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journal of MEMBRANE SCIENCE

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Joum0a of Membrane Science 138 (1998) 153-163

Effect of PEG additive on membrane formation by phase inversion


Jeong-Hoon Kim, Kew-Ho Lee
Membranes and Separation Research Center, Korea Research Institute of Chemical Technology, P. O. Box 9, Daedeog-Danji, Taejon 305-606, South Korea Received 30 April 1997; received in revised form 21 August 1997; accepted 21 August 1997

Abstract
This study investigates the effect of PEG additive as a pore-former on the structure formation of membranes and their permeation properties connected with the changes of thermodynamic and kinetic properties in phase inversion process. The membranes were prepared by using polysulfone (PSf)/N-methyl-2-pyrrolidone (NMP)/poly(ethylene glycol) (PEG) casting solution and water coagulant. The resulting membranes prepared by changing the molecular weight of PEG additive and the ratio of PEG to NMP were characterized by scanning electron microscope observations, measurements of water flux and PEG rejection. The thermodynamic and kinetic properties of membrane-forming system were studied through coagulation value, light transmittance and viscosity. The correlations between the final membrane structure/permeation properties and thermodynamic/kinetic properties of membrane forming system are discussed extensively. 1998 Elsevier Science B.V.

Keywords: Phase inversion; Polysulfone; Thermodynamics; Kinetics; Coagulation value; Light transmittance; Viscosity;
Macrovoids; PEG additive effect

1. Introduction Most of polymeric membranes used in membrane separation process have been prepared by phase inversion process [ 1-8]. In this process, a homogeneous polymer solution is cast as a thin film or a hollow fiber shape and then, immersed into a nonsolvent coagulant bath. The diffusional exchange of solvent and nonsolvent across the interface between casting solution and nonsolvent can make the casting solution phaseseparate to form a membrane with a symmetric or asymmetric structure. Because of importance of this process, many investigators have been attempted to elucidate the membrane-forming mechanism during the phase inversion process. Consequently, the membrane formation by phase inversion process
0376-7388/98/$19.00 1998 Elsevier Science B.V. All rights reserved. Pll S0376-7388(97)00224-X

could be well understood with the help of thermodynamic/precipitation kinetic theories in the polymer solution. The addition of organic or inorganic components as a third component to a casting solution has been one of the important techniques used in membrane preparation. But, the role of organic and inorganic additives such as methyl cellulose, glycerine, poly(vinyl pyrrolidone) (PVP), PEG, water, LiC1 and ZnC12 etc. in casting solution has been reported as a pore-forming agent enhancing permeation properties, This behavior was explained in terms of their water-soluble character [8-11]. Other attempts to explain the additive effect on membrane formation have also been made. Krausetal.[ll]andDarcovichetal.[12]reportedthat the influence of the addition of inorganic salts on the

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J.-H. Kim, K.-H. Lee et al./Journal of Membrane Science 138 (1998) 153-163

membrane formation was explainable in terms of the salt effect based on activity and surface tension, but they are not thermodynamic and kinetic factors frequently used in phase inversion theory. Tai-Ping et al. tried to explain their membrane-forming process using the thermodynamic properties obtained only from their system [13]. But, it may be more reasonable to explain the organic and inorganic additive effect on the membrane formation using the thermodynamic and kinetic terms of the system such as coagulation value, viscosity, precipitation type, precipitation rate, diffusion coefficient, etc. But, the studies with such viewpoint have been rarely reported because there exist the complexities of the theoretical description and quantitative analysis of the thermodynamics and precipitation kinetics of these multi-component systems [14-18]. In this study, poly(ethylene glycol) (PEG) is employed as an additive to control the thermodynamics and kinetics in casting system. It will be investigated and discussed how the morphology of the resulting membrane can be changed with changing the molecular weight of PEG additive and the ratio of PEG additive to NMP in the casting solution, through SEM pictures, UF test, coagulation value, viscosity and intensity change of light transmittance,

Table 1 The compositions and viscosities of the PSf/PEG/NMPsolutions


Compositionw t % ) ( (PSf/PEG/NMP) Molecular weight of PEG (g/mole) Viscosity (cps)

15/10/75

600 2000 6000 12000 600 600 600 600 600 600

470 980 1960 260 470 910 1200 2400 6800

15/0/85 15/10/75 15/20/65 15/30/55 15/40/45 15/50/35 15/60/25

2. Experimental

2.1. Materials
Polysulfone (PSf) (Udel P3500) supplied by Amoco was used as a membrane material. N-Methyl-2-pyrrolidone (NMP) from Aldrich as a good solvent for polysulfone was used without further purification, Poly(ethylene glycol) (PEG)s obtained from Fluka AG. were used as organic additives in PSf/NMP solution and their average molecular weights were 600, 2000, 6000, 12000 g/mole, respectively. PEGs of molecular weight of 12 000 and 35 000 g/mole were also used in the solute rejection test. Pure water (H20) was used as a nonsolvent (coagulant).

positions and viscosities are shown in Table 1. They are of two groups. One group were prepared by changing the molecular weight of PEG from 600 to 12 000 g/mole in 15/10/75 (w/w/w) of PSf/PEG/NMP solution. The others were prepared by changing the ratio of PEG to NMP concentration from 0/85 to 60/25 (w/w) in 15 wt% PSf solution. The total concentration of PEG/NMP mixture remained at 85 wt% in casting solutions. These solutions prepared were kept for five days without stirring at room temperature to remove air bubbles in the solution. The casting solution became slightly turbid with increasing PEG additive/NMP ratio from 0/85 to 50/35 (w/w) or molecular weight of PEG additive from 600 to 6000 g/mole. When the casting solution with 60/25 (w/w) of PEG/ NMP ratio or 12 000 g/mole of molecular weight of PEG additive was used, the solution was not prepared as a homogeneous state. The solution was cast on a clean glass plate to a predetermined thickness with a Gardener knife at 25C and then, immediately immersed into a water bath at 25C to form membranes. The membranes were heat-treated in 90C water bath for at least 24 h to remove the traces of PEG additive and NMP. They were kept in a deionized water bath until tested.

2.2. Membrane preparation


PSf/PEG/NMP solutions consist of 15 wt% polysulfone and 85 wt% PEG/NMP mixture. Their com-

2.3. Determination of coagulation value


Coagulation value can be used as a measure of thermodynamic stability of the casting solution. It is

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155

defined as the added amount of HzO/NMP mixture in a 50 g of PSf/PEG/NMP casting solution, when remarkable coagulation is visually observed and does not redissolve at temperature of 25C in 24 h. The ratios of H20/NMP mixture used are 50/50 and 25/75 (w/w), respectively,
2.4. Determination of viscosity

2.7. Membrane morphology The surface and cross-sectional membrane morphologies were observed using Scanning Electron Microscope (SEM) (Jeol JSM 35 CF Scanning Electron Microscopy) from the fracture surface after breaking the membranes in liquid nitrogen.

Viscosity of the casting solution can hinder severely the exchange rate of solvent and nonsolvent during phase inversion process, and therefore, it can be used as an important parameter to influence the precipitation kinetics and thus, the formation of resulting membrane morphology. It was measured by Brooksfields viscometer at 25C.
2.5. Light transmittance measurement

3. Results and discussion


3.1. Thermodynamics of membrane-forming system

During the phase inversion process, precipitation kinetics gives important informations in interpreting the membrane-formation process. A similar experimental apparatus introduced by Smolders group's was used for light transmittance measurement to indicate the precipitation kinetics [5,19]. From the experiments, the light transmittance curves as a function of time were obtained and reorganized.
2.6. Permeation test

In order to understand the membrane-forming mechanism by the phase inversion process, the thermodynamics of membrane-forming system should be investigated. The 'coagulation value' can be used as a measure of thermodynamic stability of the casting system. The term 'coagulation value' was used originally by Ziabicki to represent thermodynamics in dry-wet spinning of fiber [20]. In membrane field, coagulation value was often used by Yao et al. [21]. The plots of coagulation value against the molecular weight of PEG additive and the ratio of PEG additive (molecular weight of 600 g/mole) to NMP are presented in Figs. 1 and 2, respectively. The coagulation

30

A common permeation test apparatus was used to measure the pure water flux and solute rejection of the PSf membranes. Pure water flux (PWP) and solute rejection (R) were determined with de-ionized water and 2000 ppm of aqueous PEG solutions at 1 atm and room temperature, respectively. The pure water flux is defined as, Pure Water Flux (cm3/cm 2 rain atm) = Q/(A x T) where Q is the volume of the permeate (cm3), A is the area of the membrane (cmZ), and T is the permeation time (min). The solute rejection (R) is defined as R (%) = (1
-

ek'x ~ _ ~ 20 > ~
~ 10
r,j

+ _ ~

25/75(water/NMP) 50/50(w,tcr/NMe)

~ - - - - o

m.

Cp/ff) x

100

'

2000

'

4000

'

6000

where Cp and Cf are the PEG concentration in the permeate and in the feed, respectively. The molecular weights of PEG solutes used were 12000 and 35 000 g/mole,

Molecular Weight of PEG additive(g/mole) Fig. 1. Effect of the molecular weight of PEG additive in 15/15/
70(w/w/w) of PSf/PEG/NMP solution on the coagulation value of

casting solution.

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J.-H. Kim, K.-H. Lee et a l . / J o u r n a l o f M e m b r a n e Science 138 (1998) 153-163

4o --~ 25/75(waler/NMP) - . - 50/50(water/YM~) ~ e " - ~ . "~ 20 =

""~..._

the casting solution became slightly turbid with increasing the ratio of PEG/NMP ratio. When the casting solution with more than 50/35 (w/w) of PEG/NMP ratio was used, the solution was not prepared as a homogeneous state. They indicate that the casting solution became thermodynamically less stable with increasing the ratio of PEG additive to NMP due to the increase in the concentration of PEG incompatible with PSf membrane material instead of NMP solvent. The similar behaviors were observed in previous works [13,15].

3.2. Precipitation kinetics


0 I I i

0/85

20/65

40/45

60/25

Ratio of PEG additive to NMP Fig. 2. Effect of the ratio of PEG additive to NMP (w/w) in 15 wt% PSf solution on the coagulation value of casting solution,

value was determined using water/NMP mixture of 25/75 and 50/50 (w/w). Fig. 1 shows that when the molecular weight of PEG additive increases from 600 to 6 000 g/mole, the coagulation value decreases. It was found that initial casting solution became slightly turbid with increasing the molecular weight of PEG additive. When the PEG additive with molecular weight of 12000 g/mole was used, the prepared solution almost became turbid state at 25C in five days. They indicate that the casting solution becomes thermodynamically less stable with increasing the molecular weight of PEG additive. A similar behavior in quaternary membrane-forming system was observed by Boom et al. [17,18]. Through the theoretical and experimental results in PES/PVP/NMP/water system based on thermodynamic concept, they showed that higher molecular weight of PVP additive as a more strong nonsolvent for PES reduced the concentration of water at clouding point curve, though the data obtained from experimental method shows large deviations from theoretical data. Their work agrees well with our experimental results in Fig. 1. The plots of coagulation value against the ratio of PEG to NMP from 0/85 to 60/25 (w/w) in 15 wt% PSf solution are presented in Fig. 2. Fig. 2 shows that the coagulation value decreases with increasing the PEG / NMP ratio from 0/85 to 50/35 (w/w). It was found that

Precipitation kinetics is very important in understanding membrane-forming mechanism. Two experimental techniques have been used to investigate the precipitation kinetics: Optical microscopy m e a s u r e m e n t technique was used by Strathmann [22] and light transmittance measurement technique by Smolders and Mulder's works [5,19]. In this study, light transmittance measurement technique was used. 'Precipitation rate' was used in Strathmann's work [22]. 'Precipitation type' was used in Smolders and Mulder's works [5,19]. In many cases, 'precipitation type' and 'precipitation rate' have often been used as the same meaning without discriminating each other. So to speak, delayed demixing of precipitation type has been considered as slow precipitation rate, while instantaneous demixing of precipitation type as fast precipitation rate. But, in this study, precipitation type and precipitation rate are both used with slightly different meanings in order to describe the precipitation kinetics more effectively.'Precipitation rate' is defined as the time length needed to almost achieve turbidity after immersing the transparent film in a nonsolvent bath; slow or fast precipitation rate. 'Precipitation type' is defined as the type of phase separation or demixing observed after immersion of transparent cast film in a nonsolvent; 'instantaneous demixing' or 'delayed demixing'. When water is used as a coagulant, the plots of the light transmittance curve against the molecular weight of PEG additive and the PEG (600 g/mole)/NMP ratio are presented in Figs. 3 and 4, respectively. Fig. 3 shows that when the molecular weight of PEG additive increases from 600 to 6000 g/mole, precipitation rate becomes slower while the instantaneous demixing of

J.-H. Kim, K.-H. Lee et al./Journal of Membrane Science 138 (1998) 153-163

157

100 No additive -+- PEC (600g/mo~e) - - - P E C (2000g/mole) PEC (6000g/mole)


i

-50 ~"

~\ ~ ' ~ ' ~ " ~ \~ 50 ~00 Time (see)

150

Fig. 3. Effect of the molecular weight of PEG additive in 15/15/ 70 (w/w/w) of PSf/PEG/NMP solution on the light transmittance curve,

100
, I)~ }/\~

0/85(PEG/NMP) t0/75(PEG/NMP)
30/55(PEG/NMP) 50/35(PEG/NMP)

maintained in all the given conditions. The delayed demixing of precipitation type is not observed in Figs. 3 and 4. It may be explained by Mulder et al.'s explanation that instantaneous demixing was observed when DMF, D M A c or N M P with a high mutual affinity for a nonsolvent (water) were used as a solvent for polysulfone material [5]. They suggested that instantaneous demixing of precipitation type was observed in thermodynamically less stable casting system such as PSf/DMF/water, CAfDMF/water, etc.. It is interesting to note that the instantaneous demixing of precipitation type is maintained under the thermodynamic less stable system produced by the addition of PEG. Another interesting point is that the overall precipitation rate also becomes slower with increasing molecular weight of PEG additive or the increase in P E G / N M P ratio in PSf solution. This result seems to be very interesting when considering Strathmann, Smolders and Mulder's previous works [5,19,22]. These precipitation behaviors may be originated from the viscosity of the casting solution as shown in Table 1. However, the exact reason is not yet clear. A detailed discussion on the precipitation rate behaviors will be given below in connection with the thermodynamics data, the permeation properties and the membrane morphologies.

"~ ~ ~ ~

--0-- Water Flux ~Rejection(12000 g/mole) " mole)

~ " ~ ~
50

. . . .
100

~
150

~
~

=
,~

Time (see) Fig. 4. Effect of the ratio of PEG additive to NMP (w/w) in 15 wt% PSf solution on the light transmittance curve.

~+

precipitation type is still maintained. A similar behavior is also observed in Fig. 4. As the ratio of PEG to N M P increases from 0/85 to 50/35 (w/w) in 15 wt% PSf solution, precipitation rate becomes slower while the instantaneous demixing of precipitation type is

0 2000 4000 6000 Molecular weight of PEG additive(g/mole) Fig. 5. Effect of the molecular weight of PEG additive in 15/15/ 70 (w/w/w) of PSf/PEG/NMP solution on pure water flux and solute rejection of the membranes.

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J.-H. Kirn, K.-H. Lee et al./Journal of Membrane Science 138 (1998) 153-163

3.3. P e r m e a t i o n p r o p e r t i e s a n d m e m b r a n e morphologies

The plot of pure water flux and solute rejection against the molecular weight of PEG additive from 600 to 6000 g/mole is presented in Fig. 5. No membrane was obtained from the solution with 10 wt% of PEG additive with molecular weight of 12 000 g/mole because the solution turned turbid before casting, Fig. 5 shows that when the molecular weight of PEG additive increases from 600 to 6000 g/mole, pure water flux increases and solute rejection decreases, when the molecular weights of PEG of 12 000 and 35000 g/mole are used as solutes (Note that they are not used as additives in Figs. 5 and 7). The membranes prepared under the above conditions are found to have

good ultrafiltration properties. In order to understand the permeation results, the overall cross-section, the toplayer and the top surface of the membranes prepared were carefully studied with SEM. The SEM observations are presented in Fig. 6. The top surface of the membranes are on the right, the toplayer on the middle and the cross-sections on the left. The pores of the top surfaces seem to be unclear, but those roughness increases slightly with the addition of higher molecular weight of PEG. Generally, it can be said that the pore size of the membrane depends upon the size of such aggregated particles as macromolecules, nodules or nodule aggregates [23,24]. The increase in pore size can be roughly estimated from the increase in the roughness and size of aggregated particle observed at the top surface. This analysis seems to

--1

m
ii

Fig. 6. Morphologies of the membrane prepared by varying the molecular weight of PEG additive in 15/15/70 (w/w/w) of PSf/PEG/NMP solution. Molecular weight of PEG additive directing from top to bottom: 0 (no PEG), 600, 2000 and 6000 g/mole. The top surface of the membranes are on the right, the toplayer on the middle and the cross-sections on the left.

J.-H. Kim, K.-H. Lee et al./Journal of Membrane Science 138 (1998) 153-163

159

be reasonable because it agrees well with the permeation results in this study, which can be influenced not only by overall membrane morphologies but also especially, by the toplayers in case of asymmetric structures. SEM observations and permeation properties illustrate that the addition of the high molecular weight of PEG increases the pore size of the top surface and the porosity of the toplayer in the membranes. From the SEM observations, it can be said that when the molecular weight of PEG additive increases, i) the pore size of the top surface becomes bigger, ii) the toplayer becomes more porous, iii)the distance from the top surface to the starting point of macrovoid formation becomes larger, and iv) the shape of macrovoid is less sharp, though the cross-section remains asymmetric, finger-type structures, The plot of pure water flux and solute rejection of the membranes prepared against the ratio of PEG additive (600 g/mole) to NMP from 0/85 to 50/35 (w/w) of 15 wt% polysulfone casting solution is presented in Fig. 7. When the casting solution of the ratio of PEG additive to NMP of 60/25 (w/w), no membrane was prepared as the polymer solution turned turbid before casting. Fig. 7 shows that the membranes prepared by increasing the ratio of PEG to NMP have higher pure water flux, but lower rejection with two

~ P~,reW,ter ~J,x
~ Rejectlon(12000 g,/r~le)

100

le) -~ " so "~~ "~

~1

PEG solutes with molecular weights of 12 000 and 35 000 g/mole The resulting membranes show the transition of permeation properties from ultrafiltration to microfiltration range with increasing the PEG/NMP ratio. In order to understand these permeation results, the membrane morphologies prepared were carefully studied with SEM. Fig. 8 shows the SEM photographs of the surface, the toplayer, and the cross-section of the membranes. In the SEM observations and permeation properties measured, when the PEG/NMP ratio increases from 0/85 to 50/35 (w/w), i) the pore size of the top surface becomes bigger, ii) the toplayer becomes more porous, iii) the distance from the top surface to the starting point of the macrovoid formation becomes larger, and iv) the shape of the macrovoid is less sharp until the cross-section changes from the asymmetric, finger type to the symmetric, sponge type (macrovoid-free) structure. The macrovoid formation in the cross-section is suppressed by increasing the ratio of PEG to NMP. It is also interesting to note the relationship between the initial developing point of the macrovoids, the shape of macrovoids and the porosity of toplayer. These relationships is largely related to the macrovoid formation mechanism. They will be given where the membrane-forming mechanism is discussed. The SEM observations also illustrate that the increase in pure water flux and the decrease in solute rejection are largely influenced by the increase in the pore size of the top surface and the porosity of toplayer. The membrane morphologies and permeation results in Figs. 5-8 agree well with early studies on the role of various additives: the pore-forming agents enhancing permeation properties. The results appear to suggest that the introduction of the PEG of the different molecular weights as additive, and the change of PEG/NMP ratio may be used to prepare the desire membrane for ultrafiltration or microfiltration.

3.4. Membrane-forming mechanism


The results in Figs. 1-4 show that when the ratio of PEG to NMP or the molecular weight of PEG additive in PSf solution increases, i) the casting solution becomes thermodynamically less stable and coagulation value decreases, ii) in the transmittance curve, the rapid initial decrease in transmittance and the slower or sluggish decrease over time are observed, iii) the

0 0/85
2o/es

"v 40/45

0
~o12s

Ratio of PEG additive to NMP Fig. 7. Effect of the ratio of PEG additive to NMP (w/w) in 15 wt% PSf solution on pure water flux and solute rejection of the membranes,

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J.-H. Kim, K.-H. Lee et al./Journal of Membrane Science 138 (1998) 153-163

...................

I~IIIIIIL._

Fig. 8. Morphologies of the membrane prepared by varying the ratio of PEG additive to NMP (w/w) in 15 wt% PSf solution. Ratio directing from top to bottom; 20/65, 30/55, 40/45, and 50/35 (w/w). The top surface of the membranes are on the right, the toplayer on the middle and the cross-sections on the left.

instantaneous demixing of precipitation type is maintained in all the given conditions. From the results in Figs. 5-8, it is also found that, i) the pore size of the surface becomes bigger and the toplayer becomes more porous, ii) the shape of finger-like structure becomes less sharp, iii) the distance from the top surface to the starting point of macrovoid formation becomes larger, and iv) in a extremely case that the solution with 50/35 (w/w) of P E G / N M P ratio was used, a macrovoid-free, symmetric cross-section is obtained, It has been generally accepted as a c o m m o n rule that thermodynamically less stable membrane-forming systems can enhance the precipitation rate and make more porous membranes and vice versa

[5,19,22]. Membrane morphologies and thermodynamic data in this study, may apparently seem to follow the common rules. The increase in the pore size and the porosity of toplayer observed in this study can be explained qualitatively by the theories based on the ratio of nonsolvent inflow to solvent outflow suggested by Young et al. [25,26]. With increasing the ratio of PEG to N M P or the addition of higher molecular weight of PEG, nonsolvent (water) inflow and outflow of solvent (NMP) of the toplayer is changed greatly. With the existence of a larger amount of PEG or a higher molecular weight of PEG with lower diffusion rate also disturbs the aggregation of the polymer molecules in the toplayer resulting in the same effect as when the ratio of nonsolvent inflow to

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161

solvent outflow increases and thus, yielding a membrane with more porous toplayer and possibly, more porous sublayer, But, the relationship between the thermodynamic and precipitation kinetic data shows poor agreement with the above common rules. Recently, Smolders et al. suggested the following empirical rule that membranes with macrovoids are formed in case of instantaneous demixing, except when the nonsolvent concentration in casting solution exceed a minimum value [27]. This study would provide a good explanation for the Smolders's exceptional empirical rule. In order to understand these phenomena, it is assumed that the initial rapid decrease in transmittance time indicates the phase-separation behaviors in the toplayer; and the slow or sluggish decrease in light transmittance over time points to the phase-separation behaviors in the sublayer. In spite of the change of thermodynamic stability, no changing pattern in light transmittance of the toplayer is clearly observed, which is likely to be due to the fast precipitation rate in the toplayer. The more sluggish decrease or slower precipitation rate in the sublayer can be considered to be originated from the large increase in viscosity of the casting solution. The viscosity data of the casting solutions by changing the molecular weight of PEG and the ratio of PEG to NMP are presented in Table 1. With increasing the molecular weight of PEG and the ratio of PEG to NMP, the viscosity of the casting solution increases. The increase in viscosity due to the organic additives were observed in many papers [13,15]. Two reasons are likely to be related to the increase in viscosity: one is the addition of PEG of higher molecular weight than NMP. The other is the addition of PEG with nonsolvent character for polysulfone instead of NMP, which can result in the interand intra-molecular aggregations or entanglements of the polymer chains in the casting solution. Consequently, the increase in viscosity of casting solution can hinder the diffusional exchange rate of solvent (NMP) and nonsolvent (water) in sublayer, which makes the precipitation rate of sublayer become slower, It is interesting to note the developing pattern of macrovoids. Strathmann explained that macrovoids are the results of rapid penetration of nonsolvent at certain weak spots in the toplayer of the membrane [1,22]. Young et al. proposed that it is necessary for

forming macrovoids that has a skin to limit the large amount of nonsolvent into the sublayer to induce many nuclei formation [28]. So to speak, porous toplayer can suppress the macrovoids formation of sublayer and result in porous, sponge type crosssection. SEM observations in this study show that when the pore size of the surface becomes bigger and toplayer becomes more porous; the shape of macrovoid structure becomes less sharp, the distance from the top surface to the starting point of the macrovoid formation increases. In an extremely case that the casting solution with 50/35 (w/w) of PEG to NMP was used, macrovoid-free, symmetric and porous cross-section was obtained. These SEM observations can be easily understood by combining two macrovoid-formation theories suggested by Strathmann et al. [1] and Young et al. [28], respectively. It can be assumed that the distance from the top surface to the starting point of macrovoids means the resistance to be able to limit the large amount of nonsolvent into sublayer which can induce many nuclei formation. The formation of many nuclei cannot make the macrovoids. In order to form the macrovoids, the more porous toplayer needs the larger distance from top surface to starting point of the macrovoids and vice versa. As a result, the porous sponge-type membrane with no macrovoids is formed under the highly less stable system, because the toplayer is too porous to form the resistance layer which can limit many nuclei formation in the sublayer and form macrovoids.

4. Conclusions Thermodynamic and kinetic considerations were given for the effect of PEG as a pore-forming agent in the casting solution on the membrane-forming mechanism including the toplayer and the macrovoid in phase inversion process. PSf/PEG/NMP solution and water were used as a casting solution and a coagulant, respectively. In order to understand the mechanism of membrane formation, thermodynamics and precipitation kinetics of the membrane-forming system were carefully investigated by measuring coagulation value, viscosity and light transmittance. It is found that with increasing the ratio of PEG additive (600 g/mole) to NMP, or the molecular

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w e i g h t o f P E G additive, the coagulation value decreases; it m e a n s that the casting solution b e c o m e s t h e r m o d y n a m i c a l l y less stable. Instantaneous d e m i x ing o f precipitation type is also maintained in all the given conditions. It is postulated that the initial rapid decrease indicates the phase separation behaviors o f the toplayer and the sluggish decrease o v e r t i m e points to the phase separation o f sublayer. B y introducing the viscosity o f the casting solution, the relationship o f the o b s e r v e d precipitation rate with t h e r m o d y n a m i c data is analyzed m o r e reasonably. U n d e r the s a m e preparation conditions, it is also found that the pore size o f the surface b e c o m e s b i g g e r and the toplayer b e c o m e s m o r e porous. Also, the distance f r o m the top surface to the starting point o f m a c r o v o i d f o r m a t i o n b e c o m e s larger. In an e x t r e m e case that the 15 w t % o f P S f solution of 50/35 (w/w) o f P E G / N M P ratio is used, a m a c r o v o i d - f r e e , s y m m e t r i c cross-section is obtained. With increasing the m o l e cular weight of P E G additive or the ratio o f P E G additive to NMP, water flux increases and solute rejection decreases. These p e r m e a t i o n properties agree w e l l with the S E M observations. The increase in toplayer porosity is e x p l a i n e d in terms o f the decrease in t h e r m o d y n a m i c stability and the mass ratio o f n o n s o l v e n t inflow and solvent outflow. As to the m e m b r a n e m o r p h o l o g i e s , toplayer porosity is closely related to the m a c r o v o i d formation. W h e n a m o r e porous toplayer is obtained, the m a c r o v o i d s f o r m a t i o n is largely suppressed. The m o r e porous toplayer needs the larger distance f r o m the top surface tO the starting point o f m a c r o v o i d s to limit the large n o n s o l v e n t inflow to the sublayer because a large n o n s o l v e n t inflow induce m a n y nuclei f o r m a t i o n in the sublayer and thus, prevent the m a c r o v o i d s formation. Therefore, a porous sponge-type m e m b r a n e with no m a c r o v o i d s is f o r m e d under the highly less stable system, because the toplayer o f the m e m b r a n e is too porous to f o r m the resistance layer w h i c h can limit m a n y nuclei formation in the sublayer,

References [I] H. Strathmann, Production of microporous media, in: D.R. Lloyd (Ed.), Materials Science of Synthetic Membranes, ACS Symposium Series, No. 269, American Chemical Society, Washington, D.C., 1985, pp. 165-197.

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