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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

Full Talk

Polymer Intercalated Clay Nanocomposite

Changde Zhang

Department of Chemistry, LSU

February 11, 2005

outline
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.

clay species and structure
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

clay species and structure4
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.

clay species and structure classification of phyllosilicate related to clay minerals
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.

four types of polymer clay composite
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.

why picn
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.

principle of picn
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.

principle of picn9
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.

applications of picn
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.

approaches for preparing picn
Approaches for preparing PICN
  • 3 categories:
      • In-Situ Polymerization
      • Melt Insertion
      • Polymer solution insertion
  • First step: modification of Clay Surface: Cation-Exchange
picn by in situ polymerization

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.

picn by in situ polymerization13

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.

picn by in situ polymerization14
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.

slide15

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.

polymer intercalated clay by melt insertion

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.

raychem

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.

slide18

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.

slide19

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.

abstract
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.

slide21

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.

preparation of peo clay nanocomposite
Preparation of PEO clay nanocomposite

Synthesis of clay

Synthesis of PEO clay nanocomposite

slide23

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

figure 3 x ray powder diffraction pattern of slh the inset shows the major diffraction peaks
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
figure 4 x ray powder diffraction pattern of peo the inset shows the major diffraction peaks
Figure 4. X-ray powder diffraction pattern of PEO. The inset shows the major diffraction peaks.
  • Sharp peak 4, 6: big crystal
slide26
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
slide27

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
slide28
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.
slide29

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.
slide30

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.
slide31

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
slide32
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.

slide33

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.

figure 12 tem of a 1 1 peo slh mass ratio nanocomposite membrane
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.

conclusions
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
acknowledgements
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.
references
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.