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Polymer Intercalated Clay Nanocomposite

Full Talk. Polymer Intercalated Clay Nanocomposite. Changde Zhang Department of Chemistry, LSU. February 11, 2005. Outline. Background and introduction : Clay species and Structure Advanced Properties of Polymer Nanocomposites Principle of polymer nanocomposite

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Polymer Intercalated Clay Nanocomposite

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  1. Full Talk Polymer Intercalated Clay Nanocomposite Changde Zhang Department of Chemistry, LSU February 11, 2005

  2. Outline • Background and introduction : • Clay species and Structure • Advanced Properties of Polymer Nanocomposites • Principle of polymer nanocomposite • Applications of polymer clay nanocomposites • Methodology for preparing polymer intercalated clay nanocomposites (PICN) • Recent progress in preparing PICN • Literature discussion: PICN with electrochemical function “In Situ SAXS Studies of the Structural Changes of Polymer Nanocomposites Used in Battery Application” Sandi, G.; Joachin, H.; Seifert, R.; Carrado, K. A. Chem. Mater. 2003, 15, 838.

  3. Clay species and Structure tetrahedral • Two main structure of Clay species: 1:1 type: alumina octahedral (metal –hydroxide) sheet sitting on the top of silica tetrahedral(Silicone-oxygen) sheet: serpentines; Kaolins Nonswelling due to the binding of oxygen and hydrogen between two sheets 2:1 type: One octahedral aluminia sheet sanwitched between 2 tetrahedral silica sheets (Montmorrillonite, smectites, Mica; Talc) octahedral tetrahedral Background and Introduction

  4. Clay species and structure Cairns-Smith, A. G. Clay Minerals and the Origin of Life, Cairns-Smith, A. G., Hartman, H., Eds.;Cambridge University Press: New York, USA, 1986;pp 17-18.

  5. Clay species and Structure: Classification of phyllosilicate related to clay minerals ax refers to an O10(OH)2 formula unit for smectite, vermiculite, mica, and brittle mica. bOnly a few examples are given. Background and Introduction Bailey, S. W. Layer Silicate Structures, Cairns-Smith, A. G., Hartman, H., Eds.;Cambridge University Press: New York, USA, 1986;pp 26. ax refers to an O10(OH)2 formula unit for smectite, vermiculite, mica, and brittle mica. bOnly a few examples are given.

  6. Four types of Polymer-Clay composite "Polymer-Clay Nanocomposites: Synthesis and Properties," S. Qutubuddin and X. Fu, in Nano-Surface Chemistry, M. Rosoff, ed., Marcel Dekker, p. 653-673, 2001.

  7. Why PICN? • Popular clay in PICN: Montmorillonites clay (smectite type) • Japanese Toyota group: montmorillonite exchanged by ω-amino acid) + ε-caprolactam 1993 • Advanced performance: • Gas barrier • Fire proof • Improved mechanical properties (tough, increased tensile strength and impact strength) • Better flow property • Better electronic property and optical property Krishnamoorti, R.; Varia, R. A., Ed. Polymer Nanocomposites; American Chemical Society: Washington, DC, 2001.

  8. Principle of PICN • Nanoscale morphologies model: Equilibrium distance between uniformly aligned and dispersed plates of thickness at various fractions of plates. Vaia, R. A.; Giannelis, E. P. MRS Bulletin 2001, 26, 394.

  9. Principle of PICN B Tortuous path model for Gas Barrier material: tortuous path due to high aspect ratio Model: Pf/Pu = Vp/1 + (L/2w)Vf Nielson equation L/W ratio: A Beall, T. J. P. a. G. W., Ed. Polymer-Clay Nanocomposites; John Wiley & Sons, Ltd:New York, 2001.

  10. Applications of PICN • Fire-proof material: substitute PVC product • Anti-corrosive Coating: Epoxy/Clay • Barrier packaging material (film and container: gas barrier and liquid barrier): EVOH film Recyclable/disposable bottle (PE/clay) • Hand-carried device for battle-field • Automotive and Air space PP/Clay, PS/Clay, Nylon/Clay PB/Clay (Reinforced tire) • Electrical device: Polymer solid electrolyte PEO/Clay/Li+ • Optical transparent material Krishnamoorti, R.; Varia, R. A., Ed. Polymer Nanocomposites; American Chemical Society: Washington, DC, 2001.

  11. Approaches for preparing PICN • 3 categories: • In-Situ Polymerization • Melt Insertion • Polymer solution insertion • First step: modification of Clay Surface: Cation-Exchange

  12. Recent progress in preparing PICN PICN by In-situ Polymerization Free Radical Polymerization • Modification of clay surface with different cation species • Modification of clay surface with monomer cation AIBN + Zeng, C.; Lee, L. J. Macromolecules 2001, 34, 4098-4103. Huang, X.; Brittain, W. J. Macromolecules 2001, 34, 3255-3260. Zhu, J.; Morgan, A. B.; Lamelas, F. J.; Wilkies, C. A. Chem. Mater. 2001, 13, 3774.

  13. Recent progress in preparing PICN PICN by in-situ polymerization • Modification of clay surface with initiator cation Huang, X.; Brittain, W. J. Macromolecules 2001, 34, 3255. Fan, X.; Xia, C.; Advincula, R. C. Lanmuir 2003, 19, 4381.

  14. PICN by in-situ polymerization • Living Free Radical Polymerization • Initiator cation for living free radical polymerization • Living anionic polymerization • Condensation polymerization Weimer, M. W.; Chen, H.; Giannelis, E. P.; Sogah, D. Y. J. AM. Chem. Soc. 1999, 121, 1615 Fan, X.; Zhou, Q.;Xia, C.; Cristofoli, W.; Mays,J.; Advincula, R. C. Lanmuir 2002, 18, 4511. Kojima, Y.; Usuki, A.; Kawasumi, M.; Okada, A.; Kurauchi, T.; Kamigaito, O. J. Polymer Science: Part A: Polymer Chemistry 1993, 32, 983-986.

  15. Recent progress in preparing PICN 3M • Epoxy-clay nanocomposites Gilman, J. W. K., T.; Morgan, A. B.; Harries, R. H.; Brassell, L.; VanLandingham, M.; Jackson, C.; U.S. Department of Commerce, Technology Administration, National Institute of Standards and Technology, 2000; pp 1-55.

  16. Recent progress in preparing PICN Polymer Intercalated Clay by Melt Insertion • PA6-clay nanocomposites were compounded by GE on a twin screw extruder. Improved flammability, strength, stiffness. Gilman, J. W. K., T.; Morgan, A. B.; Harries, R. H.; Brassell, L.; VanLandingham, M.; Jackson, C.; U.S. Department of Commerce, Technology Administration, National Institute of Standards and Technology, 2000; pp 1-55.

  17. Recent progress in preparing PICN Raychem • Poly (ethylene vinyl acetate) EVA-Clay Nanocomposites. Improved flammability, Young’s modulus Sekisui • PP-Clay Nanocomposites with improved flammability Great Lakes Chemical • PS-Clay Nanocomposites with improved flammability Gilman, J. W. K., T.; Morgan, A. B.; Harries, R. H.; Brassell, L.; VanLandingham, M.; Jackson, C.; U.S. Department of Commerce, Technology Administration, National Institute of Standards and Technology, 2000; pp 1-55.

  18. Recent progress in preparing PICN GE • PBT-clay nanocomposite with improved tensile strength Chrisholm, B. J. M., R. B.; Barber, G.; Khouri, F.; Hempstead, A.; Larsen, M.; Olson, E., Kelly, J.; Balch, G.; Caraher, J. Macromolecules2002, 35, 5508.

  19. PICN by solution processing Literature Discussion In Situ SAXS Studies of the Structural Changes of Polymer Nanocomposites Used in Battery Application Presented by Changde Zhang Department of Chemistry, LSU February 11, 2005 Main Reference: Sandi, G.; Joachin, H.; Seifert, R.; Carrado, K. A. Chem. Mater. 2003, 15, 838.

  20. Abstract In situ small-angle X-ray scattering studies have been conducted to monitor the structural changes of polymer nanocomposites upon heating. These nanocomposites are made of different mass ratios of poly(ethylene oxide) and synthetic lithium hectorite. The samples were heated under nitrogen to avoid oxidation of the organic matrix. On the basis of the in situ results, it was found that the polymer matrix losses its crystallinity at about 60 °C and the composite is stable up to 150 °C.

  21. PEO Li+ Figure 1. Schematic representation of PEO inserted lithium hectorite clay polymer electrolyte. The gallery region shows one PEO layer and exchangeable Li(I) cations.

  22. Preparation of PEO clay nanocomposite Synthesis of clay Synthesis of PEO clay nanocomposite

  23. Rigaku Miniflex diffractometer Beam: Cu Kαirradiation (λ: 1.54Å) Detector: NaI Scan Rate: 0.5o/min Step size 0.05 CCD camara X-ray diffraction: sensitive to electron cloud Bragg equation : dhkl = λ/(2sinθ) = 2π/q

  24. Figure 3. X-ray powder diffraction pattern of SLH. The inset shows the major diffraction peaks. • Distance between clay sheet: d001=12.74Å • Gallery region: 3.1Å • Clay lattice unit cell: 9.6Å

  25. Figure 4. X-ray powder diffraction pattern of PEO. The inset shows the major diffraction peaks. • Sharp peak 4, 6: big crystal

  26. Figure 5. X-ray powder diffraction pattern of a film containing a PEO/SLH 1:1 ratio. The inset shows the major diffraction peaks. • d001 increased 5.89Å. • PEO was intercalated into gallery region. • Peak 4 and 6 of PEO became broadened: PEO crystal disappeared

  27. Figure 6. In situ SAXS of a PEO/SLH 1.2:1 mass ratio filmtaken at room temperature. The inset shows the diffractionpeaks attributed to PEO and SLH. • PEO/SLH 1.2 :1 film has strong sharp peak4 and 6 of PEO. • d001 increase only 4.2Å. • Excess PEO

  28. Figure 7. In situ SAXS of a PEO/SLH 1.2:1 mass ratio filmtaken at 60 °C. The sample was heated under nitrogen at 5 °C/min. • d001 : 17Å. Gallery region became a little narrower. • Sharp peak 4 and 6 of PEO became broadened: PEO crystal disappeared.

  29. Figure 8. (a) In situ SAXS of a PEO/SLH 1.2:1 mass ratio film taken at 60, 80, 100, 120, and 150 °C. The sample was heated under nitrogen at 5 °C/min. (b) Same as (a), but with the x-axis expanded. • ≥ 60oC, sharp peaks 4 and 6 of PEO became broadened. • The loss of crystallinity of PEO is irreversible.

  30. Figure 9. (a) In situ SAXS of a PEO/SLH 0.8:1 mass ratio film taken at 60, 80, 100, 120, and 150 °C. The sample was heated under nitrogen at 5 °C/min. (b) Same as (a), but with the x-axis expanded. • ≥ 60oC, sharp peaks 4 and 6 of PEO became broadened; PEO lost its crystallinity.

  31. Figure 10. (a) In situ SAXS of a PEO/Laponite 1.2:1 mass ratio film taken at 60, 80, 100, 120, and 150 °C. The sample was heated under nitrogen at 5 °C/min. (b) Same as (a), but with the x-axis expanded. • ≥ 60oC, sharp peaks 4 and 6 of PEO became broadened; PEO lost its crystallinity. • The conductivity of PEO/Laponite film is 1 order lower than PEO/SLH. • The author guess it resulted from the 20nm SiO2 particles in PEO/SLH

  32. Figure 11. Conductivity as a function of temperature of thenanocomposite with nominal composition PEO/SLH 1:1 mass ratio. σ = σ0 exp [ - Ep / ( T – T0)] (1) T0 Tg – 50K (2) Polymer Electrolyte Reviews-1; Maccallum, J. R.; Vincent C. A., Eds.; Elsevier Applied Science: London, 1972; p 91.

  33. Transference number: the fraction of the total current carried in a solution by a given ion Dee, D. W.; Battaglia, V. S.; Redey, L.; Henriksen, G. L.; Atanasoski, R.; Belanger, A. J. Power Sources2000, 89, 249.

  34. Figure 12. TEM of a 1:1 PEO/SLH mass ratio nanocomposite membrane. • JEOL 100CXII TEM • 100kV • Copper grid (dipped into 1:1 PEO/SLH slurry and dried for 2h in vacuum at 100oC) Silica spheres (20-nm disks) are visible throughout the background.

  35. Conclusions • PEO/SLH nanocomposite was obtained using a synthetic clay SLH. • Above 60oC, PEO loses its crystallinity and the film became more conductive (4.87×10-3S/cm). Its conductivity is 4.26×10-3S/cm at RT • PEO/SLH had high transference number (~0.90). • The structure of PEO/SLH nanocomposite did not change significantly up to150oC. PEO/SLH film was stable. • PEO/SLH showed better conductivity than PEO/Laponite

  36. Acknowledgements • Professor William H. Daly’s Instruction, Professor Gudrun Schmidt’s discussion. • Group colleagues: Mrunal Thatte, Ahmad Bahamdan, Veronica Holmes, Codrin Daranga, Lakia Champagne, and Ionela Chiparus. • Elena Loizou’s discussion.

  37. References • Fan, X.; Xia, C.; Advincula, R. C. Lanmuir 2003, 19, 5381-4389. • Kojima, Y.; Usuki, A.; Kawasumi, M.; Okada, A.; Kurauchi, T.; Kamigaito, O. J. Polymer Science: Part A: Polymer Chemistry 1993, 32, 983-986. • Chrisholm, B. J.; Moore, R. B.; Barber, G.; Khouri, F.; Hempstead, A.; Larsen, M.; Olson, E.; Kelley, J.; Balch, G. ; Caraher, J. Macromolecules 2002, 35, 5508-5516. • Ishida, H.; Campbell, S.; Blackwell, J. Chem. Mater. 2000, 12, 1260-1267. • Weimer, M. W.; Chen, H.; Giannelis, E. P.; Sogah, D. Y. J. AM. Chem. Soc. 1999, 121, 1615-1616. • Huang, X.; Brittain, W. J. Macromolecules 2001, 34, 3255-3260. • Zeng, C.; Lee, L. J. Macromolecules 2001, 34, 4098-4103. • Fan, X.; Zhou, Q.; Xia, C.; Cristofoli, W.; Mays, J. Advincula, R. C. Lanmuir 2002, 18, 4511-4518. • Holmes, V. K. General Exam: Research Progress Report, Louisiana State University Chemistry Department, Baton Rouge, 2003 • Zhu, J.; Morgan, A. B.; Lamelas, F. J.; Wilkies, C. A. Chem. Mater. 2001, 13, 3774. • Fan, X.; Xia, C.; Advincula, R. C. Lanmuir 2003, 19, 4381. • Sandi, G.; Joachin, H.; Seifert, R.; Carrado, K. A. Chem. Mater. 2003, 15, 838. • Nano-Surface Chemistry; Rosoff M., Ed; Marcel Dekker, Inc.: New York, 2001; P653.

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