Lecture 9

Characterization of Porous Membranes

• Porous micro- or ultrafiltration membranes are generally characterized in terms of their

trans-membrane flux, pore size, pore size distribution, and molecular mass cut-off.

• Electron Microscopy

• Bubble-Point Test

• Filtration Tests

• Molecular Weight Cut-Off

Electron Microscopy

• The structure of porous membranes can be determined by electron microscopy.

• Scanning Electron Microscopy (SEM) gives an especially clear picture of membrane

structure and requires minimum sample preparation;

• However, resolution is limited to about 50-nm.

• Higher resolution can be obtained with Transmission Electron Microscopy (TEM), but
sample preparation is significantly more complex and the structure is not nearly as clear
as that obtained by scanning electron microscopy.

Bubble-Point Test

• The "bubble-point" test is a simple method for determining the maximum pore size of a
membrane.

• One side of the membrane is filled with liquid such as water, although i-propanol is often
used as the standard liquid.

• If the other side of the membrane is exposed to air at a certain pressure

• Air bubbles will penetrate through the pores of the membrane when the radius of the air
bubble is equal to the radius of the pore.

• The pressure needed to penetrate a pore is inversely proportional to the pore size.

• Thus, penetration occurs first through the largest pores. When the pressure is increased
further, pores with smaller diameters are also penetrated.

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 • Because the surface tension between water and air is rather high, high pressure is
required for the determination of small pores.

• In practice, pore sizes between 0.1 and 10 mm are determined by hydrostatic pressures of
1500 - 15 kPa. The main application of the bubble-point test is to determine pinholes and
leaks in micro- and ultrafiltration membranes and modules.

•
Filtration Tests

• In filtration tests, trans-membrane flux and membrane solute retention are determined.

• To avoid the influence of concentration polarization or any other boundary layer

phenomenon, the trans-membrane flux is generally measured as a function of applied
hydrostatic pressure with ultra-pure water.

• Membrane flux often decreases with time during the filtration test due to compaction of
the membrane structure under pressure.

• A compaction factor has been defined, which is determined from the slope of the curve
obtained when the trans-membrane flux at constant pressure is plotted versus time on a
semi-logarithmic scale.

• Unfortunately, the fluxes measured with ultra-pure water, at least in ultra- and
microfiltration, often bear little relation to those obtained with solutions containing
macromolecules or suspended particles.

Molecular Weight Cut-Off

• Many membranes, especially those used in ultrafiltration, are also characterized in terms
of their molecular mass cut-off. Here, the rejection of a given membrane for various
molecular mass components is determined in filtration tests. Rejection is plotted versus

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 molecular mass and the resulting curve describes the membrane's solute retention
properties. Components with a diameter smaller than the smallest pores pass through the
membrane unhindered; all components with a diameter smaller than the largest pores but
larger than the smallest pores are rejected in proportion to the pore size distribution of the
membrane.

• The early UF membranes were used for purification of biological solutions for retaining
macromolecules such as proteins.

• Since macromolecules are characterized by their molecular weights, the ability of UF

membranes to retain these macromolecules is based on their molecular weight.

• Thus, the term MWCO came into being for characterizing UF membranes.

• It is arbitrarily defined as the molecular weight at which 90% of the macromolecular

solute is rejected by the membrane.

• Molecular weight cut-off or MWCO refers to the lowest molecular

weight solute (in daltons) in which 90% of the solute is retained by the membrane or the
molecular weight of the molecule (e.g. globular protein) that is 90% retained by the
membrane.

• Molecular weight cut-off (MWCO) is a term used to describe a pore size of a membrane.

• The smaller the MWCO, the tighter the membrane pore size.

• RO elements have ~100 Dalton molecular weight cut-off

• NF has 200-400 Dalton molecular weight cut-off.

• A membrane with MWCO of 100 means it can reject molecules with the molecular
weight of 100 well (i.e. >90%).

• MWCO has emerged as one of the most useful tools for characterizing UF membranes.

• The molecular weight at 90% solute retention

indicates roughly the molecular weight cut off of the membrane

• The retention R is a dimensionless number expressed simply as:

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• where cm and cP are the solute concentration in the feed and permeate respectively. The
value of R varies between 100% (complete retention of the solute) and 0% (solute and
solvent pass through the membrane freely).

• Some commercial membranes have a very narrow pore size distribution and thus a sharp
molecular mass cut-off. Others have a wider pore size distribution and therefore a more
diffuse cut-off.

• Real retention is a constant that defines the partition of the solute concentration across the
membrane, i.e., between the membrane-solution interface and the permeate side.

• It indicates the true separation efficiency of the solute by the membrane.

• since, membrane surface concentration of solute is always greater than the bulk
concentration, real retention is always greater than observed retention.

• For complete solute retention, Rr = 1.0.

• Molecular weight cut off curves may be a sharp cut off or a diffused cut off.

• If the retention curve rises sharply to 90% level over a small span of molecular weight
regime, then the cut off curve is called a sharp cut off curve.

• If the retention curve rises over a wide span of molecular weight region, it is a diffused
cut off curve.

• One has to have an accurate control over the operating conditions to achieve the sharp cut
off membranes.

• In fact, most of the commercial membranes are diffused type

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Membrane Permeability (Lp):

This parameter shows how porous the membrane is. If Lp is more, then the membrane is more
porous.

Estimation of retention & permeability:

• Retention:

• Observed retention (Ro): Estimate by direct experimental measurement

• Real retention (Rr): One has to conduct batch experiments at high stirring speed,
low feed concentration and low operating pressure.

• In that case, it is assumed that there is no formation of concentrated solute layer over the
membrane surface and in absence of polarized layer, observed retention is almost same as
retention.

Permeability:

• Membrane permeability is measured by distilled water runs.

• Experiments are conducted using distilled water at various transmembrane pressure drops
values.

• At various pressure drops, the water flux is measured.

• A plot of permeate flux versus operating pressure would be a straight line through the
origin, as shown in Fig.

• The slope of this curve indicates the permeability (Lp) of the membrane.

• Permeability of the membrane is independent of turbulence (stirring speed or cross flow

velocity) in the flow channel.

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Membrane fouling:

• Membrane fouling is characterized by the accumulation of feed stream components onto

the surface of or within the pores of a membrane, resulting in an increase in hydraulic
resistance and accompanied by a decrease in permeate flux.

• There are several different means by which fouling can occur.

• Static membrane fouling can take place in the absence of a permeate flux and occurs
due to the adsorption of feed components onto the membrane itself, which is driven by
both physical and chemical interactions.

• Dynamic membrane fouling, on the other hand, occurs when a permeate flux is
generated and occurs through one or more mechanisms. One of these is through the
partial or full pore blockage caused by the accumulation of foulants within the pores
of a membrane. Another is through the development of a cake layer via the continuous
deposition of feed particulates on the membrane surface.

• Similarly, a gel layer may form near the membrane surface depending on the extent of
concentration polarization.

• Membrane fouling can be characterized as reversible or irreversible depending on both

the extent and type of fouling observed

Fouling potential

• Fouling potential is an important factor to consider when selecting a membrane for any
given separation process

• Membrane fouling can easily be examined through monitoring permeate flux [of a
compacted membrane], with both pressure and temperature held constant.

• This is due to the inverse relationship between flux and total resistance, as the latter
increases as fouling progresses.

• An optimal membrane would show minimal flux decline as time goes on.

• However, a drastic and rapid flux decline would indicate that the membrane is highly
prone to fouling with that particular feed stream. for fouling potential rather than the
membrane.

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Methods to Reduce Membrane Fouling

• Feed stream properties.

– This includes characteristics such as concentration, pH and ionic strength,

dissolved solid content, suspended solid content, etc.

• Membrane material and its physical-chemical properties.

– Membrane pore size, porosity and pore distribution, and membrane surface charge
and hydrophobicity in certain pH and ionic strength conditions can contribute to
fouling.

• Processing variables:

– Transmembrane pressure, temperature, and cross-flow velocity have a big impact

on membrane fouling.

• Optimize pH and ionic strength of the feed solution to minimize the adsorption or
deposition of the feed materials.

• Select an appropriate pre-filtration procedure or other means to remove large molecules,

since the presence of larger molecules or particles could cause a steric hindrance to the
passage of smaller molecules through the membrane.

• Select a membrane with an optimum pore size to result in good separation performance
as well as optimized permeate flux.

• Optimize the operating conditions. This includes increasing transmembrane pressure to

maximize flux without introducing more fouling potential.

• Increase the cross-flow velocity, which generally results in an improvement in permeate

flux.

Resistance to solvent flow: • It prevents initial flux of solvent, • Require more pressure

• Concentration polarization

• Gel formation

• Adsorption

• Pore blockage

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Concentration Polarization (CP):

• When pressure is applied to the feed side of a membrane during the filtration process, the
solute is partially or totally retained by the membrane and will accumulate on the surface,
while the solvent passes through the membrane more freely. Due to the membrane’s
solute retention, the concentration of the solute in the permeate (Cp) is lower than the
concentration in the bulk (Cb) 1.

• The concentration of the solute gradually increases on the surface of the membrane, due
to solute accumulation from convective flow.

• At some point, the convective solute flow to the surface of the membrane will be
balanced by the solute flux through the membrane and the diffusive flow from the
membrane surface to the bulk. A concentration polarization profile, in which the
concentration at the membrane surface (Cm) is typically higher than the Cb, will be
established in the boundary layer.

• It is the reversible accumulation of the rejected solute in the fluid phase at the membrane
interface

• If steady state prevails the solute restrained will be transported back into the bulk solution
through the boundary layer because of concentration difference.

Theoretical Analysis of CP:

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Characterization of Dense, Homogeneous Membranes:

• Dense membranes are normally used to perform separations on a molecular level.

• As such, the chemical nature and morphology of the polymeric membrane and the extent
of interaction between the polymer and permeate are important factors to consider.

• Characterization methods used with porous membranes need to be supplemented with

other procedures.

• One of the simplest methods of characterizing these membranes is to determine the

membrane permeability towards gases and liquids.

• Various physical methods can be used to characterize the parameters that affect the
permeability, such as the glass transition temperature and polymer crystallinity (degree,
size and shape).

Pore size distribution:

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Pore blockage: (It prevents initial flux of solvent, require more pressure)

• Membrane pore blockage

• The pores are not uniform size

• May have cracks, non-cylindrical

• The molecule separated are not spherical

• Some solute may get stuck into the pore during filtration and creates pore blockage

Driving forces for transport

• Passive Transport

• Facilitated transport

• Active transport

Driving force for transport is provided by the activation energy of chemical reaction in the
membrane phase.

In this case, the upstream chemical potential is higher than that of downstream potential.

Passive Transport:

The upstream chemical potential of a component is more than that in the downstream.

Passive transport is a movement of ions and other atomic or molecular substances

across cell membranes without need of energy input.

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Active transport:

• Transports molecules through the cell membrane against the concentration

gradient.

• So more of the substance is inside the cell (i.e. a nutrient) or outside the cell (i.e. a waste)
than normal. Disrupts equilibrium established by diffusion.

• Components are transported against driving force.

• Driving force for transport is provided by the activation energy of chemical reaction
in the membrane phase (Living Cell).

• In this case, the upstream chemical potential is higher than that of downstream potential.

Facilitated transport:

• In this case also the chemical potential of a species in upstream is more than that in the
downstream. However, as shown in Fig., components to be transported are coupled with
a carrier in the membrane phase.

• So, it is a special form of passive transport and very selective and at the same time, the
transport is facilitated by the carrier component.

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