Characterization of Free volumes in Nano-scale Polymeric and Composite Membrane Systems Using Positron
Annihilation Spectroscopy*
Y.C. Jean1,2
1Department of Chemistry, University of Missouri-Kansas City
2R&D Center for Membrane Technology and Department of Chemical Engineering, Chung-Yuan Christian
University, Taiwan Collaborators: NIST:T. Nguyen, X. Gu; AIST: R. Suzuki, T. Ohdaira; CMT: J.I.Lai, Y.M. Sun, R. Lee, C.C. Hu*Supports: NSF and NIST, Ministry of Education (Taiwan)
Outline
• Positron and Positronium Annihilation
• I. Positrons in Polymeric Nano-Scale Films
(1) Multi-Layer Structures
(2) Tg-depth dependence
• II. Polymeric Composite Membranes
(1) Surface layer structures
(2) Permeability and selectivity
The Positron
1930: Anti-electron (Positron) predicted by P.A.M. Dirac, Quantum Electrodynamics Theory.
1932: The Positron (positive electron), detected by C.D. Anderson in the cloud chamber from cosmic radiation.
1946: The Positronium atom (positron and electron bound state) detected by M. Deutch from positron annihilation in gases.
1960: Solid state physics: positron is localized in defects; positron is delocalized in lattices-Fermi surface.
1970: Nuclear medicine: positron emission tomography (PET)1975: Surface science: positron has a negative work function.1980-presence: Positron chemistry, material defect and surface tools.
Positron Annihilation Processes
1. When positron and electron meet, they can form Positronium (Ps). Positronium exists in two states, p-Ps (spins anti-aligned) and o-Ps (spins aligned): 2 photons (for p-Ps with 125 ps, or a few ns for pick-off with electrons with molecules) or 3 photon (for o-Ps 142 ns) produced by annihilation.
2. Positrons can freely annihilate with electrons without forming Ps with lifetime ~10-9 s to ∞ (in UHV 10-11 torr, live one hour).
3. The Feynman diagram shows that the annihilation distance starts 10-12.5 m (Δx~ħ/mc) and the time 10-21 s (t~ħ/mc2)-delta function and sudden approximation.
4. Annihilation characteristics depend on electron properties of matter.
Positron Annihilation Spectroscopy (PAS)
PAS monitors annihilation γ-rays properties, which are related to materials and electronic properties of systems studied. Four experimental techniques are currently used in PAS:
1. Positron annihilation lifetime spectroscopy (PAL): atomic and molecular free volumes and holes in polymers, solids.
2. Doppler broadening of annihilation energy spectroscopy (DBES): atomic defects in semiconductors, polymers.
3. Angular correlation of annihilation radiation (ACAR): Anisotropy structures of free volumes, defects, Fermi surface.
4. Variable mono-energetic positron beam: surface and interfaces.
PAS contains the most fundamental properties of molecules (chemistry):
wave function and electron density
• PAL measure positron annihilation lifetime τ:
τ= n |xyz n(x,y,z)* +(x,y,z) dxdydz |2
• DBES measures electrons’ momentum distributions at the longitudinal direction (z):
N(pz)=n pxpy |xy zn(r)* +(r) e-iP•r d r|2 dpxdpy
• 2D-ACAR measures electrons’ momentum distribution at the transverse directions (x,y):
N(px, py)=n pz|xy zn(r)* +(r) e-iP•r d r|2 dpz
Localization of positron and Ps
The Decay Scheme of 22Na
10Ne22
3 ps
0+
2+
E2
1.2746 EC 10%
+ 0.05%
+ 90%
+, EC
3+ 2.60 y
11Na22
0.511 MeV0.511 MeV
180 o
(e-e+)
-
Two-photon Annihilation of a Positron-Electron Annihilation Pair
Calibrated defect radius(Å)
0 i
EE i
)E(N
)E(NS
2
1
N(E
)
E( keV)
Low momentum (S-parameter)
E2E
1 511
S is a measure of defect property:
(1) Large hole Large Sp•x /2
(2) Large defect concentration large S
Doppler broadening S parameter
Positron Annihilation Lifetime
0 5 10 15 20 25
10
100
1000
10000
100000
ç3=1.8 ns
ç2=0.45 ns
ç1=0.125 ns
Cou
nts
Time (ns)
)BAI(Vf
)R
R2sin
2
1
R
R1(
2
1
3fv
1
003
tλii ieλIN(t)
Res
olve
d D
efec
t Siz
e
1 cm
1000
100
10
1
1000
100
10
1Å
OM
TEM X-ray Scattering
Positron Spectroscopy
1 Å 10 100 1000 1 10 100 1000
Depth
Mech
Def
ect C
once
ntra
tion
(pp
m)
10
OM TEM
X-ray Scattering
Positron Spectroscopy
1Å 10 100 1000 1 10 100 1000
Depth
Mech1%
1000
100
1 ppm
STM/AFM
STM/AFM
PAS can resolve size, concentration and distribution of atomic
scale defects
Comparison of PAS and other techniques
A sow positron beam (0- 30 keV) for depth profile (0-10 µm) of free volume
22Na e+ source 50mCi
Moderator
ExB e+ filter
Lifetime detector attachment
Sample chamber
S.S. Detector
Data acquisition system
Accelerator 0- 30kV
Magnetic coils 75G
Depth and dispersion of depth
6.10
400)( EEZ
Free-volume Concept in Macromolecules (polymers)
Free volume is the free moving (very fast, ps-ns) open space (very small, sub-nm) inside a molecule or system.
A simple expression of the free volume (Vf) can be written as the total volume (Vt) minus the “occupied volume” (V0):
Vf = Vt – V0
The existence of free volume (1-10%) makes polymers as the most widely used materials in our human life today.
Polymer film
Substrate
Diagram Of Nano-scale Polymeric Film On Substrate
1. Free-volume S-parameter for different thickness of polystyrene films on Si
0 5 10 15 20 25 300.42
0.43
0.44
0.45
0.46
0.47
0.48
0.49
0.50
S P
ara
me
ter
Positron Incident Energy (keV)
silicon 5 nm 12 nm 20 nm 30 nm 42 nm 55 nm thick film
8796459815175000
Thickness (nm)
S parameter spectrum and profilometry measurement on 80 nm PS film
Thickness (nm)
Density
(g/cm3)
e+ Diffusion length
(nm)
I and II 80 8 1.10 40 5
III 21 3 0.4 0.3 4 2
VEPFIT fitting result from S parameter spectrum
20 40 60 80 100 120 140 160 1801.9
2.0
2.1
2.2
2.3
2.4
2.5
2.6
2.8
2.9
3.0
3.1
3.2
3.3o
-Ps
life
time
(n
s
Temperature (°C)
Tg = 972 C
Ho
le R
ad
ius
(Å)
2. Tg of thick polystyrene film measured by conventional PAL spectroscopy
1.8 2.0 2.2 2.4 2.6 2.8 3.0 3.2
0.0
0.5
1.0
1.5
2.0
PD
F
Lifetime (ns)
30C 50C 80 C 90 C 110 C 130 C 150 C
3.50 3.64 3.773.353.203.032.86
Free Volume radius (Å)
Free volume distribution of thick PS film at different temperature, Spectchim Acta A,
61,1681, 2005
20 40 60 80 100 120 140 160
0.15
0.20
0.25
0.30
0.35
F
WH
M (Å
)
Temperature (ºC)
FWHM of free volume distribution of thick PS film as a function of temperature
200 400 600 800 1000100
101
102
103
104
105
C
ou
nts
Channel
0.3 keV 0.5 keV 0.7 keV 1.0 keV 1.5 keV 2.0 keV 3.0 keV 5.0 keV 10.0 keV
Raw PAL spectrum measured on thin 80 nm PS film on Si
0 2 4 6 8 101.5
2.0
2.5
3.0
0
10
20
30
40 3 (
ns)
Energy (keV)
o-PsLifetime
I 3 (%
)
0 210 640 1223Mean Depth (nm)
o-Ps intensity
o-Ps lifetime and intensity as a function of depth in 80 nm PS film
Depth profile of Free-volume distribution
A larger hole size and broader free-volume distribution near the surface are observed.
J. Phys. Cond. Matt. 10, 10429 (1998)—a lower Tg near the polymer surface.
1.8 2.0 2.2 2.4 2.6 2.8 3.0 3.2 3.4
0.0
0.2
0.4
0.6
0.8
1.0
1.2
1.4
1.6
1.8
2.0
2.2
P
DF
Lifetime (ns)
0.3 keV, surface (mean depth 5 nm) 0.5 keV, (mean depth 12 nm) 1 keV, center (mean depth 36 nm) 1.5 keV, interface (mean depth 70 nm) Bulk thick film
2.86 3.03 3.20 3.35 3.50 3.64 3.77
Free volume radius (Å)
Hole size distribution of 80 nm supported PS film at room temperature
20 40 60 80 100 120 140
2.0
2.2
2.4
2.6
2.8
3.0
3.2
5 nm, Tg =80 5C
36 nm, Tg =98 3 C
70 nm, Tg = 86 2 C
o-P
s lif
etim
e (
ns)
3.03
3.20
3.50
3.64
3.77
Fre
e V
olu
me
ra
diu
s (Å
)
Temperature (C)
2.86
3.35
Glass transition temperature determined from o-Ps lifetime result at different depth of the supported PS film
1.8 2.0 2.2 2.4 2.6 2.8 3.0
0.0
0.2
0.4
0.6
0.8
1.0
1.2
1.4
1.6
1.8
2.0
P
DF
Lifetime (ns)
30 C 50 C 80 C 100C 115 C 130 C
2.67 2.86 3.03 3.20 3.35 3.50 3.64
Free volume radius (Å)
Free volume distribution of 80nm PS film at different temperature
3. FWHM of Free volume distribution of 80nm PS film as a function of temperature
Locations Tg (PAL)Vf/VfT
( below Tg), K-1
Vf/VfT
( above Tg), K-1
FWHM (Å)of free-volume
radiusdistribution
Surface (5 nm)of 80-nm film
80 ± 5ºCβg = 2.3 ± 0.3
×10-3
βr = 5.6 ± 0.4
×10-30.263 0.010
Center (36 nm)of 80-nm film
98 ± 3ºCβg = 1.6 ± 0.3 ×
10-3
r = 7.0 ± 0.4 ×10-
30.159 0.006
Interface (70 nm) of 80-nm film
86 ± 2ºCβg = 1.3 ± 0.2
×10-4
r = 6.7 ± 0.4 × 0-
30.167 0.008
Bulk of thick film 97 ± 2ºCβg = 2.0 ± 0.2 ×
10-3
βr= 6.2 ± 0.3 ×10-
30.156 0.005
Free-volume thermal expansion coefficients and FWHM of distribution in
an 80-nm polystyrene film.
Interpretation: Tg-depth dependence (suppression) in nano-
scale polymeric films:
• Free-volume is distributed at a different degree as a function of the depth
• Near the surface, the free-volume is distributed widest, therefore the Tg is the lowest
• At interface, the free-volume is distributed next widest, Tg is also suppressed.
• Loosely packing, end chains, incomplete entangling of chains, etc. lead to broad distribution.
I. PAS for polymers and nano-films
• PAS is a novel spectroscopic method in determining free-volume physical properties of polymers.
• PAS could provide sub-nano and nano-scopic free-volume size, fraction, distribution and structures.
• PAS is monitoring glass transition of polymer film as a function of depth from surface, films and interfaces.
• Tg is found to be 17 K lower near the surface and 11 K lower in interface than the center of the film.
• Tg suppression can be interpreted as the broadening of free-volume distribution in the surface and interfaces.
P: Permeability
S: Solubility
D: Diffusivity Coefficient
D=A exp(-B/FFV)
FFV: Fractional Free Volume
P’s unit is Barrer=1.0{10 -10 cm3 (STP) cm}/{cm Hg cm2 s}
II. Membrane Composites:
Permselectivity (A/B) of a polymer film is a ratio of permeability PA/PB
DSPB
A
B
A
B
A
DD
SS
pP
BA
)()(/
oMolecule A
Molecule B
Polymer
o
o
oo
o
o
oo
Polyamide Composite membrane: Pervaporation
polyamide composite membranes Interfacial polymerization
2 wt% aqueous TETA solution
Doping temperature: 50 oC
Doping time: 1, 5,10, 30 min
1 wt% TMC/ toluene solution
R. T. and 3 min(dried at R. T.)
Hydrolyzed PAN Polyamide thin-film
Free-volume distributions of base polymers
0.5 1.0 1.2 1.4 1.6 1.8 2.0 2.2 2.4 2.6 2.8 3.0 3.2 3.4
0.0
0.1
0.2
0.3
0.4
Dry PAN
Drym-PAN
Dry PA
3.32 Å
3.13 Å2.84 Å
3.88
P
DF
o-Ps lifetime (ns)
PAN Polyamide m-PAN
1.2 Å (water)
2.9 Å (isopropanol)
3.62
Free-volume radius (Å)3.343.022.662.221.66
Doppler Broadening Free-volume S (free-volume) and R (pore) parameters in PA and m-PAN membranes
0 5 10 15 20 25 300.450
0.455
0.460
0.465
0.470
0.475
0.480
S p
aram
eter
Positron Energy (keV)
PA m-PAN
0 0.53 1.59 4.35 6.90 9.86 13.2
Mean Depth (m)
Porous m-PANTransition from
dense skin to
porous m-PAN
dense skin
m-PAN
0 5 10 15 20 25 300.30
0.32
0.34
0.36
0.38
0.40
Transition layer from dense skin to porous m-PAN
2 annihilation dense skin in m-PAN
3 annilhilation: Large pores in m-PAN
PA m-PAN
R p
aram
eter
Positron Energy (keV)
0 0.53 1.59
Mean Depth (m)
4.35 6.90 9.86
3-Layer structure of m-PAN from PAS
0.45
0.46
0.47
0.48
0.49
Porous m-PAN layer
Dense
skin
m-PAN
Transition layerfrom dense skin to porous m-PAN
10.03.00.3
S p
ara
me
ter
Mean depth (m)
SEM Cross-section image of m-PAN
402 ± 70 nm
S free volume parameters for interfacial polymerized polyamide on m-PAN at different TETA doping time
0 5 10 15 20 25 30
0.450
0.455
0.460
0.465
0.470
0.475
0.480
0.485
S p
ara
me
ter
Positron Energy (keV)
doped 1min doped 5min doped 10min doped 30min
0 0.44 1.33 3.39 5.36 7.67 10.3
Mean Depth (m)
m-PAN
PA
dense skin to porousm-PAN
R (Pore) parameter of PA/m-PAN at different TETA doping time
0 5 10 15 20 25 300.28
0.30
0.32
0.34
0.36
0.38
PA Porous m-PANTransition layer from dense skin to porous m-PAN
7.365.123.221.660.54
Mean depth (m)
0
Doped 50oC
PA/m-PAN 30 min PA/m-PAN 10 min PA/m-PAN 5 min PA/m-PAN 1 min
R
par
amet
er
Positron incident energy (keV)
SEM skin thickness 100-500 µm249 ± 16 nm PA
326 ± 10 nm
203 ± 29 nm
186 ± 10 nm
402 ± 16 nm m-PAN skin
1 min
5 min
10 min
30 min
TETA doping time deceases PA film thickness: Both PAS and SEM data
0 5 10 15 20 25 30
0
50
100
150
200
250
300
350
400
PAS SEM
Doping time of TETA (min)
PA
th
ick
ne
ss
, PA
S (
nm
)
150
200
250
300
350
400
450
500
PA
th
ick
ne
ss
, SE
M (
nm
)
Three-layer structure of PA/m-PAN;1:PA (50-300 nm); 2:Transition skin to porous PAN (.5-4 µm); 3: porous PAN
0.45
0.46
0.47
0.48
0.49
Polyamidetop layer
3.0
Transition layer from dense skin toporous m-PAN
Porous m-PAN
10.00.2
S p
ara
met
er
Mean depth (m)
Polyamide top layer
Pervaporation performance of polyamide/PAN membranes
Polyamide skin layer of composite membranes reduced the permeation rate, but enhanced the selectivity of water effectively.
PA layer (1): Correlations
0 50 100 150 200 250 3001000
1050
1100
1150
1200
1250
1300
1350
1400
1450
1500
Flux Water concentration
Thickness of the first layer, L1 (nm)
Flu
x (
g/m
2h
)
95
96
97
98
99
100
Wa
ter
co
nc
en
tra
tio
n in
pe
rme
ate
(w
t%)
0.460 0.462 0.464 0.466 0.4681000
1050
1100
1150
1200
1250
1300
1350
1400
1450
1500
Flux Water concentration
S parameter in the first layer, S1
Flu
x (
g/m
2 h)
95
96
97
98
99
100
Wa
ter
co
nc
en
tra
tio
n in
pe
rme
ate
(w
t%)
1. PA thickness increases selectivity
2. Free-volume S decreases selectivity
PA layer (2): Correlations
1. Transition layer thickness increases selectivity
2. Less relationship between S (transition) and selectivity
0 1000 2000 3000 4000 5000 6000 70001000
1050
1100
1150
1200
1250
1300
1350
1400
1450
1500
Flux Water concentration
Thickness of the second layer (nm)
Flu
x (
g/m
2h
)
95
96
97
98
99
100
Wa
ter
co
nc
en
tra
tio
n in
pe
rme
ate
(w
t%)
0.477 0.478 0.479 0.480 0.4811000
1050
1100
1150
1200
1250
1300
1350
1400
1450
1500
Flux Water concentration
S parameter in the second layer, S2
Flu
x (g
/m2
h)
95
96
97
98
99
100
Wat
er c
on
cen
trat
ion
in p
erm
eate
(w
t%)
Temperature of TETA doping (25, 50, 70 o)Temperature increases PA thickness
0 5 10 15 20 25 300.44
0.45
0.46
0.47
0.48
0.49
7.365.123.221.660.54
Mean depth (m)
0
Doped 10 min:
PATFC021 : 25oC
PATFC025 : 50oC
PATFC003 : 70oC
S p
aram
eter
Positron incident energy (keV)
20 25 30 35 40 45 50 55 60 65 70 75
0.46
0.47
0.48
0.49
0.50
0.51
0.52
0
50
100
150
200
250
300
350
400
S parameter
S p
aram
eter
Temperature (oC)
Thi
ckne
ss (
nm)
Layer 1
Thickness
20 25 30 35 40 45 50 55 60 65 70 750.475
0.476
0.477
0.478
0.479
0.480
0.481
0.482
0
500
1000
1500
2000
2500
3000
3500
4000
S parameter
S p
ara
me
ter
Temperature (oC)
Th
ickn
ess
(n
m)
Layer 2
Thickness
Temp increases both layer 1 and layer 2 thickness but decreases free-volume S parameters
PA layer (1) correlations
0.46 0.47 0.48 0.49 0.50 0.51 0.52600
800
1000
1200
1400
1600
1800
2000
40
60
80
100
Flux
Flu
x (g
/m2 hr
)
S parameter (Layer 1)
Wa
ter
Co
ncen
trat
ion
(wt%
)
Water concentration
0 100 200 300 400500
1000
1500
2000
40
60
80
100
Flu
x (g
/m2 h
r)
Thickness L1 (nm)
Wa
ter
Co
nce
ntr
atio
n in
pe
rme
ate
(w
t%)
Flux
Water concentration
1. Flux (permeability) and S1 free-volume parameter follows D=A exp(-B/ffv)
2. Selectivity decreases as S1 and PA thickness increases
Transition layer (2) correlations
1. Flux (permeability) and S2 free-volume parameter follows D=A exp(-B/ffv)
2. Selectivity decreases as S2 and PA thickness increases
0.476 0.477 0.478 0.479 0.480600
800
1000
1200
1400
1600
1800
2000
40
60
80
100
Flux
Flu
x (g
/m2h
r)
S parameter (Layer 1)
Wa
ter
Co
nce
ntr
atio
n in
pe
rme
ate
(wt%
)
Water concentration
1. A 3-layer structure of the PAN membranes is determined: (1) Skin m-PAN (300-400 nm); (2) Transition larer from dense to porous PAN (2 µm)(3) Porous m-PAN
2. A 3-layer polyamide thin-film composite PAN membrane is(1) polyamide layer: a very near surface layer (50-300 nm)(2) Transition layer from dense to porous m-PAN (0.5-4 µm)(3) Porous m-PAN layer
3. Correlation between free volume S parameter and flux in the free-volume theory: Flux=A(-B/S)
4. Selectivity is mainly controlled by thickness of skin polyamide layer, and secondary affected by the transition layer.
5. Effect of free volume size and selectivity can be investigated using PAS
6. Future applications of PAS to membrane technology for RO and NF are promising.
II. Conclusions based on PA/m-PAN of pervaporation of membrane separation
Summary
I. Nano-scale polymeric films:(1) Depth and interfacial structures for layers and nano-
composite systems.(2) Tg-depth dependence of polymeric systems on
different substrates with different interfacial interactions and UV irradiations.
II. Membranes and coatings:(1) Free-volume depth profile of membranes and
coatings(2) Early detection of polymeric degradations.(3) Effects of free volume size and struture on
membrane performances (permeselectivities)
Jack Liu, Lakshmi Chakka, Dr. Jean, Dr.Hongmin Chen, Wassen