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Characterization of nanofiltration membrane using

microscopic methods
1.

INTRODUCTION

The main objectives for this analysis is to compare the surface properties of two
nanaofiltration membranes (NF11 and NF12) and to investigate the influence of
membrane factor on fouling relationship of the membranes used to treat waste
water (sewage water). Scanning Electron Microscope (SEM) and Atomic Force
Microscope (AFM) in-conjunction with image processing softwares (WSxM 5.0
Develop 6.4 and Image J) were used to obtain the following surface parameter of
the membranes, pore size distribution and surface roughness parameters (RMS
roughness, peak height, skewness and kurtosis). Hwang and Lin [1] used
observations made using SEM to qualify the nature of the pores of 3 microfiltration
membranes used to treat waster with a cut-off of 0.1m. They also observed the
fouling of these membranes after filtration of a solution containing model particles
of polymethyl methacrylate (mean diameter = 0.4m). The major disadvantage of
this technique is the sample preparation by gold metallization, which entails a less
accurate pore size determination [2].
Atomic Force Microscopy (AFM) was first used in 1988 to study the structure of
polymeric membranes [3]. This technique can be used in three different modes:
contact [4], non-contact [5] and tapping mode [6] and can be applied to all
membranes, from microfiltration to reverse osmosis [78], for organic. This
technique makes it possible to represent no conducting surfaces with a resolution of
the order of the nanometer in either dry or wet environments [910]. Therefore,
using AFM makes it possible to avoid drying the sample under vacuum.
The AFM measurements give access to the roughness, pore size, pore density and
pore size distribution of a membrane [11]. They can also provide information on the
surface electrical properties of a membrane, its fouling potential towards a specific
colloid [12] and its filtration performance as a function of its roughness. All this can
help to predict fouling without process measurements [13]. Hirose et al. and
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Warczock et al. [14] studied by AFM the relationship between the skin layer surface
structure of NF membranes and their filtration performances. It was shown that the
roughest membranes provided the best performances in terms of flux, the flux
increases quasi-linearly with the roughness. However, some drawbacks of the AFM
technique were pointed at: due to the size of AFM scanning probe tips, there are
some limitations to the scanning depth; also, AFM may distort membrane pore size
due to rounded corners near pore entrance [15]. Boussu et al. [16] compared the
results obtained using contact and non-contact mode AFM.
It was concluded that when comparing surface roughness for different membranes,
the same AFM method and the same scan size must be used. However in this work,
contact mode was used to analyze surface properties of the two membranes. In
non-contact mode, the tip of the cantilever does not contact the surface of the
sample therefore the sample does not surfer from sample degradation effects
compared to the other modes. In terms of analyzing wet samples, non-contact mode
will be more advantageous since it will just oscillate above the adsorbed fluid layer
to image both the liquid and surface. Images obtained by AFM were further
analyzed using image processing software (WSxM 5.0 Develop 6.4) to obtain the
statistical measures (bearing ratio, Power Spectrum Density). The results in the
literature shows that the membrane with the highest roughness will perform better
in waste water treatment.

2.

EXPERIMENTAL ANALYSIS

Analyses of two different nanofiltration membrane materials NF11 and NF12 were
performed using Atomic Force Microscope (AFM). The materials were of unused
nanofiltration membranes used to treat waste water. The membranes were scanned
on two scan sizes (1.0m1.0m and 5m5m). The four topographic images
obtained from the microscope were stored in a computer and further analyses using
the image processing software WSxM 5.0 Develop 6.4 (see Figure 1 below).
2.1.

Experimental Set-up

Figure 1: Experimental set up.

2.2.

Experimental Procedure

2.2.1. Atomic Force Microscope (AMF)


Atomic force Microscope operated under ambient conditions was used to analyze
the surface roughness of two unused nanofiltration membrane materials. The
materials were obtained by sawing the membranes with a diamond blade. Images
were acquired in taping mode using a comitial AFM probe (Cantilever length of
215um, nominal tip height of 40um, tip radius <10nm, force constant 3N/m,
resonant frequency 275 kHz). The images obtained were further processed using
Image processing software WSxM 5.0 Develop 6.4 to determine the surface
roughness measures (RMS roughness, peak height, skewness and kurtosis), bearing
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ratio and power spectrum density (PSD). Bearing ratio analysis was used to
calculate the potential microgap size between the membrane pores and to calculate
the depth of the valleys on the membrane surface, while power spectral density
(PSD) measurements were performed to measure the percentage of the surface
membrane.
2.2.2. Scanning Electron Microscope (SEM)
Scanning Electron Microscope (SEM) analysis is still to be performed and the images
from this technique will be processed using the image J software to determine the
pore size of both the unused and used membranes.
3.

RESULTS AND DISCUSSION

Atomic Force Microscope (AFM) was used to obtain information of the topography of
two unused nanofiltration membranes to determine their roughness measures. The
results obtained are presented below graphically in Figure 2 to Figure 8 and in
Tabular form in Table 1 and Table 2. Four topographic images at the following scan
size (1.0m1.0m and 5m5m) were taken for each membrane. Table 1 present
the top view of 2D and 3D images of the membrane surface obtained using the
Image processing software WSxM 5.0 Develop 6.4. From these results bearing ratio
plot curve, Power Spectrum Density curve and roughness Histogram determine for
each membrane with the associated scan size. From Table 1, the first observation
that can be made is that the roughness on the surface of the membrane increase
with the scan size.

3.1.

Images obtained with AFM

Table 1: 2D and 3D images of the membrane surface obtaining by Image processing


software (WSxM 5.0 Develop 6.4).
NF membranes and scan size

45 View

Top view

3.2.

Information obtained by WSxM 5.0 Develop 6.4 at scan size

1.0m1.0m

Figure 2: Bearing ratio plot curve for NF11 and NF12 at 1.0m1.0m.
Figure 2 above present the comparison of the bearing ratio of NF 11 and NF12 at
the same scan size 1.0m1.0m. NF11 membrane depicted the greatest peak
height (Rpk) value (4157.68) at a bearing area of 0.86m 2 while NF11 had the lowest
(3273.32) at a bearing area of 0.69m2.

Figure 3: Power spectral density curve for NF11 and NF12 at 1.0m1.0m.
The PSD plot above (Figure 3) obtained from 2D profiles shows that NF11 had the
highest critical surface area than NF12. The critical surface area for NF11 can be
estimated to be 290m2 and 165m2 for NF12. It can also be observed that both
membranes had similar surface roughness properties at 1.0m1.0m scan size.

Figure 4: Roughness histogram for NF11 and NF12 at 1.0m1.0m.


Figure 4 present the surface height distribution of the two membranes at
1.0m1.0m scan size. The histogram support the observation made from the
images in Table 1 that NF11 has the roughest surface than NF12.

3.3.

Information obtained by WSxM 5.0 Develop 6.4 at scan size

5.0m5.0m

Figure 5: Bearing ratio plot forNF11 and NF12 at 5.0m5.0m.


Figure 5 above present the comparison of the bearing ratio of NF 11 and NF12 at
the same scan size 1.0m1.0m. NF11 membrane depicted the greatest peak
height (Rpk) value (1225.44) while NF11 had the lowest (1152.42) at same bearing
area of 25m2.

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Figure 6: Power spectral density curve for NF11 and NF12 at 5.0m5.0m.
The PSD curve above (Figure 6) obtained from 2D profiles shows that NF11 had
almost the same critical surface area than NF12. The critical surface area for NF11
can be estimated to be 3.54 104 m2 and 3.55 104 m2 for NF12. It can also be
observed that both membranes had similar surface roughness properties at
5.0m5.0m scan size.

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Figure 7: Roughness histogram for NF11 and NF12 at 5.0m5.0m.


Figure 7 also present the surface height distribution of the two membranes at
5.0m5.0m scan size. The histogram support the observation made from the
images in Table 1 that NF11 has the roughest surface than NF12.

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Figure 8: Evolution of the roughness obtained by AFM for 1.0m1.0m and


5.0m5.0m windows.
The above graph shows RMS roughness of the two membranes at the associated
scan size. It can be seen that whatever the membrane, the RMS roughness obtained
for the 1.0m1.0m is higher than for 5.0m5.0m scan size. The RMS
roughness for 1.0m1.0m ranged between 846.263(NF11) and 691.314 (NF12),
whereas for the 5.0m5.0m scan size, the range between 275.804 (NF11) and
242.406 (NF12). In both scan size, the NF11 membrane had the highest RMS
roughness.

Table: 2 below summarize the roughness measures obtained from the roughness
histogram plot in Figure 4 and Figure 7. The peak height (R p) for 1.0m1.0m scan
size is also higher than that for 5.0m5.0m scan size in both membranes.
However the Skewness (R sk) of NF11 for 1.0m1.0m (0.1267) was higher than
that of 5.0m5.0m (0.031) while the Skewness (R sk) of NF12 was positive for
1.0m1.0m (0.368) and negative for 5.0m5.0m (-0.0459). This shows that
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the surface NF11 at 1.0m1.0m scan size has deep valleys or high peaks
compared to 5.0m5.0m scan size and lack of peaks on the surface of NF12. The
Kurtosis (Rku) was higher for 1.0m1.0m and less for 5.0m5.0m scan size.
Table 2: Analysis of the AFM profiles of NF11 and NF12

4.

CONCLUSION

The results obtained shows that the determination of the membrane roughness
depends on the observation scale. The roughness parameters of the membranes
decrease with increase in observation scale. The RMS roughness, peak height,
skewness and kurtosis for 1.0m1.0m scan size were higher than 5.0m5.0m
scan size. NF11 membrane had the highest RMS roughness (846.263), highest peak
height (4157.68), highest skewness (0.1267) and kurtosis (3.75) at 1.0m1.0m
scan size while NF than NF12 had the lowest (refer in Table 2). The results clearly
show that NF11 had the roughest surface than NF12 since it had the highest
roughness even for 5.0m5.0m scan size. As per the results in the literature, the
membrane with the highest roughness (NF11) will perform better in waste water
treatment.

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5.

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