01 letter-toc · Title: 01_letter-toc.qxd Author: Londa Scott Forte Created Date: 2/5/2003 5:47:28 PM
NANOCOMPOSITES: NEW MATERIALS AND IMPROVED · PDF fileNANOCOMPOSITES: NEW MATERIALS AND...
Transcript of NANOCOMPOSITES: NEW MATERIALS AND IMPROVED · PDF fileNANOCOMPOSITES: NEW MATERIALS AND...
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
BUILDING BLOCKS FOR BUILDING BLOCKS FOR CLAY MINERALSCLAY MINERALSCLAY MINERALSCLAY MINERALS
Aluminum OctahedralSilicon - Oxygen Tetrahedron
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
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
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
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
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 ,
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