Opportunities for Food Packaging Barrier...Polymer/Inorganic Nanocomposites Opportunities for Food...
Transcript of Opportunities for Food Packaging Barrier...Polymer/Inorganic Nanocomposites Opportunities for Food...
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Polymer/Inorganic NanocompositesPolymer/Inorganic NanocompositesOpportunities for Food Packaging BarrierOpportunities for Food Packaging Barrier
Evangelos ManiasDirector, Polymer Nanostructures LabMaterials Science & Engineering DeptPenn State University
814-863-2980
http://zeus.plmsc.psu.edu
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NanocompositesNanocomposites
A Definition1:
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 ).
Today’s focus:
Polyolefin/Clay Nanocomposites Barrier (…and beyond)
1 E. Manias, Nature Materials 6, 9-11 (2007)
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starting particle: agglomerate
• several μm in size (5-20 μm)
• millions of individual plateletsmorelikely
The Challenge: Achieving MiscibilityThe Challenge: Achieving Miscibility
desired
Courtesy: RA Vaia, AFRL, 2oo4
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Thermodynamic ArgumentsThermodynamic Arguments
Designing miscible nanocomposites
introduce favorable excess interactionsi.e. polymer-clay interactions better than
clay-surfactant interactions
( )( ) ( )
fillerinorganic,surfactant,polymer:,
2with
2
jijiji
ABij
LWj
LWi
LWijAB
ijLWijij
−−++ −−=
−=+=
γγγγγ
γγγγγγ
Vaia & Giannelis, Macromolecules, 30, 7990 (1997)
0<− fillersurffillerpol γγ
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Barrier properties of CompositesBarrier 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
Rel
ativ
e Pe
rmea
bilit
y
Nanocomposite(PCL Nanocomposites)
Conventionally filled systems
AB
Manias, Giannelis, et al. (1997)
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‘Tortuous Path’
Macromolecules 2001, 34, 9189
effective α alignment
Permeability Permeability vs. vs. Path Path TortuousityTortuousity
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Origins:path tortuosity
Similar Trends seenfor (Penn State work):(amorphous polymers)PDMS PU PUUPS Elastomers...(few semi-crystalline) PVA polyamides
Nanocomposites: Permeability Nanocomposites: Permeability vs. vs. StructureStructure
R. Xu, E. Manias, A.J. Snyder & J. Runt Macromolecules, 34, 337-339 (2001)
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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)
HighHigh--Barrier Barrier PUUPUU Nanocomposites:Nanocomposites:elastomeric character retainedelastomeric character retained
R. Xu, E. Manias, A.J. Snyder & J. Runt Macromolecules, 34, 337-339 (2001)
Still Highly Rubbery !!Still Highly Rubbery !!
barrier incr. bybarrier incr. by 500%500%modulus incr. modulus incr. 500%500%strength incr.strength incr. 400%400%
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Wilson high performance tennis ballsWilson high performance tennis balls
http://www.wilsonsports.com.au/tennis/doublecore.html
*InMat Inc. Air D-Fence Butyl-Rubber/Vermiculite nanocompositeWD Callister “Materials Science and
Engineering” 7th Ed. (Fig. 16.19)
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Typical tactoid orientationTypical tactoid orientation
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Orientated TactoidsOrientated Tactoids
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Strategies to Orient Strategies to Orient nanofillersnanofillers
Sd = 0.8 @ mg systemsabove 20mg sample aligned
with 1500VAC for 10min @ AFRL
Sd = 0.6 @ kg/h systems
above made at 50–150 lb/h blow molding *
(2D nanoparticles)(2D nanoparticles)Electric-field AlignmentEpoxy/Epoxy/MMTMMT
Flow-induced AlignmentPE/PE/MMTMMT
* E. Manias, J. Zhang, MM Jimenez-Gasco, et al. Macrom. Rapid Comm., 30, 17-23 (2009)
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What are effective aspectWhat are effective aspect--ratios?ratios?
0 200 400 600 800
0.0
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0.8
1.0
R
elat
ive
Per
mea
bilit
y (P
com
p/Ppo
lym
)
filler aspect ratio (a)
φ=0.03 Nielsen modified Nielsen modified Cussler-Aris Fredrickson-Bicerano
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0.00 0.05 0.10 0.15 0.200.0
0.2
0.4
0.6
0.8
1.0
R
elat
ive
Per
mea
bilit
y (P
com
p/Ppo
lym
)
volume fraction of filler (φ )
a=200 Nielsen modified Nielsen modified Cussler-Aris Fredrickson-Bicerano
How much filler does it take?How much filler does it take?
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100μm
Poly(ethylene oxide)Poly(ethylene oxide) PolypropylenePolypropylene syndiosyndio‐‐PolystyrenePolystyrene
PEO/3 wt% PEO/3 wt% mmtmmt PP/3 wt% PP/3 wt% mmtmmt sPS/3 wt% sPS/3 wt% mmtmmt
Path Path TortuousityTortuousity around the fillers is around the fillers is notnot thethemost relevant quantity for crystalline polymersmost relevant quantity for crystalline polymers
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More effective barrier structuresMore effective barrier structures
HouseHouse‐‐ofof‐‐Cards Structures Filler SequestratioCards Structures Filler Sequestration at Interfacesn at Interfaces
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More effective barrier More effective barrier structuresstructures
HouseHouse‐‐ofof‐‐Cards Structures Filler SequestratioCards Structures Filler Sequestration at Interfacesn at Interfaces
200nm
M.Okamoto, P.H.Nam, P.Maiti, et al.Nano Letters, 1: 295 (2001)
Chung, Mason, Heidecker, ManiasPatent Pending, WO/2008/094167
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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 barriermoving on ...beyond barrier
One approach, one can add other polymers:
LLDPE-graft-MAH / mmt LDPE-random-VA / mmt
Bridging !!
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110 115 120 125 130 135 1400
2
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16
0
10
20
30
Sealing Temperature ( °C )
Sea
l Stre
ngth
( N
/cm
)
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
Frac
ture
Stre
ngth
( M
Pa
)
easy-openstrengths
HeatHeat--sealing: PEsealing: PE--based nanocompositesbased 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
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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 fracturenanocomposites w/ prescribed fracture
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(nanocomposite PE-MAH / alkyl-MMT diluted by EVA & PE)
110 115 120 125 130 135 1400
2
4
6
8
10
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0
5
10
15
20
25
30
Seal
Stre
ngth
( N
/cm
)
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
Frac
ture
Stre
ngth
( M
Pa )
LDPE-random-VA
2Me-2alkyl-N+ MMT
E. Manias, J. Zhang, et al., Macromolecular Rapid Comm. 30: 17 (2009)
nanocomposites w/ prescribed fracturenanocomposites w/ prescribed fracture
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Strategy to introduce new functionalitiesStrategy to introduce new functionalities
Our best performing polyolefinnanocomposites are basedon alkyl-ammonium surfactant-OLSand are not antimicrobial
How can we design a compositethat affords antimicrobial activity?
Employ surfactants on the fillers that:have antimicrobial activity
andstill promote dispersion and good materials properties !
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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%
Dia
met
er (c
m)
Time (Day)
Cationic surfactant candidates for Cationic surfactant candidates for OLSOLS
DDOAB
BDDACPEDPA
“alkyl”-only
benzyl-containing ethylene-oxide based
Penicillium roqueforti
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Antimicrobial activity maintained even for Antimicrobial activity maintained even for surfactants tethered surfactants tethered (immobilized)(immobilized) on LSon LS
0 1 2 3 4 5 6 7 8
0123456789
10 Control MMT-DDOAB MMT-BDDAC MMT-PEDPA
Dia
met
er (c
m)
Time (Day)
P. roqueforti
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Antifungal PE nanocomposite filmsAntifungal PE nanocomposite films
Control 6%MMT-BDDAC6%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
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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-BDDAC6%MMT-DDOAB 9%MMT-BDDAC
Antifungal PE nanocomposite filmsAntifungal PE nanocomposite films
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SummarySummary
Polymer/organoclay nanocomposites offer: concurrent property improvements (barrier + +)control of nanostructures at ton quantities (using industry’s 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 !!
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Grad. students:Grad. students:Ken StrawheckerZhiming WangVikram KuppaSung Woo WeeAlexei KisselevMatt HeideckerGreg HogsheadTheresa FoleyPonusa SongptiyaNgoh ManokruangRomesh PatelFelipe Salcedo Financial Support:Financial Support:NIST NSF PDA DoE ONR AFOSR
Air Products UTC/IFC BAYER MATSCCoca-Cola Asahi-Kasei Arrow-BioMedSumitomo Chem PPG Samsung Kraft
Fuel-Cells/Solar-Cells:Zijie Lu Hungoo ChoA. Karatrantos Y. ChangD. 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 JiangHiroyoshi NakajimaM. RackaitisS. ChowdhuryJin-Huh YoungGeorge PolizosJinguo ZhangK.S. AndrikopoulosLingbin LuGlenna Malcolm
AcknowledgementsAcknowledgements all cited papers (full-text) here:http://zeus.plmsc.psu.edu/
Manias groupManias group
...
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Thank YouThank You
PRESENTED BY
Evangelos ManiasDirector, Polymer Nanostructures LabMaterials Science & Engineering DeptPenn State [email protected]
Please remember to turn in your evaluation sheet...