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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

13

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