Mixed matrix membranes (MMMs)

The first invention of MMMs

Universal Oil Products (UOP) scientists:

Drs. Santi Kulprathipanja, R.W. Nousil and Norman N. Li

Separation of fluids by means of mixed matrix membranes in gas

permeation, US Patent No. 4,740,219 (1988)

▪ However, in the beginning, it had received many reservations from

membrane scientists and engineers.

▪ Then it has received a lot of attention after being confirmed by U

of Twente, Prof. Koros, and others.

Dr. Santi Kulprathipanja

1
 Robeson’s Upper Bound Trade-Off Curve Between
Oxygen/Nitrogen Selectivity and Oxygen Permeability

Glassy Polymer
Rubber

L.M. Robeson, Correlation of separation factor versus permeability for polymeric membranes, J. Membrane Sci. 62 (1991), 165.
2
A comparison of gas separation properties between polymeric
membranes vs. zeolite and carbon molecular sieves

Advantages of mixed
matrix membranes:

• Superior separation
performance after
incorporating porous
inorganic particles with
molecular sieving properties
into the polymer matrix

• Scalable for large

membrane production

Mahajan and Koros, Pushing the limits on possibilities for large scale gas separation: which strategies? J. Membrane
Science, 175, 181 (2000). 3
 Mixed Matrix Membranes and Dual-layer Mixed Matrix Composite
Membranes UOP (Universal Oil Products-NUS collaboration of
S$500,000 (2003-2005) and NRF CRP S$9,700,000
1. L. Y. Jiang, T. S. Chung, D. F. Li, C. Cao, S. Kulprathipanja, Fabrication of Matrimid/ polyethersulfone dual-layer hollow
fiber membranes for gas separation, J. Membrane Science, 240, 91-103 (2004).
2. L. Y. Jiang, T. S. Chung, C. Cao, Z. Huang, S. Kulprathipanja, Fundamental understanding of nano-sized zeolite
distribution in the formation of the mixed matrix single- and dual-layer asymmetric hollow fiber membranes, J. Membrane
Science, 252, 89-100 (2005).
3. P. S. Tin, T. S. Chung•, L. Y. Jiang, S. Kulprathipanja, Carbon-zeolite composite membranes for gas separation, Carbon,
43, 2025-2027 (2005).
4. Y. Li, C. Cao, T. S. Chung, S. Kulprathipanja, The effects of polymer chain rigidification, zeolite pore size and pore
blockage on polyethersulfone (PES)-zeolite A mixed matrix membranes, J. Membrane Science, 260 (1-2): 45-55 (2005).
5. H. M. Guan, T. S. Chung, Z. Huang, M. L. Chng, S. Kulprathipanja, Poly(vinyl alcohol) multilayer mixed matrix
membranes for the dehydration of ethanol–water mixture, J. Membrane Science, 268, 113–122 (2006).
6. Y. Li, H. M. Guan, T. S. Chung, S. Kulprathipanja, Effects of novel silane modification of zeolite surface on polymer chain
rigidification and partial pore blockage in polyethersulfone (PES)–zeolite A mixed matrix membranes, J. Membrane
Science, 275, 17-28 (2006).
7. L. Y. Jiang, T. S. Chung, S. Kulprathipanja, An investigation to revitalize the separation performance of hollow fibers with
a thin mixed matrix composite skin for gas separation, J. Membrane Science, 276, 113–125 (2006).
8. Y. Li, T. S. Chung, Z. Huang, S. Kulprathipanja, Dual-layer polyethersulfone (PES)/BTDA-TDI/MDI co-polyimide (P84)
hollow fiber membranes with a submicron PES–zeolite beta mixed matrix dense-selective layer for gas separation, J.
Membrane Science, 277, 28–37 (2006).
9. L. Y. Jiang, T. S. Chung, S. Kulprathipanja, Fabrication of mixed matrix hollow fibers with intimate polymer-zeolite
interface for gas separation, AIChE J. 52, 2898 - 2908 (2006).
10. T. S. Chung, L. Y. Jiang, Y. Li, S. Kulprathipanja, Mixed matrix membranes (MMMs) comprising organic polymers with
dispersed inorganic fillers for gas separation, Progress in Polymer Science, 32, 483–507 (2007).
11. Y. Li, T. S. Chung, S. Kulprathipanja, Novel Ag+-zeolite/polymer mixed matrix membranes with a high CO2/CH4
selectivity, AIChE J. 53 (3): 610-616 MAR (2007).
12. N. Widjojo, T. S. Chung, S. Kulprathipanja, The fabrication of hollow fiber membranes with double-layer mixed-matrix
materials for gas separation, Journal of Membrane Science. 325, 326–335 (2008).

4
Some selective ones
• M. L. Chua, L. Shao, B. T. Low, Y. C. Xiao, T. S. Chung, Poly(ethylene oxide)-Polyhedral oligomeric silsequioxane
(PEO-POSS) organic-inorganic hybrid membranes for CO2/N2 separation, J. Membrane Science 385– 386, 40– 48
(2011).
• M. Askari, Y. C. Xiao, P. Li, T. S. Chung, Natural gas purification and olefin/paraffin separation using cross-linkable
6FDA-Durene/DABA co-polyimides grafted with α, β, and γ-cyclodextrin, J. Membrane Science 390– 391, 141–
151 (2012).
• L. Hao, P. Li, T. X. Yang, T. S. Chung, Room temperature ionic liquid/ZIF-8 mixed-matrix membranes for natural
gas sweetening and post-combustion CO2 capture, J. Membrane Science, 436, 221–231 (2013).
• M. Askari, T. S. Chung, Natural gas purification and olefin/paraffin separation using thermal cross-linkable co-
polyimide/ZIF-8 mixed matrix membranes, J. Membrane Science 444, 173–183 (2013).
• S. Japip, H. Wang, Y. C. Xiao, T. S. Chung, Highly permeable zeolitic imidazolate framework (ZIF-71) nano-
particles enhanced polyimide membranes for gas separation, J. Membrane Science 467, 162-174 (2014).
• S. Japip. Y. C. Xiao, T. S. Chung, Particle size effects on gas transport properties of 6FDA-Durene/ZIF-71 mixed
matrix membranes, Industrial & Engineering Chemistry Research 55, 9507−9517 (2016).
• S. Japip. K. S. Liao, T. S. Chung, Molecularly tuned free volume of vapor cross-linked 6FDA-Durene/ZIF-71 MMMs
for H2/CO2 separation at 150°C, Advanced Materials 29, 1603833 (2017).
• J. T. Liu, Y. C. Xiao, T. S. Chung, Flexibly thermally treated 3D PIM-CD molecular sieve membranes exceeding the
upper bound line for propylene/propane separation, Journal of Materials Chemistry A 5, 4583–4595 (2017).
• K. S. Liao, S. Japip, J. Y. Lai, T. S. Chung, Boron-embedded hydrolyzed PIM-1 carbon membranes for synergistic
ethylene/ethane purification, Journal of Membrane Science 534, 92-99 (2017).
• A. Raza, S. Japip, C. Z. Liang, S. Farrukh, A. Hussain, T. S. Chung, Novel cellulose triacetate (CTA)/cellulose
diacetate (CDA) blend membranes enhanced by amine functionalized ZIF-8 for CO2 separation, Polymers 13, 2946
(2021).
• J. Wu, C. Z. Liang, A. Naderi, T. S. Chung, Tunable supramolecular cavities molecularly homogenized in polymer
membranes for ultra-efficient precombustion CO2 capture, Advanced Materials 34, 2105156 (2022).
• K. Y. Wang, M. Weber, T.S. Chung, Polybenzimidazoles (PBIs) and state-of-the-art PBI hollow fiber membranes
for water, organic solvent and gas separations: a Review, Journal of Materials Chemistry A. 10, 8687 - 8718
(2022).
• D. L. Zhao, F. Feng, L. Shen, Z. Huang, Q. Zhao, H. Lin, T. S. Chung, Engineering metal–organic frameworks
(MOFs) based thin-film nanocomposite (TFN) membranes for molecular separation, Chemical Engineering Journal
454, 140447 (2023).
 Transport of penetrants in polymers and molecular sieves
Flexible
polymeric Thermally-induced motions
chain

Molecular sieving mechanism

zeolite

In Polymers
The permeation depends on the free
volume, penetrant size, interaction
between penetrants and membrane, and
the creation and destruction of transient
gaps (or holes) induced by thermally-
induced motions of polymer chains.
In Zeolite
Penetrants are adsorbed in the large
cavities and diffuse by making
activated jumps through the narrow
porous channels. The primary barrier
for diffusion is the repulsive force
when passing through the narrow
constrictions. 6
 Gas transport in zeolite 4A and degrees of
rotational freedom of gases in zeolite 4A
Molecule Length, Å Width, Å

O2 3.75 2.68
N2 4.07 3.09

O2
To pass through the narrow constrictions
(shown as S’). O2 molecule can rotate along
its two axes since both its dimensions are
smaller than 3.8 Å , while N2 molecule cannot N2
rotate around either of its axes, since its
length is greater than 3.8 Å . This restricted
state in the constriction is entropically O2 has a higher degree of freedom
unfavorable to the nitrogen and leads to a to go through the pore than N2
lower diffusion coefficient and thus cause a
high selectivity for the gas pairs. O2 比 N2 具有更高的自由度通過孔隙

Entropic selectivity 熵選擇性

A. Singh, Membrane materials with enhanced selectivity: an entropic interpretation, Ph.D dissertation, U of Texas at Austin (1997).

7
 Entropic selectivity
Molecule Length, Å Width, Å N2 has a less degree of
rotational freedom to
O2 3.75 2.68 diffuse through the pore
N2 4.07 3.09 N2 通過孔隙擴散的旋轉
自由度較小

N2 3.8 Å
O2 O2


O2
O2 N2 3.8 Å
X

O2: 3.46 Å N2: 3.64 Å

8
 Roles of Molecular Sieves on Diffusion Coefficient
Diffusion coefficient may be expressed as follows
kT S   H 
D = 2
exp d  exp − d 
h R  RT 
where Sd and Hd are the differences in partial molar entropy and enthalpy,
respectively, between activated and normal (ground) state of diffusive
jumps, T is the absolute temperature, R is the universal gas constant,  is
the average diffusive jump length, and k and h are Boltzmann's and
Planck's constants, respectively.
The diffusivity selectivity for gases A to B is as follows if the ratio of
diffusive jump A/B does not differ much.
DA  S d , A − S d ,B   H d , A − H d ,B   S   H d 
= exp  exp −  = exp d  exp − 
DB  R   RT   R   RT 
Entropic selectivity Enthalpic selectivity
熵選擇性 焓選擇性
Dominant in nano- Dominant in polymer
porous fillers membranes
It reduces the degrees of
9
freedom for some gases
Enthalpic selectivity
焓選擇性
1. Chain-penetrant
interactions O2
2. Thermal motion of
chains
3. Critical temp of the gas
4. Condensability of the
gas

10
 Approach to Fabricate Mixed
Matrix Membranes

Polymer/zeolite solution

stirrer glass plate

cast

glass plate

solvent
evaporates
Polymer/zeolite
Solution About 50 m, too thick!
Vacuum dry at elevated temperatures in an oven

11
Cross-section SEM morphology of PES-zeolite MMMs

enlarge

(x 1K) (x 4K)

(x 10K)
12
Performance predicted by the Maxwell equation (Ideal cases)
 PD + 2 PC − 2vD (PC − PD ) numerator
Peff = PC  
 DP + 2 PC + v D ( PC − P )
D 
denominator

where Peff is the effective composite permeability, v is the volume fraction, and
the subscripts D and C refer to the dispersed (zeolite) and continuous
(polymer) phases, respectively.

PC > PD , increasing vD will decrease Peff

 PC < PD , increasing vD will enhance Peff
Real case Preferred
Ideal case Preferred In the real
case, selectivity
goes higher,
Selectivity but permeability
● Peff goes lower.
One should choose Why?
PD > P C
Matrimid/zeolite MMMs
Permeability
13
 3 Major challenges in mixed matrix membranes

1. Unexpected low permeability, why? (2)

Delamination
2. Delamination (voids), how to eliminate them?

3. How to fabricate mixed matrix hollow fiber

membranes with an ultra-thin selective layer
as a useful product

(1) 9
(3)
H2 of PES-zeolite 4A membranes
Permeability H2 of PES-zeolite 5A membranes
Permeability (Barrer)

(barrer)

MMMs with an ultra-

thin selective layer
3
as a useful product
0 10 20 30 40 50 60
Zeolite loading
Zeolite (wt%)
loading (%)
14
 1. Delamination (voids) at Interfaces and its effects
zeolite 4A – Matrimid® MMMs Gas diffusion pathway

Delamination
polymer

zeolite

Preferred

Gas bypasses the zeolite

The possible reasons of the void interfaces:
1) Poor interaction and adhesion between the polymer and sieve
2) Different shrinkages generated during solvent removal
3) Poor relaxation of a rigid polymeric matrix material The expensive zeolite particles
Potential solutions are not fully used for gas
• Surface modifications separation. The MMMs have a
• Slow evaporation low selectivity and permeability
• High boiling point solvents 昂貴的沸石顆粒未完全用於氣體
分離。這 MMM具有低選擇性和
滲透性. 15
Enrichment
Can we reduce voids at the interface between the polymer
and zeolite phases?
Hydrolysis
R(CH2)nSi(OMe)3 + 3H2O R(CH2)nSi(OH)3
zeolite surface
Silane Condensation

R R R
OH OH OH (CH2)n (CH2)n (CH2)n

+ OH Si O Si m O Si OH
zeolite surface
OH OH OH TAP
adsorption on zeolite surface and reaction

R R R
(CH2)n (CH2)n (CH2)n
OH Si O Si m O Si OH

O O O

zeolite surface

Chemical modification of zeolite surface Filling voids by compatibilizer

using silane coupling agents** 2,4,6-triaminopyrimidine (TAP)***

Mahajan et al, Challenges in forming successful mixed matrix membranes with rigid polymeric materials, J. App. Polym. Sci., 86
(2002) 881
M. Duval et al, Preparation of zeolite filled glassy polymer membrane, J. Appl. Polym. Sci., 54 (1994) 409
H.H. Yong et al, Zeolite-filled polyimide membrane containing 2,4,6-triaminopyrimidine, J. Membr. Sci., 188 (2001) 151
16
 2. Unexpected low permeability: Experimental permeability
results of PES-unmodified zeolite MMMs
9 0.6
O2 of PES-zeolite 4A membranes
H2 of PES-zeolite 4A membranes N2 of PES-zeolite 4A membranes
O2 of PES-zeolite 5A membranes
H2 of PES-zeolite 5A membranes N2 of PES-zeolite 5A membranes

Permeability (Barrer)
Permeability (Barrer)

6 0.3

3 0
0 10 20 30 40 50 60 0 10 20 30 40 50 60
Zeolite loading (%) Zeolite loading (%)

Effect of zeolite loading on H2, O2 and N2 permeability of PES-zeolite 4A

and PES-zeolite 5A mixed matrix membranes
(left: H2 permeability; right: O2 and N2 permeability)

Y. Li, C. Cao, T. S. Chung, S. Kulprathipanja, The effects of polymer chain rigidification, zeolite pore size and pore blockage on
polyethersulfone (PES)-zeolite A mixed matrix membranes, J. Membrane Science, 260 (1-2): 45-55 (2005).
17
 Predicted O2 permeability vs. experimental results of
PES-4A zeolite MMMs
1.2

O2 (experimental data) O2 (prediction by Maxwell model)

0.9
Permeability (Barrer)l

The Maxwell model

0.6

0.3
Experimental results

0
0 10 20 30 40 50 60
Zeolite loading (%)
Why permeability decreases with an increase in zeolite loading?
1. Chain rigidification upon the zeolite surface聚合物鏈在沸石表面變得剛性
2. Partial pore blockage 部分沸石孔隙被聚合物鏈堵塞
18
Effects of chain rigidification & pore blockage on permeability

聚合物鏈在沸石表面變得剛性 部分沸石孔隙被聚合物鏈堵塞
1. Chain rigidification upon the zeolite surface, chains cannot
thermally vibrate as freely as normal chains, thus the diffusion jumps
become slow, the gas cannot diffuse as fast as before.

Diffusion jumps in normal polymer chain motions

2. Partial pore blockage: reduce the pore size for gas transport

R. Mahajan et al, Challenges in forming successful mixed matrix membranes with rigid
polymeric materials, J. App. Polym. Sci., 86 (2002) 881

Y. Li, C. Cao, T. S. Chung, S. Kulprathipanja, The effects of polymer chain rigidification,

zeolite pore size and pore blockage on polyethersulfone (PES)-zeolite A mixed matrix 19
membranes, J. Membrane Science, 260 (1-2): 45-55 (2005).
 The effects of chain rigidification and partial pore blockage
 is a factor of permeability reduction

The first phase (polymer matrix)

Rigidified polymer
Polymer matrix PC
region Prig = PC/β
Bulk of zeolite 4A PD

Zeolite permeability r r’
reduction by the partial
pore blockage
Pblo = PD/β’ β’ >>β Polymer chains

Zeolite 4A
3.8Ǻ

The second phase [the rigidified
polymer region (continuous phase)
on zeolite (dispersed phase)]
聚合物鏈在沸石表面變得剛性
20
The third phase [the zeolite with a partially
blocked pore by polymer chains (the
continuous phase)]部分沸石孔隙被聚合物鏈堵塞
 Changes of O2 and N2 permeability in different regions of
PES-zeolite 4A mixed matrix membranes
β is a factor of permeability reduction
Permeability in the Permeability in the Permeability in Permeability in the
PES matrix (PC)a rigidified PES region the bulk of zeolite-4A skin with
(Prig=PC/βc) zeolite-4A (PD)b partial pore blockage
(Pblo=PD/β’d)
1/3 1/250
O2 0.479 0.160 0.770 0.00308

1/4 1/10
N2 0.0825 0.0206 0.0208 0.00208

a: Permeability data of the PES matrix from experiment results of pure PES dense films.
b: Permeability data of the bulk zeolite-4A from the reference 26.
c: β is 3 for O2 gas, while β is 4 for N2 gas.
d: β’ is 250 for O2 gas, while β’ is 10 for N2 gas.
Zeolite permeability
reduction by the partial pore
Rigidified polymer region blockage
Prig = PC/β β’ >>β P = P /β’ blo D

R. Mahajan et al, Challenges in forming successful mixed matrix membranes with rigid polymeric materials, J. App. Polym.
Sci., 86 (2002) 881 21
 Why β’ is 250 for O2 gas, Zeolite permeability reduction
by the partial pore blockage
while β’ is 10 for N2 gas?
Pblo = PD/β’

Permeability in the Permeability in the Permeability in Permeability in the

PES matrix (PC)a rigidified PES region the bulk of zeolite-4A skin with
(Prig=PC/βc) zeolite-4A (PD)b partial pore blockage
(Pblo=PD/β’d)
O2 0.479 0.160 0.770 1/250 0.00308

N2 0.0825 0.0206 0.0208 1/10 0.00208

Without the partial pore blockage of zeolite 4A, the O2 molecule can rotate freely along
either of its two axes since both its dimensions are slightly smaller than the 3.8 Å
aperture, while the rotational motion of O2 molecule is significantly hindered and
can only characterize the vibrational motion with the partial pore blockage. For N2
molecule, it cannot rotate around either of its axes and can only characterize the
vibrational motion no matter if the partial pore blockage happens. Therefore, the
average decline of O2 permeability in the zeolite skin with partial pore blockage
is much larger than that of N2 permeability, thus leading that the O2/N2 selectivity in
this region should be much smaller than that in the bulk of zeolite 4A.
22
The O2 molecule can rotate
freely through the pores because Molecule Length, Å Width, Å
The N2 molecule has
both its dimensions are slightly to rotate at a right
smaller than the 3.8 Å aperture, O2 3.75 2.68 direction in order to
while the rotational motion of transport through
O2 molecule is significantly N2 4.07 3.09
the pores
hindered after pore blocking

3.8A N2 3.8A


3.8A N2 3.8A
X

O2: 3.46 Å N2: 3.64 Å

23
Partial pore blockage has a much higher effect on O2 than N2
Molecule Length Width
The O2 molecule has to rotate Å Å Thus,
at a right direction in order to O2 3.75 2.68
β’ is 250 for O2 gas,
transport through the pores β’ is 10 for N2 gas
N2 4.07 3.09

O2 N2 3.8 Å
3.8A

X

O2
3.8A N2
3.8 Å
 X

O2: 3.46 Å N2: 3.64 Å

24
 Performance predicted by the Maxwell equation
(ideal vs. real cases) numerator

 PD + 2 PC − 2vD (PC − PD ) PPD/β’+ 2PPC/β− 2vD(P(PCC/β−- PPDD/β’)

) 
Ideal case Real case
Peff = PC  Peff = PP/β
D C

 C 
 DP + 2 PC + v D ( PC − P )
D 
C

 D
PP/β’D+ 2 PC (
P /β+ v (PP
D CC
/β−C- P
P D )
D 
/β’)

denominator
Even though originally PD > PC , in real cases, PC/β > PD/β’
(1) PC/β is the real permeability in the rigidified polymer region
(2) PD/β’ is the real Zeolite permeability PD after partial pore blockage
(3) Because β’ >>β PC/β > PD/β’, thus an increase in vD decreases Peff
1.2

O2 (experimental data) O2 (prediction by Maxwell model)

0.9
Permeability (Barrer)l

Why permeability
0.6 The ideal Maxwell model decreases with an
increase in zeolite
0.3
loadings?
Experimental results
0
0 10 20 30 40 50 60
Zeolite loading (%)
25
 Can we overcome it? reduce the deviation from the
calculated Maxwell equation and experimental data?

RO room temperature
OH
N2, 24 h
+ RO Si (CH2)3 NH2
OH In toluene
H3C
zeolite silane Because CH3 is hydrophobic, it
3A, 4A and 5A APDEMS (R = CH3CH2) does not like the hydrophilic
zeolite surface因為CH3 是疏水的
，所以不喜歡親水性沸石表面

Filtering Drying O
Si (CH2)3 NH2
Washing with At 110C for 1 h O
toluene and methanol under vacuum H3C

Modified zeolite (zeolite-NH2)

Y. Li, H. M. Guan, T. S. Chung, S. Kulprathipanja, Effects of novel silane modification of zeolite surface on polymer chain
rigidification and partial pore blockage in polyethersulfone (PES)–zeolite A mixed matrix membranes, J. Membrane
Science, 275, 17-28 (2006).

26
 Silanes with 3-point and 2-point attachments on the interface
of the zeolite surfaces
Hydrolysis
R(CH2)nSi(OMe)3 + 3H2O R(CH2)nSi(OH)3

Silane Condensation
Conventional silane New silane
R R R
OH OH OH (CH2)n (CH2)n (CH2)n

+ OH Si O Si m O Si OH
zeolite surface
OH OH OH

R R
adsorption on zeolite surface and reaction

R
CH3
(CH2)n (CH2)n (CH2)n pore pore
OH Si O Si m O Si OH

O O O zeolite zeolite
zeolite surface
Three-point Two-point
attachments attachments
Chemical modification of zeolite surface
using silane coupling agents**

Mahajan et al, Challenges in forming successful mixed matrix membranes with rigid polymeric materials, J. App.
Polym. Sci., 86 (2002) 881
M. Duval et al, Preparation of zeolite filled glassy polymer membrane, J. Appl. Polym. Sci., 54 (1994) 409
H.H. Yong et al, Zeolite-filled polyimide membrane containing 2,4,6-triaminopyrimidine, J. Membr. Sci., 188 (2001) 151
27
 PES-Un modified zeolite MMMs
A B C

PES-modified zeolite MMMs

D E F

A comparison of cross-section images of MMMs before and after the

chemical modification of zeolite surface
(A, B, C: PES-zeolite 3A, 4A and 5A MMMs, respectively;
D, E, F: PES-modified zeolite 3A, 4A and 5A MMMs, respectively)
32
 Effect of zeolite loadings on gas permeability of PES-
modified zeolite MMMs
1
O2 of PES-modified 4A membranes CH3
Permeability (Barrer)

O2 of PES-modified 5A membranes pore

New silane zeolite

Two-point
0.5 attachments

Old silane

0 pore

zeolite
0 10 20 30 40 50 60 Three-point
Zeolite loading (%) attachments
If one chooses a right silane to modify the zeolite
surface, it may not block zeolite pores for gas transport
Y. Li, H. M. Guan, T. S. Chung, S. Kulprathipanja, Effects of novel silane modification of zeolite surface on polymer chain
rigidification and partial pore blockage in polyethersulfone (PES)–zeolite A mixed matrix membranes, J. Membrane
Science, 275, 17-28 (2006). 29
 9
PES-modified 4A membranes
PES-modified 5A membranes The new MMM
O 2/N 2 selectivity

concept really
works, the
7 selectivity
increases with
an increase in
C zeolite loading

5
0 10 20 30 40 50 60
Zeolite loading (%)
Effect of zeolite loading on the gas pair selectivity of
PES-modified zeolite MMMs
Y. Li, H. M. Guan, T. S. Chung, S. Kulprathipanja, Effects of novel silane modification of zeolite surface on polymer chain
rigidification and partial pore blockage in polyethersulfone (PES)–zeolite A mixed matrix membranes, J. Membrane
Science, 275, 17-28 (2006). 30
Change of glass transition temperatures of MMMs over neat PES dense
film before and after the chemical modification of zeolite surface

Glass transition temperature (oC)

membrane name
before modifying after modifying

neat PES dense film 215± 1oC

PES-zeolite 4A
216± 1oC 216± 1oC
(20 wt% loading)
PES-zeolite 4A
217± 1oC 217± 1oC
(30 wt% loading)

PES-zeolite 4A
218± 1oC 218± 1oC
(40 wt% loading)

PES-zeolite 4A
219± 1oC 219± 1oC
(50 wt% loading)

Chain rigidification apparently stays the

same even with the new silane modification
Y. Li, H. M. Guan, T. S. Chung, S. Kulprathipanja, Effects of novel silane modification of zeolite surface on polymer chain rigidification
and partial pore blockage in polyethersulfone (PES)–zeolite A mixed matrix membranes, J. Membrane Science, 275, 17-28 (2006). 31
Schematic of Desired Mixed Matrix Membranes
Molecular sieves or
porous nano-particles

A thin mixed matrix selective layer

Neat polymeric inner layer

Cross-section of Asymmetric
Hollow Fibers Membrane
32
Traditional Approach to Fabricate Asymmetric
Hollow Fiber Membranes

Bore fluid

Dope inlet

spinneret

Dope fluid
Water
Bore fluid spray
Syringe
pump

Flushing bath
Coagulation bath
33
 Single-layer and dual-layer spinnerets
Single layer spinneret Dual layer spinneret

Inner passage
Outer passage

Advantages of dual-
layer hollow fibers:
• save the material cost
Cross-section of single- Cross-section of dual-
layer hollow fibers layer hollow fibers • control the particles’
distribution
雙層中空纖維的優點：
• 節省材料成本
• 控制顆粒的分佈 34
 Schematic of Un-Desired Mixed Matrix Membranes
in a single-layer hollow fiber
Dispersed molecular sieves
voids or porous nano-particles

Shear Rate

No mixed matrix selective layer

Waste a lot of zeolite in the cross-section

Cross-section of the Spinneret or

Asymmetric Hollow Fibers Membrane
35
 Molecular sieves or
porous nano-particles

Particles stay in
the middle of the
fiber wall
because of low
shear stress
(minimal energy)
由於剪切應力低
(a) Axial velocity profile (b) （最小能量），顆
粒停留在纖維壁的
中間

(a) Schematic of the axial velocity and shear rate

profiles along the radial length within the spinneret;
Shear rate profile
(b) Schematic of the particle distribution in the
cross-section of the single-layer hollow fiber.
36
The dope compositions of the mixed matrix hollow fibers.

Polymer Zeolite

Solution Molecular Zeolite

Layer Concentration Solvent
No. Polymer sieve Loading in
in solvent
type polymer

SL single Matrimid 20% Beta 20wt% NMP

layer

SL -single layer

L. Y. Jiang, T. S. Chung, C. Cao, Z. Huang, S. Kulprathipanja, Fundamental understanding of nano-sized zeolite distribution in the
formation of the mixed matrix single- and dual-layer asymmetric hollow fiber membranes, J. Membrane Science 252, 89-100 (2005).

37
 Air gap =0 Air gap=1.5 cm Air gap=6 cm
Wet spun
Air gap=2.5 cm
Die swell

(a1) (b1) (c1) (d1)

b1

Parabolic
or Convex
Parabolic
or Convex

10 20 30

(a2) (b2) (c2) (d2)

SEM-EDX silicon line scanning spectra for the cross-section of the single
layer mixed matrix hollow fibers made from solution SL (Table 1) with air
gap (a). 0; (b) 1.5cm; (c) 2.5cm; (d) 6cm.
38
 Die swell Dj/D > 2

D Dj

When a viscoelastic fluid is extruded from a

pipe, the diameter of the extruded jet usually
increases, even to three or four times the
diameter of the pipe.

http://www2.mech.kth.se/~luca/html_lib/dieswell.html http://www.mie.utoronto.ca/labs/rheology/objectives.html

39
 Bore fluid
Why does the particle profile follow
a parabolic curve? Dope inlet
Axial velocity (cm/s)

6
5
4
3
2
1
0
0.2 0.25 0.3 0.35 0.4 0.45

Particles stay
in the middle
because of low
Shear rate (s-1)

2000
shear stress
1500
(minimal
1000
energy)
500

0
0.2 0.25 0.3 0.35 0.4 0.45
Radial length (mm)

Axial velocity and shear rate profiles with radial length

at the outlet of the single layer spinneret.

40
 Effect of air gap distance on the outer surface
morphology of single-layer mixed matrix hollow fibers

Air gap 0 cm Air gap 1.5 cm

Air gap 2.5 cm Air gap 6 cm

L. Y. Jiang, T. S. Chung, C. Cao, Z. Huang, S. Kulprathipanja, Fundamental understanding of nano-sized zeolite distribution in the
formation of the mixed matrix single- and dual-layer asymmetric hollow fiber membranes, J. Membrane Science 252, 89-100 (2005).
41
 Inner passage
for bore fluid

Middle passage for

the inner- layer dope
Matrimid

Outer passage for the

outer layer dope
Matrimid + beta zeolite

Structure of the dual-layer spinneret

L. Y. Jiang, T. S. Chung, C. Cao, Z. Huang, S. Kulprathipanja, Fundamental understanding of nano-sized zeolite distribution in the
formation of the mixed matrix single- and dual-layer asymmetric hollow fiber membranes, J. Membrane Science 252, 89-100 (2005).
42
 The dope compositions of the mixed matrix hollow fibers.

Polymer Zeolite

Solution Molecular Zeolite

Concentration Solvent
No. Layer sieve Loading in
Polymer In solvent
type polymer
outer
OL Matrimid 20% Beta 20wt% NMP
layer
inner
IL Matrimid 20% / / NMP
layer

SL -single layer
OL-outer layer
IL -inner layer

L. Y. Jiang, T. S. Chung, C. Cao, Z. Huang, S. Kulprathipanja, Fundamental understanding of nano-sized zeolite distribution in the
formation of the mixed matrix single- and dual-layer asymmetric hollow fiber membranes, J. Membrane Science 252, 89-100 (2005).

43
 Interface
(a1) (a1) (b1) (c1)
(c1)
a

x 500

(a2) (b2) (c2)

x 2000

SEM graphs of cross sectional view of the dual-layer hollow fibers.

Dope composition: OL1 and IL1. Spinning condition: (a) DL1A; (b) DL1B; (c) DL1C.
(1) x 500 magnification; (2) x 2000 magnification. The small picture in (a1)
shows the particles distribution borderline. 44
L. Y. Jiang, T. S. Chung, C. Cao, Z. Huang, S. Kulprathipanja, Fundamental understanding of nano-sized zeolite distribution in the
formation of the mixed matrix single- and dual-layer asymmetric hollow fiber membranes, J. Membrane Science 252, 89-100 (2005).
air gap distance: (a) 0 (b) 1.5 cm (c) 2.5 cm

Parabolic
concave
or Convex

(a) (b) (c)

SEM-EDX silicon line scanning spectra for the cross-section of the dual-layer
mixed matrix hollow fibers made from solution OL1 and IL1 (Table 1) and
spinning condition DL1 with air gap: (a). 0; (b) 1.5 cm; (c) 2.5 cm.
45
Enrichment
(a) Inner layer solution (b) Outer layer solution
4 1.4
1.2
Axial 3
1
0.8
velocity 2
0.6
(cm/s) 1 0.4
0.2
0 0
0.2 0.25 0.3 0.35 0.4 0.45 0.5 0.55 0.6 0.65

2000 600
500
1500
Shear 400

rate (s-1) 1000 300

200
500
100
0 0
0.2 0.25 0.3 0.35 0.4 0.45 0.5 0.55 0.6 0.65

Radial length (mm) Radial length (mm)

(a) (b)
Axial velocity and shear rate profiles with radial length at the outlet
of the dual layer spinneret: (a) Inner layer solution IL ; (b) Outer
layer solution OL.
46
 a(a) (b)

 =2.07  =3.91
(c) SEM graphs of the particle distribution
on the outer skin of the dual layer
hollow fiber,
(a) air gap 0;
(b) air gap 1.5;
(c) air gap 2.5cm,
The higher the air gap and draw
ratio, the higher the particle number
on the outer surface 氣隙和拉絲比越
 =10.13 高，外表面的顆粒數越高
47
 Middle passage
Inner passage

OD / ID
Outer passage

 -draw ratio
OD -outer diameter
ID -inner diameter

=
(OD 2
− ID 2 )
spinneret

(OD 2
− ID 2 )
hollow− fiber

48
 Dual-layer spinning is much
better than single-layer
spinning for MMMs with an
outer MMM selective layer
Dual-layer fiber (a) (b) (c)

55

50

Dual-layer fiber
45
Particle number/area

Particle
40
number per
area at the 35
outer-
selective 30

surface Single layer

25 Dual layer
Single-layer fiber
20

2 4 6 8 10
Draw ratio
Outer surface
Particle number per outer surface area vs. draw ratio
Jiang et al., JMS 2005 49
How do we explain the particle distribution
varying with the air gap distance?

Parabolic
or Convex concave

(a) (b) (c)

Particle distribution as a function of air gap distance

air gap: (a). 0; (b) 1.5 cm; (c) 2.5 cm.

Jiang et al . Membrane Science, 2005 50

 The Dry-Jet Wet-Spinning Process for MMM hollow fibers

Bore-fluid
dope
Spinneret Capillary flow
(hot)

solvent Internal coagulation

vaporisation
Air-gap
Region Moving boundary
Stretch
Vr inward flow

Elongation induced outward flow

Solvent exchange induced outward flow

Coagulation Bath
External coagulation

51
The sudden rapid shrinkage of fiber dimension induced by the
elongational draw may force the internal solvents to flow outside
radially, that may inhibit the non-solvent (coagulants) intrusion.

Nonsolvent intrusion

solvent outflow

The elongation reduces the hollow fibers’ wall thickness, which results in
faster solidification and small minuscule space left for the nonsolvent to
propagate, and hence leads to the formation of macrovoid-free structure.

Xiao, Wang, Chung. Chem. Eng. Sci. 2006;61:6228-6233. 52

The effect of elongational stretch on nascent fibers and
solvents within the fiber if the solvents can be
exchanged with surrounding medium

Inward hoop outward

stress radial flow

Membrane aspect Solvent aspect

(Under stretch) (under squeeze)

53
 (a)Take-up speed = 8.6 m / min (b)Take-up speed = 17.6 m / min (c)Take-up speed = 26.6 m / min

Scale bar: 100 μm.

(d)Take-up speed = 35.5 m / min (e)Take-up speed = 44.5 m / min (f)Take-up speed = 53.5 m / min

The effects of elongational draw ratio on membrane morphology of dry-

jet wet-spin PES hollow fiber membranes
Chemical Engineering Science, 59 4657 – 4660 (2004)
Spinneret dimensions: OD/ID = 800/400 μm
Draw ratio: a) φ = 2.42; b) φ = 4.55; c) φ = 7.31; d) φ = 9.78;
e) φ = 12.00; f) φ = 15.20 54
A B C

Macrovoid - free
D E F

The effects of elongational draw ratio on the morphology of

dry-jet wet-spun single-layer P84/TiO2 hollow fiber membranes
Draw ratio: (a) φ = 1.31; (b) φ = 4.11; (c) φ = 8.60; (d) φ = 13.5; (e) φ = 16.8; (f) φ = 22.3.
Xiao et al., Chem Eng Sci 2006 55
 B C
A Parabolic
Relative Ti Intensity
or Convex

Relativ
e
intensit
y

D E F
concave
Relative Ti Intensity

0 50 100 0 50 100 0 50 100

μm μm μm

The effects of elongational draw ratio on the TiO2 distribution across

membrane cross-section of P84/TiO2 hollow fiber membranes
Draw ratio: (a) φ = 1.31; (b) φ = 4.11; (c) φ = 8.60; (d) φ = 13.5; (e) φ = 16.8; (f) φ = 22.3.
56
 Number/Area2 Area

100
The higher the
80
Number/100μm

Particle draw ratio, the

Number/100μm2 60 higher the TiO2
Area 40 particle number
Partical

on the outer
Particle

20
surface
0
0 5 10 15 20 25

Draw
Drawratio
Ratio

Particle number at the outer surface vs. Draw Ratio

57
Enrichment
For melt spinning (not solution spinning) of a single fiber, the
axial (z) and radial (r) velocities of the fiber satisfy the
continuity equation:
v z 1  Polymer
+ (rvr ) = 0 melt
z r r Spinneret Capillary flow
v z 1  (hot)
= constant = − (rvr )
z r r Die swell
r
B.C.
1) v z  0 at z = 0
2) vz = U at z = L(t),
Vr Air-gap = L
3) vr = 0 at r = 0,
z
The solutions are:
Stretch
vz = U • z / L Speed = U

vr = −U • r / 2 L Moving boundary inward

58
 Moving surface
Moving boundary inward flow vr = −U • r / 2L

Shell side
Particles move
Lumen Moving surface Moving surface outward due to the
side moving surface and
under squeeze

Parabolic
or Convex
Particle
distribution Particle
density outward distribution
density
radial flow

Radial length Radial length

a) Initial status at b) at small air gap

the outlet of the Later stage
Particles move outward and (immersion in the
spinneret Particles
level off due to die swell coagulation bath)
Solvent

Particle distribution profiles induced by the air gap

(particle profile difference near the shell side) Page
C) at higher air gap
73
 Dope compositions for the dual-layer hollow fibers.
Polymer Zeolite Solvent
Solution
Conc. in Molecular Loading in Weight
No.
Layer Polymer solvent sieve polymer Solvent ratio
(wt. %) type (wt. %)
OL10 outer layer Polysulfone 30 Beta 20 NMP /

IL inner layer Matrimid 5218 23 / / NMP/EtOH 4/1

Bore fluid / / / / NMP/H2O 95/5

Inner passage
Bore fluid
Middle passage for
the inner-layer dope
(Matrimid)
Outer passage for the Matrimid is chosen
outer- layer dope because it has Tg
PSf/Beta Zeolite of 302 C
Polysulfone (PSf) is
chosen because it has
Tg of 185 C

60
 SEM of the outer layer partial cross-section and surface of
as-spun dual-layer hollow fibers
PSf / beta mixed
Matrimid inner matrix outer layer
layer
(b) The PSf /Beta
Tg =302 C Tg = 185 C (a)
layer are loose
in the as-spun
hollow fiber, it
cannot separate
10μm gas, how can
Scale bar 1 μm we overcome
(c) (d) it?
PSf /Beta層在紡
絲的中空纖維中
是鬆散的，它不
能分離氣體，我
們如何克服它？

Scale bar 1μm Scale bar 100 nm

(a), (b) cross-section; (c), (d) surface 61

 SEM of the cross-sectional view of the dual-layer hollow fibers
after heat treatment (i.e., annealing) at 200oC
Matrimid inner PSf / beta mixed During annealing, PSf chains soften and adhere with
layer matrix outer layer beta zeolite, thus the voids are eliminated.
(a) (b) (c)
Tg =302 C
Tg = 185 C

Scale bar 10 μm Scale bar 10 μm Scale bar 10 μm

(d) (e) (f)

(c)

Scale bar 10 μm Scale bar 1 μm Scale bar 1 μm

10μm 10μm
From (a) to (d) the outer layer dope flow rate decreases or air gap increases.
L. Y. Jiang, T. S. Chung, S. Kulprathipanja, An investigation to revitalize the separation performance of hollow fibers with a thin
mixed matrix composite skin for gas separation, J. Membrane Science, 276, 113–125 (2006). 62
 (A) (B) During annealing at 200 C,
PSf/beta zeolite mixed PES chains soften and
PSf/beta zeolite mixed
matrix outer layer matrix outer layer adhere with beta zeolite,
thus eliminated the voids
between them. Because
Matrimid has a high Tg of
302 C, its structure is not
Tg = 185 C Tg = 185 C
affected by annealing at
200 C.

在 200 C下退火期間，PES
鏈軟化並粘附在 β 沸石上，
從而消除了它們之間的空隙
。由於Matrimid具有302 C
的高Tg，因此其結構不受
Scale bar 1 μm 200 C退火的影響。

Comparison of the cross-section of the outer mixed matrix layers

with (A) and without (B) proprietary chemical modification
L. Y. Jiang, T. S. Chung, S. Kulprathipanja, Fabrication of mixed matrix hollow fibers with intimate polymer-zeolite interface
for gas separation, AIChE J. 52, 2898 - 2908 (2006).
63
O2/N2 selectivity of the dual-layer mixed matrix hollow fibers as
a function of zeolite loading. Testing condition: 5 atm, 35oC.

6
O2 /N2
selectivity
4

0 10 20 30

Zeolite loading (wt. %)

The MMM + dual-layer spinning concept really work if you choose

right inner and outer layer materials and spinning conditions
L. Y. Jiang, T. S. Chung, S. Kulprathipanja, Fabrication of mixed matrix hollow fibers with intimate polymer-zeolite interface
for gas separation, AIChE J. 52, 2898 - 2908 (2006).

64