D. Breite,
M. Went,
A. Prager and
A. Schulze*
Leibniz Institute of Surface Modification, Permoserstraße 15, Leipzig, D-04318, Germany. E-mail: agnes.schulze@iom-leipzig.de; Tel: +49 341 235 2400
First published on 10th October 2016
The zeta potential of membrane surfaces and the resulting electrostatic interactions are determining factors of membrane fouling. This study investigates the influence of environmental parameters like pH value, salt concentration, or ion valence on the zeta potential of polymer membranes and the resulting fouling. To control electrostatic forces charged polystyrene beads were used as fouling reagents. Also, polyethersulfone and polyvinylidene fluoride membranes were modified to possess an either positive or negative surface charge. Afterwards, suspensions of beads were filtered through the membranes in different electrolytic environments. Fouling occurred when membrane and beads are oppositely charged. Bead adsorption was not observed when both surfaces are evenly charged. The latter was found to be influenced by electrolyte concentration. High salt concentrations or present bivalent ions reduced the electrostatic repulsion between evenly charged surfaces and led to membrane fouling. Low salt concentrations did not influence the electrostatic repulsion. Thus, critical salt concentrations were determined and used to identify the critical zeta potential. In addition, the fouling of a zwitterionic membrane surface was investigated regarding its pH dependence. A critical zeta potential that is associated with membrane fouling was identified. The critical zeta potentials are similar for both pH and salt concentration dependence.
So far, membrane fouling was thought to be mainly caused by hydrophobic interactions. The often used membrane polymers like polyvinylidene fluoride (PVDF) or polyethersulfone (PES) are very hydrophobic. Due to the interaction of the hydrophobic surfaces of both membrane and foulant the latter adsorbs to the membrane surface.3–11 To prevent this, membranes need to be hydrophilized. Typical methods are surface grafting reactions,4,6,7,9,11–13 electron-beam modifications,14,15 or plasma treatments.5,8,16–21 The anti-fouling property of a membrane is usually evaluated by its hydrophilicity which is determined by water contact angle measurements.22
Nevertheless, also hydrophilized membrane can foul. The reason is electrostatic interaction between the membrane and fouling reagents.23–36 These interactions are known for a long time and were already considered in the Derjaguin–Landau–Verwey–Overbeek theory.37,38 However, in membrane science the research focus shifted towards electrostatic interactions just recently. Electrostatic interactions are investigated by the charged state of a membrane surface. Determination of this charged state can be conducted by measurement of the membrane surface's zeta potential.23,28,30
In our prior studies we designed a new fouling test system to investigate electrostatic interactions undisturbed by other types of interactions.39,40 Differently charged polystyrene beads (PS, 0.2 μm) were filtered through the investigated microfiltration membranes (average pore size: PES 0.8 μm, PVDF 0.9 μm). Fouling occurred when membrane surface and beads were oppositely charged. In contrast, no bead adsorption was observed for evenly charged membranes and beads. Therefore, the electrostatic interactions are considered to be the dominant forces of this set-up. Being solely focused on electrostatic interactions is a significant advantage. This benefit is obvious especially when compared to common protein fouling tests where many different interactions overlap.40 Following the results of our previous studies, we now aim to further identify the impact of pH value and salt concentration of the surrounding media on membrane fouling.
Elzo et al.41 did extensive work on the fouling of ceramic membranes using silica particles. They found that the particle adsorption depend on the pH value of the solution because the particle's zeta potential changes.
As described above, a lot of studies have already been done to show how membrane fouling is influenced by pH value, salt concentration, or ion valence. Unfortunately, the conditions (pH value, ionic strength) that are critical for membrane fouling were not completely determined, and the corresponding critical zeta potential was not identified.
Nevertheless, knowing the critical zeta potential enables to predict the fouling of a membrane. Therefore, the concept of critical zeta potential23 gives valuable insight in the process of membrane fouling and enables the prediction the latter. By determining critical zeta potential values, this paper will contribute further understanding of the conditions that are critical for membrane fouling and the adjustments which are necessary to prevent it.
Furthermore, this study is essential to fully comprehend the fouling test system introduced in our previous works.39,40 This fouling test is designed to investigate electrostatic interactions undisturbed by other types of interactions. The presented results demonstrate the impact of environmental parameters to this test system and reveal that it can still be applied when the electrolytic environment is changed. In addition, the test is applied to different membranes to demonstrate that the system is not bound to a specific membrane and can be applied to other systems as well.
2-Aminoethyl methacrylate hydrochloride (AEMA, Acros Organics), polyethylene glycol (PEG, 400 g mol−1, Acros Organics), and sodium bicarbonate were purchased from Thermo Fisher Scientific (Geel, Belgium). Other purchased chemicals: glutaraldehyde (GA, Merck, Darmstadt, Germany), n-hexane (Merck, Darmstadt, Germany), hydrochloric acid solution (0.1 M, VWR, Radnor, USA), polyethersulfone (PES, Ultrason E2010, BASF, Ludwigshafen, Germany), sodium carbonate (anhydrate, VWR, Radnor, USA), sodium hydroxide solution (0.1 M, VWR, Radnor, USA).
All chemicals are used as received. Ultrapure water was taken from a MilliQ-System (Merck Millipore, Billerica, USA). The dialysis membranes used for the bead purification were purchased from Carl Roth (cellulose acetate, Nadir, molecular weight cut-off (MWCO): 10–20 kDa, Wiesbaden, Germany).
The PS bead suspensions were characterized (bead size, zeta potential, isoelectric point (IEP)) using the Malvern Zetasizer (Zetasizer Nano ZS with multipurpose titrator MPT-2, Malvern Instruments, Worcestershire, UK). Scanning electron microscopy (SEM) images (Ultra 55 SEM, Carl Zeiss Ltd, Goettingen, Germany) were taken from beads spin-coated on a silica wafer.
An aqueous solution of PSS (2 wt%) was used to create the PVDF–PSS and PES–PSS membranes. The EB irradiation dose was adjusted to 200 kGy.55
To generate the PVDF–TEPA and PES–TEPA membranes several reaction steps were necessary. First, EB irradiation was performed using an aqueous solution of AEMA (0.5 wt%) and a irradiation dose of 150 kGy. The membranes were rinsed with water three times for 30 min, respectively. Then, the membranes were dipped into an aqueous solution of GA (2 wt%) at pH 9.2 (NaHCO3/Na2CO3 buffer system) for 2 h. The GA solution was removed and the membranes were roughly rinsed before they were immersed into an aqueous solution of TEPA (2 wt%) at pH 9.2 for another 2 h. The reactions with GA and TEPA were repeated as described before to create a dendrimeric structure.56
The PVDF–lysine and PES–lysine membranes were prepared similar to the membranes modified with TEPA. EB irradiation was performed using a 2 wt% solution of AEMA and an irradiation dose of 200 kGy. The membranes were rinsed with water three times for 30 min, respectively. The reaction with GA was performed as described above but in the next step lysine was used instead of TEPA.39
Finally, all modified membranes were rinsed three times for 30 min, respectively.
Membrane morphology was investigated using SEM imaging (Ultra 55 SEM, Carl Zeiss Ltd., Goettingen, Germany). The samples were chromium coated (30 nm) using a Z400 sputter system (Leybold, Hanau, Germany).
Pore size distribution and porosity of the membranes were measured with a mercury porosimeter (PoreMaster 30, Quantachrome Instruments, Odelzhausen, Germany). Values of at least three different samples were averaged.
The water permeability was determined using a stainless steel pressure filter holder (16249, Sartorius, Goettingen, Germany) for dead-end filtration. A volume of at least 200 mL of deionized water was passed through the membrane (active area: 17.3 cm2) at 1 bar and the time of flow-through was recorded. Values of at least three different samples were averaged. Pure water permeation flux J was calculated following eqn (1).
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The chemical composition was determined using X-ray photoelectron spectroscopy (XPS, Kratos Axis Ultra, Kratos Analytical Ltd., Manchester, UK).
Surface wettability was investigated using a static water contact angle measurements system (DSA 30E, Krüss, Hamburg, Germany) and the sessile drop method. Values of at least three different samples were averaged.
Membrane zeta potentials were measured using streaming potential measurements performed with the adjustable gap cell in the SurPASS system (Anton Paar, Graz, Austria). The zeta potential ζ can be calculated based on the Smoluchowski eqn (2). Values of at least three different samples were averaged.
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Furthermore, it should be noted that this study is focused on interactions between membrane and beads. The initial fouling is caused by interactions between membrane and beads. If beads are adsorbed to the membrane surface the membrane's pores will be blocked. The following cake layer formation and the according interactions between beads are merely consequences of this size exclusion effect. Without the initial fouling interactions between beads will also not occur. The origin of fouling can be attributed to the initial interaction between membrane and beads. Therefore, the discussion in the following will focus on interactions between membrane and beads instead of interactions between the beads itself.
The synthesis of 0.2 μm PS beads as well as the modification of polymer membranes (average pore size: PES 0.8 μm, PVDF 0.9 μm) is known from literature. Detailed information regarding the characterization of PS beads and membranes are therefore presented in the ESI.†
Fig. 1a and b show the zeta potential vs. pH of PES and PVDF membranes modified with PSS (polystyrene sulfonic acid, Fig. 1) or TEPA (tetraethylpentamine, Fig. 1). The salt concentrations presented are 0.01 M and 0.05 M for sodium chloride, and 0.01 M for the respective salt containing bivalent ions. The results for other concentrations are shown in Fig. S4 in the ESI.† All error bars shown represent 95% confidence values.
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Fig. 1 Zeta potential vs. pH at different salt concentrations and charged moieties of (a) PVDF–TEPA and –PSS membranes; (b) PES–TEPA and –PSS membranes. |
The zeta potential of the PVDF–TEPA membrane was determined to be +23 mV at pH 7 and 0.01 M sodium chloride. The membrane surface is highly positively charged. This can be explained by the large amount of protonated amino functions (Fig. 1) present on the membrane surface. The isoelectric point (IEP) was found at a pH value of 9.1 and does not change for the different salt concentrations because it only depends on the surface material. However, the zeta potential at pH 7 varied depending on the electrolyte solution conditions. When the sodium chloride concentration was increased to 0.05 M the PVDF–TEPA membrane's zeta potential decreased to +15 mV. This can be explained by a compression of the electrochemical double layer and the therefore shifted slipping plane. The same is true for an electrolyte solution containing 0.01 M of sodium sulfate. The bivalent sulfate ions decreased the zeta potential even stronger than the chloride ions at the same concentration.
A similar trend was found for the PVDF–PSS membrane. The sulfonic acid groups (Fig. 1) led to a highly negatively charged membrane surface. The zeta potential at pH 7 was −54 mV at a sodium chloride concentration of 0.01 M. When the concentration was increased to 0.05 M the absolute value of the zeta potential decreased to −45 mV. The same is true for calcium chloride at a concentration of 0.01 M (potential of −20 mV) due to the bivalent calcium ions. Again, these results can be explained by a compression of the electrochemical double layer. The IEP of the PVDF–PSS membrane was not recorded within the measurement range and is expected to be lower than pH 3.
Similar results were obtained for the PES membranes. The PES–TEPA membrane has a zeta potential of +18 mV, +7 mV or +6 mV at pH 7 when 0.01 M NaCl, 0.05 M NaCl, or 0.01 M Na2SO4 are used as electrolyte solutions, respectively. For the PES–PSS membrane the zeta potential at pH 7 was −49 mV, −43 mV or −17 mV at pH 7 using 0.01 M NaCl, 0.05 M NaCl, or 0.01 M CaCl2 as electrolyte solutions, respectively.
Fig. 2a shows the zeta potential vs. pH of cationic and anionic PS beads. The salt concentrations presented are 0.01 M and 0.05 M for sodium chloride, and 0.01 M for the respective salt containing bivalent ions. The results for other concentrations are shown in Fig. S2 in the ESI.† All error bars shown represent 95% confidence values. The charged moieties are presented in Fig. 2b.
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Fig. 2 (a) Zeta potential vs. pH at different salt concentrations of charged PS beads; and (b) charged moieties of beads. |
It was found that cationic PS beads possess a positive zeta potential of +29 mV at pH 7 and a sodium chloride concentration of 0.01 M. The potential just slightly changes (+23 mV) when the sodium chloride concentration is raised to 0.05 M. The IEP was found at a pH value of 9. A similar trend was found for the anionic PS beads. At a sodium chloride concentration of 0.01 M and 0.05 M the zeta potential was −65 mV and −50 mV, respectively. The IEP was not recorded in the applied measurement range. The results for other concentrations are shown in Fig. S2 in the ESI.†
For both bead species a significant reduction of the absolute values of the zeta potential was found when bivalent ions were used for the electrolyte solution. The potential of cationic beads was reduced to +10 mV at pH 7 when sulfate ions were present. The presence of calcium ions led to an extenuated potential of −27 mV of the anionic beads.
Sodium chloride concentrations of 0.01 M and 0.05 M were chosen to demonstrate how fouling depends on the salt concentration. For the filtration of anionic PS beads through the anionic PVDF–PSS membrane no fouling occurred for sodium chloride concentrations of 0.001 M (Fig. S5a in the ESI†) and 0.01 M (Fig. 3a). Neither permeation flux nor PS bead concentration declined and the structure remained predominantly open as shown in Fig. 3b. When the salt concentration was further increased fouling of the membrane occurred. Due to the decreased zeta potential (see Section 3.1.1) the electrostatic repulsive interactions were extenuated and PS beads were adsorbed to the membrane surface. The subsequent pore blocking led to a complete fouling of the membrane as shown for concentrations of sodium chloride of 0.05 M (Fig. 3) or 0.1 M (Fig. S5a†). Here, permeation flux and bead concentration decreased during the experiment and a complete pore blocking was visible in the SEM images.
Similar results were found for the fouling of the PES–PSS membrane using anionic PS beads. No flux decline or reduced concentration of PS beads was found at a sodium chloride concentration of 0.001 M (Fig. S5a†) and 0.01 M (Fig. 3a). The corresponding SEM images (Fig. S5b in the ESI† and Fig. 3b) show no pore blocking. When the salt concentration was increased to 0.05 M permeation flux and bead concentration remained unchanged. Nevertheless, incipient pore blocking was visible in the SEM image (Fig. 3a). Complete membrane fouling was observed when the sodium chloride concentration was further increased to 0.1 M (Fig. S5 in the ESI†).
Furthermore, the influence of bivalent ions was studied. The respective results are presented in Fig. S6 in the ESI.† Both PVDF–PSS and PES–PSS did not show any fouling at 0.001 M concentrated calcium chloride solution. Strong fouling occurred when the concentration was raised to 0.01 M.
The fouling of the positively charged PVDF–TEPA and PES–TEPA membranes was investigated accordingly. For both membranes electrostatic repulsion of cationic PS beads was preserved at a sodium chloride concentration of 0.001 M (Fig. S5a†) and 0.01 M (Fig. 3a). The permeation flux and the bead concentration in the filtrate remained unaffected, and no pore blocking was observed according to the SEM images. Nevertheless, when the concentration was raised to 0.05 M fouling occurred for the PES–TEPA membrane. For the PVDF–TEPA membrane only changes in the SEM images were found while permeation flux and bead concentration remained unchanged. Complete fouling for both membranes was found at a sodium chloride concentration of 0.1 M.
Then, the fouling of the PVDF–TEPA and PES–TEPA membranes towards cationic beads using sodium sulfate as electrolyte was investigated. Just like the anionic membranes the repulsive interactions remained unchanged when a 0.001 M solution of the bivalent sulfate was present. Raising the concentration to 0.01 M led to a reduced zeta potential and a less efficient repulsion of the evenly charged beads. The subsequent pore blocking and reduced permeation flux and bead concentration are presented in Fig. S6 in the ESI.†
Overall, it can be concluded that the prevention of membrane fouling due to electrostatic repulsion highly depends on the salt concentration and the valence of the ions of the electrolyte solution. At low salt concentrations the zeta potential of evenly charged membranes and beads is high enough to result in electrostatic repulsion. Nevertheless, when the concentration of sodium chloride is raised to a value of 0.05 M or higher first fouling effects can be observed. We already discussed the effect of electrolyte concentration on the corresponding zeta potential in Section 3.1.1. Combining the latter and the results of fouling experiments conducted with different electrolyte concentrations we can now define the critical zeta potential. This should be that value which is associated with membrane fouling. In our fouling experiments first fouling occurred at a sodium chloride concentration of 0.05 M. For the cationic PVDF–TEPA and PES–TEPA membranes this corresponds to a zeta potential of ∼+10 mV. This is the critical zeta potential for the repulsion between cationic surfaces. The critical zeta potential of the anionic PVDF–PSS and PES–PSS membranes was identified at a value of ∼−40 mV.
When the salt concentration is increased the zeta potential of the PS beads is decreased as well. Nevertheless, for all investigated combinations the absolute value of zeta potential of the PS beads is always higher compared to the zeta potential of the membranes. Therefore, when the absolute values of zeta potential are lowered, the zeta potential of the membranes will reach the critical value first.
When the salt concentration is increased the zeta potential of both membrane and bead is decreased. Therefore, the electrostatic attractive interactions should also decrease and become negligible at a certain critical value as shown above for the repulsive interactions. Nevertheless, fouling occurred for all conducted experiments to different degrees. The fouling was investigated using sodium chloride solutions in a range of 0.001–0.1 M. The attractive forces must be stronger than the repulsive ones. Therefore, a much higher concentrated salt solution would be necessary to successfully suppress the electrostatic attractive forces. Unfortunately, the PS bead suspensions are not stable at sodium chloride concentrations higher than 0.1 M. Therefore, it was not possible to conduct the respective experiments.
For the filtration of cationic PS beads fouling could be prevented at pH 4. At pH 5 and pH 6 the permeation flux slowly decreased due to the reduced electrostatic repulsion between membrane and beads. For all pH values higher than 6 fouling occurred due to the missing (pH 7) or attracting (pH 8 and 9) electrostatic interactions. Compared to the assessment in Section 3.1.2 the critical zeta potential is found at pH 5 and has a value of +20 mV. This value is comparable to the critical zeta potential (+10 mV) found for the salt concentration dependence.
The adsorption of anionic beads can be prevented at pH 9 where the membrane is highly negatively charged. A medium permeation flux decline as detected for the cationic beads does not occur. The repulsive interactions at pH 8 are already too small and the critical zeta potential was ∼−30 mV. Again, this value is comparable to the critical value that was found for the salt concentration dependence (−40 mV). For all pH values below pH 8 electrostatic interactions are either too weak (pH 8–6) or attractive (pH 5 and 4).
When the pH value is varied from pH 4–9 the zeta potential of the PS beads remains unaffected in case of the anionic beads. The zeta potential of the cationic beads slightly decreases when the pH value is increased. Nevertheless, the zeta potentials of the PS beads remain stable compared to the drastic changes of the zeta potential of the PES–lysine membrane. Therefore, it can be assumed that fouling occurs because the zeta potential of the membrane falls below the critical value. An influence of the PS beads is not expected in the investigated range of pH.
The conducted experiments regarding the dependence on salt concentration and ion valence revealed that:
Electrostatic repulsion between evenly charged surfaces occurs at low salt concentrations when the corresponding zeta potential's absolute values are high.
• Repulsive forces are extenuated when the salt concentration is high. Due to a compression of the electrochemical double layer the absolute value of the zeta potential is decreased. Fouling occurs when a critical zeta potential is reached.
• Electrostatic attractive interactions between oppositely charged surfaces cannot be prevented by increased salt concentrations. The remaining attractive forces are still strong enough. A zwitterionic membrane (PES–lysine, IEP at pH 6.2) was used to investigate the pH impact on fouling with PS beads. The experiments revealed that:
• Cationic beads are repelled at low pH values. Here, the membrane is positively charged and electrostatic repulsion occurs. When the pH value is increased the zeta potential decreases and fouling is observed after a critical zeta potential is reached.
• Anionic PS beads are not adsorbed to the membrane at high pH values. Here, the membrane is negatively charged and evenly charged beads are repelled. Fouling occurs when the pH value is decreased and the absolute value of the zeta potential is decreased to a critical value.
A critical zeta potential (∼−10 mV) has been theoretically predicted by Cai et al.23 for the repulsion between negatively charged membrane and foulant surfaces. Our experiments now confirm their hypothetic zeta potential value. Electrostatic interactions and the critical zeta potential need to be considered alongside the mainly investigated hydrophobic interactions. The zeta potential must be determined using the same conditions as in the desired application. If the zeta potential's absolute value is higher than the critical zeta potential, fouling should not occur. The presented bead test system can be used to investigate if a membrane is prone to fouling due to electrostatic forces. If this is the case, variations in salt concentration or pH value will reveal the critical zeta potential value.
Footnote |
† Electronic supplementary information (ESI) available. See DOI: 10.1039/c6ra19239d |
This journal is © The Royal Society of Chemistry 2016 |