NANO LETTERS

Gas Permeability of a Buckypaper Membrane

Sarah M. Cooper, Helen F. Chuang, Martin Cinke, Brett A. Cruden,*, and M. Meyyappan
NASA Ames Center for Nanotechnology, Moffett Field, California 94035
Received November 25, 2002; Revised Manuscript Received December 13, 2002

2003 Vol. 3, No. 2 189-192

ABSTRACT
Gas permeability has been measured through a carbon nanotube-based buckypaper membrane and through commercially available porous anodized alumina membranes with 200 nm nominal pore dimensions. Permeation relationships through the alumina membrane are consistent with Knudsen-type diffusion. Permeation behavior in the buckypaper membrane, however, shows a strong dependence of permeability on pressure that is not explained by typical transport mechanisms. It is suggested that elastic deformation of the membrane from the pressure differential may contribute to this behavior.

Since the discovery of carbon nanotubes (CNTs) in 1991, great interest has been generated in taking advantage of their remarkable properties. Besides applications in electronic and structural materials, CNTs have also been proposed for use in chemical applications, including gas separation, purification, and storage.1-6 If nanotubes are to be employed in applications of these sorts, it is important to understand the properties of gas transport and general fluid flow through this media. In this work, we report the characterization of gas transport through a membrane comprised of single walled carbon nanotubes (SWNTs), commonly referred to as buckypaper. To measure gas transport properties through these types of membranes, we have constructed a gas flow/diffusion cell to make measurements in a manner similar to that of the so-called manometric method.7,8 In our setup, flow through a 1 in. diameter Pyrex tube is controlled by an upstream mass flow controller (MKS M100B). Downstream of the flow controller, the membrane is mounted on a Teflon showerhead support. The showerhead provides mechanical support to the membrane, but presents a negligible resistance to flow through the membrane. Because of the lower permeabilities of the membranes studied, gas is able to diffuse into the plane between the membrane and showerhead, allowing permeation through the entire area of the membrane, rather than just through the showerhead holes. In this study, two types of membranes were studied. Commerically available porous alumina membrane filters (Whatman Anodisc) with nominal 200 nm diameter straight cylindrical pores were mounted on a tape backing, with a measured area of the Anodisc exposed. Portions of the
* Corresponding author. E-mail: bcruden@mail.arc.nasa.gov. Also at Eloret Corporation. 10.1021/nl0259131 CCC: $25.00 Published on Web 01/10/2003 2003 American Chemical Society

Anodisc not exposed were sealed with Vac Seal to prevent gas diffusion between the tape/Anodisc interface. Permeability of the tape was measured independently and determined to be negligible in comparison to the Anodisc permeability. The buckypaper samples, however, were less permeable than the tape, so were mounted on aluminum foil and sealed with epoxy. Independent measurement of aluminum/epoxy permeability showed it to be negligible in comparison to the buckypaper permeability. The buckypaper was prepared by a procedure similar to that reported elsewhere in the literature.9 Raw laser ablation material was procured from Johnson Space Center. The raw nanotubes were refluxed in 2.6 M nitric acid for approximately 160 h. This solution was then centrifuged and the solvent mixture decanted. This step was repeated two more times with double-distilled water to remove the acid from the nanotubes. The nanotubes were then resuspended in a 3:1 mixture of H2SO4/HNO3 and sonicated for approximately 24 h. This solution was again centrifuged and decanted three times, then resuspended in double-distilled water and filtered through a cellulose nitrate filter. Finally, the cellulose filters were placed in a vacuum oven at approximately 60 C to form the buckypaper when the nanotubes dried and separated from the filter membrane. Following preparation, the buckypaper was characterized by a variety of procedures. A scanning electron microscope (SEM) image of the buckypaper surface is shown in Figure 1a. Many SWNT bundles can be observed in the image. These bundles run across larger impurities due to amorphous carbon or metal catalyst incorporated in the buckypaper. Nitrogen adsorption isotherms were collected at 77 K (Micromeritics ASAP 2010) and pore size analysis was performed by the BJH method. The pore size distribution

Figure 1. (a) SEM image of the buckypaper membrane. Visible are individual carbon nanotube ropes and larger chunks of metal catalyst and amorphous carbon. (b) BJH pore analysis of the buckypaper membrane, showing a wide distribution of pores in two different regions, indicating some porosity due to open nanotubes and other porosity due to spaces between nanotubes.

(Figure 1b) shows broad distributions between 1 and 10 nm and 10-100 nm. The former distribution is likely due to the internal pores of the nanotubes and nanotube ropes, while the second represents larger pores in the membrane between nanotube ropes, catalyst particles, and amorphous carbon. BET analysis of the adsorption isotherms allows estimation of the specific surface areas of the material in the range of 350-450 m2/g. Note that this is significantly less than areas obtained in purified HiPco nanotubes (1580 m2/g),4 though tubes formatted as a paper typically possess smaller areas. The surface area-to-volume ratio from this analysis would imply an average pore diameter in the range of 4-10 nm. Thermogravimetric analysis (TGA) of the buckypaper sample indicates that 10.5% of the material remains after heating in air to 1000 C, indicating that this much of the buckypaper is metal impurity. It is important to note that, unlike many theoretical studies of transport through nanotubes, in this work the nanotubes are not well aligned and open. While some of the nanotubes may be open, the relatively low specific surface area and pore analysis suggests that many of the nanotubes are in fact closed. It is also apparent from the SEM that the nanotubes are oriented more or less randomly with respect to the plane of the membrane. Thus, it is expected that flow is directed around the nanotube bundles rather than through the nanotube itself. Flow was first characterized with Whatman Anodisc samples. SEM images collected from various samples
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Figure 2. Gas flow through Anodisc membranes with 200 nm pore sizes. (a) Pressure differential and flow rate show a linear relationship, indicative of a normal pressure-independent diffusion mechanism. (b) Pressure decay rates at zero flow are described by a single exponential, consistent with a one-dimensional diffusion problem. The diffusion coefficients estimated from these data are both consistent with one another and with a Knudsen diffusion mode.

indicated a pore diameter of approximately 212 nm and a pore density between 5 and 8 1012 pores/cm2. Based on these measurements, we can estimate the porosity of the Anodisc membrane to be between 0.2 and 0.29. We measured both steady-state pressure drop across the membrane and pressure decay from steady state. The results are shown in Figure 2. The steady-state pressure/flow relationship is indicative of a 1-D gaseous diffusion problem with constant diffusion rate. In this case, the relationship is described by p F )D A RTl (1)

where F is the flow rate, p is the pressure drop, R is the ideal gas constant, T is the ambient temperature, and D is the diffusion coefficient. The terms , A, , and l are the porosity, exposed area, thickness, and tortuosity, respectively, of the membrane. Diffusion coefficients obtained in this fashion are summarized in Table 1. The transient for pressure decay is well described by a first-order exponential decay,
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Table 1. Estimated Diffusivities in Anodisc Membranes from Knudsen Diffusion Equation, Steady-State Pressure Flow Relationship, and Transient Pressure Decay Behaviora
Knudsen Diffusivity ( 10-5 m2/s) Oxygen Nitrogen Argon 3.13 3.35 2.80 Steady Diffusivity ( 10-5 m2/s) 3.01 3.26 2.66 Transient Diffusivity ( 10-5 m2/s) 2.76 3.30 2.75

a The values are all within the expected uncertainty of the membrane porosity measurement (20%).

and is consistent with the solution of the 1-D transient diffusion problem, given by p(t) = p0e- AD/Vu(l)
2

(2)

where Vu is the volume upstream of the membrane, determined experimentally by using the ideal gas law and a mole balance for pressure rise with an impermeable membrane. The value for D extracted from these data are also shown in Table 1 and show an excellent agreement with the estimated steady diffusivities. Also shown in Table 1 is the calculated Knudsen diffusivity, applicable for rarified flow through a cylindrical pore. The numbers measured here agree with the Knudsen diffusivities given the uncertainty in membrane porosity. This agreement is consistent with what has been observed in similar porous alumina membranes with smaller diameter pores.10 The permeability of the buckypaper membrane was also measured as shown in Figure 3. These samples proved to be significantly less permeable than the previously measured samples and required several days to reach anything approaching steady state. Steady-state pressure drops across the membrane were measured for argon and found not to vary in the flow regime examined. For flow rates between 0.38 and 1.54 sccm, the membrane maintained a pressure drop between 2000 and 2250 Torr, with a very weak dependence of pressure on flow rate. For larger flow rates, the pressure differentials were beyond the maximum measuring capability of the apparatus. Figure 3 depicts pressure decay transients when the cell was pressurized up to various pressures, following which the flow was shut off. The behavior obtained does not follow a single-exponential decay, but may be described by a multiple exponential decay. This multiple exponential decay, however, does not behave as the solution to the one-dimensional diffusion problem,8,11 in which the exponential decay constant varies with time in the same manner, regardless of initial pressure. In this case, the decay rate appears to be a function of the pressure, not time, as is apparent from Figure 3b. The rates of decay measured from different initial pressures agree well when plotted against pressure. If the cell was pressurized at 400 Torr, this pressure remained constant for several days. The only fluctuation in pressure across the membrane was found to correlate to fluctuations in ambient temperature, though the dependence was stronger than variations derivable from
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Figure 3. Gas flow through the carbon nanotube based buckypaper membrane. The different points in each plot represent independent experimental runs. (a) Transient data for argon flow through the membrane at zero flow rate. The rate of pressure decay depends on the pressure in the cell rather than the time of operation. (b) The same data plotted as the rate of pressure decay versus pressure. Data collected at 400 Torr are omitted as effectively no change in pressure is measured over the time of operation. Other data show a strong dependence of rate on pressure. Superimposed on these data are expected dependencies from common transport mechanisms. Also shown is an empirical power law dependence fit to the data.

the ideal gas law, indicating significant temperature dependence in the absorbance of gas on the buckypaper. In a normal diffusion mode, the rate of decay is proportional to pressure and would give a linear relationship in Figure 3b. In general, the pressure decay rate can be found by a mole balance on the volume upstream of the membrane: dp dt )ART J(0,t) Vu (3)

where J(0,t) is the species flux entering membrane pores at the upstream side of the membrane. The flux can be estimated by solving a one-dimensional diffusion equation: 1 p(x,t) J(x,t) ) RT t x (4)

where p(x,t) is the pressure at a distance x along the

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membranes pore. The flux can generally be written in the form of Ficks Law with a pressure-dependent diffusivity: J(x,t) ) Deff(p) p(x,t) RT x

(5)

If the upstream volume is sufficiently large, one can make a pseudo-steady-state approximation and assume that the time scale for eq 4 to equilibrate is significantly less than that of eq 3. This is to say that the upstream pressure remains approximately constant in the amount of time it takes to establish a steady diffusion profile within the membrane. In this case, eq 4 will be equal to zero and eq 5 can be integrated along x to become (after change of variable) dp dt )ART Vul

0p D(p) dp

(6)

assuming the downstream pressure to be effectively 0. Using this sort of relationship, several common effective diffusion relationships observed12 have been overlaid on Figure 3b. Included among them are mechanisms involving normal (pressure independent) diffusion, combined diffusion, and viscous flow and surface diffusion with Langmuir isotherm type adsorption (other common isotherms, e.g. BET, show similar qualitative behavior on a semilog plot). None of these relationships capture the strong dependence of pressure decay rate on pressure. The measured pressure decay shows an empirical power law dependence with Deff p7.3. Such an observation is not explained by commonly observed diffusion phenomena. One possibility may be that the buckypaper is deforming under the applied stress of the pressure differential. The deformation may cause pores between the nanotubes to widen and permit gas to flow through at higher rates when larger pressure differentials exist across the membrane. If this were the case, the deformation would have to be occurring in the elastic regime, as the permeability measurement is generally reproducible on pressure cycling. In conclusion, we have examined mass transport of various gases through carbon nanotube-based membranes, as well

as nanoporous alumina. The behavior in nanoporous alumina mimics an idealized structure of flow through straight cylindrical tubes, and the result is consistent with what is expected in a Knudsen-type diffusion regime. The buckypaper, however, presents entirely different trends that are not well described with typical transport models. The behavior shows that diffusion rates are dependent on pressure but not time of operation. The pressure dependence is extremely strong, and apparent membrane permeability rises quickly as pressure is increased. In this sense, the membrane acts in a fashion similar to a check valve, allowing greater flows through when larger pressures (in this case near 3 atm) are encountered. A likely mechanism for this behavior is an elastic deformation of the membrane allowing flow between the nanotubes. Work by B.A.C. and M.C. was supported by NASA contract NAS2-99092 to Eloret. S.M.C. is an intern through Educational Associates. H.F.C. is a senior at Cal Tech whose work was done during a summer internship at Ames. The authors would also like to acknowledge Jeff Ifland, Anthony Lombardi, and Gabriel Laden for project support. References
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