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.

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