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Department of Materials and Fibers, Nanya Institute of Technology, Chung-Li, Tao-Yuan 320, Taiwan, ROC
Department of Polymer Engineering, National Taiwan University of Science and Technology, Taipei 106, Taiwan, ROC
c Department of Materials and Textiles, Oriental Institute of Technology, Pan-Chiao, Taipei County 220, Taiwan, ROC
Received 30 September 2006; received in revised form 29 March 2007; accepted 12 April 2007
Abstract
Asymmetric cellulose acetate (CA) hollow fiber membranes were prepared by dry/wet spinning process from a dope composed of cellulose
acetate (CA), N,N-dimethylformamide (DMF), and polyethylene glycol (PEG). Herein, PEG was the additive; DMF was the solvent; whereas
water was the nonsolvent. The spinning parameters in this study were the contents and molecular weights of PEG and the external coagulation
temperature. The surface and cross-section morphology of the resulting hollow fibers were examined using scanning electron microscopy (SEM).
The pure water permeability (PWP) and retention of dextran were also measured. The results showed that the addition of PEG would suppress the
formation of macrovoids. The effect on the suppression was more obvious for PEG with higher molecular weight and higher content. When PEG
was added, the outer surfaces changed from smooth to microporous, whereas the inner surface remained smooth and dense. The PWP increased
with the additive content but slightly decreased with the increase of molecular weight. Oppositely, the retention of dextrans decreased with the
increase of additive contents but increased with the molecular weight. When adding PEG and coagulating at higher temperature simultaneously,
the outer surface and cross-section of CA/PEG blended membrane exhibited macrovoids on outer surface and finger-like voids near the inner and
outer edges. The resulting membranes showed higher PWP (47 times) with slight decrease in the retention. Hence, adding PEG and elevating
coagulant temperature will promote the permeation performance of CA hollow fibers.
2007 Elsevier B.V. All rights reserved.
Keywords: Ultrafiltration; Hollow fiber; Cellulose acetate; PEG additive; Drywet spinning
1. Introduction
Since the successful development of cellulose acetate (CA)
asymmetric membranes with a very dense and thin active layer
on the top of a porous substrate [1], CA membranes have been
applied in reverse osmosis for converting sea water into freshwater. Furthermore, CA hollow fiber membranes are widely used
for clinical hemodialysis. For instance, Kell and Mahoney [2]
invented a CA hollow fiber suitable for use in artificial kidneys
to provide superior water and solute clearances.
Hemodialysis is one of the most important methods for blood
purification. In general the characteristics of a hemodialyzing
material are ultrafiltration rate, solute permeability, mechani-
Corresponding author. Tel.: +886 2 2737 6528; fax: +886 2 2737 6544.
E-mail address: myang@mail.ntust.edu.tw (M.-C. Yang).
1383-5866/$ see front matter 2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.seppur.2007.04.005
210
Value
1. Polymer composition
2. PEG molecular weight (Dalton)
3. PEG concentration (PEG vs. CA by
weight)
4. CA concentration (by weight)
5. Spinneret temperature ( C)
6. Dope extrusion rate (g/min)
7. Spinneret OD/ID
8. Bore liquid
9. Bore liquid flow rate (ml/min)
10. Dope pressure (kPa)
11. Air-gap distance (cm)
12. Take-up velocity (m/min)
13. Coagulant composition
14. Coagulant temperature ( C)
15. Drying procedure
CA/DMF/PEG
1 k, 10 k, 40 kDa
7%, 14%, 21%
25%
Room temperature
11
0.6 mm/0.4 mm
H2 O
7.6
100
20
35
Tap water
2570
A few days in deionized water. One
day in 50% (w/w) glycerin aqueous
solution at room temperature and
dried at room temperature
nitrogen and then sputtered with a thin layer of gold using Jeol
JFC-11-E sputtering device. The outer and inner surfaces of the
hollow fibers were examined using a field emission scanning
electrical microscopy (FESEM) (S-800, Hitachi, Tokyo, Japan).
2.4. Ultrafiltration experiments
The experimental setup for measuring the pure water permeability (PWP) and retention of dextran for CA hollow fiber
was shown in our previous work [20]. Hollow fibers were tested in bundles of 10 fibers of 15 cm in length. Each end of the
module was a piece of Teflon tubing, 6.35 mm (1/4 in.) in diameter and 2.5 cm in length. The fibers were potted at both ends
with epoxy resin and mounted in a test module. While not taking
measurements, the modules were preserved in 50 wt% glycerol.
The preserving solution was flushed out first with water before
taking data. The feed was held in the hopper under a pressure of
50 kPa. To prevent concentration polarization [32], the feed was
recirculated at a flow rate of 25 ml/min with a metering pump
(RH1CKC, Fluid Metering, Inc., USA) through the lumen of the
hollow fibers, and the permeate was collected from the shell side
to simulate hemodialysis. The PWP was determined when the
flow rate stabilized. The pore size distribution was determined
using dextran of different molecular weights (10.2k, 35k, 66.7k)
to simulate the 2 -MG (MW: 11,800), pepsin (MW: 35,000) and
bovine serum albumin (MW: 68,000) protein. The dextran solutions concentration in the feed solution was kept at 1000 ppm.
The concentrations of dextran solutions were determined by
sulfuric acid phenol solution titration [33,34] and the absorbance at 490 nm was determined using an ultraviolet-visible
spectrophotometer (CE7200, Aquarius, England). The PWP, or
the ultrafiltration rate (UFR), was calculated by the following
equation:
PWP =
Q
Q
=
AP
nDi LP
(1)
211
Cp
Cf
(2)
Fig. 1. SEM photograph of hollow fiber membrane: (a) CA/DMF/water system (magnification: 140) and (b) CA/PEG/DMF/water system (magnification: 150).
212
Fig. 2. Effect of the PEG (MW 10 kDa) contents (PEG vs. CA weight ratio) on the morphology of cross-section of CA hollow fiber membranes: (a) 0%; (b) 7%; (c)
14% and (d) 21%.
Fig. 3 indicates that the droplet macrovoids was obviously suppressed as higher molecular weight of PEG was added. Although
those hollow fiber membranes were spun from the same PEG
content (21%-CA), Fig. 3(a) and (b) (1 kDa PEG was added)
apparently show a few macrovoids near the inner edge, whereas Fig. 3(c) and (d) (10 kDa PEG was added) and Fig. 3(e)
and (f) (40 kDa PEG was added) show that macrovoids were
inhibited. The difference between Fig. 3(c)(f) was only in the
thickness, and the thickness of membrane increased with the
molecular weight (Fig. 3(f)). The effect of the contents and molecular weights of PEG on the thickness of membranes were also
exhibited in the Table 2.
Table 2 lists the dimensions of the resulting CA/PEG hollow fibers. In general, higher PEG content and higher molecular
weight of PEG led to larger wall thickness of the hollow fiber,
since the total polymer content (CA and PEG) was higher. In
addition, larger PEG molecules would be more difficult to be
leached, and leading to thicker hollow fibers.
It has been known that the formation of macrovoid is
influenced by the molecular weight of additives [42,43]. Lower
molecular weight PEG is more soluble in water than higher
213
Fig. 3. SEM overall and partial cross-section photographs of membranes made from of CA solutions containing various molecular weight and same content of PEG
(21 wt%): (a and b) PEG (1 kDa); (c and d) PEG (10 kDa) and (e and f) PEG (40 kDa).
concentration and molecular weight of PEG during the membrane formation. In summary, as more PEG is added, the number
of macrovoids gradually disappears, regardless of the molecular
weight of PEG. When the same amount of PEG is added, the
wall thickness increased with the molecular weight of PEG, as
shown in Figs. 2 and 3 and Table 2.
Fig. 4 shows that the CA hollow fiber membranes with or
without PEG additive exhibited a dense and sponge-like structure. Fig. 4(b)(d) clearly show that CA/PEG membranes were
denser than original CA membrane in Fig. 4(a). This is because
CA/PEG membranes were spun from a dope with higher poly-
214
Table 2
The dimensions of CA/PEG blend hollow fiber membranes
PEG content (wt%-CA)
PEG (Da)
Do (m)
Di (m)
dry (m)
wet (m)
0
7
7
7
14
14
14
21
21
21
1k
10k
40k
1k
10k
40k
1k
10k
40k
473.5 (5.1)
444.2 (3.3)
416.7 (5.1)
449.0 (4.9)
475.2 (6.2)
487.9 (7.3)
500.0 (4.6)
433.9 (3.3)
512.0 (3.8)
515.1 (4.3)
350.0 (4.3)
315.8 (2.4)
293.3 (4.8)
300.0 (2.3)
336.6 (5.1)
330.3 (4.9)
329.6 (6.3)
283.5 (6.5)
341.2 (4.0)
322.1 (5.3)
61.6 (2.0)
64.2 (2.1)
70.0 (4.1)
74.5 (3.4)
69.3 (2.6)
78.8 (3.7)
85.2 (3.5)
73.2 (2.1)
83.5 (2.2)
95.5 (2.2)
81.3 (2.7)
83.7 (2.5)
86.3 (3.3)
94.0 (2.6)
89.3 (2.3)
94.3 (3.1)
100.3 (2.8)
90.3 (2.3)
96.9 (2.9)
110.7 (3.7)
Note: The numbers in the brackets are the standard deviation (n = 46).
(3)
Smaller PEG molecules can quickly diffuse out to the coagulant during the drywet spinning process which would lead to
a looser structure, while larger PEG molecules were more difficult to be removed which would retard the exchanging rate of
solvent and nonsolvent and result in a denser structure. Furthermore, when PEG and CA polymer chains entangled with each
other, higher molecular weight would make the entanglements
tighter. Hence the wall structure of membrane appeared denser
when adding higher molecular weight PEG. On the other hand,
because higher molecular weight PEG would diffuse out slower
and were entrapped in the CA matrix, after leaching out the resi-
Fig. 4. SEM image of partial cross-section of outer edge of membranes made from various molecular weight and same content of PEG (14 wt%): (a) original; (b)
PEG (1 kDa); (c) PEG (10 kDa) and (d) PEG (40 kDa).
215
Fig. 5. SEM image of inner surface of membranes made from various contents and same molecular of PEG (10 kDa): (a) original (magnification: 50,000); (b) PEG
(7%, magnification: 1000); (c) PEG (14%, magnification: 1000); (d) PEG (21%, magnification: 1000); (e) PEG (14%, magnification: 10,000) and (f) PEG
(21%, magnification: 10,000).
216
Fig. 6. SEM image of outer surface of membranes made from various coagulant temperature and same content molecular weight of PEG (14%, 10 kDa): (a) pure
CA, 25 C, magnification: 50,000; (b) pure CA, 75 C, magnification: 50,000; (c) 25 C, magnification: 10,000; (d) 50 C, magnification: 10,000; (e) 75 C,
magnification: 5000.
process at higher external coagulant temperature. Therefore, raising the coagulant temperature could result in porous surface
due to faster phase separation at higher temperature. In general,
macrovoid formation occurs under rapid precipitation conditions and the precipitation is faster at higher temperature [36].
Besides, higher temperature would increase the effusion rate
of the solvent from the spinning jet, hence the polymer molecules precipitated faster that shortened the time for molecular
rearrangement.
The other important parameter affecting the outer surface
morphologies is that PEG additive is water-soluble, especially
at higher temperature. Higher coagulant temperature could
217
Fig. 7. SEM image of partial cross-section of membranes made from various coagulant temperature with same content and molecular weight of PEG (14%, 10 kDa):
(a) pure CA, 25 C, magnification: 1000; (b and c) 25 C, magnification: 700; (d) 50 C, magnification: 700; (e) 75 C, magnification: 700.
218
Table 3
Effect of various content and molecular weight of PEG additive on the performance (the membranes were spun at 25 C)
PEG content (PEG vs. CA ratio)
0
7%
7%
7%
14%
14%
14%
21%
21%
21%
PEG (MW)
Pure CA
1k
10k
40k
1k
10k
40k
1k
10k
40k
5.6
4.4
3.9
12.4
10.1
8.6
18.4
15.9
14.0
35k
66.7k
89.5
88.8
90.3
85.8
87.3
89.3
83.0
84.1
85.9
96.2
94.7
95.2
94.6
93.5
94.4
89.3
90.5
90.4
99.5
97.4
97.7
95.7
94.5
95.3
95.1
94.5
95.2
seems that the PEG content is more influential on the permeation performance than the molecular weight of PEG. Higher PEG
content would lead to higher PWP. This is because that PEG is
a pore-forming agent that creates pores in the polymer matrix
of CA. On the other hand, higher molecular weight would be
less soluble and more difficult to effuse out than a lower molecular weight of PEG. Therefore the resulting CA hollow fiber
would have less but larger pores. It has been generally accepted
that performance of hollow fiber membranes were mainly affected by both of inner and outer skin. Micropore was observed
on the outer surface but not on the inner surface, even though
the PWP increased from 0 to 18.4 L/m2 h atm. The retention of
dextran slightly decreased with the increase of PEG content but
increased with the increase of the molecular weight of PEG.
This implies that the size of micropores increased with the PEG
content. However, the number of micropore decreased with the
increase of the molecular weight of PEG.
During the coagulation of hollow fiber, a substantial portion
of PEG may be entrapped in the pores and the entrapping amount
depends on the molecular weight of PEG. When the hollow fibers
were coagulated at lower temperature, the resulting membranes
exhibited dense structure, higher tensile force, and lower PWP.
By destroying the dense skin in either surface, the PWP can
be improved while retaining the retention. This can be achie-
Table 4
Effect of the coagulant temperature on the performance of CA/PEG blend hollow fiber membrane
PEG (MW and content) (PEG vs. CA ratio)
Coagulant temperature ( C)
35k
66.7k
Pure CA
25
50
75
8.4
15.6
87.6
78.7
93.8
88.2
97.2
93.1
25
50
75
12.4
25.8
45.9
85.8
83.5
72.3
94.6
90.2
85.3
95.7
93.1
90.5
25
50
75
10.1
30.1
55.3
87.3
75.3
59.3
93.5
84.6
74.9
94.5
92.4
90.2
25
50
75
8.6
35.6
62.5
89.3
74.9
41.9
94.4
80.8
65.3
95.3
90.6
88.5
[8]
[9]
[10]
[11]
[12]
[13]
[14]
[15]
[16]
[17]
[18]
[19]
[20]
[21]
[22]
[23]
[24]
[25]
[26]
[27]
[28]
[29]
[30]
[31]
[32]
[33]
[34]
[35]
[36]
[37]
References
[1] G.S. Loeb, S. Sourirajan, Adv. Chem. Ser. 38 (1963) 117.
[2] M.J. Kell, R.D. Mahoney, GB Pat., 2,000,722 (1979).
[3] R.E. Kesting, Synthetic Polymeric MembranesA Structure Perspective,
Wiley, New York, 1985.
[4] T. Tsuruta, T. Hayashi, K. Kataoka, K. Ishihara, Y. Kimura (Eds.), Biomedical Applications of Polymeric Materials, CRC Press, Boca Raton, FL,
1993.
[5] R. Deppisch, M. Storr, R. Buck, H. Gohl, Sep. Purif. Technol. 14 (1998)
241.
[6] D. Gustav, S. Lothar, A. Wolfgang, US Pat. 5,403,485 (1995).
[7] Teijin Ltd., EP 0,697,242 (1996).
[38]
[39]
[40]
[41]
[42]
[43]
[44]
[45]
[46]
[47]
[48]
219
J.J. Qin, Y. Li, L.S. Lee, H. Lee, J. Membr. Sci. 218 (2003) 173.
S.A. Mckelvey, D.T. Clausi, W.J. Koros, J. Membr. Sci. 124 (1997) 223.
T. Liu, D. Zhang, S. Xu, S. Sourirajan, Sep. Sci. Technol. 27 (1992) 161.
J.J. Qin, T.S. Chung, J. Membr. Sci. 157 (1999) 35.
T.S. Chung, E.R. Katchniski, J. Appl. Polym. Sci. 65 (1997) 1555.
T.S. Chung, S.K. Teoh, X. Hu, J. Membr. Sci. 133 (1998) 161.
T.S. Chung, E.R. Kafchinski, P. Foley, J. Membr. Sci. 75 (1992) 181.
M. Henmi, T. Yoshioka, J. Membr. Sci. 85 (1993) 129.
T.S. Chung, E.R. Kafchinski, R. Vora, J. Membr. Sci. 88 (1994) 21.
W.L. Chou, M.C. Yang, Polym. Adv. Technol. 16 (2005) 1.
W.L. Chou, D.G. Yu, M.C. Yang, J. Polym. Res. 12 (2005) 219.
W.L. Chou, M.C. Yang, J. Membr. Sci. 250 (2005) 259.
M.C. Yang, M.T. Chou, J. Membr. Sci. 116 (1996) 279.
P. Aptel, N. Abidine, F. Ivaldi, J.P. Lafaille, J. Membr. Sci. 22 (1985)
199.
X. Miao, S. Sourirajan, H. Zhang, W.W.Y. Lau, Sep. Sci. Technol. 31 (1996)
141.
G.C. East, J.E. McIntyre, V. Rogers, S.C. Senn, Proceedings of the Fourth
BOC Priestly Conference, Royal Society of Chemistry, London, 1986, p.
63.
H. Kim, Y.I. Park, J. Jagel, K.H. Lee, J. Appl. Polym. Sci. 57 (1995) 1637.
H.A. Tsai, D.H. Huang, S.C. Fan, Y.C. Wang, C.L. Li, K.R. Lee, J.Y. Lai,
J. Membr. Sci. 198 (2002) 245.
M. Khayet, Chem. Eng. Sci. 58 (2003) 3091.
Z.L. Xu, F.A. Qusay, J. Membr. Sci. 233 (2004) 101.
J.H. Kim, K.H. Lee, J. Membr. Sci. 138 (1998) 153.
E.W. Merrill, S. Wan, E.W. Salzman, Trans. Am. Soc. Artif. Intern. Organs
20 (1986) 1517.
Y. Liu, G.H. Koops, H. Strathmann, J. Membr. Sci. 223 (2003) 187.
D. Li, T.S. Chung, R. Wang, J. Membr. Sci. 243 (2004) 155.
H. de Balmann, V. Sanchez, Int. Chem. Eng. 32 (1992) 665.
M. Dubois, K.A. Gilles, J.K. Hamilton, P.A. Rebers, F. Smith, Nature 168
(1951) 167.
M. Dubois, K.A. Gilles, J.K. Hamilton, P.A. Rebers, F. Smith, Anal. Chem.
28 (1956) 350.
Y.S. Park, J. Won, Y.S. Kang, Langmuir 16 (2000) 9662.
C.A. Smolders, A.J. Reuvers, R.M. Boom, I.M. Wienk, J. Membr. Sci. 73
(1992) 259.
R.M. Boom, I.M. Wienk, T. van den Boomgaard, C.A. Smolders, J. Membr.
Sci. 73 (1992) 277.
J.Y. Lai, F.C. Lin, C.C. Wang, D.M. Wang, J. Membr. Sci. 118 (1996) 49.
K. Kimmerle, H. Strathmann, Desalination 79 (1990) 283.
M.J. Han, Desalination 121 (1999) 31.
I.M. Wienk, R.M. Boom, M.A.M. Beerlage, A.M.W. Bulte, C.A. Smolders,
H. Strathmann, J. Membr. Sci. 113 (1996) 361.
Z.L. Xu, T.S. Chung, Y. Huang, J. Appl. Polym. Sci. 74 (1999) 2220.
Z.L. Xu, F.A. Qusay, J. Appl. Polym. Sci. 91 (2004) 3398.
M.J. Han, S.T. Nam, J. Membr. Sci. 202 (2002) 55.
L.Y. Lafreni`ere, F.D.F. Talbot, T. Matsuura, S. Sourirajan, Ind. Eng. Chem.
Res. 26 (1987) 2385.
B. Jung, J.K. Yoon, B. Kim, H.W. Rhee, J. Membr. Sci. 243 (2004) 45.
K. Devanand, J.C. Selser, Macromolecules 24 (1991) 5943.
H. de Balmann, P. Aimar, V. Sanchez, J. Membr. Sci. 45 (1989) 17.