Polymers

Carbon Additives for

Polymer Compounds

Conductive Carbon Black

Graphite & Coke

www.timcal.com
1
Who are we?

TIMCAL Graphite & Carbon has a strong tra- agement and continuous process improve-
dition and history in carbon manufacturing. Its ment, all TIMCAL manufacturing plants comply
first manufacturing operation was founded in with ISO 9001-2008.
1908. TIMCAL Graphite & Carbon is committed to
Today, TIMCAL facilities produce and market a produce highly specialized graphite and car-
large variety of synthetic and natural graphite bon materials for today’s and tomorrow’s cus-
powders, conductive carbon blacks and water- tomers needs.
based dispersions of consistent high quality. TIMCAL Graphite & Carbon is a member of IMERYS,
Adhering to a philosophy of Total Quality Man- a world leader in adding value to minerals.

Where are we located?

With headquarters located in Switzerland, TIMCAL The Group’s industrial and commercial activities
Graphite & Carbon has an international pres- are managed by an experienced multinational
ence with production facilities and commercial team of more than 430 employees from many
offices located in key markets around the globe. countries on three continents.

HQ Bodio, Switzerland Willebroek, Belgium Lac-des-Îles, Canada Terrebonne, Canada

Graphitization & pro- Manufacturing & pro- Mining, purification and Exfoliation of natural
cessing of synthetic cessing of conductive sieving of natural graphite, processing of
graphite, manufacturing carbon black graphite flakes natural and synthetic
of water-based dispersions, graphite
processing of natural
graphite & coke and
manufacturing & pro-
cessing of silicon carbide

Baotou, China Changzhou, China Fuji, Japan For the updated list of
Purification, intercalation, Manufacturing of Manufacturing of commercial offices and
exfoliation, size reduc- descaling agents and water-based dispersions distributors please visit
tion, shape modification processing of natural www.timcal.com
and sieving & classifying graphite
of natural graphite

What is our vision?

To be the worldwide leader and to be recog-

nized as the reference for innovative capability
in the field of carbon powder-based solutions.

2
Contents

ENSACO® Conductive Carbon Black

TIMREX® Graphite and Coke
Carbon additives for polymer compounds

The products

• Introduction to ENSACO® Conductive Carbon Black p. 4

• Introduction to TIMREX® Graphite and Coke p. 5

• ENSACO® Conductive Carbon Black for polymer compounds p. 6

• TIMREX® Graphite and Coke for polymer compounds p. 8

Typical applications for ENSACO® Conductive Carbon Black

• Electrically conductive plastics p. 10

• Rubber p. 14

• Power cables and accessories p. 17

Typical applications for TIMREX® Graphite and Coke

• Self lubricating polymers p. 18

• Filled PTFE p. 20

• Thermally conductive polymers p. 22

3
 Introduction to ENSACO®
Conductive Carbon Black

Conductive carbon blacks are carbon blacks TEM picture of ENSACO® 250 G
Carbon Black showing the high
with high to very high stucture (or void volume) level of aggregation.
allowing the retention of a carbon network at
By courtesy of University of
low to very low filler content. The void volume Louvain (Louvain-La-Neuve)
can originate from the interstices between the
carbon black particles, due to their complex ar-
rangement, and from the porosity.

100 nm

How ENSACO® Conductive Carbon STM picture of the surface of

ENSACO® 250 G Carbon Black
Blacks are produced 5x5 nm.
The Timcal carbon black process has been de-
By courtesy Prof. Donnet - Mulhouse
veloped around 1980 and is commercially ex-
ploited since 1982. The plant uses most modern
the product

technology. The process is based on partial oil

oxidation of carbochemical and petrochemical
origin. The major difference with other partial
combustion carbon black technologies lies in
the aerodynamic and thermodynamic condi-
tions:
• low velocity;
• no quench;
• no additives. SEM picture of ENSACO® 250 G
Carbon Black illustrating the
high void volume.
This leads to a material with no or nearly no
By courtesy of University of
sieve residue on the 325 mesh sieve and allows Louvain (Louvain-La-Neuve)
the highest possible purity.
The granulation process has been developed to
achieve an homogeneously consistent product
maintaining an outstanding dispersibility. It is in
fact a free-flowing soft flake characterised by a
homogeneous and very low crushing strength 100 nm
that guarantees the absence of bigger and
harder agglomerates.
The process enables the production of easily
dispersible low surface area conductive carbon
blacks as well as very high surface area conduc-
tive carbon blacks. The unique combination of
high structure and low surface area also con-
tributes to give outstanding dispersibility and
smooth surface finish. The low surface area ma-
terials show a chain-like structure comparable
to acetylene black. The very high surface area
materials belong to the Extra Conductive (EC)
family. Although ENSACO® Carbon Blacks are
slightly more graphitic than furnace blacks, they
are quite close to the latter ones as far as rein-
forcement is concerned.
ENSACO® Carbon Blacks combine to a certain
extent both the properties of furnace and acet-
ylene black, reaching the optimal compromise.

4
Introduction to TIMREX®
Graphite and Coke

Graphite finds wide application thanks to its carbon atom and participate in covalent bond-
favourable combination of properties such as: ing with three surrounding carbon atoms in the
graphite planes. The fourth electron is located
• low friction, chemical inertness and in the remaining 2p orbital, which projects
absence of inherent abrasiveness; above and below the graphite plane, to form
• high thermal conductivity, thermal part of a polyaromatic π-system.
stability and electrical conductivity;
• film forming ability on metal surfaces; Delocalisation of electrons in π-electron sys-
• relatively inoffensive nature of both tem is the reason of graphite’s high stability
powders and products of combustion. and electrical conductivity. Interlamellar bond-
ing was once thought to be weak and mainly
These properties are a consequence of the la- the result of Van der Waals forces, however, it
mellar graphite structure and the anisotropic now appears that interlamellar bonding is re-
nature of chemical bonding between carbon inforced by π-electron interactions. Graphite is
atoms. In graphite, three sp2 hybrid orbitals therefore not intrinsically a solid lubricant and
(each containing one electron) are formed requires the presence of adsorbed vapours to

the product
from the 2s and two of the 2p orbitals of each maintain low friction and wear.

How TIMREX® Graphite and Coke

powders are produced

TIMREX® Primary Synthetic Graphite

TIMREX® Primary Synthetic Graphite is pro-
duced in a unique highly controlled graphitiza-
tion process which assures narrow specifications
and unequalled consistent quality thanks to:
monitoring of all production and processing
stages, strict final inspection, and clearly de-
fined development processes.
TIMREX® Primary Synthetic Graphite shows
unique properties thanks to the combination of
a consistent purity, perfect crystalline structure
and well defined texture.

SEM picture of TIMREX® Graphite showing the perfect

crystalline structure.
TIMREX® Natural Flake Graphite
TIMREX® Natural Flake Graphite is produced
in a wide range of products distinguished by
particle size distribution, chemistry and carbon
content. Timcal mines the graphite from its own
source in Lac-des-Îles, Quebec, Canada. Further
processing can be done either in Lac-des-Îles or
in our processing plant in Terrebonne, Quebec,
Canada. All TIMREX® “Naturals” are thoroughly
controlled in our laboratories to ensure quality,
consistency and total customer satisfaction.

Lc
c
TIMREX® Coke
TIMREX® Petroleum Coke is calcined at appro-
priate temperature with low ash and sulphur
c/2
content, well defined texture and consistent
particle size distribution.

c/2 = Interlayer distance

Lc = Crystallite height

5
 ENSACO® Conductive Carbon Black
for polymer compounds

Typical values

Property Test Method UNIT ENSACO® 150 G ENSACO® 210 G ENSACO® 250 G ENSACO® 260 G ENSACO® 350 G

Form Granules (*) Granules Granules (*) Granules Granules

BET Nitrogen Surface Area

m2/g 50 55 65 70 770
ASTM D3037

OAN
Absorption ml/100 g 165 155 190 190 320
ASTM D2414 (1)

COAN Crushed OAN

ml/100 g 95 95 104 104 270
ASTM D2414 (1)

Pour Density
kg/m3 190 210 170 170 135
ASTM D1513
the product

Moisture (as packed)

% 0.1 0.1 0.1 0.1 1 max
ASTM D1509

Sieve residue
325 mesh (45 μm) ppm 2 2 2 2 10
ASTM D1514

Ash Content
% 0.1 0.1 0.01 0.01 0.03
ASTM D1506

Volatile Content
% 0.2 max 0.2 max 0.2 max 0.2 max 0.3 max
TIMCAL Method 02 (2)

Sulphur Content
% 0.5 max 0.5 max 0.02 0.02 0.02
ASTM D1619

Toluene Extract
% 0.1 max 0.1 max 0.1 max 0.1 max 0.1 max
ASTM D4527

pH
8–11 8–11 8–11 8–11 8–11
ASTM D1512

Volume Resistivity
Ohm.cm 2000 max (3) 500 max (3) 10 max (3) 5 max (3) 20 max (4)
TIMCAL Method 11 (3) (4)

(1) Spring: 0.9 lbs/inch; 10 g of carbon black

(2) Weight loss during heating between 105 and 950°C
(3) 25% carbon black in HDPE Finathene 47100
(4) 15% carbon black in HDPE Finathene 47100

(*) ENSACO® 150 and ENSACO® 250 are also available in powder form.

6
ENSACO® Conductive Carbon Black
for polymer compounds

Typical effects on polymer compounds

Property ENSACO® 150 G ENSACO® 210 G ENSACO® 250 G ENSACO® 260 G ENSACO® 350 G

Form Granules (*) Granules Granules (*) Granules Granules

BET Nitrogen Surface Area (m2/g) 50 55 65 70 770

OAN Oil Absorption (ml/100 g) 165 155 190 190 320

Conductivity     

Dispersibility     

the product
Purity     

Water absorption very low very low very low very low high

Surface smoothness     

Electrical/Mechanical
properties balance
    

Resistance to shear     

MRG
Comments to Easy strippable
(Mechanical All polymers
application domains insulation shields
Rubber Goods)

excellent 
very good 
good 
quite good 
difficult 

(*) ENSACO® 150 and ENSACO® 250 are also available in powder form.

7
 TIMREX® Graphite and Coke
for polymer compounds

Typical values

Particle size range Grade Ash Scott density Surface area

d90 (µm) (%) (g/cm3) Bet (m2/g)
Synthetic Graphite
KS Graphite KS 6 0.06 0.07 26.0
KS 15 0.05 0.07 20.0
KS 5-25 0.03 0.23 8.6
KS 44 0.06 0.19 9.0
KS 5-44 0.02 0.31 5.9
KS 150 0.06 0.42 3.0
0 25 50 75 150

SFG Graphite SFG 6 0.07 0.07 17.0

SFG 44 0.07 0.19 5.0
SFG 150 0.03 0.29* 2.5
the product

0 25 50 75 150

T Graphite T 15 0.08 0.10 13.0

T 44 0.07 0.18 10.0
T 75 0.07 0.21 9.8
0 25 50 75 150

Natural Graphite

PP Flake PP 10 <5 0.05 10.0

Graphite
PP 44 <5 0.11 4.8
0 25 50 75 150

LSG Flake LSG 10 <1 0.08 9.3

Graphite
LSG 44 <1 0.20 5.4
0 25 50 75 150

cumulative size
Large flake min. 80% <150 mesh (105 µm) M150 <6 0.4* 1.9
graphite
min. 80% >150 mesh (105 µm) 80X150 <6 0.6* 0.9

Coke

oversize control
PC Coke min. 98% <45 µm (air jet sieving) PC 40-OC 0.15 0.47* 10.0
max. 0,1% >106 µm (air jet sieving)

Grade Ash Density Particle size Solid content

(%) (g/cm3) distribution (%)
20°C d90 (µm)
Water-based dispersion

LB Dispersion LB 1300 0.10 1.17 6.5 27.5

Grade Ash Scott density Form d90

(%) (g/cm3) (µm)

Special Grade

C-THERM™ C-THERM™001 <0.3 0.15* soft granules

C-THERM™011 <2.5 0.15* soft granules

C-THERM™002 <0.3 0.04* powder 81

C-THERM™012 <2.5 0.04* powder 81

* bulk density

8
EnSACo® Conductive Carbon Black
TIMREX® Graphite
for polymer compounds

Conductivity
Targets

9
 Electrically
conductive plastics
Typical applications for ENSACO® Conductive Carbon Black

The selection of a Some typical final

conductive carbon black plastics applications
ENSACO® Conductive Carbon Blacks find their • handling of electronic components: carrier
applications in an unlimited number of plastics. boxes, carrier trays, carrier tapes, etc.;
The combination of the polymer type and grade • films: antistatic and conductive films,
and the carbon black grade are determining the packaging films, garbage bags, etc.;
overall electrical and mechanical performance. • automotive industry: fuel injection systems,
The main parameter influencing the final con- anticorrosion systems, fuel tank inlet,
ductivity of a finished part in a given polymer is electrostatically paintable parts, etc.;
the type and level of carbon black used. • transport: mobile phone parts, wheels,
The higher the structure of the carbon black, containers, bins, pallets, etc.;
the lower the level of carbon black needed to • computer: antistatic articles for computer &
achieve the required conductivity. Nevertheless, accessories, CD player, etc.;
in a minor way, other parameters like the ad- • health: medical applications, cleanroom
ditives in presence, the compounding or pro- equipments, articles for antistatic
cessing conditions may also influence the final workplaces, etc.;
conductivity of parts. • antistatic flooring;
Low surface area conductive carbon blacks • heating element;
show a particular advantage on dispersion and • sensors;
processing. • PTC switches;
Percolation curves – correlating the volume re- • UV protection and pigmentation.
sistivity and the carbon black percentage – are
a useful comparative tool to predict the con- In the following pages there are some of the re-
ductivity in place and to select the more appro- sults of experimental work carried out on EN-
priate system. These curves are valid for a given SACO® Conductive Carbon Blacks in different
formulation and sample preparation technique. polymer compounds.
The selection of the conductive carbon black
will also influence: The data shown here are given as orientation
• the compounding behaviour and are valid for the particular formulations and
(dispersibility, resistance to shear, mixing sample preparation technique mentioned.
cycle, melt flow index, extrusion throughput); Results in other polymers, full studies and pub-
• the surface appearance of the finished mate- lications are available upon request.
rial (number of surface defects);
• the mechanical properties
(polymer property retention, reinforcement);
• the overall price – performance ratio.

The preparation
of a conductive compound
Suitable mixing equipments for the preparation
of black conductive compounds include inter-
nal mixers, twin screw extruders, single screw
kneader machines and LCM. The feeding of low
bulk density, soft flake-type carbon blacks into
extruders requires the use of twin screw feeders
and separate introduction on an already molten
polymer (split feeding technology).

10
 TYpICAL AppLICATIonS FoR EnSACo® ConduCTIvE CARBon BLACk
EnSACo® ConduCTIvE CARBon BLACkS In HdpE

Influence of the carbon black type on the various carbon blacks in HdpE
resistivity
109
ENSACO® 250 G
Compounding: laboratory Brabender internal mixer.
Processing: compression moulding. ENSACO® 260 G

Volume Resistivity [Ohm.cm]

107
ENSACO® 350 G
The higher the structure of the carbon black,
the lower the percolation threshold. 105

103

10

0.1
0 10 20 30 40 50

Carbon Black %

At a concentration very near to the percolation Resistivity vs mixing time - 18% carbon black
level, when overmixed, ENSACO® 260 G offers a
higher consistency in resistivity resulting from 800
ENSACO® 250 G
its higher shear stability in extreme working 700 ENSACO® 260 G
Volume Resistivity [Ohm.cm]

conditions. 600

500

400

300

200

100

0
4 5 6 7 8 9 10

Brabender Mixing Time [min]

At a concentration far above the percolation Resistivity vs mixing time - 25% carbon black
level, both blacks are very stable in resistivity
when overmixed. ENSACO® 260 G shows a con- 7.0
ENSACO® 250 G
sistent lower resistivity. 6.5 ENSACO® 260 G
Volume Resistivity [Ohm.cm]

6.0

5.5

5.0

4.5

4.0

3.5

3.0
4 5 6 7 8 9 10

Brabender Mixing Time [min]

11
TYpICAL AppLICATIonS FoR EnSACo® ConduCTIvE CARBon BLACk

EnSACo® ConduCTIvE CARBon BLACkS In LdpE

Influence of the carbon black type and of the various carbon black in LdpE MFI 0.3 and 36 (g/10 min)
MFI of the starting polymer on the resistivity
108
Compounding: laboratory Brabender internal mixer. E250 G LD 0.3
Processing: compression moulding. E250 G LD 36

Volume Resistivity [Ohm.cm]

106 N472 LD 0.3

N472 LD 36
The higher the structure of the carbon black,
P-type LD 0.3
104
the lower the percolation threshold.
P-type LD 36
At equal structure, the carbon black of lower
surface area gets an advantage on resistivity 102
that may be coming from the easier dispersion
resulting in smoother compounding. The higher 100
the meltflow index of the starting polymer, the 0 5 10 15 20 25 30 35
lower the percolation threshold.
Carbon Black Concentration [%]

EnSACo® ConduCTIvE CARBon BLACkS In pp

Influence of the carbon black type on the ppH MI54 (230 °C/5 kg) with various conductive carbon blacks
resistivity. Relation between resistivity and
melt flow index 104
E250 G
high structure
low surface area
Volume Resistivity [Ohm.cm]

Compounding and processing: twin screw extruder Haake PTW16

and realization of tapes. 103 N472
high structure
high surface area

102
At same structure level, the carbon black with
the lowest surface area has the smallest impact
on fluidity reduction. 101

100
0 10 100

MFI [230 °C/5 kg] [g/10 min]

Influence of carbon black loading and

106
processing on the resistivity 13.50% E250 G
4.6E + 10 15% E250 G
105
Volume Resistivity [Ohm.cm]

Compounding: ZSK25 twin screw extruder.

Processing: injection moulding.
104

103
Injection moulding generates more shear than 171
54
compression moulding. The closest to the per- 102
24
colation, the more visible is that effect. A con- 10
6
101
centration safety margin can overcome this
phenomenon. 100

strands pellets + pressed pellets +

plaques injection moulding

12
 TYpICAL AppLICATIonS FoR EnSACo® ConduCTIvE CARBon BLACk
EnSACo® ConduCTIvE CARBon BLACkS In pC

Influence of the carbon black type volume Resistivity (vR) in function of carbon black loading
on the resistivity
12
ENSACO® 250 G
Compounding: ZSK57 twin screw extruder.

Volume Resistivity [log (Ohm.cm)]

11
Processing: injection moulding. ENSACO® 350 G
10
9
8
7
6
5
4
3
2
1
5 10 15 20 25

Carbon Black concentration [%]

Influence of the carbon black type on Izod impact strength, notched, in function of vR
mechanical and rheological performances
12
ENSACO® 250 G
Compounding: ZSK57 twin screw extruder.
Processing: injection moulding. 11 ENSACO® 350 G
10

9
Izod [kJ/m2]

Although the concentration for percolation is

8
double the level with ENSACO® 250 G, most
mechanical properties are still better. 7

4
1 2 3 4 5 6 7 8 9 10 11 12

Volume Resistivity [log (Ohm.cm)]

Tensile Strength for both carbon blacks is almost Tensile strength in function of vR
at the same level.
68
ENSACO® 250 G
67 ENSACO® 350 G
Tensile Strength [MPa]

66

65

64

63

62

61

60
1 2 3 4 5 6 7 8 9 10 11 12

Volume Resistivity [log (Ohm.cm)]

13
 Rubber
Typical applications for ENSACO® Conductive Carbon Black

Carbon black is one of the main ingredients A few conductive applications:

of any rubber compound. Conductive carbon • belt cover compounds;
blacks are before all carbon blacks, to be mixed • flooring;
and handled as any other reinforcing or semire- • conveyer belts;
inforcing carbon black. They are high structure • hoses for fuel, for conveying of powders, etc.;
materials bulky by nature. Although the com- • cylinder coating;
mon carbon blacks are conductive by nature • shoe soles;
and impart also conductivity to the compounds • seals.
when used in sufficiently high loading, conduc-
tive carbon blacks have the advantage to reach ENSACO® 150 and 250 are also used in non con-
conductivities at lower loading and are often ducting applications where the compounder
used to give the final boost to a compound al- can take profit of the low surface area and high
ready filled with other carbon blacks. As carbon structure of those blacks:
black structure is the parameter determining • low hysteresis with relatively high hardness;
the conductivity, structure being an additive • good thermal aging;
property, the combinations of conductive and • very good tear strength;
normal black can be predicted. • very good dispersion, very good mechani-
Specifications of rubber compounds being usu- cal performance at thin layer.
ally quite complex and conductivity being only
one of the numerous physical requirements, the
use of carbon black blends is very often the A few non-conductive applications:
only solution. In some specific cases, especially • antivibration systems;
in special polymers, it occurs that the conduc- • textile coating;
tive carbon black is used by its own in order to • membranes;
maintain mechanical properties and processing • articles exposed to chipping and chunking.
at a good level.
ENSACO® carbon blacks are, quite close to fur- In the following pages there are some of the re-
nace blacks as far as the reinforcing activity is sults of experimental work carried out on EN-
concerned. Especially the low surface area car- SACO® Conductive Carbon Blacks in different
bon blacks, grades 150, 250 and 260, are, due to rubber compounds.
their very easy dispersion, quite performing in The data shown here are given as orientation
most rubber compounds. ENSACO® 350 is also and are valid for the particular formulations and
used in some compounds where small additions sample preparation technique mentioned. Re-
are required. sults in other polymers, full studies and publica-
tions are available upon request.

14
 Typical applications for ENSACO® Conductive Carbon Black
NBR conductive hose compound

A B A B

Compound Compound Compound Compound

ENSACO® 250 N-472 ENSACO® 250 N-472

NBR NT 3945 100 100 t90% (min) 11.46 11.37

ENSACO® 250 25 Mooney ML (1+4) at 100° C 45.7 47.2

N-472 25 Vulcanizate data unaged at RT

N-550 40 40 Shore A Hardness 70.9 72.2

ZnO 4 4 Stress-strain

Stearic acid 0.5 0.5 Elongation at break (%) 339 311

DOP 30 30 Tensile Strength (MPa) 13.8 14.8

Sulphur 0.4 0.4 Modulus 100% (MPa) 3.9 4.6

Methyl Thuads 2 2 Modulus 300% (MPa) 8.6 10.3

Amax 2 2 Modulus 500% (MPa) 12.6 14.4

By courtesy of Bayer Resistivity (Ohm.cm) 79 360

Tear Strength (N/mm) 32.4 31.8

Conductive CR conveyor belt cover compound

A B A B

Compound Compound Compound Compound

ENSACO® 250 N-472 ENSACO® 250 N-472

Bayprene 610 (CR) 100 100 Dispersion Rating DIK 86.8 85.8

Buna CB 10 2 2 t90% (min) 20.7 21.8

MgO Powder 4 4 Mooney ML(1+4) at 100°C 62 64

N-472 30 Vulcanizate data unaged at RT

ENSACO® 250 30 Shore A hardness 62 64

Vulkanox DDA 1.5 1.5 Stress-strain

Vulkanox 4020 0.5 0.5 Elongation at break (%) 676 540

Ingralen 450 15 15 Tensile Strength (MPa) 23.4 22.4

ZnO Powder 5 5 Modulus 50% (MPa) 1.2 1.4

Rhenogran ETU-80 0.2 0.2 Modulus 100% (MPa) 2.4 2.7

Stearic acid 0.5 0.5 Modulus 300% (MPa) 9.2 11.5

By courtesy of Bayer Modulus 500% (MPa) 16.1 20.6

Compression Set 24h at

18 19
70°C (%)

Resistivity (Ohm.cm) 100 800

15
TYpICAL AppLICATIonS FoR EnSACo® ConduCTIvE CARBon BLACk

FkM ConduCTIvE CoMpoundS

1 2 3 4 5 6 7 8 9

vITon A-32J - Fluoroelastomer 100 100 100 100 100 100 100 100 100

Mgo 3 3 3 3 3 3 3 3 3

Ca(oH)2 3 3 3 3 3 3 3 3 3

MT black (n990) 20 - - - - - - 20 20

EnSACo® 250G - 10 20 30 - - - 10 20

n-472 SCF - - - - 10 20 30 - -

vpA-2 1 1 1 1 1 1 1 1 1

Total phr 127.0 117.0 127.0 137.0 117.0 127.0 137.0 137.0 147.0

MT black % 15.7 0.0 0.0 0.0 0.0 0.0 0.0 14.6 13.6

E250G % 0.0 8.5 15.7 21.9 0.0 0.0 0.0 7.3 13.6

SCF N-472 % 0.0 0.0 0.0 0.0 8.5 15.7 21.9 0.0 0.0

Experimental data provided by DuPont Dow Elastomers, Japan

Mooney viscosity ML (1+10’), 100°C t 90% (min)

180 20
(*) *
160 18

140 16
14
120
12
100
10
80
8
60
6
40 4
20 2
0 0
1 2 3 4 5 6 7 8 9 1 2 3 4 5 6 8 9

(*) Rejected because uncurable.

Vulcanizate properties at 177°C for 10 min.

Log Resistivity (ohm.cm) Compression set (%)

14 70

12 60

10 50

8 40

6 30

4 20

2 10

0 0
1 2 3 4 5 6 8 9 1 2 3 4 5 6 8 9

Shore A

100
90
80
70
60
50
40
30
20
10
0
1 2 3 4 5 6 8 9

16
Power cables and accessories

Typical applications for ENSACO® Conductive Carbon Black

Conductive carbon black is used in semicon Typical EVA/NBR strippable compounds
compounds for conductor and insulator shields.
The requirements for those compounds are be- Compound Compound Compound
N-472 ENSACO® 210 ENSACO® 250
sides processing, a sufficient electrical conduc-
tivity, a smooth or even supersmooth surface Levaprene 450 90 90 90
finish, and high purity.
For strippable or easy strippable compounds Perbunan NT 8625 10 10 10
these requirements are added to a specific ad- Rhenogran P60 3 3 3
hesion strength between the insulating layer
N-472 40
and the insulator shield. These strippable or
easy strippable layers have to peeled of by hand E 210 40
or using a specific peeling device. E 250 40
Typical polymer compositions are polyolefins or
N-550 40 40 40
copolymers; for strippable compounds quite of-
ten blends of EVA and NBR are used. Antilux 654 10 10 10

Zn Stearate 1 1 1

Rhenovin DDA-70 1.4 1.4 1.4

Rhenofit TAC/CS 4.3 4.3 4.3

Percadox BC-408 5 5 5

Viscosity ML (4+1) 56 44 48

Rheometer@180 t90% 3.6 3.6 3.8

Mechanical properties

Non aged (diff. aged)

Tensile strength MPa 16.5 (-19) 16.9 (-15) 16.9 (-15)

Elongation at break % 215 (-58) 180 (-50) 170 (-53)

Modulus 100% MPa 11 12.2 12.7

Shore A 87 (+7) 90 (+4) 89 (+7)

Peel strength hot air 100°C N 7 3 4

- after 3 days N 5 4 3
- after 21 days N 5 3 4

Volume resistivity (Ohm.cm) 210 6600 410

Typical EEA/EBA semicon compounds

Compound Compound
EEA EBA

EEA 100

EBA 100

E 250 30 30

Peroxide

Mixing cond. L/D15; Feed BC; Truput 30

Resistivity @ RT 7.2 5.6

Resistivity @ 90°C 37 22

Carbon black dispersion: <3µm 97.9 99.4

Die pressure (bar) 229 239

MFI (g/10 min) 23.12 21.39

Specific net mixing energy (KWh/kg) 0.313 0.326

Protrusion N°/m2 0 0

17
 Self lubricating
polymers

The choice of a polymer-based self lubricating Graphite powder is widely used in polymer
Typical applications for TIMREX® Graphite and Coke

solid for a particular application depends mainly composites, either alone or in combination with
upon the operating conditions of: temperature, reinforcing fibres, PTFE or various inorganic
chemical environment and the maximum values fillers, e.g. mica, talc (bottom, right table). Ap-
of pressure (p) and sliding speed (v). For each plications include gears, dry sliding bearings,
polymer or composite material, a pv limit is quot- seals, automotive and micro-mechanical parts.
ed, which corresponds to the pressure times the
sliding speed at which the material fails, either The properties of graphite which favour its use
due to unacceptable deformation, or to the high in polymer composites are:
frictional energy dissipated causes surface melt- • low friction lamellar solid
ing, softening and excessive wear. (reduces friction);
The pv limit of a polymeric material may be in- • tendency to form a transfer film on the
creased by increasing its mechanical strength countersurface
(resistance to deformation), thermal con- (assists in wear reduction, particularly when
ductivity (reduction in surface temperatures) graphite is applied as water based dispersion
and by decreasing friction (reduces frictional i.e. LB 1300);
heating). In practice, thermoplastics (with the • high thermal conductivity
exception of PTFE) are mainly used as pure (decreases temperature rise due to frictional
solids, since their wear resistance and frictional heating);
coefficient, are satisfactory for most applica- • electrical conductivity
tions. Solid lubricant fillers or fibre reinforce- (prevent build-up of static charge which may
ment (glass fibres, carbon fibres, textiles) are be a problem in some cases);
only employed under the more extreme condi- • chemically inert
tions of load and speed. (used in conjunction with PTFE in corrosive
The major polymers employed as self lubricat- environments);
ing solids/composites, are illustrated below. • high thermal stability
(favours use in high temperature applica-
tions, e.g. polyimide graphite composites
may be used up to 350°C).

18
Incorporation of graphite powder into a ther- Ball/disc Friction & Wear data: polystyrene/graphite filler

TYpICAL AppLICATIonS FoR TIMREX® GRApHITE And CokE

moplastic polymer will generally result in a
reduction in the friction coefficient (with the ex- 12 0.4 wear
ception of PTFE) but rarely improves the wear
friction
resistance. This behaviour is illustrated in the 10

specific wear (m3/Nm)x10-12

0.3
two graphs, which show the mean friction co-

friction coefficient
8
efficient and specific wear rate for a stainless
steel ball (ø = 5 mm) rubbing on discs of graph- 6 0.2

ite filled polystyrene and polyamide at constant

4
load (32.5 N) and speed (0.03 m/s). The specific 0.1
wear rates of the graphite-polymer composites 2

were calculated from the diameters of the wear

0 0
tracks and the contact geometry. pure 30% 50%
polystyrene T 75 T 75

In the case of polystyrene, addition of 30–50%

of a high purity macrocrystalline synthetic Influence of graphite addition on the specific wear rate and friction of polystyrene
graphite (T 75), reduced both friction and wear
rate. With polyamide however, addition of a
graphite similar to T 75 reduced the friction Ball/disc Friction & Wear data: polyamide 6/graphite filler
coefficient, but caused a slight increase in the
wear rate, with the finer particle size powder 20 0.4 wear
(KS 6) giving the better result. In the case of
friction
low density polyethylene and polypropylene,
specific wear (m3/Nm)x10-12

15 0.3
graphite incorporation causes both an increase

friction coefficient
in friction and wear.
10 0.2

The results described above are thought to be

related to the strength of adhesion at the pol- 5 0.1
ymer-graphite interface, which depends upon
the wettability of the powder by the molten pol-
0 0
ymer, powder surface area to volume ratio, sur- pure 30% 30%
face chemistry, etc. In simple terms, polystyrene polyamide KS 6 KS 44

shows a strong affinity for the graphite surface,

while polyolefins show a weak affinity. Interfa- Influence of graphite addition on the specific wear rate and friction of polyamide 6

cial adhesion increases with increasing powder

surface area to volume ratio, or decreasing par-
ticle size.

For this reason relatively fine graphite pow-

ders (95%<15 microns) are recommended for
thermoplastics. The strength of thermosetting
polymers is much less sensitive to filler-polymer
interactions, therefore coarser graphite pow-
ders may be used (typically 95%<75 microns).
For thermoplastics, the viscosity of the poly-
mer-graphite melt during extrusion/ moulding
will also depend on the graphite particle size,
which should be appropriate. Excessive graph-
ite surface area may also lead to void formation
in the finished composite, due to desorption of The above mentioned results are the confir-
physisorbed vapours in the hot melt. mation that TIMREX® graphite powder is an
excellent additive to produce self-lubricated
High graphite purity is generally desirable in or- polymers. The addition of TIMREX® graphite
der to minimize wear, although this parameter powder to the unfilled polymers allow for a re-
is unlikely to be important in the presence of duction of the friction coefficient and in most
abrasive fillers (glass fibre, carbon fibre). of the cases to a reduction of the wear rate.
These results are achieved by a synergic com-
binations of all the good properties of TIMREX®
graphite powder that among the others are:
the high degree of crystallinity, the extremely
high purity, the optimal texture and the perfect
particle size distribution. All of them linked by
a common factor: the consistency!

19
 Filled PTFE

Polytetrafluoroethylene (PTFE) exhibits a very TIMREX® Graphite

Typical applications for TIMREX® Graphite and Coke

low coefficient of friction and retains useful me- and Coke fillers in filled-PTFE
chanical properties at temperatures from -260
to +260 °C for continuous use. TIMREX® PC 40-OC Coke
The crystalline melting point is 327 °C, much TIMREX PC 40-OC Coke is calcined at high tem-
higher than that of most other semi-crystalline peratures offering low sulphur concentration,
polymers. Furthermore, PTFE is nearly inert low content of oversize particles, high apparent
chemically and does not adsorb water, leading density and high chemical stability against most
to excellent dimensional stability. On the one chemical substances. TIMREX® PC 40-OC Coke
hand, these characteristics of PTFE are very is added to the virgin PTFE in a percentage by
useful in the matrix polymer of polymer-based weight between 10 and 35% along with small
composites which are used in sliding applica- percentage of graphite.
tions. On the other hand, PTFE is subjected to Compounds made of PTFE and TIMREX® PC
marked cold flow under stress (deformation 40-OC Coke have excellent wear resistance
and creep) and reveals the highest wear among and deformation strength and compared to the
the semicrystalline polymers. virgin PTFE, they have practically unchanged
However, these disadvantages are very much chemical resistance and friction behaviour.
improved by incorporating suitable fillers, al- Typical final materials that can be produced
lowing the use of PTFE in fields otherwise pre- with coke filled PTFE are:
cluded to this polymer. engineering design components, slide bearings,
The treated PTFE is generally known as filled- valve housing and valve seats for chemical ap-
PTFE. There are many kinds of filled- PTFE plications, piston sealing and guiding elements
composite because various fillers are incorpo- for dry-running compressors.
rated into PTFE and one or more materials can
be used simultaneously. Usually, these fillers are TIMREX® KS44 Synthetic Graphite
in form of powders or fibers intimately mixed NTIMREX® KS 44 is a Primary Synthetic Graph-
with the PTFE. ite obtained by the full graphitisation of amor-
The addition of fillers to the PTFE improves or phous carbon materials through the well known
modifies its properties depending upon the na- Acheson process. The process parameters in the
ture and quantity of filler: Acheson furnace such as temperatures and resi-
• remarkable increase in wear resistance; dential times are all optimised in order to achieve
• decrease of deformation under load and of the perfect degree of crystallinity and the lowest
creep; level of impurities whereas others minor adjust-
• reduction of thermal expansion; ments are made during the material sizing and
• some types of filler increase the thermal and conditioning.
electric conductivity. The percentage of TIMREX® KS 44 used in the
filled PTFE vary between 5 and 15%.
Filled PTFE is often not as strong and TIMREX® KS 44 can be used alone or in combina-
resilient as virgin PTFE. Sometimes, the filler tion with glass or coke.
limits the resistance to chemical agents and TIMREX® KS 44 lowers the coefficient of friction
modify the electrical properties. and is, therefore, often added to other types of
filled PTFE for improving this property (and also
to improve the lifetime of the cutting tools dur-
ing for instance the production of gaskets and
seals). It improves the deformation under load,
strength and, to a minor degree the wear. Like
coke, it serves well in corrosive environments.
PTFE filled with TIMREX® KS 44 are often used in
steering and shock-absorber gasket, bearings as
well as in slide films for anti-static applications.

20
Influence of TIMREX®Graphite

Typical applications for TIMREX® Graphite and Coke

and Coke fillers in filled-PTFE

Wear resistance
virgin PTFE shows much high wear as a result of
the destruction of the banded structure due to
easy slippage between the crystalline lamellae
in the bands.
The presence of well distributed carbon parti-
cles in the filled PTFE partially avoid the slip-
page between the crystalline lamellae in the
bands and therefore the wear resistance is im-
proved.

Deformation strength
virgin PTFE deformation behaviour is somehow
similar to the mechanism previously described.
In someway the deformation phenomena could
be explained by the tendency of slippage that
occurs between the crystalline lamellae. How-
ever, in this case the presence of well distributed
carbon particles in the filled PTFE offers only a
partial explanation to the phenomena because
also hardness of these particles is important in
determine an improvement of the deformation
behaviour.

Friction Coefficient
the coefficient of friction for various filled PTFE
composites is weakly dependent upon the in-
corporated filler, because a thin PTFE film gen-
erally exists at the interface between the body
and counter-body. Consequently the coefficient
of friction is both similar in the filled PTFE and
virgin PTFE. This evidence is true as long as no
oversize particles are present in the filler. In fact
the presence of oversize particles could lead
to a radically modification of the coefficient of
friction. Because of that in carbons as well as in
other fillers is very important the control of over-
size particles.

21
 Thermally
conductive polymers

What is thermal conductivity? Thermal conductivity

Typical applications for TIMREX® Graphite and Coke

The ability of a material to conduct heat is known of graphite

as its thermal conductivity. Thermal conductiv- Graphite is an excellent solution for making
ity itself is nothing else than the transportation polymers thermally conductive when electri-
of thermal energy from high to low tempera- cal conductivity is also tolerated. Graphite
ture regions. Thermal energy within a crystalline operates by a phonon collision mechanism,
solid is conducted by electrons and/or discrete very different from the percolation mechanism
vibrational energy packets (phonons*). Each ef- occurring with metallic powders. This mecha-
fect, phonons and movement of free electrons, nism, together with the particular morphology
contributes to the rate at which thermal energy of graphite particles, helps to meet the re-
moves. Generally, either free electrons or phon- quired thermal conductivity at lower additive
ons predominate in the system. levels without any abrasion issues. In addition,
due to its particular structure, thermal con-
*Phonons ductivity is different in the different directions
In the crystalline structures of a solid mate- of the crystal. It is highly conducting along
rial, atoms excited into higher vibrational fre- its layers (ab direction or in-plane) and less
quency impart vibrations into adjacent atoms conducting perpendicular to the layers (c dir-
via atomic bonds. This coupling creates waves ection or through-plane) because there is no
which travel through the lattice structure of a bonding between the layers.
material. In solid materials these lattice waves, In particular, expanded graphite, is well known
or phonons, travel at the velocity of sound. as an excellent thermally and electrically con-
During thermal conduction it is these waves ductive additive for polymers. On the way to
which aid in the transport of energy. graphene, high aspect ratio expanded graph-
ite is thermally more conductive when com-
pared to conventional carbon materials such as
standard graphite and carbon fibres. However,
the very low bulk density of expanded graphite
makes it very difficult to feed into a polymer
melt using common feeding/mixing technolo-
gies. In order to overcome the feed issues en-
countered by compounders with expanded
graphite, TIMCAL has developed a range of
products belonging to the TIMREX® C-THERM™
carbon-based product family.

Grade Features Form Ash Effect on

content (%) thermal conductivity

TIMREX®KS family Standard powder < 0.1 medium

(spheroids) (through-plane +)

TIMREX®SFG family Standard powder < 0.1 medium

(flakes) (in-plane +)

TIMREX®C-THERM™011 High aspect ratio soft granules < 2.5 high

(pure)

TIMREX®C-THERM™001 High aspect ratio soft granules < 0.3 high

(pure +)

22
THERMALLY ConduCTIvE poLYMERS ing the measurement, but also on the type of

TYpICAL AppLICATIonS FoR TIMREX® GRApHITE And CokE

Thermally conductive polymers are able to polymer, the sample history (type and condi-
evenly distribute heat generated internally tions of compounding and processing) and the
from a device and eliminate “hot spots.” Pos- measurement method.
sible applications for thermally conductive A full set of measurements to determine me-
plastics include heat sinks, geothermal pipes, chanical properties in PP were performed and
LED light sockets, heat exchangers, appliance are available to customers. When tested at the
temperature sensors and many other industrial same loadings, C-THERM™ 001/011 imparts
applications. Also thermally conductive elas- similar mechanical properties as conventional
tomers can be found in a wide variety of in- carbon materials.
dustrial applications such as gaskets, vibration
dampening, interface materials, and heat sinks.
As highlighted in the figure, the low thermal
conductivity of virgin PPH (~0.38 W/m.K)
could be increased by one order of magni- 4.0
In-plane
In-plane
tude already at relatively low addition level Thermal Conductivity [W/m.K] 3.5 inj > Through-plane
(~3.5 W/m.K at 20% C-THERM™). The “through- 3.0
Through-plane

plane” thermal conductivity is about the half of

2.5
the longitudinal “in-plane” thermal conductiv-
2.0
ity. These results indicate that the anisotropy
of the graphite particles is conferred to the 1.5

final compound, due to their alignment dur- 1.0

ing the injection molding process. This is an 0.5

important property that has to be taken into 0
account by design engineers. Of course the Virgin PPH 20% 20% 20%
thermal conductivity strongly depends not ENSACO® TIMREX® TIMREX®
250G KS25 C-THERM™
only on the sample orientation (direction) dur-

Timcal locations

production plants

Commercial offices

Distributors present in
many countries. For the
updated list please visit
www.timcal.com

23
 EUROPE Asia-Pacific Americas

TIMCAL Ltd. TIMCAL Japan K.K. TIMCAL America Inc.

Group Head Office Tokyo Club Building 13F 29299 Clemens Road 1-L
6743 Bodio 3-2-6 Kasumigaseki, Westlake (OH) 44145
Switzerland Chiyoda-ku USA
Tel: +41 91 873 20 10 Tokyo 100-0013 Tel: +1 440 871 75 04
Fax: +41 91 873 20 19 Japan Fax: +1 440 871 60 26
[email protected] Tel: +81 3 551 032 50 [email protected]
Fax: +81 3 551 032 51
TIMCAL Belgium NV/SA [email protected] TIMCAL Canada Inc.

© 2012 TIMCAL Ltd., CH-Bodio. No part of this publication may be reproduced in any form without the prior written authorisation of TIMCAL Ltd.
Appeldonkstraat 173 990 rue Fernand-Poitras
2830 Willebroek Changzhou TIMCAL Terrebonne (QC) J6Y 1V1
Belgium Graphite Corp. Ltd. Canada
Tel: +32 3 886 71 81 188# Taishan Road Tel: +1 450 622 91 91
Fax: +32 3 886 47 73 Hi-Tech Zone Fax: +1 450 622 86 92
[email protected] Changzhou 213022 [email protected]
China
TIMCAL Deutschland GmbH Tel: +86 519 851 008 01
Berliner Allee 47 Fax: +86 519 851 013 22
40212 Düsseldorf [email protected]
Germany
Tel: +49 211 130 66 70 Changzhou TIMCAL
Fax: +49 211 130 667 13 Graphite Corp. Ltd.
[email protected] Shanghai Branch Office
c/o IMERYS (Shanghai)
France Representative Office 288, Jiu Jiang Road
c/o IMERYS Hong Yi Plaza
154-156 rue de l’Université Unit 1102-1105
75007 Paris, Shanghai 200001
France China
Tel: +33 1 495 565 90/91 Tel: +86 21 613 782 88
Fax: +33 1 495 565 95 Fax: +86 21 613 780 02
[email protected] [email protected]

UK Representative Office Singapore Representative Office

Tel: +44 1 270 212 263 c/o IMERYS Asia Pacific (Singapore)
Fax: +44 1 270 212 263 80 Robinson Road #19-02
[email protected] 068898 Singapore
Tel: +65 67 996 060
Fax: +65 67 996 061
[email protected]

www.timcal.com
24