MEMBRANE CHARACTERIZATION

A small change in one of the membrane

formation parameters can change the (top
layer) structure and consequently have a
drastic effect on membrane performance.
REPRODUCIBILITY is also problem
Why need Membrane Characterization ?
To relate structural membrane properties
such as pore size, pore size distribution,
free volume and crystallinity to membrane
separation properties

To obtain impression about size of particles

and molecules and ions to encountered, a
wide range of particles and molecules with
various dimensions are available

MEMBRANE CHARACTERIZATION BECOMES

PROGRESSIVELY MORE DIFFICULTS AS THE
PORE SIZE DECREASES.

Membranes will be classified in two main

groups
i.
porous
ii.
nonporous
MF/UF fixed pores are present, can be
characterized by several techniques
Defination of porous (IUPAC)
i. Macropores > 50 nm
ii.Mesopores 2 nm <pore size < 50 nm
iii.
Micropores < 2 nm
Pore diameter or more arbitrarily pore width
MF porous media containing macropores,
UF also porous with mesopores in top layer.
Therefore, it is not the membrane material
which is characterized, but the pores in the
membrane

Pore and pore size distribution (PSD) mainly

determines which particles or molecules
are retained and which will pass through
the membrane

The material is of little importance in

determining the separation performance.

Dense
pervaporation/gas
separation
membranes no fixed pores are present
and the material itself mainly determines
the performance.

The morphology of the polymer material

used for membrane preparation directly
affects
its
permeability
(crystalline,
amorphous, glassy, rubbery)

Factors such as temperature and the

interaction of the solvent and solute with
the polymeric materials, have a large
influence on the segmental motions
(molecular orientation).

CHARACTERIZATION
MEMBRANE

OF

POROUS

Shape of the pore or its geometry is not

well defined in membrane characterization
techniques.

In order to relate pore radii to physical

equations, several assumptions have to be
made about the geometry of the pore.

Poiseuille equation pores are considered

to be parallel cylinders,

Kozeny-Carman eqn pores are the voids

between the close-packed spheres of equal
diameter

Actuality, such pores do not exist. However,

in order to interpret the characterization
results, it is often essential to make
assumptions about the pore geometry

In addition, it is not the pore size which is

the rate-determining factor, but the
4

smallest restriction. Indeed, some

characterization techniques determine the
dimensions of pore entrance rather than
the pore size. better info about
permeation related characteristics

PSD in a porous UF and MF membrane

means pores do not have same size but
exist as a distribution of size.

Surface porosity is also a very important

variable in determining the flux through the
membrane. SP is a factor of a
combination with the thickness of the top
layer or the length of the pore.

Two different types of characterization

method for porous membranes :i. Structure-related
parameter

determination of pore size, PSD, top

layer thickness and surface porosity.
ii.Permeation-related
parameters

determination of the actual separation

parameters using solutes that are more

or less retained by the membrane (cutoff measurements)

It is often very difficult to relate the (i) and

(ii) because the pore size and shape is not
very well defined.

The configuration of the pores (cylindrical,

packed-spheres) used in simple model
descriptions deviate sometimes dramatically
from the actual morphology, in
MICROFILTRATION

Pores : 0.1 10 m range

Techniques
used
such
as
Electron
microscopy, Bubble point method, Mercury
intrusion
porometry,
permeation
measurements

EM - SEM, TEM (Transmission Electron

microscopy).

SEM provides a very convenient and simple

method for characterizing and investigating
the porous structure of MF.
The resolution limit lies in the 0.01 m (10
nm).
SEM principle
A narrow beam of electrons with kinetic
energies in the order of 1-25 kV hits the
membrane sample. The incident electrons
are called primary (high-energy) electrons,
and those reflected are called secondary
electrons.
Sec electrons (low energy) are not reflected
but liberated from atoms in the surface
mainly determine the imaging what is
seen on the screen or micrograph.
To avoid sample damaged or burned due to
the electron beam, sample is coated (thin
gold layer coating)
SEM allows a clear view of the overall
structure of a MF membrane (top surface,
7

x-section and bottom surface) and any

asymmetry structures. Also the geometry
of the pores can be clearly visualized.

Atomic Force Microscopy (AFM)

Latest development
Suitable for NF (even though only on the
surface morphology)
A sharp tip with a diameter smaller than 100
Angstrom is scanning across a surface with a
constant force. London-van der Waals
interactions will occur between the atoms in
the tip and surface of the sample and these
forces are detected.
Bubble-point method
Provides a simple means of characterizing
the maximum pore sizes in a given
membrane.

The method essentially measures the

pressure needed to blow air through a liquidfilled membrane.
The top of the filter is placed in contact with
a liquid (eg. Water) which fills all the pores
when the membrane is wetted.
The bottom of the filters in contact with air
and as the air pressure is gradually increased
bubbles of air penetrate through the
membrane at a certain pressure.
The relationship btw pressure and pore
radius is given by Laplace equation:This method can only be used to measure
the largest active pores in a given
membrane.
BUBBLE POINT WITH GAS PERMEATION
(WET AND DRY FLOW METHOD)

BP method gives limited information, and

disadv.

Eg. Depends on the liquid use (different

wetting mechanisms, but not reflected in
equations), rate at which the pressure is
increased, affinity btw wetting liquid and
membr material etc.
BP with gas permeation combines the
bubble-point concept with the
measurement of the gas low through the
emptied pores.
2 steps:gas flow is measured through a dry
membrane as a function of the pressure is
generally a straight line.
Then, the membrane is wetted and again
the gas flow is determined as a function of
the applied pressure
At very low pressures the pores are still
filled with the liquid and the gas flow
(which is determined by diffusion through
the liquid) is very low
At a certain minimal pressure (bubble
point), the largest pores will be empty and
the gas flow will increase by convective
flow through these pores.
At the highest press the gas flow of the dry
membrane must be equal to the wet
membrane.
10

Suitable for characterization of macropores,

eg MF with sizes up to 50 nm.

Permeability Method
If capillary pores are assumed to be present,
the pore size can be obtained by measuring
the flux through a membrane at a constant
pressure using the Hagen-Poiseuille eqn.

J = water (flux) through the membrane at a

driving force of P/X,
r-pore radius (m),
= liquid viscosity (Pa.s)m,
= surface porosity of the membrane,
=
tortuosity factor.
When the pressure is increased further the flux
increases linearly with pressure.

11

HP assumes the pores in the membrane are

cylindrical but generally this is not the case.
Kozeny-Carman eqn pores are interstices
btw close-packed spheres. Such pores are
not
commonly
found
in
synthetic
membrane.

ULTRAFILTRATION

Considered
as
porous,
asymmetric compared to MF.

Characterization

involves
the
characterization of the top layer (thickness,
PSD and surface porosity).

Typical pore diameter of top layer : 20

1000 Angstrom.

Techniques for MF cannot be used for UF

but

more

12

Resolution of SEM is too low to determine

the pore sizes in top layer accurately.

Mercury
intrusion
and
bubble-point
methods cannot be used because the pore
sizes are too small, so that very high
pressures would be needed which would
destroy the polymeric structure.

Permeation exp can still be used. Other

techniques are :Gas adsoption-desorption
Thermoporometry
Permporometry
Liquid displacement
Fraction or rejection measurement
TEM

SOLUTE REJECTION MEASUREMENT

Use concept of cut-off to characterize UF
membranes

13

Cut off is defined as that molecular weight

which is 90% rejected by the membrane
Eg. Membrane has a cut-off value of 40,000
implying that all solutes with a molecular
weight > 40K are more than 90 % rejected.
However, it is not possible to define the
separation characteristics of a membrane a
single
parameter,
i.e
MWCO.
Other
parameters such as shape, flexibility of the
macromolecular solute, its interaction with
the membrane material and membrane
fouling have drastic/significance effect on
separation characteristics.
To
characterize
the
membrane
(determination of membrane structure such
as pore size and etc) Solute rejection data
is combined with the models (developed for
the particular membrane system) such as

Nernst Planck-equation
Irreversible Thermodynamic model (SPiegler
and Kedem Model)
14

Donnan Steric Pore Model

Electrostatic model

CHARACTERIZATION OF NONPOROUS
MEMBRANE

In nonporous, the chemical nature and

morphology of the polymeric membrane
and the extent of interaction between the
polymer and the permeates are the
important factors to consider.

The
determination
of
the
physical
properties related to the chemical structure
is now more important and, the methods
such as :Permeability
15

Other physical properties

Plasma etching
Surface analysis

PERMEABILITY

Using a simple experimental setup

The
cell
containing
a
homogenous
membrane of known thickness is pressurized
with a chosen gas. The extent of gas
permeation through the membrane is
measured by means of a mass flow meter or
by a soap bubble meter.
Sophisticated method use a calibrated
volume connected to the permeate side with
the small pressure increase in the calibrated
volume being measured with a pressure
transducer.
The gas permeability or permeability
coefficient , P can be determined
J = Pl

16

17