1. 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

2. 2 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.

3. 3 Halloysite Nanotubes (HNT)

4. 4 Platy Clays Exfoliation required Complex chemistry Non-standard equipment Dispersion challenges

5. 5 Ease of processing: - No exfoliation - Standard processing equipment Improved Dispersion Effective coupling to polymer Compatible with more polymer systems Halloysite Nanotubes

6. 6 Applications Platy Clays - Reinforcement (plastics) - Barrier (packaging films) - Dyeable (fibers) Halloysite Nanotubes (HNTs) - Reinforcement (plastics) - Emerging –Controlled release: –Antimicrobial –Fragrances

7. 7 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

8. 8 Cornell Laboratory ExtruderManufacturing Scale Extruder DSM twin screw Microcompounder – 5g capacity Werner – Pfleiderer 29mm, 44:1 – 10kg/hr. 100 rpm – Co-rotating, under flowing N 2 400 rpm - Co-rotating 250°C operation, single controller 250°C operation, multiple zone controlled Extrusion Comparison

9. 9 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

10. 10 Values relative to neat nylon Lab Scale Validation Nylon/5% HNT

11. 11 Pilot Scale Trial – Nylon/HNT Dynamic Mechanical Analysis

12. 12 Pilot Scale Trial – Nylon/HNT Dynamic Mechanical Analysis

13. 13 Nylon/20% HNT BSE ESEM Fracture Image

14. 14 SurfaceFracture Nylon/30% HNT BSE ESEM Images

15. 15 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.

16. 16 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% HNT Lab Scale

17. 17 Polypropylene – Pilot scale Elastic Modulus

18. 18 Polypropylene – Pilot Scale Tensile Strength and Elongation

19. 19 Polypropylene/13% HNT BSE ESEM Fracture Image

20. 20 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

21. 21 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