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Fabrication of Nano porous membrane for Ultra filtration

Supervised by: Dr. M. Mujahid

ADNAN ALAM MS MATERIAL AND SURFACE ENGINEERING REG#2011-NUST-MS PhD-MS-E-02

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Contents
Phase Inversion Process Membrane Fabrication SEM Results AFM Results FT-IR Results XRD Results De-Ionized water Flux Results Future Work

Phase Inversion Process

Liquid Liquid Phase Inversion Mass transfer takes place, i.e. the solvent from the polymer solution diffuses into the precipitation bath, whereas the non-solvent diffuses into the polymer solution. Thus, solution composition is changed which takes to a de-mixing process.

Pore Formation Mechanism

The polymer solution in solvent results in homogenous polymer-solvent solution. When this solution in exposed in precipitation bath containing non-solvent, exchange between solvent and nonsolvent takes place. Solvent leaves polymer solution creating voids while non-solvent diffuses in polymer, precipitating it into membrane structure.

Membrane Modules

UF membrane modules are Tubular Hollow-fiber Spiral wound configurations Flat sheet

Materials for Membrane

Polymer (Cellulose Acetate)

Pore gen (Chitosan)

Solvent (Formic Acid)

Non-solvent (Water)
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Limitations of Cellulose Acetate Membrane

Thermal stability Poor film making properties Mechanical properties

Improvement in CA by Chitosan
Hydrophilic properties increase Mechanical strength and mechanical toughness increase Anti bacterial activity Excellent film forming ability Chitosan non-toxic Chitosan as crosslinking agent

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BLEND RATIO
Cellulose Acetate =1gm Chitosan = 0.3 gm Formic Acid = 15 ml

Cellulose Acetate: Chitosan: Formic Acid 10 : 3 : 150

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Cellulose acetate based membrane

Cellulose acetate Formic Acid

(CA) and Chitosan

Constant stirring De-aeration casting on glass Solvent Evaporation

Non-solvent addition
Membrane drying

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Casting & Blending

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Method # 1

Method # 2

1. Membrane immersion in aqueous isopropyl alcohol solution for 24 hrs. 2. Immersion in a mixture of isopropyl alcohol and hexane solution for 24 hrs. 3. Immersion in pure Hexane and than drying in desiccators.

Drying in desiccators keeping membrane stretched.

Solution To Avoid Membrane Shrinkage

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SEM RESULTS(Air dried membrane)

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SEM RESULTS(Air dried membrane)

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Cont

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Cont

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(Solvent dried membrane)

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Cont

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Cont

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Cont

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Cont

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Cont

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Cont

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SEM Conclusions
Membrane is porous Uniform distribution of pores Pore size ranges in UF limits (10100nm) Reproducibility of results

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AFM (Air dried membrane)

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AFM (Solvent dried membrane)

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Conclusions of AFM
Pore diameter confirmation Surface Roughness Presence

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Comparison of AFM & SEM

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Structure Of Cellulose Acetate

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Structure Of Chitosan

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FT-IR
cellulose acetate
80

Chitosan

70

50

60

50

45

Transmittance %

40

30

Transmittance %
0 500 1000 1500 2000 2500 3000 3500 4000 4500

40

20

10

35

-10

30 0 500 1000 1500 2000 2500 3000 3500 4000 4500

Wave number(cm-1)

wave number(cm-1)

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membrane
100

80

60

Transmittance %

40

20

500

1000

1500

2000

2500

3000

3500

4000

wave number (cm-1

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Comparison
cellulose acetate
100 90 80 70 60

membrane Chitosan

Transmittance %

50 40 30 20 10 0 -10 500 1000 1500 2000 2500 3000 3500 4000

Wave number (cm-1)

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Conclusion Of FT-IR
The absorption peaks in FTIR spectrum of cellulose acetate is attributed to the vibrations of the acetate group at 1790 cm-1 (C=O), 1370 cm-1 (C-CH3), and 1045 cm-1 (C-O-C). The FTIR spectrum of Chitosan is characterized by absorption bands at 3352 (-OH stretching), 2878 cm-1 (-CH3 stretching), 1560 (N-H bending), 1404 cm-1 (-OH bending), 1077 cm-1 (C-O bending),
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Cont
All prominent peaks in both cellulose acetate and Chitosan are present in membrane spectrum, also broad hydroxyl peak in cellulose acetate become narrow and shift in Position. Therefore, these changes in the IR spectra suggested that there is homogenous blending between Chitosan and cellulose acetate in membrane.

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XRD
Cellulose acteate
300
Chitosan

250

600

200

500

Intensity

400

150

Intensity
100 50 0 10 15 20 25 30 35 40

300

200

100

10

15

20

25

30

35

40

Thetea

Thetea

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Membrane
160

140

120

100

Intensity

80

60

40

20

10

15

20

25

30

35

40

Thetea

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Membrane Cellulose acteate Chitosan

500

400

intensity

300

200

100

0 10 15 20 25 30 35 40

Thetea

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Conclusions of XRD

XRD pattern of Chitosan exhibited characteristic crystalline reflections at approximately 21 . Cellulose acetate XRD spectrum indicates an obvious broad peak at 22 and this peak verified that Cellulose acetate had denser semi crystalline structure. In XRD spectrum of membrane, both above mentioned characteristics peaks of Chitosan and cellulose acetate shifts their position along with intensity. This change clearly confirms successful blending of both Chitosan and cellulose acetate in membrane
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Porosity Confirmation by Flux Rate

Water flux was measured by Jw = Q/A . t Where Q: Amount of permeate A: Area of membrane t: Time of sampling

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0.01 0.02
0.03 0.04 0.05

10.3 24.5
41.1 48 74.9

0.0103 0.0245
0.0411 0.048 0.0749

0.00422 0.00422
0.00422 0.00422 0.00422

2.440758 5.805687
9.739336 11.37441 17.74882

0.01666666 0.01666666
0.01666666 0.01666666 0.01666666

146.445556 348.341372
584.360423 682.464728 1064.92934

1200 1000

flux(L/m2 hr)

800
600 400 200 0 0.01 0.02 0.03 Pressure(bar) 0.04 0.05

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0.01 0.02 0.03 0.04 0.05

1200 1000 800 600 400

10.1 23.9 40.7 54.7 76.3

0.0101 0.0239 0.0407 0.0547 0.0763

0.00422 0.00422 0.00422 0.00422 0.00422

2.393365 5.663507 9.64455 12.96209 18.08057

0.01666666 0.01666666 0.01666666 0.01666666 0.01666666

143.601953 339.810562 578.673217 777.72543 1084.83456

flux(L/m2 hr)

200
0 0.01 0.02 0.03 Pressure(bar) 0.04 0.05

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0.01 0.02 0.03 0.04 0.05

800

17.8 24.9 31.3 37.4 44

0.0178 0.0249 0.0313 0.0374 0.044

0.00422 0.00422 0.00422 0.00422 0.00422

4.218009 5.900474 7.417062 8.862559 10.42654

0.01666666 0.01666666 0.01666666 0.01666666 0.01666666

253.08067 354.028578 445.023875 531.753767 625.592667

600 flux(L/m2 hr)

400

200

0 0.01 0.02 0.03 Pressure(bar) 0.04 0.05

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1200

1000

800

F l u x R a t e

600

flux(L/m2 hr) 11feb flux(L/m2 hr) 13 feb flux(L/m2 hr) 14feb

400

200

0 0 0.01 0.02 0.03 0.04 0.05 0.06

Pressure (bar)

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Future Work

Optimization of the process by varying the Chitosan content. Waste water treatment/ protein rejection and results analysis

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