Encyclopedia of Polymers and Composites

DOI 10.1007/978-3-642-37179-0_32-1
# Springer-Verlag Berlin Heidelberg 2013

Carbon Black for Electrically Conductive Polymer Applications

Michael E. Spahr*, Raffaele Gilardi and Daniele Bonacchi
IMERYS Graphite & Carbon Switzerland Ltd., Bodio, TI, Switzerland

Keywords
Conductive polymer composites; Carbon black; Carbon black structure; Carbon black dispersion;
Compound processing; Electrical conductivity; ESD protection; Percolation

Definition
Carbon black is incorporated in polymers for permanent electrostatic charge protection, explosion
prevention, and polymer applications that require electrical resistivities below 106 O cm. At the
critical volume fraction of the carbon black grade, the carbon black-polymer compound percolates
from an electrically insulating to a conducting domain. The capability of a carbon black material to
impart electrical conductivity to a polymer compound depends on its ability to establish and
maintain in the insulating polymer matrix a conductive network in which the electronic charge
carriers move mainly by a tunneling mechanism. Conductive carbon black fillers impart electrical
conductivity to polymers at lower critical volume fractions than conventional carbon blacks and
hence influence to a lower degree the mechanical properties of the resulting conducting polymer
compound. The key property of this family of special carbon black grades is a carbon black high
structure, i.e., a high void volume. High-structured carbon black materials are preferred fillers to
make polymers conductive as they allow high polymer concentrations to be maintained while
establishing the conductive network. Besides the carbon black properties, also the polymer proper-
ties and the processing of the carbon black-filled polymer compound influence the critical volume
fraction and insulator-conductor transition. Statistical, thermodynamic, and structure-oriented per-
colation models are the best applicable to describe at a theoretical scientific level the formation of the
conductive carbon black network in the polymer matrix.

Introduction
Polymers are usually electrically insulating with electrical surface resistivities of above 1012 O cm.
However, some polymer applications require lower electrical resistivity which can be achieved by
dispersing special additives above a threshold concentration into the polymer matrix. Such polymer
composites are classified according to their electrical volume or surface resistivity in ranges
determining the final application of the polymer compound (Norman 1970; Funt et al. 1993;
Markarian 2008). Polymer compounds within a surface resistivity range of 1010–1012 O sq
1
achieved by the addition of organic antistats provide low static decay rates required in antistatic
applications. Antistats are widely used in packaging such as films, thermofused containers, and PET
bottles in all of which they reduce the attraction of dust or help to keep surfaces separate.

*Email: [email protected]

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Electrostatic dissipation at faster static decay occurs within a surface resistivity range of 106–1010 O
sq
1. The optimum surface resistivity range of polymer compounds used for permanent electrostatic
discharge (ESD) protection spans from 106 to 109 O sq
1 and is required, e.g., for packaging of
electronics, trays, conveyor belts, casings, containers or hoses for flammable or explosive substances,
and antistatic flooring. Conductive polymer materials are classified in the surface resistivity range of
101–106 O sq
1 which is above the range of 10
1–10
5 O sq
1 being typical for metals. Conductive
polymer composites are used for electromagnetic interference (EMI) shielding applications that
require surface resistivities lower than 10 O sq
1 and in self-limiting switches and heaters. Electrically
conducting polymer compounds with volume resistivities below 103 O cm are used in the jacketing,
insulator, and conductor shielding of power cables. Used in these shielding layers around the the
conductor, they prevent partial discharge at the interface between the insulation layers and conductor
and eliminate any field stress by homogenizing the electrical field around the conductor. In addition
they smooth out any sharp edges at the conductor surface. Specific conductive carbon black-polymer
composites are positive temperature coefficient (PTC) materials that, when heated, become resistive at
a defined temperature.
Carbon black is electrically conductive; most carbon black grades have an electrical volume
resistivity in the range of 10
1–102 O cm. Carbon black therefore imparts conductivity to polymers
(Funt et al. 1993). High carbon black concentrations are required with conventional carbon blacks to
achieve good electrical properties, and this reduces certain composite mechanical properties and
ease of processing while increasing the costs. Generally special carbon black grades, so-called
conductive carbon blacks, are used which allow to reach the final resistivity level in filled polymer
composites at lower concentration than conventional carbon black grades. Over the past few
decades, static dissipative and conductive polymer composites have become part of the polymer
world, and conductive carbon black remains the major conductive filler, due to the fact that in most
cases conductive carbon black grades offer the best performance as well as the most economical
solution. Conductive carbon blacks are specialty blacks that represent only about 1 % of the global
annual carbon black production estimated at about 11 Mio. tons (calendar year 2012). About 50 % of
the conductive carbon black volumes are used for power cables, 36 % for plastic, and 14 % for
rubber compounds. Alternative more recent conductive additives used for ESD protection applica-
tion are inherently dissipative polymer (IDP) materials. Although metal powders are intrinsically
more conductive than carbon black, they are less frequently used in conductive polymer composites.
Some conductive metal powders or fibers of steel, aluminum, and copper have the tendency to
oxidize to form an electrically insulating layer on their surface. Noble metals like gold and silver
powders are economically not feasible for most conductive polymer applications. Nevertheless,
metal-coated polymers (MCP) or metal powder-filled polymer composites are applied, in particular
for EMI shielding.

Conductive Carbon Black Properties and Manufacture

A general overview about the primary and secondary properties of carbon black, typical related
analysis methods, and the principles of the carbon black manufacturing processes are given in the
cross-reference Carbon Black as Polymer Filler or in other reviews (Medalia 1982; Hess and Herd
1993; Kühner and Voll 1993; Probst 1993; Taylor 1997; Wang et al. 2004). The section below
focuses on the main material characteristics of conductive carbon black, reviews the intrinsic
conductivity and conductivity mechanism of carbon black, and describes the specific manufacturing
processes of conductive carbon black grades used at an industrial level.

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Material Characteristics Describing Conductive Carbon Black

The microstructure of conductive carbon black can range from paracrystalline primary particles
consisting of concentrically arranged continuous layers of hexagonally arranged carbon atoms to
primary particles containing small graphitic or turbostratic domains. In Fig. 1 HRTEM images
compare the microstructure of an acetylene black indicating small graphitic domains with a planar
arrangement of the carbon layers with the microstructure of ENSACO® 250G showing distorted
carbon layers that are concentrically arranged within the particle around the growth center or
nucleus.
Characteristic feature of the conductive carbon black family is the large carbon black structure
formed by more or less spherically shaped primary carbon particles with an average diameter of
typically several tens of nanometers. The coalesced primary particle units are coated by continuous
carbon layers that in this manner bind them by strong covalent bonds to rigid aggregates as it is
indicated for ENSACO® 250G by the transmission electron microscope (TEM) image in Fig. 1a.
The major fraction of aggregates in conductive carbon black contains a multitude of primary
particles arranged in three-dimensionally branched particle chains, fibrous, or grape-like shapes
that can have sizes of up to several hundred of nanometers. The aggregates form agglomerates which
are held together physically. The carbon black structure of a typical conductive carbon black,
ENSACO® 250G, is illustrated by transmission electron microscope (TEM) and scanning electron
microscope (SEM) images in Fig. 2.
The complexity of the arrangements of the carbon black particles, aggregates, and agglomerates
results in a relatively high void volume and the possibility to establish and maintain a carbon
network in polymer compounds. The void volume is a measure to compare the structure of carbon
blacks. The void volume depends on the size and shape of the aggregates, the aggregate agglom-
eration and the porosity of the primary particles. Therefore the carbon black structure can be
considered as the sum of a number of accessible voids by unit weight given by: (i) the inter-
aggregate space, (ii) the interstices within the aggregates, and (iii) the porosity of elementary
particles. The higher structure level of the carbon black is, the higher is the volume of the voids.
Dibutyl phthalate absorption, DBPA, today replaced by Oil Absorption Number (OAN) (ASTM
D2414) is employed to measure the void volume and thus the average structure level of carbon

Fig. 1 HRTEM images of typical primary particles for ENSACO® 250G (a) and acetylene black (b)

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Fig. 2 Mechanical work required to compact carbon black grades with different levels of carbon black structure in equal
pressure increments from 1 to 5 kN cm−2 at the corresponding compression density of the sample. The numbers given in
brackets in the graph legend indicates the OAN of the corresponding carbon black grade in mL (100 g carbon)−1.

Fig. 3 TEM images indicating the different level of porosity in the primary particles of extra-conductive ENSACOTM
350G (Image a, BET SSA of 770 m2 g−1) and ultra-conductive carbon black (Image b, BET SSA of 1,400 m2 g−1).

black. The OAN is higher the more complex the carbon black structure is. Carbon black grades with
an OAN of above 170 mL/100 g are specified as conductive carbon black.
The carbon black structure is very sensitive to the state of compression of the carbon black.
Important stages during carbon black production and processing that can cover a broad range of
compression states are the (1) carbon black powder after the gas separation step in the manufacturing
process, (2) compacted carbon black flakes or pelletized carbon black, and (3) the polymer
compound. The crushed oil absorption number (COAN) measured by ASTM D3493 at a given
compression state is attributed to the difference in sensitiveness of the carbon black structure
towards compression observed for different carbon black grades. Therefore the COAN can indi-
rectly indicate the resistance of the carbon black structure towards shear stress during the
compounding process as well as its ability to form a conductive network and maintain it in the
polymer compound. A similar concept takes into account the mechanical resistance of carbon black
to compression by measuring the decrease of void volume with increasing compaction pressure at a
given weight (ASTM D6086). Probst et al. suggested that the mechanical work being necessary to
compact carbon black is ruled by electrostatic surface charges contained in the carbon black
aggregates (Grivei and Probst 2003). These electrostatic surface charges are responsible for the
aggregate agglomeration which consequently is reversible and depends on the interaction with the
physical environment. Figure 3 shows the mechanical compaction energy calculated from the

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Fig. 4 TEM (a) and SEM (b) images indicating the high carbon black structure of ENSACO® 250G consisting of
agglomerates of carbon black aggregates with branched shape. An example of one aggregate is indicated by the circle.

volume changes achieved by incremental pressure increases at the corresponding compression

density of the carbon black samples. Higher structured carbon blacks require significantly higher
mechanical work to achieve a given volume density. With a model based on the electrical interpre-
tation of the mechanical properties, it was possible to calculate a superficial charge carrier concen-
tration in the range of 1016 cm−3 increasing with the OAN of the carbon black materials. Intrinsic
electrical resistivity values calculated with this model were found to be consistent with values
obtained from measurements of the pure carbon black at high pressure (see also following section).
These results supported the possible relationship between the resistance of the structure to mechan-
ical stress and the electrical behavior of carbon black governed by electrostatic surface charges
ruling the carbon black agglomeration.
The surface area is, besides the OAN, the other secondary carbon black property used to describe
conductive carbon black. The specific surface areas calculated from nitrogen isotherms (ASTM
D6556) according to the Brunauer, Emmett, and Teller model (BET SSA) of conductive carbon
black grades can largely vary from low surface area ENSACO® carbon black grades or acetylene
black (45–75 m2 g−1) to supra-conductive carbon black grades (ca. 200 m2 g−1), extra-conductive
carbon black (ca. 800 m2 g−1) and ultra-conductive carbon black (above 1,200 m2 g−1). The porosity
can be neglected in the low surface area carbon black grades for which the BET SSA increases with
the primary particle size. For carbon black above ca. 150 m2 g−1 pores in the primary particles
contribute to the BET SSA. A further increasing BET SSA is created mainly by an increasing
porosity of the primary particles. The TEM images of the high surface area ENSACO® 350G and
ultra-conductive carbon black in Fig. 4 indicate the existence of a significant amount of pores in the
primary particles. For the latter carbon black material, the large pores hollowed the primary particles
that almost completely lost the typical spherical character.
Table 1 lists a selection of commercial conductive carbon black grades categorized according to
their OAN in conductive carbon black, extra-conductive carbon black, and ultra-conductive carbon
black and gives their main properties.

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Table 1 Physical properties of commercial conductive carbon black grades (according to supplier information)
Medium particle BET SSA [m2 Iodine Absorption Number OAN [mL (100 Volatiles
Carbon black grade diameter [nm] g−1] [mg g−1] g)−1] [%]
Conductive carbon black
Vulcan XC 72R 30 250 255 175 1.5
(N472)
ENSACO 250G 35 65 82 190 0.1
Acetylene black 35 65 93 160 0.01
granules
Conductex 7055 42 55 50 170 1
Ultra
Extra-conductive carbon black
Ketjenblack 40 800 790 365 0.4
EC300J
ENSACO 350G 30 770 860 320 0.2
Printex XE2 35 1,000 1,075 380 1
Black Pearls 2000 12 1,475 1,050 330 2
Ultra-conductive carbon black
Ketjenblack 34 1,400 1,050 495 0.5
EC600JD

Intrinsic Electrical and Thermal Conductivity of Carbon Black

Carbon black materials are semiconducting with intrinsic electrical resistivity values between 101
and 10−2 Ω cm. Figure 5 shows the electrical resistivity of carbon black grades under compression at
the corresponding compression density of the sample. For all carbon black types the intrinsic
electrical resistivity is decreasing with increasing applied pressure. A certain electrical resistivity
level is usually achieved at lower volume density of the carbon black material the higher its structure
is. Elevated resistivity values at high compression density observed for some of the carbon black
materials could be explained by the microstructure or the high volatile content.
The influence of the particle size on the intrinsic conductivity of carbon black does not seem to be
established but porosity plays a role once the porosity level is very high: Ultra-conductive carbon
black composed of hollow particles show a higher intrinsic electrical conductivity as it could be
expected from its specific volume. On the contrary, the high carbon black structure of conductive
carbon black causes high specific volume and consequently low intrinsic conductivity (Probst
1993). Voet et al. showed that for most carbon black grades the logarithm of the resistivity is a
function of the cube root of the specific volume; the limiting element being the interparticle distance
(Donnet and Voet 1976). It was concluded that the resistivity of the carbon black is an exponential
function of the average particle distance at prevailing pressure and that the predominant conduction
mechanism is electron tunneling.
At very high compression most carbon blacks approach the same limiting level of conductivity.
With increasing pressure, since the aggregates becoming more tightly packed and pressed against
each other, and with very low contact resistance, the conduction mechanism is considered to be by
direct contact and therefore more graphitic in nature (Hess and Herd 1993). In this regime, due to the
mostly concentric nature of the superficial carbon layers in the carbon black particles, most of the
contacts are between graphitic basal planes. The electronic conductivity along the graphite basal
planes in the chemical structure of graphite is four orders of magnitude higher than perpendicular to

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Fig. 5 Electrical volume resistivity obtained from two-point electrical resistivity measurements of pressed carbon black
samples at the corresponding compression density. The carbon black samples were compacted by increasing the
pressure in equal increments from 1 to 5 kN cm−2 with two brass pistons that at the same time acted as sensing
electrodes for the electrical resistivity measurement. The numbers given in brackets in the graph legend indicates the
OAN of the corresponding carbon black grades in mL (100 g carbon)−1.

them. This explains the higher intrinsic electrical resistivities found for carbon black compared to
graphite powders usually having a higher probability of contacts between prismatic edges. Surface
oxides and impurities absorbed at the carbon black surface significantly increase the electrical
resistance. Due to these reasons, heat-treated carbon black materials show a resistivity minimum
at about 1,200 °C when all surface oxides are completely desorbed from the surface. Above this
temperature, the layers show an increased tendency to form around the aggregates a continuous
encapsulating shell consequently causing an increase of the electrical contact resistance.
Compared to graphite powders, carbon black materials show significantly lower level of thermal
conductivity ranging from 0.1 to 0.5 W (mK)−1. Graphitic materials therefore would be preferred
usually as carbon filler if a high thermal conductivity was required. The electrical and thermal
conductivity of graphitic carbons is described in more details elsewhere in this encyclopedia*.

Manufacture of Conductive Carbon Black

Conductive carbon black grades can be obtained via both manufacturing process principles, the
oxygen-free thermal decomposition and the thermal-oxidative decomposition of hydrocarbons
(Kühner and Voll 1993; Taylor 1997; Wang et al. 2004). The creation of highly branched aggregates
of small primary carbon black particles and the stabilization of these structures are key features in the
manufacturing process. Their achievement in the oil-furnace process usually is accompanied by a
significant reduction of the process yield. Conductive furnace blacks are produced by co-injecting
pre-heated oil feedstock and air in a closed flow reactor creating a turbulent flame. The most
important process stages influencing the carbon black properties are the atomization and vaporiza-
tion of the oil droplets in the reactor, the partial combustion and pyrolysis of the atomized feedstock
in the turbulent flame, and the secondary reactions between the carbon black particles and the
components of the reactor off-gas. The carbon black structure formed in the reactor is largely
dependent on the formation and concentration of solid primary particles being determined by the
concentration of feedstock vapor and reactor temperature (Kühner and Voll 1993). Low feedstock/
air ratios increase the concentration of feedstock vapor and reactor temperature and therefore cause
small primary particle sizes and large carbon black structures. To stop the particle growth and

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moreover to avoid carbon black loss occurring at these temperatures due to the Boudouard and water
gas reaction with CO2 and H2O gas, respectively being both present in the reactor, a cooling step and
subsequently the separation from the tail gas is performed. These stages are followed by the reaction
of the carbon black with oxygen upon the first contact with air, and a densification and eventual
pelletization step.
The production process of acetylene black is based on the exothermic decomposition of acetylene
to carbon black and hydrogen occurring above 800 °C in the absence of oxygen. Once the reaction is
started, the acetylene decomposition reaction autogenously provides the energy required for the
cracking of acetylene to carbon followed by the synthesis of the carbon black:

nC2 H2 →2nC þ nH2 þ Energy

The high synthesis temperatures above 2,000 °C being typical for the acetylene black production give
rise to a relatively high graphitization degree of the primary particles that show low surface area. The
high surface area gasification blacks are by-products from the production of synthesis gas based on the
in-complete combustion of hydrocarbons. Hereby, the preheated oil feedstock reacts with air and vapor
at relatively high temperatures to form synthesis gas (H2/CO) and a carbon black by-product that is
separated by filters or extraction. The process has no flexibility in producing different grades or
changing the carbon black properties as the carbon black production is not the main purpose.
Acetylene black and conductive furnace black were the only conductive carbon black grades
available on the market until the mid-seventies when the gasification black products like Ketjen
EC300J and Philblack XE-2 (later name: Printex XE-2), known as extra-conductive carbon black
and both being by-products from the Shell gasification process, became available. In the early
nineties the low surface area high structure ENSACO® carbon black grades were introduced
together with the extra-conductive high surface area ENSACO® 350 carbon black being all
manufactured out of a specifically designed process for conductive carbon black by IMERYS
(IMERYS Belgium, ex-MMM Carbon).
The development of new conductive carbon additives for polymers has been ongoing since more
than three decades. The major effort has been made to decrease the required carbon black concentra-
tion with no deterioration of the level of conductivity of the carbon black-filled polymer compound.
The family of the extra-conductive carbon blacks is the result of this effort. Oxidative after-treatment of
those extra-conductive carbon blacks made another step in this direction. After-treated extra-conduc-
tive carbon blacks, also called ultra-conductive carbon blacks, generate in some polymers sufficiently
high conductivities at concentrations below 2 wt%. Other development directions have been:

A. High purity: low sulfur, low grit, low metal content

This trend was mainly pushed by the power cable industry. With increasing voltage, higher purity
for conductor shields has been demanded. However, purity also has been beneficial for other
numerous plastic applications, e.g.: plastic films and reduced degradation of sensitive plastics
(like alkaline catalyzed hydrolyzation).
B. Stability of the conductivity, i.e., resistance to shear occurring in the extrusion process to prepare
conductive polymer compounds.
C. Very high conductivities for specific applications
D. Reduced viscosity for conductive compounds
E. Reduced or increased positive temperature coefficient (PTC) effect

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Carbon Black-Polymer Composites

The Insulator-Conductor Transition
Carbon black-filled conductive polymer compounds have been studied extensively since the 1970s,
and the results are published in numerous technical articles and patents. Several reviews give an
overview about the phenomenological aspects that have to be considered when creating conductive
polymer compounds with the help of carbon black fillers (Probst 1993; Probst et al. 2009; Huang
2002; Davidson 2010). The incorporation of conductive particles into a polymer matrix fundamen-
tally modifies the electrical and dielectrical behavior as well as the mechanical properties. The
electrical resistivity decreases, typically abruptly by several orders of magnitude, at a critical
conductive particle concentration at which the polymer composite becomes electrically conductive.
Electrical resistivity curves show with increasing concentration of conductive particles three
consecutive distinct zones, an insulation zone, a percolation zone, and a conduction zone, respec-
tively (Fig. 6). Three parameters describe the percolation from the insulating to the conducting
domain: the critical concentration or critical carbon volume fraction at which the percolation occurs
(percolation threshold), the slope of the percolation, and the ultimate electrical resistivity level.
In carbon black-filled polymer compounds, the percolation threshold and slope from the insulat-
ing to the electrically conducting domain as well as the ultimate resistivity level are influenced by the
carbon black type, the polymer type, as well as the mixing/compounding and finishing process.
These variables will be elucidated in the following sections.

Carbon Black Properties, Critical Carbon Black Concentration, and Mechanical

Compound Properties
Carbon blacks is electrically conductive and impart electrical conductivity to the typically insulating
polymer. Generally, conductive carbon black grades are preferred as they allow reaching the
percolation at lower concentration than conventional carbon black and therefore influence to
a lower degree the mechanical properties of the resulting polymer compound. The capability of
a carbon black to impart electrical conductivity to a polymer compound depends on its ability to
establish and maintain a conductive network in the insulating polymer matrix. Hereby, the carbon
black aggregates assemble continuous paths that allow the transport of electrical charges through the
polymer matrix. The key property of conductive carbon black is the high carbon black structure, i.e.,
the high void volume. Conductive carbon black can accept high polymer levels while maintaining

Fig. 6 Schematic representation of the electrical resistivity of a polymer compound as a function of the conductive
particle filler concentration

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Fig. 7 Electrical volume resistivity of carbon black compounds at different carbon black loadings. (a): ENSACO ®
350G (E350G, OAN ¼ 320 mL (100 g)
1), ENSACO ® 250G (E250G, OAN ¼ 190 mL (100 g)
1), Ketjenblack
EC300J (EC300J, OAN ¼ 330 mL (100 g)
1), and ultra-conductive carbon black (UCCB, OAN ¼ 560 mL (100 g)
1)
in high-density polyethylene (compounding by twin-screw extruder, compound processing by injection molding); (b):
ENSACO ® 350G (E350G, OAN ¼ 320 mL (100 g)
1), ENSACO ® 250G (E250G, OAN ¼ 190 mL (100 g)
1),
VULCAN ® XC72R (N-472, OAN ¼ 175 mL (100 g)
1), and P-type carbon black (P-type, OAN ¼ 100 mL (100 g)
1)
in low-density polyethylene (compounding by twin-screw extruder, compound processing by compression molding at
2 min/170  C)

the carbon black network. The higher the OAN and COAN of the carbon black grade, i.e., the higher
the carbon black structure and the ability to maintain the carbon black structure under the influence
of mechanical stress like compression and shear forces occurring during the compounding process,
the lower is the carbon black concentration required to make the polymer compound conductive. At
the percolation threshold, all carbon black materials show quite a constant total volume calculated
from the product of COAN and volume fraction of the carbon black grade. This underlines the fact
that all carbon black materials can achieve a low electrical resistivity level but the selection is based
on other criteria as well, for example, mechanical properties and dispersion. In addition, the carbon
black surface should be free of any organic residue or chemical groups that could deteriorate the
electrical contacts or act as electron traps. The quality and number of carbon black interparticle
contacts as well as the carbon black microstructure mainly influence the ultimate resistivity level.
Figure 7 illustrates the electrical volume resistivity as a function of the carbon black loading in
polypropylene for several examples of commercial conductive carbon black grades. The percolation
threshold decreases with increasing OAN of the carbon black grades indicating the influence of the
carbon black structure on carbon black concentration at which the compound becomes conductive.
A proper selection of a conductive carbon black is made in such a way that other performance
criteria, especially the mechanical properties, are met while the compound is electrically conductive.
With the addition of carbon black into thermoplastics at low loadings usually an increase of the
tensile and flexural modulus, i.e., the stiffness and rigidity of the resulting polymer compound can be
observed. At high carbon black concentration, the tensile strength decreases again. The tensile
elongation at break generally decreases but much variety can be observed depending on the polymer
grade and especially the dispersion quality. Also the impact properties typically decrease when
incorporating carbon black in the polymer due to the increased brittleness of the resulting polymer
composite. The increase of the melt viscosity and stiffness accompanied with the incorporation of
carbon black in a polymer are drivers to minimize the carbon black content in a conductive
compound.

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Table 2 Melt flow index and mechanical properties of ENSACO ® 250G and ENSACO ® 350G containing compounds
of HDPE with adjusted carbon black loadings resulting in the same level of electrical volume resistivity
Pure HDPE (Hostalen GD HDPE/ENSACO ® HDPE/ENSACO ®
7255) 350G 250G
Carbon loading [wt%] 0 17.5 25.0
Electrical volume resistivity [O cm] >1011 7.3 6.9
Melt flow index at 190  C/5 kg 11 0.89 2.46
[g (10 min)
1]
Tensile modulus [MPa] 886 1,234 1,259
Stress at yield [MPa] 23.40 31.13 31.10
Strain at yield [%] 10.2 7.7 7.4
Flexural strength at conventional deflection 18.85 28.87 29.36
[MPa]
Flexural modulus [MPa] 943 1,364 1,547
Impact strength [kJ m
2] 8.89 5.41 5.49

However, a low critical volume fraction is not always equivalent to best performance.
Low-surface-area conductive carbon black ENSACO ® 250G achieves in a high-density polyethyl-
ene (HDPE) compound at equal electrical resistivity level a higher fluidity and similar mechanical
properties compared to extra-conductive carbon black ENSACO® 350G, as summarized in Table 2.
The reason for this behavior could be found in the lower surface area of ENSACO ® 250G together
with the higher achievable dispersion degree. For many carbon black grades, the melt viscosity of
corresponding polymer compounds at the same weight percent carbon loading is highly dependent
on the BET SSA. In high-surface-area carbon blacks, the DBP absorption or OAN usually follows
the surface area mostly created by the particle porosity and is also related to the melt viscosity (Fox
1982). The critical pigment volume concentration (CPVC) of a carbon black grade is a function of its
OAN and apparent density, dCB:

100
CPVC ¼ (1)
dCB
1 þ ðOANÞ
100
It can be seen that both electrical resistivity and melt viscosity show a threshold behavior at the
CPVC. Both properties change as a function of the carbon loading at the critical volume fraction at
which a continuous carbon network is established throughout the sample. The carbon network, once
established, makes the polymer compound more rigid, as well as more conducting. The melt
viscosity has an influence on the mobility of the carbon black aggregates. As described below in
more detail, a high melt viscosity can significantly retard the coagulation (structuring) of the
aggregates to the conductive network. In that case a higher carbon black volume fraction is needed
to reach the critical concentration of carbon black in the polymer compound.

Polymer Nature and Properties

The carbon black and polymer properties influencing the organization and stability of the conducting
network are those having an impact on the coagulation of the carbon black aggregates and improving
or inhibiting their mobility. The percolation threshold is determined by a balance of the interactions
between the carbon black aggregates and the interaction between the carbon black aggregates and
the polymer molecules. If the interactions between the carbon black aggregates are stronger, the

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Fig. 8 Electrical resistivity of ENSACO ® 250G/polymer compounds with high-density polyethylene (HDPE), poly-
styrene (PS), polycarbonate (PC), and polypropylene copolymer (PP-c) as polymer component as a function of the
carbon black concentration (compounding, twin-screw extruder; processing, injection molding)

carbon black agglomerates tend to stick together in the melt-mixing process typically used to prepare
the compounds and the carbon black agglomerates are difficult to disperse. If the interactions
between the carbon black aggregates and the polymer prevail, the carbon black aggregates are
dispersed separately without contact and the formation of conductive paths is retarded until a higher
concentration of carbon black is provided. Miyasaka et al. (Miyasaka et al. 1982) proposed to
consider the surface tension of carbon black and polymer component as a parameter to quantify these
interactions. They found that the percolation concentration increases with increasing polymer
surface tension due to the stronger interaction between carbon black filler and polymer matrix.
Figure 8 illustrates with examples of ENSACO® 250G/polymer compounds the influence of the
polymer on the electrical compound resistivity.
The crystallinity of polymer is another parameter influencing the percolation threshold. For
amorphous polymers, the carbon black particles are uniformly dispersed in the polymer matrix
and high electrical conductivity is achieved when the carbon black concentration reaches the
percolation threshold. In crystalline polymers the carbon black is mostly ejected from the crystalline
regions during the crystallization of the polymer in the cooling process and concentrated in the
amorphous regions leading to a decrease of the critical volume fraction of the carbon black. As
mineral fillers or glass fibers do not incorporate the carbon black, the carbon black is concentrated in
the polymer phase and a similar effect can be observed. The increase of the molecular weight of the
polymer always causes an increase in percolation concentration as high molecular weight polymers
make it more difficult to wet the carbon black surface and slow the formation of the conducting
network. The increase of molecular weight increases the melt viscosity, i.e., decreases the melt flow
index (MFI), which moves the percolation threshold to higher carbon black concentration, as
illustrated in Fig. 9. A plasticizer lowers the melt viscosity and therefore the percolation concentra-
tion should be lower. Plasticizers may also intervene in the mixing and finishing process by reducing
or increasing the shear energy involved. Some of them intervene in the coagulation process of the
carbon black and thus influence the percolation threshold. In elastomers the chemical cross-linking
system could significantly influence the electrical resistivity of the carbon black-elastomer
composite.
Recently, multiphase polymer blends are considered as technical solutions to achieve a sufficient
electrical conductivity in the polymer compound at low loadings of conductive carbon black. The
phase separation in these polymer blends and selective distribution of the carbon black into one

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Fig. 9 Electrical resistivity of ENSACO ® 250G at different weight percentages in polypropylene homopolymers (PPH)
with MFI of 4, 23, and 50 g (10 min)
1 (MFI measured at 190  /5 kg, compounding, twin-screw extruder; processing,
injection molding)

Fig. 10 Schematic representation of a crystalline polymer (P) segregating the carbon black in the continuous amor-
phous domain of the carbon black-polymer composite (CB/P)

phase can lead to conducting polymer compounds at lower carbon black filler content which can
provide better compound processability and avoid poor mechanical properties caused by high filler
loading. The percolation threshold depends strongly on the phase morphology and the distribution
of carbon black in the polymer blend. The carbon black distribution in a blend of two immiscible
polymers occurs in different proportions depending upon its affinity to the polymer components and
the compound processing. The carbon black could be distributed predominantly in one continuous
phase or located preferentially at the interface of the two polymer phases. The first case includes
a multiple percolation effect: The polymer phase predominantly containing the carbon black
becomes conductive after the carbon black concentration reaches the percolation threshold in this
phase. With increasing volume fraction of the carbon black-rich phase, the phase changes from
a dropwise domain into a continuous structure and the polymer mixture becomes conductive. The
decrease of the percolation threshold in a crystalline polymer can be considered as the result of
a multiphase system: The amorphous phase is enriched with carbon black while the crystalline phase
contains no or only small amounts of carbon black. Since the amorphous phase is the continuous
domain, the crystalline polymer compound becomes conductive at lower overall carbon black
concentration as shown in the schematic drawing of Fig. 10.

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Compound Processing
The dispersion of the carbon black in the polymer matrix can have significant effects on the
compound resistivity and therefore is the most important stage in the preparation of conductive
polymers. Hereby, extrusion mixing, typically performed by co-rotating twin-screw extruders, is the
most important technique to disperse carbon black in polymers. Other major mixing equipment are
kneaders, internal intensive batch mixers, two-roll mills, and intensive dry mixers. Usually it is
preferred to add the carbon black to the molten polymer, e.g., by the split feed technology in twin-
screw extruders, as it avoids carbon black compaction and, consequently, poor dispersion.
Compounding conductive carbon black means incorporating materials with extremely low bulk
density and therefore high filler volume into the polymer. Controlled compression or pelletizing is
applied to facilitate the feeding or incorporation process of the carbon black filler. In the early stage
of mixing polymer penetrates into the interstices between the particle aggregates. A high carbon
black void volume supports this process and makes the dispersion of highly structured carbon black
easier than the dispersion of lower structured carbon black. In addition, a low carbon black specific
surface area facilitates the occurring wetting process of the carbon black surface by the polymer. The
best property combination for carbon black as far as dispersion is concerned is given by a high
carbon black structure and a low BET SSA. All mixing types allow generation of predominantly
high shearing forces which are responsible for the dispersion of the carbon black agglomerates.
Carbon black agglomerates are mainly based on weak electrical interactions of the aggregates and as
such are sensitive to shear. The shearing forces disentangle to a certain degree the agglomerates into
aggregates and consequently have an impact on the final structure (agglomerate size) in the
compound. Perfect dispersion is achieved when the agglomerates are separated into discrete
aggregates with surfaces that are completely covered with polymer. This structure break-down
increases the electrical resistivity of the compound with increasing mixing time. In the first stages of
the mixing process the electrical compound resistivity rapidly decreases as electrical pathways are
established between the carbon black agglomerates but reaches an optimum when further mixing
gradually increases the resistivity due to the structure breakdown and the related increase of the gap
between primary particle aggregates. In addition, especially highly viscous polymer matrices and
high-shear mixing processes can generate very high shearing forces acting on carbon black and may
cause an over-shearing effect which leads to the compression, deformation and finally to the
breakage of the carbon black aggregates. In such case an extended mixing time would increase
the electrical volume resistivity. The contrary effects of the shearing forces on the formation of the
carbon black network in the polymer matrix result in an optimum mixing time that depends on the
specific process and formulation. A very careful and consistent mixing procedure ensures good
conductivity and a homogeneous mix and avoids over- and under-dispersion. The break-down of the
carbon black structure usually can be partially recovered in the filler-polymer network by a
rearrangement of the carbon black aggregates and polymer molecules occurring after mixing or
finishing. This restructuring called coagulation or flocculation is mainly controlled by the carbon
black aggregate and polymer interactions as well as the aggregate mobility. Carbon black and
polymer surface tension as well as melt viscosity influence coagulation. Consequently, specific
surface area and specific superficial energetic sites of the carbon black as well as polymer nature and
MFI play an important role. Mixing can also reduce the polymer crystallinity and hence move the
percolation threshold to higher carbon black concentration.
The finishing processes may also influence the polymer compound properties. Finishing tech-
niques such as extrusion, injection, film blowing, thermoforming, and calendering influence the
compound properties to a different degree and change the conductive properties of the resulting
carbon black-filled polymer specimen. Hence, the total compounding and finishing process has to be

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Fig. 11 Electrical volume resistivity of ENSACO ® 250G/HDPE and ENSACO ® 350G/HDPE compound bars at
different loadings produced by compression (Comp) and injection (Inj) molding (compounding by twin-screw extruder,
220  C)

considered when formulating the recipe. Figure 11 shows the electrical volume resistivities of bars
containing ENSACO® 250/HDPE compounds at different loadings. The higher percolation thresh-
old of the injection molded bars can be explained by a sum of different effects taking place. The non-
uniform shear flow during mold filling, i.e. higher shear near the mold surface leads to polymer
segregation and lower carbon black concentration at the surface-near regions of the sample bar. This
effect together with decreased polymer crystallinity at the surface of the compound specimen is the
reason for the so-called skin effect observed in the case of the injection molding process. In addition,
the higher shearing forces of the injection molding compared to the compression molding can cause
overall higher structure breakdown of the carbon black as well as higher reduction of polymer
crystallinity. Typically the influence of shear on the electrical properties during finishing is reduced
at lower electrical compound resistivities corresponding to higher carbon black concentration and is
higher near the percolation threshold where small changes in carbon black structure or concentration
have larger impact on the electrical conductivity. Compounding at higher concentrations cause
higher structure breakdown due to the higher shearing forces required. Consequently, the structure
suffers less in further breakdown when additional shear is applied during finishing. In elastomer
compounds shear could also occur during service of the finished parts, hence increasing its
resistivity by dynamic deformation. Resistivity plateaus reached at a certain number of deformations
indicate maximum structure breakdown linked to the COAN. Recovery of the conductivity is
possible quantitatively by relieving the compound thermally.

Conduction Mechanisms in Carbon Black-Polymer Composites

Random dispersion of carbon black in an electrically insulating polymer matrix changes, above
a critical carbon black volume fraction, the resulting polymer compound from an insulator to
a conductor. At this percolation threshold, a sudden change in the dispersal state of conducting
particles, the coagulation of conducting primary aggregates to a conducting network, facilitates the
electronic conduction through the polymer-filler composite. The total electrical resistance of
a compound is the sum of all aggregate resistances, Ra, and interaggregate resistances, Re,

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X
n X
n
R¼ Ra, j þ Re, i (2)
i¼0 i¼1

of the conducting network and depends, beyond the percolation threshold, on the microstructure and
surface of the carbon black as well as the polymer type. In general, conductive carbon black-polymer
composites have semiconducting character. As the polymer can only affect Re in Eq. 2, it influences
the electrical contacts between the aggregates. In fact, a conduction mechanism through real
physical contacts between the carbon black particles in the conducting network without any
influence of the polymer, as it is found in the case of carbon fibers and graphite, can only be
found for carbon black primary particles larger than 300 nm. In this case, the electrical compound
conductivity increases with temperature (Carmona 1988, 1989; Probst 1993).
Most of the carbon black grades have smaller primary particle sizes and their polymer composites
like in the case of direct particle contacts have semiconducting character. However, thin polymer
films between the carbon black particles form discontinuities in the conducting network being
responsible for a tunneling mechanism of the charge carriers (Sichel et al. 1982). The probability for
electron tunneling decreases with an increasing gap width. The electrical resistivity rel therefore
decreases with decreasing particle distance (polymer film thickness) and at the same time depends
on the electrical field E and the temperature T according to the following expression:
 2
T

T þT1 e 1
EE
rel ¼ r0el e 0
(3)

where T1, T0, and E0 are constants and r0el is carbon black concentration dependent. The influence of
the temperature is attributed to thermal fluctuations lowering the inter-aggregate gap and modulating
the potential barrier. A higher electrical field can excite electrons and maintain a higher kinetic and
potential energy level required for the tunneling of electrons. The theory of fluctuation-induced
tunneling can qualitatively account for the temperature, the electrical field, and the pressure
dependences of the electrical polymer compound resistivity.
Also the positive temperature coefficient (PTC) phenomenon can be explained by this theory. The
PTC stands for an increase of the electrical resistance when the temperature increases. In the case of
a carbon black-polymer compound, the PTC is based on the higher thermal expansion of polymer
matrix than the conductive network. With increasing temperature the higher thermal expansion of
the polymer increases the gap between the particle aggregates in the conductive network. The
potential barrier increases and the electrical compound resistivity increases. The opposite mecha-
nism explains the possible negative temperature coefficient (NTC), the increase of the electrical
resistance of a high temperature conductor when the temperature is decreased. Based on the concept
of double percolation and two-step percolation, PTC and NTC compositions based on polymer
blends with balanced performance, improved processability, and reproducibility could be made.
Mixtures of carbon black grades could cause a sharper resistivity change with temperature than
a single carbon black at loadings near the percolation range. The PTC or NTC effect could lead to
new specific technical features or could be problematic: A sharp resistivity increase or decrease
could be used, e.g., for switch applications. In contrast, in a semiconductive cable compound, it
would be preferable to avoid significant changes in electrical resistivity with temperature.
Above the percolation threshold, the electrical resistivity of carbon black compounds reaches
values that are often 1–2 orders of magnitude higher than that of compressed pure carbon black in air.
However, the thickness of the polymer film between the carbon black aggregates decreases with

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higher loadings and decreasing carbon black-polymer interactions. Grivei and Probst showed that
for very high carbon black loadings as well as carbon black-polymer interactions that are negligible
or do not affect the interparticle contacts, the ratio between the electrical resistivity of the carbon
black under high compression in air and the electrical compound resistivity based on the same
carbon black at the corresponding volume fraction becomes unity, indicating a conduction mech-
anism by direct contact (Grivei and Probst 2003).

Percolation Models
Since the 1970s the insulator-conductor transition occurring during the incorporation of conductive
particles in an insulating polymer matrix has been the subject of extensive research. Related
activities have developed mathematical models that explain on a scientific level the network
formation as well as the behavior of the electrical resistivity near the percolation threshold
(Carmona 1988, 1989; Lux 1993). The models being the most applicable to carbon black-filled
compounds are the statistical and thermodynamic percolation models (Probst 1993; Huang 2002).
Due to the assumptions made therein, all models have their limitations that have to be considered
when predicting percolation curves from the properties of different carbon black and polymer types
(Balberg 1998, 2002; Rubin et al. 1999; Carmona and Ravier 2002).
The statistical model proposed by Kirkpatrick and Zallen treated conduction in a composite of an
insulator filled with conductive spherical particles as a theoretical percolation problem. They
approached the problem by starting with a regular finite array of points and randomly assigning
bonds between the points until a cluster of connected particles spans the relevant boundary of the
array and percolation occurs. They assumed that conduction through the compound bulk is
controlled by conduction over a number of paths of randomly formed particle chains. With
increasing number of particles, the number of continuous chains or conductive paths through the
compound increases. The local effect is largest where the first chains have formed. The total
resistance for any chain consists of the sum of individual resistances at each contact point. If these
individual resistances remain constant, the electrical resistivity rel of a composite at a filler volume
fraction f follows the expression

rel ¼ r0el ðf
fcrit Þ
t (4)

where fcrit is the critical volume fraction of carbon black filler, r0el is a scaling factor corresponding
to the compound resistivity at the percolation threshold, and the exponent t is a geometrical factor
being 1.5 for three-dimensional systems but commonly about two for real carbon black-polymer
composites for carbon black volume fractions above the percolation threshold.
Aharoni and Janzen developed the concept of average number of contacts between filler particles,
c being the product of a contact probability, p, and a maximum number of contacts a particle can
have with its neighbors, C. Janzen calculated based on the statistical model of Kirkpatrick and Zallen
the critical average contact number at the percolation threshold ccrit ¼ 1.5 and concluded with

f
c¼ (5)
ð1
fÞ

and with the carbon black density r and the crushed DPB absorption, v in (mL g
1), for the critical
volume fraction:

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1
fcrit ¼   (6)
C
1 þ r
ccrit

Based on his assumption that the maximum number of contacts C ¼ 6, Eq. 7 becomes

1
fcrit ¼ (7)
1 þ 4r

Equation 8 predicts a decreasing critical volume fraction with increasing crushed DBP absorption
being considered to correspond to the carbon black structure in the polymer compound. Although
the relation predicts the critical volume fraction of many carbon black grades satisfactorily, the
experimental values of fcrit for very low structured carbon blacks usually having large particle sizes
are higher than predicted. For these carbon blacks, also the values obtained for the geometrical factor
t are much higher than 2.0. For carbon black types with very high structures and small particle sizes,
the experimental values of fcrit are lower. An explanation could be that the statistical percolation
models do not consider the geometrical form of the aggregates as well as the filler-filler and filler-
polymer interactions. Balberg took into account the spatial geometrical and electrical properties of
the carbon black-polymer composites and proposed to introduce the tunneling conductance mech-
anism into the statistical percolation theory (Balberg 1998, 2002; Rubin et al. 1999). This tunneling-
percolation model showed a better agreement with the experiments.
The thermodynamic percolation models emphasize the importance of interfacial interactions and
consider the percolation phenomenon as a phase separation process. Sumita et al. took into account
the overall interfacial free energies in the compounds. They assumed that the interfacial excess
energy in the compound is increasing with increasing carbon black particles from an interfacial free
energy K0 at the start of the mixing process at a linear rate c up to an overall mixture-independent free
energy, g*, at which the network formation begins. This can explain the experimental finding that
a greater value of specific free energy is accompanied by a lower volume percolation concentration
and vice versa. The model also considers the melt viscosity of the polymer, Z, which if high in value
has an inhibiting influence on the coagulation process, the mixing time, t, and the diameter of the
carbon black particles, R. The final equation has the form
 
 

gct
1
e
gc þ K 0 e P
ct
(8)

where gc and gP are the surface tension values of the carbon black particles and the polymer,
respectively. The dynamic boundary model of Wessling et al. introduced additional assumptions on
the basis of the nonequilibrium thermodynamics and a formation mechanism of the conducting
network. Below the percolation, the particles are covered by a stabile absorbed polymer layer and are
distributed nonhomogeneously in the polymer matrix in the form of flat agglomerates. Near the
critical volume fraction with increasing particle number creating compression forces, the absorption
layers are partially destroyed and the particles come closer until they are in electrical contact at
a distance of 10 nm or less. In this way two-dimensional conductive islands are formed that

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coagulate to a three-dimensional network in a subsequent phase separation process by the interfacial

energies at the carbon black particles and the absorption polymer/polymer boundaries.
Many experimental findings are in agreement with the argument that percolation is a phase
separation like the abrupt increase of the tensile strength and compound hardness. However, some
assumptions seem rough for a general thermodynamic explanation of the percolation phenomenon
of carbon black-polymer composites. The highly structured geometry of the carbon black particles
aggregate, the aggregate agglomeration, compound inhomogeneities like isolated particle clusters,
the temperature dependence of the surface energies, the different miscibility of the conducting
particles with the polymer constituents of polymer blends, and the carbon black segregation in the
amorphous part or crystallite boundaries of semicrystalline or crystalline polymers are examples that
limit the applicability of such models.
Most recent approaches have considered inhomogeneities in the distribution of the conductive
phase within the polymer compound created by the applied compounding and finishing method as
only the compression molding route ensures the lack of any inhomogeneity in the distribution of the
conductive phase. Structure-oriented percolation models are based on parameters which have to be
determined from the microlevel structure of the composite part after the final processing step.
A detailed substitution of the real compound structure by a theoretical model structure is needed
for the determination of such parameters. The setup of this model structure requires suitable
analytical tools and powerful image analysis techniques, but the resulting models lead to the most
realistic theoretical predictions (Lux 1993; Carmona and Ravier 2002).

Cross-References
▶ Carbon Black as Polymer Filler
▶ Graphitic Carbon Powders for Polymer Applications

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