2 tests to monitor the change of gas permeation properties as a function of aging time. Experimental results also suggest that chain rigidity and configuration play important roles in physical aging. As a result, the thin 2,2′‐bis(3,4′‐dicarboxyphenyl) hexafluoropropane dianhydride (6FDA) based polyimide films studied here have different permeability versus time relationship from conventional polyarylate in the early stage of aging, and the experimental data seem to fit the proposed equation well. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 1758–1764, 2004  相似文献   

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