Polymer Intercalated Clay Polymer Intercalated Clay NanocompositeNanocomposite
Changde ZhangChangde ZhangDepartment of Chemistry, LSUDepartment of Chemistry, LSU
February 11, 2005
Full Talk
OutlineOutline• Background and introduction : Background and introduction :
Clay species and StructureClay species and Structure Advanced Properties of Polymer NanocompositesAdvanced Properties of Polymer Nanocomposites Principle of polymer nanocompositePrinciple of polymer nanocomposite Applications of polymer clay nanocomposites Applications of polymer clay nanocomposites Methodology for preparing polymer intercalated clay Methodology for preparing polymer intercalated clay
nanocomposites (PICN)nanocomposites (PICN)
• Recent progress in preparing PICNRecent progress in preparing PICN
• Literature discussion: PICN with electrochemical Literature discussion: PICN with electrochemical functionfunction
““In Situ SAXS Studies of the Structural Changes of Polymer In Situ SAXS Studies of the Structural Changes of Polymer Nanocomposites Used in Battery Application”Nanocomposites Used in Battery Application”Sandi, G.; Joachin, H.; Seifert, R.; Carrado, K. A. Sandi, G.; Joachin, H.; Seifert, R.; Carrado, K. A. Chem. Mater. Chem. Mater. 20032003, 15, , 15, 838.838.
Clay species and Structure Clay species and Structure • Two main structure of Clay Two main structure of Clay
species: species:
1:1 type: alumina 1:1 type: alumina octahedraloctahedral (metal –hydroxide) sheet (metal –hydroxide) sheet sitting on the top of silica sitting on the top of silica tetrahedraltetrahedral (Silicone-oxygen) (Silicone-oxygen) sheet: serpentines; Kaolinssheet: serpentines; Kaolins
Nonswelling due to the Nonswelling due to the binding of oxygen and binding of oxygen and hydrogen between two sheets hydrogen between two sheets 2:1 type: One octahedral 2:1 type: One octahedral aluminia sheet sanwitched aluminia sheet sanwitched between 2 tetrahedral silica between 2 tetrahedral silica sheets (Montmorrillonite, sheets (Montmorrillonite, smectites, Mica; Talc)smectites, Mica; Talc)
Background and Introduction
octahedroctahedralal
tetrahedrtetrahedralal
tetrahedrtetrahedralal
Clay species and structureClay 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 Clay species and Structure: Classification of phyllosilicate related to clay
mineralsminerals
Background and Introduction
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
2:1 Talc-pyrophyllite(x~0)
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 inverted ribbons
Sepiolite-palygorskite(x variable)
Sepiolites Sepoolite, loughlinite
Palygorskites Palygorskite
ax refers to an O10(OH)2 formula unit for smectite, vermiculite, mica, and brittle mica.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.
Four types of Polymer-Clay compositeFour 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 Popular clay in PICN: Montmorillonites clay (smectite type)(smectite type)
• Japanese Toyota group: montmorillonite Japanese Toyota group: montmorillonite exchanged by exchanged by ωω-amino acid) + -amino acid) + εε--caprolactam 1993caprolactam 1993
• Advanced performance:Advanced performance: Gas barrierGas barrier Fire proofFire proof Improved mechanical properties (tough, Improved mechanical properties (tough,
increased tensile strength and impact strength)increased tensile strength and impact strength) Better flow propertyBetter flow property Better electronic property and optical Better electronic property and optical
property property Krishnamoorti, R.; Varia, R. A., Ed. Polymer Nanocomposites; American Chemical Society: Washington, DC, 2001.
Principle of PICNPrinciple of PICN
• Nanoscale Nanoscale morphologies model: morphologies model: Equilibrium distance Equilibrium distance between uniformly between uniformly aligned and dispersed aligned and dispersed plates of thickness at plates of thickness at various fractions of various fractions of plates.plates.
Vaia, R. A.; Giannelis, E. P. Vaia, R. A.; Giannelis, E. P. MRS Bulletin MRS Bulletin 20012001, 26, , 26, 394.394.
Principle of PICNPrinciple of PICN
Tortuous path modelTortuous path model for Gas Barrier Gas Barrier material: material: tortuous path due to high aspect ratio Model: PModel: Pff/P/Puu = V = Vpp/1 + (L/2w)V/1 + (L/2w)Vff Nielson equation L/W ratio:Nielson equation L/W ratio:Beall, T. J. P. a. G. W., Ed. Polymer-Clay Nanocomposites; John Wiley & Sons, Ltd:New York, 2001.
A
B
Applications of PICNApplications of PICN• Fire-proof material: substitute PVC productFire-proof material: substitute PVC product• Anti-corrosive Coating: Epoxy/ClayAnti-corrosive Coating: Epoxy/Clay• Barrier packaging material (film and container: gas barrier Barrier packaging material (film and container: gas barrier
and liquid barrier): and liquid barrier): EVOH filmEVOH filmRecyclable/disposable bottle (PE/clay) Recyclable/disposable bottle (PE/clay)
• Hand-carried device for battle-fieldHand-carried device for battle-field• Automotive and Air spaceAutomotive and Air space
PP/Clay, PS/Clay, Nylon/ClayPP/Clay, PS/Clay, Nylon/ClayPB/Clay (Reinforced tire) PB/Clay (Reinforced tire)
• Electrical device: Polymer solid electrolyte Electrical device: Polymer solid electrolyte PEO/Clay/LiPEO/Clay/Li++
• Optical transparent materialOptical transparent material
Krishnamoorti, R.; Varia, R. A., Ed. Polymer Nanocomposites; American Chemical Society: Washington, DC, 2001.
Approaches for preparing Approaches for preparing PICNPICN
• 3 categories:3 categories: In-Situ Polymerization In-Situ Polymerization Melt InsertionMelt Insertion Polymer solution insertionPolymer solution insertion
• First step: modification of Clay First step: modification of Clay Surface: Cation-ExchangeSurface: Cation-Exchange
PICN by In-situ PolymerizationPICN by In-situ Polymerization
Free Radical PolymerizationFree Radical Polymerization• Modification of clay surface with different cation Modification of clay surface with different cation
speciesspecies
• Modification of clay surface with monomer cationModification of clay surface with monomer cation
AIBN +AIBN +
P+N+OH
N+
Zhu, J.; Morgan, A. B.; Lamelas, F. J.; Wilkies, C. A. Zhu, J.; Morgan, A. B.; Lamelas, F. J.; Wilkies, C. A. Chem. Mater. Chem. Mater. 20012001, 13, , 13, 3774.3774.
ON+(CH3)3
O
Cl-
Huang, X.; Brittain, W. J. Huang, X.; Brittain, W. J. Macromolecules Macromolecules 20012001, 34, , 34, 3255-3260.3255-3260.
ON+
O
Br-
Zeng, C.; Lee, L. J. Zeng, C.; Lee, L. J. Macromolecules Macromolecules 20012001, 34, , 34, 4098-4103.4098-4103.
Recent progress in preparing PICN
PICN by in-situ polymerizationPICN by in-situ polymerization
• Modification of clay surface with initiator cationModification of clay surface with initiator cation
NN
CN
CN
O
O
N+ON+
O
Br-Br-
NN
CN
CN
O
O
N+O
O
Fan, X.; Xia, C.; Advincula, R. C. Fan, X.; Xia, C.; Advincula, R. C. Lanmuir Lanmuir 20032003, 19, , 19, 4381.4381.Huang, X.; Brittain, W. J. Huang, X.; Brittain, W. J. Macromolecules Macromolecules 20012001, 34, , 34, 3255.3255.
Recent progress in preparing PICN
NN
NH2
NH2+
Cl-H2N
H2NCl-
PICN by in-situ polymerizationPICN by in-situ polymerization• Living Free Radical Living Free Radical
PolymerizationPolymerization– Initiator cation for living free Initiator cation for living free
radical polymerizationradical polymerization
• Living anionic Living anionic polymerization polymerization
• Condensation Condensation polymerizationpolymerization
O(CH2)12N+(CH3)3
Br-
OO
N
O
N+ Cl-
Weimer, M. W.; Chen, H.; Giannelis, Weimer, M. W.; Chen, H.; Giannelis, E. P.; Sogah, D. Y. E. P.; Sogah, D. Y. J. AM. Chem. Soc. J. AM. Chem. Soc. 19991999, 121, , 121, 16151615
Fan, X.; Zhou, Q.;Fan, X.; Zhou, Q.; Xia, C.; Cristofoli, W.; Mays,J.; Advincula, R. C. Xia, C.; Cristofoli, W.; Mays,J.; Advincula, R. C. Lanmuir Lanmuir 20022002, 18, , 18, 4511.4511.
Kojima, Y.; Usuki, A.; Kawasumi, M.; Okada, A.; Kurauchi, T.; Kamigaito, O. Kojima, Y.; Usuki, A.; Kawasumi, M.; Okada, A.; Kurauchi, T.; Kamigaito, O. J. Polymer J. Polymer Science: Science:
Part A: Polymer Chemistry Part A: Polymer Chemistry 19931993, 32, , 32, 983-986.983-986.
Mont-Clay
+ HN
O
H3NCOOH
260oCN2, 6h
Nylon 6-clay nanocomposite
Cl
3M3M
• Epoxy-clay nanocompositesEpoxy-clay nanocomposites
Recent progress in preparing PICN
OO O O
OH n
OO
+ + N
HO OH
RR Mont-Clay
shear mixer
80oC mixing 1h
100oC, 1h curing 150oC, 1h 175oC, 1hEpox-Nanocomposite
O
O
O
N+
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 Polymer Intercalated Clay by Melt InsertionInsertion
• PA6-clay nanocomposites were compounded by GE on a twin PA6-clay nanocomposites were compounded by GE on a twin screw extruder. Improved flammability, strength, stiffness. screw extruder. Improved flammability, strength, stiffness.
Recent progress in preparing PICN
PA-6 powderOrganic modified Clay
mixing PA-6 pellet, or some PPO
Counter rotating Twin screw extruder400rpm, 246oC, 6kg/h
PA-6 Clay nanocomposite
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• Poly (ethylene vinyl acetate) EVA-Clay Nanocomposites. Poly (ethylene vinyl acetate) EVA-Clay Nanocomposites.
Improved flammability, Young’s modulusImproved flammability, Young’s modulusEVAOrganic modified Clay
mixing
Co-rotating twin screw extruder400~500rpm, 90~130oC, barrel 700~1200psi
EVA Clay nanocomposite
Recent progress in preparing PICN
Sekisui• PP-Clay Nanocomposites with improved flammabilityPP-Clay Nanocomposites with improved flammability
PP, PP-g-MAOrganic modified Clay
mixing
Co-rotating twin screw extruderZone 170~190oC, 15kg/h
PP Clay nanocomposite
Great Lakes Chemical
PSOrganic modified Clay
mixing
Co-rotating twin screw extruderZone 170oC, 200rpm, 1.5kg/h
PS Clay nanocomposite
• PS-Clay Nanocomposites with improved flammabilityPS-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.
GEGE
• PBT-clay nanocomposite with improved PBT-clay nanocomposite with improved tensile strengthtensile strength
Recent progress in preparing PICN
PBT-IonomerR4N+ -Clay
mixing
Twin screw extruderZone 250oC, 400rpm
Sulfonated PBT-Clay nanocomposite
(5%SO3Na)
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.
In Situ SAXS Studies of the Structural Changes of In Situ SAXS Studies of the Structural Changes of Polymer Nanocomposites Used in Battery Polymer Nanocomposites Used in Battery
ApplicationApplication
Presented by Changde ZhangPresented by Changde ZhangDepartment of Chemistry, LSUDepartment of Chemistry, LSU
February 11, 2005
Literature Discussion
Main Reference:Main Reference:Sandi, G.; Joachin, H.; Seifert, R.; Carrado, K. A. Sandi, G.; Joachin, H.; Seifert, R.; Carrado, K. A. Chem. Mater. Chem. Mater. 20032003, 15, , 15, 838.838.
PICN by solution PICN by solution processingprocessing
AbstractAbstract
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.
Figure 1. Schematic representation of PEO inserted lithium hectorite clay polymer electrolyte. The gallery region shows one PEO layer and exchangeable Li(I) cations.
PEO
Li+
Preparation of PEO clay Preparation of PEO clay nanocompositenanocompositeSynthesis of clay
Synthesis of PEO clay nanocomposite
1g SLH/100mL water suspention
PEO (MW=100k)Stirred 24h
Casting on Teflon coated glass plate
Air-drying film of 40um thinkness120oC, Ar, 48h
MgCl2 6H2O + NH4OH Mg(OH)2
H2O
Fresh
Mg(OH)2 + LiF + SiO2 LiF:Mg(OH)2:SiO2:H2OH2O
Reflux 40-48h(1.32:5.3:8:n)
Synthetic lithium hectorite clay (SLH)
2
sin4 n
q
X-ray diffraction: sensitive to electron
cloudBragg equation :
dhkl = λ/(2sinθ) = 2π/q
Rigaku Miniflex diffractometer Beam: Cu Kαirradiation (λ: 1.54Å) Detector: NaI Scan Rate: 0.5o/min Step size 0.05 CCD camara
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.
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 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
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.
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 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.
Transference number: the fraction of the total current carried in a solution by a given ion
VV
Vt
Dee, D. W.; Battaglia, V. S.; Redey, L.; Henriksen, G. L.; Atanasoski, R.; Belanger, A. J. Power Sources 2000, 89, 249.
t+ when T
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.
ConclusionsConclusions
• PEO/SLH nanocomposite was obtained using a PEO/SLH nanocomposite was obtained using a synthetic clay SLH.synthetic clay SLH.
• Above 60Above 60ooC, PEO loses its crystallinity and the C, PEO loses its crystallinity and the film became more conductive (4.87film became more conductive (4.87×10×10-3-3S/cm). Its S/cm). Its conductivity is conductivity is 4.264.26×10×10-3-3S/cm at RTS/cm at RT
• PEO/SLH had high transference number (~0.90).PEO/SLH had high transference number (~0.90).• The structure of PEO/SLH nanocomposite did not The structure of PEO/SLH nanocomposite did not
change significantly up to150change significantly up to150ooC. PEO/SLH film was C. PEO/SLH film was stable. stable.
• PEO/SLH showed better conductivity than PEO/LaponitePEO/SLH showed better conductivity than PEO/Laponite
AcknowledgementsAcknowledgements
• Professor William H. Daly’s Instruction, Professor William H. Daly’s Instruction, Professor Gudrun Schmidt’s discussion.Professor Gudrun Schmidt’s discussion.
• Group colleagues: Mrunal Thatte, Group colleagues: Mrunal Thatte, Ahmad Bahamdan, Veronica Holmes, Ahmad Bahamdan, Veronica Holmes, Codrin Daranga, Lakia Champagne, and Codrin Daranga, Lakia Champagne, and Ionela Chiparus.Ionela Chiparus.
• Elena Loizou’s discussion.Elena Loizou’s discussion.
ReferencesReferences
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