Preparation of Synthetic

Membranes

Introduction: Module-1
 Outline

• Introduction
– Preparation of synthetic membranes
Sintering, Stretching, Track-etching, Template leaching, Phase inversion, etc.
• Phase inversion membranes
– Preparation techniques for immersion precipitation
• Phase separation in polymer systems
• Influence of various parameters on membrane
morphology
• Preparation techniques for composite membranes
 Introduction

Porous membrane Dense membrane Carrier

membranes
(microfiltration/ultrafiltration) (gas separation/pervaporation)

Fig. 1 Three basic types of membranes

 Three basic types of membranes
• Porous membranes
– Separation depends on pore size and pore size distribution
• Nonporous membranes
……………..
– Separation depends on intrinsic properties of membranes
– Thickness of the membrane
…………….. matters!!!
• Carrier mediated transport membranes
– Separation depends on affinity and reactivity of
membranes ……………..
– Extremely high selectivity possible
– Two types: mobile carrier & fixed site carrier
 Membrane Material & Preparation
M em b ran e
M ateria ls Polymers: most common
Inorganic: more stable
B io lo g ic al S y n th etic

e.g . L u n g s O rg a n ic In o rg a n ic
C ell m e m b ran es (p o ly m eric ) hybrid

G la ssy R u b b e ry C eram ic G la ss M etallic Z eo litic

Symemetric / Asymmetric / composite

Sintering Stretching
Stretching Track-etching
Track-etching Template leaching Sol-gel
Sol-gel process
process

Solution
Solutioncoating
coating Phase
Phaseinversion
inversion
List of most important membrane
preparation techniques
– Sintering
– Stretching
– Track-etching
– Template leaching
– Sol-gel process
– Phase inversion technique
– Coating

- Membrane modification
 Sintering
• Compressing a powder consisting of particles of given
size and sintering at high temperatures.
– For both polymeric and inorganic membranes with
outstanding chemical, thermal and mechanical stability
– Sintering temperature depends on the material (polymers,
metals, ceramics, carbon, glass)
– Pore size & distribution depends on the particle size &
distribution (0.1-10µm)
– Porosity 10-20%

HEAT
pore
 Stretching
• Stretch extruded film
perpendicular to the extrusion
& crystallite orientation
– Only semicrystalline polymers
(PTFE, PE, PP) used
– Rapture to make reproducible
microchannels
– Pore size 0.1-3µm
– Porosity is very high (up to 90%)
Stretched PTFE membrane
Extrusion of thermoplastic polymers
Track-etching
• Thin membranes (up to 20µm)
perpendicularly exposed to a high
energy bean of radiation to break
chemical bonds in the polymer
• The membrane is then etched in a
bath which selectively attacks the
damaged polymer.
• Features
– uniform cylindrical pores
– Pore size 0.02-10µm
– Surface porosity <10%
– Track-etched 0.4 µm PCTE membrane
Narrow pore size distribution
Track-etching process
radiation source
Membrane with
capillary pores

polymer film
etching bath

t0 t1 t2 t3
 Phase inversion
A polymer transformed in a controlled manner from a liquid to a solid state

Phase inversion covers different techniques

For example: preparing asymmetric membranes:
 A dense(r) skin layer integrally bonded in series with a thick porous substructure
 Same material in each layer

 The solidification initiated by the

transition from one liquid state into
two liquids (liquid-liquid demixing)
 By controlling the initial stage of the
phase transition the membrane
morphology can be controlled.
 III.3 Phase inversion techniques
• Precipitation by solvent evaporation
– Simple evaporation, coating
 Precipitation from the vapour phase
 Vapour phase: nonsolvent + saturatedsolvent
 Prepare porous without top layer
 Precipitation by controlled evaporation
 Polymer dissolved in mixture of solvent and nonsolvent
 Prepare membranes with skinned layer
 Thermal precipitation
 Polymer solution is cooled to enable phase separation
 Prepare membranes with skinned layer
 Immersion precipitation
 III.4 Immersion precipitation
– Polymer solution cast on a support (/or not)
– Immersed in a coagulation bath containing a
nonsolvent
– Precipitation (solidification) occurs because of the
exchange of solvent and nonsolvent
– Membrane structure results from a combination of
mass transfer and phase separation
– Asymmetric membranes obtained- most
commercial membranes prepared by this
technique
 1. Flat membranes

GKSS
equipment

 Preparation parameters:
 Polymer concentration (viscosity)
 Casting thickness
 Evaporation time
 Humidity
 Temperature
 Additives (composition of the
Fig. III-5 Preparation of flat sheet membranes
casting solution)
 Solvent/solvents & non-solvent
Factors affect membrane structure
• Choice of polymer, choice of solvent/nonsolvent
• Composition of casting solution
• Composition of coagulation bath
• Gelation and crystallization behavior of the polymer
• Location of the liquid-liquid demixing gap
• Temperature of the casting solution and coagulation bath
• Evaporation time
2. Tubular form membranes
• Tubular form membranes
– Hollow fiber (d<0.5mm), self-support
– Capillary (d: 0.5-5mm), self-support
– Tubular (d>5mm), on support

• Techniques for preparation of HF and capillary

membranes
– Dry-wet spinning (wet spinning)
– Melt spinning
– Dry spinning
Dry-wet hollow fiber spinning process
 Spinning of hollow fiber membranes
• Preparation parameters
(dry-wet process)
– Extrusion rate of the polymer solution
– Flow rate of the bore fluid
– Tearing rate
– Residence time in air gap
– Dimensions and types of the spinneret
– Composition of polymer solution
– Composition and temperature of
coagulation bath
 Membrane SEM images

Fig 31.8 Hollow fiber membrane by phase inversion process, using high elongational draw ratios to
elimiate macrovoids, reduce fiber dimension and increase fiber production
Ref. TAI-SHUNG NEAL CHUNG, Chapter 31, FABRICATION OF HOLLOW-FIBER MEMBRANES BY PHASE INVERSION, in
Advanced membrane technology and application.
 Lab-scale spinning rigs in Memfo

Ref.: Xuezhong He Blog

Pilot scale spinning rig in Memfo
Tubular membrane preparation
P81

Fig.III-9 Tubular membrane preparation

 III.6 Phase separation in polymer system
General thermodynamic description of the phase separation

• Polymer-solvent-nonsolvent
ternary system
• From stable homogeneous
polymer solution to demixing
– Solvent and nonsolvent miscible
– If the solvent is removed from the
mixture at the same rate as the
nonsolvent enters, the composition of
the mixture will change following the
line A–B.
- A, casting solution;
Qualitatively, not quantitatively described! - B, membrane porosity;
- B’, polymer-lean phase;
Ref. H Strathmann, L Giorno and E Drioli,1.05 Basic Aspects in Polymeric - B’’, polymer-rich phase
Membrane Preparation in book Comprehensive membrane science and technology
 Relationships among dope composition,
precipitation kinetics, & membrane morphology
Delayed demixing - dense toplayer
Instantaneous demixing – microporous toplayer

Ref. TAI-SHUNG NEAL CHUNG, Chapter 31, FABRICATION OF HOLLOW-FIBER MEMBRANES

BY PHASE INVERSION, in Advanced membrane technology and application.
III.7 Influence of parameters on membrane
morphology

• Choice of solvent/nonsolvent system

• The polymer concentration
• The composition of the coagulation bath
• The composition of the polymer solution
• The use of additives
• The temperature of the polymer solution and of the
coagulation bath
 Choice of solvent/nonsolvent system

Fig.III-44. Delay time of demixing for 15% cellulose acetate/sovent

solution in water, P127

Delayed demixing - dense toplayer

Instantaneous demixing – microporous toplayer Figure. Asymmetric membrane with a dense top layer (a) and a porous
top layer (b),
Ref. Braz. J. Chem. Eng. vol.28 no.3 São Paulo July/Sept. 2011
Classification of solvent/nonsolvent
P129

In general

•High mutual affinity pairs –

•Instant demixing
• porous

•Low mutual affinity pairs –

•Delayed demixing
• nonporous
 Polymer concentration
• Higher concentration results in
P130
– lower top layer porosity, thicker top layer

P131

Fig.III-46 Calculated composition paths for the

system CA/dioxan/water for varying CA
concentrations in the casting solution
Factors promotes the formation of
porous membrane

• Low polymer concentration

• High mutual affinity between solvent and nonsolvent
• Addition of nonsolvent to the polymer solution
• Vapour phase instead of coagulation bath
• Addition of a sencond polymer
Formation of integrally skinned membranes

P135
• Toplayer: thin & defect-free
– By delayed demixing
• Sublayer: open with negligible
resistance
– By instantaneous demixing
• Generate a polymer concentration
profile (as Fig III-51):
– By introducing an evaporation step
before immersion
– Immersion in a nonsolvent with a low
mutual affinity

Fig.III-51 Volume fraction of polymer in the casting

solution after a short period of time
 Formation of macrovoids
• Porous sublayer - part of an asymmetric
membrane

• Factors that favours the formation of porous

membranes also favours the formation of
macrovoids
– Instantaneous demixing
– A high affinity between the solvent-nonsolvent
– Polymer poor phase - macrovoids

• Weak spot for membranes for high pressures

Ref. http://www.polyu.edu.hk/riipt/tech-platforms/biosensing.html
 Effects of tear rate

Fig 31.8 Hollow fiber membrane by phase inversion process, using high elongational draw ratios to
eliminate macrovoids, reduce fiber dimension and increase fiber production

Ref. TAI-SHUNG NEAL CHUNG, Chapter 31, FABRICATION OF HOLLOW-FIBER MEMBRANES BY PHASE INVERSION, in
Advanced membrane technology and application.
 Coating
• To prepare composite
membranes
– Dense top layer
(defect-free, ultrathin)
– Porous support
(low resistance –surface pores)
– Coating techniques:
• Dip-coating
• spray coating
• spin coating
• Plasma polymerization
• Interfacial polymerization
• In-situ polymerization

Ref: Mulder, Basic principles of separation technology

 Sample dip-coating membrane

Top layer

porous
support
Porous
support

non-woven
support
 III.5 Preparation techniques for composite
membranes

• Composite membrane • Preparation techniques

– Dense layer on porous – Dip-coating
substrate of different materials
– Spray coating
– Each layer can be optimized
– Spin coating
– Materials for selective layer
are not limited – Interfacial polymerization
(mechanical, chemical, thermal – In-situ polymerization
stability, processibility, etc.) – Plasma polymerization
– Applications: RO, GS, PV – Grafting
 Dip-coating
• Dip & controlled evaporate p85

• Post-treatment
– Cross-linking
– Heat treatment
• Main effects on coating thickness
– Coating velocity, viscosity, types of
polymers, types of solvent and
concentration of polymers
– Equilibrium thickness:

2  (III-1)
h 
3 g
 Dip-coating considerations

• State of polymers
– Glassy: coating may rupture during
evaporation (Tg passed)
– Rubbery: mostly defect-free coating

• Solvent
– Good solvent-larger coil
Poor solvent-polymer aggregate
– Entanglement during evaporation
– Hydrophilic vs. hydrophobic support
surface
 Dip-coating considerations
 Pore penetration
 Capillary force may cause pore
penetration of solution
 Resistance increases due to the blocked
pores

 Methods to avoid pore penetration

 Pre-filling the pores
 Chose polymer of higher MW
 Chose support of smaller pores
 Narrow pore size distribution
 Match surface tension of the solution to
the support membranes
 Spray coating
An example

Also for polymeric membranes in solution

Spin coating
 Interfacial polymerization
Thickness<50nm

Fig. III-10 The formation of a composite membrane via interfaciaol polymerisation P82
 Plasma polymerization:
Plasma (physics & chemistry)
• Plasma: a state of matter similar to
gas, in which a certain portion of
the particles is ionized
• Charged particles: equal positive
ions and negative ions/electrons
 Ionization is generally
accompanied by the
dissociation of
molecular bonds
• Ionization methods:
– Heating
– Applying strong electromagnetic field
with a laser or microwave generator

Glow Discharge
 Plasma polymerization setup

Plasma zone Sample

To vacuum pump Gas inlet

I nductively coupled
Matching Network
RF generator and
Pulse generator
 Plasma polymerization
• Plasma polymerization refers to formation of polymeric materials under
the influence of plasma (also termed as Glow Discharge Polymerization)

 Plasma polymer films can be easily

formed with thickness of 0.05m.
 These films are highly coherent and
adherent to variety of substrates like
conventional polymers, glass, metals.
 Films are highly dense & pinhole free.
 Multilayer films or films with grading
of chemical and physical
characteristics can be easily prepared .
 One step process .