Teknik Pembuatan Membran

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.

Proses pembuatan larutan membran

Motor Feed tunnel

Vessel clip

Dope solution Stirrer

Heating element

Heater

Phase inversion dapat dibagi:

- 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 desolvenation 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.

Teknik Pembuatan dengan 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

Spinning Machine Melt Spinning Machine Casting Machine

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.

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 2

Figure2

Purge valve Mass flow controller

Steel Mixing Vessel

Nitrogen Cylinder

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 28 b Zeta potential (mV) -27 -15.5 MWCO 68 kDa 50 kDa c Pure water flux Jpwf 13.91.65 27.622.27 -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 m 300 m Outside diameter 600 m 600 m Effective area potted 565 cm2 bundle of 100 filaments 565 cm2 _________________________________________________________________

Membrane autopsy by contact angle

Contact angle characterization of clean and fouled membrane

Membrane Fouled with Sg. Ulu Pontian PSF (68 kDa) CA (50 kDa) Fouled with Bekok Dam PSF (68 kDa) CA (50 kDa) Fouled with Yong Peng PSF (68 kDa) CA (50 kDa)

Before contact Angle () 56 28 56 28 56 28

After contact Angle () 48 21 53 23 68 30

% of contact angle Incremental - 14.2 - 25.0 - 5.3 - 17.8 + 21.4 + 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 Dense skin layer Composite membrane

Porous substructure

Symmetric

Figure 4: PSF membrane

Figure 5: CA 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

d
0.09

b
0.05

a
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:
1725 cm-1 COOH-1 1640 cm-1 amide I 1550 cm-1 amide II

Yong Peng water

Figure 11:

1034 -1040 cm-1 C-O polysacc-N-acetyl sugar

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 0 0 2

60 10 4

80 6

100 20 8

120 10 30

140 12

160 14 40

180 16

200 50 18

220

240 20 60 22

260 24 70

280 26

300 8028

320 C 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-K 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 /s. The diffraction patterns were recorded over a range 2 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 A

Distilled water B

Gas Permeability
To Atmosphere 2) Pressure Regulator 5) Valve

3) Flexible Hose

4) Permeation Cell

7) Bubble Flow Meter

6) Pressure Purge

5) Valve

1) Gas Cylinder

Calculation
Permeability/Fluks= Q/A.P Rejection = 1-(Cp/Cf) x 100%