nylon/halloysite nanotube composites dr. cathy fleischer, president and cto prof. emmanuel...
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Nylon/Halloysite Nanotube Composites
Dr. Cathy Fleischer, President and CTO
Prof. Emmanuel Giannelis, Cornell University
Dr. Aaron Wagner, R&D Director
15 Schoen Place
Pittsford, NY 14534
Phone: 585-267-4850
Fax: 585-267-4855
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• Company founded December 2004
• Initial focus on halloysite nanotube applications in many markets
• Current focus on commercialization of nanocomposite products
• Longer term focus on filled tubes
NaturalNano, Inc.
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Halloysite Nanotubes (HNT)
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Platy Clays
• Exfoliation required
• Complex chemistry
• Non-standard equipment
• Dispersion challenges
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• Ease of processing:- No exfoliation- Standard processing equipment
• Improved Dispersion
• Effective coupling to polymer
• Compatible with more polymer systems
Halloysite Nanotubes
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Applications
• Platy Clays
- Reinforcement (plastics)
- Barrier (packaging films)
- Dyeable (fibers)
• Halloysite Nanotubes (HNTs)
- Reinforcement (plastics)
- Emerging
– Controlled release:
– Antimicrobial
– Fragrances
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Conventional Filler Nanoclay
Features:• High strength
• Not brittle
• Lower weight
Process:• Non-standard equipment
• Specialized chemistry
• Limited compatibility
Features:• High strength
• Brittle
• High weight
Process:• Standard equipment
HNTs
Features:• High strength
• Not brittle
• Lower weight
Process:• Standard equipment
• Lower process costs
• Broad compatibility
HNT Nanocomposites
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Cornell Laboratory Extruder Manufacturing Scale Extruder
DSM twin screw Microcompounder – 5g capacity
Werner – Pfleiderer
29mm, 44:1 – 10kg/hr.
100 rpm – Co-rotating, under flowing N2
400 rpm - Co-rotating
250°C operation, single controller
250°C operation, multiple zone controlled
Extrusion Comparison
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• Tensile testing
• Dynamic Mechanical Analysis (DMA)
• Environmental Scanning Electron Microscopy (ESEM)
- FEI Quanta 200 with a Field Emission Gun
- Operating at 25 KeV, working distance of 10mm
- Low Vacuum
Testing and Analytical Techniques
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Modulus
Tensile Strength
Elongation
HNT as received
Platy clay
NaturalNano process
0
0.2
0.4
0.6
0.8
1
1.2
1.4
1.6
1.8
Values relative to neat nylon
Lab Scale ValidationNylon/5% HNT
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0
1000
2000
3000
4000
5000
6000
-50 0 50 100 150 200 250
Temperature (°C)
Sto
rag
e M
od
ulu
s (M
Pa
)
20% HNT
Neat Nylon 6
5% HNT
Pilot Scale Trial – Nylon/HNT Dynamic Mechanical Analysis
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0
2000
4000
6000
0 50 100 150 200
Temperature (°C)
Sto
rag
e M
od
ulu
s (
MP
a)
Neat, No heat history
HNT 6.79%
HNT 21.5%
HNT 32.8%
HNT Letdown 7%
Pilot Scale Trial – Nylon/HNT Dynamic Mechanical Analysis
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Nylon/20% HNT BSE ESEM Fracture Image
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Surface Fracture
Nylon/30% HNT BSE ESEM Images
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Nylon Nanocomposite Summary
• Mechanical property enhancement obtained in the lab are reproduced at pilot scale.
• DMA results indicate that mechanical property improvements are enhanced at elevated temperatures.
• Excellent dispersion is observed up to 30% HNT levels.
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• Increase in decomposition temperature
– PP/PP-g-maleic anhydride (14/1) /5% HNT composites
– Decomposition temperature increased from 370°C to 420°C (temperature at 1.5% weight loss)
Polypropylene/5% HNTLab Scale
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600
700
800
900
1000
1100
1200
0.0 2.0 4.0 6.0 8.0 10.0 12.0 14.0
% HNT
Ela
stic
Mo
du
lus
(MP
a)
Polypropylene – Pilot scale Elastic Modulus
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34
36
38
40
0.0 2.0 4.0 6.0 8.0 10.0 12.0 14.0
% HNT
Te
nsi
le S
tre
ng
th (
MP
a)
0
50
100
150
200
250
300
350
400
Elo
ng
atio
n (%
)Polypropylene – Pilot Scale Tensile Strength and Elongation
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Polypropylene/13% HNT BSE ESEM Fracture Image
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• Strength and modulus improvements are observed without sacrificing elongation.
• 2X improvement in elastic modulus is obtained at levels of 8-10% HNTs.
• Good dispersion is observed up to levels of 10 -13% HNTs.
Polypropylene Nanocomposite Summary
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• Nylon and polypropylene HNT nanocomposites have enhanced mechanical properties, without sacrificing elongation.
• Highly concentrated nanocomposite additives were made which exhibit excellent dispersion.
• Lab scale demonstrations were validated at the pilot scale.
• Future experiments will be conducted to drive to higher concentration and greater property enhancement.
Conclusions and Path Forward