S. Marques, H. Sai, U. Vainio, W. A. Phillip, K.-V. Peinemann, S. P. Nunes, U. Wiesner, ACS Macro Letters, 2012, 1, 614-617. 4. D. S. Marques, R. M. Dorin, ...
Probing the structure formation of block copolymer membranes using SAXS and time-resolved GISAXS B. Sutisna,a V. Musteata,b G. Polymeropoulos,c K.-V. Peinemann,d D.-M. Smilgies,e N. Hadjichristidis c and S. P. Nunesb* King Abdullah University of Science and Technology (KAUST), Thuwal, 23955-6900, Saudi Arabia, a. Physical Science and Engineering Division (PSE), b. Biological and Environmental Science and Engineering Division (BESE), c. KAUST Catalysis Center (KCC), Physical Science and Engineering Division (PSE), d. Advanced Membranes and Porous Materials Center (AMPMC), Physical Science and Engineering Division (PSE), e. Cornell High Energy Synchrotron Source, Wilson Laboratory, Cornell University, Ithaca, New York 14853, USA
•
PS-b-PHS-b-PS membrane formation
SAXS of the annealed terpolymer film d)
b)
c)
a) 3
10 8
10
50
100
150
200
250
300
350
400
400
2
10
350
300
250
6
10
950
900
850
800
750
700
650
600
550
500
450
Self-assembly of diblock copolymer
100 nm
Intensity / a.u.
• Membranes with well-ordered pore structures are greatly advantageous for water purification or protein separation due to their high flux and sharp selectivity • The membrane structures were formed via block copolymer self-assembly and non-solvent induced phase separation (SNIPS)
RESULTS AND DISCUSSION
Intensity / a.u.
INTRODUCTION
4
10
0.1
1
1
0.1
-1
q / nm
q / nm
The fabricated membranes
0.01
180
200
220
240
260
280
300
320
40
340
60
80
100
120
140
160
180
200
220
240
260
280
300
320
340
50
360
100
150
200
250
300
350
50
400
200
250
300
350
50
400
300 s
600
100
150
200
250
300
350
400
450
dry
Dry
740
700
750
760
800 850
850
900
900 950
950
960
950
MaxInt=11662
950
940
920
900
900
900
880
850
860
850
840
800
800
800
750
780 800 820
100
48
80
Rejection / %
c)
b) 46 44
Solvent Evaporation
PS-b-P4VP membranes and its
Immersion in Water
d - spacing / nm
Solution Casting
BSA 66.5 kg mol-1
PEG 10 kg mol-1
650
650 700 750
600
120 s
650
700
150
300 s
700
60 s
650
680
0s
100
120 s
60 s
750
0s
550
160
600
140
0.1
550
120
550
100
720
SNIPS
80
700
a)
60
660
640
Time-resolved GISAXS of the film casting 40
-1
performance1
42
60
Cyt c 12.4 kg mol-1
40 Lysozyme 14.3 kg mol-1
40 38
20
1:1 Imidazole 5:1 Pyridine
36
0
34
10
20
Molecular Weight / kg mol-1
32 0
100
200
300
400
500
60
600
time / s
• PS-b-PB-b-PS membrane formation
SAXS of the annealed terpolymer film
SAXS of terpolymer in solution 1012
6
1
1/2
1011
31
8
10
7
RESEARCH OBJECTIVE
Intensity / a.u.
Intensity / a.u.
1010 7
10
22
1/2 1/2
40 1/2 50
6
10
9
12
1
25 wt%
109 3
108
2
107
18 wt%
106 13 wt%
5
10
• Investigate the structure formation of block copolymer membranes from ABA terpolymers and obtain the optimum condition for the membrane preparation
105 9 wt%
104
4
10
0.1
0.1
1
q / nm
-1
Time-resolved GISAXS of film casting
METHOD
0s 10 s 22 s 30 s 60 s 120 s 200 s
105
Intensity / a.u.
• Time-resolved grazing incident X-ray scattering (GISAXS) 104
103
1
0s
10 s
30 s
60 s
120 s
200 s
q / nm-1
AFM of the membrane
3 2
102
101 0.2
0.4
0.6
0.8
1.0
q / nm-1
CONCLUSIONS • SAXS and time-resolved GISAXS reveal the influence of polymer concentration and evaporation time during the membrane formation • Time-resolved GISAXS combined with SAXS is powerful to characterize the membrane formation mechanism and to obtain the optimum condition
REFERENCES 1. 2. 3. 4. 5. 6.
S. P. Nunes, R. Sougrat, B. Hooghan, D. H. Anjum, A. R. Behzad, L. Zhao, N. Pradeep, I. Pinnau, U. Vainio and K.-V. Peinemann, Macromolecules, 2010, 43, 8079-8085. S. P. Nunes, Macromolecules, 2016, 49, 2905-2916. R. M. Dorin, D. b. S. Marques, H. Sai, U. Vainio, W. A. Phillip, K.-V. Peinemann, S. P. Nunes, U. Wiesner, ACS Macro Letters, 2012, 1, 614-617. D. S. Marques, R. M. Dorin, U. Wiesner, D.-M. Smilgies, A. R. Behzad, U. Vainio, K.-V. Peinemann, S. P. Nunes, Polymer, 2014, 55, 1327-1332. B. Sutisna, G. Polymeropoulos, E. Mygiakis, V. Musteata, K.-V. Peinemann, D.-M. Smilgies, N. Hadjichristidis, S. P. Nunes, Polymer Chemistry, 2016, 7, 6189-6201. B. Sutisna, G. Polymeropoulos, V. Musteata, R. SougratD.-M. Smilgies, , K.-V. Peinemann, N. Hadjichristidis, S. P. Nunes, Small, 2017
ACKNOWLEDGEMENT Funding of this work was provided by King Abdullah University of Science and Technology (KAUST) Grant 1671 - CRG2. The authors thank The Cornell High Energy Synchrotron Source (CHESS), USA and LNLS in Brazil for access to the GISAXS and SAXS synchrotron facilities.
