Neuere Entwicklungen auf dem Gebiet der CNT … = 1200 μm ρ= ca. 150 kg·m-3 „Expanding Universe ... Dr. Helmut Meyer • Page 32 BMS-CAS-INN-CNT Baytubes are firmly embedded in

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Neuere Entwicklungen Neuere Entwicklungen auf dem Gebiet der auf dem Gebiet der

CNTCNT--Herstellung und Nutzung Herstellung und Nutzung im Faserverbundleichtbauim Faserverbundleichtbau

Wissenschaftstag 2008 Wissenschaftstag 2008 NanotechnoscienceNanotechnoscience in Faserverbundleichtbau und in Faserverbundleichtbau und AdaptronikAdaptronik

9.10.2008 Braunschweig9.10.2008 BraunschweigDr. Helmut MeyerBMS-CAS-INN-CNT

Dr. Helmut Meyer Page 2BMS-CAS-INN-CNT

1863 Company founded by F. Bayer and J.F. Weskott 1912 Corporate headquarters established in Leverkusen 1951 Re-establishment of Farbenfabriken Bayer AG

1863 Company founded by F. Bayer and J.F. Weskott 1912 Corporate headquarters established in Leverkusen 1951 Re-establishment of Farbenfabriken Bayer AG

Corporate HistoryCorporate HistoryE

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as at December 31, 2005as at December 31, 2005Dr. Helmut Meyer Page 2BMS-CAS-INN-CNT


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Bayer GroupBayer Group


326 Gesellschaften326 Gesellschaften

Forschungs-ausgaben

2,6 Mrd. Euro

Forschungs-ausgaben

2,6 Mrd. Euro

Umsatz 2007:32,4 Mrd. EuroUmsatz 2007:32,4 Mrd. Euro

106.200Mitarbeiter**

106.200Mitarbeiter**

***

Stand: 31.12.2007Mitarbeiter auf Vollzeitkrfte umgerechnet.


Bayer: Science For A Better LifeBayer: Science For A Better LifeE

0604

A



Bayer Bayer MaterialScienceMaterialScience::Facts and Facts and FiguresFigures 20072007

Produktions-standorteca. 30

Mitarbeiterca. 15.400*

Absatzca. 9,7 Mio.Tonnen

Umsatzca.10,4 Mrd.Euro

F&E-Investitionenca. 340 Mio. Euro**

***

Stand 31.12.2007, Vollzeit-quivalenteinkl. kundennahe Entwicklungen


Bayer MaterialScience:Bayer MaterialScience:Sales in 2007 by Business Units Sales in 2007 by Business Units

51%51%EUR 10.4 billion

27%

15%15%

2%2%4%4%

ThermoplasticPolyurethanes

Others 1%

Polyurethanes

Polycarbonates

Coatings, Adhesives,Specialties

Basic Chemicals


Carbon NanotubesAlt bewhrt und Material der Zukunft

Properties of Carbon NanotubesTear strength > 10 GPaE-modulus > 1 TPaThermal conductivity > 2000 W/mKElectrical conductivity > 104 S/cm


MechanicalMechanical StrengthStrength

www.montrealhockey.com


Carbon Nanotubes

Single-Wall Carbon Nanotubes (SWNT): Diameter: 0,4 - 3 nm

Ideal structure, low defects

Complex manufacturing process, high prices(current medium term target >1000 $/kg)

High catalyst residue if CVD process is applied

High carbon black residue (up to 50% if arc-discharge process is applied)

Multi-Wall Carbon Nanotubes (MWNT): Diameter : 5 - 100 nm High defects, high aspect ratio Low cost process possible (CCVD) (high yield, low catalyst residue) Already in use in polymers in order to promote

electrical conductivityBTS

20 nm

20 nm25 nm

BTS


Catalytic Chemical Vapor DepositionCatalytic Chemical Vapor Deposition

Dp = 80 m

= 2000 kgm-3

CNT-Agglomerate

Dp = 1200 m

= ca. 150 kgm-3

Expanding Universe

Mechanism

Movie Source: Stig Helveg et al., Atomic-scale imaging of carbon nanofiber growth, Nature 427 (2004), 426-429

Scheme of the metal-catalyzed growth of a carbon nanofiber from gaseous hydrocarbons

Agglomerated catalyst particles


CNT Synthesis: CCVD / Fluidized BedCNT Synthesis: CCVD / Fluidized Bed

CNT-Agglomerate

Agglomerated primary catalyst

particles

High carbon yields of catalyst

High space-time yield

Agglomerated / entangled producteasy to handle

Product agglomerates must be disentangled during processing

Hydrocarbons / H2 / inert gas

Catalyst

Agglomerates of CNT( > 95 % C-purity)

Heating

H2, inert gas

Filter &Incineration


CNT Synthesis: CVD / Fluidized BedCNT Synthesis: CVD / Fluidized Bed

0

10

20

30

40

50

60

70

80

90

100

0,1 1 10 100 1000 10000

cum

ulat

ive

volu

met

ric c

onte

nt Q

3 [%

]

500m73,7 : 1 B096501RE101

CNT-Agglomerate(> 95 % purity)

200nm93910 : 1

X1300

Magnification

Particle-Size Distribution

100m


ProductionProduction ScaleScale Up Up FluidizedFluidized BedBed

Bench Scalein operation

Pilot Scale-1

in operation

Production Scale

design and planning

ID = 0.1 m reactor3-5 tons p.a.

Reactor 1 30 tons p.a.

Reactor 230 tons p.a

Fluidized bed3000 tons p.a.

Pilot Scale-2

In realization

Fluidized bed200 tons p.a.

2009 Vision 2012?2006/07


BaytubesBaytubes -- PropertiesProperties

Multi-wall carbon nanotubes agglomerates of very high purity

Low fraction of catalyst residues enables immediate application in most polymers without costly purification processes


BaytubesBaytubes -- Polymer Polymer ApplicationsApplications

Electrical conductivity Mechanical strength

Thermal conductivity

Antistatic behaviourAutomotive partsAutomotive fuel lines

Electrostatic paintingCar body panelsMirror housings

Electrical conductivityIC trays, carrier tapesIntermediate container

Electromagnetic shieldingMobile phonesHousings

Sporting goodsAircraft partsLightweight constructionAdhesivesPolymer fibersCoatings

Electronic components

Elastomers


0,01 w.-% CNT

TechniquesIn-situ polymerisation

Melt impregnation

Solvent impregnation

Achieved complete dispersion of original agglomerates by optimizing dispersion in twin screw extruder or three roll calander

0,05 w.-% CNT

200 nm 200 nm200 nm

PA PolyolPC

DispersionDispersion

PC


BaytubesBaytubes --ElectricalElectrical ConductivityConductivity in Polymersin Polymers

Baytubes carbon nanotubes show higher conductivity at lowerloadings compared to high end conductive carbon blacks

Quelle: Hyperion


BaytubesBaytubesComparisonComparison withwith Carbon BlackCarbon Black

Baytubes show higher conductivity at lower loadings comparedto high end conductive carbon black in polycarbonate.

1,E+00

1,E+01

1,E+02

1,E+03

1,E+04

1,E+05

1,E+06

1,E+07

1,E+08

1,E+09

1,E+10

1,E+11

0 2 4 6 8 10 12

Baytubes C150P

High End Conductive CB

Baytubes content [wt%]

Surface Resistivity [Ohm/sq]

Polymer: Makrolon 2805Dispersion machine: ZSK 26McScrew speed: 400 1/minTorque: 80%Temperature profile: 280 C (standard)Parts Injection Moulded


BaytubesBaytubes -- ElectricalElectrical ConductivityConductivityPC PC InfluenceInfluence of of ProcessingProcessing ConditionsConditions

1,E+00

1,E+01

1,E+02

1,E+03

1,E+04

1,E+05

1,E+06

1,E+07

1,E+08

1,E+09

1,E+10

1,E+11

0 1 2 3 4 5 6 7 8CNT-content [wt%]

Pressed Plaque

Injection Moulding - StandardCondition for PC

Injection Moulding - OptimizedCondition for PC/ Baytubes

Polymer: Makrolon 2805Additive: Baytubes C150PDispersion machine: ZSK 26Mc

Surface Resistivity [Ohm/sq]

Processes and processing conditions show strong influence on thesurface resistivity of the final part.

OptimizationOptimizationof IM of IM processprocess


BaytubesBaytubes -- ElectricalElectrical ConductivityConductivityPBT PBT InjectionInjection MoldingMolding

PBT-CNT composites show improved conductivity withincreased molding temperature and reduced feed rate

1,0E+00

1,0E+01

1,0E+02

1,0E+03

1,0E+04

1,0E+05

1,0E+06

1,0E+07

1,0E+08

1,0E+09

1,0E+10

1,0E+11

0 20 40 60 80 100 120

Injection speed [mm/s]

Surfa

ce re

sist

ivity

[ /

]

PBT B 1600 Tp = 230 - Tw = 120 Tp = 260 - Tw = 120 Tp = 290 - Tw = 120 Vergleich PC 2805 Tp = 340 - Tw = 120

PBT B 1600Baytubes C150P5 Gew.-% CNTZSK 26Mc


BaytubesBaytubes --ApplicationsApplications in in ThermoplasticsThermoplastics

Addition of Baytubes results in improved electrical conductivity improved mechanical strength at low CNT loadings


BaytubesBaytubesColourColour of of CompositeComposite MaterialMaterial

0,05 w.-% CNT 0,01 w.-% CNT

Compounded material likely to be blackCertain transparency achievable at low loading level


BaytubesBaytubes --ElectricalElectrical ConductivityConductivity in in EpoxiesEpoxies

Epoxide: Araldite564/ HY2954


BaytubesBaytubes --MechanicalMechanical StrengthStrength in in EpoxiesEpoxies


BaytubesBaytubes -- MechanicalMechanical StrengthStrengthApplicationsApplications in in SportingSporting GoodsGoods

The worlds toughest Hockey Stick

lightestand

strongestxc-ski to

day

Ultra-light weight Exel sticks


BaytubesBaytubes -- Low Low WeightWeight and and Proper Proper FlexuralFlexural Response in Response in EpoxiesEpoxies


BaytubesBaytubesUseUse in in LightweightLightweight Construction Construction


BaytubesBaytubes -- ConcreteConcrete ReinforcementReinforcementApplicationApplication Potentials in ConstructionPotentials in Construction


Health & Health & SafetySafety


HSEQ HSEQ ActivitiesActivities

2 0 0 5

BMBF Project

PACTE Project

HSEQ Project

T R A C E RStart 01/06

Start 9/05

Start 8/05

2 0 0 6 2 0 0 7 2 0 0 8

720.000 (AG), applied for 50% grant

B A Y T U B E S End 12/07 200.000 (BMS)

Producers Association of Carbon NanoTubes in Europe (PACTE) - Sector Group within Chemical Industry AssociationKey objectives: Science Advocacy - Dialogue


EcotoxicologyNo Acute aquatic toxicity (Daphnia, Algae, Fish)

No Bacterial toxicity (activated sludge)

ToxicologyNo Acute toxicity (dermal, oral)No Acute local irritation (Eye & Skin); No Sensitization (Skin)

No Mutagenicity (Ames test and in vitro cytogenicity test)

Acute inhalation toxicity: LC50 rat: > 241 mg/m (micronised Baytubes)Concentrations 11 mg/m cause a poorly soluble particle effectPulmonary toxicity of Baytubes and Quartz are markedly differentNo extrapulmonary effects

Planned: Sub-chronic inhalation toxicity

: performed (GLP studies conducted according to OECD Guidelines)

: ongoing/planned (2007)

All standard studies performed so far with Baytubes show no relevant adverse effect at realistic exposure level (GLP studies according to OECD Guidelines). Results continuously published

:

:

:

:

:

:

:

Baytubes Baytubes --InternalInternal TestingTesting ProfileProfile


Baytubes are firmly embedded in matrix of polymer or coatings

Key branches are automotive, electronics and sport industry

E.g. sport articles (hockey, baseball bat), rotor blade for windturbine or antistatic packaging for computer chips

End-products can be safely used

Product categories foreseen for Baytubes all have a low potential of exposure

No Exposure during Use of EndNo Exposure during Use of End--productsproducts

* Report to the European Parliament IP/A/ENVI/ST/2006-41 Nanomaterials in Consumer Products (April 2007)


Communication for Baytubes Communication for Baytubes

Product Stewardship at BMS for Nanomaterials BayCare Webpage

www.baycareonline.com(Free registration, see Whats new section) Baytubes Webpage

www.baytubes.com

Scientific presentations of (eco)-toxicological results Clean ecotoxicity profile at SETAC-UK (London, 2007-09)www.sebiology.org/Documents/Meetings/Nanoparticles/nano_abstracts.pdf

Clean genotoxicity profile presented EEMS (Basel, 2007-09)www.eems-2007-basel.ch/eems/files/EEMS2007

Basel_ultimaVersion_04.09.07.pdf

Acute Inhalation Study with Baytubes at SOT 2008 Annual Meeting (Seattle, 2008-03)


TheThe WinningWinning TeamTeam


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Closing Motif

Neuere Entwicklungen auf dem Gebiet der CNT-Herstellung und Nutzung im FaserverbundleichtbauCorporate HistoryBayer GroupBayer: Science For A Better LifeBayer MaterialScience:Facts and Figures 2007Bayer MaterialScience: Sales in 2007 by Business Units Mechanical StrengthCatalytic Chemical Vapor DepositionCNT Synthesis: CCVD / Fluidized BedCNT Synthesis: CVD / Fluidized BedProduction Scale Up Fluidized BedBaytubes - PropertiesBaytubes - Polymer ApplicationsBaytubes - Electrical Conductivity in PolymersBaytubes Comparison with Carbon BlackBaytubes - Electrical ConductivityPC Influence of Processing ConditionsHealth & SafetyHSEQ ActivitiesBaytubes - Internal Testing ProfileCommunication for Baytubes Closing Motif