1. Science For A Better Life
Application of
Carbon Nanotubes in Plastics
Themadag „Nanotechnology“
Mikrocentrum
Feb. 4, 2010, Eindhoven
2. 108,600 employees
Full year sales: EUR 32.9 billion
316 subsidiaries
R&D expenditures: EUR 2.7 billion
As of December 31, 2008
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3. Corporate History
1863 Company founded by F. Bayer and J.F. Weskott in Wuppertal
1912 Corporate headquarters established in Leverkusen
1951 Re-establishment of Farbenfabriken Bayer AG
2001 Acquisition of Aventis CropScience
2002 / 2003 Reorganization of the Bayer Group
2005 Lanxess AG is spun off from the Bayer Group
2006 Takeover of Schering AG, Berlin, Germany
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5. Bayer MaterialScience
Full Year 2008
Employees* 15,100
Sales (2008) EUR 9,738 million
EBITDA before special items EUR 1,088 million
Chairman of the
Executive Committee Patrick Thomas
* Employees in full-time equivalents.
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6. Bayer MaterialScience – Business Units
Polycarbonates Polyurethanes Coatings, Adhesives,
Specialties
Bayblend Baydur Bayhydrol
Makrolon Bayfill Baytubes
Bayfit Desmodur
Desmopan Desmophen
Multitec Dispercoll S
Vulkollan Makrofol
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8. Mechanical Strength
www.montrealhockey.com
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9. Carbon Nanotubes
20 nm
25 nm
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
BTS
High carbon black residue (up to 50% if arc-
discharge process is applied)
20 nm
Multi-Wall Carbon Nanotubes (MWNT):
Diameter : 5 - 100 nm
High defects, high aspect ratio
Cost effective process possible (CCVD)
(high yield, low catalyst residue)
Already in use in polymers
BTS
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10. Catalytic Chemical Vapor Deposition
„Expanding Universe“
Mechanism
Dp = 80 µm Dp = 1200 µm
ρ = 2000 kg·m-3 ρ = ca. 150 kg·m-3
Agglomerated catalyst particles CNT-Agglomerate
Scheme of the metal-
catalyzed growth of a
carbon nanofiber from Movie Source: Stig Helveg et al., Atomic-scale imaging of
gaseous hydrocarbons carbon nanofiber growth, Nature 427 (2004), 426-429
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11. CNT Synthesis: CCVD / Fluidized Bed
H2 / inert gas
High carbon yields of catalyst
Filter &
High space-time yield
Incineration
Agglomerated / entangled product
easy to handle
Catalyst
Product agglomerates must be disentangled during
processing
Heating
Agglomerates of CNT
( > 95 % C-purity)
Agglomerated
primary catalyst
particles CNT-Agglomerate
Hydrocarbons /
H2 / inert gas
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12. CNT Synthesis: CVD / Fluidized Bed
Magnification
X1300
73,7 : 1 B096501RE101
500µm
Particle-Size Distribution
100 93910 : 1
200nm
c u m u la tiv e v o lu m e tric c o n te n t Q 3 [% ]
90
80
CNT-Agglomerate
70 (> 95 % purity)
60
100µm
50
40
30
20
10
0
0,1 1 10 100 1000 10000
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13. Baytubes® - Properties
Multi-wall carbon nanotube agglomerates of very high purity
Low fraction of catalyst residues enables immediate application
in most polymers without costly purification processes
1µm
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14. Production Scale Up – Fluidized Bed
Bench Scale Pilot Scale-1 Pilot Scale-2
in operation 2006/07 2010
in operation In operation
ID = 0.1 m Reactor 1 Fluidized bed
reactor 30 tons p.a. 200 tons p.a.
3-5 tons p.a.
Reactor 2
30 tons p.a
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15. Baytubes® - Applications
CURRENT SHORT TERM MID TERM LONG TERM
Conductive &
Sporting Goods
Reinforced
Polymers
EMV Shielding Automotive
Metal Reinforcement
Sensors and Actuators
Li Ion Batteries Electro/Electronic
Textiles and Fibers
Solar Energy Converters
Catalyst Support Aerospace
Advanced Ceramics
Fuel Cell Membranes
Radar Absorbing coatings
Self Assembling Yarns
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16. Baytubes® -
Electrical Conductivity in Polymers
Carbon nanotubes
Spherical particles
Quelle: Hyperion
Baytubes® carbon nanotubes show higher conductivity at lower
loadings compared to high end conductive carbon blacks
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17. Baytubes® -
Electrical Conductivity in Polycarbonate
Surface Resistivity [Ohm/sq]
1,E+11 Baytubes C150P
1,E+10
High End Conductive CB
1,E+09
1,E+08
1,E+07
1,E+06
1,E+05
1,E+04
1,E+03 Polymer: Makrolon 2805
Dispersion machine: ZSK 26Mc
1,E+02 Screw speed: 400 1/min
Torque: 80%
1,E+01
Temperature profile: 280 ° (standard)
C
1,E+00 Parts Injection Moulded
0 2 4 6 8 10 12
Baytubes content [wt%]
Baytubes® show higher conductivity at lower loadings compared
to high end conductive carbon black in polycarbonate.
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18. Baytubes® Dispersion
50 µm 50 µm 50 µm
High electrical conductivity can only be achieved when primary CNT
agglomerates have been sufficiently dispersed in the polymer
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19. Baytubes® Dispersion
Medium to low viscous materials
High viscous materials •Three roll calander
•Melt impregnation •Ultrasonic probe
•High shear extrusion •Pearl mill
•In-situ polymerization •High shear dispenser
PC PA Polyol
200 nm 200 nm
200 nm
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20. Baytubes®
Optimization of molding conditions
Best surface conductivities can be obtained by:
- high melt temperatures - reduced injection speed
- high CNT content - lower polymer viscosity
- higher part thickness
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21. PC-CNT Composites
Optimization of molding conditions
Polymer Makrolon M2200 Makrolon M2200
Part thickness [mm] 3 3
Injection speed [cm/sec] 10 40
Fast and efficient development of PC-CNT plastics parts
with model for optimized molding conditions
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22. Baytubes® -
Applications in Thermoplastics
Addition of Baytubes results in
• improved electrical conductivity
• improved mechanical strength
• at low CNT loadings
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23. Baytubes® -
Electrical Conductivity in Thermosets
Torus mill
Three roll
calander
Baytubes® in epoxy; data from IVW Kaiserslautern
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24. Baytubes® - Mechanical Strength
Applications in Sporting Goods
„The worlds toughest Hockey Stick“ Ultra-light weight Exel sticks
„lightest
and
stronges
t
xc-ski to
day“
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25. Baytubes® -
Use in Lightweight Construction
Addition of Baytubes® results in
• 10 – 30% increase in mechanical strength
… for improved
mechanical stability
at constant weight
and/or
distinct weight reduction
(material savings)
at constant strength
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27. CNT-dyed Multifilament Yarns
Dye-printing of
polyester yarns by CNT
dispersions for use in
heating textiles
voltage
Filaments with CNT network Fugetsu et al., Carbon (2008), in press
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29. BMS Product Stewardship
Our Goal:
Safe Use “The safe and
of Bayer environmentally
Products sound handling is
essential for every
new technology.”
Safety Concept Bayer Code on
based on Nanomaterials
Risk Assessment
www.baycareonline.com
Hazard x Exposition = Risk
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30. Product Stewardship for Nanomaterials
Bayer MaterialScience is committed to the
generation of knowledge for safety aspects for nanotechnology
Work in Harmonisation Participation to
Associations (DIN, ISO, research projects
(DECHEMA, VCI, OECD) e.g. NanoCare,
CEFIC, ACC) TRACER,
CarboSafe
Development
and validation of Internal testing
measurement programme
Cooperations with for (eco)-tox profile
methods academic institutes determination
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31. Safe Use of Baytubes®
over the Whole Life Cycle
Production
e.g. closed system, automated filling,
End of Life e.g. proper disposal; exhaust gases incinerated
Baytubes® undergo complete
combustion below 600°
C
100
90
80
TGA
70
Product
Gewicht [%]
60
50
40
30
Life
B L Q 1 7 9 6 8 : M IV -0 5 -18 2
20
10
0
0 100 200 300 400 500 6 00 700 800 900
T e m p e ra tu r [°C ]
Cycle
Further Processing
Use Phase e.g. proper use to ensure safe
e.g. nanoparticles embedded in a polymer handling, use of engineering controls,
matrix have a negligible exposure potential use of personal protection measures
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32. (Eco)-Toxicological Test Program Baytubes®
Acute toxicity, oral (OECD 423)
LD50 rat: >= 5.000 mg/kg
Acute toxicity, dermal (OECD 402) All standard studies performed so
LD50 rat: > 2.000 mg/kg
far with Baytubes show no relevant
Primary skin irritation (OECD 404)
Non-irritant (rabbit) adverse effect at realistic exposure
Primary eye irritation (OECD 405) level (GLP studies according to
Non-irritant (rabbit)
Sensitization (OECD 406)
OECD Guidelines).
Negative (Guinea pig)
Genotoxicity in vitro
Not clastogenic in chromosome aberration test in vitro (OECD 473)
Not mutagenic in AMES Test (OECD 471)
Acute bacterial toxicity (OECD 209)
EC50 > 10.000 mg/l (activated sludge)
Acute toxicity to fish (OECD 203)
LC50 > 100 mg/l (Brachydanio rerio (zebra fish); 96 h)
Acute toxicity for daphnia (OECD 202)
EC50 > 100 mg/l (Daphnia magna (Water flea); 48 h)
Acute toxicity for algae (OECD 201)
EC50 134 mg/l (Desmodesmus subspicatus (Green algae); 72 h)
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33. Baytubes® -
Inhalation Toxicology
Toxicology
:
Acute inhalation toxicity: No mortality (micronized Baytubes) Baytubes®
as sold
(LC50 rat: > 241 mg/m³)
Concentrations ≥11 mg/m³ cause a poorly soluble particle effect
No effect outside lungs
Pulmonary toxicity of Baytubes and Quartz are markedly different
: micronization
Sub-chronic inhalation toxicity (90d)
no evidence of any toxicity outside the respiratory tract
(mode of action was typical of other poorly soluble particles)
Baytubes®
as tested
Bayer Occupational Exposure Limit: inhalative
OEL (8-hour TWA): 0.05 mg/m3
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