Antec Nanocor Tie Lan 5 07[1]
Post on 01-Jan-2016
37 Views
Preview:
DESCRIPTION
Transcript
1
Nanocomposite Materials for Nanocomposite Materials for Packaging ApplicationsPackaging Applications
Tie LanGeneral ManagerNanocor, Inc.1500 Arlington Heights, IL 60004USA
2
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
3
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
4
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)
5
Nanoclay
Bentonite
Nanoclay
Selective Mining
Purification &Surface Modification
Ancient Clay
montmorillonite
Kaolinite
Quartz
Silica
Lime stone
7
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
8
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%
9
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
10
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)
11
Nanocomposites
Hydrophiilic Hydrophobic
1st StepSurface Treatment
Nanocomposites
Hydrophobic
Monomer Polymerization
NanocompositeNanocompositeNanomerNanomer®®
Melt Compounding
Polymer MeltPolymer Melt
12
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
13
• 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)
14
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
16
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
17
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.
18
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
19
Co-injection MoldingKortec, Inc.
Stretch Blow Molding
Heat
Pressure
PET/Multilayer Bottles
Oxygen Sensitive Products
21
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
22
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
23
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
24
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
26
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
27
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
28
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
29
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%
30
• 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
31
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.
top related