Separation and Purication Technology 98 (2012) 298307

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Separation and Purication Technology

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Synthesis of sulfonated polyphenylsulfone as candidates for antifouling ultraltration membrane

Yang Liu, Xigui Yue, Shuling Zhang, Jiannan Ren, Lilong Yang, Qinhong Wang, Guibin Wang
College of Chemistry, Engineering Research Center of High Performance Plastics, Ministry of Education, Jilin University, Changchun 130012, PR China

a r t i c l e

i n f o

a b s t r a c t
This work focused on the synthesis of a series of sulfonated polyphenylsulfone (SPPSU) random copolymers with various controlled sulfonation levels by using sulfonated monomer in direct copolymerization method and the preparation of antifouling SPPSU ultraltration membranes via the conventional immersion precipitation phase inversion method. The chemical structures of the SPPSU copolymers were conrmed by using Fourier transform infrared spectrometer (FTIR) and their thermal properties were thoroughly characterized by differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). The morphologies of the SPPSU membranes were investigated by scanning electron microscopy (SEM), and the morphology changes of these resultant membranes had been detailedly explained and veried by Hansen solubility parameters (HSPs) from thermodynamic theory. In addition, the surface hydrophilicity and charged property of the SPPSU membranes were studied by water contact angle and membrane potential measurements, and the results indicated that the sulfonation of membrane material is really an effective way to enhance the hydrophilicity and negatively charge the membrane. The pure water ux and protein solution permeation through the prepared membranes were increased with the increase of the degree of sulfonation. The cycle ultraltration experiments for protein solution revealed that nonspecic protein adsorption, especially irreversible protein adsorption, for the SPPSU membranes was signicantly reduced, suggesting superior antifouling performance. Crown Copyright 2012 Published by Elsevier B.V. All rights reserved.

Article history: Received 5 March 2012 Received in revised form 20 June 2012 Accepted 20 June 2012 Available online 28 June 2012 Keywords: Sulfonated polyphenylsulfone Ultraltration Antifouling Membrane morphology

1. Introduction Membrane technology, especially ultraltration (UF), as an effective and powerful technique has in recent years superseded other traditional separation processes in industry for removal of dispersed or dissolved contaminants from water and as it involves a number of attractive features mainly low energy consumption, mild operating conditions, no additive requirements, no phase change and environmentally friendly [1]. However, the use of ultraltration in most applications is often limited by membrane fouling caused by inorganic and organic substances which can adsorb on the surfaces or adhere to the pores, resulting in progressive deterioration of membrane performance, alteration of membrane selectively and increase in costs of energy and membrane replacement [2]. Therefore, it is critical to develop advanced antifouling ultraltration membranes that have high chemical and biological stability, high resistance to fouling, and tailored separation ability to meet various demands. The state-of-the-art materials used for manufacturing of commercial ultraltration membrane are generally made from poly-

Corresponding author. Tel./fax: +86 431 8516 8889.

E-mail address: wgb@jlu.edu.com (G. Wang).

mers [3], such as cellulose [4], poly(vinylidene uoride) [5], polyetherimide [6], polysulfone [7] and polyethersulfone [8]. Among other potential membrane materials, polyphenylsulfone (PPSU) is an amorphous high performance engineering polymer that is reported to offer more toughness, strength, rigidity, hydrolytic stability, chemical and mechanical resistance than other polymer materials, and capacity to operate at high temperatures. Its glass transition temperature of 220 C is higher than that of polysulfone (190 C) and almost equal to that of polyethersulfone (225 C). However, PPSU has a higher solvent resistance than other polymers [9,10], which should be paid more attention for its potential application in some solvent-sensitive membrane separation processes. The excellent chemical and physical characteristics of PPSU resin make it an ideal candidate for the preparation of ultraltration membranes. However, the PPSU membrane application in aqueous phase separation is limited by its inherent hydrophobic property. On the one hand, the hydrophobicity restricts the permeate ux that is a key parameter in dening the membrane performance; on the other hand, when feed solutions containing substances like proteins are ltered, the hydrophobic interaction between the PPSU membrane and protein molecules often causes nonspecic adsorption and deposition of proteins on the membrane surface or in pores, and results in serious membrane fouling [11,12]. Although the membrane fouling is a very complicated pro-

1383-5866/$ - see front matter Crown Copyright 2012 Published by Elsevier B.V. All rights reserved. http://dx.doi.org/10.1016/j.seppur.2012.06.031

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cess, many studies have demonstrated that an increment in the hydrophilicity of membrane material could possibly inhibit the protein hydrophobic adsorption and thus signicantly reduce the membrane fouling caused by the non-specic protein adsorption and deposition [13,14]. Therefore, the chemical structure of PPSU must be altered to induce controlled levels of hydrophilicity to enable high rate of water transport, and to suppress the membrane fouling. It is well known that the sulfonation of membrane materials is a straightforward and effective method to improve the membrane water permeability and meanwhile charge the membrane [15]. To data, many researches relating to sulfonated materials have been reported and used successfully to improve the membrane resistance toward fouling in several membrane separation processes, such as ultraltration [1517], nanoltration [18] and reverse osmosis [19,20]. However, previous sulfonated membrane materials were prepared by post-polymerization sulfonation methods [1517]. In general, the sulfonation of membrane materials with strong acids (sulfuric acid and chlorosulfuric acid) is a harsh chemical treatment, which can lead to undesirable side reactions, chain cleavage and cross-linking. Especially, control of the sulfonation level is very difcult since the sulfonation occurs on the activated ring, which may deteriorate thermal stability of the nal polymer [20]. Although a sulfonated polymeric material with a high degree of sulfonation is considerably benecial to ultraltration process, the highly sulfonated material readily compromises the mechanical properties of membrane because the material is difcult to precipitate and solidify in water or other commonly used non-solvent during the membrane formation [15]. Therefore, increasing need for the precise control of the degree of sulfonation has driven the new development of sulfonation methods to overcome the synthetic challenges of traditional method. In contrast, an alternative route was employed to synthesize sulfonated polymer using sulfonated monomer in direct copolymerization, which is fundamentally different approach from the sulfonation of polymer mentioned earlier. In the sulfonated monomer approach, the modication of monomer makes feasible control of the molecular structures. Meanwhile, this method completely circumvents those disadvantages of post-polymerization sulfonation, and leads to highly reproducible sulfonated materials [20,21]. Most importantly, due to the degree of sulfonation is easily controlled by adjusting the ratios of the sulfonated monomer to non-sulfonated monomer, the direct copolymerization method can provides a good opportunity to improve the membrane performance without sacricing mechanical strength. The present study reports on the synthesis of a series of random sulfonated polyphenylsulfone (SPPSU) with various tailorable sulfonation levels, which were used in the preparation of antifouling ultraltration membrane. The chemical structures and thermal properties of the SPPSU copolymers were thoroughly characterized by Fourier transform infrared spectrometer (FTIR), differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). The morphology, surface hydrophilicity and charged property of the SPPSU membranes were studied by scanning electron microscope (SEM), water contact angle and membrane potential measurements. The membrane performances during BSA cycle ultraltration experiments were evaluated and the antifouling performances of the SPPSU membranes were examined in detail. It was expected that the SPPSU membranes provide a good opportunity to improve antifouling property.

for mutual solubility of membrane material and solvent, their free energy of mixing, DGm, should be negative. DGm is dened as

DGm DHm T DSm

where DSm describes the entropy of mixing, which is usually positive, DHm is the enthalpy of mixing, which can be correlated with the Hildebrand solubility parameter (d), as

DHm /1 /2 V m d1 d2 2 /1 /2 V m DdI 2

where the subscripts 1 and 2 denote membrane material and solvent, respectively. / is the volume fraction and Vm denotes the molar volume. It is clear that, to reaching DGm negative, the difference in Hildebrand solubility parameter between d1 (membrane material) and d2 (solvent), DdI, should be as small as possible. However, Hildebrand solubility parameter was t only for nonpolar solvents. In fact, the solubility parameter theory was true not only for non-polar systems, but also for polar systems including permanent dipolepermanent dipole and hydrogen bonding interactions. Consequently, Hansen extended the original Hildebrand single solubility parameter theory to the concept called Hansen solubility parameters (HSPs) in 1967 [22]. In the HSP theory, the total solubility parameter is divided into three separate parts: the non-polar/dispersion force, dd, the permanent dipolepermanent dipole force, dp, and hydrogen bonding force, dh [2124].
2 2 d2 d2 d dp dh

HSP are intrinsic physicochemical property of a substance, which provide an easy numerical method for fast predicting the basic properties of substances and estimating interactions between different substances, which appears to be more precise. According to Hansens interpretation of solubility parameter, different substances with sufciently close three-dimensional solubility parameters are likely to be compatible and miscible when they mix together, which reect strong interaction between different substances. The difference in Hansen solubility parameters (DdII) between membrane material and solvent was calculated using the equation:

DdII

q d1;d d2;d 2 d1;p d2;p 2 d1;h d2;h 2

3. Experimental 3.1. Materials Commercially available 4,40 -dichlorodiphenylsulfone (DCDPS) and 4,4-biphenol (BP) were purchased from Yanji Chemical plant, China, and dried under vacuum at 60 C for 24 h prior to use. The sulfonated monomer, 3,30 -disulfonate-4,40 -dichlorodiphenylsulfone (SDCDPS) was synthesized from DCDPS according to a procedure (Scheme 1) described in literature [25]. Bovine serum albumin (BSA, pI = 4.8, Mw = 67,000) and phosphate buffer solution (PBS, 0.1 mol/L, pH 7.4) were both purchased from Dingguo Biotechnology Co., Ltd. (Beijing, China). Coomassie brilliant blue G250 was purchased from Aldrich. Dimethyl formamide (DMF) was purchased from Shanghai chemical company, China. Other solvents and reagents were obtained from Beijing chemical company, China. The polymerization solvent, N-methyl-2-pyrrolidinone (NMP) and toluene were dried as follows: NMP was dried overnight over calcium hydride with a nitrogen purge and distilled at reduced pressure; toluene was dried over molecular sieves prior to use. Anhydrous potassium carbonate was dried under vacuum at 110 C for at least 24 h before use. Poly(vinylpyrrolidone) (PVP 30 K), which was used as pore-former, was purchased from Fluka

2. Theory The nature of membrane material in casting solution is believed to affect membrane performance. Like for all the mixing processes,

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Scheme 1. Synthesis of 3,30 -disulfonate-4,40 -dichlorodiphenylsulfone (SDCDPS).

Chemika, Switzerland. Deionized water was used through out this study. 3.2. Polymers synthesis Sulfonated polyphenylsulfone (SPPSU) random copolymers with various disulfonation levels were prepared via the direct polymerization method by aromatic nucleophilic substitution copolymerization (Scheme 2) as reported previously [25,26], and these references provide background on general synthesis of poly(arylene ether)s. 3.3. Membranes preparation The procedure of preparing ultraltration membranes by the conventional immersion precipitation phase inversion method was as follows. First, SPPSU with various disulfonation levels were dried at 80 C under vacuum for at least 24 h before use, and SPPSU and PVP were dissolved in DMF to form homogeneous casting solutions. The mass ratio of polymer, PVP, and DMF were 17:8:75. After ltering and degassing, the polymer solution was cast on non-woven fabric support with a casting knife with a nominal thickness of 200 lm at room temperature. Then, after exposing in air for 30 s, the formed membrane with fabric support was immerged in a water bath (20 C) to form the asymmetric membrane structure. During the preparation of the membranes, the relative humidity was about 55%. Finally, the membrane was kept in deionized water for at least 48 h until all of solvent and water-soluble polymer were removed, the at sheet ultraltration membranes were visually inspected for defects and good areas were chosen for ultraltration membrane experiments. 3.4. Characterization 3.4.1. Polymer characterization Fourier transform infrared spectroscopy (FTIR, Bruker Vertex 80V) was used to investigate the chemical structures of the SPPSU copolymers via the KBr pellet method by using a Bruker Vertex 80V FTIR spectrophotometer. All the spectra were baseline corrected.

Thermal transitions of the SPPSU copolymers were studied by using a modulated DSC (Model Mettler DSC821e) instrument at a heating rate of 20 C/min under a nitrogen ow of 200 mL/min. The second heat was used to assess glass transition temperatures (Tg). The thermogravimetric analysis (TGA) was employed to assess the thermal stability of the copolymers with a Perkine Elmer Pyris 1 analyzer under nitrogen atmosphere (100 mL/min) at a heating rate of 10 C/min. The inherent viscosity measurements were carried out with an Ubbelohde viscometer at a concentration of 0.5 g/dL in DMF at 25 0.1 C. All samples used for chemical structure and thermal stability characterization were dried under vacuum at 80 C for 24 h. 3.4.2. Membrane characterization The cross-section morphologies of the SPPSU membranes were examined by a scanning electron microscope (SSX-550, Shimadzu equipped with energy dispersive X-ray (EDX) spectroscopy). The membranes were frozen in liquid nitrogen and fractured to avoid destroying the structure of the cross-section, and sputtered with gold prior to SEM observation. The static water contact angles of the membranes were estimated by sessile drop method with a contact angle goniometer from Drop Shape Analysis (DSA 100 KRUSS GMBH, Hamburg) at room temperature. About 4 lL of deionized water was dropped onto the membrane surface with a microsyringe, and the value of water contact angle was recorded after 3 s. At least ve measurements in different locations of the membrane samples were carried out and averaged to yield the contact angles. 3.5. Membrane potential measurements The membrane potentials of the SPPSU membranes were measured in KCl solutions through a method as described in literatures [27,28]. The membranes (area of 10.4 cm2) were clamped between two self-made polyamide half-cells with volume of 95 cm3 by using silicone rubber rings. KCl solutions with the concentrations of 1 103 mol/L, 2 103 mol/L, 3 103 mol/L, 4 103 mol/L, 5 103 mol/L, 6 103 mol/L and 7 103 mol/L were used.

Scheme 2. Synthesis of sulfonated polyphenylsulfone.

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Each compartment was lled with 88 mL of KCl solution, which was circulated through its compartment by a peristaltic pump at a rate of 80 mL/min. The bottom surface of the membranes was contacted with the solution of 1 103 mol/L. The top surface of the membranes was contacted with other KCl solutions. The electrical potential difference of the cell (Ecell) was measured with two Ag/AgCl electrodes which were inserted directly into the bulk solutions. In order to eliminate the effect of the asymmetry potential, the potential difference was measured by exchanging the electrodes in the two compartments and the average of two values was calculated. The membrane potential Em is dened as follows:

the recycling property of these membranes, the ux recovery ratio (FRR) during the ltration cycle was calculated using the following expression:

 FRR%

J w2 J w1

 100 7

The higher FRR value means the better the antifouling property of the membrane. The membrane rejection ratio (R) was calculated by using the following equation:

  Cp 100 R% 1 Cf

Em Ecell

RT c2 ln F c1

where R is ideal gas constant, T is absolute temperature, F is Faraday constant, c2 and c1 is the concentration of Cl ions in bulk solutions (c1 > c2), respectively. 3.6. Protein adsorption experiments The amount of proteins adsorbed on membrane is one of the most important evidence in evaluating the fouling resistant ability of membranes, and BSA was used as model protein to evaluate the anti-protein adsorption performance of three investigated membranes in phosphate buffered saline (PBS, pH 7.4). The membrane samples were cut into a round shape with a diameter of about 30 mm, and treated by ultrasonication for 30 min in 0.1 M PBS solution for cleanness. Then the pre-treated membranes were immersed into PBS solution containing BSA (1.0 mg/mL) at 25 C for 4 h. After adsorption, each membrane was rinsed three times in the fresh PBS by gentle shaking. Then these membranes were transferred into a well-plate lled with PBS solution, and the protein adsorbed on the membrane surface was completely desorbed by ultrasonic treatment at room temperature for 3 min. The obtained PBS solution was dyed with Coomassie Brilliant Blue and measured by a UVvis spectrophotometer (UV3600, Shimadzu) to determine the total amount of adsorbed protein. The nal results were averaged from three specimens for each membrane. 3.7. Ultraltration experiments The performances of at sheet ultraltration membranes were tested using a stirred dead-end ltration cell at room temperature, and the effective area of the membranes was 12.6 cm2. At rst, each membrane was compacted at 0.2 MPa for 1 h prior to performing the ultraltration experiments. Then the pressure was lowered to 0.1 MPa and all the ultraltration experiments were carried out at this pressure. After compacted, deionized water was passed through the membrane to obtain the beginning pure water ux (Jw1, L/m2 h), and the ux was measured every 5 min. After 1 h of water ltration, a BSA solution with a concentration of 1.0 mg/ml in PBS (pH 7.4) was ltrated for 2 h, and the ux during protein ltration was recorded which called Jp. After BSA solution ltration, the membrane was washed thoroughly and passed through deionized water for another 30 min (the washing time was not counted in the ltration cycle). Thereafter, the pure water ux was measured again within 1 h for the membrane, which was recorded as Jw2. The ux (Jw and Jp) of the membrane was determined by direct measurement of permeate volume, which was calculated by the following equation:

In which Cp (mg/L) is the permeate concentration and Cf (mg/L) is the feed concentration. The solute concentration of permeation was measured by a UVvis spectrophotometer (UV3600, Shimadzu).To study the antifouling property in more detail for these investigated membranes, the degree of total ux loss caused by total protein fouling in the ltration cycle, Rt, was dened as

Rt %

  J w1 J p 100 J w1

A high value of Rt corresponds to a large ux decay and serious membrane fouling. The total ux loss was caused by both reversible and irreversible protein fouling. Rr was calculated by follow equation:

Rr %

  J w2 J p 100 J w1

10

which was the reversible fouling ratio caused by reversible fouling, and could be eliminated by hydraulic cleaning. And Rir was calculated by follow equation:

Rir %

  J w1 J w2 100 Rt Rr J w1

11

which was the irreversible fouling ratio caused by irreversible fouling, and can only be eliminated by chemical cleaning or enzymatic degradation [12,2931]. Rt was the sum of Rr and Rir. 4. Results and discussion In this work, sulfonation of the dihalide monomer, DCDPS, results in sulfonic acid functionalization on both deactivated phenyl rings ortho to the chlorine moiety and allows for two sulfonic acid groups per repeat unit after copolymerization. In the sulfonated monomer approach, the sulfonic acid groups are located at inherently more chemically stable positions than those obtained by post polymerization sulfonation, which sulfonates the most reactive, least stable positions of the polymer chain. Since no post-polymerization synthesis steps are required, these disadvantages of postpolymerization sulfonation are completely eliminated with the monomer sulfonation route. Additionally, use of sulfonated monomers affords precise control of the ionic group concentration in the nal polymer, which leads to make the sulfonated membrane material with reproducible properties and excellent membrane performance without sacricing mechanical properties. 4.1. SPPSU copolymer synthesis and characterization A series of sulfonated polyphenylsulfone (SPPSU) random copolymers with various disulfonation levels described herein were synthesized by direct polymerization of a sulfonated monomer (SDCDPS) and other monomers (DCDPS and BP), and the degree of sulfonation (DS) was controlled by varying the molar ratio of SDCDPS to DCDPS. The molar percentages of the monomers for the copolymers preparation are listed in Table 1, and the

V At

where V was the volume of permeation, A was the effective membrane area and t was the permeation time. In order to evaluate

302 Table 1 Fundamental properties of the SPPSU copolymers. Sample Feed (mol %) SDCDPS PPSU SPPSU-5 SPPSU-10 SPPSU-15 SPPSU-20 0 2.5 5.0 7.5 10.0 DCDPS 100 97.5 95.0 92.5 90.0 BP 100 100 100 100 100

Y. Liu et al. / Separation and Purication Technology 98 (2012) 298307

Viscosity

Tg (C)

T5% (C)

DS

gsp/c (dL/g)
0.59 0.65 0.62 0.72 0.83 220.8 226.4 228.5 233.5 234.2 547.3 533.8 530.2 526.5 522.5 0 0.05 0.10 0.15 0.20

nomenclature is SPPSU-X, where X is the concentration of hydrophilic sulfonic acid groups. The viscosity characterization indicates that all obtained copolymers have high molecular weight. FTIR was used to verify the incorporation of the sulfonic acid groups and chemical structures of the sulfonated polyphenylsulfone copolymers. As shown in Fig. 1, two absorption peaks were clearly observed at 1030 cm1 and 1103 cm1 for all sulfonated copolymers from SPPSU-5 to SPPSU-20, which could be attributed mainly to symmetric and asymmetric stretchings of the sulfonic acid group. Additionally, the densities of the characteristic peak of the sulfonic acid group symmetric stretching increase with SDCDPS contents. The FTIR spectrum aids in concluding that the sulfonated monomers are introduced into the copolymers successfully as expected. The glass transition temperatures (Tg) of the sulfonated polyphenylsulfone copolymers had been investigated with differential scanning calorimetry (DSC) under nitrogen. Fig. 2 shows the DSC thermograms of the SPPSU copolymers as a function of the degree of sulfonation. All the investigated copolymers are amorphous polymers. The DSC results showed an increase of Tg with the increase of sulfonated monomer content. This phenomenon could be explained by the introduction of sulfonic acid groups: rstly, increase the intermolecular interaction between molecular chains by pendant ions; and secondly, increase molecular bulkiness will result in difculty in segment movement. The thermal stability of the SPPSU copolymers had been investigated by thermogravimetric analysis (TGA) measurement under nitrogen. There was only one weight loss step for PPSU above 500 C, which was assigned to the degradation of the polymer chain. However, the SPPSU copolymers showed two weight loss steps. The initial weight loss was assigned to the loss of the sulfonic acid groups, and the second thermal degradation above 500 C was assigned to the decomposition of the copolymer back-

Fig. 2. DSC curves of the SPPSU copolymers: (a) PPSU, (b) SPPSU-5, (c) SPPSU-10, (d) SPPSU-15 and (e) SPPSU-20.

bone. The theoretical weight percents of the sulfonic acid groups in the SPPSU copolymers are less than 5%. Therefore, the 5% weight loss temperatures of these copolymers were above 500 C, indicating their good thermal stability (Table 1). In addition, the weight percents of the sulfonic acid groups in the SPPSU copolymers increased with the increase of the degree of sulfonation, and the initial weight losses of the SPPSU copolymers corresponding increased, so the 5% weight loss temperature shifted toward low temperature with the increase of sulfonated monomer content. 4.2. Morphologies of SPPSU membranes The scanning electron microscopy (SEM) was employed to investigate the morphology changes of the SPPSU membranes, and the SEM photographs are shown in Fig. 3. It is apparent that the SPPSU membranes have typical asymmetric structures, which consist of the thin dense skin layer and the porous sublayer. As can be seen in Fig. 3, the PPSU membrane has a long and thin nger-like structure while the SPPSU-5 membrane shows that the nger-like macrovoid structure become slightly wider. The morphological change of the SPPSU-5 membrane is rather unperceivable, but when the degree of sulfonation is higher, the change of morphology is quite noticeable. In particular, it is obvious that the number of macrovoids gradually decreased with the increase of the degree of sulfonation (the SPPSU-10, SPPSU-15 and SPPSU20 membranes). Another obvious difference among these membranes is their pore sizes in the inner of sublayer macrovoids. This phenomenon may result from the delayed phase separation as the hydrophilic SPPSU precipitates slowly and thus creates more and larger pores [32,33]. The delayed phase separation mechanism may be able to explain why the SPPSU-5 membrane shows a large number of pores in the inner of sublayer macrovoids, while only few pores can be observed in the inner of sublayer macrovoids of the PPSU membrane. When the content of the sulfonated monomer further increased, the pore sizes in the inner of sublayer macrovoids of the SPPSU-10 membrane increased dramatically, and an interpenetrating network of the pores in the inner of sublayer macrovoids formed are observed in the SPPSU-15 and SPPSU-20 membranes. It is well known that the morphology and performance of the resulting membrane strongly depend on both the kinetics and thermodynamics of the phase separation process. The former is related with the precipitation kinetics and the exchange rate between solvent and nonsolvent, and the latter with the polymer

Fig. 1. FTIR spectrum of the SPPSU copolymers: (a) PPSU, (b) SPPSU-5, (c) SPPSU-10, (d) SPPSU-15 and (e) SPPSU-20.

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Fig. 3. SEM images of the cross-sectional of the SPPSU membranes: (a) PPSU, (b) SPPSU-5, (c) SPPSU-10, (d) SPPSU-15 and (e) SPPSU-20.

solvent interactions, solvent-nonsolvent interactions and interfacial stability [34]. It is actually a diffusion-induced phase separation process, which involves conversion of a liquid polymer solution of two or more components into a two-phase system: the polymer-rich phase and the polymer-lean phase. When the concentration of nonsolvent exceeds a certain threshold, complete

precipitation occurs and the structure is xed, the polymer-rich phase forms the membrane structure while the polymer-lean phase forms the membrane pores. The precipitation rate can be considered to determine the amount of the available for the nucleation and growth of masses of polymer-lean phase within a matrix of polymer-rich phase after phase separation is induced [35,36].

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Simply put, a lower precipitation rate provides more time before precipitation is reached, enabling nucleation and growth of the polymer-lean phase to progress further, so that larger pores can form. The exchange rate between solvent and nonsolvent during the phase inversion process plays a crucial role in controlling the precipitation rate, and further governing the resulting membrane morphology [37,38]. The viscosity of the casting solution can hamper the exchange between components during the demixing process, thus, inuencing the resulting membrane morphology. From Table 1, it is seen that the viscosity of the SPPSU copolymers increase with the increase of the degree of sulfonation. Therefore, the viscosity of the casting solution is raised with higher DS of the SPPSU copolymers, which plays an important role by hindering severely the exchange rate between solvent and nonsolvent during the phase inversion process. There is a greater amount of time between when phase separation is induced and when precipitation is reached, nucleation and growth of the polymer-lean phase is able to process further. The sizes of pore and macrovoid therefore both become larger when the degree of sulfonation is higher. On the whole, the kinetics of the phase separation process explains the relationship between the change of the membrane morphology and the degree of sulfonation of the SPPSU copolymers. It is commonly accepted that the morphological change of the SPPSU membranes is also correlated to the interaction between membrane material and solvent. The relative strength of polymersolvent interaction determines the morphology and performance of the nal membrane. To study the morphology change in more detail from theory point, afnity of solvent to membrane material can be estimated by the introduction of HSP theory. However, Hildebrand and Hansen solubility parameters have been determined experimentally for a limited number of polymers. For most polymers, several useful prediction methods based on molecular structures have been proposed to estimate HSP values by Van krevelen (1976), Hoy (1985) and Beerbower (1984) [22,39]. In this work, the Van krevelen group contribution method was applied for calculating HSP values of the SPPSU polymers. This method requires decomposition of the repeat unit of the polymer into functional groups, and cohesion parameters listed in Table 2 are used in the calculation of HSP values. And HSP values were calculated by the following equations [22]:

The summary of the components of the Hansen solubility parameters for the SPPSU copolymers with different DS and the Dd values between DMF and SPPSU is presented in Table 3. As for Hansen solubility parameters, it is evident from Table 3 that the values increase with an increase in DS of polymer. This increase is not the same for all parameters, and the maximum increase is observed for dh, which is not surprising considering that the sulfonic acid groups are very electrophilic and have a strong tendency to form hydrogen bonds. It is well known that a smaller value of Dd leads to a stronger interaction. It can be noticed that the intensity of the interaction between SPPSU and DMF increases with the increase of the sulfonated monomer content. When the polymer solution contacts with water in a phase inversion process, the strong interactions between SPPSU and DMF restrict the diffusion process of water and suppress the exchange rate of DMF and water, which increase the time to reach precipitation and induce the delayed liquidliquid dimixing process take place. This means that the liquidliquid dimixing rate decrease with the increase of the degree of sulfonation. This thermodynamically indicates that the addition of the sulfonic acid groups can induce the more weakened coagulation. Generally speaking, a highly porous sublayer (with many nger-like macrovoids) and a nely porous, thin skin layer are formed when the precipitation process is fast due to instantaneous liquidliquid dimixing process, whereas the slow precipitation rate (the delayed liquidliquid dimixing process) results in a porous sublayer (often fewer macrovoids) with a dense, relatively thick skin layer [41,42]. In sum, the experiment results reect the qualitative relationship between the morphological change and the degree of sulfonation, and the relationship has been explained and veried by Hansen solubility parameters from theory discussion.

4.3. Membrane potentials, surface hydrophilicity and protein adsorptions of SPPSU membranes In order to investigate the surface charged properties of the SPPSU membranes, the membrane potentials were measured as a function of concentrations in KCl solutions and their corresponding values calculated using Eq. (5), and the results are shown in Fig. 4. It can be seen that the membrane potentials are always negative to the SPPSU membranes and become more negative with an increase in the DS values. Clearly, the sulfonation of membrane materials is really an effective way to prepare negatively charged membrane, which may be very useful to suppress the membrane fouling and promote the protein binding. Surface hydrophilicity is one of the most important factors in determining antifouling property and performance of ultraltration membrane. The hydrophilicity and wettability of the SPPSU membranes in this study was evaluated by contact angle measurement, which was also used to assess the surface (interfacial) free energies of substrate surfaces. It is commonly accepted that the lower contact angle represents the greater tendency for water to wet the membrane, the higher surface energy and the higher hydrophilicity. Fig. 5 shows the detailed water contact data from the measurements on these different membranes, and the surface free energy was also calculated according to the following equation:

dd

RF di
V gi q RF 2 pi V gi

12

dp

13

s REhi dh V gi

14

where Vgi is the molar volume and Fdi, Fpi, Ehi are the dispersion force, the dipole force, the hydrogen bonding force components of the solubility parameter, respectively.

Table 2 Group contributions to Hansen (Vgi, Fdi, Fpi and Ehi) solubility parametersa[22,40]. Group Frequency 4-2DS 2DS O SO2 OH
a

Vgi (cm3/ mol) 65.5 65.5 10.0 31.8 9.7

Fdi (J1/2 cm3/2/ mol) 1270 1270 100 587 210

Fpi (J1/2 cm3/2/ mol) 110 110 400 1455 500

Ehi (J/ mol) 0 0 3000 11347 20000

cos h 1 2

r cs bcs cl 2 e

cl

15

2 1 + 2DS 2DS

The SO3H group can further be divided in to SO2 and OH groups.

where cs and cl represent the solid and liquid surface free energy, respectively. The value of water surface free energy is 72.8 mJ/m2. b is the constant coefcient related to a specic solid surface and the value of 0.0001247 is adopted from previously reported literature [43].

Y. Liu et al. / Separation and Purication Technology 98 (2012) 298307 Table 3 The HSP values of SPPSU and DMF, and Dd between SPPSU and DMF. dd (MPa1/2) DMF PPSU SPPSU-5 SPPSU-10 SPPSU-15 SPPSU-20 17.4 18.7 18.7 18.7 18.7 18.7 dp (MPa1/2) 13.7 5.0 5.2 5.3 5.5 5.6 dh (MPa1/2) 11.3 7.4 8.0 8.6 9.1 9.5 d (MPa1/2) 24.86 20.72 20.99 21.25 21.51 21.71

305

DdI (MPa1/2)
4.14 3.97 3.61 3.35 3.15

DdII (MPa1/2)
9.62 9.21 8.92 8.59 8.40

Fig. 4. Membrane potential vs. ln(c1/c2) for the SPPSU membranes.

From Fig. 5, it is seen that the contact angles decreased with the increase of the degree of sulfonation, and the surface free energies increased gradually. The PPSU membrane has the highest contact angle of 83.47 and the lowest surface free energy of 33.26 mJ/ m2, indicating the lowest hydrophilicity. The SPPSU membrane has a more hydrophilic surface than the PPSU membrane, and this tendency was attributed to the hydrophilic nature of the sulfonic acid groups. The decrease of contact angle indicated that a highly hydrophilic surface was created. These results indicated that the introduction of the sulfonic acid groups could effectively enhance the hydrophilicity and improve antifouling property of PPSU-based ultraltration membrane. The static protein adsorption is one of the dominant factors in determining the membrane fouling, and the reduction of protein

adsorption will enhance the antifouling property of membrane. Herein, BSA was used as the model protein to evaluate the static protein adsorption on the surface of the SPPSU membranes. In many cases, the nonspecic protein adsorption on the membrane surface due to the inherent hydrophobic characteristic often causes serious membrane fouling. Therefore, the increment in the membrane hydrophilicity is a straightforward and effective method to enhance the antifouling property of membrane. As is shown in Fig. 6, the adsorption amount for measured protein exhibited the following tendency: the BSA adsorption amount declined drastically with the increase of sulfonated monomer content. Interestingly, this tendency is very similar to the tendency found in the static water contact angle measurement. The phenomenon can be explained as follows: on the one hand, the sulfonic acid groups form a regular hydration layer on the membrane surface via hydrogen bond, and the protein was excluded from the hydration layer to avoid the substantial entropy loss caused by the entrance of large protein molecules into the membrane surface; on the other hand, the isoelectric point for BSA appears when pH is 4.8, BSA molecules show negative potential in phosphate buffered saline (PBS, pH 7.4), and the presence of the same charge (negative charge) on the surface of the SPPSU membrane was believed to repel the BSA molecules and decrease the BSA adsorption amount by the electrostatic repulsive interaction. 4.4. Permeation properties of SPPSU membranes Ultraltration experiments were carried out to investigate the separation performance of a series of SPPSU membranes. Fig. 7 shows the changes in water permeation and protein rejection of the different membranes. The water ux was gradually increased with an increase of the degree of sulfonation, while BSA rejection ratio was slightly decreased from 98.8% to 92.2% as the DS value increase from 0 to 0.2. The pure water ux (Jw1) of the PPSU mem-

Fig. 5. Water contact angles and surface free energies of the SPPSU membranes.

Fig. 6. BSA adsorption on the SPPSU membranes.

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brane is 142.8 L/m2 h, which is lower than that of the SPPSU membranes. This result may be attributed to the increased hydrophilicity and surface morphology change of the SPPSU membranes. Fig. 8 presented time-dependent ux during ultraltration operation. It is apparent that the ux decreased dramatically at the initial operation of BSA solution ultraltration due to membrane fouling caused by protein adsorption or deposition on the membrane surface. When the adsorption and deposition of protein molecules may reach equilibrium, a relatively steady ux (Jp) was retained in the nal operation of BSA solution ultraltration. After 2 h of BSA solution ltration, the membranes were washed thoroughly and passed through deionized water for another 30 min, and the water uxes of the cleaned membranes (Jw2) were measured again. FRR is introduced to reect the resistant fouling ability of the membranes, and higher value of FRR means the higher resistant fouling ability. The FRR values were calculated and presented in Fig. 9. The FRR value is only 55.7% for the PPSU membrane, meaning the existence of serious membrane fouling. The SPPSU membranes have larger FRR values, suggesting that adsorbed and deposited protein on the SPPSU membrane surfaces could be easily washed away. The SPPSU-20 membrane has the highest FRR value (77.8%), which is consistent with the protein adsorption experiment results. The protein molecules adsorbed or deposited on the surface and inside the membrane pores causing membrane fouling, which could be further divided into reversible and irreversible fouling. One part of fouling, recognized as reversible fouling, was caused by reversible protein adsorption or deposition and could be eliminated through hydraulic cleaning (hydrodynamic method); while the other part of fouling, dened as irreversible fouling, could not be eliminated only through hydraulic cleaning. More detailed results of the total fouling ratio (Rt), the reversible fouling ratio (Rr) and the irreversible fouling ratio (Rir) of the all investigated membranes are given in Fig. 9. It can be seen that the Rt value of the PPSU membrane is larger than that of the SPPSU membranes. The bigger Rt value indicates higher total ux loss, corresponding to more protein adsorption and deposition on the membrane surface. Meanwhile, the Rir value of the PPSU membrane is the largest among the all investigated membranes. It can be concluded that the protein fouling on the PPSU membrane is so serious that the fouling cannot be removed by hydraulic cleaning. The SPPSU membranes have not only the lower Rt values but also the lower Rir values, and the protein fouling in the SPPSU membrane was suppressed signicantly under the ultraltration process. In addition, the SPPSU membranes possess a negatively charged character experience electrostatic repulsions between the negatively

Fig. 8. Time-dependent uxes of the SPPSU membranes during the protein ultraltration experiment.

Fig. 9. Summary of the ux recovery ratio (FRR), the total fouling ratio (Rt), the reversible fouling ratio (Rr) and the irreversible fouling ratio (Rir) of the SPPSU membranes during the protein ultraltration experiment.

charged surface and the negatively charged protein, which leads to a decrease in BSA adsorption on the membrane surface. Generally speaking, when protein molecules contacted with the membrane surface, water molecules between protein and the membrane surface would be replaced. The polar sulfonic acid groups can take up large quantities of free water, which possibly prevents protein molecules from close contact with the membrane surface. These results indicated obviously that the introduction of the sulfonic acid groups efciently reduces total membrane fouling, especially irreversible membrane fouling.

5. Conclusions This study is aimed at optimizing polymer design by employing sulfonated monomer in direct copolymerization method that provides a good opportunity to improve the resultant membrane performance without sacricing mechanical strength. A series of sulfonated polyphenylsulfone (SPPSU) random copolymers with various well controlled sulfonation levels were synthesized by precise adjusting the ratios of the sulfonated monomer to non-sulfonated monomer, and their chemical structures were conrmed

Fig. 7. Water uxes and BSA rejections of the SPPSU membranes.

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by using FTIR. The thermal properties of the SPPSU copolymers were thoroughly characterized by DSC and TGA study. The morphologies of the SPPSU membranes were investigated by SEM, and the remarkably change of morphology had been explained and veried by Hansen solubility parameters from theory point that opened a way for establishing a complete qualitative relationship between the membrane morphology and polymer structure. In addition, both water contact angle and membrane potential experiments conrmed the highly hydrophilic and negatively charged characteristics of the SPPSU membranes. The cycle ultraltration experiments showed the pure water ux and protein solution permeation through the SPPSU membranes were increased with the increase of the degree of sulfonation. Meanwhile, the SPPSU membranes had higher ux recovery ratio and lower extent of membrane fouling, especially irreversible membrane fouling, as compared to those of the PPSU membrane, which displayed a superior antifouling performance. In sum, this study demonstrated that the application of sulfonated PPSU material with the help of direct copolymerization method can effectively enhance the hydrophilicity, negatively charge the membrane and signicantly improve ultraltration membrane performance. Acknowledgements This work was supported by a Grant from the National High Technology Research and Development Program of China (863 Program) (No. 2012AA03A212). References
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