Silica incorporated membrane for

wastewater based filtration

Cite as: AIP Conference Proceedings 1891, 020041 (2017); https://doi.org/10.1063/1.5005374
Published Online: 03 October 2017

C. S. Fernandes, M. R. Bilad, and N. A. H. M. Nordin

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AIP Conference Proceedings 1891, 020041 (2017); https://doi.org/10.1063/1.5005374 1891, 020041

© 2017 Author(s).
 Silica Incorporated Membrane for Wastewater Based
Filtration
C.S. Fernandes1,a), M.R. Bilad1, b) and N.A.H.M. Nordin1,c)
1
Department of Chemical Engineering, Universiti Teknologi Petronas, Bandar Seri Iskandar, Perak 32610,
Malaysia
a)
[email protected]
b)
[email protected]
c)
Corresponding author: [email protected]

Abstract. Membrane technology has long been applied for waste water treatment industries due to its numerous advantages
compared to other conventional processes. However, the biggest challenge in pressure driven membrane process is membrane
fouling. Fouling decreases the productivity and efficiency of the filtration, reduces the lifespan of the membrane and reduces the
overall efficiency of water treatment processes. In this study, a novel membrane material is developed for water filtration. The
developed membrane incorporates silica nanoparticles mainly to improve its structural properties. Membranes with different
loadings of silica nanoparticles were applied in this study. The result shows an increase in clean water permeability and filterability
of the membrane for treating activated sludge, microalgae solution, secondary effluent and raw sewage as feed. Adding silica into
the membrane matrix does not significantly alter contact angle and membrane pore size. We believe that silica acts as an effective
pore forming agent that increases the number of pores without significantly altering the pore sizes. A higher number of small pores
on the surface of the membrane could reduce membrane fouling because of a low specific loading imposed to individual pores.

INTRODUCTION
Membrane technology is an established option for treating water and wastewater as well as for desalinating
sea water. Among the emerging application of membrane is in a form of membrane bioreactor (MBR) that system that
combines the activated sludge process and the membrane filtration process [1-3]. The former provide biological
treatment, while the latter acts as a physical barrier to retain the sludge. The membrane in MBR is highly beneficial
as it integrates the primary clarifier, activated sludge, secondary filtration and polishing steps (i.e., disinfection) of the
traditional activated sludge system into one single system. Furthermore, membrane treatment uses lesser chemicals
and lesser energy and henceforth drastically reduces the cost of operation when the effluent is aimed for reuse [2, 4-
6]. Another popular membrane applications are for treatment of secondary effluent, known as tertiary treatment to
polish the effluent of conventional activated sludge process. Membrane technology has also shown potential for
application of microalgae harvesting as well as to concentrate organic during raw sewage filtration.
The biggest constraint associated membrane for water and wastewater treatment is membrane fouling.
Membrane fouling is caused mainly by the contaminants clogging the membrane’s pores, thus increases the transport
resistance for treated water to be permeated [7, 8]. Membrane fouling is thus highly undesirable as in increases cost
of operation and would eventually reduce the life span of the membrane [2, 4, 9].The primary reasons of membrane
fouling are membrane pore clogging caused by contaminants adsorption, gel layer formation, bio-fouling due to
formation of biofilm, concentration gradient and cake layer formation. The particle size, density and roughness of the
foulants affect the rate of fouling[6, 7, 10]. A higher concentration of particle would eventually lead to a higher rate
of fouling. Also, ionic strength increases the fouling potential because of the double layer compression formed around
the colloids [8, 11, 12]
The primary aim of membrane development is to produce membranes with a high permeability, stability and
excellent resistant from foulants. The four most essential design parameters to consider in membrane process are flux,

The 2nd International Conference on Applied Science and Technology 2017 (ICAST’17)
AIP Conf. Proc. 1891, 020041-1–020041-6; https://doi.org/10.1063/1.5005374
Published by AIP Publishing. 978-0-7354-1573-7/$30.00

020041-1
inter-membrane pressure, permeability and recovery. A good membrane is one with maximum resistance towards
fouling [4, 7, 13-15].
In this study, fumed silica is used as an additive to improve the structural properties of a polyvinylidene
fluoride (PVDF) membrane. The proposed hypothesis is that silica will increase the viscosity of the polymer solution
which would then promote the formation of a higher number of pores on the membrane surface. The addition of a
small amount fumed silica will substantially increase solution viscosity, while leaving ample solvent to facilitate
formation of a more pores on the membrane surface. It is expected that incorporating silica into PVDF membrane
would improve its surface structure by forming more pores. A higher number of pores helps in reducing membrane
fouling and ensures higher efficiency of the membrane process [4, 16, 17].

MATERIALS AND METHODS

Dope solution preparation

A solution of PVDF polymer and solvent together with addition of silica nanoparticles was first prepared.
Silica was first added to 41 g of solvent and it was stirred well until a clear suspension was formed. The solution wass
sonicated for around 1 hour to remove bubbles. A little polymer about 10wt % of the total polymer weigh is then
added slowly into the solution and priming occurred. Priming is a process to reduce the surface tension of the solution
for easier silica loading. The remaining 7wt% of the polymer solution was then added into the solvent-silica suspension
until completely dissolved. The solution was further sonicated for around 1 hour to ensure optimum mixing before
used for casting. Table 1 shows the amount of silica loadings that were applied.

Table 1: Amount of Silica Loading for PVDF Membrane.

Silica loading PVDF

Sample
(wt%) (wt%)

PVDF 0 15

PVDF-1.0 1 14

PVDF-1.5 1.5 13.5

PVDF-2.0 2 13

PVDF-3.0 3 12

Fabrication of Polyvinylidene Fluoride (PVDF) Membrane

All membranes were prepared via immersion precipitation method. The prepared polymer solution were
casted using a doctor blade with net casting thickness of 220 μm at room temperature & humidity atop a non-woven
support (Noratexx 2471). The cast film then immediately immersed in a water bath where precipitation takes place
due to the solvent and non-solvent exchange that facilitate formation of membrane matrix. The membrane were stored
in wet conditions until usage.

Membrane Characterizations
Contact angle is a measurement of the hydrophilicity of the membrane. A Goniometer was used to measure
the angles between the surface of the membrane with the meniscus formed by the water. An average of 5 readings
were taken and the average reading is reported. Scanning Electron Microscopy (SEM) and Field Emission Scanning
Electron Microscopy (FESEM) are devices used to study the topography and microscopic observation of the

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membrane. Porosity is a measure of the empty spaces in the membrane (pores). Porosity was calculated by measuring
the volume of water retained in the membrane after drying and comparing it with the initial weight of the membrane.

Filterability Test

The permeability (L) of the membrane was calculated as:

௏
‫ ܮ‬ൌ (L/ (m2h bar)) (1)
஺௧்ெ௉
2
Where V is permeate volume (L), A is effective filtration area (m ), t time (h) and TMP trans-membrane pressure
(bar). The volume of filtered water was collected every 10 minutes continuously for an hour. Steady state flux was
observed after 1 h of filtration, as such the presented data are the one obtained after 1 h of test. The membranes
permeability were evaluated using 4 different feeds, namely: pure water, algae, activated sludge, secondary effluent,
raw wastewater. The same membrane cut was used for all tests to avoid variation among membranes coupon. The
membranes were rinsed in running water and soaked in 1000 ppm sodium hypochlorite solution overnight in between
filtrations.

RESULTS AND DISCUSSION

Membrane Characteristics
Table 2 Summary of membrane characteristics
Membrane PVDF Silica Thickness Overall Contact angle Pore Size Clean Water
code content content porosity Permeability
(μm) (°)
(%) (%) (%) (μm)a
(L/m2 h bar)
M-0 15 0 182± 2 52.5±1.5 87.0 0.12 204±5

M-1 14 1 198±2 51.7±1.5 88.6 0.09 200±5

M-1.5 13.5 1.5 198±2 50.5±1.5 97.6 0.13 347±5

M-2 13 2 196±2 64.7±1.5 96.9 0.09 352±5

M-3* 12 3 196±2 52.0±1.5 96.8 0.18 447±5

* This membrane appears nonhomogeneous, and seems to be defectives.

± represent the standard deviation from three (3) measurement a measured
from series of SEM images

Figure 1 SEM images of the membranes.

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 Figure 2 FESEM Images of membranes

The membrane characteristics are summarize in Table 1. The porosity of the membrane is depending on the
content of silica where increasing silica content shows higher overall membrane porosity. The porosity of M-2 shows
the highest with a 12% increase compared to M-0. However, a further increase in the silica content to 3% shows a
reduction in porosity. This is most likely due to the high viscosity of the dope solution at a high silica content which
caused slower solvent-nonsolvent demixing rate thus lower overall membrane porosity[18]

The contact angle measures membrane hydrophilicity where lower contact angle shows more hydrophilic
membrane. Theoretically, a larger pore size of membrane allows more water retention on the membrane surface that
lowers the contact angle values [14, 18]. However, the results obtained in this study show that there is no clear trend
on the impact of silica loading to contact angle. It should be noted that the silica used in this study is hydrophobic in
nature. Thus, the membrane becomes more hydrophobic at low silica content (M-0 to M-1.5). In contrary, insignificant
changes in hydrophilicity were observed despite higher content of hydrophobic silica were incorporated into the
membrane (M-1.5 to M-3). It can be postulate that at high silica content, the insignificant changes in hydrophilicity is
contributed due to the trade-off between changes in surface morphology that as a results of an increase in viscosity
after silica were added, and the presence of hydrophobic silica. These effect compensating itself and changes in
hydrophilicity was not observe.

The SEM images of the membranes shows that M-2 has the largest pore size and they are very well
distributed. M-3 has an uneven pore size with uneven pore distribution. Initial observation showed that the dope
solution with a higher silica loading was more viscous and very hard to dissolve. This could be the reason for the
uneven distribution of pores in M-3. The FESEM images showed that a higher loading of silica produced larger pores
on the membrane.

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 Membrane Performance

Figure 3 Hydraulic Performance of Membrane for different feed using a) secondary effluent, b) raw wastewater
(municipal wastewater), c) activated sludge, and d) algae solution. The steady state permeability using different feed.

The hydraulic performance of the membrane using different feeds and silica contents are presented in Figure
3. There were four feeds being tested namely secondary effluent, raw wastewater, activated sludge, and algae
solutions. A higher silica content show the highest permeability for all feed tested. Overall, the permeability of the
membranes increased despite the membrane become more hydrophobic with the increasing silica contents. The
increase in permeability of the membranes is due to increased overall membrane porosity overwhelmed the
hydrophobicity of the membrane. In addition, the increase in permeability from M-2 to M-3 is due to the increase in
pore size, thus reduced the mass transport resistance across the membrane.

The characteristic of the feed also have an impact on the permeability of the membrane. The permeability of
the membrane is highest for pure water (because it absent from any fouling) and shows a significant decrease when
tested with contaminated feed for all different silica content (Figure 3a-d). While permeation of the secondary effluent
and raw wastewater is almost comparable, the permeability of activated sludge and algae solution as feed shows
significant decrease. This decrease most likely is due to higher amount of suspended solids in the feed (i.e. activated
sludge and algae) that blocked the membrane pores thus causing severe membrane fouling. As fouling occurs, the
availability of active sites for permeation to occur are limited hence cause the drop in the permeability.

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 CONCLUSION
The effect of the silica as additive for PVDF membranes on the properties of the membrane was investigated.
Higher silica loadings enhance the pure water permeability (i.e., 3% of silica content increased the permeability by
125% of the pristine PVDF membrane). Besides that, this study also investigated different feed characteristic on
membrane permeability. A highly contaminated feed (activated sludge and algae solution) would promote faster
membrane fouling and cause a severe membrane fouling. Nevertheless, higher silica content makes the membrane
more permeable, regardless of the feeds. Overall, incorporating silica into PVDF membrane would be beneficial to
improve the performance of the PVDF membrane.

ACKNOWLEDGEMENTS
We acknowledge Universiti Teknologi PETRONAS for providing grants (grant number: 0153AA-F58 and
0153AA-F59) and facilities for conducting the research activities.

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