CONFINED CRYSTALLIZATION OF

POLYETHYLENE OXIDE IN
NANOLAYER ASSEMBLIES

Work by Haopeng Wang et al.

Science, Vol. 323, 6 February 2009 [1]

A critical review by Lewis Marshall

 Overview
2

  Background
  Why confinement?
  What are the samples under investigation?
  Permeability Observation
  How does confinement change oxygen transport?
  Material Characterization
  How does confinement change the morphology?
  Permeability Interpretation
  How should we connect our observations about the material
with the changes in permeability?
  Conclusions
 Motivation
3

  We wonder how
polymers change as we Rg

confine them below the

the radius of gyration or
crystal size.

  Previous work shows that

confinement can change
mechanical or transport
properties. [8] ?
 Materials
4

Polyethylene Oxide (PEO)

  Random acrylic acid
units decrease EAA
crystallinity. [2]

Polyethylene co-acrylic acid (EAA)

  Materials probably
chosen for low and
high oxygen
permeability.
[3]
 PEO Melt EAA Melt
Film Production Extruder Extruder

  Layer-multiplying
co-extrusion.
Flow

  For n die, 2(n+1)+1 EAA

sheets are created. ABA 3 layers 1st Die Element 5 layers

Flow Flow
Figure S1"! #$%&'()*+,-.+%-/0! 12&3,'*4-2/! 52'! 52'1&6($
85,&'! ,9&! .2+%)&'! )&+,4! $'&! 12)7-/&6! -/! ,9&! 8:8! 5&
No information is given about ,9'2*09!$!4&'-&4!25!+$%&'()*+,-.+%-/0!6-&!&+&)&/,4>!&$19!
the crystallization temperature. 5
4.'&$64!-,!92'-@2/,$++%<!$/6!5-/$++%!'&12)7-/&4!-,!=-,9!,
layers
ABA 3 layers 1 Die Element
st
5-0*'&! -++*4,'$,&4! 292=! ,=2! &+&)&/,4!
Die Element
nd
)*+,-.+%!
9 layers
! ,9&! /*)
E/FGH
$44&)7+%!25!/!6-&!&+&)&/,4!.'26*1&4!D
Layer-multiplying dies. [4] FG!+$%&'4!=-,9
25!,9&!5-+)"!!I-/$++%<!,9&!)&+,!-4!4.'&$6!-/!$!5-+)!6-&!,2!5*'
Figure S1"! #$%&'()*+,-.+%-/0! 12&3,'*4-2/! 52'! 52'1&6($44&)7+%! 25! .2+%)&'! /$/2+$%&'4"!!
85,&'! ,9&! .2+%)&'! )&+,4! $'&! 12)7-/&6! -/! ,9&! 8:8! 5&&67+21;<! ,9&! )&+,! 4,'&$)! 5+2=4!
6 Permeability Observation
How does confinement change oxygen transport?
 Permeability Measurement
7

  Series model of
permeability
−1
 φ PEO 1− φ PEO 
P|| =  + 
 PPEO PEAA 

PPEO=0.38 Barrer PEAA=2.30 Barrer

P=Permeability ø=Volume Fraction Permeability of 50/50
1Barrer [=] 1010cm3(STP) cm cm-2 s-1 cmHg-1 EAA/PEO films.
Figure 1.A of primary text.
 Permeability Calculation
8

  Rearrange to find PPEO,eff.

 1 1− φ PEO −1
PPEO,eff = φ PEO  − 
P PEAA 

Assumption: PEAA is constant.

EAA thickness not specified. Figure 1.B from Primary Text
No further data reported for
PPEO=0.38 Barrer PEAA=2.30 Barrer
8nm PEO layers. 1Barrer [=] 1010cm3(STP) cm cm-2 s-1 cmHg-1
9 Material Characterization
How does confinement change the morphology?

• Differential Scanning Calorimetry

• X-ray scattering

• Atomic Force Microscopy

 Lamella
10

  Literature shows that

lamellar regions are
functionally gas-
impermeable. [5]

Lamella structure [6]

 Heating Thermograms (DSC) !
11

  A ~3ºC decline in PEO 1W/g

melting temperature is EAA

reported for nanolayers. 90/10

Endothermic Heat
80/20
∞ 2 γ ∞ [7]
T − Tm =
m Tm
l ΔHV∞ 70/30

50/50
This is could reflect a ~4nm
change in lamella thickness. 2W/g

€ PEO

-40 0 40 80 120
ϒ=Surface Energy l=Lamella Thickness
Temperature (oC) !
Tm∞ = Melting temperature, infinite size
Heating thermogram from
∆HV∞ = Heat of Fusion
Supplemental Materials. [4]
Figure S2!"#$!%&'()!#$*)&+,!)#$'-.,'*-(!.%!/0012/3!%&4-(!5&)#!6789!*4)$'+*)&+,!4*
*+;!).)*4!)#&<=+$((!*>.?)!687!-@!!"#$!/0012/3!<.-A.(&)&.+(!BC1CD!*'$!*(!4*>$4$;@!!
#$*)&+,!'*)$!5*(!67EF1-&+@!
!
 Crystallinity
12

PEO crystallinity,
PEO Layer
  Permeability could Thickness (nm)
(wt%, based on
heat of melting)
also be affected by a
change in crytallinity. 20 70

50 79

This does not conform to 70 76

previous HDPE/PS results. [8]
125 73
No uncertainty reported.
Bulk 78
 Equatorial
SAXS Data !
Meridian

13 Bulk Films 3.6um PEO 110nm PEO 20nm PEO

ND Meridian ND Meridian ND Meridian
log I (Iq2), a.u., off-set

Bulk EAA ND Equatorial ND Equatorial

ND Equatorial

ED Meridian ED Meridian
Bulk PEO ED Meridian

ED Equatorial ED Equatorial ED Equatorial

PEO: D=23nm q, nm-1 !

Figure S3 "#$! %&! '()'! *+,,$-./! 01! 2((3425! 1678/! 96,#! :611$-$.,! 425! 7+;$-!
EAA: D=10nm EAA EAA
,#6<=.$//$/>! ! "#$! *+,,$-./! 9$-$! 8$+/?-$:! +70.@! ,#$! .0-8+7! :6-$<,60.! AB&C! +.:! ,#$!
$D,-?/60.!:6-$<,60.!A2&CE!A(C!F>G!!8!425!7+;$-/H!AIC!JJK!.8!425!7+;$-/H!+.:!ALC!%K!.8!
425! 7+;$-/>! ! "#$! 425! 16-/,M0-:$-N! 425! /$<0.:M0-:$-! +.:! 2((! 16-/,M0-:$-! *$+=/! +-$! EAA
8+-=$:! 96,#! +--09/>! ! "#$! /<+7$! O+-! 6.! A(C! :$16.$/! ,#$! /<+,,$-6.@! P$<,0-! Q! /<+7$>! ! "#$!
This is the opposite of PEO PEO
6.,$./$!8$-6:60.+7!/,-$+=!6.!,#$!2&!*+,,$-./!6/!:?$!,0!@-+R6.@!6.<6:$.<$!/<+,,$-6.@>
PEO
HDPE results. !

Structure was confirmed

with WASX.
Assumed lamella structure:
J%
!
 Atomic Force Microscopy
14

AFM images from Primary Text

B: 3.6 um PEO layers D: 110nm PEO layers

Images in phase contrast.
15 Permeability Interpretation
How should we connect the changes in
morphology with the changes in permeability?
 the film by creating a tortuous path for diffusion. Clearly, this mo
complex for simple analysis.
To make this simple analysis, we idealize the model in Fig. 1 (a) in
First, we assume that the flakes are not randomly located in the film, b

Permeability Model from Text

occur periodically in a discrete number of planes within the film. We
this assumption in all three models detailed here.
Second, we assume a particular shape and spacing for the flakes. W
16 three such geometries. Most simply, we assume that the flakes are r
A.

PEAA α 2φ 2
= 1+ B. slits
P (1− φ ) _;;_

α [=] d/a C.

σ [=] s/a

Φ [=] a/(a+b)
D. random
flakes

[9]

Fig.permeability
This model assumes that 1. Models of barrier membranes.
in slits and bulk Theis first
the drawing
same, is a sketch of the actual memb
second and third drawings, diffusion occurs through regularly spaced slits or pores. In
and isotropic. Treatsoccurs
the through
problem as 2-D.
randomly Assumes
spaced slits. small slits.
 Platelet Permeability Theory
17

A simplified   Periodic Slits

version of the
platelet Po α 2φ 2
permeability = 1+ σαφ +
equation was
P (1− φ )
used.
  Random Slits
€ Po α 2φ 2
Other models = 1+ u
could have
P (1− φ )
been used, but AFM of 20nm films
slits are   Pores from primary text
probably
appropriate.
€ Po 4 α 2 α 2φ 2  α 
= 1+  2 φ + ln 2 
P π σ (1− φ )  2σ 
 Possible Further Analysis

Flow
18
of Permeability
  Assuming simple Change of Aspect Ratio
impermeable flakes,
PEO Lamella
confinement could
have several effects.
Change of Angle

Random Po α 2φ 2 [10]
= 1+
Orientation P 3(1− φ )

Change of Spacing
2 2
Random
€ Po α φ
Flat Flakes = 1+ u ⋅β
(Corrected)
P (1− φ )

ß = Density of Platelets in Layer

€
 Conclusions
19

  Contributes to both science and

technology.
  Thorough characterization of morphology.

  Never validates the permeability model

used.
  Never reports information for 8nm film.
  Never compares with earlier HDPE results
  Never mentions role of polymer interactions.
 References
20

  [1] Haopeng Wang, et. al. "Confined Crystallization of Polyethylene Oxide in Nanolayer
Assemblies." Science 323 (February 2009).
  [2] Wikipedia. Polyethylene Glycol. March 21, 2009. http://en.wikipedia.org/wiki/
Polyethylene_glycol (accessed March 24, 2009).
  [3] Sigma-Aldrich. 426717 Poly(ethylene-co-acrylic acid). March 24, 2009. http://
www.sigmaaldrich.com/catalog/ProductDetail.do?N4=426717|
ALDRICH&N5=SEARCH_CONCAT_PNO|BRAND_KEY&F=SPEC (accessed March 24, 2009).
  [4] Wang, Haopeng. "Supporting Online Material for Confined Crystallization of Polyethylene
Oxide in Nanolayer Assemblies." Science 323 (Feb 2009): online.
  [5] Weinkauf, D., & Paul, D. (1989). Effects of Structural Order on Barrier Properties. In W.
Koros, Barrier Polymers and Structures (p. 60). Washington, D.C.: American Chemical Society .
  [6] University of Cambridge. Dissemination of IT for the Promotion of Materials Science.
January 18, 2005. http://www.doitpoms.ac.uk/tlplib/polymers/images/img003.gif (accessed
March 24, 2009).
  [7] Hiemenz, Paul C., and Timothy P. Lodge. Polymer Chemistry. 2nd Edition. Boca Raton, FL:
CRC Press, 2007.
  [8] T.E. Bernal-Lara et. al. "Structure and Thermal Stability of Polymer Nanolayers." Polymer
46 (March 2005): 3043-3055.
  [9] al., E.L. Cussler et. "Barrier Membranes." Journal of Membrane Science 38 (1988):
161-174.
  [10]  Hiltner, A. (2005). Oxygen Transport as a Solid-State Structure Probe for Polymeric
Materials: A Review. Journal of Polymer Science, Part B: Polymer Physics , 43, 1047.
21 Thanks for your time.
Any questions?
 Appendix I: X-Ray Scattering
22

SAXS WAXS

  Uses a stationary   Uses moving detector.

detector.

  Shows information on   Shows information on

order of 10s of nm. crystal lattice,
angstrom scale.
 Appendix Ia: Full SAXS Images
23
!

A: 3.6 um
PEO

B: 110nm
PEO !

C: 20nm

!
Figure S3 "#$! %&! '()'! *+,,$-./! 01! 2((3425! 1678/! 96,#! :611$-$.,! 425! 7+
,#6<=.$//$/>! ! "#$! *+,,$-./! 9$-$! 8$+/?-$:! +70.@! ,#$! .0-8+7! :6-$<,60.! AB&C! +.:!
 Appendix Ib: WAXS Pole Images
24

A: PEO
Control

B: 50/50,
3.6um PEO

C: 70/30,
110nm PEO

D: 90/10,
20nm PEO
 Appendix Ic: WAXS images, cont.
25

ND ED
EAA A PEO
(120) PEO
(032)

PEO

WASX measures A: 3.6um PEO EAA

(110)
the features of B
the crystal EAA
lattice, so the
spectrum shows B: 110nm PEO
PEO
isotropy at a
right angle to
C
that found in C: 20nm PEO
SAXS. EAA
PEO

Figure S5 !"#$%&$'()*$+,--#./0$12$3((4536$27890$:7-"$;722#.#/-$536$8,<#.$
-"7=>/#00#0?$$@(A$!"#$B&$,/;$3&$+,--#./0$2.19$-"#$C?D$!9$536$8,<#.0$=1/27.9$-"#$E0E,8$
91/1=87/7=$=.<0-,8$21.9$12$536$,/;$0"1:$-"#$701-.1+7=$1.7#/-,-71/$12$-"#$E/7-$=#88?$$@FA$
!"#$B&$,/;$3&$+,--#./0$2.19$-"#$GGH$/9$536$8,<#.0$0"1:$,$"7I"$;#I.##$12$1.7#/-,-71/$
 Appendix II: ASTM D3985
26

  Oxygen concentration
is measured in the
nitrogen outlet port.

http://www.ides.com/property_descriptions/ASTMD3985.asp
 Appendix III: Free Volume
27
HIGHLIGHT 1051

Diffusion
through
amorphous
region
conceptualized
as taking place
through free
volume.

[10]

Figure 2. Schematic representation of the volume–temperature relationship for an amorphous

polymer following the concepts of Vrentas and Duda.22

permeation proceeds by jumps through the excess-hole the density of sorbed oxygen (#O2) in the free-volume
free volume. In simplified terms,29 the permeant gas holes at Ttest:24
molecule spends most of the time in free-volume holes

! "
and occasionally jumps into a neighboring hole. The
%" 1 Mw
jump motion proceeds by the formation of a channel # O2 $ (4)
30 #e 22,400
 Appendix IV: Radius of Gyration
28

[7]
2
Nb Rg, PEO~5nm
Rg =
6

MW~20,000g/mol Rg, EAA~6nm

 Appendix V: Scattering
29

4π  θ 
q≡ sin 
λ  2
Scattering Criterion:

2π
q=
D
http://en.wikipedia.org/wiki/File:Bragg_law.png