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Nanocomposite Materials for Nanocomposite Materials for Packaging ApplicationsPackaging Applications

Tie LanGeneral ManagerNanocor, Inc.1500 Arlington Heights, IL 60004USA

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OutlineOutline

• Concept of Nanocomposites• Manufacturing Technologies• Enhanced Properties• Applications in Packaging

Nanotechnology

Nanotechnology concepts have been widely adopted:• Biology and medicine• Electronics and photonics• Patterning and nanofabrication• Quantum phenomena• Sensing and actuating• Materials: synthesis or self-assembly• Materials: properties, characterization, modeling or tools

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Nanotechnology

Nanotechnology in our daily life:• Faster and smaller computers• Light and bigger storage media• More potent medicines• More fuel efficient cars• Fresher and tastier foods and beverages

Nanotechnology

Nanotechnology in Plastics• nano-sized particles into plastic resin

nanoclaysMechanical reinforcementBarrier improvement Flame retardation

carbon nano-tubes/nano-graphiteImproved conductivities

nano oxidesUV resistance

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Nanocomposites

From composite to nanocomposite:One continuous phase and at least one discontinuous phase

• At least one dimension in 100-nm scale

Nanoclay platelets are one-ten thousandth the diameter of a human hair!!

Nanoclay (montmorillonite)

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Nanoclay

Bentonite

Nanoclay

Selective Mining

Purification &Surface Modification

Ancient Clay

montmorillonite

Kaolinite

Quartz

Silica

Lime stone

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US Patents: 6,050,509 and 6,235,533

Nanoclay

Nanoclay

montmorillonite

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Nanoclay platelets are one-ten thousandth the diameter of a human hair!!

Nanoclay (montmorillonite)

400 nm

TEM of Nanoclay Dispersed in Plastics1 nm

Nanoclay platelets are one-ten thousandth the diameter of a human hair!!

200-300 nm

Nanocomposite

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Clay Platelets Create Tortuous PathPMatrix

(Matrix Volume Fraction)*(Pmatrix)1 + (Clay Volume Fraction)*(Clay Aspect Ratio)/2Pnanocomposite =

Barrier Enhancement: Tortuous Path

L. E. Neilson, J. Macromol. Sci. (Chem.), A1(5), 929-942 (1967)

PMatrix

(Matrix Volume Fraction)*(Pmatrix)1 + (Clay Volume Fraction)*(Clay Aspect Ratio)/2Pnanocomposite =

Barrier Enhancement: Tortuous Path

L. E. Neilson, J. Macromol. Sci. (Chem.), A1(5), 929-942 (1967)

What does it take to reduce 50% permeability?

Aspect ratio Volume %20 9%200 1% 400 0.5%

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Mechanism for Barrier Improvement

PolymerFilm

Tortuous Path

Dispersed Nanomer®

• Barrier property enhancement

• Mechanical properties improvement• Increase stiffness without loss of flexibility• Increased dimensional stability

• Chemical and thermal stability

• Flame retardation in combination with FR agents

• Processing Characteristics

Nanocomposites

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Nanocomposites

Leading international producer and marketer of Bentonite clay based products Major markets: Metal casting, Pet care products, Water proofing products, Waste water treatment, , Detergents, Oil drilling, Cosmetics, and plastic additives

Headquartered in Arlington Heights, Ill., AMCOL operates 68 facilities in Asia, Australia, Europe and North America. The Company employs 1,750+ employees in more than 26 countries. The Company, established in 1927.

www.amcol.com (NYSE: ACO)

nanoclay based plastic additives

Nanocomposites

Tactoid(hundreds to thousands

of layers)

Single Layer (1 nm thick)Clay Particles

(10~20 um)

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Nanocomposites

Hydrophiilic Hydrophobic

1st StepSurface Treatment

Nanocomposites

Hydrophobic

Monomer Polymerization

NanocompositeNanocompositeNanomerNanomer®®

Melt Compounding

Polymer MeltPolymer Melt

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Nanocomposites

Basal Spacing Change of Nanomer in Nano-PA6 Production Process-XRD

0

100

200

300

400

0 5 10 15 20 252Theta

Inte

nsity

(cou

nts)

1.3 nm

1.8 nm3 nm

disordered

Nanocomposites

Nano-PA6 was the first clay-plastic nanocomposite

In situ polymerization

Nanopolymer Corp. Taiwan.80,000 lb/day

CP Polymers

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• In situ polymerization process with patented technology• FDA/EU approval status for direct food contact

C

N+

H H

O OH

H

C

N+H H

O OH

H

C

N +

H H

O OH

H

I.24TL

NHC O

M onom ere-caprolactam

HN

C

N+

H H

O

H

CO

NH

HN

C

N+

H H

O

H

HN CO

NH

C

N+H H

O

H

CO

NH

Nylon 6 N anocom posite

Nanocomposites

Nano-PA6

Barrier Improvement of nano-PA6

0

1

2

3

OT

R (c

c-m

il/1

00in

2 .day

)

0 2 4 6 8

I.24T L Loading (%)

-48% -64%-71%

-82%

Oxygen

0

100

200

300

400

I.24T L loading (%)

WV

TR(g

mil/

m2

day)

0% 2% 4% 6%

-48%-68%

-82%

Water Vapor

(Cast Films)

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Barrier Improvement of nano-PA6

0102030405060708090

0 4% I.24TL

cc.m

m/m

2 d

-63%

Helium

(Cast Films)

Barrier Improvement of nano-PA6 (Cast Films)

0%RH

65%RH90%RH

0

1

2

3

4

5

6

7

0%RH

65%RH

90%RH

0%2% 4%

15

OTR (65%RH, RT)

0

0.5

1

1.5

2

2.5

% nanom er

cc.m

il/10

0in2

day

-62%

Pure PA6

nano-PA 64% Nanomer

Barrier Improvement of nano-PA6 (Blown Films)

Film Mechanical Properties of Nano-PA6

Cast Monolayer Films (20-30 micron)Flow Direction

650352703%Nano-PA6

70012150n/aNylon 6 B135WP

Strain @ break (%)

Yield Strength

(Mpa)

Young’s Modulus (Mpa)

%Nano Loading

Testing Sample

Perpendicular Direction

550283803%Nano-PA6

60016200n/aNylon 6 B135WP

Strain @ break (%)

Yield Strength

(Mpa)

Young’s Modulus (Mpa)

%Nano Loading

Testing Sample

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Nanocomposites

• Same Tm, Tg ---Same processing • Smart design

Use less resin ---same strength and barrierPE//PA6//PE = 40//20//40

PE//nano-PA6// = 40//10//40 10% saving in film weight

• Flexible Packaging: multi-layer polyolefin/PA-6 films cast and blown films

• Extrusion Coating of Paperboard• barrier to moisture and oxygen• juice packaging, milk cartons

• Stand-up Pouches: barrier, strength• BOPA: barrier, strength

• Total package solution: barrier improvement along with high stiffness and high heat resistance

Nanocomposites

Applications of Nano-PA6

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Nanocomposites

MXDA Adipic acid

Nylon-MXD6

H HNCH2 CH2NHC(CH2)4C

O O

OHn

H2NCH2 CH2NH2 HOOC(CH2)4COOH+

H2O +

Nano-Nylon MXD6

Nano Nano -- Nylon MXD6 Nylon MXD6 --Ultra Barrier SystemUltra Barrier System

Commercial StatusProduct Name:

Imperm® 103 and 105 Applications:

Multilayer bottlesMultilayer films with PET, PA, and PP

Regulatory: Fully approved for multilayer applications for all types of foods under FDA’s Conditions of Use A through H.

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Oxygen Barrier of nano-MXD6

Imperm 103 and 105

Oxygen

0.58 1.36 g･mm/m2･dayWVTR(40oC, 90%RH)

0.15 0.30 cc･mm/m2･day･atmCO2TR(23oC, 60%RH)

0.02 0.09 cc･mm/m2･day･atmOTR(23oC, 60%RH)

Imperm a)MXD6 a)UnitsProperty

a) Non-oriented monolayer film

Imperm® 103 Barrier Properties

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Co-injection MoldingKortec, Inc.

Stretch Blow Molding

Heat

Pressure

PET/Multilayer Bottles

Oxygen Sensitive Products

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CO2 Sensitive Products

Barrier LayerMXD6EVOH

PET/Multilayer Bottles

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O2 SHELFLIFE

0

1

2

3

0 20 40 60 80 100 120 140 160 180

Storage(day)

Perm

eate

d ox

ygen

am

ount

(ppm

)

5 wt% Imperm 103

5 wt% N-MXD6PET

3 weeks 7 weeks 24 weeks

CO2 SHELFLIFE

85

90

95

100

0 5 10 15 20 25

Storage time (week)

CO

2 r

ete

nti

on

(%

)

5% Imperm 103

5% N-MXD6PET

7 weeks 13 weeks 22 weeks

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Days on test

0 50 100 150 200

Net

oxy

gen

ingr

ess,

ppm

(w/v

)

0

1

2

3

4

5

1% dfc/5% Imperm 103PET/5% Imperm 103PET monolayer

1 ppm O2

IMPERM® COMBINATION WITH AMOSORB®

Beer bottles500 ml, 28 gImperm 5% 23C storage

• 500ml, 28-g PET/Imperm/PET, 3% barrier• 1% Amosorb in PET layers

Delivers shelf-life:Oxygen: 1 ppmCarbon Dioxide: 6 month<10% loss (3 V)

Solutions for PET Beer Bottles

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212128Weight (g)

35n/aBarrier content (%)

959550CO2 Shelf-life (day)(RT, 4V, 17.5% loss)

2x2xBIF

Multi-ImpermMulti-MXD6 Mono-PET Bottle (12 oz)

Solutions for PET CSD Bottles

• 12 oz, 21 g Multilayer, 3% Imperm

Delivers shelf-life:Carbon Dioxide: 3 month<17.5% loss (4 V)

Solutions for CSD Bottles

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Imperm for Food Packaging

• Imperm® is designed for PET multilayer applications: Beer, CSD and Juices

• Multilayer PP containers, single serve, retort

• Imperm® is fully cleared for use as non-food contact layersAll food group and Condition-of-Use A

• Synergy with oxygen scavengers, e.g., Amosorb®

N-MXD6 Imperm®

0.001

0.01

0.1

1

10

50 60 70 80 90 100

R.H. (%)

OTR

(cc･

mm

/m2 ･

day･

atm

)

EVOH (ethylene 32mol% )

Imperm 107

23 °C

Imperm 105

Oxygen Barrier of nano-MXD6

25

35 °C

Imperm 105

Oxygen Barrier of nano-MXD6

0.001

0.01

0.1

1

10

60 70 80 90 100

R.H. (%)

OTR

(cc.

mm

/m2 .d

ay.a

tm)

Imperm 105

EVOH (ethylene 38mol%)

I I I

35 °C

Nanocomposites for Military Food Packaging

ObjectivesEliminate Foil Layer in Meal Ready to Eat (MRE) Packaging

Capability of Microwave Processing, High Pressure Pasteurization, Radio Frequency Sterilization.

Reduction of Stress-Cracks and Pin-Holes

Reduce Processing Steps

(No-lamination required)

Decrease MRE weight

Reduce Solid Waste

MRE Barrier Specifications:

OTR ≤ 0.06cc/m²-day-atm

WvTR ≤ 0.01g/m²-day-atm

Shelf Life = 3 Years at 80˚F, 6 Months at 100˚F

US ARMY NATICK SOLDIER RD&E CENTER. The Science Behind the Warrior: Yesterday, Today and TomorrowUS ARMY NATICK SOLDIER RD&E CENTER. The Science Behind the WarUS ARMY NATICK SOLDIER RD&E CENTER. The Science Behind the Warrior: Yesterday, Today and Tomorrowrior: Yesterday, Today and Tomorrow

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US ARMY NATICK SOLDIER RD&E CENTER. The Science Behind the Warrior: Yesterday, Today and TomorrowUS ARMY NATICK SOLDIER RD&E CENTER. The Science Behind the WarUS ARMY NATICK SOLDIER RD&E CENTER. The Science Behind the Warrior: Yesterday, Today and Tomorrowrior: Yesterday, Today and Tomorrow

Nanocomposites for Military Food Packaging

MRE Retort Pouch Structure

Imperm Nanocomposite MXD6 Multilayer FilmNylon Layer = 83μm

LDPE Tie Imperm 105 Tie LDPE

US ARMY NATICK SOLDIER RD&E CENTER. The Science Behind the Warrior: Yesterday, Today and TomorrowUS ARMY NATICK SOLDIER RD&E CENTER. The Science Behind the WarUS ARMY NATICK SOLDIER RD&E CENTER. The Science Behind the Warrior: Yesterday, Today and Tomorrowrior: Yesterday, Today and Tomorrow

Nanocomposites for Military Food Packaging

SEM

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Oxygen Transmission of Multilayer MXD6 and Imperm Films

US ARMY NATICK SOLDIER RD&E CENTER. The Science Behind the Warrior: Yesterday, Today and TomorrowUS ARMY NATICK SOLDIER RD&E CENTER. The Science Behind the WarUS ARMY NATICK SOLDIER RD&E CENTER. The Science Behind the Warrior: Yesterday, Today and Tomorrowrior: Yesterday, Today and Tomorrow

MRE Specification

0.06

2.02

0.97

0.61

< 0.050

0.5

1

1.5

2

2.5

0 60Relative Humidity (%)

OTR

(cc/

m2-

day)

Multilayer MXD6 - 11.5 mil

Multilayer Imperm Nano MXD6 - 10.0 mil

Nanocomposites for Military Food Packaging

• Improved barrier @ high RH and temperature

• High performance resin for PET bottles

• Same processing as neat MXD6 in cast and blown film processing

• Reduced gel formation in recycling process

• Excellent barrier for retort applications

Advantage of nano-MXD6 Resin

Nano Nano -- Nylon MXD6 Nylon MXD6 --Ultra Barrier SystemUltra Barrier System

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Blend of nano-PA6 with nano-MXD6

0

0.01

0.02

0.03

0.04

0.05

0.06

100% Imperm 20% NF3040; 80%Imperm

30% NF3040; 70%Imperm

OTR

(cc

mm

/m2

day)

00.050.1

0.150.2

0.250.3

0.350.4

0.450.5

100% Imperm 20% NF3040;80% Imperm

30% NF3040;70% Imperm

100% NF3040(PA6 w ith 4%

Nanomer)

OTR

(cc

mm

/m2

day)

Reduce cost and enhanced processing

Amorphous PA Nanocomposite

• Selar from DuPont and G21 from EMS• Can make the composite through blending with

PA 6 nanocomposite masterbatch • Barrier increases with the addition of Nanoclay

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0

0.5

1

1.5

2

2.5

3

3.5

4O

TR (c

c m

il/10

0in2

day

) 0%RH

65%RH

0% Nanomer 4% Nanomer

-45%

-45%

Blend of 80% amorphous PA and 20% of nanoMax®-NPC NPC: in-situ master batch with 20% Nanomer

Amorphous PA Nanocomposite

PP and HDPE NanocompositesLet down from nanoMax® HDPE, nanoMax® PP

OTR of HDPE and PP nanocomposite

0

10

20

30

40

50

60

70

OTR

(cc

mm

/m2

day)

HDPE9608XD

3.5% Nanomerin HDPE

PP 4772(Exxon)

3.5% Nanomerin PP 4772

57% 20%

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• Combination of passive with active barrier mechanism

• Nanoclay as coating additives to enhance barrier

• Nanoclay as additives to enhance barrier of bio-degradable resins

• Nanoclay as moisture scavenger in multilayer structure to protect barrier layer

Recent Development

Nanocomposite MarketData Source: BCC Researchwww.bccresearch.com

Global Consumption of Nanocomposites

Average Annual GrowthRate (AAGR)24.4%

$0$100$200$300$400$500$600$700$800$900

2004 2006 2008 2010 2012

year

Glo

bal C

onsu

mpt

ion

(mill

ion

$)

$252$288

$857

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Packaging

Transportation FR Compounds

Coating

Nanocor Markets

Summary• Nanoclays are effective additives to plastics.• Plastic nanocomposite are commercially produced and

used.• Nanocomposite resins offer same processability.• Plastic nanocomposite are the same class of plastics but

with better properties:• Higher performance package with same amount of resin• Equal performance with less resin.

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Thank You