Membrane Manufacturing

Techniques
4.1: Phase Inversion Membrane
● Membranes are fabricated by a process known as phase inversion.
● Phase inversion has been universally accepted as a standard technique
for fabricating commercial membranes.
- A homogeneous polymer solution is transformed or inverted in a
controlled condition into a gel comprising a polymer rich phase and
polymer poor phase.
- This is a very versatile technique.
 Motor

Feed tunnel

Vessel clip

Dope solution
Stirrer

Heating element
Heater
● The technique can be classified as:
- precipitation by solvent evaporation,
evaporation
- precipitation by controlled evaporation,
- thermal precipitation,
- precipitation from the vapour phase and
- immersion precipitation
● The differences between these techniques are based on differences in
the desolvation mechanisms.
4.1.1: Precipitation by Solvent Evaporation

● This is the simplest technique for preparing phase inversion membranes.

● In this method a polymer is dissolved in a solvent and the polymer

solution is cast on a suitable support, e.g. a glass plate.

● The solvent is allowed to evaporate in an inert atmosphere, in order to

exclude water vapour, allowing a dense homogeneous membrane to be
obtained.
4.1.2: Precipitation from the Vapour Phase

● A cast film, consisting of a polymer and a solvent, is placed in a vapour

● atmosphere where the vapour phase consists of a nonsolvent saturated

with the same solvent.

● The high solvent concentration in the vapour phase prevents the

evaporation of solvent from the cast film.
● Membrane formation occurs because of the penetration (diffusion) of
nonsolvent into the cast film.
● This leads to a porous membrane without skin layer.
4.1.3: Precipitation by Controlled Evaporation

● In this technique the polymer is dissolved in a mixture of solvent and

nonsolvent. .

● Since the solvent is more volatile than the nonsolvent, the composition
shifts during evaporation to a higher nonsolvent and polymer content.

● This leads eventually to the polymer precipitation leading to the

formation of skinned membrane.
4.1.4: Thermal Precipitation

● A solution of polymer in a mixed or single solvent is cooled to enable

phase separation to occur.

● Evaporation of the solvent often allows the formation of a skinned

membrane

● This method is frequently use to prepare microfiltration membrane.

4.1.5: Immersion Precipitation

● Most commercially available membranes are prepared by immersion

precipitation.

● The polymer solution is cast on a suitable support and immersed in the

coagulation bath containing a nonsolvent.

● Precipitation occurs because of the exchange of solvent and nonsolvent.

● The membrane structure ultimately obtained results from the

combination of mass transfer and phase separation.
4.2: Manufacturing Techniques for Immersion Precipitation

● Membranes can be produced in the form of flat sheets and hollow fibers.

● These geometries are commercially produced by the phase inversion

process

● Although the phase inversion mechanism involved in these two

geometries is similar, the production techniques are not the same.

● The flat sheet is a very simple geometry which is normally produced by

spreading a polymer solution on a support glass plate using a casting
knife - the phase separation occurs from one side only.

● Hollow fibers are self-supporting and give a higher surface area per unit
volume of membrane module.
● Hollow fibers are formed by simultaneous phase separation from both
the bore side and the outer side.

● The behaviour of the dope is crucial.

crucial

● This section will briefly discuss the manufacturing techniques and

procedures for the fabrication of these two membrane geometries.
 Membrane Fabrication

ª Spinning Machine

ª Melt Spinning Machine

ª Casting Machine
4.3: Flat Sheet Casting

● Flat sheet casting is the oldest technique used to form membranes.

● The dope is then cast over a suitable base or support (e.g. glass plate or
non-woven polyester) by a casting knife.

● The cast film undergoes a partial evaporation of solvent or mixture of

solvents before immersion into a coagulation bath.

● The partial evaporation may result in solidification and pre-orientation of

the skin.

● When the film is immersed in the coagulation bath the phase separation
is completed

● Water is often used as a nonsolvent for many types of polymers

Casting machine
● Parameters influencing membrane structure and properties include
solvent/nonsolvent, polymer concentration, evaporation time, humidity,
temperature and composition of the casting solution.

● The membranes obtained after precipitation can be used directly or

subjected to drying.
drying

● The resultant membranes are used in plate-and-frame and spiral wound

systems.
4.4: Hollow Fiber Spinning

● Spinning is a physical process involving the extrusion of a polymer

solution through an annular spinneret.
spinneret

● The term spinning originates from the production of man-made textile

fibers

● Hollow fiber spinning is a tricky practical process and generally involves

four main steps namely, solution formulation, extrusion, coagulation and
treatment of the coagulated fibers.

● A number of processing parameters influence the structure and hence

the separation performance of hollow fiber membranes.
● Hollow fiber membranes can be fabricated in the form of dense and
asymmetric structures.

● These structures differ only in the method used to solidify the gel
filament.

● A dense structure is usually fabricated by melt spinning while solution

spinning (phase inversion) yields asymmetric membranes.

● The major techniques used in the fabrication of hollow fiber membranes

as summarise in Figure 4.1
 Purge valve

Mass flow
Steel Mixing controller Nitrogen Cylinder
Vessel

Spinneret

AIR GAP
Metering Pump
Quench Bath
Take-up drum
Explosion-proof oven
 Hollow Fiber Spinning Techniques

Melt Spinning Solution Spinning

Dry Spinning Wet Spinning Dry/Wet Spinning

Figure 4.1: Hollow fiber spinning techniques.

Membrane Fabrication – Melt Spinning
 Membrane Characterization

Table 4.1: Characteristics of the experimental membranes

_________________________________________________________________
Parameter PSF membrane CA membrane
_________________________________________________________________
Membrane type Hollow fiber Hollow fiber
Membrane material Polysulfone Cellulose acetate
a
Contact angle 56° 28º
b
Zeta potential (mV) -27 -15.5
MWCO 68 kDa 50 kDa
c
Pure water flux Jpwf 13.9±1.65 27.62±2.27
-2 -1
(Lm h )
Pure water specific flux 43 ± 5 85 ± 7
-2 -1 -1
(Lm h bar )
Surface property Hydrophobic Hydrophilic
2
Nominal surface area (300mm) 565.48 mm 565.48 mm2
Internal diameter 300 µm 300 µm
Outside diameter 600 µm 600 µm
Effective area potted
bundle of 100 filaments 565 cm2 565 cm2
_________________________________________________________________
 Membrane autopsy by
contact angle
Table 8: Contact angle characterization of clean and fouled membrane

Membrane Before contact After contact % of contact angle

Angle (°) Angle (°) Incremental
Fouled with Sg. Ulu Pontian
PSF (68 kDa) 56 48 - 14.2
CA (50 kDa) 28 21 - 25.0
Fouled with Bekok Dam
PSF (68 kDa) 56 53 - 5.3
CA (50 kDa) 28 23 - 17.8
Fouled with Yong Peng
PSF (68 kDa) 56 68 + 21.4
CA (50 kDa) 28 30 + 7.1
SCANNING ELECTRON
MICROSCOPE
 Filament
aperture
Primary
electron

Condenser
aperture

Detector

Sample
Sample holder

Prinsip Kerja Scanning Electron

Microscope
• Scanning electron microscope (SEM) is a very
simple and useful technique to determine the
membrane structure. The samples of
membrane were snapped under liquid nitrogen
to give a clean break. The samples are taken
out and mounted on sample stubs using double
surface scotch tape with the surface to view
facing up. These are then spurred-coated with
gold using SEM sputter coater before being view
with the scanning electron microscope.
 Membrane Structures
Asymmetric membrane

Integrally-skinned Asymmetric Composite membrane

Dense skin layer

Porous substructure

Symmetric
 Figure 4: PSF Figure 5: CA
membrane membrane

a) cross section b) outer edge

a) cross section b) outer edge cross section

c) inner edge d) partial cross section

 Morphological analyses

Fouled SEM image of Yong Peng water Clean surface of PSF membrane

Fouled SEM Image of Bekok Dam Fouled SEM image of Ulu Pontian

Figure 27: SEM micrograph of fouled UF PSF membrane

 Fourier Transform Infra Red
• Molecular orientation in the active layer of flat sheet membranes was
directly measured using plane polarized reflectance infrared spectroscopy
because the preferred orientations of specific functional groups can be
easily and clearly determined.
•
• Infrared spectroscopy measures vibrational energy levels of molecules and
records characteristics band parameters in terms of frequency (energy),
intensity (polar character), band shape (environment of band) and
polarization of various modes.

• This technique can reveal anisotropy on the molecular level within a

sample. A preferential alignment of randomly coiled chain molecules leads
to differences in absorption of plane-polarized infrared spectra between
parallel and perpendicular directions. This phenomenon is known as linear
dichroism.

• The samples of membranes were mounted at the sample position with the
outer skin surface facing the infrared beam and were rotated according to
the shear direction (either vertical or horizontal). Then, spectra of linear
dichroism were obtained by straightforward subtraction of plane polarized
infrared spectra perpendicular to shear direction from plane polarized
infrared spectra parallel to shear direction.
 0.13

0.09

b
0.05

0.01

2000 1800 1600 1400 1200 1000 800

Wavenumbers (cm-1)
Bekok Dam reservoir Ulu Pontian river

1723 cm-1 - C=O carboxylic groups

Figure 9: Figure 10:

Yong Peng water
1725 cm-1 – COOH-1
1640 cm-1 amide I
1550 cm-1 amide II
1034 -1040 cm-1 – C-O polysacc-N-acetyl sugar
Figure 11:

1720 cm-1 - C=O Carboxylic groups

Higher than BD
 Differential Scanning Calorimetry
• Differential scanning calorimetry (DCS) is
performed using a Mettler Toledo DSC at
a heating rate of 10 oC/min to measure Tg
that will provide a qualitative estimation of
the flexibility of polymer chains.
^exo

2
mW

5
mg
Glass Tra nsition
Onset 218.36 °C
Midpoint 220.29 °C

Glass Tr ansition
Onset 216.74 ° C
Midpoi nt 220.10 ° C

40 60 80 100 120 140 160 180 200 220 240 260 280 300 320 °C

0
0 2 10 4 6 20 8 1030 12 14
40 16 50 18 20 60 22 24
70 26 8028 min
min
Lab: METTLER STARe SW 9.00
X-Ray Diffraction (XRD) Analysis

• X-ray diffraction analysis were carried

out on a Siemens Diffractometer D5000
using a Cu-Kα radiation source. Each
sample was grounded using agate
mortar in order to get very fine powder.
Scanning speed and interval of the data
collection was 0.05 ° and 2 θ/s. The
diffraction patterns were recorded over a
range 2θ of from 5 ° to 70 ° .
 Hydrogen Nuclear Magnetic
Resonance (H-NMR)

• H-NMR spectroscopy was used to

determine the degree of sulfonation, DS
of SPEEK. The spectrometers were
recorded on a Varian Unity Inova
spectrometer at a resonance frequency
of 399.961 MHz at room temperature.
For each analysis, 3 wt% polymer
solution was prepared in deutrated
dimethyl sulfoxide (DMSO-d6).
 Water Uptake

• The membranes were first dried at 60 °C for 48

hours. The dried films were then immersed in
deionized water overnight at ambient
temperature. The water on the surface of
wetted membranes was removed using tissue
paper before weighing. Water uptake was
then calculated as follows:-
• Water Uptake (%) = (Ww-Wd)/Wd
• where Ww and Wd are the weight of the
membranes after keeping in water and initial
dried membranes, respectively
Methanol Permeability

Membrane

Sampling point

1 M methanol Distilled water

A B
 Gas Permeability

To Atmosphere
2) Pressure Regulator
5) Valve

4) Permeation
3) Flexible Hose

7) Bubble Flow Meter

Cell

6) Pressure Purge

5) Valve

1) Gas Cylinder
 Calculation
• Permeability/Fluks= Q/A.ΔP
• Rejection = 1-(Cp/Cf) x 100%