Meeting Application Requirements with Conductive

Carbon Black

Christine Van Bellingen, Nicolas Probst, Eusebiu Grivei

TIMCAL Belgium S.A., Appeldonkstraat 173, BE-2830 Willebroek, Belgium

High structure or so-called conductive carbon blacks aggregates agglomerate into ramified complex structures.
(CCBs) constitute the major family of conductive addi- These agglomerates network into a three-dimensional struc-
tives. They enable one to make polymers permanently
conductive at “low” to “very low” loadings, for technical
ture. Electron flow occurs through the aggregates and also
applications involving, e.g., the transport of energy, pro- from one aggregate to another by tunneling or by direct
tection against arcing or discharge. Designing conduc- contact depending on the interdistances and the interfaces
tive parts requires certain know-how, as many parame- [2]. This explains why the switch from an insulating mate-
ters influence the final electrical conductivity, and many rial to a conductive material is quite sudden when CB
other requirements have to be fulfilled. This paper high-
lights the impact of the carbon black (CB) type and
content is increased. The sudden change occurs when the
loading, the polymer type, and the compounding condi- additional CB aggregates complete an overall network con-
tions on the conductive, mechanical, dispersion, and necting the open spaces. This phenomenon is called perco-
flow properties of various plastics compounds. The lation, and the concentration of CB at which this is occur-
study especially positions a unique family of low surface ring is called the percolation threshold. Conductive carbon
area (LSA) CCBs, suggests means to make conductive
parts with compounding and transformation ease, and
blacks (CCBs) all have high structure (HS) (DBP/oil ab-
points out that more conductive additive does not auto- sorption ⬎160 ml/100 g). The higher the structure of the
matically give the best overall performance. J. VINYL AD- CB, the lower the concentration necessary to reach the
DIT. TECHNOL., 12:14 –18, 2006. © 2006 Society of Plastics percolation level. However, it is not obvious that the most
Engineers
conductive additive will give the highest conductivities and
best overall properties; very high structure (VHS) CBs are
INTRODUCTION indeed more difficult to disperse and some other properties
may be affected.
Carbon Black and Conductivity
Some Plastics Applications for CCBs
Most polymers are insulating materials. When submitted
CCBs are essential for people safety and material pro-
to friction, they can quickly accumulate electrostatic
tection against deterioration. They are used in a wide range
charges, which may then damage parts, induce an arcing,
of polymer applications like semiconducting layers of
and injure people. A solution is to make polymers perma-
power cables, electronic packaging, computer assembly sta-
nently conductive by using carbon black (CB). Thanks to its
tions, transporting elements (i.e., discharge hoses, carrier
partially graphitic structure made of nanosized graphitic
trays), clean room equipment, antistatic flooring, automo-
stacks embedded in amorphous carbon, forming small par-
tive fuel piping, or conductive primers for electrostatic
ticles organized in aggregates; CB is able to easily carry an
painting [3, 4].
electron flow [1]. However, when incorporated into a poly-
mer matrix, it will only confer its inherent activity to the
system from a certain concentration corresponding to the Route to Make CCB-Filled Plastics Parts
percolation threshold. From this critical concentration, the As the transition from an insulating to a conductive
electrons can flow throughout the part for dissipation. CB material occurs very quickly in a narrow window of a
minimum CB concentration, it is highly recommended to
make a compound rather than a masterbatch. Processors
Correspondence to: Christine Van Bellingen; e-mail: c.vanbellingen@be.
should use a conductive compound rather than diluting a
timcal.com masterbatch, for the main technical and practical reasons:
DOI 10.1002/vnl.20061
Published online in Wiley InterScience (www.interscience.wiley. ● The sharp transition from insulating to conductive prop-
com). erties would require constant very accurate dilution/dos-
© 2006 Society of Plastics Engineers age.

JOURNAL OF VINYL & ADDITIVE TECHNOLOGY—2006

 TABLE 1. Description of the CCBs used in our studies.

Structure oil BET surface area

absorption N2 adsorption
CCB grade Process ID CCB type (ml/100 g) (m2/g)

P-type Furnace CB1 LS 115 140

Ensaco 150G Timcal CB2 MS/LSA 165 44
N472 Furnace CB3 HS/HAS 177 254
Ensaco 250G Timcal CB4 HS/LSA 190 65
Ensaco 260G Timcal CB5 HS/LSA/HSS 190 70
Ensaco 350G Timcal CB6 VHS/VHSA 320 770
UHSA (experimental) Timcal CB7 UHS/UHSA 700 1,600

LS, low structure; MS, medium structure; HS, high structure; HSS, high structure stability; VHS, very high structure; UHS, ultra high structure; LSA,
low surface area; HAS, high surface area; VHSA, very high surface area; UHSA, ultra high surface area.

● The minimum level of CB necessary in the final part may ture/low surface area (HS/LSA) CBs. They have a low-
be in the range of 8 –20% by weight; a masterbatch would oxygen content (low number of chemisorbed oxygenated
have to contain very high levels of CCB to allow a species), a high graphitization level (favoring both electrical
profitable dilution. and thermal conductivity), a very high-purity level (metal,
● Viscosities of masterbatches and dilution polymers would
sulphur, coke. . . ) and a soft, flake-type form as neither
be very different.
●
water nor additives are used in any of the fabrication steps
Quality control of “conductive masterbatches” would be
hard to monitor. including granulation [3, 5]. The HS/LSA family is aside
from the most common furnace CCBs, which have a HS/
The compound route puts together the chances to make HSA.
more homogeneous final parts, but the realization of a
conductive compound requires a certain know-how, as con- Compounding and Processing
ductivity is also rarely the only final requirement.
Suitable compounding equipments include internal mix- Our results have been generated using different types of
ers, mixing extruders (co-kneaders or twin screws), or mix- compounding and processing equipments (Table 2 and all
techniques like long continuous mixers (LCM). Figures). Here is an example of compounding and feeding
Compounding can be subdivided into incorporation and equipment used to make conductive polypropylene com-
mixing/dispersion. Dispersion can be split into polymer-CB pounds with HS/LSA CBs [6]:
wetting, CB deagglomeration, and forced inclusion of the
● ZSK 25 TWIN SCREW EXTRUDER, co-rotating, closely
polymer into the high void volume of the CCB. The han-
intermeshing, L/D ⫽ 44, 11 barrels.
dling and incorporation of HS/low-bulk density, soft-type ● Split feeding: the polymer is introduced first, and the
CB is probably the most critical step of compounding. low-bulk density CCB is added downstream in the barrel
Theoretically: 4 of the extruder via a twin screw side feeder, itself fed
with a K-Tron gravimetric twin screw feeder with agita-
● The HS tends to ease the de-agglomeration step (higher tor.
average distance between the CB agglomerates, leading to
lower van der Waals attraction forces).
● The LSA tends to ease the wetting step (better mobility). TABLE 2. Description of compounding and processing (C&P)
● HS/LSA combination leads to easy dispersion and smooth equipments used to generate results presented.
surface finish, but VHS CBs, having also a higher surface
area (or inner particle porosity), are harder to disperse, C&P Compounding Processing
probably because of their lower mobility for wetting,
higher interface with the polymer, and more chain entan- A Internal mixer (lab size/ Compression molding
glements. Brabender, 50 ml)
B Twin screw extruder Extruded tapes
(lab size/Haake, 16 coming out of the Haake
EXPERIMENTAL mm)
C Twin screw extruder Injection molding
(semi-industrial/ZSK25,
CCBs Description L ⫽ 44D)
D Twin screw extruder Injection molding
Most of the CCBs studied (Table 1) are ENSACOTM- (industrial/ZSK57)
type coming from the proprietary partial combustion pro- E Buss Co-Kneader (lab Injection molding or
cess of Timcal Belgium, which delivers either very high size/30 mm, L ⫽ extrusion
18D)
structure/very high surface area (VHS/VHSA) or high struc-

DOI 10.1002/vnl JOURNAL OF VINYL & ADDITIVE TECHNOLOGY—2006 15

 FIG. 3. Volume resistivity (VR) versus melt-flow index of conductive
FIG. 1. Percolation curves of various CCBs in high-density polyethylene
polypropylene homopolymer (PPH) Novolen 1100N MI 54 (5 kg/230°C).
(HDPE) MI 0.1 (2.16 kg/190°C) Finathene 47,100. C&P: A.
C&P: B.

Volume Resistivity Measurements ings but also a more negative impact on the fluidity (Fig.
3, CB6/CB4).
Volume resistivity (VR) was measured using a method
based on ASTM D257 when antistatic (via an electrometer),
The combination of HS/LSA seems to favor:
or ASTM D4496 when conductive (4-point contact
method). ● A higher mobility/lower viscosity increase.
● A lower energy input necessary to get optimized mixing,
RESULTS AND DISCUSSION also leading to improved conductivities.

Apart from adding specialty additives, an easy way to

Influence of the CB Type on the VR and Flow of the orient the final VR and flow of a compound is to play either
Compound on the CB type (Fig. 3) or on the flow of the starting
Our experiments have outlined the following trends: polymer (Figs. 4 and 5).

● The higher the structure of the CB, the lower the perco- Influence of the Fluidity and Crystallinity of the Starting
lation level (Figs. 1 and 2). Polymer on the VR
● CBs of higher structure stability impart percolation at
lower loadings (Fig. 1, CB5/CB4). Figures 2 and 5 clearly show that higher fluidity poly-
● Depending on the polymer type, at equal structure, HS/ mers displace the CB percolation level to lower concentra-
HSA blacks may show a percolation at a higher concen- tions, as if it was easier for a fluid polymer to fill the CB
tration than HS/LSA blacks (Fig. 2, CB3/CB4); this is voids and to ease the wetting step.
most probably due to the higher mixing energy required Figure 6 shows that polypropylene homopolymer (PPH)
for the dispersion wetting step, which compresses more exhibits lower resistivities than polypropylene copolymer
the structure and makes the CB less active. (PPC), below 100 ⍀ cm. The CB, which always stays in the
● At equal VR, HS/HSA blacks impart a higher viscosity
than HS/LSA (Fig. 3, CB3/CB4).
● VHS/VHSA blacks give a percolation at very low load-

FIG. 2. Percolation curves of various CCBs in low-density polyethylene FIG. 4. VR versus MFI of CCB filled PPH and polypropylene copolymer
(LDPE) MI 0.3 Stamylan 2810 and MI 36 Stamylan LD1938T (2.16 (PPC) from BP (*) , of different starting MFI (4; 20; 23; 50 at 2.16
kg/190°C). C&P: A. kg/230°C). C&P: C (screw speed ⫽ 600 min⫺1).

16 JOURNAL OF VINYL & ADDITIVE TECHNOLOGY—2006 DOI 10.1002/vnl

FIG. 5. Percolation curves of CCBs in HDPE MI 0.1 Finathene 47,100 FIG. 7. Correlation between VR and CCB dispersion in various PP
and MI 8 metallocene (mPE) M3582 (2.16 kg/190°C). C&P: A. compounds. C&P: C. (*) Starting PP polymers from BP (MI: 2.16 kg/
230°C) (g/10 min): PPH MI 4 (100-GA04), PPH MI 23 (100-XA23), PPH
MI 50 (100-CA50), PPC MI 20 (500-GA20).
amorphous phase of the polymer, has less volume available
in a more crystalline polymer like PPH, and appears to be
over-concentrated [7]. Influence of the Compounding and Processing on the VR
CCBs are shear sensitive [8]. During compounding (Fig.
Correlation Between VR and Dispersion 9) and further transformation steps (Fig. 10), the CB aggre-
Some PP compounds [6] filled with CB4 and CB5 were gates may overdisperse and loose structure. Aggregates
diluted with LDPE MI2 to 1% CB and ⬃50 ␮m blown films must be weak enough to allow proper mixing and dispersion
were made. These translucent films were visually analyzed within the polymer matrix, but strong enough to overcome
by transmission, and spots were visually counted: shear and compression work, which tends to reduce their

● Four groups could be distinguished, having 0, 0 –1, 1–2,

or 2–3 specs per gram; all results were very good, indi-
cating that we can achieve excellent surface smoothness
with HS/LSA CBs.
● For each of these four groups, the average of the VR has
been plotted (Fig. 7); the groups showing the best disper-
sion qualities also impart the best conductivities.

Conductive polycarbonate (PC) compounds [3] of 103 ⍀

cm can be made with either ⬃17% of HS/LSA CB4 or 8%
of VHS/VHSA CB6, but the Izod impact strength is still
much higher with CB4 (Fig. 8), indicating the better “in
FIG. 8. Izod impact strength (ISO 180), notched, in function of the VR of
bulk” dispersion and improved mechanical properties
CCB filled polycarbonate (PC) Caliber 200 compounds. C&P: D.
achieved with CB4.

FIG. 6. Percolation curves of CB4 in PPH from BP (*), of about the same
starting MFI (20; 23 at 2.16 kg / 230°C). C&P: C (screw speed ⫽ 600 FIG. 9. Influence of the screw speed on the VR of 15% CCB filled PPH
min⫺1). MI 4 (2.16 kg/230°C) 100-GA04 from BP. C&P: C.

DOI 10.1002/vnl JOURNAL OF VINYL & ADDITIVE TECHNOLOGY—2006 17

 and overall plastics properties. Realizing conductive com-
pounds is not just a matter of taking the more conductive
additive, an adequate selection of raw materials is neces-
sary, and a balance between conductivity and easy disper-
sion is welcome.
There is evidence for the need to find the compromise
between the necessity to make a good dispersion of the CB
particles and the avoidance of the structure breakdown. The
main problem of the compounder is to determine the limit
when the good dispersion is reached, and the structure
breakdown is limited to negligible effects. This limit varies
as a function of the polymer (low-melt index produces an
extra work into dispersing agglomerates but also break-up
the CB structure), of the carbon black (some CBs present a
FIG. 10. Influence of the processing type (extrusion or injection molding) higher mechanical resistance to the stresses) and of the
of CCB-filled high-impact polystyrene (HIPS) compounds on the VR. processing (injection is more aggressive than extrusion).
Tests performed by PREMIX, Finland. C&P: E.

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18 JOURNAL OF VINYL & ADDITIVE TECHNOLOGY—2006 DOI 10.1002/vnl