Journal of Membrane Science 174 (2000) 177188

Air separation properties of at sheet homogeneous pyrolytic carbon membranes

Anshu Singh-Ghosal1 , W.J. Koros
Department of Chemical Engineering, University of Texas at Austin, Austin, TX 78712, USA Received 12 February 1999; accepted 7 March 2000

Abstract Carbon molecular sieve (CMS) membranes with attractive separation properties were formed by pyrolysis of a polymeric precursor. Defect-free membranes with oxygen/nitrogen permselectivities three times greater than the polymer precursor were obtained. Gas separation properties were also measured at intermediate stages during the pyrolysis protocol to study the evolution of entropic selectivity, which distinguishes molecular sieving materials from typical polymeric materials. Initially, permeabilities increase dramatically during the pyrolysis process due to an increase in overall sorption coefcients. In the nally pyrolyzed membrane, however, permeabilities are three times lower than in the polymer precursor due to signicantly lower oxygen diffusion coefcients. Nevertheless, the separation properties of the pyrolyzed membranes are well above the so-called property upper-bound trade-off curve often used to compare conventional polymeric materials. The increase in permselectivity is entirely due to an increase in mobility selectivity. Entropic selectivity increases are responsible for the higher mobility selectivity in the nally pyrolyzed membranes; however, energetic contributions were more signicant for materials at the intermediate stage. Signicant conclusions about the structure of the evolving molecular matrix can be drawn from the gas separation results. 2000 Elsevier Science B.V. All rights reserved.
Keywords: Carbon molecular sieves; Membrane separations; Pyrolysis; Entropic selectivity; Air separation

1. Introduction Polymers have conventionally been used as materials for solutiondiffusion gas separation membranes with useful separation properties. For non-polar gas mixtures, the separation is based largely on molecular size, and for similar-sized molecules like oxygen and nitrogen, limited permselectivities can be achieved using polymer membrane materials. A previous study
Corresponding author. Tel.: +1-512-471-5238; fax: 1-512-471-7060. 1 Present address: General Electric Co. 1, LEXAN Lane, Mount Vernon, IN 47620, USA.

compared diffusivity selectivities offered by glassy polymeric and molecular sieving materials and identied a term referred to as entropic selectivity [1]. This selectivity arises from the ability of molecular sieving media to selectively reduce the rotational degrees of freedom of nitrogen versus oxygen in the diffusion transition state. The signicant segmental motions present in polymers prevent exercising this ne level of control, thereby limiting the performance of polymeric materials compared to molecular sieves. In recent years, researchers have produced carbon molecular sieving (CMS) membranes by the pyrolysis of polymeric precursors already processed in the form of membranes. Typically, improved selectivi-

0376-7388/00/$ see front matter 2000 Elsevier Science B.V. All rights reserved. PII: S 0 3 7 6 - 7 3 8 8 ( 0 0 ) 0 0 3 9 2 - 6

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ties for oxygennitrogen separation were observed. Jones and Koros [2] used hexauoroisopropylidene (6FDA)-based co-polyimide hollow bers with O2 /N2 selectivities of 4, to yield asymmetric carbon membranes with selectivities of 1114 after pyrolysis at 550 C. Koresh and Soffer [3] used hollow bers of cellulosic or phenolic resins, pyrolyzed at 800 and 950 C to yield carbon membranes with selectivities of 78. Some post-pyrolysis steps were required to open the structure of the 950 C membranes which had sintered pores. Shusen et. al. [4] pyrolyzed at dense lms of phenol formaldehyde resin at temperatures of 800950 C with a post-pyrolysis activation step to yield membranes with selectivities of 11. Hatori et al. [5] made at homogeneous carbon lms from KaptonTM polyimide pyrolysis at 800 C to yield O2 /N2 selectivities of 4.2. Suda and Haraya [6] report hollow-ber membranes, also from KaptonTM pyrolysis at temperatures up to 800 C, with selectivities of 11 and at temperatures up to 1000 C with selectivities of 23. Hayashi et. al. [7] produced carbon membranes from a polyimide lm coated on porous alumina tubes pyrolyzed at 700 C to yield O2 /N2 selectivities of 9.7 which could be increased to 14 after a post pyrolysis carbon deposition step. In addition to producing carbonized membranes from pyrolysis of a polymer precursor, it was the objective of this work to systematically study the development of entropic contributions to diffusivity selectivity as the polymer matrix evolved to a rigid carbon matrix. Diffusion coefcients and activation energies for diffusion were calculated from temperature-dependent steady-state permeation and equilibrium sorption. Polymer precursor, nally pyrolyzed membranes and membranes pyrolyzed at intermediate steps in the pyrolysis protocol were tested to study the development of gas separation properties as the material progresses from a polymer to a completely carbonized membrane.

malized by partial pressure difference and membrane thickness. Permeability of component A can be expressed as the product of a kinetic factor, the diffusion coefcient (DA ), and a thermodynamic factor, the sorption coefcient (SA ) [8]: PA = DA SA (1)

When the downstream pressure is negligibly low, the sorption coefcient, SA , equals the secant slope of the sorption isotherm of A evaluated under the upstream permeation partial pressure conditions. The average diffusion coefcient, DA , can then be calculated as the ratio of PA and SA . The ideal permselectivity, A/B , characterizes the overall ability of a membrane to separate penetrants A and B. This is an inherent property of the material and its molecular morphology. The permselectivity can be factored into a diffusivity selectivity and a sorption selectivity term viz. A/B = PA DA SA = PB DB SB (2)

The sorption selectivity term for the O2 /N2 pair lies in the range of 12 in almost all glassy polymers, and between 0.7 and 2 for molecular sieving materials like zeolite 4A and CMS. It is the diffusivity selectivity in all three classes of materials that is responsible for the remarkable differences in their separation properties, as observed in Fig. 1. Permeation and diffusion in high-selectivity media are activated phenomena, and their temperaturedependence can be described by the following Arrhenius relationship shown for diffusion: D = D0 exp ED RT (3)

where, D0 is the pre-exponential factor and ED is the activation energy for diffusion. The pre-exponential factor can be expressed as the following equation [9]: D0 = e2 SD kT exp h R (4)

2. Background Non-porous polymers and molecular sieving media like zeolites and carbon molecular sieves (CMS) transport gases by a similar sorptiondiffusion mechanism. The permeability of a penetrant through a membrane is measured as a steady-state ux, nor-

where is the average jump length a penetrant molecule executes in one diffusive jump, SD is the activation entropy of diffusion and k and h are the Boltzmanns and Plancks constants, respectively. The diffusive jump length depends slightly on the

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As noted above, although conventional CMS materials and zeolite 4A have a favorable entropic contribution to overall diffusion selectivity, conventional polymeric membrane materials generally lack this factor.

3. Experimental 3.1. Pyrolysis Carbon molecular sieves (CMS) are readily made from the pyrolysis of suitable polymeric precursors. Carbon membranes were produced in this work by the pyrolysis of easily processable polyimide precursors. The polyimide (AP) used in this study was a co-polymer with the structure shown in Fig. 2, supplied by E.I. DuPont de Nemours. This material has a rigid backbone with CF3 groups and the trimethyl-substituted meta-linked diamine providing signicant hindrance to inter-segmental rotation about the chain axis. The polyimide material and the temperaturetime protocol used for our pyrolysis experiments were the same as that used by Jones and Koros. In that work, however, asymmetric hollow-ber polymer membranes were pyrolyzed to CMS membranes. To compute the entropic selectivity of materials, the diffusion coefcient must be factored out of Eq. (1) by determination of PA . Homogeneous membranes are required to unambiguously know the membrane thickness to convert observed uxes to permeabilities; hence, symmetric, dense polymeric lms rather than asymmetric membranes were pyrolyzed in this study. The polymer was cast from methylene chloride to produce strong, exible 2560 m lms. Films were pyrolyzed under vacuum (<0.03 mm Hg) in a quartz tube furnace supported on a quartz plate. A schematic

Fig. 1. Permeabilitypermselectivity trade-off curve for O2 /N2 separation properties of polymeric materials (taken from [1]).

penetrant molecule in polymeric media, while it tends to be a xed average length between sorption sites for all molecules in rigid molecular sieving media. In the case of the O2 /N2 pair, where the molecular size of the two gases is very similar, the differences in diffusion jump length can be neglected to a rst approximation, so by combining Eqs. (3) and (4), the diffusivity selectivity can be factored into a product of an energetic selectivity and an entropic selectivity term viz. SDA SDB (EDA EDB ) DA = exp exp DB R RT
Entropic selectivity Energetic selectivity

(5)

Fig. 2. Co-polyimide precursor for pyrolyzed carbon membranes (AP).

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Fig. 3. Schematic of pyrolysis furnace.

of the pyrolysis furnace is shown in Fig. 3. A 2 in. ID, 33 in. long quartz tube with a glass end cap was used for pyrolysis in a Thermcraft mufe furnace equipped with four heating elements to minimize the axial and radial temperature gradients. A distance of at least 6 in. was maintained between the samples and the open ends of the furnace. An Omega CN2011 Programmable Temperature Controller with a triac output and PID control was used to control the precise temperaturetime protocol. A standardized protocol was followed carefully to obtain reproducible gas separation properties for the carbonized membranes. The tube was evacuated to pressures of 0.03 mm Hg, as measured by McLeods gauge on the furnace, prior to starting the heating cycle. At this point, the valve connecting the vacuum gauge to the tube was closed and the pyrolysis cycle was started. An important objective of this work was to study the changes in properties of the material as it progresses from a low-selectivity exible polymer to a rigid high-selectivity carbon. To study this transformation progressively, pyrolysis was terminated at intermediate steps in the protocol as described below. The properties of the material were tested for the partially pyrolyzed membranes to observe how the entropic selectivity (Eq. (5)) changes with the structure of the material along the pyrolysis path. The temperaturetime protocol shown in Fig. 4 was developed by trial and error optimization to yield optimum properties for the nal carbon membrane made from this specic polymer precursor and it could vary for other polymers.

The initial rate of heating employed was 13.3 C/min. The heating rate was slowed to 3.85 C/min until the temperature reached 535 C (PM535). Some membranes were tested for gas separation properties at this point. This is the initial part of the pyrolysis protocol. From 535 C, the heating rate was slowed to 0.25 C/min as it approached an intermediate temperature of 550 C. The membranes were held at this temperature for a period of 2 h (PM550). Membranes were tested at this point for gas separation properties and entropic selectivity. From 550 C, the heating rate was again increased to 3.85 C/min. The nal pyrolysis temperature of 800 C was again approached at a rate

Fig. 4. Temperaturetime protocol for pyrolysis of carbon membranes.

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of 0.25 C/min and the membranes were held at this temperature for another 2 h (PM800). The approach rate for the temperatures of interest were maintained at these low values to avoid an overshoot in the nal temperatures. The furnace was allowed to gradually cool to temperatures below 40 C before samples were removed from the furnace and placed in a dessicator. 3.2. Permeation and sorption The dense polymeric lms and carbon membranes were tested in a standard pressure rise type cell where the membranes were pressurized on the upstream surface, while the downstream face was maintained at vacuum. The permeation ux was calculated using the ideal gas law by measuring the pressure rise in a standard volume on the downstream side of the membrane using a 010 Torr MKS Baratron pressure transducer. The equipment has been described in detail elsewhere [10]. A 5-minute epoxy resin was applied along the periphery of the carbon membranes to seal them to the metal ange of the permeation cell. After curing of the epoxy, the membranes were outgassed in a vacuum oven at 150 C for at least 8 h before permeation measurements to ensure complete removal of adsorbed molecules in the ultramicropores of the material. Mixed gas permeation experiments were also performed on the carbonized membranes using equipment described previously [11]. The membranes were tested primarily for oxygen and nitrogen separation only. Ultra-high purity grade oxygen and nitrogen were used. For the mixed gas experiments, dry compressed air was used. Temperature-dependent permeabilities were also measured for the polymer and carbonized membranes. The temperature of measurement was increased gradually, with the membranes being tested at lower temperatures rst. After testing at the highest temperatures, the membrane was tested once again at 35 C to ensure that no defects or changes had appeared during the testing procedure. Exposure to some organics can cause an irreversible loss in ux for the carbonized membranes [12]. Back-diffusion of vacuum pump oil was prevented by using a cold trap with liquid nitrogen or an FL20K Foreline trap with activated alumina adsorbent purchased from Edwards High Vacuum International. High-pressure sorption isotherms were generated for all polymeric materials, and membranes car-

bonized at 550 and 800 C. To determine the heats of sorption, the isotherms were generated at several temperatures using standard pressure decay equipment described earlier [10]. As in the permeation experiments, the lower temperature experiments were carried out prior to the higher temperatures for sorption studies. This procedure prevents the material from being subjected to undue thermal cycling and reduces history-dependent behavior. The sample was evacuated for at least 10 h at the new temperature before performing the higher-temperature experiments. Compressibility factors for the gases were used at each temperature and pressure to account for non-ideality of the gas. These were calculated from reliable PVT data for oxygen and nitrogen [13]. 3.3. Investigation of possible asymmetry in carbon membranes Extremely high oxygen and nitrogen ux values observed for samples pyrolyzed at 550 C (PM550) led to the concern that some asymmetry may have developed in the samples during the pyrolysis process. A thin selective surface layer in the pyrolyzed samples could conceivably lead to an overestimation of permeability coefcients. The membranes were not strong enough to be tested for separation properties before and after removing a thin surface layer from the samples, so gas transport data was used to probe the structural symmetry of the carbonized materials. Nitrogen sorption at 77 K and a relative pressure of 0.995 are typically used to measure the total porous volume [14]. No observable sorption of nitrogen was observed for PM550 and PM800 membrane materials at this temperature. The lack of any observable nitrogen sorption at 77 K implies that both surfaces of the membrane, the one in contact with the quartz plate and the one on top, have a similar inaccessible porous structure where diffusion is in the activated regime [15]. This eliminates the possibility of a selective surface layer at only one surface in the pyrolyzed samples. There may still have been a possibility of asymmetry in the bulk of the membrane with thin selective layers at either surface. To test this hypothesis, porous volume of the carbonized samples was measured using high- and low-pressure CO2 sorption isotherms at 0 C. This data can be analyzed by the DubininAstakhov equation to estimate the porous volume in the micro-

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pore range (<20 ) [1618]. Isotherms for the pyrolyzed membranes show about 87% of the total pore volume in PM550 and 83% in PM800 to be in the microporous range (<20 ), indicating that no large scale asymmetry was present in the bulk of the carbonized samples. This was further supported by SEM micrographs, which showed no asymmetry in the samples. The only features visible were a few pores of roughly 3000 in rare samples, which gave rise to obvious leaks in the membranes when present. Transient uptake measurements have been used to analyze the mass transfer mechanism in CMS [1921]. The diffusion of penetrant molecules in a material prior to equilibrium conditions is commonly described by Ficks laws of diffusion. The validity of this equation is dependent on an evenly distributed diffusive resistance within the membrane. The uptake versus time plots in Fig. 5 for PM550 show a typical Fickian response with some deviations. Data reported here are for nitrogen at 6 C. Oxygen diffusion was too rapid to study the transient sorption in a reliable manner with the equipment used. For an idealized Fickian case, when the resistance to diffusion is evenly distributed in the bulk of the sample, the relative uptake Mt /M plotted against the square root of time gives a linear plot for Mt /M values <0.6 as observed in Fig. 5(b). Idealized Fickian case also yields a linear plot of ln((1Mt )/M ) versus t for Mt /M values >0.6. A non-linearity at short times in this log plot is characteristic of an idealized Fickian response due to the linear behavior of Mt /M with t1/2 at short times. The plot in Fig. 5(a) shows a deviation from linearity at Mt /M >0.85 also. This is believed to be a result of the small variations (10%) in membrane thicknesses comprising the total sample size of 2 g [22]. Transient sorption for nitrogen shows conformance to Ficks laws of diffusion within reason, implying that the diffusion to resistance is evenly distributed throughout the membranes for PM550. It was concluded that membranes were indeed symmetrical in nature, so permeabilities were calculated using the entire thickness of the membranes.

Fig. 5. Nitrogen transient sorption at 6 C showing Fickian response in PM550; (a) long-time analysis; (b) short-time analysis.

4. Results and discussion The pyrolyzed membranes undergo a signicant weight loss and shrinkage in area but otherwise are an

exact replica of the polymer precursor. Details of the physical changes in the membrane with the progress in pyrolysis are presented in [23]. Air separation properties of the polymer precursor (AP), partially carbonized membranes (PM535 and PM550) and the nally pyrolyzed membrane (PM800) are plotted in Fig. 6 with respect to the upper-bound curve. The multiple points shown in Fig. 6 represent replicate pyrolysis samples and illustrate the magnitude of scatter observed under nominally identical pyrolysis conditions. It is evident from this plot that, despite the variability in numbers, the results for a material do lie within a specic region. The properties of one membrane from each type of material are presented in

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Table 2 Mixed and pure gas permeability and permselectivity for PM550 pyrolyzed membranesa PO2 (Barrer) Mixed gas Pure gas
a

PN2 (Barrer) 108 115

PO2 /PN2 7.5 7.2

812 826

Pure gas data for oxygen at 10 psi, nitrogen at 48 psi, mixed gas data at 57 psi, total pressure with 19% O2 and 81% N2 for PM550.2 membrane.

Fig. 6. Air separation properties of polymer precursor and pyrolyzed membranes with respect to the upper-bound curve (multiple points on graph represent replicate pyrolysis samples).

Table 1 to enable comparison of properties. The membranes chosen were good representatives of the properties of the material. These membranes are referred to as PM535.1, PM550.1 and PM800.1. All values reported in Table 1 have been calculated from a curve t equation obtained from temperature-dependent raw data for each membrane. Results reported here are
Table 1 Air separation properties of polyimide precursor and pyrolyzed membranes at 35 Ca Property PO2 (Barrer) PO2 /PN2 DO2 (108 cm2 /s) DO2 /DN2 SO2 (ccSTP/cc atm) SO2 /SN2 AP 69 4.1 35.6 2.9 1.5 1.4 PM535 952 4.6 PM550 239 9.9 35 7.3 5.2 1.3 PM800 23 12.3 1.8 8.5 9.7 1.4

a Pure gas data for oxygen at 20 psi, nitrogen at 75 psi for AP, PM550.1 and PM800.1; mixed gas data at 30 psi total pressure for PM535.1; all values have been calculated form curve t equation obtained from raw data on each membrane.

from pure gas permeation experiments for AP, PM550 and PM800. Only mixed gas permeation runs were performed for PM535. Due to the extremely high uxes observed for this material, membranes were tested with mixed gas and at lower pressures in order to keep the uxes measurable by the chart recorder being used. In amorphous polymers, pure gas permeabilities are reasonable approximations of mixed gas permeation. This was shown to be true for the pyrolyzed membranes as well. In separate experiments with PM550, it was conrmed that pure gas permeability and permselectivity were within 3% of mixed gas permeability and permselectivity [18]. The pure gas and mixed gas permeabilities and permselectivity data are presented in Table 2. Pressures used in the pure gas runs maintain the same ratio of oxygen and nitrogen partial pressures as those used in the mixed gas runs. The co-polyimide AP is a high-permeability, low-selectivity polymer compared to current generation polymeric materials. The separation properties for this polymer fall below the upper-bound curve and outside the rectangular region which encloses properties for commercially attractive membrane materials. The polymer has high oxygen permeabilities compared to current generation polymers despite its moderate fractional free volume (FFV) of 0.158. The high permeabilities are a result of high diffusivities and high solubilities as well. The low selectivities of this polymer are primarily due to the low mobility selectivity, as solubility selectivities for amorphous glassy polyimides do not vary signicantly around unity. The polymer backbone, despite its rigid chain with hindered inter-segmental motion, is likely to have a signicant degree of intra-segmental mobility (see Fig. 2). The methyl substituents in the diamine moiety and the biphenyl linkage in the dianhydride moiety are likely to display short-range motion use-

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ful for the diffusion of both oxygen and nitrogen molecules. This reduces the ability of the molecular matrix to selectively restrict the mobility of the penetrants on the basis of size and shape. Membranes pyrolyzed at 535 C (PM535) had extremely high oxygen permeabilities in the range of 8001200 Barrer. The selectivities, however, did not change very signicantly from AP. There was at most a 20% increase in the O2 /N2 selectivities which was not enough to place the material in the commercially attractive rectangular region. The tremendous increase in permeabilities indicates a more open molecular matrix in the partially pyrolyzed material than in the polymer precursor. Sorption experiments were not carried out on this material as it failed to show properties in the commercially attractive region. Further pyrolysis at 550 C (PM550) subjected the membranes not only to a higher temperature but also to longer times of pyrolysis. The total cycle time for PM550 was longer by 3 h than in PM535 and resulted in a reduction in oxygen permeabilities and an increase in permselectivities. The permeabilities are lower than for PM535 but are still signicantly higher than those of the original polymer precursor. Moreover, the permselectivities are still 100150% higher than the original polymer precursor. This suggests a matrix, which is beginning to condense, yielding greater size and shape selectivity than in PM535, and leading to separation properties in the commercially attractive region well above the upper-bound curve. The order of magnitude increase in permeabilities is a result of increased sorptivities, which are higher than those for AP by about a factor of 4. The diffusion coefcients for the particular membrane mentioned here, PM550.1, were similar to those of the polymer; however, other membranes with higher permeabilities had diffusion coefcients which were higher by a factor of 34. The increase in permselectivity, on the other hand, resulted from increases in mobility selectivity alone. The mobility selectivities for PM550 were greater than those of AP by nearly a factor of 2. The sorption coefcients increased for both oxygen and nitrogen with practically no change in the sorption selectivities, going from the polymer precursor to the carbonized membrane. The nally pyrolyzed membranes at 800 C (PM800) show a further increase in permselectivities accompanied by a reduction in permeabilities. Oxygen

permeabilities in PM800 are lower than in PM550 and AP as well. However, PM800 still has a high oxygen permeability, near 20 Barrer, with overall separation properties lying well within the commercially attractive rectangular region in Fig. 6. Of the membranes compared in Table 1, the PM800 membrane had permeabilities which were a factor of 10 lower than the permeability of the PM550 membrane, because of signicantly lower diffusion coefcients, around 20 times lower in PM800 compared to PM550. The sorption coefcients for PM800 are actually higher than those for PM550 by a factor of 1.8 and partly compensate for the lower diffusion coefcients. The PM800 permselectivities are 30% higher than those of PM550, which is a result of a further increase in mobility selectivity. It is interesting to note that the permselectivity of PM800 is greater by a factor of 3, or more, than that of AP. The increase in sorption coefcients points to a molecular matrix which has a large free volume, or porous volume. The decrease in diffusivities and increase in mobility selectivities is consistent with an accompanying tightening of periodic pore mouths believed to exist between the free volume sorption sites, thereby allowing greater size and shape selectivity. 4.1. Temperature dependence and activation energies The activation energies for permeation were measured for the polymer, AP and the various carbonized membranes from temperature-dependent permeation data. Temperature-dependent sorption was measured for AP, PM550 and PM800 and effective heats of sorption were calculated. Activation energies and pre-exponential factors for diffusion were calculated for these materials using the permeation activation energies and the apparent heats of sorption [10]. The activation energies and the pre-exponential factors were also obtained as a range due to variability in the permeation data. In this case as well, values for PM535.1, PM550.1 and PM800.1 are reported in Tables 3 and 4 in order to make specic comparisons. Permeabilities increased with temperature for all materials, for both oxygen and nitrogen as indicated by the positive activation energies. The activation energies for permeation increase in general as the level of pyrolysis increases. Possible interpretations of these trends are considered below.

A. Singh-Ghosal, W.J. Koros / Journal of Membrane Science 174 (2000) 177188 Table 3 Permeation activation energies and pre-exponential factors for polymers and pyrolyzed materialsa Property AP PM535 PM550 PM800 EPO2 (kcal/mol) 0.8 0.7 4.1 5.2 3.1 6.1 6.6 EPN2 (kcal/mol) 1.8 EPO2 ,N2 1.02 2.4 2.0 1.4 (kcal/mol) 2.42 E+2 2.8 E+3 1.65 E+5 1.14 E+5 P0O2 (Barrer) 3.11 E+2 3.19 E+4 4.09 E+5 8.66 E+5 P0N2 (Barrer) PO2 /PN2 4.1 4.6 9.9 12.3
a Data for oxygen at 20 psi, nitrogen at 75 psi for AP, PM550.1 and PM800.1 membranes; mixed gas data for PM535.1 at 30 psi total pressure; all values have been calculated form curve t equation obtained from raw data on each membrane.

185

4.3. PM535 to PM550 changes A very large increase in EPO2 takes place as the membranes are pyrolyzed between 535 and 550 C, which is accompanied with a substantial change in EPN2 as well. The EPO2 ,N2 is lower than that for PM535 but signicantly higher than that for AP. There is a further increase in the pre-exponential factors in PM550 as compared to PM535. This increase somewhat compensates for the higher activation energies in this material and results in only a small loss in permeabilities for PM550. 4.4. PM550 to PM800 changes

4.2. AP to PM535 changes The large increase in permeabilities when going from the polymer precursor to PM535, as seen in Fig. 5, reects the much higher pre-exponential factors in PM535. There was no change in the activation energies for permeation of oxygen as the membrane evolved from the polymer precursor AP to PM535. A small decrease in EPO2 was observed in some PM535 membranes tested. No such variation was observed for EPN2 , which increases when going from AP to PM535. This indicates an increasing resistance to nitrogen transport, while oxygen transport remains practically unaffected. Despite the small change in permselectivities there was a large change in EPO2 ,N2 . The higher EPO2 ,N2 values for PM535 indicate a greater temperature dependence of overall permselectivity, i.e. the loss in permselectivity with temperature will be greater for PM535 than for AP.
Table 4 Diffusion activation energies and pre-exponential factors for various materials from pure gas experimentsa Property EDO2 (kcal/mol) EDN2 (kcal/mol) EDO2 ,N2 (kcal/mol) D0O2 (cm2 /s) D0N2 (cm2 /s) DO2 /DN2 AP 4.09 4.69 0.6 2.8 E-4 2.6E-4 2.9 PM550 6.83 8.56 1.74 2.0 E-2 4.6 E-2 7.3 PM800 8.01 8.88 0.87 8.6 E-3 4.2 E-3 8.5

Going to PM800, a further increase in both EPO2 and EPN2 is observed; however, the increase in activation energies for oxygen is twice as much as the increase for nitrogen. The EPO2 ,N2 values for PM800 are lower than in PM550. No further increase in pre-exponential factors is observed in this case and hence, the higher activation energies lead to the signicantly lower permeabilities of this material. 4.5. Overall changes in activation energies for diffusion Activation energies for permeation are a sum of the activation energies of diffusion and the effective heats of sorption for a penetrant in a material. Comparison of activation energies for diffusion, rather than those for permeation is more direct for understanding diffusional effects. In this regard, subtracting the heats of sorption from the activation energies for permeation yields the activation energy for diffusion. The values compared in Table 4 are for PM550.1 and PM800.1 membranes. The activation energies for diffusion increased for both oxygen and nitrogen as the level of pyrolysis increased. The higher activation energies for both oxygen and nitrogen for PM550, compared to AP, indicate increased resistance to diffusion in the molecular matrix. The larger EDO2 ,N2 for PM550 also indicates a greater temperature dependence of mobility selectivity. The increase in EDN2 was larger than the increase in EDO2 for PM550, implying that nitrogen diffusion faces more resistance than oxygen diffusion, which is reected in the higher mobility selectivity

a Data for oxygen at 20 psi, nitrogen at 75 psi for AP, PM550.1 and PM800.1 membranes; all values have been calculated form curve t equation obtained from raw data on each membrane.

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for PM550 than for AP. The mobility of the polymer chains may have become severely hindered after partial pyrolysis in PM550, thereby restricting the motion of the larger nitrogen molecule to a greater extent. In going from AP to PM550, O2 diffusion coefcients do not decrease despite the large increase in activation energies because the two-orders of magnitude increase in pre-exponential factors also occur. From Eq. (4), the large values of D0 could result from increased activation entropy of diffusion for the gas molecules or from an increase in the jump lengths of oxygen and nitrogen, or a combination of the two effects. Increase in activation entropy of diffusion for a gas molecule would mean that the entropy of the penetrant-matrix system is larger in the activated state than in the normal sorbed state, or the penetrant gains entropy when making a diffusive jump. Increase in jump lengths would be possible by the formation of large open regions in the molecular matrix through which the penetrant would make large diffusive jumps. It is difcult to imagine an order of magnitude increase in jump lengths, considering the increase in mobility selectivity. Hence, the larger pre-exponential factors for diffusion in PM550 are most likely to be a result of the increase in activation entropy with some contributions from increase in jump lengths. For a single gas it will be difcult to separate the contributions from the two effects by gas transport measurements alone. Fortunately, by considering differences, EDO2 ,N2 , some insights may be possible, since diffusion jump length issues should be essentially eliminated for the similarly sized oxygen and nitrogen molecules. In PM800, EDO2 increases further by about 17% while there is only a 4% increase in EDN2 as compared to PM550. The EDO2 ,N2 values are lower for PM800 than for PM550 indicating a lower temperature depenTable 5 Energetic and entropic contributions to overall diffusivity selectivity Property DO2 DO2 /DN2 EDO2 (kcal/mol) Energetic contribution exp[ EDO2 ,N2 /(RT)] Entropic contribution exp[ SDO2 ,N2 /(R)]
a a b

dence of diffusivity selectivity in PM800. Compared to AP, there is nearly a similar increase in EDO2 and EDN2 values for PM800. The diffusion coefcients for PM800 were much lower than in PM550, indicating that at the higher temperature of pyrolysis the material has developed a greater resistance to diffusion for both oxygen and nitrogen. The pre-exponential factors are somewhat lower in PM800 as compared to that in PM550, but there is some variation in these numbers. 4.6. Energetic and entropic contributions to diffusivity selectivity The energetic and entropic contributions to overall mobility selectivity were calculated from the activation energies and the pre-exponential factors for diffusion using Eq. (6). These are presented in Table 5. The results are compared with properties for a commercial CMS pellet used in pressure swing adsorption based xed bed systems for air separation. The polymer AP has low mobility selectivities with energetic selectivities providing nearly all of the contribution to overall mobility selectivity. The polymer, with its rigid backbone and hindered inter-segmental mobility, may still have sufcient intra-segmental motion to prevent selective restriction of rotational motion of nitrogen in the activated state, thereby limiting entropic selectivities to only around unity. The structure evolution between the polymer and PM550 leads to a remarkable increase in the mobility selectivity and oxygen diffusion coefcients. Accompanying these changes are increases in oxygen activation energies for diffusion and increased energetic selectivity contributions. However, in this case, the entropic selectivities are surprisingly lower than those in AP, and the energetic selectivity, which is

AP 35.6 2.9 4.09 2.72.9 1.01.1

PM550 30150 5.98.2 5.66.8 1730 0.20.4

PM800 1.52.0 7.99.0 7.59.6 4.17.0 1.22.1

Commercial CMS pellets 0.07c 2545 5.5b 5.1 4.98.8

108 cm2 /s. [29]. c Based on 4 m Bergbau CMS pellets with diffusivity selectivity of 30.

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largely responsible for the much higher mobility selectivities in PM550. The higher oxygen and nitrogen pre-exponential factors for PM550 compared to AP suggest a gain in entropy in the activated state as discussed in the previous section. Relatively exible well-packed glassy polymers have been found to have similarly low entropic selectivities [24]. The molecular matrix of PM550 is in transition from exible polymer chains to a rigid molecular sieving environment. We speculate that in the normal sorbed state nitrogen, which is slightly larger than the oxygen molecule, may be more effectively restrained from rotation in the tightly packed regions of the hindered mobility structure. To make a diffusive jump still requires the opening of a transient gap in the tightly packed region, thereby allowing nitrogen to gain entropy in the more open transition state environment while making a diffusive jump. The longer nitrogen molecule, therefore, may gain more entropy as it achieves the ability to rotate freely in the diffusion transition state. On the other hand, if oxygen can already rotate freely in the sorbed state, it will gain relatively less entropy in the equivalent activated state. Such a hypothetical situation would make the PM550 molecular structure entropically selective towards nitrogen, i.e., giving an O2 /N2 entropic selectivity less than unity, as is observed. The increased activation energies are also indicative of a more restricted motion of the molecular matrix. In a rather well-packed matrix a diffusion step would require a greater deformation to allow the diffusion of the larger nitrogen molecule again consistent with the data. In PM800, there is a further increase in mobility selectivity accompanied by a large decrease in diffusion coefcients. The diffusion activation energies for oxygen are much higher than in PM550, but the difference in activation energies for oxygen and nitrogen is less than it was for PM550. This material has significant contributions from both energetic and entropic selectivities, which are responsible for its increased mobility selectivities. The energetic contributions for PM800 decrease relative to PM550, but are greater than those for the polymer precursor. It is most likely that the material nally evolves to a rigid molecular matrix like those of other molecular sieving materials. As the matrix becomes rigid, the activation energies would be required only to overcome the repulsions from the walls of the pore, and are likely to be similar

for the non-polar oxygen and nitrogen molecules with similar kinetic diameters. Comparing these data with that for a commercial CMS sample, the energetic contributions for PM800 are similar to those for the CMS, however, the entropic selectivity has further room for improvements. It is interesting to note, that commercial CMS materials typically involve a post-pyrolysis deposition step which reduces the pore size distribution in these materials and increases their mobility selectivities [2528]. Similar post-pyrolysis steps may allow further increases in the contributions from entropic factors.

5. Summary and conclusions Pyrolysis of polymer lms yield defect-free carbonized membranes with oxygennitrogen separation properties in the regime of commercial interest. The permselectivities of the material increase as the level of pyrolysis increases in terms of time and temperature of pyrolysis. The nally pyrolyzed material(PM800) had selectivities three times higher than the polymer precursor(AP). Permeabilities show a large increase initially with subsequent decrease as the level of pyrolysis increases. The permeability of the partially pyrolyzed membranes(PM550) was 410 times greater than that of the polymer precursor; however, permeability of the nally pyrolyzed material reduces to a third of the polymer permeability. The increase in permselectivity was a result of the increase in mobility selectivity alone for both PM550 and PM800. The thermodynamic sorption selectivity of the materials did not change measurably between the polymer precursor and the carbonized membranes. The increase in permeabilities for PM550 was a result of increase in absolute sorption coefcients, which continue to increase between PM550 and PM800 as well. The lower permeabilities of PM800 are a result of signicantly lower diffusion coefcients. The preceding changes suggest a material where the total free volume, or porous volume, increases with a simultaneous restriction of the access path (pore mouths) to these free volume regions. Activation energies for diffusion increased in the materials with increasing pyrolysis, indicating an increasing resistance to diffusion. The PM550 material had high energetic selectivities but no contributions

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