Carbon Nanotubes : Carbon Nanotubes : An additive with multiAn additive with multi--

functional properties and current functional properties and current commercial applicationscommercial applications

Andrew RichAndrew RichNanocyl s.aNanocyl s.a

Contact: Contact: arich@nanocyl.comarich@nanocyl.comwww.nanocyl.comwww.nanocyl.com

SPE Automotive Composites Conference and Exposition , Troy MI 2006

Outline

1. Introduction to carbon nanotubes2. Overview of Nanocyl3. Current commercial applications for

carbon nanotubes4. Reviewing their benefits in polymers5. Automotive applications of CNTs

Two Forms:Single Wall (SWNT) and

Multi Wall(MWNT)

• Nanotubes are, with C60, the third Crystaline form of Carbon• Basically just a tube made from hexagonally bonded Carbon

Courtesy of J. Coleman, Trinity College of Dublin

Carbon black

MWNT 10 nm

Carbon nanotubesCarbon nanotubesMechanical propertiesMechanical properties

MaterialMaterial SpecificSpecificDensityDensity

E (TPa)E (TPa) Strength Strength (GPa)(GPa)

Strain at beakStrain at beak(%)(%)

CNT CNT (SW&MW)(SW&MW)

1.3 1.3 -- 22 11 10 10 -- 6060 > 10> 10

Silicate Silicate nanoplateletnanoplatelet

2.8 2.8 -- 33 0.170.17 11 < 10< 10

Carbon Carbon nanofiber nanofiber

(VGCF)(VGCF)

22 0.4 0.4 -- 0.60.6 3 3 -- 77 < 10< 10

Unique combination of Unique combination of stiffness, strength stiffness, strength and tenacityand tenacity

Carbon nanotubesCarbon nanotubesTransport propertiesTransport properties

MaterialMaterial ThermalThermalConductivityConductivity

(W /m.K)(W /m.K)

ElectricalElectricalConductivityConductivity

(S/m)(S/m)

CNTCNT 30003000 101055 –– 10107 7 (axial)(axial)

SilverSilver 429429 6.3 x 106.3 x 1077

CopperCopper 400400 5.9 x 105.9 x 1077

Carbon Carbon nanofiber nanofiber

(VGCF)(VGCF)19501950 2 x 102 x 1033

High thermal & electrical conductivityHigh thermal & electrical conductivity

Catalyst support

The challenge: To disperse

Nanocyl ® 7000/3100Multi-wall CNT

D: 9.5 nm L = 1.3 micronNC7000 C purity = 90%

NC3100 C purity = 99+%BET : 300 m2/g

Nanocyl ® 2100Double Wall CNT

D: 3.7 nm L = several micronsC Purity 90+%

BET : 550 m2/g

Product lines -Double-wall, Multi-wall,

dispersions, and surface treatments

Capacity developmentCapacity development

Laboratory scale and

continuous prototype

2002

Commercial pilot Operation5+ Tonnes

2005

Industrial Unit100+ Tonnes

2008

2004

2006

2007

Intermediate 30+ Tonnes

Product development Product development assistanceassistance

nn InIn--house applications laboratoryhouse applications laboratory

nnDSM microDSM micro--extruder with films & injection molding extruder with films & injection molding devicesdevices

nn InIn--situ polymerization unitsitu polymerization unitnn Inks, slurries & films manufacturingInks, slurries & films manufacturingnnTensile properties, MFI, electrical measurementsTensile properties, MFI, electrical measurements

nn External External

nnPilot twinPilot twin--screw extruder and injection moldingscrew extruder and injection moldingnnAssociate research laboratoriesAssociate research laboratories

Markets and products Markets and products DevelopmentDevelopment-- Short termShort term

nn Thermoplastic & Thermoset Thermoplastic & Thermoset CompoundsCompounds

nnESD ESD nn AutomotiveAutomotivenn ElectronicsElectronicsnn Chemical processing Chemical processing

industryindustrynnElectrostatic paintingElectrostatic paintingnnStructural & ThermalStructural & Thermal

nn Specialty films and coatingsSpecialty films and coatingsnnTransparent electrodesTransparent electrodesnnConductive coatingsConductive coatingsnnStructural & ThermalStructural & Thermal

Markets and products Markets and products Development Development -- Medium Medium

to Long termto Long term

nn Electron sourcesElectron sourcesnnField Emission DisplayField Emission DisplaynnSolar panel coatingsSolar panel coatings

nn PEM Fuel cells and batteriesPEM Fuel cells and batteriesnnElectrode materialElectrode materialnnCatalyst supportCatalyst support

Commercializing of Commercializing of carbon nanotubes carbon nanotubes ––

Current status Current status

Carbon nanotubesCarbon nanotubesCommercialization of their propertiesCommercialization of their properties

nn MechanicalMechanical

nn Babolat VS Nanotube Drive tennis racket (Babolat VS Nanotube Drive tennis racket (20012001))

nn Völkl DNX tennis racket (Völkl DNX tennis racket (20052005))

www.voelkl-tennis.com

Carbon nanotubesCarbon nanotubesCommercialisation of their propertiesCommercialisation of their properties

nn MechanicalMechanicalnn Bicycles (Bicycles (20052005))

nn Baseball Bats (Baseball Bats (20062006))

The Benefits of CNTs in The Benefits of CNTs in polymers and how to polymers and how to

increase their efficiency increase their efficiency

nn Electrically conductiveElectrically conductivenn ESD & conductive polymersESD & conductive polymers

nn Thermally conductiveThermally conductivenn Thermal managementThermal management

nn Flame retardantFlame retardantnn FireFire--proof compoundsproof compounds

nn High strength & stiffnessHigh strength & stiffnessnn Structural & tribological compoundsStructural & tribological compounds

Properties of interest in Properties of interest in polymer applicationspolymer applications

Structure of the nanotubes after synthesis - Nanocyl ® 7000

Aggregates are large: they need to be disentangled during the dispersion process – Strong influence of the texture of the

aggregates on the dispersion process

Manufacturing Manufacturing carbon nanotubes compoundscarbon nanotubes compounds

Source: IPF Dresden

Electrical resistivity of polycarbonate vs. Carbon loading

1,E+001,E+021,E+041,E+061,E+081,E+101,E+121,E+141,E+161,E+181,E+20

0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15

Carbon loading, wt %

Nanocyl 7000

Cabot VulcanXC-72Akzo Ketjenblack300J

Res

istiv

ity, O

hm.c

m

Carbon Nanotubes for Carbon Nanotubes for ESD applicationsESD applications

Carbon Nanotubes for Carbon Nanotubes for ESD applicationsESD applications

Influence of the additive on Impact strengthConductive PC/ABS compounds designed with Rv < 103 Ohm.cm

0% additive

0

10

20

30

40

50

60

PC/ABS MWNT CF CB

Not

ched

Cha

rpy

(kJ/

m2)

Source: CRIF

Carbon Nanotubes for Carbon Nanotubes for structural compoundsstructural compounds

nn Superior mechanical properties of the carbon Superior mechanical properties of the carbon nanotubesnanotubes

High expectationsHigh expectations Results are PROCESS dependantResults are PROCESS dependant ScaleScale--up of laboratory dataup of laboratory data-- challengingchallenging

nn Increased properties reported in the literatureIncreased properties reported in the literaturenn Wear resistanceWear resistancenn Stiffness & strength of elastomersStiffness & strength of elastomersnn Adhesion in fibre reinforced compositesAdhesion in fibre reinforced compositesnn Interlaminar shear strength and stiffnessInterlaminar shear strength and stiffness

nn Surface modification increases efficiencySurface modification increases efficiency

Application in Application in Epoxy composites Epoxy composites

N

Source: F. Gojny et al. , TU Hamburg

Improvement of epoxy toughness by ~ 45% at Improvement of epoxy toughness by ~ 45% at only 0.5% loading !only 0.5% loading !

Fracture toughness KIC (MPa m1/2) enhancement of epoxy resin using very low loading of carbon nanotubes

0

0,2

0,4

0,6

0,8

1

1,2

0 wt.% CNT 0.5 wt.% Nanocyl 2152 (DWNT-NH2)

Application to Application to Epoxy composites Epoxy composites

NSource: F. Gojny et al. , TU Hamburg

Epoxy toughness improved by crack bridging Epoxy toughness improved by crack bridging mechanismmechanism

Epoxy composites Epoxy composites --Application inApplication in

Glass Fiber Reinforced Composites made by Resin Glass Fiber Reinforced Composites made by Resin Transfer MoldingTransfer Molding

N

Source: F. Gojny et al. , TU Hamburg

Improvement of ILSS by 20% at only 0.3% Improvement of ILSS by 20% at only 0.3% loading in the resin !loading in the resin !

Interlaminar Shear Strength (MPa) enhancement of Glass Fiber Reinforced Epoxy using very low loading of carbon nanotubes

25

27

29

31

33

35

37

39

41

0 wt.% CNT 0.3 wt.% Nanocyl 2152 (DWNT-NH2)

Polypropylene Polypropylene –– Exxon MobilExxon Mobil (HP MFI 4.5)(HP MFI 4.5)

CarbonCarbonloadingloading

Tensile Tensile ModulusModulus(MPa)(MPa)

Tensile Tensile Strength at Strength at

breakbreak(MPa)(MPa)

Elongation at Elongation at breakbreak(%)(%)

Charpy Impact Charpy Impact –– NotchedNotched(kJ/m(kJ/m22))

0 %0 % 16721672 20.720.7 114.1114.1 5.25.2

NC7000NC70001 %1 % 17911791 24.824.8 13.813.8 5.95.9

3 %3 % 20562056 35.935.9 13.613.6 5.15.1

5 %5 % 22112211 3838 10.610.6 5.25.2

Carbon nanotubesCarbon nanotubesas reinforcementas reinforcement

Carbon nanotubes as Carbon nanotubes as flame retardantsflame retardants

MechanismMechanism

Source: Dr. Beyer, Carbon Nanotubes as a New Class of Flame Retardants for PolymersSource: Dr. Beyer, Carbon Nanotubes as a New Class of Flame Retardants for Polymers

Clays-based nanocomposites char

+ MWNT =

Nanotubes/Clays composite char

Carbon nanotubes addition promotes strong char formation Improved flame retardancy properties

Carbon Nanotubes in Carbon Nanotubes in Automotive applicationsAutomotive applications

CurrentCurrentnn Fuel systems Fuel systems –– fuel pumps, filters and lines, fuel pumps, filters and lines,

which need to dissipate staticwhich need to dissipate staticnn Electrostatic PaintElectrostatic Paint--able body exterior plasticsable body exterior plasticsFutureFuturenn AdhesivesAdhesivesnn FlameFlame--retardant interior reinforcementretardant interior reinforcementnn Heat reflective / dissipative coatingsHeat reflective / dissipative coatingsnn PEMPEM fuel cell componentsfuel cell components

Review of Applications for Review of Applications for Carbon nanotubesCarbon nanotubes

nn Carbon nanotubes are being used today in commercial Carbon nanotubes are being used today in commercial applicationsapplications

nn ConductiveConductive thermoplastics & coatings (automotive & thermoplastics & coatings (automotive & electronics)electronics)

nn Sporting goodsSporting goods

nn They can meet technical specifications from below 0.5% They can meet technical specifications from below 0.5% up to 2.5% loading depending on applicationup to 2.5% loading depending on application

nn Effectiveness vs. loading can be increased by specific preEffectiveness vs. loading can be increased by specific pre--treatments or posttreatments or post--treatmentstreatments

nn Larger availability and better price/performance ratio will Larger availability and better price/performance ratio will enable larger uses in polymer applicationsenable larger uses in polymer applications

Thank you for your interest Thank you for your interest !!