Professional Documents
Culture Documents
Pan 1 PDF
Pan 1 PDF
Abstract
Saufi, S.M. and Ismail, A.F.
Development and characterization of polyacrylonitrile (PAN)
based carbon hollow fiber membrane
Songklanakarin J. Sci. Technol., 2002, 24(Suppl.) : 843-854
This paper reports the development and characterization of polyacrylonitrile (PAN) based carbon
hollow fiber membrane. Nitrogen was used as an inert gas during pyrolysis of the PAN hollow fiber mem-
o
brane into carbon membrane. PAN membranes were pyrolyzed at temperature ranging from 500 C to
o
800 C for 30 minutes of thermal soak time. Scanning Electron Microscope (SEM), Fourier Transform
Infrared Spectroscopy (FTIR) and gas sorption analysis were applied to characterize the PAN based carbon
membrane. Pyrolysis temperature was found to significantly change the structure and properties of carbon
membrane. FTIR results concluded that the carbon yield still could be increased by pyrolyzing PAN mem-
o
branes at temperature higher than 800 C since the existence of other functional group instead of CH group.
o
Gas adsorption analysis showed that the average pore diameter increased up to 800 C.
1999). There are numerous PAN fibers advan- lution and bore fluids were extruded simultane-
tages including a high degree of molecular ously through a spinneret to form a nascent
orientation, higher melting point (PAN fiber hollow fiber at an ambient temperature. The
tends to decompose before its melting point, Tm internal surface of hollow fiber was contacted
o
of 317-330 C) and a greater yield of the carbon with a bore fluid and experienced wet phase
fiber (Donnet and Bansal, 1984). PAN fibers separation in order to form a circular hollow
form a thermally stable, highly oriented mole- lumen. Water was chosen as bore fluid with flow
cular structure when subjected to a low tempera- rate of lml/min (Pesek and Koros, 1994; Clausi
ture heat treatment, which is not significantly and Koros, 2000), which was controlled by high-
disrupted during the carbonization treatment at pressure syringe pump.
higher temperatures, meaning that the resulting The fiber was then directed to a force con-
carbon fibers have good mechanical properties vective chamber, which provides a controlled
(Donnet and Bansal, 1984). force convective environment for inducing dry
On the other hand, it is possible to blend phase separation through an air gap. The inert gas
the PAN with other polymers to alter the final nitrogen was used to allow the fiber skin forma-
pore size distribution of carbon membrane. tion. The hollow fiber was then immersed into
Linkov et al., (Linkov et al, 1994a) prepared nonsolvent (water) coagulation bath for wet
PAN hollow fiber membrane by varying the vis- separation and then the washing treatment bath.
cosity of the precursor solution by blending it The coagulation bath temperature was controlled
o
with methyl methacrylate. They also applied at 14 C by a refrigeration/heating unit to ensure
phase inversion by casting PAN with poly (ethyl- rapid solidification, while the washing bath was
ene glycol) (PEG) and poly (vinylpyrrolidone) kept at ambient temperature.
(PVP) in order to synthesize membranes with 50- The resulting hollow fibers had an outer
400 nm pore sizes. The pore size distribution was diameter of 600µm with a 300µm inner diam-
very narrow in the case of the PAN-PVP precursor eter. The fully formed PAN hollow fiber was
(Linkov, 1994b). subjected to solvent exchange in methanol for 2
One of the main problems of unsupported days and hexane for another 2 days before being
carbon membrane (i.e. hollow fiber) is brittleness dry in ambient atmosphere.
of the carbon structure. We believe that by the
application of PAN precursors, which is widely Inert gas pyrolysis
used in the production of high strength carbon Inert gas nitrogen was set up for pyrolysis
fiber, this problem can be minimized. However, in of PAN hollow fiber membrane as shown in
this case, first task is to develop PAN-based car- Figure 2. PAN hollow fiber bundles were in-
bon membrane. Furthermore, some improvement serted into a quartz tube and wrapped with stain-
and optimization must be done in the next stage less steel wire type 304 (outside diameter
in order to achieve high performance PAN-based 3 mm) at both ends. Then, the quartz tube was
carbon membrane. inserted into Carbolite wire wound tube furnace
(Model CTF 12/65/550) that can be set to a maxi-
o
Preparation of carbon membrane mum temperature of 1200 C. The pyrex socket
Dry/Wet spinning process was connected at the front of quartz tube to
A binary polymer solution consisting of channel the nitrogen gas during pyrolysis and
150g PAN (Aldrich 18131-5) and 850g dime- the other side of quartz tube was located in a fume
thylformamide (DMF) was prepared for making cupboard to purge the volatile gas evolved. All
1000g of spinning solution. Dry/wet-spinning pro- the connection were properly tighten to prevent
cess was applied in preparing asymmetric PAN air from entering the quartz tube which could
hollow fiber membranes precursor. Spinning so- interrupt the inert gas pyrolysis process.
Songklanakarin J. Sci. Technol. Polyacrylonitrile (PAN)
846 Saufi, S.M. and Ismail, A.F.
Vol. 24 (Suppl.) 2002 : Membrane Sci. &Tech.
The PAN membrane was subjected to ther- pared under different carbonization condition can
o
mostabilization process in air at 250 C for 30 be viewed clearly. Before passing through SEM,
o
min at heating rate of 5 C/min before the pyro- the membrane samples had to go through the gold
lysis was conducted. Thermostabilization is nec- coating process. After that, the samples were
essary in order to cross-link the PAN chains and imaged and photographed by employing a scan-
to prepare a structure that can withstand high ning electron microscope (SEMEDAX; XL40:
temperature process. This can also ensure both the PW6822/10) with potentials of 10kV in achieving
molecules and the fibrillar orientation will not be magnification ranging from 500x to 5000x.
eliminated during the final heat treatment process.
Before the pyrolysis process started, the Fourier transform infrared spectroscopy
inert gas needed to be purged into the pyrolysis (FTIR)
system to remove the unwanted air or oxygen. Fourier Transform Infrared Spectroscopy
This was to prevent the oxidation from occurring (FTIR) is a very useful tool to detect the exist-
during high temperature pyrolysis process. Then, ence of functional groups in a membrane. The
the precursor was heated to a required pyrolysis FTIR results display changes of functional groups
o
temperature in the range of 500-800 C and main- and elements in the membranes when they are
tained at that temperature for 30 min by setting heated from room temperature to pyrolysis temp-
up the temperature control systems. The heating erature.
o
rate was set at 3 C/min and nitrogen gas flow rate
3
was maintained at 200 cm /min. The resulting Gas sorption analysis
carbon membrane was cooled down to ambient Nova 1000 Gas Sorption Analyzer, Quanta-
temperature in an inert gas atmosphere. chrome Corporation was used to determine the
average pore size and micropore volume of car-
Characterization of carbon membrane bon membrane. The sample was pretreated in a
o
Scanning electron microscopy (SEM) vacuum at 400 C for about 2 hours. The heated
Scanning Electron Microscopy (SEM) has sample cell was immersed into liquid nitrogen to
been used to investigate the resultant membrane maintain the temperature at 77 K before testing.
morphology. Images of fiber surface, skin layer Nitrogen gas was used as an analysis gas.
structure and cross sections of membrane pre-
Songklanakarin J. Sci. Technol. Polyacrylonitrile (PAN)
847 Saufi, S.M. and Ismail, A.F.
Vol. 24 (Suppl.) 2002 : Membrane Sci. &Tech.
Figure 3. Cross section of PAN membrane and PAN based carbon membrane
Songklanakarin J. Sci. Technol. Polyacrylonitrile (PAN)
848 Saufi, S.M. and Ismail, A.F.
Vol. 24 (Suppl.) 2002 : Membrane Sci. &Tech.
C≡N 2216.42
o
500 C C-N 1265.90
C=C 1595.42
Figure 5. Structure of ladder polymer from PAN
C≡N 2224.05
C=N 1649.36
process, cyclization and oxidation taking place to
C-N 1265.77
form a ladder polymer as shown in Figure 5 o
600 C C=C 1539.65
(David and Ismail, 2003). This ladder structure N-H 3445.29
is thermally stable and ready to withstand high C=O (Aldehydes) 1739.53
temperature of pyrolysis process. C=O (Ketones) 1701.79
Pyrolysis of PAN membrane involves
C=N 1653.23
many process such as chain scission, chain break- C-N 1021.84
down, by-products evolution or cross linking de- o
700 C C=C 1540.69
pending on heat treatment history. The principal N-H 3442.13
scission products releases from PAN precursor in C=O (Ketones) 1701.01
o
the temperature ranging from 400 to 1000 C are C-H 2924.63
hydrogen cyanide (HCN), ammonia (NH3) and C=N 1649.58
nitrogen (N2). Depending on the extent of pre-oxi- C-N 1021.39
dation, various amounts of water (H2O), carbon o
800 C C=C 1541.42
monoxide (CO) and carbon dioxide (CO2) were N-H 3442.97
also formed. In addition, small quantities of hy- C-H 2923.64
drogen (H2) and methane (CH4) were released
during the carbonization process (Lewin and
Preston, 1983). Figure 6 shows the proposed existence of other compounds.
mechanism of the stabilization chemistry and The C=C groups exist in all pyrolyzed
carbonization of PAN-based carbon fiber. PAN membrane. This group is formed by aroma-
Figure 7 and Figure 8 show the spectrum of tization process that occurred during thermosta-
pyrolyzed PAN membrane at different pyrolysis bilization of PAN membrane. The nitrile groups
temperatures. Meanwhile Table 2 gives a summa- (C≡N) disappear when PAN membrane is pyrolyzed
o
ry of FTIR results for PAN membrane pyrolyzed at temperature of 700 C. Aldehydes and ketones
using nitrogen pyrolysis system. The original can be detected at pyrolysis temperature of
o
PAN molecule consists of functional groups such 600 C and aldehydes disappeared when reaching
o o
as methyl (CH3) and nitrile (C≡N). During oxida- 700 C. A ketone group disappeared at 800 C
tion, numerous new transition structures were spectrum but nitrogen atom can still be found at
formed, such as ketones, aldehydes, carboxilyc this spectrum. It can be concluded that pyrolysis
o
acid etc. as in Figure 6. After carbonization, all temperature at 800 C seems not enough to re-
of these transition compounds were expected to move all non-carbons atoms (i.e. N, O, etc) in
evolve as volatilities and only carbon and hydro- PAN membrane because of the existence of other
gen atoms remain. However, 100% conversion of functional group instead of CH group as detected
polymer to carbon is not achieved due to the by FTIR spectrum.
Songklanakarin J. Sci. Technol. Polyacrylonitrile (PAN)
850 Saufi, S.M. and Ismail, A.F.
Vol. 24 (Suppl.) 2002 : Membrane Sci. &Tech.
Effects of pyrolysis temperature on the porous Generally, the pore size of carbon mem-
structure of carbon membrane brane is non-homogeneous, comprised of rela-
The mechanism of gas permeation and up- tively wide openings with a few constrictions
take through porous solids is closely related to (Koresh and Soffer, 1980). The pores are varying
internal surface area, dimension of the pores and in size and dimensions depending on the mor-
surface properties of the solid, rather than to the phology of the organic precursor and the chem-
bulk properties of the solid as in the case with istry of pyrolysis. The idealized structure of
polymers (Koresh and Soffer, 1987). Therefore, it carbon material is shown in Figure 9. The pore
is important to study and analyze the porous mouth “d”, often referred to as an ultramicropore
structure in carbon membrane. The porous struc- (<10Å) (Suda and Haraya, 1997; Centeno and
ture in carbon membrane contains pore or ap- Fuertes, 1999), which allows molecular sieving of
ertures that approach the molecular dimension of the penetrate molecules. The larger micropores,
the diffusing gas molecules (Jones and Koros, “D” of the material (6-20Å) may allow for diffu-
1994; Lafyatis et al, 1991). According to the sion of gas molecules through the carbon material
IUPAC, three different types of pore have been (Steel, 2000).
defined; macropores that are larger than 50 nm; The extent and nature of the porous struc-
mesopores, between 2 and 50 nm in size; and ture and the surface area will be largely dependent
finally, micropores, that are smaller than 2 nm. on the nature and morphology of the precursor
Songklanakarin J. Sci. Technol. Polyacrylonitrile (PAN)
851 Saufi, S.M. and Ismail, A.F.
Vol. 24 (Suppl.) 2002 : Membrane Sci. &Tech.
o
(a) 500 C
o
(b) 600 C
o o
Figure 7. FTIR spectrum of pyrolyzed PAN membrane at (a) 500 C (b) 600 C
polymer and the history of its heat treatment oxides (David, 2001). However, at a very high
(Donnet and Bansal, 1984). The imperfect stack- temperature, pore size start to decrease and
ing between the microfibrils of graphite basal eventually the pores will shrink and collapse
plane in carbon fiber gives rise to empty spaces owing to progressive annealing (Suda and
between the microfibrils that form pores or Haraya, 1997; Centeno and Fuertes, 1999). The
voids. Generally, low temperature carbon fibers BET surface area is increased as the pyrolysis
have small but numerous pores that are distri- temperature reaches the maximum to a value of
2
buted throughout the carbonized material (Donnet 103 m /g, and then decreases rapidly. This trend
and Bansal, 1984). also agrees with the results reported by Lee and
This is in agreement with the results Tsai (Lee and Tsai, 2001).
shown in Table 3. It can be observed that the
average pore diameter increases with increasing Conclusion
o
the pyrolysis temperature up to 800 C due to
the expelling of the carbon atoms as carbon mon- Based on the results presented, it can be
Songklanakarin J. Sci. Technol. Polyacrylonitrile (PAN)
852 Saufi, S.M. and Ismail, A.F.
Vol. 24 (Suppl.) 2002 : Membrane Sci. &Tech.
o
(a) 700 C
o
(b) 800 C
o o
Figure 8. FTIR spectrum of pyrolyzed PAN membrane at (a) 700 C and (b) 800 C
Songklanakarin J. Sci. Technol. Polyacrylonitrile (PAN)
853 Saufi, S.M. and Ismail, A.F.
Vol. 24 (Suppl.) 2002 : Membrane Sci. &Tech.
Koresh, J. E. and Soffer, A. 1980. Study of molecular Linkov, V. M., Sanderson, R. D. and Jacobs, E. P. 1994.
sieve carbons. Part 1 pore structure, gradual Highly asymmetrical carbon membranes. J.
pore opening and mechanism of molecular Membr. Sci. 95. 93-99.
sieving. J. Chem. Soc. Faraday Trans. I. 76. Pesek, S. C. and Koros, W. J. 1994. Aqueous
2457-2471. quenched asymmetric polysulfone hollow fiber
Koros, W. J. and Rajiv Mahajan 2000. Pushing the prepared by dry/wet phase separation. J. Membr.
limits on possibilities for large scale gas Sci. 88. 1-19.
separation: Which strategies? J. Membr. Sci. Robeson, L. M. 1999. Polymer membranes for gas
175. 181-196. separation. Current Opinion in Solid State &
Lafyatis, D. S., Tung, J. and Foley, H. C. 1991. Poly Materials Science. 4. 549-552.
(furfurylalcohol)-derived carbon molecular Sedigh, M. G., Xu, L., Tsotsis, T. T. and Sahimi, M.
sieves: Dependence of adsorptive properties 1999. Transport and morphological charac-
on carbonization temperature, time and poly teristics of polyetherimide-based carbon mo-
(ethylene glycol) additives. Ind. Eng. Chem. Res. lecular sieve membranes. Ind. Eng. Chem.
30. 865-873. Res. 38. 3367-3380.
Lee, L. L., and Tsai, D. S. 2001. Synthesis and perm- Steel, K. M. and Koros, W. J. 2003. Investigation of
eation properties of silicon-carbon-based inor- porosity of carbon materials and related ef-
ganic membrane for gas separation. Ind. Eng. fects on gas separation properties. Carbon. 41.
Chem. Res. 40. 612-616. 253-266.
Lewin, M. and Preston, J. 1983. Handbook of Fiber Steel, K. M. 2000. Carbon Membranes for Challeng-
Science and Technology, Volume III: High ing Gas Separations. University of Texas: Ph.D.
Technology Fibers. Parts A. New York and Thesis.
Basel: Marcel Dekker Inc. Suda, H. and Haraya, K. 1997. Gas permeation
Linkov, V. M., Sanderson, R. D. and Jacobs, E. P. through micropores of carbon molecular sieve
1994. Carbon membranes from precursors membranes derived from kapton polyimide,
containing low-carbon residual polymers. Polym. J. Phys. Chem. B. 101. 3988-3994.
Inter. 35. 239-242.