CONDUCTIVE ELASTOMERS:

PARAMETERS AFFECTING THEIR PROPERTIES AND CONDUCTIVITY

C. Mangone, W. Kaewsakul, W.K. Dierkes, A. Blume
Elastomer Technology and Engineering, Department of Mechanics of Solids, Surfaces and
Systems, Faculty of Engineering Technology, University of Twente, The Netherlands

M. Klein Gunnewiek, L.A.E.M. Reuvekamp

Apollo Tyres Global R&D B.V., Enschede, The Netherlands

presented at
Tire Technology Conference, Hannover, Germany
March 06, 2019
 1. INTRODUCTION
MARKET TREND – NEW TYRE LABELLING
European Regulation no. 1222/2009

Wet grip
Fuel Efficiency.
 The difference between F and A  The difference between G and A
could reduce fuel consumption up to could be up to 30% shorting braking
7.5%. distance.
 For A class the proposed RR labels  For A class the proposed WG labels
for C1, C2 and C3 tyres are below for C1, C2 and C3 tyres are above
5.4, 4.4 and 3.1 Kg/t respectively. 1.68, 1.53 and 1.38 respectively.
.

Noise Levels Snow and Ice grip

2
TERMA's position on the review of the Tyre Labelling proposal, 2018.
 1. INTRODUCTION
MARKET TREND – INFLUENCE OF FILLERS
Magic Triangle

High vinyl S-SBR / BR

HR-Silica / Silane

 E-SBR / Carbon Black

Higher wet grip (~7%)
 Lower rolling resistance (~30%)
 Reduced fuel consumption (~5%)
 Improved winter properties The CB can promote the
conductivity to rubber
× Low conductivity compounds!

3
EVONIK industries, Customer seminar, 2009.
 1. INTRODUCTION
IMPORTANCE OF THE CONDUCTIVITY FOR A TYRE
Volume Resistivity (Ω∙cm)

Conductivity 1016

Insulative
of a tyre Glass
1014
1012 Diamond

Electrostatic/
Dissipative
1010
Carbon black-
Discharged static 108
filled polymer
electricity for a tyre 106
while rolling 104
102 Silicon

Conductive
1
10-2
A safer
drive 10-4
10-6 Gold, Copper, Silver
Birla Carbon, Rubber Carbon Black Technology, 2017. 4
Pank H. et al., Prog. Polym. Sci., 39, 2014.
 1. INTRODUCTION
CONDUCTIVE MECHANISM - ELECTRON TUNNELING EFFECT
Carbon black network

Gaps for the

electrons
10-30 nm

Fritzsche J. et al., J. Phys.: Condens. Matter, Vol. 23, 11, 2011. 5

Orion Engineered Carbons, 2012.
2. FACTORS INFLUENCING ELECTRICAL CONDUCTIVITY
OVERVIEW

CB loading CB properties

CB filled rubber

Polymer &
CB = Carbon black Dispersion
processing
6
 2. FACTORS INFLUENCING ELECTRICAL CONDUCTIVITY
CARBON BLACK LOADING
Percolation theory

Percolation zone

Volume Resistivity (Ω∙cm) 1014 - 1018 Ω∙cm

Insulating Zone
108 Ω∙cm

<102 Ω∙cm
Conductive Zone

ϕc ϕ (wt%) 7
Liu X., PhD thesis, Friedrich-Alexander University of Erlangen-Nurnberg, Germany 2016.
 2. FACTORS INFLUENCING ELECTRICAL CONDUCTIVITY
CARBON BLACK PROPERTIES
Morphology of carbon black Structure of carbon black particles

Spheroidal Branched

Ellipsoidal

Linear

Araby S. et al., Nanotechnology, Vol 26, 23 2015. 8

Martinez R.F., Comput. Mater. Sci, Vol 91, 2014.
 2. FACTORS INFLUENCING ELECTRICAL CONDUCTIVITY
DISPERSION OF CARBON BLACK
Possible structure and surface area of carbon black
dispersed in an elastomeric matrix

Requirements and challenging:

- Very good dispersion of carbon black
- Low amount of conductive carbon
black is needed
- High structure and high surface area
of CB are required to minimize its
amount used
- Very efficient technique to mix the
compound is challenging
9
http://www.cabotcorp.com/solutions/applications/industrial-rubber-products/dispersion
 2. FACTORS INFLUENCING ELECTRICAL CONDUCTIVITY
CB PROPERTIES - PARTICLE SIZE AND STRUCTURE OF CARBON BLACK
CB/EPDM composites

1016

1014 Basic properties of carbon blacks used

Volume Resistivity (Ω∙cm)

1012 A
A B C D E
B
CTAB [m2/g] 23 23 24 31 40
10 10

DBP
90 102 114 130 121
10 8
C [ml/100g]
D
Mean agg
106 362 343 339 295 240
size [nm]
104 E
- Sulphur cure
102
- Internal mixer with dump
100 temperatures at 100-160oC
50 140 70 80 90 100 110 120 130 140

ϕ, phr
10
Niedermeier W. et al., KGK Kautschuk Gummi Kunststoffe, 2003.
 2. FACTORS INFLUENCING ELECTRICAL CONDUCTIVITY
CB PROPERTIES – SHAPE
Multiwalled Carbon Nanotubes

1014

1012

Volume Resistivity (Ω∙cm)

d=10 nm
l=1.5 mm • Sulphur cure
1010
• Solution blending
using a sonication
108 process
- High surface area (250-300 m2/g)
- High aspect ratio
- Improvement of mechanical properties, 106
especially strength
- Excellent electrical properties 104

100
0 1 2 4 5 6 8 10
11
Mensah B. et al., International Journal of Smart and Nano Materials, Vol. 6 , 211, 2015. ϕ (phr)
 2. FACTORS INFLUENCING ELECTRICAL CONDUCTIVITY
CB PROPERTIES – SHAPE
Graphite

0,14 nm

1018 • Silicone
SR
rubber
• Room temperature

0,34 nm
1016 curing agent
• Solution blending

Log ρ (Ω∙cm)
using a sonication
1014
process

1012

- High surface area (2630 m2/g) 1010

- High aspect ratio (0,188)
- Improvement of mechanical properties, 108
especially strength
0 1 2 3 4 5
- Excellent electrical properties
ϕ, wt%

12
Sadasivuni K.K. Et al., Progress in Polymer Science, 39, 2014.
 2. FACTORS INFLUENCING ELECTRICAL CONDUCTIVITY
POLYMER TYPE AND PROCESSING METHOD
Percolation Threshold of MWCNT/elastomeric composites

Rubber Processing Percolation threshold

SBR Dry mixing (IM) 5 phr
SBR/BR Dry mixing (IM) <3 wt%
SBR/NBR Dry mixing (IM) ~1 wt%
NR/NBR Dry mixing (IM) 2 phr IM = Internal Mixer
IIR Dry mixing (IM) 6-8 phr
CR Dry mixing (IM) 5 phr
CR Dry mixing (two-roll mill) 3 phr
NR Dry mixing (two-roll mill) 9-16 wt%
NR Solvent 0,5-1 phr
EPDM Solvent 4 phr
SBR Solvent 2-3 phr

13
Mensah B. et al., International Journal of Smart and Nano Materials, Vol. 6, 211, 2015.
 2. FACTORS INFLUENCING ELECTRICAL CONDUCTIVITY
POLYMER PROPERTIES

 Chemical similarity between carbon black

surface and polymer chain
o e.g. chemical nature, macrostructure of
chain, surface energy distribution

 Viscosity (preferably low)

 Compatibility of polymer blend affects the

migration of filler particles

Mostafa A. et al., Journal of Testing and Evaluation, Vol. 38, 347, 2010.
Jiang Z. et al., Colloids and Surfaces A: Physicochem. Eng. Aspects, Vol. 395, 105, 2012. 14
Bokobza L., ESPCI ParisTech, 2012.
3. ELECTRICAL CONDUCTIVITY UNDER STATIC STRAIN
SETUP

15
 3. ELECTRICAL CONDUCTIVITY UNDER STATIC STRAIN
UNIAXIAL TENSION
CB/NR composites

• 70 phr CB
Resistivity ρ, Ω∙cm

Alignment of aggregates

Breakdown of agglomerates
Breakdown of filler agglomerate
structure under strain

N330
Extension ratio
BET (m2/g) 78
DBP (ml/100g) 102 16
Yamaguchi K. et al, Journal of Polymer Science: Part B Polymer Physics, Vol. 41, 2079, 2003.
 3. ELECTRICAL CONDUCTIVITY UNDER STATIC STRAIN
LOADING/UNLOADING
CB/NR composites
50 phr CB N330 10 phr of CCB

Log Resistivity ρ, Ω∙cm

Log Resistivity ρ, Ω∙cm

Extension ratio Extension ratio

N330 CCB
BET (m2/g) 78 1000 CCB = conductive carbon black
DBP (ml/100g) 102 370
17
Jha V. et al., Journal of Applied Polymer Science 116, 2010.
4. ELECTRICAL CONDUCTIVITY UNDER DYNAMIC STRAIN
SETUP
DMA Breadboard Voltage Power
module Supply

Voltage module

Sample Breadboard Power

DMA Supply

18
 4. ELECTRICAL CONDUCTIVITY UNDER DYNAMIC STRAIN
TIME SWEEP
CCB/S-SBR composites

S-SBR 25% vinyl - 25% styrene

• Sulphur cure system
CCB 12 phr BET = 1000 m2/g • Internal mixer
DBP = 420 ml/100g

19
Bhagavatheswaran E.S. et al., 190th Technical Meeting of Rubber Division ACS, 2016. CCB = conductive carbon black
 4. ELECTRICAL CONDUCTIVITY UNDER DYNAMIC STRAIN
TIME SWEEP

Tan δσ-ε Tan δσ-R

Sinusoidal trend of resulting

stress (linear viscoelasticity)
and resistance.

20
Bhagavatheswaran E.S. et al., 190th Technical Meeting of Rubber Division ACS, 2016.
 4. ELECTRICAL CONDUCTIVITY UNDER DYNAMIC STRAIN
TEMPERATURE SWEEP
CCB/S-SBR composites

□ 12 phr CCB
○ 13 phr CCB

21
Bhagavatheswaran E.S. et al., 190th Technical Meeting of Rubber Division ACS, 2016.
5. CONCLUSIONS

 The electrical conductivity of a tyre promoted by carbon blacks can improve the dissipation of static charge
accumulated on the tread surface
 The factors influencing the electrical conductivity of an elastomer are:

 Loading level of CB: above the percolation threshold

 CB properties: high surface area and high structure

 Filler dispersion: very good dispersion is desired

 Polymers & processing: good affinity and interaction with CB, good technique to disperse the carbon black
particles
 The conductivity of carbon black-filled elastomer composites can be monitored under both static and dynamic
circumstances

22
ACKNOWLEDGEMENTS

 Apollo Tyres Global R&D B.V. (Enschede, The Netherlands) for the permission to present this
work

 Dr. Michel Klein Gunnewiek, Dr. Louis Reuvekamp and the other colleagues of Apollo Tyres for
the scientific support

 Dr. Wisut Kaewsakul, Dr. Wilma Dierkes, Prof. Anke Blume, Andries van Swaaij and the other
colleagues of ETE
 THANK YOU
FOR YOUR
ATTENTION
Carmela Mangone
c.mangone@utwente.nl
carmela.mangone@apollotyres.com