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

18

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