Anti-fouling potential evaluation of PVDF

membranes modified with ZnO against

polysaccharides

Made by:
Paulina Meiliani/ 1406547111
Stephanie Sabhanindita/
1406575241

Table of contents
1. Membrane Characterization
2. Modification Method (PVDF depositioning, XRD & SEM
Results)
3. Filtration Behavior (Flux & Fouling)
4. Comparison before and after modification

Membrane Characterization:
Polyvinylidene Fluoride (PVDF)
PVDF microfiltration membrane has generally been used in
membrane bioreators (MBRs)
- Average pore size: 380 nm
- Thickness: 118 m
- Diameter : 50mm

Hydrophilic Modification: Atomic Layer Deposition

ALD is a thin film deposition technique that is based on the use of
a sequential gas phase chemical process, considered to be a
subclass of chemical vapor deposition.
Precursors: Diethylzinc (DEZ) and deionized water (H2O)

Nitrogen is used as precursor carrier gas & purging gas

Sodium Alginate (SA) is used as a model foulant of Polysaccharide

ALD Process

Conducted in
ALD Reactor at
80oC and 0.3 Torr

Operation
time for
pulsing DEZ;
100 ms, 5 s,
Operation
& 30s
time for
pulsing H2O;
15 ms, 5 s, &
ALD cycles
30s
was set to 50,
100, 150, and
200

PVDF membrane first

dried for 0.5 hr

DEZ and H2O

precursors
alternately pulsed
into ALD chamber for
ZnO growth
Purging gas N2 (also
the carrier gas) with
steady rate of 20
sccm

Exposure mode to
ensure both
precursors were
diffused sufficiently

Characterization of modified membrane

The intensity of diffraction peak for
ZnO crystal structure became stronger
with the number of deposition cycles.
Through this XRD measurement
confirms that ZnO layer was
successfully deposited on the
membrane surface
The appearence of O 1s and Zn 2p
peaks also showed the successful
deposition of ZnO
ZnO deposition layer grown faster at
higher ALD cycles. This is because the
hydrophobic nature become
hydrophilic during deposition, which
further accelerated the chemical
adsorption & reaction of precursors on
the membrane

SEM (Scanning Electron Microsope)

SEM was performed to investigate the difference of surface morphology between the original and
modified membrane
The thickness of original membrane is nearly 118 m
The average thickness of each layer increased from 4.3 x 10-2 to 9.1 x 10-2 nm with the rise of
ALD cycles from 50 to 200.
Leading to the thickness of 18.3 nm for the modified membrane at 200 ALD cycles

EDX mapping

The map scan spectra

subjected to 200 ALD
cycles shows the
particle distribution
profile of Zn(green
spots) and O(red
spots) on the surface
and cross section

 To investigate the water flux variation

& the fouling behavior of the modified
membrane
Using a stirred dead-end cell with a
volume of 300 mL is applied for pure
water and SA (pH=6,8) at 20oC
The membrane first submerged in 60%
alcohol for 1 hr
Then transferred to deionized water for
24 hr
The filtration pressure of 0,1 bar and
the stirring speed of 250 rpm are
maintained constant

MEMBRANE
FILTRATION

Filtration behavior and fouling propensity of modified membranes

Water flux

Pure water flux of original PVDF membrane :

1.5 x 10-2 cm/s
Obvious increase, reaching maximum flux of
1.8 x 10-2 cm/s (at 100 deposition cycles of
ZnO)
Sudden drop and decreased to 1.3 x 10-2 cm/s
at 200 ALD cycles
Pure water flux increased because of enhanced
hydrophilicity, declined due to reduced pore size
resulting from thicker modified layer

Relative flux during SA filtration

Flux decline of ZnO modified membranes after SA

filtration was lower than that of the original
membrane and it decreased with the increasing
number of deposition cycles.
The flux of original PVDF membrane dropped by
54% after collecting 300ml permeate, while the flux
of ZnO modified membranes with 50, 100, 150, 200
ALD cycles declines by 52%, 48%, 44%, 42%
SA was not easily adsorbed to the surfaces of
modified membranes -> reduced fouling potential

Only standard blocking model fitted well with

flux data 4
(R2Classic
>0.99)
Filtration

Models Evaluating

Flux decline of membranes during SA filtration

due to high
potential
of SA particulates
Fouling
Potential
of
accumulating on membrane pore walls

SA on ZnO modified
Fouling process of SA
occurred mainly in the
membranes
form of adsorption fouling

Content of SA Adsorbed
The mass of adsorbed SA on
original membrane: 0.2mg/cm2
Decreased with higher ALD
cycles due to enhanced
hydrophilicity and increased
negative charges of modified
membranes -> confirming better
anti-fouling property of
membranes after modification

Physicochemical Properties
Physicochemical parameters -> determined
interaction energies between foulant and
membrane surfaces -> influencing fouling
behavior of membranes
Contact angles of pure water and formamide
decreased after modification, while contact
angle of diiodomethane increased
ZnO modification resulted in higher negative
zeta potential of membrane surfaces ->
increased with rise of deposition cycles->
indicating chemical property had been changed

Influence of ZnO modified layer on the interaction

energy between membrane surfaces and SA foulant

- values were much higher than + values (with the increasing rate of - higher), suggesting the
enhanced electron-donating ability of modified membranes
The increased negative charges on the membrane surface made it harder for the attachment of SA
colloidal particles which also exhibited negative potential with the value of 16.3 Mv
Hydrodynamic drag forces-> foulant close to membrane surface-> colloidal interaction-> adhesion of
foulant to membrane surfaces
The value decreased after modification, resulting a significant decrease of 94.4% for total interaction
energy between membrane and SA foulant , means total interaction energies were lower after
modification, resulted in slower adsorption of SA onto ZnO modified membranes

Interaction Energy
profiles

SA experienced weak attraction at the far

distance(25 nm), reach maximum at 15 nm near
membrane surface
Attractive force declines more as the ALD cycles rise
Indicated it was difficult for SA to attach on ZnO
modified membranes
The interaction energy curves between modified
membrane surfaces and SA foulant exhibited higher
energy barriers and lower second minimums
compared to those between original membrane and
SA
Higher energy barriers : larger repulsive energy
needed to be overcome for the SA adsorption onto
the surfaces of ZnO modified membranes than onto
the original membrane.
Lower second minimum : weaker attractive
energy was experienced by the SA adsorption onto
the modified membranes than onto the original
membrane.

Fouling potential evaluation of modified membranes based

on surface morphology and roughness
Colloidal particles more likely to accumulate on rough surfaces -> leading to
membrane fouling and flux decline

The surface morphologies of fouled membranes became coarser than clean

membranes, after fouling, part of membrane pores blocked.
Membrane with higher cycles of ZnO modification still maintained original
morphology

 The original membrane has slightly

higher R values than those of
modified membrane -> indication
more fouling potential of modified
membranes
The surface roughness increased
after fouling
The ZnO modified membrane (200
ALD cycles) after SA fouling
exhibited lower roughness values
of Rms and Ra compared to the
clean membrane.

 Original PVDF membrane fouled by SA has much higher

values of roughness comparing to modified membranes
Means roughness values of modified membranes
decreased with increase of ALD cycles
Smaller protuberance occurred on surfaces of modified
membranes
Small attractive regions surrounding asperities, reducing
contact opportunity
Confirmed anti-fouling property of ZnO modified
membranes

Conclusion
ZnO modified layer formed on membrane surface by ALD
Thickness of deposition layer on pore walls increased with rise of ALD cycles
and reducing pore sizes
Modified membranes and increasing number of ALD cycles:
-Smaller flux decline after SA filtration, less fouling propensity
-Both free energies reduces, larger repulsive, and weaker attractive energy
-Smaller protuberances, lower roughness
Attachment of polysaccharide onto membrane surface weakened after ZnO
modification -> membrane modification by ALD was potential and promising
way for fouling control of polysaccharide

References

Li, Ning, Jun Zhang, Yu Tian, Jianhui Zhao, Jian Zhang, Wei Zuo,
June 2016, Anti-fouling potential evaluation of PVDF
membranes modified with ZnO against polysaccharides, http
://remote-lib.ui.ac.id:2086/S1385894716308956/1-s2.0-S13858
94716308956-main.pdf?_
tid=36b03506-7daf-11e6-8d10-00000aacb360&acdnat=14742
10397_66be2984bcae7a6e408e07ab48304d1
b, 14 September 2016