Polymer/InorganicNanocomposites

Polymer/InorganicNanocomposites
OpportunitiesforFoodPackagingBarrier
OpportunitiesforFoodPackagingBarrier
Evangelos Manias
Director, Polymer Nanostructures Lab
Materials Science & Engineering Dept
Penn State University
manias@psu.edu
814-863-2980
http://zeus.plmsc.psu.edu
Nanocomposites
Nanocomposites
A Definition
1
:
Polymer Nanocomposites The proper incorporation of
nanoscale inorganic fillers to polymer matrices, so as to
achieve novel (non-bulk) properties and multifunctionality
(molecular hybrids or genuine nanocomposites
1
).
Or (more common approach) design concurrent property
improvements across a selected set of properties
(nanofilled composites
1
).
Todays focus:
Polyolefin/Clay Nanocomposites Barrier (and beyond)
1
E. Manias, Nature Materials 6, 9-11 (2007)
starting particle: agglomerate
several m in size (5-20 m)
millions of individual platelets
more
likely
The Challenge: Achieving Miscibility
The Challenge: Achieving Miscibility
desired
Courtesy: RA Vaia, AFRL, 2oo4
Thermodynamic Arguments
Thermodynamic Arguments
Designing miscible nanocomposites
introduce favorable excess interactions
i.e. polymer-clay interactions better than
clay-surfactant interactions
( )
( ) ( )
filler inorganic , surfactant , polymer : ,
2
with
2
j i
j i j i
AB
ij
LW
j
LW
i
LW
ij
AB
ij
LW
ij ij
+ +
=
=
+ =



Vaia & Giannelis, Macromolecules, 30, 7990 (1997)
0 <
filler surf filler pol

Barrier properties of Composites
Barrier properties of Composites
0.0
0.2
0.4
0.6
0.8
1.0
0 0.05 0.1 0.15 0.2 0.25 0.3 0.35 0.4
Volume Fraction Silicate
R
e
l
a
t
i
v
e

P
e
r
m
e
a
b
i
l
i
t
y

Nanocomposite
(PCL Nanocomposites)
Conventionally
filled systems
A
B
Manias, Giannelis, et al. (1997)
Tortuous Path
Macromolecules 2001, 34, 9189
effective
alignment
Permeability
Permeability
vs.
vs.
Path
Path
Tortuousity
Tortuousity
Origins:
path tortuosity
Similar Trends seen
for (Penn State work):
(amorphous polymers)
PDMS PU PUU
PS Elastomers...
(few semi-crystalline)
PVA polyamides
Nanocomposites: Permeability
Nanocomposites: Permeability
vs.
vs.
Structure
Structure
R. Xu, E. Manias, A.J. Snyder & J. Runt Macromolecules, 34, 337-339 (2001)
0
0.005
0.01
0.015
0.02
0.025
0.03
0 200 400 600 800 1000 1200 1400
Extension (%)
PUU
0.3%
0.8%
2%
3.8%
5.9%
vol% silicate
Microtensile die (ASTM D1708-93)
High
High
-
-
Barrier
Barrier
PUU
PUU
Nanocomposites:
Nanocomposites:
elastomeric character retained
elastomeric character retained
R. Xu, E. Manias, A.J. Snyder & J. Runt Macromolecules, 34, 337-339 (2001)
Still Highly Rubbery !!
Still Highly Rubbery !!
barrier incr. by barrier incr. by 500% 500%
modulus incr. modulus incr. 500% 500%
strength incr. strength incr. 400% 400%
Wilson high performance tennis balls
Wilson high performance tennis balls
http://www.wilsonsports.com.au/tennis/doublecore.html
*InMat Inc. Air D-Fence Butyl-Rubber/Vermiculite nanocomposite
WDCallister MaterialsScienceand
Engineering 7thEd.(Fig.16.19)
Typical tactoid orientation
Typical tactoid orientation
Orientated Tactoids
Orientated Tactoids
Strategies to Orient
Strategies to Orient
nanofillers
nanofillers
S
d
= 0.8 @ mg systems
above 20mg sample aligned
with 1500V
AC
for 10min @ AFRL
S
d
= 0.6 @ kg/h systems
above made at 50150 lb/h
blow molding *
(2D nanoparticles)
(2D nanoparticles)
Electric-field Alignment
Epoxy/ Epoxy/MMT MMT
Flow-induced Alignment
PE/ PE/MMT MMT
* E. Manias, J. Zhang, MM Jimenez-Gasco, et al. Macrom. Rapid Comm., 30, 17-23 (2009)
What are effective aspect
What are effective aspect
-
-
ratios?
ratios?
0 200 400 600 800
0.0
0.2
0.4
0.6
0.8
1.0


R
e
l
a
t
i
v
e

P
e
r
m
e
a
b
i
l
i
t
y

(
P
c
o
m
p
/
P
p
o
l
y
m

)
filler aspect ratio (a)
=0.03
Nielsen
modified Nielsen
modified Cussler-Aris
Fredrickson-Bicerano
0.00 0.05 0.10 0.15 0.20
0.0
0.2
0.4
0.6
0.8
1.0


R
e
l
a
t
i
v
e

P
e
r
m
e
a
b
i
l
i
t
y

(
P
c
o
m
p
/
P
p
o
l
y
m

)
volume fraction of filler ( )
a=200
Nielsen
modified Nielsen
modified Cussler-Aris
Fredrickson-Bicerano
How much filler does it take?
How much filler does it take?
100m
Poly(ethyleneoxide) Poly(ethyleneoxide) Polypropylene Polypropylene syndio syndio Polystyrene Polystyrene
PEO/3wt% PEO/3wt%mmt mmt PP/3wt% PP/3wt%mmt mmt sPS/3wt% sPS/3wt%mmt mmt
Path
Path
Tortuousity
Tortuousity
around the fillers is
around the fillers is
not
not
the
the
most relevant quantity for crystalline polymers
most relevant quantity for crystalline polymers
More effective barrier structures
More effective barrier structures
House House of of CardsStructuresFillerSequestratio CardsStructuresFillerSequestrationatInterfaces natInterfaces
More effective barrier
More effective barrier
structures
structures
House House of of CardsStructuresFillerSequestratio CardsStructuresFillerSequestrationatInterfaces natInterfaces
200nm
M.Okamoto, P.H.Nam, P.Maiti, et al.
Nano Letters, 1: 295 (2001)
Chung, Mason, Heidecker, Manias
Patent Pending, WO/2008/094167
In a first approach, controlled dispersion of wisely-
selected nanoparticles can concurrently improve
barrier with thermal and mechanical enhancements.
But, what about:
-fine tuning a specific property (dialing in a value) ?
-introducing a completely new functionality ?
moving on ...beyond barrier
moving on ...beyond barrier
One approach, one can add other polymers:
LLDPE-graft-MAH / mmt LDPE-random-VA / mmt
Bridging !!
110 115 120 125 130 135 140
0
2
4
6
8
10
12
14
16
0
10
20
30
Sealing Temperature ( C )

S
e
a
l

S
t
r
e
n
g
t
h

(

N
/
c
m

)
PE/EVA on PE/EVA
PE/EVA on PE/mmt
PE/EVA on PE
PE/mmt on PE/mmt
PE on PE/mmt
PE on PE
1000psi / 8sec
F
r
a
c
t
u
r
e

S
t
r
e
n
g
t
h

(

M
P
a

)
easy-open
strengths
Heat
Heat
-
-
sealing: PE
sealing: PE
-
-
based nanocomposites
based nanocomposites
E. Manias, et al. Macrom. Rapid Comm. 30: 17 (2009) & J Adhesion Sci & Techn 23: 709 (2009)
(nanocomposite PE-MAH / alkyl-MMT diluted by unfunctionalized PE)
LLDPE-graft-MAH
2Me-2alkyl-N
+
MMT
seal interface
crack path
(cohesive fracture)
EVA copolymer
(grey regions)
mmt tactoids
( )
Macromolecular Rapid Communications 30,17 (2009)
Manias et al. J Adh Sci Techn 23,709 (2009)
nanocomposites w/ prescribed fracture
nanocomposites w/ prescribed fracture
(nanocomposite PE-MAH / alkyl-MMT diluted by EVA & PE)
110 115 120 125 130 135 140
0
2
4
6
8
10
12
14
16
0
5
10
15
20
25
30


S
e
a
l

S
t
r
e
n
g
t
h

(

N
/
c
m

)
Sealing Temperature ( C )
PE/EVA/mmt on PE/EVA/mmt
PE/EVA/mmt on PE/EVA
PE/EVA/mmt on PE/mmt
PE/EVA/mmt on PE
PE/EVA/mmt on HDPE
1000psi / 8sec
F
r
a
c
t
u
r
e

S
t
r
e
n
g
t
h

(

M
P
a

)
LDPE-random-VA
2Me-2alkyl-N
+
MMT
E. Manias, J. Zhang, et al., Macromolecular Rapid Comm. 30: 17 (2009)
nanocomposites w/ prescribed fracture
nanocomposites w/ prescribed fracture
Strategy to introduce new functionalities
Strategy to introduce new functionalities
Our best performing polyolefin
nanocomposites are based
on alkyl-ammonium surfactant-OLS
and are not antimicrobial
How can we design a composite
that affords antimicrobial activity?
Employ surfactants on the fillers that:
have antimicrobial activity
and
still promote dispersion and good materials properties !
0 1 2 3 4 5 6 7 8
0
1
2
3
4
5
6
7
8
9
Surfactant Reduction
None 0%
DDOAB 0%
BDDAC 100%
PEDPA 100%
D
i
a
m
e
t
e
r

(
c
m
)
Time (Day)
Cationic surfactant candidates for
Cationic surfactant candidates for
OLS
OLS
DDOAB
BDDAC
PEDPA
alkyl-only
benzyl-containing
ethylene-oxide based
Penicillium roqueforti
Antimicrobial activity maintained even for
Antimicrobial activity maintained even for
surfactants tethered
surfactants tethered
(immobilized)
(immobilized)
on LS
on LS
0 1 2 3 4 5 6 7 8
0
1
2
3
4
5
6
7
8
9
10
Control
MMT-DDOAB
MMT-BDDAC
MMT-PEDPA
D
i
a
m
e
t
e
r

(
c
m
)
Time (Day)
P. roqueforti
Antifungal PE nanocomposite films
Antifungal PE nanocomposite films
Control 6%MMT-BDDAC 6%MMT-DDOAB 9%MMT-BDDAC
Experiment #2: Prevents germination and (thus) growth away from film
P.claviforme
Experiment #1: Prevents growth on film
P.roqueforti
Fungi Time
Spore Germination (%)
PE
(control)
PE+6%
MMT-
DDOAB
PE+6%
MMT-
BDDAC
PE+9%
MMT-
BDDAC
PE+6%
MMT-
PEDPA
PE+9%
MMT-
PEDPA
F.graminearum
10h 46 32 18 21 24 24
P.claviforme
48h 5 3 0 0 2 0
P.roqueforti
48h 7 6 0 0 3 2
Experiment #2: Prevents germination and (thus) growth away from film
Control 6%MMT-BDDAC 6%MMT-DDOAB 9%MMT-BDDAC
Antifungal PE nanocomposite films
Antifungal PE nanocomposite films
Summary
Summary
Polymer/organoclay nanocomposites offer:
concurrent property improvements (barrier + +)
control of nanostructures at ton quantities (using
industrys current processing methods)
fine tuning of properties (e.g. prescribed value of
fracture toughness, viz. peel strength)
new functionalities (e.g. antimicrobial, FR)
Viable Technology: Multiple commercial products
However: They are not the solution to all materials
properties problems or performance requirements !!
Grad. students: Grad. students:
Ken Strawhecker
Zhiming Wang
Vikram Kuppa
Sung Woo Wee
Alexei Kisselev
Matt Heidecker
Greg Hogshead
Theresa Foley
Ponusa Songptiya
Ngoh Manokruang
Romesh Patel
Felipe Salcedo Financial Support: Financial Support:
NIST NSF PDA DoE ONR AFOSR
Air Products UTC/IFC BAYER MATSC
Coca-Cola Asahi-Kasei Arrow-BioMed
Sumitomo Chem PPG Samsung Kraft
Fuel-Cells/Solar-Cells:
Zijie Lu Hungoo Cho
A. Karatrantos Y. Chang
D. Lentz
Collaborators: Collaborators:
T.C. Chung (PSU)
J. Runt (PSU)
R. Krishnamoorti (UH)
R. Vaia (AFRL)
C. Wilkie (Marquette)
M. Jimenez-Gasco (PSU)
D. Macdonald (PSU)
J. Genzer (NCSU)
J. Floros (PSU)
C. Randall (PSU)
R. Hedden
Postdocs: Postdocs:
Lixin Wu
Yang Jiang
Hiroyoshi Nakajima
M. Rackaitis
S. Chowdhury
Jin-Huh Young
George Polizos
Jinguo Zhang
K.S. Andrikopoulos
Lingbin Lu
Glenna Malcolm
Acknowledgements
Acknowledgements
all cited papers (full-text) here:
http://zeus.plmsc.psu.edu/
Manias group Manias group
...
...
Thank You
Thank You
PRESENTED BY
Evangelos Manias
Director, Polymer Nanostructures Lab
Materials Science & Engineering Dept
Penn State University
manias@psu.edu
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