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Membrane Science and Engineering

(CHE F423)

BITS Pilani Dr. Bhanu Vardhan Reddy

Pilani Campus
Assistant Professor in Chemical Engineering

BITS Pilani
Pilani Campus

Module 2: Membrane materials and properties

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Review of previous lecture

• Types of membrane materials

• Basics of Polymers

• Polymers classification

• Stereoisomerism

Molecular Weight
• The chain length is an important parameter in determining the properties of a polymer.

• Polymers generally consist of a large number of chains and these do not necessarily have the
same chain length. Hence there is a distribution in molecular Weight.

• The length of the chain can often be expressed quite adequately by means of the molecular
weight.

• The consequence of the existence of different chain lengths in a polymer is that a uniform
molecular weight does not exist but rather a molecular weight average

• The molecular weight distribution is an important property relative to membrane

preparation and particularly to membrane characterisation

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Molecular Weight distribution

• Number average molecular weight 𝑀"
Fraction
Of
∑! 𝑛! 𝑀!
𝑀" =
Molecules ∑! 𝑛 !

𝑛!
• Weight average molecular weight 𝑀"

∑! 𝑤! 𝑀!
𝑀# =
∑! 𝑤!
Molecular weight of the fraction i
𝑀!

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Molecular Weight

Polydispersity
Example:
• When 1 gram of long molecules with a molecular weight equal to 10,000 g/mol is
mixed with 1 gram of smaller molecules having a molecular weight equal to 1000
g/mol the weight average molecular weight is 5500.
• However since there are now ten times as many as small molecules as there are large
molecules this implies that the number average molecular weight is:
#$∗#$$$&#∗#$$$$
##
= 2000.
• Broad distribution is expressed as Polydispersity:
• Polydispersity = ratio of 𝑀' to 𝑀(
• For most commercially available polymers the polydispersity is greater than 2.

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Lecture 4: Polymeric membrane materials

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Chain interactions

• In linear and branched polymers only secondary

interaction forces act between the different chains. Type of force kJ/mole
• In network polymers the various chains are bound to Covalent 400
each other covalently. Ionic 400
• Secondary intermolecular forces are considerably Hydrogen 40
weaker than primary covalent bonds. bonding
• Nevertheless, secondary intermolecular forces have a Dipole 20
strong effect on the physical properties of the polymer Dispersion 2
(and consequently on its permeability) because of the
large number of interactions possible.

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Entanglement

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State of the polymer

• The state of the polymer is very important relative to its mechanical,
chemical, thermal, and permeation properties.

• The state of a polymer is defined as the phase in which the polymer

appears.

• Compared to low molecular weight compounds this is more complex

with polymers.

• The solid phase may be rubbery or glassy but the properties differ
drastically.

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State of the polymer

• When a non-crystalline (amorphous)

polymer is heated, a temperature exists at
which the polymer changes from a glassy
to a rubbery state
Tensile Modulus

• The temperature at which transition from

the glassy to the rubbery state occurs is
defined as the glass transition temperature
(𝑇) ).

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State of the polymer

• In addition to the modulus all kind of physical properties change at 𝑇$ such as specific volume, specific
heat, refractive index and permeability.
• The free volume can be defined simply as the volume.
unoccupied by the macromolecules (the occupied volume
contains both the van der Waals volume of the atoms and
𝑽𝑺 the excluded volume.
• In the glassy state (𝑇 < 𝑇$ ) the free volume fraction is
virtually constant.
• Above the glass transition temperature, the free volume
increases linearly according to
𝑣' = 𝑣',)! + Δ𝛼(𝑇 − 𝑇$ )
• The free volume is very important for the transport of non-
𝑻 interacting permeants such as oxygen, nitrogen, helium.
𝑻𝒈
• For interacting permeants such as organic vapours and
liquids segmental motions are a function of permeant
concentration.

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Effect of polymer structure on 𝑇!

• The physical properties of a polymer are determined to a large extent by

the chemical structure.
• The thermal motion of the polymer chains is dependent on the ability to
rotate around the main chain.
• This is mainly determined by two factors:
i. chain flexibility
ii. chain interaction

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Effect of polymer structure on 𝑇!

• An aliphatic polyamide has a much lower

glass transition temperature than that of
an aromatic one.
−120
• For example, Nylon-6 has a glass transition
−15
temperature of 50°C while Nomex has 𝑇)
87
−15 of 273°C.
100
120 • Flexible side groups (eg. alkyl group) does
not not affect on the mobility of the main
167
Table shows glass transition
chain.
temperature for various vinyl • However, they increase the inter-chain
polymers containing different distance and cause a decrease in Tg
side groups
208 because inter-chain interactions decrease

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State of the polymer

• In addition to the glass transition temperature, another important parameter, the
degree of crystallinity, also determines the state of the polymer.
• Some polymers have very regular structural units and can crystallize because the
chains can be packed in a regular pattern.
• Atactic vinyl polymers are generally too irregular to allow crystallization. Only when
strong intermolecular interactions such as hydrogen bonding occur between the
various chains crystallization may occur. Thus although poly(vinyl alcohol) is an
atactic polymer because of hydrogen bonding, it still exhibits a semi-crystalline
character.
• On the Other hand, isotactic and syndiotactic polymers generally crystallize.
• The degree of crystallinity provides no information about the size and shape of the
crystallites.

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State of the polymer: Crystallinity

• With unsaturated polymers crystallisation occurs when all the chains have the same
conformation i.e. are either cis or trans. Cis-1,4 polybutadiene or cis-1,4-
polyisoprene for example are semi-crystalline elastomers.
• Since various kinds of irregularities can disturb the crystallization process,
copolymers do not generally crystallize.
• Some polymers are not completely crystalline, the degree of crystallinity being far
less than 100%.
• These polymers are called semi-crystalline and consist of an amorphous and a
crystalline fraction.
• Many semi-crystalline generally polymers exist such as polyethylene, polypropylene,
various polyamides and polyesters

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State of the polymer: Crystallinity

• The degree of crystallinity provides no information about the size and the shape of
the crystallites.
• Two types of crystallites often found are the ‘fringed micelles' and the spherulites

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State of the polymer: Crystallinity

• Crystallites have a large influence not only on the mechanical properties of a polymer
but also on its transport properties.

Tensile modulus of a semi-crystalline

polymer as a function of the
temperature.
a) (completely) crystalline polymer;
b) semi-crystalline polymer;
c) amorphous polymer.

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Chemical and Thermal Stability

• Thermal and chemical stability:

i. change or loss of properties which is a reversible process and often referred to
as softening
ii. decomposition or degradation which is an irreversible process.
• Temperature below 200°C polymer membrane can be used
• High-resistant polymers can be applied up to a temperature of 400°C
and some even to 600°C
• Factors that lead to an increase in the thermal stability also increase the
chemical stability: i) those that increase Tg and Tm and ii) those that
increase the crystallinity.

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Chemical and Thermal Stability

• The presence of resonance structures, as in polybenzimidazoles, polyoxadiazoles and ladder
polymers increases the thermal stability.

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Mechanical stability
• Mechanical behaviour involves the deformation of a material under the influence of
an applied force.
• Mechanical properties are not very important in membrane processes because the
membrane is held by a supporting material.
• Hollow fibers and capillary membranes are self-supporting. In these cases, the
mechanical properties may become important especially when high pressures are
applied such as in gas separation.
• Example:
– When a high pressure (e.g. more than 10 bar) is applied to a capillary of a low
tensile modulus material (e.g. silicone rubber), the capillary will break.
– A material with a high tensile modulus (e.g. polyimide) can easily withstand such a
pressure and indeed much higher pressures with a proper choice of fiber diameter
and wall thickness

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Mechanical stability

Hard and
brittle hard and tough
Stress
(MPa)

Ductile and tough

Strain (%)

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• Elastomers
–Vulcanized rubbery products, has good strength and elongation.
Example: natural rubber, butyl rubber, polyisoprene
• Thermoplastic elastomers
–Polymers which soften on heating and can be converted into any
shape and shape retained. Example: polyethylene, PVC, nylon
• Polyelectrolytes
–the polyelectrolytes contain ionic groups.
–Because of the presence of fixed charges strong interactions exist in
such polymers and counterions are attracted to the fixed charges.

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Membrane polymers

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Membrane classification

• All polymers can be used as barrier or membrane materials, but the

chemical and physical properties differ so much that only a limited
number will be used in practice.

• Classification of membrane polymers

–Open porous membrane polymers
• Used for microfiltration, ultrafiltration

–Dense non-porous membrane

• Used for gas separation and pervaporation

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Porous polymer membranes

• Porous membranes contain fixed ores, in the range of 0.1–10 um for microfiltration
and 2—100 nm for ultrafiltration.

• The selectivity is mainly determined by the dimensions of the pores but the choice of
the material affects phenomena such as adsorption and chemical Stability under
condition of actual application and membrane cleaning.

• This implies that the requirements for the polymeric material are not primarily
determined by the flux and selectivity but also by the chemical and thermal
properties of the material.

• The main problem in ultrafiltration/microfiltration is flux decline because of

concentration polarisation and fouling.

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Porous polymer membranes

Polymers for microfiltration membranes Polymers for ultrafiltration membranes

• Polycarbonate • PolySulfone/poly(ether sulfone)

• Poly(vinylidene-fluoride) • Polyacrylonitrile
• Polytetrafluoroethylene • Cellulose esters
• Polypropylene • Polyimide/poly(ether imide)
• Polyamide • Polyamide (aliphatic)
• Cellulose-esters • Poly(vinylidene fluoride)
• PolySulfone • Polyetheretherketone
• Poly(ether-imide)
• Polyetheretherketone

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Non-Porous Polymer membranes

• Nonporous membranes are used in gas separation and
pervaporation.
• For these processes either composite or asymmetric
membranes are used.
• In this type of membrane the performance
(permeability and selectivity) is determined by the
intrinsic properties of the material.
• The choice of material is determined by the type of
application and the polymer type can range from an
elastomer to a glassy material.
• Gas separation frequently glassy polymers are used
with a high Tg showing high selectivities. An example is
the class of polyoxadiazoles and polytriazoles.

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Textbooks & References

Textbooks:
• Chapter 2: Nath, K. (2017). Membrane separation processes. PHI Learning Pvt. Ltd.

Reference Books:
• Chapter 2: Mulder, M (1991), Basic Principles of Membrane Technology,
Second Ed., Kluwer Acad. Pub.

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