NANOCOMPOSITES:NANOCOMPOSITES:NANOCOMPOSITES: NANOCOMPOSITES: NEW MATERIALS AND NEW MATERIALS AND IMPROVED APPLICATIONSIMPROVED APPLICATIONS

Michelle Londa, Ph.D.Michelle Londa, Ph.D.Research ProfessorResearch ProfessorTexas State UniversityTexas State University

NANOCOMPOSITE: NANONANOCOMPOSITE: NANO--PARTICLE/POLYMER COMPOSITEPARTICLE/POLYMER COMPOSITEPARTICLE/POLYMER COMPOSITE PARTICLE/POLYMER COMPOSITE WITH ENHANCED PROPERTIESWITH ENHANCED PROPERTIESOne nanometer = 1/100,000 the width of a human hairOne nanometer = 1/100,000 the width of a human hairOne nanometer 1/100,000 the width of a human hairOne nanometer 1/100,000 the width of a human hairMolecular level modification with 1 to 3% of a nanoMolecular level modification with 1 to 3% of a nano--sized sized additive.additive.

Property ImprovementsProperty Improvements ApplicationsApplications

I. Physical PropertiesI. Physical Properties Composites and CoatingsComposites and Coatings

II. BarrierII. Barrier

III. Flame RetardancyIII. Flame Retardancy

Coatings, Packaging, Automobile tiresCoatings, Packaging, Automobile tires

Composites and CoatingsComposites and Coatings

IV. Rheology ControlIV. Rheology Control

V. ConductivityV. Conductivity

Coatings, Cosmetics, Paper MakingCoatings, Cosmetics, Paper Making

Electrical / ElectronicElectrical / Electronic

VI. AbsorptionVI. Absorption Agriculture, Pharmaceuticals, PersonalAgriculture, Pharmaceuticals, PersonalCareCare

I. CLAY CHEMISTRYI. CLAY CHEMISTRY

BUILDING BLOCKS FOR BUILDING BLOCKS FOR CLAY MINERALSCLAY MINERALSCLAY MINERALSCLAY MINERALS

Aluminum OctahedralSilicon - Oxygen Tetrahedron

SILICATE FAMILYSILICATE FAMILYSILICATE FAMILYSILICATE FAMILY

SUMMARY OF CLAY MINERAL PROPERTIESSUMMARY OF CLAY MINERAL PROPERTIES

Basal

SUMMARY OF CLAY MINERAL PROPERTIESSUMMARY OF CLAY MINERAL PROPERTIES

Secondary mineral Type Interlayer condition /

Bonding CEC [cmol/kg]

Swelling potential

Specific surface area [m2/g]

Basal spacing [nm]

Kaolinite 1 : 1 (non-di )

lack of interlayer surface, t H b di 3 - 15 almost 5 - 20 0.72Kaolinite expanding) strong H-bonding 3 15 none 5 20 0.72

Montmorillonite 2 : 1 (expanding)

very weak bonding, great expansion 80 - 150 high 700 - 800 0.98 - 1.8 +

Vermiculite 2 : 1 (expanding)

weak bonding, great expansion 100 -150 high 500 - 700 1.0 - 1.5 +

Hydrous Mica 2 : 1 (non-expanding)

partial loss of K, strong bonding 10 - 40 low 50 - 200 1.0 expanding) bonding

Chlorite 2 : 1 : 1 (non-expanding)

moderate to strong bonding, non-expanding 10 - 40 none 1.4

Allophane - - 10 - 50 - -

II NANOCOMPOSITEII NANOCOMPOSITEII. NANOCOMPOSITE II. NANOCOMPOSITE STRUCTURE / PROPERTY STRUCTURE / PROPERTY

RELATIONSHIPS RELATIONSHIPS

NANOCOMPOSITE MORPHOLOGIESNANOCOMPOSITE MORPHOLOGIESNANOCOMPOSITE MORPHOLOGIESNANOCOMPOSITE MORPHOLOGIES

Polymer NanoclayPolymer – NanoclayExfoliated, Delaminated

IntercalatedIntercalated mixed w/ExfoliatedIntercalated mixed w/Exfoliated

NYLON 6 NYLON 6 –– NANOCLAY WITH NANOCLAY WITH HYDROPHOBIC SURFACE TREATMENTHYDROPHOBIC SURFACE TREATMENTHYDROPHOBIC SURFACE TREATMENTHYDROPHOBIC SURFACE TREATMENT

1500 Ä

NYLON 6 NYLON 6 –– NANOCLAY WITH POLAR NANOCLAY WITH POLAR SURFACE TREATMENTSURFACE TREATMENTSURFACE TREATMENTSURFACE TREATMENT

PROPERTIES OF NYLON 6 PROPERTIES OF NYLON 6 NANOCOMPOSITESNANOCOMPOSITES

Nanocor, ANTEC 2001Nanocor, ANTEC 2001Nanoclay Nanoclay

( t%)( t%)Flexural Flexural M d lM d l

Tensile Tensile M d lM d l

HDT (HDT (°°C)C) OTR OTR (wt%)(wt%) Modulus Modulus

(GPa)(GPa)Modulus Modulus

(GPa)(GPa)(cc(cc..mil/mmil/m2.2.

day)day)00 2.842.84 2.962.96 5656 3535

22 4.334.33 4.404.40 125125 2121

44 4.584.58 4.904.90 131131 1414

66 5.395.39 5.875.87 136136 1111

88 6 136 13 6 376 37 154154 7788 6.136.13 6.376.37 154154 77

EFFECT OF FILLER TYPE AND EFFECT OF FILLER TYPE AND CONCENTRATION ON THE TENSILE MODULUS CONCENTRATION ON THE TENSILE MODULUS

OF NYLON 6 COMPOSITESOF NYLON 6 COMPOSITES

45

OF NYLON 6 COMPOSITESOF NYLON 6 COMPOSITES(Nanocomposite data from Nanocor; all other data from RTP)(Nanocomposite data from Nanocor; all other data from RTP)

30354045

(GPa

)

202530

Mod

ulus

51015

Tens

ile M

00 10 20 30 40 50 60 70

GF Long GF Mineral Nano CF

EFFECT PP FILLER TYPE AND CONCENTRATION EFFECT PP FILLER TYPE AND CONCENTRATION ON THE TENSILE MODULUS OF PP COMPOSITESON THE TENSILE MODULUS OF PP COMPOSITES

14

(Nanocomposite data from Paul et. al., Antec 2004 p. 1516; (Nanocomposite data from Paul et. al., Antec 2004 p. 1516; all other data from RTP)all other data from RTP)

10

12

14

s (G

Pa)

6

8

Mod

ulus

2

4

Tens

ile

00 10 20 30 40 50 60 70

GF Long GF Talc Neat PP PP nano

LOW DENSITY SHEET MOLDING LOW DENSITY SHEET MOLDING CO O O CCO O O CCOMPOUND PERFORMANCECOMPOUND PERFORMANCE

Twardowska et. al., Composites 2005Twardowska et. al., Composites 2005

SteelSteel Standard SMCStandard SMC NanoNano--SMC SMC

Tensile Tensile Strength, MPaStrength, MPa

331331 65 65 –– 9090 9898

Tensile Tensile Modulus, GPaModulus, GPa

207207 1010--12.512.5 9.79.7

Specific Specific GravityGravity

7.867.86 1.8 1.8 –– 2.02.0 1.451.45

NANOCOMPOSITE PERFORMANCE IN NANOCOMPOSITE PERFORMANCE IN NITRILE RUBBERNITRILE RUBBER

Tensile vs. Elong% vs. phrC i

CLOIS POWELL, CLOISITE® NANOCLAY, SOUTHERN CLAY PRODUCTSCLOIS POWELL, CLOISITE® NANOCLAY, SOUTHERN CLAY PRODUCTS

Comparison

3500

4000

350

400

2500

3000

3500

psi

250

300

350

C10A CB

1000

1500

2000

100

150

200

10000 10 20 30 40 50 60 70 80 90 100

Loading

100

CB Tensile C10A Tensile CB Elong% C10A Elong%

TENSILE PROPERTIES OF CBDO TENSILE PROPERTIES OF CBDO COPOLYESTER NANOCOMPOSITESCOPOLYESTER NANOCOMPOSITES

BEALL ET. AL., TEXAS STATE UNIVERSITYBEALL ET. AL., TEXAS STATE UNIVERSITY

O

O OO OO

OO O O OO x y

2500

1500

2000

500

1000

0Neat

CBDO2.5%nano

5.0%nano

10.0%nanoCBDO nano nano nano

Tensile Modulus (MPa) Elongation, %

SELFSELF--HEALING OF CBDB HEALING OF CBDB COPOLYESTER NANOCOMPOSITESCOPOLYESTER NANOCOMPOSITESCOPOLYESTER NANOCOMPOSITESCOPOLYESTER NANOCOMPOSITES

BEALL ET. AL., TEXAS STATE UNIVERSITYBEALL ET. AL., TEXAS STATE UNIVERSITY

III. NANOCOMPOSITE III. NANOCOMPOSITE BARRIER PROPERTIESBARRIER PROPERTIES

NANOLOK™NANOLOK™ TECHNOLOGY PLATFORMTECHNOLOGY PLATFORM

0 1 - 2µ

thicknessNanocompositeBarrierRoll-coat

Processing 0.1 2µ

SubstrateAqueous

g

AqueousNanodispersed

Suspension

•Clay platelets ( ) 1-3 nanometers x 0.3-10µ are dispersed in a water-based resin system ( ).

•Finished coating contains 100s of platelets per micron of coating thickness. Platelets form a tortuous path for gas (O2, etc.) diffusion. 30-60,000X barrier improvement.

NanolokTM is a trademark of InMat, Inc.

SUPERIOR OSUPERIOR O22 BARRIERBARRIER

PP

LDPELeast

LDPE

PP100

1000

2 -day

)PP

NylonNylon

PET

PP

10

100c-

mil/

100i

n2

NylonPET

EVOHPVDC

LCP

PVDCEVOH0.1

1

eabi

lity

(cc

InMat®

NanolokTM PT

LCP

LCP

NanolokTM PT 0.001

0.01

0 01 0 1 1 10

O2

perm

Most

0.01 0.1 1 10

Water Vapor Transmission (gm-mil/100in2-day, 70oF)

NanolokTM PT is a trademark of InMat Inc ;Nanolok PT is a trademark of InMat, Inc.; it is coating comprised of nano-dispersed silicateIn polyester resin.

NANOCOMPOSITE BARRIER COATING SYSTEMSNANOCOMPOSITE BARRIER COATING SYSTEMS

PolymerPolymer Target Target ApplicationsApplications

Key secondary Key secondary PropertiesProperties

Current StatusCurrent Status

ButylButyl Tires, sport balls,Tires, sport balls, Flexibility, rubber Flexibility, rubber commercialcommercialyy , p ,, p , y,y,processingprocessing

ChloropreneChloroprene Gloves, rubber Gloves, rubber hoseshoses

Flexibility, flame Flexibility, flame resistance, oil resistance, oil

Customer Customer samplingsampling

resistanceresistanceNitrileNitrile Gloves, rubber Gloves, rubber

hose, bicycle hose, bicycle tubestubes

Flexibility, oil resistance, Flexibility, oil resistance, Customer Customer samplingsampling

tubestubesEPDMEPDM Bicycle tubes, Bicycle tubes,

industrial industrial Flexibility, Flexibility, environmental stabilityenvironmental stability

Limited samplingLimited sampling

P l tP l t Ri id d FlRi id d Fl T PET dT PET d C tC tPolyesterPolyester Rigid and Flex Rigid and Flex packagingpackaging

Transparency, PET and Transparency, PET and PP adhesionPP adhesion

Customer Customer samplingsampling

AcrylicAcrylic Rigid and Flex Rigid and Flex packagingpackaging

Transparency, PP Transparency, PP adhesion chemicaladhesion chemical

Customer Customer samplingsamplingpackagingpackaging adhesion, chemical adhesion, chemical

resistanceresistancesamplingsampling

IV ENHANCED FLAMEIV ENHANCED FLAMEIV. ENHANCED FLAME IV. ENHANCED FLAME RETARDANCY OF RETARDANCY OF

NANOCOMPOSITESNANOCOMPOSITES

EVA / Mg(OH)EVA / Mg(OH)2 2 / Nanoclay Compositions and / Nanoclay Compositions and Flame RatingsFlame RatingsFlame RatingsFlame Ratingswww.Nanocor.comwww.Nanocor.com

EVA wt%EVA wt% 4040 4545 4242 5050 4747EVA, wt%EVA, wt% 4040 4545 4242 5050 4747

Mg(OH)Mg(OH)22(wt%)(wt%)

6060 5555 5555 5050 5050

Nanomer Nanomer (wt%)(wt%)

00 00 33 00 33

UL94 UL94 ratingrating

VV--00 FailFail VV--00 FailFail VV--00

NANOCOMPOSITE POWER CABLENANOCOMPOSITE POWER CABLE

Nanocomposite Char formation of a cable with nanocomposite

Additionof organo-clay

Improvementson fire performanceand smoke density

ATH basedcompound

Beyer, G., 2002

FLAME RETARDANT PROPERTIES OF FLAME RETARDANT PROPERTIES OF DIFFERENT LDH FILLERS (60 wt%) in EVADIFFERENT LDH FILLERS (60 wt%) in EVADIFFERENT LDH FILLERS (60 wt%) in EVADIFFERENT LDH FILLERS (60 wt%) in EVA

Evans et. al, Chem. Comm., 2006, p. 490Evans et. al, Chem. Comm., 2006, p. 490

FillFill LOI (%)LOI (%) S k D itS k D itFillerFiller LOI (%)LOI (%) Smoke DensitySmoke Density

NoneNone 21.321.3 187.4187.4

Mg/AlMg/Al--CO3CO3 30.030.0 133.1133.1

Mg/AlMg/Al--borateborate 29.229.2 102.9102.9

V. RHEOLOGY CONTROLV. RHEOLOGY CONTROL

LAPONITELAPONITE®® SYNTHETIC SILICATESSYNTHETIC SILICATESLAPONITELAPONITE SYNTHETIC SILICATESSYNTHETIC SILICATES

Inorganic Metal Silicate Inorganic Metal Silicate ggCrystalline White Powder Crystalline White Powder Structure similar to Nature Smectite Clays Structure similar to Nature Smectite Clays

Unique aqueous system character derived from particle Unique aqueous system character derived from particle size & particlesize & particle--particle and/or particleparticle and/or particle--organicsorganicssize & particlesize & particle particle and/or particleparticle and/or particle organics organics interactionsinteractions

Critical for Synthetic consistency and puritySynthetic consistency and purity a reactant!

Laponite® is a registered trademark of Southern Clay Products

Isomorphic StructuresIsomorphic Structures

Montmorillonite

Synthetic

Silicate

Hectorite

Rheological BehaviorRheological Behavior

6

107 Particle – Particle interaction at low/no shear stressprovides gel structure that supports macro-particle

i t i lit d d d t

pois

e)

106

105

suspension -> strain amplitude dependant.

Pseudoplastic response to shear

y (c

entip 104

103

Pseudoplastic response to shearWith Yield Value

Vis

cosi

ty

102

10

The rigid discreet particles offer no entanglementand therefore essentially no high shear viscosity

2 1 0 1 2 3

V

101

100Water

10-2 10-1 100 101 102 103

Shear rate (1/sec)

SYNERGISTIC VISCOSITY w/ SYNERGISTIC VISCOSITY w/ CARBOXY POLYMERCARBOXY POLYMERCARBOXY POLYMERCARBOXY POLYMER

8,000

m-2

) Actual Gel Strength totalthickener

6 000

6,000

dyne

. cm concentration

constant at 2%

4,000

6,000

gth

(G’d

Theoretical Gel Strength

2,000

,

Gel

stre

ng

g

0100 parts 50 parts Syn. Silicate 100 parts CMC 7M

G

100 parts Synthetic Silicate

p y50 parts CMC 7M

100 parts CMC 7M

AUTOMOTIVE OEM BASE COATSAUTOMOTIVE OEM BASE COATSAdditive for Water Borne

Automotive OEM Base (Pigmented) Coat- Uniform dispersion of pigment- Plate pigment “flip flop” controlp g p p- Rheology to allow for spray-

ability with superior “edge effect” control

- Excellent consistency- No interference of color or clarity - UV and oxidatively stable

V. CONDUCTIVITYV. CONDUCTIVITY

STRUCTURES OF SINGLE WALLED STRUCTURES OF SINGLE WALLED CARBON NANOTUBES (SWCNT)CARBON NANOTUBES (SWCNT)CARBON NANOTUBES (SWCNT)CARBON NANOTUBES (SWCNT)

POTENTIAL APPLICATIONS FOR CNTPOTENTIAL APPLICATIONS FOR CNTPOTENTIAL APPLICATIONS FOR CNTPOTENTIAL APPLICATIONS FOR CNT

C b b b d

J ti b t b

Carbon nanotube yarn may be usedAs powerful actuators; exert 100xForce/area of natural muscle.Technology Review, Dec. 8, 2006Junction between carbon

nanotube and gold nanowire;Computer chips, displays, sensors.RPI, January 11, 2007

Technology Review, Dec. 8, 2006

, y ,

VI. ABSORPTIONVI. ABSORPTION

HALLOYSITE CLAY NANOTUBESHALLOYSITE CLAY NANOTUBESHALLOYSITE CLAY NANOTUBESHALLOYSITE CLAY NANOTUBESwww.naturalnano.comwww.naturalnano.com

TO FILL TUBULES:•Pull vacumm

•Hydrophilic agents infiltrate naturally

•Hydrophobic agents can infiltrate with aid of surface modification or by driving of water

CONTROLLED RELEASE APPLICATIONSCONTROLLED RELEASE APPLICATIONSCONTROLLED RELEASE APPLICATIONSCONTROLLED RELEASE APPLICATIONS

PesticidesPesticides

Household and personal productsHousehold and personal products

Flavors and FragrancesFlavors and Fragrances

Ph ti lPh ti lPharmaceuticalsPharmaceuticals

Flame retardantsFlame retardantsFlame retardantsFlame retardants

Conductive particlesConductive particles

Nanocomposite Nanocomposite Property ImprovementsProperty Improvements

ApplicationsApplicationsProperty ImprovementsProperty Improvements

I. Physical PropertiesI. Physical Properties Composites and CoatingsComposites and Coatings

II B iII B i C ti P k i TiC ti P k i TiII. BarrierII. Barrier

III. Flame RetardancyIII. Flame Retardancy

Coatings, Packaging, TiresCoatings, Packaging, Tires

Composites and CoatingsComposites and Coatings

IV. Rheology ControlIV. Rheology Control Coatings, Cosmetics, Coatings, Cosmetics, Paper MakingPaper Making

V. ConductivityV. Conductivity Electrical / ElectronicElectrical / Electronic

VI. AbsorptionVI. Absorption Agriculture, Pharmaceuticals, Agriculture, Pharmaceuticals, Personal CarePersonal Care