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Carbon Nanotubes:Applications and Benefits in the Automotive
Industry
Michael CLAES
Global Technical Director
Nanocyl SA at a glance
• Founded in 2002, Headquarter in Sambreville, BE• 50 people (80% TS, R&D, Manufacturing )• 2 sites: Essor & Vacherie, Sambreville• 460 MT of industrial MWCNT capacity, more than 3500 MT of
thermoplastic compound capacity• International certifications: ISO 9001 & RoHS• A growth y-o-y of % (GM) >20%• More than 55% Sales is NC7000; rest is formulated products
:Thermoplastics, Thermosets, Dispersions (Water or Solvent), • Sales in : Energy (batteries), Electronics, Automotive, custom-Industrial,
Utilities, Medical, etc…
A Dynamic company
2« RoHS » : Restriction of the use of certain Hazardous Substances in electrical and electronic equipment
History and milestones
Move from lab to the industrial production
20102002 2003 2004 20062005 2007 2008 2009 2011 2012 20132010
Industrial unit of 400mt of NC7000™
Stretching of the industrial unit to
> 60 mt of NC7000™
Compounding units>3500 mt capacity high temperature thermoplastics
Demonstrated industrial production
of CNTs
Investment in CNT pilot plant
unit
Foundation of a spin-off from the
Universities of Namur and Liege in Belgium
Located in Namur
University in Belgium
Transfer to current location in Sambreville,
Belgium
1st commercial use of NC7000™
in automotive
Launch of Plasticyl™
Launch Epocyl™,
Thermocyl™, Aquacyl™
Launch Sizicyl™, Pregcyl™, Biocyl™
Start of US& Korean presence
Industrial unit of 40 mt of
NC7000™
Key:
ProductionProductsStructureMarkets
Contract to develop Flat Screens
printing material
1st commercial use of NC7000™
in electronics
Extension of the Plasticyl™product range
R&D Prod. & Admin
1st sales inBatteries
1st sales inA-F Marine
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Electrical ConductivityThe electrical conductivity of CNTs is much higher than copper, allowing non-conductive plasticsto be turned into conductive materials.
Mechanical StrengthThanks to their high elasticity and excellent tensile strength, carbon nanotubes exhibit amechanical strength which is 5 times higher than steel – at only a quarter of the specific weight.
Thermal ConductivityCNTs beat the thermal conductivity of the best natural thermal conductor of all – diamonds.
Flame RetardancyCarbon nanotubes have the ability to promote flame retardancy at very low filling levels thanks tothe formation of a thermal insulating and low permeable char.
What are carbon nanotubes (CNTs)…
Carbon nanotubes are another physical form of carbo n with superior properties
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� Optimized and Easy ProcessingSuperior flowability of CNT based compounds enable more complex mold designsCustom grades exclusively developed for specific applications and processes (EBM, TPU,…)Increased yield on throughputWorldwide technical support to help OEMS & compounders successfuly develop innovations
� Improved SustainabilityWeight Reduction – lower greenhouse gas emissions (automotive parts,…)Energy Saving – Generating more efficient energy-storage solutions (batteries,…)Toxic Components Replacement – Getting rid of toxic components (Anti-fouling, Halogen-free)Recyclability – Improving the applications’ recyclability (electronic packaging,…)Future Developments – Air & waste water treatment
� Total Cost Benefits Thanks to Breakthrough Performa ncesLower loading required compared to conventional materials (carbon black, carbon fiber,…)Improved recyclability Higher mechanical retention allowing innovative and thinner featuresHigher electrical conductivity for emerging applications Higher cleanliness cuts manufacturing losses and OEM product recalls Better abrasion resistance makes plastic components last longer
Key benefits at a Glance
Importance of processing parameters:
Compounding steps
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Percolation vs Mixing - Illustration
Decent Mechanical PropertiesPoor Mechanical Properties
1 2
Torque vs Processing temperature
virgin PC
virgin PC
3% CNT
3% CNT
Torque decreases with increasing CNT%.
- flow reorientation of CNT increase flow
orientation of polymer chain.
- Anisotropy of CNT tube plasticises polymer
chain during shear flow.
3 wt%
280˚C
300 rpmPressure increase a bit with increasing
CNT%.
- Better melt strand stability, given by small
increase in die pressure.
- Increase in pressure is small, no effect on
throughput.
Ramification : Introduction of CNT at less than 5wt% actually helps to increase throughput.
This is contrary to popular believe that CNT causes reduction in throughput.
Torque & pressure decreases linearly Torque & pressure decreases linearly Torque & pressure decreases linearly Torque & pressure decreases linearly
with temperature.with temperature.with temperature.with temperature.
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Torque vs screw speed
virgin PC
virgin PC
3% CNT
3% CNT
Torque decreases linearly with screw speed up
to 300 rpm, then level off.
- possibly maximum shear thinning or full chain
stretch or alignment reached at 300 rpm.
3 wt%
280˚C
300 rpm
Die pressure reduces a little until 300 rpm, then
level off.
- same reason as above.
Ramification : CNT improves melt shear thinning effect .
In another word, introduction of CNT actually improves processability.
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Lower
transition
Temperature vs. Conductivities
Upper
transition
10
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CNT from Nanocyl: NC7000TM
Quality, intrinsic properties and cost price of the carbon nanotubes are different among manufacturers and are dependent on raw materials used ( catalyst) and on the production process (reactor).
Because of Nanocyl’s unique catalyst composition and reactor , both protected by international patents, Nanocyl is able to offer carbon nanotubes:
• with the best electrical properties on the market , leading to lower loading required compared to its competitors
• with a cost advantage over its competitors
Importance of processing parameters:
Converting compounds
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Combine surface quality and conductivity
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Decrease injection speed
to improve conductivity
Increase injection speed
to improve surface quality
Increase Mat. Temp. to improve
conductivity
Decrease Mat. Temp. to
improve surface quality
1 2
1
1
1 1
2
1 1
Antagonist effect !!!
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Combine surface quality and conductivity
� Minimize clear spots (target = 0, upper value = 0,5)� Minimize pinholes (target =0, upper value = 0,5)� Minimize SR (target = 1E+03 Ohm.sq, upper value = 1E+06
Ohm.sq)� Minimize VR (target =1E+01Ohm.cm, upper value = 1E+04
Ohm.cm)
Injection speedMold
temperatureMateiraltemp.
Plast.speed
Backpressure
Holdingpressure
Holding time
SR VR PinholesClearspots
cm³/s °C °C m/s bars bars s Ohm.sq Ohm.cm - -
30 120 300 0.4 40 450 8 7 E+03 8 E+01 0 0
Calculation of optimization according factorial desi gn
Recommendations: Mold temp : max
(120°C)Mat temp: max
(300°C)Injection speed :
medium
Model and parameters validated !
Perfect surface finish and high level of conductivity just with good injection
molding parameters !
Automotive applications
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Your title hereESD Critical Parts in Fuel Systems
Component Acetal PPS PBT HDPE HT PA PA 6/6 PA 12
Fuel filler pipes x x xFuel lines xFuel pump components x x xQuick connectors x x x x
Architecture of electrically conductive fuel supply systems
Automotive Applications
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Injection molding application:Fuel pump
• Meets SAE J1645 standards
• Weight reduction of automotive parts
• Allow innovative designs, due to easierprocessing of Nanocyl compounds
• Dimensional Stability & Creep resistance
• Cost competitive solution
• Nanocyl CNTs impart electricalconductivity at a lower loading
Conductive additive for fuel lines
Plasticyl POM1001 - Typical Performance after dilutio n and Injection Molding
2%WT 3%WT 5%WT
Volume resistivity Ohm.cm 5 2 <1
Surface resistivity Ohm/sq 540 46 10
NC7000 can be used to develop fuel pump solution :
� Approved in automotive fuel pump systems � With SR < 10 3 Ohm.sq at very low loadings (<2.5
wt%) � Fully complying with SAE J 1645 recommendation� Resistant to aggressive chemicals in fuels (Fluid
L,C, RME,SME) (retention of electrical properties)� Clean (no leaching of additives, NC7000 fully
embedded in matrix)� Cost, weight and energy saving� With good long term creep behavior� With same friction property as based POM� Fully recyclable� Compatible with standard process equipment
Injection molding application:Fuel pump
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Quick Connectors in Fuel Systems
• Electrically conductive PA
• Keeping PA properties offering ESD and conductive properties
• Conductivity not sensitive to fuel contact, fluid L , C, etc.
• Meets SAE J 1645 standards
• Fits existing machinery/tooling
• Tailor-made properties thanks to tailor-made products
Injection molding application:Quick connectors
1,00E+00
1,00E+01
1,00E+02
1,00E+03
1,00E+04
1,00E+05
1,00E+06
Fuel C Fuel CE 10 Fuel CP Fuel CE 85 Fuel B 10
Surface resistivity after fuel immersion (PA 12/C70 00) – External Data
Resisitivity min
Resitivity max
Resisitivity min 48h
Resitivity max 48h
Resistivity max SAE
Resistivity min/max measured directly taken out of fuelResitivity min/max 48h, dried for 48h
Min of SR measured
Max of SR measured
Min of SR measured after 48h of drying
Max of SR measured after 48h of drying
Max of SR permit by standard SAE J 2044 (10 6 Ohm/sq)
1,00E+00
1,00E+02
1,00E+04
1,00E+06
0 500 1000 1500 2000 2500
Su
rfa
ce r
esi
sta
nce
(O
hm
)ageing time (h)
Surface resistivity after fuel immersion
(PA12/NC7000) – Nanocyl Data
SP95 SP98 EN590 Hot air
In addition of excellent retention of SR, PA12/NC7000 composites present excellent retention
of mechanical properties (pull apart and insertion force as well as impact resistance).
Nanocyl can provide injection molding guidelines to g et the best surface conductivity in combination with the best s urface quality
Injection molding application:Quick connectors
Insertion force N
Quick Connectors Basic Requirements/ Immersion in Fuel/ Insertion Force / SAE J 2044
Max acceptable insertion force 111N (PA 12 30%GF)
Resistivity min/max measured directly taken out of fuel
Resitivity min/max 48h, dried for 48h
0
20
40
60
80
100
120
Insertion F min Insertion Fmax
Insertion F min48h
Insertion Fmax 48h
max
max accepted ins force
Fuel C
Fuel CE 10
Fuel CP
Fuel CE 85
Fuel B 10
Easy to insert – Keeps elasticity and flexibility properties
Pull apart force N
Quick Connectors Basic Requirements/ Immersion in Fuel / Pull Apart Force/ SAE J 2044
Min. acceptable pull apart force 297 N (PA12 30% GF)
Pull apart forces measured immedialtely after taken out of fuel,
48h dried values same level but in lbs, therfore not considered here
0
200
400
600
800
1000
1200
min pullapartforce
Fuel C Fuel CE10
Fuel CP Fuel CE85
Fuel B10
pull apart force min
pull apart force max
Strong connection – Keeps the tube in place
Impact resistance test
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0
50
100
150
200
250
300
350
400
450
air SP95 SP98 E5 EN590
Str
2 (
J/m
) 150h
250h
500h
Reference air RT
High conductivity and mechanical performance! No contradiction
Injection molding application: Filler system application (HDPE)
Addition of NC7000 can impart excellent surface resistivity in GF reinforced HDPE. A very good retention of mechanical properties is observed
Nanocyl can provide injection molding guidelines to g et the best surface conductivity in combination with the best s urface quality
0
2
4
6
8
Lupolen + CNT + GF Ciblene GF17/2Elo
ng
ati
on
at
Bre
ak
(%
)
Elongation at Break (%)
0
500
1000
1500
2000
2500
Lupolen + CNT + GF Ciblene GF17/2
E-M
od
ulu
s (M
Pa
)
E Modulus (Mpa)
HDPE/NC7000/GF Reference
HDPE/NC7000/GF Reference
HDPE/NC7000/GF Reference
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Multi-Layer Fuel Lines
• Conductive PA 12 (layer)
• Keeping PA 12 properties while being electrically conductive and protected from ESD
• Conductivity not sensitive to fuel contact, fluid L, C, etc.
• Fits to current MLT technology of resin manufacturers
• Highly flexible
• Fits with standard extrusion equipments
Tube extrusion application:Conductive Tubing – Fuel lines
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0
0,2
0,4
0,6
0,8
1
1,2
300h @RT FUEL
C
20% strain 50% strain 100%strain
Sur
face
res
istiv
ity -
M O
hm
Fluid C
mix of 50/50 isooctane and tolueneunleaded petrol, selective
permeation
Test specimen
2 layers corrugated tube, Outer layer = 0,7mm - PA non conductive,Inner layer = 0,3mm -PA/NC7000 composite
0
0,2
0,4
0,6
0,8
1
1,2
300h @RT
Diesel
20%strain
50%strain
100%strain
Sur
face
res
istiv
ity -
M O
hm
Nanocyl
Competition
Diesel DIN 590 Diesel
Surface resistivity of tubes after ageing in fuels and under several deformation constraints –PA12/NC7000 composites – External data SAE J 1681
• PA12/NC7000 based tubes present very good retention of SR un der up to 100 %of strain after 300h of ageing, this in different kind of fuel s (Diesel and Fluid Cbut also Biodiesel, and FAMB)
• Flexibility of tubes remains within specification too
Nanocyl can provide tube extrusion guidelines to get the best surface conductivity in combination with the best surface q uality
Tube extrusion application:Conductive Tubing – Fuel lines
Part 1 : NC7000 Loading and Process Temperature
Extruder Temperature ( °C)
Surface Resistivity (Ohm) Surface Aspect
7%wt CNT230 10E4 Roughness – mat245 10E3 Roughness – mat260 10E3 Roughness – glossy
4%wt CNT230 10E5 Roughness – mat245 10E5 Roughness – mat260 10E4 Roughness – glossy
2.5%wt CNT230 10E7 Small dots – glossy245 10E5 Glossy260 10E4 Glossy
Increase of process temperature increases strongly theconductivity of the tube, but surface keeps a certainroughness at most temperatures.
Tube extrusion process:
Part 2 : Additives
Additives help to obtain a better surface aspect.
Extruder Temperature
(°C)
Surface Resistivity
(Ohm)Surface aspect
4% wt CNTNo additive
245 10E4 Roughness – mat
260 10E4 Roughness – mat
4% wt CNTAdditive A
245 10E4 Smooth – mat
260 10E4 Smooth – glossy
4% wt CNTAdditive B
245 10E4 Roughness – mat
260 10E4 Smooth – glossy
Tube extrusion process:Recommendations for PA/NC7000
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Conductive Resins for Body Panels & Windshields (injection & extrusion)
• E-paintable
• Superior HDT resistance
• Class A surface
• Weight reduction
• No color matching
Sheet extrusion application:E-painting
Non ESD applications for Automotive
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Conductive Resins for Automotive Heating Seats mate rials
- Extrusion of thermoplastics (ABS)- 2K molding panel (TPU, PVC)- Coating over textile fabrics (PU)
Technical specifications
- SR < 10 ohm/sq- Soft finishing- 12 V adaptable
Heating systems
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Temperature control through voltage
Heating systems
Time (s)
Tem
péra
ture
Time (s)
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High stability and homogeneity
Heating systems
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Structural Composites
95%
Strong influence of NC7000 on G1C
On industrial level, Sizicyl did improveCompression strength by 7-10 % compared toreference material.
Today, application are fishing rods, formula 1
Compression after Impact is improved by 40 %thanks to localization of NC7000 at the fiberinterface.
Compression resistance
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Lithium batteries : Performance improvement by
CNT - particles bonding mechanism
Source : High-density positive electrodes containing carbon nanotubes for use in Li-ion cells,Kyuyun Sheem, Young Hee Lee, Hong S. Lim, Journal of Power Sources 158 (2006) 1425-1430
Ba
tte
ryte
mp
ratu
re(°
C)
Discharge capacity (%)
20
30
40
50
60
0 30 60 90
2% NC7000
2% conductive
CB
10C discharge
2%
MWCNT
Dis
char
geca
paci
tyre
tain
tion
Cycle number
40%
55%
70%
85%
100%
0 10 20 30 40
2% NC7000
2%
conductive
CB
1C 2C 3C
2%
MWCNT
0 1 2 3 4 5 6 7 8 9 10
Loading of carbon additive (wt.%)
Ele
ctro
de
re
sist
ivit
y(a
.u.)
NC7000Conductive CB
Graphite
Target electrode
resistivity
MWCN
T
Typical target
electrode
resistivity
Lithium batteries : Benefits brought by CNTs
LiFePO4 cathode
Discharge capacity (%)
Po
we
r d
en
sity
(W/k
g)
Improve conductivity of the
electrodeImprove number cycles /
reduce capacity loss
Improve power
density Reduce battery temperature
Sensors
Temperature sensors
Gas/liquid sensors