Lecture Notes 14 – Introduction to Membrane Science and Technology 1

Engr. Caesar P. Llapitan

A membrane is a selective barrier that permits the separation of certain species in a fluid by
combination of sieving and sorption diffusion mechanism. Separation is achieved by selectively
passing (permeating) one or more components of a stream through the membrane while retarding
the passage of one or more other components. See the Figure. Membranes can selectively separate
components over a wide range of particle sizes and molecular weights, from macromolecular
materials such as starch and protein to monovalent ions. Membranes have gained an important place
in chemical technology and are used in a broad range of applications.

The key properties determining membrane performance are high selectivity and fluxes, good
mechanical, chemical and thermal stability under operating conditions, low fouling tendencies and
good compatibility with the operating environment; and cost effective and defect-free production.

Although the major uses of membranes are in the production of potable water and separation of
industrial gases, they can be used for many other important applications such as filtration of
particulate matter from liquid suspensions, air or industrial flue gas and the dehydration of ethanol
azeotropes.

More specialized applications include ion separation in electrochemical processes, dialysis of blood
and urine, artificial lungs, controlled release of therapeutic drugs, membrane-based sensors, etc.

Membrane processes are characterized by the fact that a feed stream is divided into 2 streams:
retentate and permeate. The most general process can be depicted by the following Figure:

The retentate is that part of the feed that does not pass through the membrane, while the permeate
is that part of the feed that does pass through the membrane. The optional "sweep" is a gas or liquid
that is used to help remove the permeate. The component(s) of interest in membrane separation is
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Engr. Caesar P. Llapitan

known as the solute. The solute can be retained on the membrane membrane and removed in the
retentate or passed through the membrane in the permeate.

It is important to note that there are 3 different mechanisms by which membrane can perform
separations:
 By having holes or pores which are of such a size that certain species can pass through and
others cannot. This mechanism is called size exclusion.
 By selective retardation by the pores when the pore diameters are close to molecular sizes.
This mechanism is called pore flow.
 By dissolution into the membrane, migration by molecular diffusion across the membrane, and
re-emergence from the other side. This is called solution diffusion.

Industrial Applications of Membrane Separation Processes

Reverse Osmosis
Desalination of brackish water
Treatment of wastewater to remove impurities
Treatment of surface and ground water
Concentration of foodstuff
Removal of alcohol from beer and wine

Dialysis
Separation of nickel sulfate from sulphuric acid
Hemodialysis - removal of waste metabolites, excess body water, and restoration of
electrolyte balance in blood

Electrodialysis
Production of table salt from seawater
Concentration of brines from reverse osmosis
Treatment of wastewater from electroplating
Demineralization of cheese whey
Production of ultrapure water for semiconductor industry

Microfiltration
Sterilization of drugs
Clarification of biological stabilization of beverages
Purifications of antibiotics
Separation of mammalian cells from a liquid

Ultrafiltration
Pre-concentration of milk before making cheese
Clarification of fruit juice
Recovery of vaccines and antibiotics from fermentation broth
Color removal from Kraft black liquor in paper-making

Pervaporation
Dehydration of ethanol-water azeotropes
Removal of water from organic solvents
Removal of organics from water

Gas Permeation
Separation of CO2 or H2 from methane and other hydrocarbons
Adjustment of the H2/CO ratio in synthesis gas
Separation of air into nitrogen- and oxygen-enriched streams
Recovery of helium
Recovery of methane from biogas

Liquid Membranes
Recovery of zinc from wastewater
Recovery of nickel from electroplating solutions
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Engr. Caesar P. Llapitan

Membrane processes have a number of advantages and disadvantages compared to alternative

means of performing separations.

Advantages and Disadvantages, Challenges of Membrane Separations

Membrane processes have a number of pluses and minuses compared to alternative means of
performing separations.

The advantages include:

Because membrane processes can separate at the molecular scale up to a scale at which
particles can actually be seen, this implies that a very large number of separation needs might actually
be met by membrane processes.

Membrane processes generally do not require a phase change to make a separation (with the
exception of pervaporation). As a result, energy requirements will be low unless a great deal of energy
needs to be expended to increase the pressure of a feed stream in order to drive the permeating
component(s) across the membrane.

Membrane processes present basically a very simple flowsheet. There are no moving parts (except
for pumps or compressors), no complex control schemes, and little ancillary equipment compared to
many other processes. As such, they can offer a simple, east-to-operate, low maintenance process
option.

Membranes can be produced with extremely high selectivity for the components to be
separated. In general, the values of this selectivity are much higher than typical values for relative
volatility for distillation operations.

Because of the fact that a very large number of polymers and inorganic media can be used as
membranes, there can be a great deal of control over separation selectivity.

Membrane processes are able to recover minor but valuable components from a main stream
without substantial energy costs.

Membrane processes are potentially better for the environment since the membrane approach
require the use of relatively simple and non-harmful materials.

The disadvantages include:

Membrane processes seldom produce 2 pure products, that is, one of the 2 streams is almost
always contaminated with a minor amount of a second component. In some cases, a product can
only be concentrated as a retentate because of osmotic pressure problems. In other cases the
permeate stream can contain significant amount of materials which one is trying to concentrate in
the retentate because the membrane selectivity is not infinite.

Membrane processes cannot be easily staged compared to processes such as distillation, and
most often membrane processes have only one or sometimes two or three stages. This means that the
membrane being used for a given separation must have much higher selectivities than would be
necessary for relative volatilities in distillation. Thus the trade-off is often high selectivity/few stages for
membrane processes versus low selectivity/many stages for other processes.

Membranes can have chemical incompatibilities with process solutions. This is especially the case
in typical chemical industry solutions which can contain high concentrations of various organic
compounds. Against such solutions, many polymer-based membranes (which comprise the majority
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Engr. Caesar P. Llapitan

of membrane materials used today), can dissolve, or swell, or weaken to the extent that their lifetimes
become unacceptably short or their selectivities become unacceptably low.

Membrane modules often cannot operate at much above room temperature. This is again related
to the fact that most membranes are polymer-based, and that a large fraction of these polymers do
not maintain their physical integrity at much above 100 oC. This temperature limitation means that
membrane processes in a number of cases cannot be made compatible with chemical processes
conditions very easily.

Membrane processes often do not scale up very well to accept massive stream sizes. Membrane
processes typically consist of a number of membrane modules in parallel, which must be replicated
over and over to scale to larger feed rates.

Membrane processes can be saddled with major problems of fouling of the membranes while
processing some type of feed streams. This fouling, especially if it is difficult to remove, can greatly
restrict the permeation rate through the membranes and make them essentially unsuitable for such
applications.

Challenges of Membrane Processes

The following questions generally need to be considered when considering a membrane option:
 What is the most appropriate niche for membranes in the real, large-scale operating plant?
 How effective would the membranes be in comparison with "traditional" separation methods
such as distillation, absorption, etc?

Classification of Synthetic Membranes

A membrane can be natural or synthetic, thick or thin, its structure can be homogeneous or
heterogeneous, transport across membrane can be active or passive, passive transport can be driven
by various means (e.g. pressure, concentration, electrical difference), neutral or charged. As such,
membranes can be classified according to different viewpoints. The first classification is by nature, i.e.
biological or synthetic membranes. This is the clearest distinction possible. Synthetic membranes can
be subdivided into organic (polymeric or liquid) and inorganic (e.g. ceramic, metal) membranes.

Another means of classifying membranes is by morphology or structure - for the case of solid synthetic
membranes, the 2 types of membrane structures are the symmetric and asymmetric (anisotropic)
membranes.

The principal types of polymeric membranes are classified as shown in the Figure below:
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Engr. Caesar P. Llapitan

The Figure shows schematically the different types of membranes. This classification is, however, rather
arbitrary, and many structures fit more than one of the above-mentioned classes. For example, a
membrane may be micro-porous, asymmetric in structure, and have electrical charges.

The IUPAC classification for pores sizes are as follows:

Macropores > 50 nm
Mesopores 2 – 50 nm
Micropores < 2 nm

The following membranes are briefly discussed:

Isotropic Membranes
Isotropic membranes have a uniform composition structure throughout, and they can be porous or
dense. The resistances to mass transfer in these membranes are determined by the total membrane
thickness. A decrease in membrane thickness results in an increased permeation rate.

Micro-porous Membranes
The simplest form of micro-porous membrane is a polymer film with cylindrical pores or capillaries.
However, more commonly micro-porous membranes have a more open and random structure, with
interconnected pores. They are very similar in structure and function to conventional filters. However,
in contrast with conventional filters, these pores are extremely small, on the order of 0.01 to 10
micrometer in diameter.

The separation of particles is mainly the function of molecular size and membrane pore size
distribution.
 All particles larger than the largest pores are completely rejected by the membrane.
 Particles smaller than the largest pores, but larger than the smallest pores are partially
rejected, according to the pore size distribution of the membrane.
 Particles much smaller than the smallest pores will pass through the membrane.

In general, only molecules that differ considerably in size can be effectively separated by micro-
porous membrane, e.g. in ultra-filtration or microfiltration. These membranes are also as the substrate
(support) layer in composite membranes, and as a support matrix for liquid membranes.
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Non-Porous, Dense Membranes (Homogeneous Membranes)

This type of membranes consists of a dense film through which permeants are transported by diffusion
under the driving force of a pressure, concentration, or electrical potential gradient.

The separation of various components of a mixture is related directly to their relative transport rates
within the membrane, which are determined by their diffusivity and solubility in the membrane
material. Thus, this type of membranes can separate permeants of similar size if their concentrations
in the membrane material (i.e. their solubility) differ significantly.

Dense membranes have the disadvantage of low flux unless they can be made extremely thin. For
this reason, dense membrane properties are incorporated into the top "skin" layers of asymmetric
membranes.

Most gas separation, pervaporation, and reverse osmosis processes use dense membrane to perform
the separation.

Electrically-Charged Membranes
This type of membranes is also referred to as ion-exchange membranes. They can be dense or micro-
porous, but most commonly are very finely micro-porous, with the pore walls carrying fixed positively
or negatively charged ions.

A membrane fixed with positively-charged ions is called an anion-exchange membrane because it

binds anions (negatively charged ions) in the surrounding fluid. The reverse is true for a cation-
exchange membrane.

Separation is achieved mainly by exclusion of ions of the same charge as the fixed ions on the
membrane structure, and is affected by the charge and concentration of ions in the solution. This type
of membranes is used for processing electrolyte solutions in electrodialysis.

Anisotropic (Asymmetric) Membranes

Anisotropic (asymmetric) Membranes
These membranes consist of a number of layers, each with different structures and permeabilities. A
typical anisotropic membrane has a relatively dense, extremely thin surface layer (i.e. the "skin", also
called the permselective layer) supported on an open, much thicker porous substructure.

The separation properties and permeation rates are determined exclusively by the surface layer; and
the substructure functions as mechanical support, with virtually no separating function. The resistance
to mass transfer is determined largely or completely by the thin surface layer.

The membrane can be made thick enough to withstand the compressive forces used in separation.
The thin film is always on the high-pressure side of the membrane, that is, the feed side, since in this
way maximum use of the support layer is made in stabilizing the thin film. These membranes had the
advantage of higher fluxes, and almost all commercial processes use such membranes.

Loeb-Sourirajan Membrane
Membranes made by the Loeb-Sourirajan process consist of a single membrane material, but the
porosity and pore size change in different layers of the membrane. Anisotropic membranes made by
other techniques and used on a large scale often consist of layers of different materials which serve
different functions.

Interfacial (Thin-film) Composite Membrane

This membrane consists of a thin dense film of highly cross-linked polymer formed on the surface of a
thicker micro-porous support. The dense polymer layer is extremely thin, on the order of 0.1 mm or less,
so membrane permeability is high. Because it is highly cross-linked, its selectivity is also high.

Interfacial composite membranes are widely used in reverse osmosis and nanofiltration.
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Solution-coated Composite Membrane

This type of membrane is formed by solution coating a thin (0.5 - 2.0 micrometer) selective layer on a
suitable micro-porous support.

Because the selective layer of the composite membrane is often very thin and delicate, a sealing
layer, also formed from a highly permeable material, is frequently used to protect such membranes.
See the Figure below.

The gutter layer acts as a conduit to transport material to the support membrane pores.

Liquid Membranes
Liquid membranes have become increasingly significant in the context of facilitated transport, which
utilizes "carriers" to selectively transport components such as metal ions at a relatively high rate across
the membrane interface.

Generally, formation of a thin fluid film is not a problem. Difficulty is encountered, however, in
maintaining and controlling this film and its properties during a mass separation process.
Reinforcement is necessary to avoid break-up of the film. Liquid membranes are used on a pilot-plant
scale for selective removal of heavy-metal ions and organic solvents from industrial waste streams.
They have also been used for the separation of oxygen and nitrogen.

Other Membranes
The application of polymer membranes is generally limited to temperature below about 200 oC and
to the separation of mixtures that are chemically inert. For high temperature operation and/or with
chemically active mixtures, membranes made of inorganic materials (e.g. ceramic, metal) can be
used. These inorganic membranes can be isotropic or anisotropic.

Inorganic membranes can withstand very high temperatures up to 4,000 0C. The high temperature
resistance makes these membranes very attractive for gas separation operation, especially in
combination with a chemical reaction where the membrane is used as a catalyst as well as a selective
barrier to remove one or more of the components which has been formed.

The chemical stability of existing polymeric materials is limited with respect to pH and organic liquids.
The chemical stability of inorganic materials is superior and is especially suitable for application in harsh
environments. Another important factor is the ease of cleaning for application under high fouling
conditions. For inorganic membranes all kinds of cleaning agents can be used, allowing strong acid
and alkali treatment.

Lastly, the lifetime of inorganic membranes is generally greater than that or organic polymeric
membranes.
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Examples of Different Membranes

The following SEM pictures are obtained from Osmonics at www.osmonics.com

Membrane Materials
Almost all industrial membrane processes are made from natural or synthetic polymers. These
membranes are sometimes known as organic membranes. Natural polymers include wool, rubber
(polyisoprene) and cellulose. Examples of synthetic polymers include polyamide, polystyrene and
polytetrafluoroethylene (Teflon).

Polymeric Membranes
Synthetic polymers are produced by polymerization of a monomer (condensation or addition) or by
the co-polymerization of 2 different monomers. The resulting polymer is categorized as having:
1) a long, linear chain, such as linear polyethylene
2) a branched chain, such as polybutadiene
3) a three-dimensional highly cross-linked structure, such as phenol-formaldehyde
4) moderately cross-linked structure, such as butyl rubber

The linear-chain polymers soften with an increase in temperature and are often soluble in organic
solvents, and are referred to as thermoplastic polymers.
At the other extreme, high cross-linked polymers do not soften appreciably, are almost insoluble in
most organic solvents, and are referred to as thermosetting polymers.
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Examples of polymers used in membrane fabrication are shown in the Figures below.
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Engr. Caesar P. Llapitan

The Table below showed typical applications of various polymeric materials in selected membrane
processes.

Material Application
MF UF NF/RO GS PV MD
Cellulose acetate X X X X X
Cellulose esters X
Cellulose nitrate X
Poly (vinyl alcohol) X
Polyacrylonitrite X X
Poly (vinyl chloride) X
PVC copolymer X X
Aromatic polyamide X X X
Aliphatic polyamide X X
Polyimide X X X X
Polysulfone X X
Polyetheretherketone (PEEK) X X X
Polycarbonate X
Polyester X
Polypropylene X X X
Polyethylene X X X
Polytetrafluoroethylene (PTFE) X X X
Poly (vinylidene difluoride) (PDVF) X X X X
Polydimethylsiloxane (PDMS) X X
From: Table 1.1, "Biocatalytic Membrane Reactors", pp. 4

Membranes can also be made from other non-polymeric materials. Such membranes include
inorganic membranes (for example metal, ceramic, carbon and zeolites) and liquid membranes.

In addition, recent developments had led to the introduction of the so-called Hybrid Membranes (or
Mixed Matrix Membranes, where both organic and inorganic components are used).

Another variation in membranes application is the Bipolar Membranes (BPM). where membranes of
different ionic charge are "sandwiched" together.

Bipolar Membranes (BPM)

Principles of Bipolar Membranes

The conventional method for generating H+ and OH- ions from water uses electrolysis. Electrolysis also
generates O2 and H2 and the production of these gases consumes about half of the electrical energy
of the process. In contrast, special ion-exchange membranes such as the bipolar membranes are
capable of splitting water directly into H+ and OH- ions without generating O2 and H2.
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In its simplest form a bipolar membrane is a cation-exchange membrane laminated together with an
anion-exchange membrane, through an intermediate layer (the "junction" layer). The intermediate
layer is the most important part of the membrane. The principle of "splitting" water by using a bipolar
membrane is shown in the Figure.

Water diffuses from across the cation- and anion-exchange layer to junction layer where it dissociates
into H+ and OH- ions. The H+ ions then migrate across the cation-exchange layer towards the negative
electrode while the OH- ions migrate across the anion-exchange layer to the positive electrode.

Any other anions (X-) are excluded from the junction layer by the cation-exchange layer and any
other anions (M+) are excluded from the junction layer by the anion-exchange layer.

The 2 main factors that determine the behavior of bipolar membranes are the structure of the bipolar
junction between the 2 ion-exchange layers, and the nature of charged groups which are attached
to the polymeric matrix.

Example Application of Bipolar Membranes

Although the use of bipolar membranes is an emerging technology, several applications of this
technology are already used on an industrial scale. An example application is the treatment of
concentrated salt solutions such as Na2SO4 to produce H2SO4 and NaOH.

A cell system consisting of an anion-exchange membrane (AEM), a bipolar membrane (BPM), and a
cation-exchange membrane (CEM) as a repeating unit is shown in the Figure.

Such configuration is often referred to as a 3-compartment cell. This elementary cell is repeated and
placed between 2 electrodes.
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The Na2SO4 solution flows between the cation-exchange and anion-exchange membranes (the salt
channel), while water flows between the ion-exchange membranes and the bipolar membranes, i.e.
in the H2SO4 and NaOH channels.

When direct current is applied, Na+ will be attracted to the cathode while SO42- will be attracted to
the anode. Na+ will flow across the CEM into the NaOH channel while SO 42- will flow across the AEM
into H2SO4 channel. In the bipolar membrane, water will dissociate to form the equivalent number of
H+ and OH- ions. The H+ ions will permeate through the cation-exchange side of the BPM and form
H2SO4 with the SO42- ions in the H2SO4 channel.

Similarly, the OH- ions will permeate through the anion-exchange side of the BPM and form NaOH with
Na+ ions in the NaOH channel. The final result is the production of NaOH and H 2SO4 from Na2SO4
solution at a significantly lower cost than by other methods.

In a similar way, the use of bipolar membrane process offers an interesting alternative to the
conventional membrane electrolysis for the production of NaOH and HCl from NaCl using the same
cell as shown above. The existing method of electrolysis produces chlorine, which is an environmental
concern. However, a disadvantage in using bipolar membranes is that the concentration of HCl and
NaOH in practical situations is limited to about 20%, while using conventional process this
concentration reaches 30%.

Inorganic Membranes
Inorganic membranes refer to membranes made of materials such as ceramic, carbon, silica, zeolite,
various oxides (alumina, titania, zirconia) and metals such as palladium, silver and their alloys.
Inorganic membranes can be classified into 2 major categories based on its structure: porous
inorganic membranes and dense (non-porous) inorganic membranes. Micro-porous inorganic
membranes have 2 different structures: symmetric and asymmetric; and include both amorphous and
crystalline membranes.

Micro-porous inorganic membranes can be obtained by coating of a porous support with a colloidal
solution, called sol. The sol can consist of either dense spherical particle (colloids of oxides such as
Al2O3, SiO2 or ZrO2) or polymeric macromolecules.

The Table showed the advantages and disadvantages of inorganic membranes in comparison with
polymeric membranes. It can be seen that although inorganic membranes are more expensive than
organic polymeric membranes, they possess advantage of: temperature stability, resistance towards
solvents, well-defined stable pore structure, and the possibility for sterilization.

Arguments for Inorganic Membranes Arguments against Inorganic Membranes

Long-term stability at high temperature High capital cost
Resistance to harsh environments Brittleness
Resistance to high pressure drops Low membrane surface per module volume
Inertness to microbiological degradation Difficulty in achieving high selectivities in large scale
micro-porous membranes
Easy cleanability after fouling Generally low permeability of the highly selective
(dense) membranes at medium temperatures
Easy catalytic activation Difficult membrane-to-module sealing at high
temperatures

Application of dense inorganic membranes is primarily for highly selective separation of gases such as
hydrogen and oxygen. However, dense membranes have limited industrial application due to their
low permeability compared to porous inorganic membranes. Therefore, today's commercial
inorganic membrane market is dominated by porous membranes.

Metal Membrane
Dense, metal membranes are being considered for the separation of hydrogen from gas mixtures.
Palladium (Pd) and its alloys are the dominant material used, due to its high solubility and permeability
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for hydrogen. Palladium, however, is expensive. One alternative is to coat a thin layer of palladium on
a tantalum or vanadium support film. Alternative to palladium and less expensive are tantalum and
vanadium, which are also quite permeable to hydrogen.

Recent focus is on supported thin metallic membranes with thickness ranging from submicron to a few
ten microns. The advantages include reduced material costs, improved mechanical strength and
possibly higher flux. The main developments have been the production of composite palladium
membranes for use in catalytic membrane reactors (CMRs). This development is based on the
concept of process intensification, one important aspect if which is the potential for combining the
reaction and separation stages of a process in one unit. One such application is the CMR. Apart from
the benefit inherent in cost reduction of plant and maintenance, there is also the potential attainment
of higher conversions and product yields.

The composite palladium membrane used in the CMR is composed of a thin layer of Pd, or Pd alloy,
deposited onto a porous substrate, such as a ceramic or stainless steel.

The composite palladium membrane is placed adjacent to a catalyst bed and effects the selective
removal of hydrogen from the catalytic reaction source. Another application is the use of these
membranes to control the feed rate during partial oxidation reactions (e.g. addition of hydrogen).
A major problem associated with metal membranes is the surface poisoning effects (e.g. by a carbon-
containing source) which can be more significant for thin metal membranes.

Ceramic Membrane
These membranes are made from aluminum, titanium or silica oxides. They have the advantages of
being chemically inert and stable at high temperatures. This stability makes ceramic microfiltration
and ultra-filtration membranes particularly suitable for food, biotechnology and pharmaceutical
applications in which membranes require repeated steam sterilization and chemical cleaning.
Ceramic membranes have also been proposed for gas separations.

An example application of recent development is in the production and processing of syngas

(synthetic gas - a mixture of hydrogen and carbon monoxide). The key part of the process involves
the separation of oxygen from air in the form of ions to oxidize the methane.

A schematic representation of the process is given in the Figure.

Oxygen feeding from air is split at the perovskite-type membrane surface and is transported as O2-.
The advantage of the membrane-based process is that the production of syngas takes place in a
single-step operation occurring on one of the membrane sides, this process eliminates the need for a
separate oxygen production plant, and might lead to significantly lower energy and capital costs.
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Some remaining problems include:

Difficulties in proper sealing of the membranes in modules operating at high temperature
Extremely high sensitivity of membranes to temperature gradient, leading to membrane
cracking
Chemical instability of some perovskite-type materials in the high temperature reduction
conditions

Carbon Membranes
Carbon molecular sieve (CMS) membranes have been identified as very promising candidates for gas
separation, both in terms of separation properties and stability. Carbon molecular sieves are porous
solids that contain constricted apertures that approach the molecular dimensions of diffusing gas
molecules. As such, molecules with only slight differences in size can be effectively separated through
molecular sieving.

Carbon membranes can be divided into 2 categories: supported and unsupported. Unsupported
membranes have 3 different configurations: flat (film), hollow fiber and capillary while supported
membranes consisted of 2 configurations: flat and tube.

The Figure showed a comparison between carbon asymmetric membrane and polymeric asymmetric
membrane where the main difference is in the skin layer.

CMS membranes can be obtained by pyrolysis of many thermosetting polymers such as

poly(vinylidene chloride) or PVDC, poly(furfural alcohol) or PFA, cellulose triacetate, polyacrylonitrile
or PAN, and phenol formaldehyde.

Zeolite Membranes
Zeolites are micro-porous crystalline alumina-silicate with a uniform pore size. Zeolites are used as
catalysts or adsorbents in a form of micron or submicron-sized crystallites embedded in millimeter-sized
granules. The zeolite type prepared most often as a membrane is MFI.

Main problem - relatively low gas fluxes compared to other inorganic membranes - Due to the fact
that relatively thick zeolite layers are necessary to get a pinhole-free and crack-free zeolite layer.
Overcome: use thin layer supported on others.

Other problem: thermal effect of zeolites. The zeolite layer can exhibit negative thermal expansion,
i.e. in the high temperature region the zeolite layer shrinks …. But the support continuously expands,
resulting in thermal stress problems for the attachment of the zeolite layer to the support, as well as for
the connection of the individual micro-crystals within the zeolite layer.
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Hybrid Organic-Inorganic Membranes

Compared to certain inorganic membranes, polymeric membranes have relatively low separation
performance. However, the processing flexibility and low cost of polymers still makes them highly
attractive for many industrial applications. Most of the existing industrial polymers have been applied
to membrane preparation. However, despite many attempts at maximizing membrane performance
by varying the molecular structure, polymers still exhibit a trade-off between productivity and
selectivity, which is demarcated by a so-called "upper bound" as shown in the Figure.

As shown in the plot, there is a strong inverse relationship between flux (permeability) and selectivity.
The straight line showed links the most permeable polymers at a particular selectivity. It is known as the
"upper bound", beyond which no better material is known. The position of the upper bound has moved
significantly between 1980 and 1990, reflecting the difference the first air-separation membrane
materials and the current much-improved membrane materials. While research in membrane
materials in still on-going, the movement of the upper bound has slowed since 1990.

Hybrid organic-inorganic materials have been developed as an alternative to limitations of

conventional polymeric or inorganic materials.

Mixed Matrix Membranes

Mixed matrix membranes (MMM) essentially comprise molecular sieving materials (such as zeolite or
CMS - carbon molecular sieves) embedded (dispersed) in a polymer matrix. Mixed matrix membranes
have been proposed for gas separation applications, such as N2 production from air as an alternative
to the conventional polymeric membranes. A schematic diagram is shown in the Figure.
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Zeolites and CMS are size- and shape-selective, thus allowing molecular sieving discrimination of gas
molecules: smaller-size gas penetrants can diffuse at a much higher rate than larger-sized penetrants.
These materials thus offer very attractive permeation properties with permeabilities and selectivities
significantly higher than polymeric materials. These materials, however, has the disadvantage of
higher cost, and more difficult processing requirements. The inherent rigidity and brittleness of these
materials create difficulties in forming continuous, defect-free membranes and impractical for large-
scale industrial applications. Polymeric material processing, on the other hand, is well established.
However, separation by polymeric materials suffered from O2 permeability and O2/N2 selectivity
limitations.

The mixed matrix membrane combines the advantages of each medium: high separation capabilities
of the molecular sieving materials with the desirable mechanical properties and economical
processing capabilities of the polymers.

Material selection for both matrix and sieve phases is the key aspect of the development of mixed
matrix membranes. Polymer matrix selection determines minimum membrane performance: the
polymer selected must provide industrially acceptable performance. For example, silicone rubber
only provides an O2/N2 selectivity of 2.1 and is therefore not attractive. Similarly, the choice of
molecular sieving material is important. For example, zeolite 13X with an aperture of 10 Å is not suitable
for O2 and N2 molecules with lengths of 3.75 and 4.07 Å respectively. On the other hand, zeolite 4A
with an effective aperture of 3.8 Å is suitable for O 2/N2 separation.

Some examples of commercially available MMM are silicalite-cellulose acetate and Matrimid®-CMS
MMMs.

Example Application
An example application of hybrid inorganic membrane is the controlled vapor-phase oxidation as
shown in the Figure. In a typical process, vapor phase hydrocarbons are selectively oxidized to
produce epoxides, anhydrides, carboxylic acids and other products. The reactions are exothermic,
and the maximum allowable temperature is usually limiting.

By using a hybrid inorganic membrane, the amount of oxygen supplied into the reaction zone can be
stoichiometrically controlled, enabling a reduction in the reactor's maximum temperature and thus
decreasing the rate of sequential reactions that convert desirable products into undesirable by-
products. Also, any propensity for a temperature runaway reaction is minimized at the lower reaction
temperature.
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Bipolar Membranes (BPM)

Principles of Bipolar Membranes
The conventional method for generating H+ and OH- ions from water uses electrolysis. Electrolysis also
generates O2 and H2 and the production of these gases consumes about half of the electrical energy
of the process. In contrast, special ion-exchange membranes such as the bipolar membranes are
capable of splitting water directly into H+ and OH- ions without generating O2 and H2.

In its simplest form a bipolar membrane is a cation-exchange membrane laminated together with an
anion-exchange membrane, through an intermediate layer (the "junction" layer). The intermediate
layer is the most important part of the membrane. The principle of "splitting" water by using a bipolar
membrane is shown in the Figure.

Water diffuses from across the cation- and anion-exchange layer to junction layer where it dissociates
into H+ and OH- ions. The H+ ions then migrate across the cation-exchange layer towards the negative
electrode while the OH- ions migrate across the anion-exchange layer to the positive electrode.

Any other anions (X-) are excluded from the junction layer by the cation-exchange layer and any
other anions (M+) are excluded from the junction layer by the anion-exchange layer.

The 2 main factors that determine the behavior of bipolar membranes are the structure of the bipolar
junction between the 2 ion-exchange layers, and the nature of charged groups which are attached
to the polymeric matrix.

Example Application of Bipolar Membranes

Although the use of bipolar membranes is an emerging technology, several applications of this
technology are already used on an industrial scale. An example application is the treatment of
concentrated salt solutions such as Na2SO4 to produce H2SO4 and NaOH.

A cell system consisting of an anion-exchange membrane (AEM), a bipolar membrane (BPM), and a
cation-exchange membrane (CEM) as a repeating unit is shown in the Figure.
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Engr. Caesar P. Llapitan

Such configuration is often referred to as a 3-compartment cell. This elementary cell is repeated and
placed between 2 electrodes.

The Na2SO4 solution flows between the cation-exchange and anion-exchange membranes (the salt
channel), while water flows between the ion-exchange membranes and the bipolar membranes, i.e.
in the H2SO4 and NaOH channels.

When direct current is applied, Na+ will be attracted to the cathode while SO42- will be attracted to
the anode. Na+ will flow across the CEM into the NaOH channel while SO 42- will flow across the AEM
into H2SO4 channel. In the bipolar membrane, water will dissociate to form the equivalent number of
H+ and OH- ions. The H+ ions will permeate through the cation-exchange side of the BPM and form
H2SO4 with the SO42- ions in the H2SO4 channel.

Similarly, the OH- ions will permeate through the anion-exchange side of the BPM and form NaOH with
Na+ ions in the NaOH channel. The final result is the production of NaOH and H 2SO4 from Na2SO4
solution at a significantly lower cost than by other methods.

In a similar way, the use of bipolar membrane process offers an interesting alternative to the
conventional membrane electrolysis for the production of NaOH and HCl from NaCl using the same
cell as shown above. The existing method of electrolysis produces chlorine, which is an environmental
concern. However, a disadvantage in using bipolar membranes is that the concentration of HCl and
NaOH in practical situations is limited to about 20%, while using conventional process this
concentration reaches 30%.

Liquid Membranes
A liquid membrane (LM) is literally a membrane made of liquid. It consists of a liquid phase (e.g. a thin
oil film) existing either in supported or unsupported form that serves as a membrane barrier between
two phases of aqueous solutions or gas mixtures.

One of the benefits of using a liquid membrane is that LMs are highly selective, and, with the use of
carriers for the transport mechanism, specific molecular recognition can be achieved. LMs are
relatively high in efficiency, and as such, are being looked into for industrial applications. The major
problem restricting widespread application is stability: liquid membranes require stability in order to
be effective, and if they are pushed out of the pores or ruptured in some way due to pressure
differentials or turbulence, then they just do not work.

There are 2 basic types of liquid membranes - the Emulsion Liquid Membrane (ELM) and the
Immobilized Liquid Membrane (ILM), also called a Supported Liquid Membrane.
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An ELM can be visualized as consisting of a "bubble within a bubble". The inner most bubble is the
receiving phase and the outer bubble is the separation "skin" containing the carriers. Anything outside
the bubble is the source phase. In an ELM set-up there would be huge numbers of these bubbles, such
as shown schematically in the Figure.

The disadvantages of ELM concern the formation of the emulsion:

Anything effecting emulsion stability must be controlled, i.e. ionic strengths, pH, etc.
If, for any reason, the membrane does not remain intact during operation, the
separation achieved to that point is destroyed.
In order to recover the receiving phase, and in order to replenish the carrier phase, you
have to break down the emulsion. This is a difficult task, since in order to make the emulsion
stable; you have to work against the ease of breaking it back down.

An ILM is much simpler to visualize. It is made of some kind of rigid polymer membrane, with lots of
microscopic pores in it which are filled with organic liquid. In the liquid are the carriers that perform
the required separation. What happens then is that the ILM takes things from one side of the rigid
membrane (the source phase) and carries it to the other side (the receiving phase) through this liquid
phase. A schematic of an ILM is shown in the Figure.

In such a system, instability is caused by the removal of carrier or organic liquid in the pores of that
supporting membrane. There are two possible ways for this to occur:
carrier or solvent evaporation
a large pressure differential across the membrane that effectively pushes the fluid out

Commonly employed supported liquid membrane modules include hollow fiber and spiral wound.

Transport Mechanisms in Liquid Membranes

There are four basic types of transport systems, each of which has its own mechanisms and carrier
types, forming various complexes. Regardless of mechanism, charge-neutrality must be maintained.

The following transport mechanisms are briefly discussed:

Cation Transport
Cation Transport can occur in either of two ways, either "symport" or "antiport". In the symport
configuration as shown in the Figure, a neutral carrier moves the guest and co-transported anion
together across the membrane. One side of the membrane is in contact with Aqueous Phase I (source
phase), and the other side of the membrane is in contact with Aqueous Phase II (receiving phase).
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The process occurs in four stages:

1) At the Phase I interface of the membrane, the guest salt is complexed with the carrier.
2) That complex diffuses across the membrane to the Phase II interface of the membrane.
3) The release of that guest salt at that interface.
4) The carrier diffuses back across the membrane.

For the antiport transport (see the Figure) an anionic carrier is used, and the four stages are slightly bit
different:

1) At the Phase I interphase, the carrier tries to form a neutral complex with the guest
cation.
2) The ion-pair diffuses across the membrane.
3) Cation-exchange reaction releases the guest cation to Phase II.
4) The carrier complex with the counter-transported ion diffuses back across the
membrane.
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Anion Transport
Anionic transport is similar in mechanism to the cationic transport, save for the use of a cationic carrier
instead of an anionic one in the antiport configuration. This is shown below for symport (Figure - left)
and antiport (Figure - right).

Neutral Guest Transport

Neutral species are transported via symport using various carriers. Oxygen and CO have been
transported as gases through the liquid membrane, but they use a mechanism different that that
shown in the Figure.
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Switchable Transport
The use of photo- and electrochemistry has recently been investigated into increasing the rates at
which the carrier complexes dissociate, which would, therefore, increase the transport rate.

A sample of this is shown in the Figure, but you can use your imagination to come up with exactly what
is being drawn. Essentially, the switchable transport system works in addition to the regular transport
system, and only the second step of the reaction is accelerated.

Supported Liquid Membranes

Supported liquid membranes are very interesting in combination with selective carriers for the
selective transport of certain components in a mixture. They have been studied extensively on a
laboratory and pilot-plant scale, and a large number of important industrial applications have been
indicated. However, there had been little industrial utilization of these membranes due to certain
performance-related problems. One of the disadvantages is the short useful life. Carrier and solvent
can be lost to the feed or strip solution by dissolution and micelle formation. The rate at which the
solvent and carrier are lost depends on the process conditions, some as short as within several hours.
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MEMBRANE PROPERTIES
Various membrane properties can be classified as follows:
 Physical - porosity, pore size and pore distribution, thickness, tortousity, thermal stability, etc.

Membrane Physical Properties

Some of the more common parameters used to characterize microporous membranes include the
following:

Pore Diameter
Pore diameter is probably the most important property characterizing a micro-porous membrane.
Although micro-porous membranes are usually characterized by a single pore diameter, note that
most membranes actually contain a range of pore sizes (i.e. there exist a pore size distribution).

Porosity
Porosity is the fraction of total membrane volume that is porous. Typical micro-porous membranes
have average porosities from 0.3 to 0.7.

Tortousity
Membrane tortousity (t) is the length of the average pore compared to the membrane thickness.
Simple cylindrical pores at right angles to the membrane surface have a tortousity of 1.0. Since pores
usually take a more meandering path through the membrane, typical tortousities are in the range of
1.5 to 2.5.

Thermal Stability of Polymeric Membranes

At low temperatures, typically below 100 oC, polymers can be classified as glassy or crystalline. A
glassy polymer is one that is brittle and glassy in appearance and lacks any crystalline structure (i.e.
they are amorphous). A crystalline polymer is one that is brittle, hard, and stiff, with a crystalline
structure.

If the temperature of a glassy polymer is increased, a point may be reached where the polymer
becomes rubbery. The temperature is known as the glass-transition temperature, Tg. If the temperature
of a crystalline polymer is increased, a point known as the melting temperature Tm, is reached where
the polymer becomes a melt. (Note that a thermosetting polymer never melts)

The Table showed the Tg and Tm values for several natural and synthetic polymers from which
membranes have been fabricated. Most polymers have both amorphous and crystalline regions, that
is, a certain degree of crystallinity that varies from 5 to 90%, making it possible for some polymers to
have both Tg and Tm.

From: Table 14.3, "Separation Process Principles" J.D. Seader & E. J. Henley, pp.719.

 Separation - permeate flow rate or permeation flux, permeability, selectivity.

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Membrane Separation Properties

Permeation Flux
The membrane permeation flux is defined as the volume flowing through the membrane per unit area
per unit time. The SI unit used is m3/m2.s although other are often used as well.

For the case of transport of gases and vapors, the volume is strongly dependent on pressure and
temperature. As such, gas fluxes are often given in terms of a "standard condition" which is defined as
0 oC and 1 atmosphere (1.0013 bar).

Permeability Coefficient
The permeability coefficient, P (or simply the permeability) is defined as the transport flux of material
through the membrane per unit driving force per unit membrane thickness. It's value must be
experimentally determined. The barrer is the commonly used unit for gas separation and it is defined
as:

1Barrer  1010 (cm3 @ STP  cm)/(cm2  s  cm  Hg)

The term cm3 @STP / cm2.s refers to the volumetric trans-membrane flux of the diffusing species in terms
of standard conditions of 0oC and 1 atm, the term cm refers to the membrane thickness, and cm-Hg
refers to the trans-membrane partial pressure driving force for the diffusing species.

Other commonly used units include: kmol.m.m-2.s-1.kPa-1, or m3.m.m-2.s-1.kPa-1, or kg. m.m-2.s-1.kPa-1.

Note here that the driving force is the pressure difference across the membrane.

In general, permeability of a polymer for a gas mixture increases with decreasing size and increasing
solubility (or condensability) of the gas. The relative permeability of a gas is given below in order of
decreasing gas permeability as:

H2 > He > H2S > CO2 > O2 > Ar > CO > CH4 > N2

The permeability of component-i is a product of 2 terms:

Pi  K i Di

where Ki is the sorption (or partition) coefficient and Di is the permeate diffusion coefficient.

The sorption coefficient is an equilibrium term linking the concentration of a permeating component
in a fluid phase with its concentration in the membrane polymer phase. It accounts for the solubility
of the component in the membrane.

The diffusion coefficient is a kinetic term that reflects the effect of the surrounding environment on the
molecular motion of the permeating component. It accounts for the diffusion of the component
through the membrane.

Permeabilities (in Barrer) of several pure gases in widely used polymers are shown in the Table.
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Engr. Caesar P. Llapitan

From: Table 8.1, "Membrane Technology and Applications", R.W. Baker, p.295

Permeance
The permeance PM is defined as the ratio of the permeability coefficient (P) to the membrane
thickness (L). The permeance for a given component diffusing through a membrane of a given
thickness is analogous to a mass transfer coefficient.

Membrane Selectivity
In gas separation, the membrane selectivity is used to compare the separating capacity of a
membrane for 2 (or more) species. The membrane selectivity, a (also known as the permselectivity)
for one component (A) over another component (B) is given by the ratio of their permeabilities:

P
α AB  A
PB

Replacing for PA and PB, and re-arrange, we have:

K A DA
α AB 
K B DB

The ratio DA/DB is the ratio of the diffusion coefficients of the 2 gases and can be viewed as the mobility
selectivity, reflecting the different sizes of the 2 molecules. The ratio K A/KB is the ratio of the sorption
coefficients of the 2 gases and can be viewed as the sorption or solubility selectivity, reflecting the
relative condensabilities of the 2 gases.

In all polymer materials, the diffusion coefficient decreases with increasing molecular size, because
large molecules interact with more segments of the polymer chain than small molecules do. Hence
the mobility selectivity always favors the passage of small molecules over large ones.

However, the magnitude of the mobility selectivity depends greatly on whether the membrane
material is above or below its glass transition temperature, T g. The polymer is glassy below Tg and its
structure is tough and rigid. The polymer is rubbery above T g and there is flexibility in its structure.
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Diffusion coefficients in glassy polymers decrease much more rapidly with increasing permeate size
than diffusion coefficients in rubbers.

The sorption coefficient of gases and vapors increases with increasing condensability of the permeant.
This dependence on condensability means that the sorption coefficient also increases also increases
with molecular size. Thus sorption selectivity favors large, more condensable molecules such as
hydrocarbon vapor, over permanent gases such as O2 and N2. However, the difference between the
sorption coefficients and permeabilities in rubber and glassy polymers is far less marked than the
difference in diffusion coefficients.

Thus, the balance between the mobility term and the sorption selectivity term is different for glassy
and rubbery polymers.

In glassy polymers the mobility term is usually dominant, thus small molecules permeate preferentially.
When used to segregate organic vapor from N2, glassy polymer preferentially permeates nitrogen. In
rubbery polymers the sorption term is usually dominant, so larger molecules permeate preferentially.
When used to separate organic vapor from N2, rubbery polymer preferentially permeates the organic
vapor.

Selectivity obtained from ratio of pure gas permeabilities is called the ideal membrane selectivity or
the ideal permselectivity. This is an intrinsic property of the membrane material.

If a membrane had holes or pores which were all exactly the same diameter, then those molecules
or particles whose diameters were smaller than the pore diameter would pass through the membrane,
and those molecules or particles with larger diameters than the pore diameter would be totally
rejected. Such a membrane would show an infinite selectivity.

The selectivities of actual membranes are less than infinite due to several factors. First, seldom will all
pores in a membrane be exactly the same size. Thus smaller pores might exclude one component
while larger pores permit it to pass. In such a case, the selectivity would be a function of the relative
populations of various pore sizes.

Second, molecules may be able to deform to some extent and may actually enter pores slightly
smaller than their original diameter.

Third, molecules of one type may adsorb on the walls of the pores and reduce the effective diameters
of these pores. In this case a pore's effective diameter might vary with the feed/retentate and
permeate compositions, depending on how much of the adsorbing component is in each of the
streams.

It is also important to note that practical gas separation processes are performed with gas mixtures
rather than pure gases. If the gases in a mixture do not interact strongly with the membrane material,
the pure gas intrinsic selectivity and the gas mixture selectivity will be equal. This is usually the case for
mixtures of O2 and N2. Gas mixtures are also usually non-ideal, especially under high pressure, and thus
the actual selectivity may be quite different from the ideal value. In many cases, such as the mixture
of CO2 and CH4, the CO2 is sufficiently sorbed by the membrane that permeability of CH 4 is affected.
The selectivity for such a gas mixture will deviate from the calculated selectivity from pure gas
measurements.

Nonetheless, selectivities are usually reported under ideal conditions because pure gas permeabilities
are more frequently available.

Separation Factor
Similarly, in liquid separation, the selectivity for component A over B in a binary liquid mixture may be
expressed by the separation factor as:
 Surface and electrochemical - streaming potential, zeta potential (or electrokinetic potential),
membrane potential (voltage potential difference), surface charge density, wettability
(hydrophilic or hydrophobic), etc
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Membrane Surface Characteristics

Membranes acquire a characteristic electric surface charge when contacted with an aqueous
solution. The membrane charge interacts with ions electrostatically and affects the separation
efficiency of ions through the partition of ions from the bulk solution into the membrane. Such
interaction can have either a positive or a negative effect on the filtration process. Depending on the
sign of membrane charge and charge of ions, molecules or particles; attraction or repulsion may
occur: for example, opposite signs of charge can create attractive forces, leading to fouling and flux
decline.

The membrane surface charges can be characterized by membrane potential measurements and
zeta potential measurements.

The "Double Layer" and Zeta Potential

The development of a net charge at a membrane surface (or any particles) in contact with an
aqueous solution affects the distribution of ions in the neighboring interfacial region, resulting in an
increased concentration of counter-ions (i.e. ions of charge opposite to that of the surface) in the
solution close to the surface. This leads to the development of the "electrical double layer" to maintain
electrical neutrality of the system.

The surface of a membrane can become charged due to the dissociation of specific ionizable groups
on the base polymer, depending on the pH and concentration of the feed solution.

The Figure showed a schematic of a typical ion distribution near a negatively-charged membrane
surface. Ions in the solution are attracted and absorbed to the surface, forming the so-called Stern
layer. The ions in this layer are adsorbed relatively strongly to the surface. The extent of ion adsorption
is determined by electrical and other interactions between the individual ions and the membrane
surface. The Stern surface (also referred to as the outer Helmholtz plane) refers to the plane drawn
through the center of the adsorbed ions.

Next to this layer of ions is an outer or diffuse layering (also known as the Gouy-Chapman layer). The
Stern layer and the diffusion layer together constitute the so-called double layer.

The surface of shear (or shear plane or slipping plane) defines a region at which the fluid becomes
"mobile" and shows elastic behavior. It is an imaginary surface that is located outside the Stern layer,
but for practical reasons, is assumed to be identical to the Stern surface. The electrical potential at
the surface of shear is defined as the zeta potential.

The potential at the Stern layer is the actual potential influencing the behavior of the charged species.
However, as this potential cannot be measured directly, the zeta potential is often considered as an
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adequate substitute. Therefore, the zeta potential is the value that is typically used to characterize the
electrical properties of the surface.

From the Stern layer, and into the diffusion layer, the potential decays as the distance from the surface
increases until, at sufficient distance, it reaches the bulk solution value, conventionally taken to be
zero. See The Figure.

If an electric field (potential) is applied parallel to the surface, forces will be exerted on the double
layer. The part of the double layer closest to the surface (i.e. the Stern layer) will remain stationary
while the remainder (i.e. the diffuse layer) will move under the influence of the electric field.

When a layer of macromolecules, whether a polyelectrolyte or an uncharged polymer, is adsorbed

on the surface of the membrane, this can alter the zeta potential simply because it shifts the location
of the shear plane further from the actual surface.

The zeta potential is therefore a function of the surface charge of the membrane, any adsorbed layer
at the interface, plus the nature of the surrounding medium in which the membrane is exposed (e.g.
ionic species, pH, etc). From zeta potential measurements, the surface charge density can be
calculated.

In practice, zeta potentials are usually negative, but they can lie anywhere in the range from -100 to
+100 mV. Changes in membrane zeta potential could be used to investigate the behavior of cake
deposition and fouling during the filtration of colloids. The adsorption capacity of a membrane
decreases with decreasing (more negative) zeta potential.

 Electrical - impedance measurements to determine the membrane conductance and

capacitance

Electrical Properties of Membranes

The surface and subsurface structure of micro-porous membranes are key factors in determining their
performance. A simple micro-porous membrane can be represented using an electrical analogy of
a resistor and capacitor in a parallel circuit, as shown in the Figure. The resistance of the resistor is R
(ohm, W) and the capacitance of the capacitor is C (Farad, F).

For a composite membrane, which consists of a thin-skin layer and a much thicker sublayer (i.e. the
supporting matrix), an extension of the above analogy results in 2 sets of RC system, as shown in the
Figure, each with its own resistance and capacitance?

Often, it is more convenient to use the term conductance G instead of resistance. The conductance
is simply the reciprocal of resistance, i.e.
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The conductance G describes the ability of the membrane to conduct electrical charges while the
capacitance C describes the ability of the membrane to store electrical charges.

Note that the conductivity is related to resistivity (r) as its reciprocal (s = 1/r). Another frequently
encountered term is the reactance (X), which is the reciprocal of the capacitance.

Impedance (Z) is an expression used to describe the opposition that an electronic circuit (such as the
parallel resistor-capacitor shown above) offers to the passage of alternating and/or direct electric
current. Impedance is a vector (2-dimensional) quantity consisting of 2 independent scalars (1-
dimensional): the conductance (G) and the capacitance (C).

An alternative way of expressing the impedance is in terms of the admittance (Y), which is the
reciprocal of impedance.

Most commonly, impedance and admittance are expressed in complex number form as:

Separation properties of membranes depend not only on their physical properties, but also on their
surface charge and electrical properties. Many of these properties are inter-related, and vary from
membrane to membrane, as well as the environment in which the membrane is exposed, e.g. feed
conditions (pH, temperature, concentration of solutes, various properties of solutes, etc). Suffice to
say, each membrane-solute system is unique, and must be evaluated experimentally.

Membrane Characterization
Membrane processes can cover a wide range of separation problems with a specific membrane
being required for every problem. Membranes may differ significantly in their structure and
consequently in their functionality. To know what membrane to use in a particular separation process,
different membranes must be characterized in terms of structure and mass transport properties.
Because very different membranes are used, different techniques are required for characterization.

Membrane characterization is a very important part of membrane research and development

because the design of membrane processes and systems depends on reliable data relating to
membrane properties.

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

The basic principle of the bubble point method is shown in the Figure.
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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 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.

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.

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 the 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).
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Characterization of Charged Membranes

The methods used to determine the structural properties of ion-exchange membranes are similar to
those used for characterizing other polymer membranes. These methods are also supplemented by
various electro-kinetic parameters such as the zeta potential and surface charge density.

Because ion-exchange membranes are used mainly in separation processes with electrical potential
driving forces, their permeability and selectivity are determined under experimental conditions closely
related to their practical use, and their properties are expressed in terms commonly used in
electrochemistry (e.g. electrical resistance, ion-transfer numbers, charge densities).

Electrochemical Impedance Spectroscopy (EIS)

Electrochemical impedance spectroscopy is a relatively new non-destructive technique for
characterizing membranes in terms of its electrical properties. The method involves the measurement
of the electrical impedance of a membrane system over a wide range of frequencies (1 - 10,000 Hz).

Impedance measurements are made by injecting an alternating current (ac) of known angular
frequency (w) and small amplitude (IO) into the system. As a result, an electrical potential difference
(voltage) is developed across the membrane. The amplitude (VO) and phase difference (F) of the
developed voltage are then measured. This is achieved through comparison with complex electrical
circuits within the impedance spectrometer.

The EIS method is useful in determining the electrical properties of heterogeneous membrane system
(e.g. those composed of a thin skin on a porous support) as it permits the evaluation of contribution
of each layer separately.

The basic set-up is shown schematically in Figure x-xx for a simple 1-membrane system.

A membrane separates the container into 2 chambers, and both are filled with an electrolyte (e.g.
potassium chloride solution). The electrodes are immersed as shown. Current is injected via the
electrodes.

To determine the impedance requires the measurement of the potential difference (and phase) of
the potential developed across the "system", which in this case includes not only the membrane but
also the solution in contact with the membrane (including the unstirred layer of solution at the
membrane surface), plus the electrode-solution interface impedances which are in series with it.

A further complication arises if the potential developed is measured using the same electrodes used
to inject the current, for then we must also include the impedance of the double layer which is present
between the electrodes and the aqueous solution. The impedance of the electrode-solution double
layer is strongly dependent on the frequency, especially at low frequencies; and its effect can be very
large. The use of 2-electrode impedance measurement method is best confined to high frequencies.

This problem can be eliminated through the use of 4-electrodes system for impedance measurement
because it allows only the electrical potential developed between the voltage electrodes to be
measured. The potentials developed at the current-injecting electrodes need not be considered.
Another advantage of the 4-electrode system is that the voltage electrodes may be placed arbitrarily
close to the membrane. A typical 4-eletrodes set-up is shown in Figure x-xx. Now the membrane
"system" being considered consists of the membrane itself, plus the unstirred layers on both sides of the
membrane, and the electrolyte between the 2 voltage electrodes.

Note:
In the 4-electrode system, the voltage electrodes are connected to a measuring device with very
high input impedance. This will ensure that the current flowing in these voltage electrodes is very small,
thus eliminating any significant electrode-solution impedance effects at these electrodes.
The Figure showed the equivalent electrical circuit for the membrane system. Note that we've used
the conductance G in place of the resistance R for the membrane.
 Lecture Notes 14 – Introduction to Membrane Science and Technology 32
Engr. Caesar P. Llapitan

Subscript "M" is introduced to denote electrical properties of the membrane: CM and GM. Also, the
unstirred layers and the "slices" of electrolyte between the voltage electrodes are lumped together
and is represented as a conductance GElectrolyte, one on each side of the membrane

The impedance of the membrane system is dependent on the frequency used. The measured
capacitance and conductance of the membrane varies with the frequency, with the variation occurs
most notably around the frequency given by:

Note:
To determine the electrical properties of the membrane (CM and GM) from the measured values of
the system, GElectrolyte must be determined accurately and subtracted from the measured values.
GElectrolyte can simply be measured by making identical measurements without a membrane
present.