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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
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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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Dr. Helmut Meyer • Page 3BMS-CAS-INN-CNT
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Bayer GroupBayer Group
Dr. Helmut Meyer • Page 3BMS-CAS-INN-CNT
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 Vollzeitkräfte umgerechnet.
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Dr. Helmut Meyer • Page 4BMS-CAS-INN-CNT
Bayer: Science For A Better LifeBayer: Science For A Better LifeE
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Dr. Helmut Meyer • Page 4BMS-CAS-INN-CNT
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Dr. Helmut Meyer • Page 5BMS-CAS-INN-CNT
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-Äquivalenteinkl. kundennahe Entwicklungen
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Dr. Helmut Meyer • Page 6BMS-CAS-INN-CNT
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
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Dr. Helmut Meyer • Page 7BMS-CAS-INN-CNT
Carbon NanotubesAlt bewährt und Material der Zukunft
Properties of Carbon NanotubesTear strength > 10 GPaE-modulus > 1 TPaThermal conductivity > 2000 W/mKElectrical conductivity > 104 S/cm
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Dr. Helmut Meyer • Page 8BMS-CAS-INN-CNT
MechanicalMechanical StrengthStrength
www.montrealhockey.com
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Dr. Helmut Meyer • Page 9BMS-CAS-INN-CNT
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
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Dr. Helmut Meyer • Page 10BMS-CAS-INN-CNT
Catalytic Chemical Vapor DepositionCatalytic Chemical Vapor Deposition
Dp = 80 μm
ρ = 2000 kg·m-3
CNT-Agglomerate
Dp = 1200 μm
ρ = ca. 150 kg·m-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
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Dr. Helmut Meyer • Page 11BMS-CAS-INN-CNT
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
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Dr. Helmut Meyer • Page 12BMS-CAS-INN-CNT
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 [%
]
500µm73,7 : 1 B096501RE101
CNT-Agglomerate(> 95 % purity)
200nm93910 : 1
X1300
Magnification
Particle-Size Distribution
100µm
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Dr. Helmut Meyer • Page 13BMS-CAS-INN-CNT
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
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Dr. Helmut Meyer • Page 14BMS-CAS-INN-CNT
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
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Dr. Helmut Meyer • Page 15BMS-CAS-INN-CNT
BaytubesBaytubes®® -- Polymer Polymer ApplicationsApplications
Electrical conductivity Mechanical strength
Thermal conductivity
•Antistatic behaviour•Automotive parts•Automotive fuel lines
•Electrostatic painting•Car body panels•Mirror housings
•Electrical conductivity•IC trays, carrier tapes•Intermediate container
•Electromagnetic shielding•Mobile phones•Housings
•Sporting goods•Aircraft parts•Lightweight construction•Adhesives•Polymer fibers•Coatings
•Electronic components
•Elastomers
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Dr. Helmut Meyer • Page 16BMS-CAS-INN-CNT
0,01 w.-% CNT
Techniques•In-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
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Dr. Helmut Meyer • Page 17BMS-CAS-INN-CNT
BaytubesBaytubes®® --ElectricalElectrical ConductivityConductivity in Polymersin Polymers
Baytubes® carbon nanotubes show higher conductivity at lowerloadings compared to high end conductive carbon blacks
Quelle: Hyperion
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Dr. Helmut Meyer • Page 18BMS-CAS-INN-CNT
BaytubesBaytubes®®ComparisonComparison 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
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Dr. Helmut Meyer • Page 19BMS-CAS-INN-CNT
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
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Dr. Helmut Meyer • Page 20BMS-CAS-INN-CNT
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
[ Ω/
]
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
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Dr. Helmut Meyer • Page 21BMS-CAS-INN-CNT
BaytubesBaytubes®® --ApplicationsApplications in in ThermoplasticsThermoplastics
Addition of Baytubes results in • improved electrical conductivity• improved mechanical strength• at low CNT loadings
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Dr. Helmut Meyer • Page 22BMS-CAS-INN-CNT
BaytubesBaytubes®®ColourColour of of CompositeComposite MaterialMaterial
0,05 w.-% CNT 0,01 w.-% CNT
Compounded material likely to be blackCertain transparency achievable at low loading level
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Dr. Helmut Meyer • Page 23BMS-CAS-INN-CNT
BaytubesBaytubes®® --ElectricalElectrical ConductivityConductivity in in EpoxiesEpoxies
Epoxide: Araldite564/ HY2954
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Dr. Helmut Meyer • Page 24BMS-CAS-INN-CNT
BaytubesBaytubes®® --MechanicalMechanical StrengthStrength in in EpoxiesEpoxies
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Dr. Helmut Meyer • Page 25BMS-CAS-INN-CNT
BaytubesBaytubes®® -- MechanicalMechanical StrengthStrengthApplicationsApplications in in SportingSporting GoodsGoods
„The worlds toughest Hockey Stick“
„lightestand
strongestxc-ski to
day“
Ultra-light weight Exel sticks
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Dr. Helmut Meyer • Page 26BMS-CAS-INN-CNT
BaytubesBaytubes®® -- Low Low WeightWeight and and Proper Proper FlexuralFlexural Response in Response in EpoxiesEpoxies
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Dr. Helmut Meyer • Page 27BMS-CAS-INN-CNT
BaytubesBaytubes®®UseUse in in LightweightLightweight Construction Construction
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Dr. Helmut Meyer • Page 28BMS-CAS-INN-CNT
BaytubesBaytubes®® -- ConcreteConcrete ReinforcementReinforcementApplicationApplication Potentials in ConstructionPotentials in Construction
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Dr. Helmut Meyer • Page 29BMS-CAS-INN-CNT
Health & Health & SafetySafety
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Dr. Helmut Meyer • Page 30BMS-CAS-INN-CNT
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
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Dr. Helmut Meyer • Page 31BMS-CAS-INN-CNT
• 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/m³ (micronised Baytubes)Concentrations ≥11 mg/m³ 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
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Dr. Helmut Meyer • Page 32BMS-CAS-INN-CNT
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)
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Dr. Helmut Meyer • Page 33BMS-CAS-INN-CNT
Communication for Baytubes® Communication for Baytubes®
• Product Stewardship at BMS for Nanomaterials– BayCare Webpage
www.baycareonline.com(Free registration, see “What’s 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)
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Dr. Helmut Meyer • Page 34BMS-CAS-INN-CNT
TheThe WinningWinning TeamTeam
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Dr. Helmut Meyer • Page 35BMS-CAS-INN-CNT
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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 Conductivity�PC – Influence of Processing ConditionsHealth & SafetyHSEQ ActivitiesBaytubes® - �Internal Testing ProfileCommunication for Baytubes® Closing Motif