Polymer Intercalated Clay Nanocomposite

1
Polymer Intercalated Clay Nanocomposite
Full Talk

• 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

• Two main structure of Clay species
• 11 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
• 21 type One octahedral aluminia sheet
  sanwitched between 2 tetrahedral silica sheets
  (Montmorrillonite, smectites, Mica Talc)

tetrahedral
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 ?-amino acid) e-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, LtdNew 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
PICN by In-situ Polymerization
Recent progress in preparing PICN

• 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
PICN by in-situ polymerization
Recent progress in preparing PICN

• 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
3M
Recent progress in preparing PICN

• 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
Polymer Intercalated Clay by Melt Insertion
Recent progress in preparing PICN

• 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
Raychem
Recent progress in preparing PICN

• Poly (ethylene vinyl acetate) EVA-Clay
  Nanocomposites.
• Improved flammability, Youngs 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
GE
Recent progress in preparing PICN

• 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. Macromolecules 2002,
35, 5508.
19
In Situ SAXS Studies of the Structural Changes of
Polymer Nanocomposites Used in Battery Application
Literature Discussion
PICN by solution processing

• 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
Kairradiation (? 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 ?/(2sin?) 2p/q
24
Figure 3. X-ray powder diffraction pattern of
SLH. The inset shows the major diffraction peaks.

• Distance between clay sheet
• d00112.74Å
• 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 11 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 1.21 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 1.21 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 1.21
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 0.81
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
1.21 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 11 mass ratio.
s s0 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 Sources 2000, 89, 249.
34
Figure 12. TEM of a 11 PEO/SLH mass ratio
nanocomposite membrane.

• JEOL 100CXII TEM
• 100kV
• Copper grid (dipped into 11 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 (4.8710-3S/cm). Its
  conductivity is 4.2610-3S/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. Dalys Instruction,
  Professor Gudrun Schmidts discussion.
• Group colleagues Mrunal Thatte, Ahmad Bahamdan,
  Veronica Holmes, Codrin Daranga, Lakia Champagne,
  and Ionela Chiparus.
• Elena Loizous 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.