Desalination 207 (2007) 324339

Synthesis, characterization and performance of asymmetric polyethersulfone (PES) ultrafiltration membranes with polyethylene glycol of different molecular weights as additives
Ani Idrisa*, Norashikin Mat Zaina, M.Y. Noordinb
a

Department of Bioprocess Engineering, Faculty of Chemical and Natural Resources Engineering; b Department of Manufacturing and Industrial Engineering, Faculty of Mechanical Engineering, Universiti Teknologi Malaysia, 81300 UTM, Skudai, Johor, Malaysia Tel. +60 (7) 553-5603, Fax: +60 (7) 558-1463; email: ani@fkkksa.utm.my Received 23 March 2006; Accepted 13 August 2006

Abstract This paper reports the performance of asymmetric polyethersulfone ultrafiltration flat sheet membranes with polyethylene glycol (PEG) of different molecular weight as additives. The membranes were prepared by phase inversion process from casting solution containing polyethersulfone (PES) as polymer, N,N-dimethylformamide (DMF) as solvent and PEG of different molecular weights namely as PEG 200, PEG 400 and PEG 600 as additives. The membranes were characterized in terms of pure water permeation (PWP), molecular weight cut off (MWCO), solute separation, flux and membrane morphology. Mean pore size (p) and standard deviation (p) of the membranes were determined using solute transport data. The results revealed that membranes with PEG of higher molecular weights have higher pure water permeation and larger pores. The MWCO of the membranes increased from 26 to 45 kDa when the molecular weight of PEG is increased from 200 to 600. A significant change also occurred in pure water permeation, solute separation and flux when concentration of additives is increased from 5 to 25 wt% in casting solution. The presence of the different PEG molecular weights affect the surface roughness and morphology of the membrane as can be observed from the atomic force microscope (AFM) and scanning electron microscope (SEM) analysis. Keywords: Ultrafiltration; Polyethersulfone; Additives; Polyethylene glycol; Concentration

*Corresponding author.

0011-9164/07/$ See front matter 2007 Published by Elsevier B.V.

doi:10.1016/j.desal.2006.08.008

A. Idris et al. / Desalination 207 (2007) 324339

325

1. Introduction Membrane technology has been found to be an alternative and attractive approach for separation because the process is faster, energy efficient and does not involve any phase change [1]. Currently, the application of ultrafiltration in membrane technology is growing very rapidly in pharmaceutical, chemical, paper, semiconductor and dairy industries. Since Loeb and Sourirajan first introduced the phase inversion method, tremendous amounts of research have been performed to understand the mechanism of membrane formation. The important goal in membrane technology is to control membrane structure, which affects the membrane performance. Thus extensive research has been conducted in attempting to improve the performance of the membrane. The common technique for the preparation of asymmetric ultrafiltration membranes is the phase inversion method [2]. The production of asymmetric ultrafiltration membrane is very much influenced by many factors that include the four components, which are polymer, solvent, nonsolvent and additive. The presence of additive plays a crucial role in adjusting the membrane properties. Generally, additives create a spongy membrane structure by prevention of macrovoids formation, enhance pore formation, improve pore interconnectivity and introduce hydrophylicity [3]. Many researchers have investigated the effect of different types of additives on membrane morphology and their performance. Some researchers have studied the effect of natural additives such as maleic acid and piperazine on performance of PES ultrafiltration membranes [4]. Hydrophilic structure are obtained by the addition of additives such as glycerol, polyethylene oxide, LiCl and ZnCl2. Nonsolvent additives such as methanol, ethanol, n-propanol, diethylene glycol and deionized water were used to prepare polyethersulfone hollow fiber membranes [5,6] and their effect on separation properties of membranes

were investigated. It was reported that pure water permeation rates increased while rejections decreased as concentration of additives increased and adjusting the concentration of additives added could control the pore sizes of the PES membranes. Torrest et al. [7] investigated the effect of polyvinyl pyrrolidone (PVP) concentration on ultrafiltration membrane behavior and revealed that the presence of PVP in the solution of polyamide produced more porous membrane. Other researchers studied the effect of using different molecular weight PVP such as PVP K10, PVP K30, PVP K90 and PVP K360 on performance of PES membranes [6,810] and found that addition of small quantities of PVP of different molecular weights to a phase inversion ultrafiltration membrane resulted in an increased in permeability without significant changes in selectivity [8]. PVP proved to act as a pore forming agent, which is important in attaining appreciable porosity and pore size of the membrane [11,12]. Recently, polyethylene glycol 400 (PEG 400) has been used as an additive to enhance polyethersulfone (PES) hollow fiber membranes with its concentration range from 37 to 64 wt.% [3]. The results showed that PEG 400 can be used very well as polymeric additive [3,6,13] to increase the polymer dope viscosity and enhance the pore interconnectivity when added in appropriate amounts. It was reported that PEG 400 also acts as macrovoids suppressor and give the membrane its hydrophilic character. Nice spongy structures were obtained when sufficient nonsolvent and additive were added in the casting solution. PEG 600 has been used to prepare cellulose acetate/epoxy resin blend ultrafiltration membranes [14] but their investigations were limited to studies on its concentration effect on pure water permeation performance. However, Arthanareeswaran et al. [15] reported that concentration of additives greatly influenced the porosity and pore size of cellulose acetate membranes and

326

A. Idris et al. / Desalination 207 (2007) 324339

their protein rejection studies revealed that the increase in additive concentration has direct influence on the permeate flux and rejection rates. Kim and Lee [16] investigated the effect of various molecular weights of PEG on the formation of polyetherimide (PEI) asymmetric membrane and they reported that small molecular weights of PEG such as PEG 200 and PEG 400 work as pore reducing agent for PEI membranes. PEG with molecular of 600, 2000, 6000 and 12,000 Dalton have been used as additives to control the thermodynamics and kinetics in casting system of polysulfone (Psf) membranes [17] and the results indicated that viscosity of dope solution increased with molecular weights of additives. Some researchers also reported that PEG was used to improve membrane selectivity being hydrophilic in character and as a pore forming agent [18]. Although there has been work reported using PEG as additives, these work involved mostly polymeric systems such cellulose acetate, polyetherimide and polysulfone [1517] except for the use of PEG 400 for PES membranes [3]. There is yet no report regarding the effect of PEG 200 and PEG 600 on the performance of PES ultrafiltration membranes. In view of this, an attempt is made to investigate the effect of using PEG of different molecular weights namely as PEG 200, PEG 400 and PEG 600 as additives for PES ultrafiltration membranes. Polyethersulfone (PES) has been used as membrane material due to its excellent chemical resistant, good thermal stability and mechanical properties compared to polysulfone (Psf). PES is more suitable for liquid separation while Psf has advantages of gas separation and can be used at higher pressures [2]. In this study, the effect of different molecular weights PEG on viscosity, pure water permeation, solute separation, flux and membrane morphology were investigated and discussed in detailed. The concentration influence of the different molecular weights of PEG was also studied on

PES ultrafiltration membranes performance by changing the concentration of additive from 5 to 25 wt% in the casting solution. In addition the PES membranes with PEG of different molecular weights were characterized by using solute transport data where a sieving curve is obtained by plotting solute retention versus molar mass for each PES ultrafiltration membrane. There are two methods to determine the sieving curve [19]. The first method involves successive permeation of several solution where each contains a single solute whilst the second method was run using mixtures of solution having different molar mass where the advantage is single separation experiment is needed to determine the sieving curve. Other researchers advised that the cut off obtained by mixture solute should be interpreted with caution [20]. In this study PES membranes with additives of different molecular weights were characterized using the first method by solute transport data.

2. Experimental 2.1. Materials Polyethersulfone (PES) supplied by BASF was used as polymer in preparation of membrane casting solution. N,N-dimethylformamide (DMF) purchased from Labscan Asia Co. Ltd was used as the solvent without further purification. Polyethylene glycols with molecular weight of 200, 400 and 600 Daltons supplied by Merck were used as additives. Bovine serum albumins (BSA) with molecular weight of 67,000 Dalton and polyethylene glycols (PEG) with different molecular weight ranged from 1,000 to 35,000 Daltons purchased from Fluka were used as solutes. Feed solutions were prepared using distilled water. Other chemicals used were sodium iodide (KI) purchased from SureChe Products Ltd, barium chloride (BACl2) from Labguard, iodine (I2) from Emory and hydrochloric acid (HCl) from Merck.

A. Idris et al. / Desalination 207 (2007) 324339

327

2.2. Preparation of dope solution Dope solution was prepared by dissolving polyethersulfone in DMF and stirred for several hours. Then, additive was subsequently added with continuous stirring and heating at 80EC until the solution is completely dissolved and homogeneous. The resultant polymer solution was kept in a glass bottle and air bubbles in the casting solutions were reduced by ultrasonification process for several hours. The effect of the various molecular weights PEG was investigated by preparing the various dope solutions. The compositions of the various dope solutions consisting of different PEG such as PEG 200, PEG 400, PEG 600 and without additive are shown in Table 1. The viscosity of the different dope solutions was measured using the Brooksfield Digital Viscometer Model DV-II at 25EC. The concentration effect is also investigated by varying the concentration of the additives in the casting solution and keeping the PES concentration constant at 20%. Polyethylene glycols of different molecular weights were varied from 5 to 25 wt% concentration and the N-Ndimethylformamide (DMF) content in the casting solution was progressively reduced from 75 to 55 wt%. 2.3. Membrane casting The dope solution was poured onto a clean glass plate at room temperature and it was casted on a glass plate using a casting knife. Immediately after casting, the glass plate with the casted film was dipped into the distilled water at room temperature. Phase inversion starts and after few minutes a thin polymeric film separated out from the glass. The membrane was washed with distilled water and kept in the water bath until it is ready for evaluation. All flat sheet membranes were visually inspected for defects and good areas were chosen for membrane evaluation.

2.4. Ultrafiltration experiments Ultrafiltration experiments were performed using a stainless steel cross flow test cell at 3 bar. Membrane sample with area of 2.010!3 m2 was placed in the test cell with the active skin layer facing the incoming feed. The membrane was tested for pure water permeability experiments using distilled water. Then, separation experiments using aqueous solution of polyethylene glycol and bovine serum albumin with concentration of 1000 ppm were conducted starting from the lower molecular weight solute. The volume of permeate was collected and measured. The concentration of feed and permeate solutions were also determined for membranes characterization. In order to ensure reproducibility of results, a minimum of 3 samples were tested for each condition. System was thoroughly flushed with distilled water between runs of different molecular weight of solutes.

2.5. Concentration of polyethylene glycols and bovine serum albumin Concentrations of polyethylene glycols with molecular weight distribution range from 1,000 to 35,000 Daltons were analyzed using the following method by Sabde et al. [21]. The absorbance was run using the spectrophotometer (Shidmazu UV-160) at a wavelength of 535 nm against reagent blank. Besides, concentration of bovine serum albumin in permeates were analyzed using the Biuret Reagent [22]. Three milliliters of Buiret reagent were added to 2 ml of sample. Then it was heated in coagulation bath at a temperature of 37EC for 15 minutes. The colour of the Buiret reagent in BSA solution was allowed to change. The absorbance was tested using the spectrophotometer (Shidmazu UV-160) at a wavelength of 550 nm against a reagent blank to measure the concentration of the feed and permeate.

328

A. Idris et al. / Desalination 207 (2007) 324339

Table 1 PES ultrafiltration formulations and their viscosities Type of PEG additive Composition of casting solution, wt % Polymer Without additive PEG 200 PEG 400 PEG 600 20 20 20 20 Solvent 80 65 65 65 PEG 0 15 15 15 521 1190 1270 1590 Viscosity, cp

2.6. Membrane performance evaluation Membrane characterization of pure water permeation (PWP) for the PES ultrafiltration membrane was calculated from the equation

PWP =

Q A t

(1)

where Q is volume of the permeate (l), A is membrane surface area (m2) and t is permeation time (hour). The solute separation of the membrane was given by:

2.7. Membrane characterization by solute transport data 2.7.1. Stokes radius of polyethylene glycol The Stokes radius of a macromolecule can be obtained from its diffusivity in a solution using Stokes-Einstein equation and details of calculations were reported by Singh et al. [23]. The Stokes radius (a) was explained as radius of a hypothetical sphere that would diffuse with the same speed as the particle under study as described by Mosqueda-Jimenez et al. [24]. The Stokes radius of polyethylene glycol, a (cm) with a function of molecular weight, M is given by [23]

C R(%) = 1 p Cf

100

(2)

a = 16.73 1010 M 0.557

(4)

where Cp is solute concentration in permeate stream and Cf is solute concentration in feed stream. The flux (J) in the presence of solute for the ultrafiltration membranes is obtained by:

2.7.2. Pore size and pore size distribution The pore size of the PES membranes were calculated using solute transport data as derived by Singh et al. [23]. Solute diameter is given by d s = 2a (5)

J=

V A t

(3)

where V is volume of permeate (l), A is membrane surface area (m2) and t is permeation time (hour). A minimum of three membrane samples was tested and the tabulated results are the average values.

The solute separation curve was plotted to determine the mean pore size (p) and standard deviation (p) of the membranes. The data of solute separation versus solute diameter were plotted on a log normal graph paper. The mean pore size was calculated with ds corresponding to

A. Idris et al. / Desalination 207 (2007) 324339

329

R = 50% on the linear regression line. The standard deviation was calculated from the ratio of ds at R = 84.13% and at 50%. Moreover, MWCO can be measured from regression line at R = 90%. 2.8. Scanning electron microscopy (SEM) analysis PES ultrafiltration flat sheet membranes were snapped in liquid nitrogen so as to give a generally clean break [25]. The samples were then placed on a sample stand and sputter coated with gold. The cross section and surface morphology of PES ultrafiltration membranes were being viewed with high voltage SEM (Philip SEM Model XL-40) to characterize the membranes fabricated. 2.9. Atomic force microscopy (AFM) analysis The surface morphology (2D and 3D topographic images) and roughness analysis of mean roughness (Ra), the root mean square of data (Rz) and the mean difference in the height between the five highest peaks and the five lowest valleys (Ry) for PES ultrafiltration with PEG of different molecular weights as additives in scan area of 2 m 2 m were characterized using an atomic force microscope model Shimadzu SPM-9500J2.

The viscosities are observed to increase with the presence of additives. Increased in the molecular weights of additives increased the viscosity of the dope formulations. From Table 1, it is observed that the viscosity of casting solution without additive is 521 centipoises, which is very much lower as compared to the other casting solutions with additives. Apparently, the higher molecular weights of polyethylene glycol with long chain molecules increased the viscosity of polymer solution. Polymer solution with PEG 600 as additives has an almost three fold increase in viscosity compared to polymer solution without additive. It was reported that PEG 600 was used as additive to enhance polymer dope viscosity in cellulose acetate blend ultrafiltration membranes and their results show that presence of additive in casting solution improves the solution viscosity [14].

3.2. Pure water permeation (PWP) Fig. 1 clearly shows that the PWP is significantly affected by molecular weight of polyethylene glycol added to casting solution. PES membrane without additive exhibits pure water permeation of 14.0 l m!2 h!1. Addition of PEG 200 in the casting solution reduces PWP to 8.2 l m!2 h!1, which is much lower compared to pure water permeation for PES ultrafiltration membrane without additive. However, PES ultrafiltration membranes containing PEG 400 and PEG 600 show an excellent increase in the pure water permeation. PES ultrafiltration membrane containing PEG 400 as additive has pure water permeation of 30.5 l m!2 h!1 whilst PES ultrafiltration membrane with PEG 600 as additive shows the highest pure water permeation of 76.5 l m!2 h!1. Apparently, the results indicated that addition of additives with different molecular weights influence the formation of pore size of the membranes. Ultrafiltration membrane permeability is conceptually related to its pores [24].

3. Results and discussion 3.1. Polymer solution properties Table 1 shows the formulations and casting solution viscosities of PES ultrafiltration flat sheet membranes without and with different additives. It is observed that different molecular weight PEG has significant influence on viscosity of casting solution. PES ultrafiltration membrane without additive was used as control to compare the performance of PES ultrafiltration membranes with additives of different molecular weights.

330

A. Idris et al. / Desalination 207 (2007) 324339

Fig. 1. Pure water permeation for PES membranes without and with different additives. Fig. 2. Molecular weight cut-off profiles of polyethersulfone ultrafiltration membranes without additive and with various additives

3.3. Molecular weight cut off profiles The solute separation versus molecular weight relationship for PES ultrafiltration membranes with additives of different molecular weights are presented Fig. 2. It is observed that the solute separation increased with increase in molecular weight of solutes. By definition, molecular weight cut off is molecular weight that 90% rejected by the membrane [26]. MWCO is a pore characteristic of the membranes and it is related to rejection for a given molecular weight of solutes. The molecular weight cut off has linear relationship with pore size of the membranes [27]. It is observed that all PES ultrafiltration membranes perform diffuse profile. PES ultrafiltration membrane with PEG 200 as additive exhibits low MWCO. As can be seen in Fig. 2, it is clearly demonstrated that PES ultrafiltration membranes with PEG 400 and PEG 600 as additive exhibit higher MWCO compared to PES ultrafiltration membrane without additive. 3.4. PES membranes characterization using solute transport data Log normal plots of solute separation versus solute diameter for PES ultrafiltration membranes with additives of different molecular weight are presented in Fig. 3. Regression line was drawn

Fig. 3. Solute separation curves for PES ultrafiltration membranes without additive and with additive of different molecular weights.

with high correlation coefficient (r2 $0.98). The Stokes diameter ds can be determined using Eq. (5). The value of mean pore size (p), standard deviation (p) and MWCO of the PES ultrafiltration membranes were calculated from solute separation curves and the results are given in Table 2. Mean pore size is pore diameter when solute separation is 50% [28]. PES ultrafiltration membranes without additive exhibited 32 kDa molecular weight cut off and 3.47 nm mean pore size. The results show that an increase in

A. Idris et al. / Desalination 207 (2007) 324339 Table 2 Mean pore size, standard deviation and molecular weight cut off of different PES ultrafiltration membranes calculated from the solute separation curves Membranes Molecular Mean pore Standard deviation, weight cut off, size, p, (nm) p (kDa) 32 26 36 45 3.47 2.63 3.55 4.16 4.39 3.50 4.24 4.82

331

suitable for separation of proteins such as in dairy industries. PES ultrafiltration membranes with PEG 400 and PEG 600 as additives have MWCO of 36kDa and 45kDa was suitable used for separation of oil/water emulsion and biological suspension. Besides, the membranes can be used for waste treatment for separation of colloids and pyrogens. 3.5. Effect of different concentration of additive The effect of additive concentration in casting solution on PES ultrafiltration membranes performance such as pure water permeation, solute separation and permeate flux were investigated. Ultrafiltration experiments were run using 1000 ppm PEG 10kDa solution. The PWP changed with increased concentration of additives and this is clearly presented in Table 3. Pure water permeation decreases almost linearly when concentration of PEG 200 is increased from 5 to 25 wt%. It is observed that higher concentrations of PEG 400 in casting solution increased PWP rates only slightly. PWP rates increases gradually as higher concentration of PEG 600 is added. Maximum value for pure water permeation is 90.0 l m!2h!1 at 25 wt% of PEG 600 addition. The influence of PEG concentration on solute separation and permeate flux of the PES ultrafitration membranes are clearly indicated in Figs. 4 and 5, respectively. PES ultrafiltration membrane without additive exhibits 60.0% solute separation and 19.1 l m!2h!1 flux. It is observed that solute separation gradually decreased while flux increased when concentration of PEG 400 and PEG 600 are increased. At 5 wt% concentration of PEG 600, solute separation is 54% and when the concentration of PEG 600 increased to 25 wt%, solute separation gradually decreased to 35.2%. PES ultrafiltration membrane with PEG 400 as additive behaves in a similar manner to those containing PEG 600. At 5 wt% PEG 400 concentration, solute separation is 59.2% and

Without additive PES200 PES400 PES600

molecular weights of polyethylene glycol increase mean pore sizes from 2.63 to 4.16 nm while standard deviations decrease from 3.5 to 4.8. This indicated that pore size of the membranes increase with molecular weights of additives. For PES ultrafiltration membrane with PEG 200, PEG 400 and PEG 600 as additives, molecular weight cut off is measured to be around 26,000, 36,000 and 45,000 Daltons respectively. The results revealed that the membrane with high MWCO PEG has the largest pore radius, which explains for the increase in PWP. MWCO acts as guidance for pore sizes of the membranes where large MWCO implies large pore size of the membrane [13]. PES ultrafiltration membrane with PEG 200 as additive has small pore sizes compared to PES ultrafiltration membranes with PEG 400 and PEG 600 as additives. Thus, this study revealed that PEG 200 in PES ultrafiltration membrane increased solute separation but decreased flux rates. PES membranes with PEG 400 and PEG 600 as additive have very good flux result but slightly lower rejection rates. Adding different molecular weights additives allows production of membranes with different pore sizes thus allowing for specific application. PES ultrafiltration membranes containing PEG 200 as additive with MWCO of 26kDa are

332

A. Idris et al. / Desalination 207 (2007) 324339

Table 3 The changes of pure water permeation (PWP) with the concentration of additives PEG conc. PEG type PEG 200 PEG 400 PEG 600 5 wt% 10 wt% 15 wt% 25 wt%

Pure water permeation, PWP (l m!2 h!1) 20.1 26.0 33.5 15.2 32.3 52.0 9.4 35.5 76.5 7.4 56.0 90.0

Fig. 4. The changes of solute separation with the concentration of additives using PEG 10 kDa solution.

Fig. 5. Flux rates versus concentration of various additives using PEG 10 kDa solution.

when PEG 400 concentration is increased to 25 wt%, solute separation decreased to 43%. In contrast, solute separation increased linearly while flux decrease when concentration of PEG 200 is increased from 5 to 25 wt%. Maximum value for solute separation is 91.1% at 25 wt% PEG 200. The results indicate that the addition of PEG 200 reduced the pore size of the membranes. In this study, it is observed that PEG 400 act as pore forming agent that increased flux and decreased solute separation of PES ultrafiltration membranes. Experimental results revealed that the concentration of PEG with different molecular weights affect the size and number of pores of the PES ultrafiltration flat sheet membranes. Unlike PEG 400, PEG 200 has the tendency to behave as the pore reducing agent in PES ultrafiltration membrane indicated by the improved

solute separation. It is interesting to note that the effect of PEG 400 in this study is different from those reported on PEI membranes [16] where it was reported that PEG 400 acts as a pore reducing agent to PEI membranes and flux rate decreased and rejection increased compared to PEI membrane without additive. 3.6. Cross section of PES ultrafiltration membranes The SEM photographs of cross-sectional images of PES ultrafiltration membrane without additive and with PEG of different molecular weights are shown in Fig. 6. The morphology of the PES ultrafiltration membranes changed as the formation of macrovoids are influenced by molecular weight of PEG added. It can be observed

A. Idris et al. / Desalination 207 (2007) 324339

333

(a)

(b)

(c) (c)

(d)

Fig. 6. SEM photograph of the cross section of PES membranes containing (a) without additive, (b) PEG 200 (c) PEG 400 and (d) PEG 600 as additive.

from Fig. 6(a) that PES ultrafiltraton membrane without additive has big macrovoids and a thick asymmetric layer. Fig. 6(b) shows that the macrovoids decrease in size and the asymmetric layer thickness decreases when PEG 200 was added to the casting solution. The morphology of the bottom structure is almost similar to Fig. 6(a) except that the thickness of bottom layer with sponge like structure increased with PEG 200 as additive compared to other PES ultrafiltration membranes. Pure water permeation is strongly dependent on the top layer and sub layer of the

membranes. This probably explained for the low pure water permeation and flux rate for PES ultrafiltration membrane containing PEG 200 as additive. The thin asymmetric layer probably explains for the excellent improvement in the rejection rate but the thick spongy structure creates resistance thus resulting in rather low flux rates. As can be seen in Fig. 6(c) and 6(d), the size and shape of macrovoids are different from Fig. 6(a) and 6(b) when PEG 400 and PEG 600 were added. As can be seen in Fig. 6(c) and 6(d),

334

A. Idris et al. / Desalination 207 (2007) 324339

(a)

(b)

(c)

Fig. 7. Effect of concentration of PEG 600 on membrane morphology: (a) 10% additive, (b) 20% additive and (c) 25% additive.

the size of macrovoids gradually changed in structure from tear drop shape to elongated microvoids. PES ultrafiltration membrane with PEG 200 as additive has finger like tear drop macrovoids that ends halfway the membranes whilst PES ultrafiltration membranes with PEG 400 and PEG 600 as additive has finger like structure that almost penetrates throughout the membranes and improve pore interconnectivity. This explained for the higher flux obtained with PES UF membrane containing PEG 600. The results revealed that addition of PEG to casting solution influence the shape and size of macrovoids in the membranes.

3.7. Effect of additive concentration on membrane morphology The SEM images of PES ultrafiltration membranes changed with concentration of additives are presented in Figs. 7 and 8 respectively. The SEM images indicated that the membranes have asymmetrical structure with a skin layer at the top, intermediate layer and a bottom layer. From Fig. 7, it is obvious that when PEG 600 concentration is increased, the macrovoids increased in number and size, promoting the formation of many finger like pores. The finger like pores gradually extended to the bottom of the membranes at higher concentrations of PEG 600

A. Idris et al. / Desalination 207 (2007) 324339

335

(a)

(b)

(c)

Fig. 8. Effect of concentration of PEG 200 on membrane morphology: (a) 10% additive, (b) 20% additive and (c) 25% additive.

resulting in more porous membranes. Increased macrovoid formation leads to decrease of the effective thickness of the dense layer due to macrovoids in the support layer. This explained the results obtained where flux rates increased while solute separation decreased with increased concentration of PEG 600 in the casting solution. The effect of PEG on PES membranes have some similarity to the work done using PVP on PES membranes [10] where it was reported that PES membrane containing PVP as additive has big macrovoids and low flux resistance. Besides, the SEM results show that there are morphological changes in the membrane structure with addition of different concentration of PEG 200 in the casting solution as presented in

Fig. 8. In this study, it is observed that as the concentration of PEG 200 is increased in the casting solution the size of microvoids reduced and very thin skin layer were form. The reduction in the macrovoid size contributes to high flux resistance and thus explained for the low flux exhibited but excellent solute separation performance. However, the presence of the spongy bottom layer remains unlike that of PEG 600 where this structure almost diminished when concentration increases. Addition of PEG 200 as additive helps to improve the mechanical strength and increased the solute separation although the flux rate is quite low. The opposite effect of PEG 200 as compared to PEG 400 and PEG 600 occur because of their

336

A. Idris et al. / Desalination 207 (2007) 324339

Fig. 9. AFM topographic images of PES UF membrane without additive.

different viscosities. It was reported that when the concentration of PEG 200 is increased, its viscosity decreases sharply in the PEI/NMP solution [16]. Similarly, the same phenomenon could have occurred in the PES/DMF solution and as a result of this, PEG 200 does not act as cosolvent but as nonsolvent. Thus, greater amounts of PEG 200 added results in its rapid diffusion compared to the coagulant (water) inflow during the wet phase inversion process thus offering macrovoids free porous interconnecting channels. Also it can be seen that increasing amount of PEG 200 caused the formation of smaller and closer cells with a thin skin layer as can be associated in Fig. 8. The greater the concentration of PEG, the denser the membrane resulting in decreased flux and increased solute separation. Unlike PEG 200 the presence of high amounts of PEG 600 increase the dope solution viscosity as reported by Kim and Lee in Psf/NMP solution [17]. Such high viscosity solutions hinder the diffusional exchange rate of solvent (DMF) and nonsolvent (water) in the sublayer, which makes the precipation rate of sublayer become slower. Such rapid penetration of nonsolvent at the sublayer cause the formation of the large macrovoids as observed in Fig. 7.

3.8. Atomic force microscopy (AFM) observation Atomic force microscopy is a characterization technique, which presents very high possibilities of application in the field of microscopy observation and characterization of various surfaces [8]. AFM was used to study the characteristics of various membranes of different MWCO and also different material [23]. Several operating procedures can be applied like contact mode, non-contact mode and tapping mode. In this study the contact mode has been used to characterize different PES ultrafiltration flat sheet membranes. Fig. 9 shows the 2D and 3D AFM images of PES ultrafiltration membrane without additive at a scan area of 2 m 2 m where the nodules are not merged and in rows. 2D and 3D AFM images of PES ultrafiltration membranes with polyethylene glycol of different molecular weights are shown in Fig. 10(a)(c) respectively. The nodules are seen as bright high peaks whereas the pores are seen as dark depressions. Fig. 10(a)(c) clearly shows that the morphology of the surface changes with different molecular weights of polyethylene glycol added. On comparing Fig. 9 with Fig. 10(a), it is observed that the nodules are merged forming nodules aggregate with addition of PEG 200 as

A. Idris et al. / Desalination 207 (2007) 324339

337

(a)

(b)

(c)

Fig. 10. Series of AFM topographic images of PES membrane (a) without additive (b) PEG 200; (c) PEG 400; (d) PEG 600 as additive.

338

A. Idris et al. / Desalination 207 (2007) 324339

Table 4 Roughness parameter of PES membrane without additive and with polyethylene glycol of different molecular weight as additives PES UF membrane Without additive PEG 200 as additive PEG 400 as additive PEG 600 as additive Ra 3.401 3.288 3.417 3.854 Rq 4.322 4.225 4.382 4.790 Rz 38.193 33.787 35.490 36.050

additive. Merging of nodules results in higher separation and this was also observed in gas separation. The surface topography for PES UF membranes with PEG 400 and PEG 600 are qualitatively quite similar and showed small differences. Figs. 10(b) and (c) showed that the nodules are not merged, in row and each nodules are well defined. The results for roughness parameters,Ra, Rq and Rz for PES ultrafiltration membrane without additive and with polyethylene glycol of different molecular weights are presented in Table 4. The roughness parameter of PES ultrafiltration membranes decreased with addition of PEG 200 as additive compared to PES membrane without additive. This low molecular weight PEG 200 probably formed very tight nodules creating a very smooth surface indicated by the low roughness parameter values. However, the roughness parameters increased with addition of PEG 400 and PEG 600 as additive. As molecular weight of polyethylene glycol is increased from 200 to 600 Dalton the roughness parameter increased. It appears that the higher molecular weight PEGs, which is PEG 400, and PEG 600 tend to have less tightly packed nodule aggregates in the skin layer contributing to the increase in roughness parameters. The results indicated that PES ultrafiltration membrane with PEG 400 and PEG 600 as additives have rough surface whilst PES ultrafiltration membrane with PEG 200 as additive exhibits the smooth surface. Apparently it can be observed that membrane with high surface rough-

ness indicates high flux and membrane with smooth surface exhibits low flux. The same relationship between roughness parameter and MWCO was also observed by other researchers [22,29,30]. The change in the roughness parameters is proportional to the change in the pore size [30]. This may be explained since the roughness parameters depend on the Z values. In fact, when the surface consists of deep depressions that characterize pores and high peaks that correspond to nodules, high roughness parameters are expected. It is observed that the series of surface topographic images and roughness parameter is different for different molecular weight of PEG used as additives. Thus the molecular weight of polyethylene glycol in the casting solution affects the morphology of the skin surface of PES ultrafiltration membranes. 4. Conclusions In conclusion, the presence of polyethylene glycol of different molecular weights as additives exhibits significant effect on performance of PES ultrafiltration membranes. Addition of different polyethylene glycol as additives in casting solution improves the viscosity and influences the performance of pure water permeation rate. In determination of pore size of the membranes, it was found that ultrafiltration membrane with PEG 200 as additive exhibits the lowest value of MWCO and mean pore size compared to other membranes. The value of molecular weight cut off for PES ultrafiltration membranes with PEG 200, PEG 400 and PEG 600 are 26,000, 36,000 and 45,000 Daltons respectively. On the other hand, as concentration of PEG 400 and PEG 600 in the casting solution is increased solute separation decreased while flux increased. However, PES ultrafiltration flat sheet membranes with PEG 200 as additive performed different behavior which exhibits the highest solute separation but lowest flux rate when concentration of PEG is increased from 5 to 25 wt% in casting solution.

A. Idris et al. / Desalination 207 (2007) 324339

339

SEM photographs indicate surface and membrane morphology changes with addition of different molecular weight additives in casting solution. Addition of PEG 400 and PEG 600 in the casting solution increased the number and size of macrovoids while PEG 200 decreased the size of macrovoids in the intermediate. AFM analysis revealed that higher molecular weight PEG additives (PEG 400 and 600) exhibits higher roughness parameter compared to PEG 200. The membrane surface becomes rougher with increased molecular weight of additives. Membranes with rougher surfaces tend to have higher flux. Acknowledgement Financial support from the Ministry of Science, Technology and Environment through the IRPA funding vote no 74246 is gratefully acknowledged. References
[1] L.R. Weatherley, Engineering Processes for Bioseparation, Butterworth-Heinemann, Northern Ireland, 1994. [2] C. Barth, M.C. Goncalves, A.T.N. Pires, J. Roeder and B.A. Wolf, J. Membr. Sci., 169 (2002) 287299. [3] Y. Liu, G.H. Koops and H. Strathmann, J. Membr. Sci., 223 (2003) 187199. [4] B.K. Chaturvedi, A.K. Ghosh, V. Ramachandran, M.K. Trivedi, M.S. Hanra and B.M. Misra, Desalination, 133 (2001) 3140. [5] Z.-L. Xu and F.A. Alsalhy Qusay, J. Membr. Sci., 233 (2004) 101111. [6] B.T. Sanchez, R.I. Ortiz-Basurto and E.B. Fuente, J. Membr. Sci., 152 (1999) 1928. [7] M.R. Torrest, E. Soriono, J.D. Abejo and J.D.L. Campa, J. Membr. Sci., 237 (1993) 189197. [8] N.A. Ochoa, P. Pradanos, L. Palacia, C. Paglearo, J. Marchese and A. Hernandas, J. Membr. Sci., 187 (2004) 227237. [9] J.J. Qin, M.H. Oo and Y. Li, J. Membr. Sci., 247 (2004) 137142. [10] J. Marchese, M. Ponce, N.A. Ochoa, P. Pradanos and L. Palacio Hernandaz, J. Membr. Sci., 211 (2003)

111. [11] B. Jung, J.K. Yoon, B. Kim and H.-Whoo Ree, J. Membr. Sci., 243 (2004) 4557. [12] J. Barzin, C. Feng, K.C. Khulbe, T. Matsuura, S.S. Madaeni and H. Mirzadeh, J. Membr. Sci., 237 (2004) 7785. [13] R.E. Kesting, Synthetic Polymeric Membranes: A Structural Perspective, Wiley, New York, 1985. [14] R. Mahendran, R. Malaysamy and D. Mohan, European Polymer J., 40 (2004) 623633. [15] G. Arthanareeswaran, P. Thanikaivelan, K. Srinivasn, D. Mohan and M. Rajandran, European Polymer J., 40 (2004) 21532159. [16] I. Kim and K. Lee, J. Membr. Sci., 230 (2004) 183 188. [17] J.H. Kim and K.H. Lee, J. Membr. Sci., 138 (1998) 153163. [18] J.J. Shieh, T.S. Chung, R. Wang, M.P. Srinivasan and D.R. Paul, J. Membr. Sci., 182 (2001) 111121. [19] S. Platt, M. Nystrom, A. Bottino and G. Capennelli, J. Membr. Sci., 239 (2004) 91103. [20] C. M. Tram and A.Y. Tremblay, J. Membr. Sci., 57 (1991) 271287. [21] A.D. Sabde, M.K. Trivedi, V. Ramachandran, M.S. Hanra and B.M. Misra, Desalination, 114 (1997) 223232. [22] A.G. Gornall, C.J. Bardawill and M.M. David, J. Biol. Chem., 177 (1990) 751757. [23] S. Singh, K.C. Khulbe, T. Matsuura and P. Ramamurthy, J. Membr. Sci., 142 (1998) 111127. [24] D.B. Mosqueda-Jimenez, R.M. Narbaitz, T. Matsuura, G. Chowdhury. G. Pleizer and J.P. Santerre, J. Membr. Sci., 231 (2004) 209224. [25] I. Ani, Fabrication and optimisation of asymmetric hollow fiber membranes for reverse osmosis, Ph.D. Thesis, Department of Bioprocess Engineering, Universiti Teknologi Malaysia, Skudai, 2001. [26] C. Causserand, P. Aimar, C. Vilani and T. Zambelli, J. Membr. Sci., 149 (2002) 485491. [27] K.Y. Wang, T. Matsura, T.S. Chung and W.F. Guo, J. Membr. Sci., 240 (2004) 6779. [28] M. Cheryan, Ultrafiltration Handbook, Technomic Publishing, Lancaster, PA, 1986. [29] M. Khayet, C.Y. Feng and T. Matsuura, J. Membr. Sci., 213 (2003) 159180. [30] A. Bessieres, A. Meireles, M. Coratger, R. Beauvillain and V. Sanchez, J. Membr. Sci., 109 (1996) 271284.