MEMBRANE

CHARACTERIZATION
Flux, Permeability, Pore Size, Number of Module required
FLUX AND PERMEABILITY
CALCULATION
 Example 1:
Data obtained from one experiment using pure water is shown in Table 1. Calculate the flux
(L/m2.h) and permeability (L/m2.h.bar) from the data. What type of membrane for this case?
Please justify.

Sample collect at constant

volume, V= 25 mL
Effective membrane
diameter, d= 4 cm
Table 1
Pin(bar) Pout(bar) time

0 0 0

2 2.1 51min 29s

3 3.1 32min 6s

4 4.1 26min 17s

5 5.1 19min 46s

7 7.1 14min 9s

9 9.2 10min 48s

 120 pure water

100

pure water

80
Flux (L/m2.h)

Linear (pure water)

60

40

20

0
0 1 2 3 4 5 6 7 8 9 10

Pressure(bar)
NUMBER OF MODULES
Example 2: An ultrafiltration plant is required to treat 50
m3/day of protein containing waste stream. The waste
contains 0.5 kg/m3 by weight of protein which has to be
concentrated to 20 kg/m3 so as to allow recycling to the
main process stream. The tubular membranes to be used
are available as 30 m2 modules. Pilot plant studies show
that the flux J through these membranes is given by:
J=0.02 ln(30/Cf)
where Cf is the concentration of protein in kg/m3.
However, due to fouling the flux never exceeds 0.04 m/h.

Estimate the minimum number of membrane modules

required for the operation of this process as a single feed
and bleed stage as shown in Figure below.
where Qo is the volumetric flowrate of feed, Q2 is the
volumetric flowrate of concentrate, Co is the solute
concentration in the feed, C2 the solute concentration in the
concentrate, F is the volumetric flowrate of membrane
permeate and A the required membrane area.

Assume operation for 20 hours each day and no loss of

solute through the membrane.
EXAMPLE 3: NO OF MODULE FOR UF
MEMBRANE
 An UF flat sheet membrane has a water permeability of
Lp= 50 L/m2.h.bar. The effective size of the flat sheet
membrane is 0.5 m x 0.2 m in rectangle module. If the
system is run at 5 bar and 25 oC and protein as a feed,
how many numbers of module is required in order to
achieve permeate flow rate of 3 m3/day.
EXAMPLE 4: NO OF MODULE FOR NF
MEMBRANE
 An NF hollow fiber membrane has a water permeability
of Lp= 8 L/m2.h.bar. The external diameter of fiber is
0.1mm and the length of the module is 1m. If the system
is run at 10 bar and 25 oC and seawater (NaCl and
osmotic pressure of 2 bar) as a feed, how many numbers
of fibers is required in order to achieve permeate flow
rate of 1 m3/day.
PORE SIZE AND PORE SIZE
DISTRIBUTION

There are a few methods described in the literature regarding the determination of
pore sizes and pore size distribution. These methods can be classified into two
different approaches; i) direct quantification on membrane surface using
microscopy tools and ii) additional experimental data which related to permeation
parameters. These methods are
1. Microscopy techniques: this technique provide information about membrane
morphology which normally used to view the top, bottom or even the
membrane cross section such as SEM (Scanning Electron Microscopy), TEM
(Transmission Electron Microscopy) and STEM (Scanning Transmission
Electron Microscopy). SEM allows clear observation for MF membranes and
TEM for UF membrane. However, one of the disadvantages of this electron
microscopy (EM) is the need of special sample preparation (i.e. gold coating for
the SEM technique) which may damage the membrane sample. Recently,
development of novel microscopy technique like Atomic Force Microscopy
(AFM) lead the study of non-conducting sample/material with resolution down
to nanoscales.
2. Bubble-point method: characterisation of maximum pore size inside a
membrane by measuring the pressure required to blow air through a liquid
filled membrane. The pore size (pore radius) then correlated with the
pressure by the Laplace equation.
 
3. Bubble-point with gas permeation: In this method, combination bubble-
point method with the measurement of the gas flow through the emptied
pores was introduced in order to overcome limitation information by
bubble-point method alone. Here, the gas flow is measured through dry
membrane as a function of the pressure and generally a straight line is
obtained. In the next step, the membrane is wetted and again the gas flow
is determined as a function of the applied pressure.
4.Mercury intrusion method: mercury is forced into a dry membrane with the volume of
mercury being determined at each particular pressure. By using modified Laplace
equation (to overcome the fact that contact angle for mercury is greater than 90 o), the
relationship between pressure and pore size is analyzed.
 
5.Adsorption-desorption: pore size and pore size distribution in porous materials are
measured based on the principle that capillary condensations occur differently in
adsorption and desorption. Using the Kelvin relationship, the lowering the vapour
pressure of a liquid can be related to its pore radius. 

6.Thermoporometry: this technique is based on the fact that the solidification point (solid-
liquid transition) of the vapour condensed in the pores is a function of the interface
curvature. By using the differential scanning calorimeter (DSC), the phase transition can
be easily monitored and the pore size distribution calculated.
7.Permporometry: This method has been developed to characterize only the
active pores without considering dead-end pores (non active pores) as covered by
the thermoporometry method. It is based on the controlled blocking of pores by
condensation of vapour, present as a component of a gas mixture and the
simultaneous measurement of the gas flux through the membrane.
 
8.Liquid displacement: This method was introduced in the early century by
Bechold and Erbe and then further developed by Munari for determination of the
pore size distribution. The two immiscible liquids are employed and measures the
pressure needed to replace a liquid which already filled the pores inside the
membrane with another immiscible one.
 
9.Permeability method: Permeability can be measured by slope from the plotted
graph of volume flux through the membrane as a function of applied pressure.
By assumption of cylindrical in shape of the pores, pore size and pore size
distribution can be related to permeability through the Hagen-Poisseuile
equation.
 
10. Solute transport method: this method is based on the permeation test in
terms of flux and percentage rejection of solute. Full details of this method is
discussed in the next subchapter.
 SOLUTE TRANSPORT METHOD

In solute transport method, the membrane pores and its distribution are correlated
with the solute sizes which represented by the solute rejection percentage. In fact,
according to Paine and Scheer (1975), this solute rejection/separation was dependent
on the ratio of solute molecular size to the pore size. However, the solute size cannot
be easily determined by direct measurement. As reference, the Stokes radius of a
macromolecule can be obtained from its diffusivity in solution by Stokes-Einstein
equation as follow:
 
1
Where DAB is the diffusivity, k is the Boltzmann’s constant,  is the solvent viscosity
and is the Stokes radius. On the other hand, the diffusivity also can calculated using
Equation 2
 
2
For the known solute like polyethylene glycol (PEG), the intrinsic viscosity can be
found using the following Equation 3 which correlated to molecular weight of the
specific PEG (Meireles et al., 1995).
 
3
 
Combination of Equation 1 and Equation 2, the Stokes radius, (cm) now becomes
as:
 
4
 
Substituting from Equation 3 in Equation 4 generate the Stokes radius of PEG as:
 
5
To produce the equation in diameter term (where ds=2), the Equation 5 is now rearranged
to:
 
6
 
If PEO is considered, the intrinsic viscosity now is (Singh et al., 1998; Nabi, 1968)
 
7
 
Again using the equation 4, the Stokes radius (cm) is
 
8
 
In term of Stokes diameter of PEO, dPEO
 
9
The correlation between solute separation and solute diameter can be expressed
according to the log-normal probability function as (Singh et al., 1998)

2
𝑧 −𝑢
1
𝑓 =erf ( 𝑧 ) = ∫
√2 𝜋 −∞
𝑒 2
𝑑𝑢 10

where f is percent (%) of solute separation

ln 𝑑 𝑠 − ln 𝜇 𝑠 11
𝑧=
ln 𝜎 𝑔
s is the geometric mean diameter of solute at f =50% and g is the geometric standard
deviation about mean diameter. Combining Equation 10 and 11, a straight line
relationship between solute separation (f) and solute diameter (ds) is obtained as
 
12  
where m and c are the slope and intercept, respectively on the log-normal probability
plot. If the separation solute and Stokes diameter data plotted on a log-normal
probability paper (as shown in Figure 1 & 2) or Sigma Plot software give straight lines,
the mean pore size and geometric standard deviation () can be determined.
The mean pore size is taken that corresponds to 50% of the solute separation while
the geometric standard deviation is the ratio between the Stokes diameter
corresponding to 84.13% of the solute separation and the mean pore size (). Note
that, the reading taken from the log-normal probability plot as the mean pore size
and geometric standard deviation () instead of the geometric mean diameter of
solute (s) and the geometric standard deviation about mean diameter ( g),

respectively. These both parameters are considered same ( p=s, p=g) since the
dependence of solute separation on the steric and hydrodynamic interaction
between solute and pore sizes can be ignored (Singh et al., 1998; Ishiguro et al.,
1996; Michaels, 1980; Cooper and Van Derveer, 1979).
From the obtained mean pore size and geometric standard deviation (), the
pore size distribution can be expressed by the probability density function
described by the following equation (Khayet and Matsuura., 2003; Khayet et
al., 2002; Singh et al., 1998).

𝑑𝑓 (𝑑 𝑝 )

[ ]
2
1 ( ln 𝑑𝑝 − ln 𝜇 𝑝 ) 13
𝑑 (𝑑 ¿¿ 𝑝)= exp − ¿
𝑑 𝑝 ln 𝜎 𝑝 √ 2 𝜋 2 ( ln 𝜎 𝑝 )2
EXAMPLE 5: PORE SIZE AND PORE SIZE
DISTRIBUTION CALCULATION
 Data given in Table 2 is based on NF experiment using
polyethylene glycol (PEG) as the feed. Calculate the
mean pore size, geometric standard deviation and pore
size distribution.

Mw
(Da) Cf Cp R
PEG200 200 105.5 100
PEG600 600 115.9 78.69
PEG1000 1000 113.75 57.56
PEG3350 3350 113.6 12.65