Transcript Independent proposal - LSU Macromolecular Studies Group

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
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
• Two main structure of Clay
species:
1:1 type: alumina
octahedral (metal –hydroxide)
sheet sitting on the top of
silica tetrahedral (Siliconeoxygen) 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)
tetrahedral
octahedral
tetrahedral
Background and
Introduction
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
Layer
Type
Group
(x=charge per formula unit) a
Subgroup
Speciesb
1:1
Serpentine-Kaolin
(x~0)
Serpentines
Chrysotile, antigorite, lizardite
amesite
Kaolins
Kaolinite, dickite, nacrite
Talcs
Talc, willemseite
Pyrophyllite
pyrophyllite
Smectite
(x~0.25-0.6)
Saponites
Saponite, hectorite, sauconite
Montmorillonites
Montmorillonite, beidellite,
nontronite
Vermiculite
(x~0.6-0.9)
Trioctahedral vermiculites
Trioctahedral vermiculites
Dioctahedral vermiculites
Dioctahedral vermiculites
Mica
(x~1.0)
Trioctahedral micas
Phlogopite, biotite, lepidolite
Dioctahedral micas
Muscovite, paragonite, illite
Brittle mica
(x~2.0)
Trioctahedral brittle micas
Clintonite, anandite
Dioctahedral brittle micas
Margarite
Chlorite
(x variable)
Trioctahedral chlorites
Clinochlore, chamosite, nimite,
pennanite
Dioctahedral chlorites
Donbassite
Di, Trioctahedral chlorites
Cookeite, sudoite
2:1
Talc-pyrophyllite
(x~0)
2:1
Sepiolite-palygorskite
Sepiolites
Sepoolite, loughlinite
inverted
(x variable)
Palygorskites
Palygorskite
ribbons
ax refers to an O (OH) formula unit for smectite, vermiculite, mica, and brittle mica.
10
2
bOnly a few examples are given.
Bailey, S. W. Layer Silicate Structures, Cairns-Smith, A. G., Hartman, H., Eds.;Cambridge
University Press: New York, USA, 1986; pp 26.
Background and
Introduction
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?
• 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
• 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 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:
Beall, T. J. P. a. G. W., Ed. Polymer-Clay Nanocomposites; John
Wiley & Sons, Ltd:New York, 2001.
A
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
• 3 categories:
 In-Situ Polymerization
 Melt Insertion
 Polymer solution insertion
• First step: modification of Clay Surface:
Cation-Exchange
Recent progress in
preparing PICN
PICN by In-situ Polymerization
Free Radical Polymerization
• Modification of clay surface with different cation species
OH
N+
P+
• Modification of clay surface with monomer cation
O
AIBN +
ClN+(CH3)3
O
N+
BrO
N+
O
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.
Recent progress in
preparing PICN
PICN by in-situ polymerization
• Modification of clay surface with initiator cation
O
N+
Br-
CN
N
O
O
N
CN
O
O
CN
N
O
O
N
CN
H2N
ClH2N
+
Br- N
N
N
N+
O
NH2
ClNH2+
Huang, X.; Brittain, W. J. Macromolecules 2001, 34, 3255.
Fan, X.; Xia, C.; Advincula, R. C. Lanmuir 2003, 19, 4381.
PICN by in-situ polymerization
O
• Living Free Radical
O
O
N
Polymerization
– Initiator cation for living free
radical polymerization
N+
• Living anionic polymerization
Cl-
Weimer, M. W.; Chen, H.; Giannelis,
E. P.; Sogah, D. Y. J. AM. Chem. Soc.
1999, 121, 1615
BrO(CH2)12N+(CH3)3
Fan, X.; Zhou, Q.; Xia, C.; Cristofoli, W.; Mays,J.; Advincula, R. C. Lanmuir 2002, 18, 4511.
• Condensation polymerization
Mont-Clay H3N Cl
COOH
O
+
HN
260oC
N2, 6h
Nylon 6-clay
nanocomposite
Kojima, Y.; Usuki, A.; Kawasumi, M.; Okada, A.; Kurauchi, T.; Kamigaito, O. J. Polymer Science:
Part A: Polymer Chemistry 1993, 32, 983-986.
Recent progress in
preparing PICN
3M
• Epoxy-clay nanocomposites
O
O
O
O
+
+
O
O
o
O
O
OH n
R
R
Mont-Clay
N
HO
O
+
N
shear mixer
80oC mixing 1h
OH
Epox-Nanocomposite
o
o
100 C, 1h curing 150 C, 1h 175 C, 1h
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
• PA6-clay nanocomposites were compounded by GE on a twin screw
extruder. Improved flammability, strength, stiffness.
mixing
PA-6 powder
Organic modified Clay
PA-6 pellet, or some PPO
PA-6 Clay
Counter rotating Twin screw extruder nanocomposite
400rpm, 246oC, 6kg/h
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.
Recent progress in
preparing PICN
Raychem
• Poly (ethylene vinyl acetate) EVA-Clay Nanocomposites.
Improved flammability, Young’s modulus
mixing
EVA
Organic modified Clay
Co-rotating twin screw extruder
Sekisui
EVA Clay
nanocomposite
400~500rpm, 90~130oC, barrel 700~1200psi
• PP-Clay Nanocomposites with improved flammability
mixing
PP, PP-g-MA
Organic modified Clay
Co-rotating twin screw extruder
PP Clay
nanocomposite
Zone 170~190oC, 15kg/h
Great Lakes Chemical
• PS-Clay Nanocomposites with improved flammability
mixing
PS
Organic modified Clay
Co-rotating twin screw extruder
PS Clay
nanocomposite
Zone 170oC, 200rpm, 1.5kg/h
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.
Recent progress in
preparing PICN
GE
• PBT-clay nanocomposite with improved tensile
strength
PBT-Ionomer (5%SO3Na)
R4N+ -Clay
mixing
Twin screw extruder
Zone 250oC, 400rpm
Sulfonated PBT-Clay
nanocomposite
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.
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
In situ small-angle X-ray scattering studies have
been conducted to monitor the structural changes of
p o l y m er n an o co m p o si te s u p o n h eatin g . Th ese
n a n o c o m p o s i t e s a r e m a d e o f
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.
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
Synthesis of clay
MgCl2 6H2O + NH4OH
H2O
Mg(OH)2
Fresh
Mg(OH)2 + LiF + SiO2
H2O
Reflux 40-48h
LiF:Mg(OH)2:SiO2:H2O (1.32:5.3:8:n)
Synthetic lithium hectorite clay (SLH)
Synthesis of PEO clay nanocomposite
1g SLH/100mL
water suspention
PEO (MW=100k)
Air-drying
Stirred 24h
Casting on
Teflon coated glass plate
120oC, Ar, 48h
film of
40um thinkness
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
q
4n

sin

2
 Distance between clay sheet:
d001=12.74Å
 Gallery region: 3.1Å
 Clay lattice unit cell: 9.6Å
Figure 3. X-ray powder diffraction pattern of SLH.
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
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
Figure 6. In situ SAXS of a PEO/SLH 1.2:1 mass ratio film
taken at room temperature. The inset shows the diffraction
peaks 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
Figure 7. In situ SAXS of a PEO/SLH 1.2:1 mass ratio film
taken 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.
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.
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.
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
Figure 11. Conductivity as a function of temperature of the
nanocomposite with nominal composition PEO/SLH 1:1 mass ratio.
σ = σ0 exp [ - Ep / ( T – T0)]
T0  Tg – 50K
(1)
(2)
Polymer Electrolyte Reviews-1; Maccallum, J. R.; Vincent C. A., Eds.; Elsevier Applied Science: London, 1972; p 91.
t+
when T
Transference number:
the fraction of the total current carried in a solution by a given ion
t 
V
V  V 
Dee, D. W.; Battaglia, V. S.; Redey, L.; Henriksen, G. L.; Atanasoski, R.; Belanger, A. J. Power Sources
2000, 89, 249.
• JEOL 100CXII TEM
100kV
Copper grid (dipped
into 1:1 PEO/SLH slurry
and dried for 2h in
vacuum at 100oC)
Figure 12. TEM of a 1:1 PEO/SLH mass ratio
nanocomposite membrane.
Silica spheres (20-nm disks) are visible throughout the background.
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
• 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
1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
11.
12.
13.
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, 16151616.
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, 45114518.
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.