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CARBON BLACK: PRODUCTION,
PROPERTIES AND USES
IAN J. SANDERS
AND
THOMAS L. PEETEN
EDITORS
Nova Science Publishers, Inc.

New York
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Library of Congress Cataloging-in-Publication Data
Carbon black : production, properties, and uses / editors, Ian J. Sanders

and Thomas L. Peeten.
p. cm.
Includes index.
ISBN: (eBook)
1. Carbon-black. I. Sanders, Ian J., 1970- II. Peeten, Thomas L., 1967-
TP951.C37 2011
662'.93--dc22
2010051516
 New York
CONTENTS
Preface i
Chapter 1 Carbon Blacks in Electrochemical Energy Conversion Devices:
Uses and Applications in Fuel Cells 1
Paloma Ferreira-Aparicio
Chapter 2 Study and Application of Carbon Black Vulcan XC-72R
in Polymeric Electrolyte Fuel Cells 41
M. J. Lázaro, L. Calvillo, V. Celorrio, J. I. Pardo,
S. Perathoner and R. Moliner
Chapter 3 A Review of Current Analytical Applications Employing
Graphitized Carbon Black 69
Christine M. Karbiwnyk and Keith E. Miller
Chapter 4 Intermolecular and Intramolecular Interaction at Adsorption
on the Surface of Graphitized Thermal Carbon Black 93
V. V. Varfolomeeva and A. V. Terent‟ev

Chapter 5 Heat Transfer and Growth of Primary Black Carbon Particles
in Gas Mixture 115
Y. A. Baranyshyn, S. P. Fisenko and O. G. Penyazkov
Chapter 6 What Does Carbon Nanomaterial Cause in Human Health? 133
Masakazu Umezawa and Ken Takeda
Chapter 7 Effect of Carbon Black Fillers on the Tribological Properties
of PTFE 137
Yoshinori Takeichi
Chapter 8 The Role of Carbon Black in the Rheology of Rubber Compounds:
Dynamic Properties, Nonlinear Behavior and Modeling 157
Fabio Bacchelli and Salvatore Coppola
Chapter 9 Carbon Blacks for Energy Storage and Conversion 183
Gui-xin Wang and Kang-ping Yan
vi Contents
Chapter 10 Carbon Black Treated in Low Pressure Plasma: A New Class

of Granular Adsorbents for Acid and Basic Compounds 237
Nicoletta De Vietro
Chapter 11 Production, Properties and Applications of Carbon Blacks
in Rechargeable Lithium-Ion Batteries 263
B. Jin
Index 279
PREFACE
Carbon black is a material produced by the incomplete combustion of heavy petroleum
products. It is used as a pigment and reinforcement in rubber and plastic products. This new
book examines the production, properties and uses of carbon black. Topics discussed include
carbon blacks in electrochemical energy conversion devices; application of carbon black
vulcan XC-72R in polymeric electrolyte fuel cells; heat transfer and growth of primary black
carbon particles in gas mixture; and health risks of carbon nanomaterials. (Imprint: Nova
Press).
Chapter 1 – Carbon materials, and in particular carbon blacks, are widely used in
electrochemical applications because they combine unique properties: good electrical
conductivity, acceptable corrosion resistance, high purity, low cost, high thermal
conductivity, dimensional and mechanical stability, light weight, ease of handling, diversity
of physical structures and versatility in its surface chemistry,including composite fabrication.
This chapter describes a number of applications and uses of carbon blacks in electrochemical
energy conversion devices, and more concretely, in proton exchange membrane fuel cells
(PEMFCs). Fuel cell technology has experienced a huge advance by using carbon blacks as
the basic material for increasing the electrochemical area of metal electrocatalysts,
synthesizing microporous layers for gas diffusion and water management in electrodes, and
fabricating composites for flow field plates. Tailoring of carbon blacks by surface
modification is a powerful tool to design high performance components for these systems,
which constitutes a promising alternative for clean and efficient power in a large variety of
stationary, mobile, and portable applications.
Chapter 2 – The most developed fuel cells are those working at low temperature using a
polymeric electrolyte, PEMFC and DAFC, the latter making use of different alcohols directly
as fuel. At present, the most effective fuel cell catalysts, both in cathode and anode, are highly
dispersed platinum-based nanoparticles. These Pt nanoparticles are normally supported on
carbon materials in order to increase the active surface area of Pt and improve the catalyst
utilization. Among other factors, the performance of metal nanoparticles supported on carbon
materials depends strongly on the properties of the support. For fuel cell applications, carbon
supports should have several characteristics such as high surface area for dispersing catalytic
metal particles, high electrical conductivity for providing electrical pathways, and
mesoporous structure for the facile diffusion of reactants and by-products. Moreover, the
interaction between the carbon support and the Pt plays an important role in the properties of
the Pt/C catalyst. This interaction can be improved through the surface modification of the
support in order to form proper functional groups and chemical links at the Pt/C interface.
ii Ian J. Sanders and Thomas L. Peeten
These functional groups can significantly affect the manufacture and performance of
electrocatalysts, and they are responsible for both the acid-base and the redox properties of
the carbon supports. Nowadays, among all kinds of carbon supports, carbon blacks are the
most commonly used due to their high mesoporous distribution and their graphite
characteristics. Vulcan XC-72(R) is the most frequently used in the preparation of
commercial electrocatalysts because of its good compromise between electrical conductivity
and high surface area. In this chapter, a detailed analysis about the properties of Vulcan XC-
72R and the effect that different functionalization treatments have on them will be reported.
Subsequently, the influence of the properties of the support on platinum supported catalysts
will be established. The results of the use of these catalysts at the anode side of a PEM fuel
cell will be presented in order to demonstrate the effective application of this carbon material
in low temperature fuel cells and to establish the effect of the functionalization of the support
on the fuel cell performance.
Chapter 3 – Graphitized carbon black (GCB) is a non-porous form of amorphous carbon.
GCB materials are hydrophobic. They are often used to effectively trap organic compounds
from water or under high humidity conditions; conditions where the performance of other
sorbents is reduced. While activated carbon relies on its high surface-area-to-volume ratio to
adsorb organic compounds, the surface interactions of GCB depend solely on dispersion
(London) forces. GCB materials have been used to trap a wide range of organic compounds
from C4 hydrocarbons to polychlorinated biphenyls (PCBs). Typically, compounds are
adsorbed on the GCB surface from large volumes of air or water, and then subsequently
released either by solvent desorption or thermal desorption resulting in either a concentration
of the analytes, solvent exchange or combination of both. This review presents analytical
applications of GCBs over the last decade. It includes air monitoring, solid-phase extraction
(SPE), purge traps for purification or low-flow air sampling, and chromatography columns
utilizing GCB packing material.
Chapter 4 – The display of intermolecular interaction at adsorption on the surface of
graphitized thermal carbon black (GTCB) is not enough described even in theoretical
researches. Scientific literature almost lacks the data about the influence of the intermolecular
H-bond on adsorption of molecules of different classes. Intermolecular H-bond was not
examined as one of the types of intermolecular interaction of adsorbate molecules with the
surface of GTCB. It was considered that physically and mathematically (energetically) the
homogeneous surface of GTCB is not inclined to this specific interaction. However, the
intermolecular H-bond is in fact one of the reasons which hardens the examination of the
intramolecular interaction at adsorption. At present the only method to calculate the
thermodynamic characteristics of adsorption (TCA), based on the information about the
structure of molecules and allowing predicting this structure is the semiempirical molecular-
statistical theory of adsorbtion for quasi-rigid molecule, proposed by A.V. Kiselev and D.P.
Poshkus. This theory is based on the principle of additivity of the parameters of the
intermolecular interaction adsorbate-adsorbent. On the TCA basis it is possible to predict the
interaction of which conformational isomer with the surface of GTCB will be stronger.
However, the semiempirical molecular-statistical theory of adsorbtion does not take into
consideration the influence of the intramolecular H-bond, intermolecular H-bond and the
sorbent force field on the adsorbate geometry. The solution of this question will be possible if
the approaches are found allowing calculating the TCA taking into account the specific
interactions (intra- and intermolecular H-bond) under the influence of the sorbent force field.
Preface iii
Such calculations will allow explaining on the molecular level the reasons of difference of the
TCA of structural conformers of the compounds, stable in the gas phase and in the adsorbed
state. Not using the quantum-chemical methods with minimum permissible level of the
calculations of the hydrogen-bonded molecular systems (for example, MP2/6-311++G(d,p)
and B3LYP/6-311++G(d,p)), it is not possible to obtain the structural-energetic parameters of
the conformational isomers to calculate their TCA. The presented chapter shows the
possibility of using the ab initio and DFT methods in combination with the semiempirical
molecular-statistical theory of adsorbtion for TCA calculations of the conformation isomers
of molecules taking as the example the aromatic alcohols, amines and thiols. The detailed
examination of adsorption of these compounds on the GTCB taking into account the
hydrogen bond, its exact qualitative characteristics and quantative specification is important
for clarifying the specific features of the separate class of compounds. It is interesting to show
how the situation of lone electron pair, increase of the chain length by the -CH2 group,
differentiation in electron-donor, electron-accepting and repulsive possibilities of oxygen,
nitrogen and sulfur atoms affect hydrogen bond formation. The difficulty of the examination
of the chosen object is determined by the comparability of the values of the barriers of
internal rotation with the benefit in the heat of adsorption at the expense of the change of
molecule conformation while getting into in the GTCB force field. The results of the
optimization of the adsorbate molecules on the model fragment of the GTCB by the DFT
method have confirmed the forecast about the possibility to form the intermolecular H-bond
by -OH, -NH2, -SH groups together with graphite π electrons, which was of made by us
earlier. To calculate the TCA of the molecules the automotized system is proposed in the new
version of which the integration of all the stages of the calculation in one and the same
program system is the necessary demand to provide the TCA calculation: the initial data
input, carrying on the TCA calculations, visualization of the results, saving the final results in
the data base. The analysis of the initial and calculating data is possible with the help of the
graphic module which allows to visualize the 3D molecule model on the GTCB surface,
create the 2D and 3D diagrams of the dependence of the TCA on the torsion angles, draw the
contour maps of the potential energy surface. The modules are also worked out with the help
of which it is possible to carry on the variation of the atom-atom potential (AAP) parameters
and examine all the possible ways of conformational transfers (variation of the torsion
angles). The special attention is paid to the preparation of the geometric parameters of the
molecule in the gas phase and adsorbed state. The results of the search can form the
fundamental basis for qualitative and quantitative examination of the display of
intermolecular interaction at adsorption on the surface of GTCB.
Chapter 5 – Results of the experimental and theoretical study of the interference between
heat transfer and growth of primary black carbon particles are presented. Experimental study
was performed in shock tube with length about 7 m and inner diameter 50 mm. Black carbon
nanoparticles have been formed during the pyrolysis of ethylene, diluted with argon, behind
the reflected shock wave. The pyrolysis temperature was in the range 2000 – 3500 K, total
pressure was 7.5 - 11 bars. Home-made pulsed photoemission pyrometer with a temporal
resolution of 1 μs was used for measurements of temperature of black carbon particles during
their growth. Substantial difference (about 900 K) in temperature of black carbon particles
and the temperature of gas mixture was discovered. For simulation of nonisothermal growth
of black carbon nanoparticles the mathematical model was developed, which considers the
heat transfer and growth of black carbon nanoparticles in the supersaturated carbon vapor in
iv Ian J. Sanders and Thomas L. Peeten
the free molecular approximation (the Knudsen number Kn > 103). It was established that due
to very high supersaturation of carbon vapor and the release of the latent heat of sublimation
temperature of the particles can exceed the temperature of the gas phase more than one
thousand degree. Heat transfer between the carrier gas and black carbon nanoparticle
significantly affects on the value of this temperature difference. For determining parameters
of growth of primary black carbon nanoparticles the inverse problem was solved using the
data of electron microscopy and gasdynamic measurements. It was obtained that in order to
reach to final diameter the growth time of primary black carbon particles been less 10 μs and
the temperature difference been above 1000 K. The final diameter of primary black carbon
particles is in the range 27 - 55 nm.
Chapter 6 – Previous studies have shown that exposure to nano-sized particles through
the airway affects both the respiratory and extrapulmonary organs. The potential health risks
of inhaling nanomaterials are of great concern because of their high specific activity and their
unique property of translocation [1, 2]. Inhaled nanoparticles with a diameter of less than 100
nm are the main particles that reach and are deposited in the alveolar region. Furthermore,
they can enter the circulatory system and translocate to extrapulmonary tissue [3].
Chapter 7 – Polymer materials are widely used as the sliding surface materials because of
their excellent low frictional properties and chemical inertness. However, the wear amount of
polymer material after long period of friction is relatively larger than that of metal or ceramic.
Therefore, polymer materials are actually used in the form of composites by adding various
kinds of filler materials to enhance their wear resistance. Carbon fiber, glass fiber, graphite,
molybdenum disulfide and fine bronze powder are the typical fillers used for reducing wear
of the polymer material. Carbon black is well known as a filler of the rubber products such as
automobile tires in the field of tribology. On the other hand, in case of polymer material, the
general purpose of adding carbon black is giving electrical conductivity to polymer materials
or reducing degradation of polymer materials caused by ultraviolet light. There is little report
on the wear reducing effect of carbon black filler for the polymer materials. We used carbon
black as a filler of polytetrafluoroethylene (PTFE) in order to reduce the wear of it. PTFE is
widely used as a tribomaterial because it shows excellently low friction coefficient comparing
with other polymer materials. The wear and frictional properties of PTFE filled with twelve
kinds of carbon black were studied using ring-on-disk tribometer. The effects of the average
particle diameter, the nitrogen surface area and the DBP absorption of carbon black on the
friction coefficient and specific wear rate were studied. The friction coefficient of PTFE
composites decreased linearly with the decrease of the nitrogen surface area and specific wear
rate of PTFE composites decreased with the decrease of the average particle diameter. We
discussed wear reducing mechanisms of PTFE composites filled with carbon black by
assuming simple model of carbon black. It was considered that the wear reducing action of
carbon black is to make it difficult to extract the PTFE fibre from the composite by getting
caught in the carbon black.
Chapter 8 – Rubber compounds, even when reinforced with approximately spherical
particles, represent highly concentrated suspensions characterized by complex interactions
between filler particles and between particles and polymer. Unlike a concentrated suspensions
with low viscosity matrix, the rheological behavior of a rubber compounds can be described
using a single medium approach. In comparison with the rheology of polymer melts and
solutions, these filled systems display yield-like behavior and very long relaxation
phenomena which reflect the processes of flocculation and aggregation of particles as well as
Preface v
disruption of particle aggregates in the medium. Long memory of the deformation history is
also observed and related to slow restructuring phenomena. Additionally, rubber compounds
display highly nonlinear viscoelastic behavior and viscoelastic parameters depending on
concentration and structure of particles. Rheological properties are assessed for polybutadiene
based rubber compounds and advanced investigative techniques are used to characterize the
filler network as well as the state-of-mix. The role of filler interactions in shear and extension
is investigated. It is shown that reinforcement is due to hydrodynamic effects together with
the build-up of a secondary particulate structure within the rubber matrix and the consequent
amount of immobilized polymer. In terms of compound processability, this study attempts to
point out the effect of state-of-mix on the transient elongational response of uncured systems.
The K-BKZ model is implemented in order to describe and predict the transient rheological
response of the investigated rubber compounds in the linear and nonlinear regime. The
behavior of uncured systems is also described by means of the semi-empirical Leonov‘s
model starting form the linear viscoelastic response of the polymer matrix.
Chapter 9 – The key physicochemical properties related to energy storage and conversion
of carbon blacks, such as structure, accessible specific surface area, texture, morphology, and
surface chemistry, are summarized. The status of the applications of carbon blacks for energy
storage and conversion, including primary batteries, rechargeable batteries, supercapacitors,
air batteries, fuel cells, solar cells, hydrogen energy, biomass energy, and nuclear energy, has
been reviewed. The applications of carbon blacks as conductive additives, electrode materials,
current collectors, catalysts, catalyst supports, high efficient fuel, and reducing agents, are
described systematically. The main factors affecting the state-of the-art performance are
analyzed. The existed issues and challenges of carbon blacks for energy storage and
conversion are discussed. Besides the conventional applications of carbon blacks in batteries
and supercapacitors, it is considerably promising and competitive for the following
perspectives: green catalysts to decompose hydrocarbon, catalyst supports, electrode
materials of solar cells, accelerant of biomass energy, reductive of nuclear fuel, and high
efficient fuels for direct carbon fuel cells. Some aspects, including feedstock, manufacturing
conditions, post treatments and good dispersion, should be paid attention to further improve
the performance. Carbon blacks or carbon black composites with specific function will
become more important and more competitive for energy storage and conversion.
Chapter 10 – The surface chemical composition and morphology of carbon black play a
crucial role in its adsorption properties. To improve the adsorption ability for acid and basic
compounds in liquid and in gas phases, carbon black granules can be treated in low pressure
13,56 MHz radio frequency glow discharges, generated in suitable special reactors which
allow homogeneous processing of powders and granules. In this chapter it is shown that the
surface acid or basic character of the granules can be increased by grafting acid or basic
chemical groups utilizing glow discharges fed with different gas mixtures: e.g.
oxygen/ammonia, acrylic acid/argon and allylamine/argon. The chemical and morphological
characterization of treated carbon black was performed by means of X-ray photoelectron
spectroscopy, water contact angle measurements, Brunauer-Hemmett-Teller specific surface
area evaluations and scanning electron microscopy observations. The study of the adsorption
ability for basic and acid compounds in liquid and gas phases was accomplished with
Boehm‘s titrations, in basic and acid water solutions, and vapour adsorption tests with
ammonia, hydrochloric, acetic and propanoic acids. The results show that plasma treatments
significantly improve the adsorption ability of carbon black granules and this effect is mainly
vi Ian J. Sanders and Thomas L. Peeten
due to the surface grafting of acid/basic groups and not to a surface morphological
modification.
Chapter 11 – Carbon black is a family of small particle size carbon pigments, which are
formed in the gas phase by the thermal decomposition of hydrocarbons, and has been used
widely in lithium secondary batteries, inks, coatings, rubbers and plastics. This chapter is to
provide an introduction as to how the carbon blacks are manufactured and their most
important physical and electrochemical properties. Primary emphasis is given to introducing
the electrochemical properties and the applications in rechargeable lithium-ion batteries. Here
we will also draw the electrochemical properties from examples taken from our own work.
This contribution consists of four sections. Section 1 is entitled Introduction. The following
section (Section 2) describes the manufacturing method. Section 3 focuses on the physical
and electrochemical properties and the applications. Section 4 provides summary and future
prospects.
In:Carbon Black: Production, Properties and Uses ISBN: 978-1-61209-535-6
Editors: I. J. Sanders and T. L. Peeten, pp. 1-40 © 2011 Nova Science Publishers, Inc.
Chapter 1
CARBON BLACKS IN ELECTROCHEMICAL

ENERGY CONVERSION DEVICES:
USES AND APPLICATIONS IN FUEL CELLS
Paloma Ferreira-Aparicio
CIEMAT (Centre for Energetic, Environmental
and Technological Research)
ABSTRACT
Carbon materials, and in particular carbon blacks, are widely used in electrochemical
applications because they combine unique properties: good electrical conductivity,
acceptable corrosion resistance, high purity, low cost, high thermal conductivity,
dimensional and mechanical stability, light weight, ease of handling, diversity of physical
structures and versatility in its surface chemistry,including composite fabrication. This
chapter describes a number of applications and uses of carbon blacks in electrochemical
energy conversion devices, and more concretely, in proton exchange membrane fuel cells
(PEMFCs). Fuel cell technology has experienced a huge advance by using carbon blacks
as the basic material for increasing the electrochemical area of metal electrocatalysts,
synthesizing microporous layers for gas diffusion and water management in electrodes,
and fabricating composites for flow field plates. Tailoring of carbon blacks by surface
modification is a powerful tool to design high performance components for these
systems, which constitutes a promising alternative for clean and efficient power in a large
variety of stationary, mobile, and portable applications.
INTRODUCTION: APPLICABILITY OF CARBON

BLACK IN ELECTROCHEMICALDEVICES
Carbonaceous materials have many desirable properties that have attracted their use in
electrodes and other components for electrochemical systems: galvanic cells, electrolytic
cells, fuel cells, flow cells, batteries, etc. Properties such as their good electrical and thermal
conductivity, their dimensional, mechanical and chemical stability, their acceptable corrosion
2 Paloma Ferreira-Aparicio
resistance, high purity, low cost, light weight and easy handling are some of the main features
that explain their widespread acceptance in electrochemistry.
The important role of carbon in these devices probably started in 1792 with the discovery
by Alessandro Volta of the voltaic pile as the forerunner of the storage battery of today.
Perhaps the first practical application of carbonaceous materials in batteries was demonstrated
in 1866 by Georges Leclanché in cells that bear his name. By 1876, the wet Leclanché cell
was made with a compressed block of manganese dioxide. In 1888, Dr. Carl Gassner built the
first "dry" version by using a zinc cup as the anode and making the electrolyte with a paste of
plaster of Paris (and later, wheat flour) to gel and immobilize the electrolyte. Dry cells were
demonstrated by Gassner in 1900 for portable lighting at the World's Fair in Paris. Continual
improvements were made to the stability and capacity of zinc-carbon cells throughout the 20th
Century and by the end of the century the capacity of a zinc-carbon cell had increased four-
fold over its 1910 equivalent.
A modern version of the Leclanché cell is the alkaline-manganese dioxide (MnO2) one. A
schematic representation of the cross-section of this dry cell battery is shown in Figure 1. The
outer case is usually made of a thin metal sheet. Coarsely ground manganese dioxide is mixed
with an equal volume of carbon black to form the cathode (positive electrode).
Figure 1. Schematic representation of a zinc-carbon dry cell.

Carbon powders such as carbon black and graphite are commonly used to enhance the
conductivity of the positive electrodes that contain metal oxides in this type of battery. The
particle morphology plays a significant role in this application. A suitable carbon for this
application should have characteristics that include: a) low resistivity in the presence of the
electrolyte and active electrode material, b) absorb and retain a significant volume of
electrolyte without reducing its capability of mixing with the active material, c) exhibit
compressibility and resiliency in the cell, and d) contain low levels of impurities.
Graphite has higher electrical conductivity than carbon black but it is not capable of
retaining the same volume of electrolyte or demonstrating the same mechanical properties in
the cell. The structure of acetylene black provides the capability to retain over three times as
much electrolyte per unit of mass as graphite. As shown in Figure 2, carbon blacks consist of
aggregates, defined as the smallest dispersible units, composed of partially fused, reasonably
spherical primary isotropic particles [1]. Surface area increases as the primary particle size is
reduced. The aggregates are held together by attractive Van der Waals forces to form
agglomerates. These forces increase as the size of the primary particle is reduced and
agglomerate density is increased [2]. Therefore, higher surface areas are obtained in highly
structured carbon blacks. The capacity of Leclanché cells is dependent on the amount and
type of carbon black that is used. Generally about 55 vol. % carbon black mixed with
Carbon Blacks in Electrochemical Energy Conversion Devices 3
manganese dioxide yields the maximum capacity. This composition agrees closely with the
minimum in the electrical resistivity of the electrode mixture. The high electronic
conductivity, chemical inertness and low cost are beneficial for the use of carbon for
electrode materials in these primary batteries.
Figure 2. Isotropic carbon black structure with crystallinity in the range of nanometers.
In general, carbon black materials are widely used for a variety of components in modern
electrochemical energy conversion devices. Three main types of electrochemical energy
generation systems can be distinguished depending on the way that energy is stored: batteries
store energy within the electrode structure; flow batteries store the energy in the reduced and
oxidized species that recirculate through the system; and fuel cells store energy in the
reactants externally to the cell.
Flow batteries are a special type of rechargeable or secondary battery in which the
dissolution of active species in the electrolyte permits external storage of reactants thereby
allowing independent scale up of power and energy density specifications. Reactants are
circulated through the cell stack as required and their external storage avoids self-discharge,
which is observed in primary and secondary battery systems. The first such battery used the
couple zinc/chlorine. It was first used in 1884 by Charles Renard to power his airship La
France, that contained its own on board chlorine generator [3]. The technology was revived
in the mid 1970s, with the redox flow cell of Thaller[4]. Modern redox flow batteries are
generally two electrolyte systems in which the two electrolytes, acting as liquid energy
carriers, are pumped simultaneously through the two half-cells of the reaction system
separated by a membrane [5]. On charging, the electrical energy supplied causes a chemical
reduction reaction in one electrolyte and an oxidation reaction in the other. The thin ion
exchange membrane between the half-cells prevents the electrolytes from mixing but allows
selected ions to pass through to complete the redox reaction. On discharge, the chemical
energy contained in the electrolyte is released in the reverse reaction and electrical energy can
be drawn from the electrodes. When in use, the electrolytes are continuously pumped in a
circuit between reactor and storage tanks. High power batteries are constructed using a
multiple stack of cells in a bipolar arrangement. The power rating of the system is fixed and
determined by the size and number of electrodes in the cell stacks; however, the great
advantage of this system is that it provides almost unlimited electrical storage capacity, the
limitation being only the capacity of the electrolyte storage reservoirs. Opportunities for
thermal management are also facilitated by using the electrolytes as the thermal working
fluids as they are pumped through the cells. These facts provide a very seductive argument in
favor of flow batteries in preference to conventional secondary (rechargeable) cells. For the
same power, flow batteries are typically dimensioned to store five times the energy stored in
conventional cells [6].
In redox flow batteries, carbon blacks are mainly used in composite electrodes, which
have become one of their key components [7]. The main requirements of suitable materials
are stability in the electrolyte, high oxygen and hydrogen overvoltage and good conductivity
of the electrochemically active parts of the bipolar electrode [8,9]. Given that the performance
of the battery depends strongly on the bulk resistivities of the electrode, the bipolar plate, and
the contact resistance between them, much research has been focused on the development of
electrode-bipolar plate setups. Carbon-plastic composite electrodes were put forward in the
1980s [10] and have played an important and promising role in the last decades of flow
battery research, which has included iron/chromium, bromine/polysulphide, vanadium/
bromine, zinc/bromine, zinc/cerium, and vanadium redox couples. In such structures, graphite
felt electrodes are heat bonded to the conductive carbon-plastic composite bipolar plates.
Such carbon-plastic composite electrodes are cheap, flexible, and lightweight. Moreover, the
penetration of graphite felt fibers into the conductive carbon-plastic composite bipolar plate
during the heat bonding process leads to an increase in the contact points of the graphite felt
fibers with the bipolar plate. As a result, low contact resistances between graphite felt
electrodes and bipolar plates can be achieved for the carbon-plastic composite electrodes even
under a small assembly compact force. Because of these benefits, more and more research has
been focused on the design and manufacture of carbon-plastic composite electrodes and their
related materials.
Carbon blacks are also widely used in the development of fuel cell components. In 1842,
Grove developed the first fuel cell (which he called the gas voltaic battery) that produced
electrical energy by combining hydrogen and oxygen. Grove was interested in reversing the
process of electrolysis. In developing the cell and showing that steam could be disassociated
into oxygen and hydrogen, and the process reversed, he was the first person to demonstrate
the thermal dissociation of molecules into their constituent atoms. The first Grove cell used
zinc and platinum electrodes exposed to two acids (sulphuric acid) and separated by a porous
ceramic pot. The term "fuel cell" was coined in 1889 by Ludwig Mond and Charles Langer,
who attempted to use air and coal gas to generate electricity. In 1932, Francis Bacon
improved on the platinum catalysts of Mond and Langer, and soon Harry Karl Ihrig, of Allis-
Chalmers Manufacturing Company demonstrated a 20-horsepower fuel cell powered tractor.
NASA began using fuel cells in the late 1950s and continues to do so today. Nowadays, the
need to reduce CO2 emissions to the atmosphere from the combustion of fossil fuel is
fostering the fast development of H2 fuel cells together with the so-called hydrogen economy.
In a typical fuel cell, gaseous fuels are fed continuously to the anode (negative electrode)
compartment, and an oxidant (for example, oxygen from air) is fed continuously to the
cathode (positive electrode) compartment; the electrochemical reactions take place at the
electrodes to produce an electric current. The three major components that constitute the heart
of a fuel cell are the fuel electrode (anode), the oxygen electrode (cathode), and the
electrolyte. These elements are usually arranged in a stack of single cells connected in series
and separated by bipolar plates. The fuel (typically a hydrogen-containing gas) and the
oxidant (typically oxygen from air) flow in small channels that are part of the bipolar plate. In
final cells the end plate also serves for current collection. Because the bipolar plate serves as
part of the electron conduction path through the fuel cell stack, it must be electronically
conductive, but it must not permit gas permeation. This configuration allows a fuel cell stack
to be fabricated with over 400 elements arranged in series.
A fuel cell differs from a conventional battery in several respects. The battery is an
energy storage device; that is, the maximum energy that is available is determined by the
amount of chemical reactant stored in the battery itself. Thus, the battery will discharge and
cease to produce electrical energy when the chemical reactants are consumed. In a secondary
battery (rechargeable), the reactants are regenerated during charge, which involves putting
energy into the battery from an external source. The fuel cell, on the other hand, is an energy
conversion device, which theoretically has the capability of producing electrical energy for as
long as the fuel and oxidant are fed to the electrodes. In fact, only degradation or malfunction
of components limits the practical operating life of fuel cells.
Two major types of fuel cells rely heavily on carbon. They operate at relatively low
temperature (lower than 200ºC) and are referred to as the phosphoric-acid fuel cell (PAFC)
and the polymer-electrolyte-membrane fuel cell (PEMFC). The primary interest in PAFCs is
for stationary power generation, whereas PEMFC's have attracted widespread interest for use
in transportation applications. Without the availability of carbon as a reasonably stable and
electronically conductive component, both the PAFC and PEMFC would be even further
from commercialization. The catalysts, the electrodes and the bipolar plates in these fuel cells
usually contain highly conductive carbon blacks.
The electrochemical reactions to oxidize the fuel (hydrogen) and to reduce the oxidant
(oxygen) to generate electricity require costly catalysts usually based on platinum. In order to
minimize the amount of expensive metal electrocatalyst that is used, it is of major interest to
increase the surface area of platinum available for reaction. This is achieved by preparing
highly dispersed metal nanoparticles on a conductive high surface area support, usually
carbon black. Figure 3 shows a transmission electron microscopy (TEM) image of a typical
fuel cell electrocatalyst. The platinum particles, which are around 3 nm in diameter, are
evident as the solid black spots dispersed over the surface of larger and lighter particles of
carbon black, resulting in a surface area close to 100 m2·g-1. The surface area of the loaded
platinum is inversely proportional to the mean Pt crystallite size. Preparing such high-surface-
area-supported electrocatalysts and maintaining the small particle size in the fuel cell are
major technical challenges to increase Pt utilization to values close to 100%.
Electrodes in fuel cells also rely on carbon blacks as base material for synthesizing
conductive hydrophobic microporous layers able to manage the water flow [11]. In addition
to the catalytic layer, the gas diffusion layer (GDL) is a key component of a PEM fuel cell
electrode that fulfills several functions:
a. reactant gas permeability: providing access for reactant gases from flow-field
channels to catalyst layers;
b. liquid permeability: providing paths for product water to be removed from the
catalyst layer area to flow field channels;
c. electronic conductivity: providing passage for electron transport from bipolar plates
to catalyst layers;
d. heat conductivity: providing efficient heat conduction between bipolar plates and
MEA; and
e. mechanical strength: providing mechanical support to the MEA.
50 nm
Figure 3. Transmission electron microscopy image of a typical electrocatalyst for proton exchange
membrane fuel cells: Pt (50 wt.%) on Vulcan XC72.
These functions, especially the interfacial electrical and thermal conductivities between
the bipolar plates and catalyst layers, depend significantly on the GDL compression behavior.
GDLs are usually formed by a carbon fiber substrate, such as carbon cloth or carbon paper,
and a microporous layer (MPL). The micro-porous layer (MPL) consisting of a mixture of
carbon black powder and a hydrophobic agent is utilized on one side or two sides of the GDL.
This layer is the crucial part in GDL to improve the fuel cell performance as it acts both as a
valve that pushes water away from the GDL to the flowfield to minimize water flooding and
also transports the input gas from the flow field into the catalyst layer. So it is one of the
bottlenecks in fuel cell developments, and many R&D activities during last decade have
accomplished amazing achievements in this area [12]. It is an industrial practice to refer to
this MPL as a carbon sub-layer. Acetylene black, Black Pearls 2000 or Vulcan XC72R have
been widely used materials for this application [13].
Other important components of the PEMFC stack are the bipolar plates [14]. They
perform a number of functions including:
a) provide series of electrical connections across adjacent cells in the fuel cell stack;
b) support intricate gas flowfield design pattern which help in directing and uniformly
distributing the reactant gases to the membrane electrode assembly and at the same
time allow byproduct water to leave the cell
c) act as separator plates in between different cells, thereby separating the fuel on one
side from coming in direct contact with the oxidant on the other side;
d) help in thermal control of the cell stack via heat removal from the active area; and
e) provide the basic support infrastructure for the MEA in the PEM fuel cell stack.
A high proportion of the fuel cell weight is due to the bipolar and end plates. Therefore,
weight reduction is a very important factor, especially for mobile applications. Composite
materials are lightweight and can be molded into any shape and size [15]. Thermoplastic
polymer-carbon black composites are an interesting alternative to fulfill the requirements of
bipolar plates for PEMFC stacks: i.e., specific electrical conductivity higher than gas
diffusion electrode (2.5 S cm−1), hydrogen permeability equal or below the range of the
permeability of the ionic conducting membrane, thermal and mechanical stability at working
conditions, low density, high corrosion resistance, low thermal expansion coefficient,
reproducibility, easy finishing and recyclability. Coatings of metal separators with
carbon/resin composite layers have been also proposed as viable alternative to produce high
performance lightweight bipolar plates [16].
Carbon blacks are not only used as base material for fuel cell components. Another main
use includes its application as fuel in high-operating-temperature fuel cells such as solid oxide
fuel cells (SOFCs) and molten carbonate fuel cells (MCFCs). Fuel cells able to operate with
carbon as fuel are designed as direct carbon fuel cells (DCFCs). In a DCFC, complete
oxidation of carbon to gaseous CO2 is accompanied by almost no entropy change, and means
that the thermodynamic efficiency is close to 100%. In conventional fuel cells, such as
SOFCs fueled with gaseous hydrogen, the entropy variation is negative and the theoretical
efficiency is reduced. Hydrogen fueled SOFCs, for example, have a theoretical efficiency
limit of 70% at high temperatures – i.e., about 70% of the chemical energy converts to
electricity, with the remaining 30% converting to heat. In contrast, virtually all the chemical
energy can convert to electrical energy in a DCFC.
The DCFC concept is not new. William W. Jacques, a US electrical engineer and
chemist, described a DCFC in 1896 [17]. Jacques used coke electrodes in a molten NaOH
electrolyte. There were problems, such as including the cost of making carbon electrodes and
electrolyte degradation as a result of ash in the fuel and interactions between the fuel and the
electrolyte. In addition, the carbon anode also served as the fuel source, and the NaOH
electrolyte was consumed in the reaction when it reacted with the CO2 product to form
Na2CO3. Because an operator would need to shut down the entire device periodically to refuel
and replace the electrolyte, it ran as a battery and not as a fuel cell. In practical terms, the cell
was expensive (in part because of the high cost of NaOH). Furthermore, when the energy
required to make NaOH is taken into account, the cell was very inefficient. Researchers had
trouble duplicating Jacques‘ results until the 1970s, when a series of studies at SRI
International (Menlo Park, California) verified that complete electrochemical oxidation of
carbon can generate electricity. Although the SRI group proved the concept and added several
innovations to the DCFC approach, the system was still impractical. In the 1990s, several
other organizations began working on DCFCs and related areas. The latest advances in
materials science, fuel cells and basic electrochemistry have given researchers hope that the
technology will be commercially viable in limited small-scale applications within five years,
and in large-scale applications within 20 years [18]. As in the rest of the applications,
research has revealed that the carbon properties affecting DCFC performance include
crystallographic disorder, electrical conductivity, contaminants and number of surface
reactive sites [19].
Copyright © 2011. Nova Science Publishers, Incorporated. All rights reserved. 8 Paloma Ferreira-Aparicio
Figure 4. Main electrochemical energy conversion devices using carbon blacks in their manufacture.
These applications illustrated in Figure 4 show the relevant role of carbon blacks in the
development of electrochemical devices such as galvanic cells, redox flow batteries, and fuel
cells. The structure, morphology and surface chemistry of this carbon material determine
numerous physical properties on which the electrochemical performance relies. This chapter
will be focused in the application of carbon blacks in proton exchange membrane (PEM) fuel
cell components, especially in catalytic and gas diffusion layers of electrodes and in bipolar
plates.
CARBON BLACKS IN GAS DIFFUSION ELECTRODES FOR PEM FUEL

CELLS
Gas diffusion electrodes are important components in PEMFCs thatrely heavily on
carbon blacks. They are integrated by a carbon fibermacroporous substrate (usually carbon
cloth or carbon paper) on which a first layer composed of carbon black and
polytetrafluoroethylene (PTFE) is deposited (Figure 5). PTFE is usually added to the carbon
fiber support and to the microporous layer (MPL) to increase the hydrophobicity of the
electrode and improve water management and gas accessibility to the catalytic layer.
Figure 5. Cross-sections of a) a gas diffusion substrate of carbon paper with PTFE treatment, and b) the
hydrophobic substrate in image a with a microporous layer of carbon black and PTFE.
In addition to the functions of mechanical support to strengthen the MEA and providing
paths for the electrical and thermal conductivity, the GDL acts as a valve to regulate water
ejection, avoid flooding and guaranteeing gas accessibility. Although the diffusion layer is
seemingly a minor component in a fuel cell, it has been shown that altering the composition
of the diffusion layer can lead to substantial improvements in the performance of the cell [20].
These improvements are related to the PTFE content, the effect of sintering the microporous
layer, its thickness, and the properties of the carbon black used in its fabrication [21]. The
final permeability of the gas diffusion layer, which depends on all those structural parameters,
has a large impact on the cell performance. This influence can be appreciated in Figure 6, in
which the polarization curves obtained for MEAs with GDLs of different characteristics and
air permeability are shown.
Figure 6. a) Polarization curves obtained for PEM single cells with carbon catalyzed membranes using
gas diffusion layers in anode and cathode with different characteristics; b) correlation between the cell
performance and the permeability of the gas diffusion electrodes used [22].
The surface chemistry of the carbon black will determine its hydrophilic/hydrophobic
properties, which are essential for the microcroporous layer synthesis. The addition of low
PTFE loadings as hydrophobic agent to the microporous layer will contribute to reduce the
GDL resistivity.
Carbon black is not only used to synthesize microporous layers but also to disperse the
electroactive metals in the catalytic layer. The state-of-the-art PEMFC electrocatalysts
typically consist of Pt nanoparticles (2-8 nm) or Pt alloys dispersed on a high surface support
material which provides a good combination of electron conductivity, corrosion resistance,
surface properties, and low cost [23,24]. Pt loadings in these catalysts are usually in the range
between 20 and 60 wt %. A large variety of carbon blacks and numerous carbon materials
including carbon aerogels, cryogels, high surface area graphites, single and multiwall carbon
nanotubes, graphitic carbon nanofibers, carbon nanohorns, carbon nanocoils and ordered
uniform porous carbon networks have been used as supports to synthesize them [25−34].
Despite of the numerous attempts at looking for materials providing high performance
catalysts with low corrosion rates, the traditionally used Vulcan XC-72 carbon black (CB)
(Cabot Corp.) remains as the most popular and extensively used material because of its
superior behavior in catalysts for PEMFC electrodes [31,35−39].
Vulcan XC-72 CB and PEMFC catalysts prepared on it have been extensively studied in
electrochemical devices [40−54] but just a few studies deal with their surface
properties[55,56]. Few papers can be found regarding the particularities of the surface
chemistry of this CB or its composites [57−60] dealing with the effects that the surface
functional groups confer to the Pt nanoparticles in the surroundings, or analyzing the Pt-
support synergy, especially in catalysts with high metal loadings [24,61−66]. Most of these
studies are mainly focused in oxygen containing groups [61,66,67] and little attention is paid
to surface species containing other heteroatoms [56,68] and are relevant for some catalysts
properties, such as their activity and durability.
A number of reviews related to the degradation mechanisms affecting the activity and
durability of carbon supported Pt catalysts in PEMFC electrodes have been recently published
[24,63,66,69−73]. In general, the strategies proposed for improving catalyst durability involve
increasing the graphitization degree of the supports, modifying their surface chemistry by
building proper surface functional groups, increasing the density of basic sites on carbon
supports to enhance the Pt–C interaction, increasing surface stability of carbon support,
improving the hydrophobicity of the carbon support through proper surface treatment and
preparing catalysts with high platinum uniformity and low platinum load. As a matter of fact,
some new trends in PEMFC catalysts research follow these strategies by applying sulfonation
treatments [74−77] or modifying the carbon surface with sulfonated polymers [65,68,78,79].
The introduction of surface functional groups on the carbon surface induces properties and
characteristics in the supports and the catalysts that must be carefully analyzed, especially
regarding their thermal stability [55,66] and their behavior under different atmospheres
[67,80,81]. Carbon functional groups like carboxyls, lactones, anhydrides, carbonyls, phenols,
quinones or lactones do not exert, in general, a beneficial effect on PEMFC catalysts [66,82].
Anchoring of the metal precursor is improved in the presence of oxygen containing groups
during the catalyst synthesis process, but some drawbacks must be considered. They can both
decrease the conductivity of catalysts and weaken the interaction between the support and the
catalytic metal nanoparticles resulting in an accelerated metal sintering. Furthermore, they
contribute to increased hydrophilicity in the electrodes with the subsequent repercussion on
the water and gas transport mechanisms.
There are some scarcely explored issues on this type of catalysts such as the interaction
of probes with surface groups and the thermal stability of surface species that will be
analyzed here on the base of desorption, adsorption, and exchange experiments.
Surface Chemistry of the Vulcan XC-72 Carbon Black
By analyzing the thermal desorption profiles of a pristine sample of the Vulcan XC-72
under vacuum, some particular characteristics can be found in this carbon black (CB) with its
support surface groups. Figure 7a shows the temperature programmed desorption (TPD)
curve obtained from the pressure increase in a vacuum chamber resulting from the
decomposition of surface species when heating a Vulcan XC-72 sample up to 773 K. Three
main desorption processes can be distinguished between 600 and 753 K. The ion current
profiles registered by mass spectrometry for the most significativem/z ratios contributing to
the global pressure increase are presented in Figure 7b. At the lowest temperature, ion
currents corresponding to species like CFx+ (m/z=19, m/z =31, m/z =50, m/z =69), CHy+ (m/z
=15), H2+ (m/z =2), CO+ (m/z =28) and COF+ (m/z =47) increase. The ion current intensity for
m/z=19, that can be assigned to fluoride ions, contains an important contribution from H2O
(m/z=18) as secondary mass. The differences existing between the profiles for masses 18
(H2O+) and 19 (naturally occurring isotopes of H2O+, H3O+, F+), concur with the increase of
ion current intensity for the mass 31, to confirm the presence of fluoride species. The
formation of a more intense peak at ca. 660 K (S-II in Figure 7a) corresponds mainly to H2O
release (m/z =18), although there is also a contribution of CO (m/z =28) and some sulfur-
containing compounds, such as COS (m/z =60). The third peak (S-III in Figure 7a) is mainly
due CO2 and to SO2 with contributions of several ion currents (m/z =64, m/z =48, m/z =50,
m/z =32).
The spectral IR features obtained for the Vulcan XC-72 CB in the range between 2000-
500 cm-1 confirm the presence of fluorine- and sulfur-containing species (Figure 8). IR bands
corresponding to CFx species and sulfonic groups can be assigned by comparison with those
reported in the literature for fluoride carbon materials [83,84,97,98] and fluoropolymers
[85−93]. Two main regions with bands between 750-500 cm-1 and 1300-900 cm-1 can be
attributed to characteristic IR absorption modes for CFx species and sulfonic groups.
Symmetric and asymmetric stretching bands of C-F bonds appear at ca. 1154 and 1230 cm-1,
respectively. Several vibration frequencies of oxygen containing groups probably present in
the carbon black surface also lay in this region. These species are probably contributing to
poorly defined peaks in overlapped bands. The absorption peaks lying in this frequency range
can be ascribed to –SO2OH groups with characteristic vibration modes at 970, 1150, 1230,
and 1425 cm-1[93]. No clear bands can be assigned to the asymmetric stretching of –SO3- in
the 1300-1320 cm-1 region[94,95]. However, their presence cannot be completely ruled out
because of the numerous low intensity absorption bands in the spectrum. According to the
literature, when a substituent, C=O, is directly conjugated to aromatic rings, a doublet is
observed at 1625-1575 cm-1[96]. Based on this consideration, the strong band centered at ca.
1590 cm-1 in Figure 8 can be assigned to quinone groups in the Vulcan XC-72[97,98].
Aromatic C=C stretching vibrations such as naphthalene- or anthracene-like structures also lie
in the same region resulting in bands within 1620-1580 and 1550-1505 cm-1. Bands
corresponding to the different CHx absorption modes can be also identified at 1465, 1380 and
720 cm-1 together with the C-H stretching vibrations in the low-frequency region between
2950 and 2850 cm-1. The bands at 2926 and 2952 cm-1 correspond to the asymmetrical C-H
stretching modes of -CH2 and -CH3 groups respectively, and that centered at 2856 cm-1 to
their symmetrical C-H stretching modes. The strong and broad band at ca. 3428 cm-1 in
Figure 8 reveals the presence of adsorbed water. In addition to the H2O stretching vibration,
the contribution due to its bending mode is probably superposed to the bands previously
assigned to quinone groups in the region of ca. 1590 cm-1.
Figure 7. Temperature programmed desorption profiles for the pristine Vulcan XC-72 carbon black
under dynamic vacuum: a) pressure increase in the analysis chamber; b) ion current profiles
corresponding to the mass spectrometric analysis of desorbed species.
Figure 8. FTIR spectra obtained for the pristine Vulcan XC72 carbon black.
XPS analysis of the CB indicates a surface composition corresponding to C, O, and S in

atomic proportions of 99.3, 0.5, and 0.2%. Fluorine has not been evaluated due to a very weak
signal partially masked by the noise. Its low concentration in combination with a
defluorination process induced by the X-ray radiation can be some of the reasons making its
detection difficult. Halogen-containing compounds have been found to be especially sensitive
to X-ray exposure, resulting in a decrease in the halogen peak intensity and an increase in the
C 1s signal [99−102]. Figure 9 shows the signals in the binding energy regions corresponding
to C 1s, O 1s,and S 2p.
The main C 1s signal from the Vulcan XC-72 is observed at 287.4 eV (74.1%) probably
due to C-C/C-H bonds. A broad contribution at higher binding energy was deconvoluted into
four contributions at 286.1(13.9%), 287.4 (4.6%), 289.2 (3.6%), 291.0 (3.8%) eV which can
be assigned to –COH, –C=O, –COOH or –CF, and CF2 groups, respectively [100−102]. The
O 1s signal could be fitted into four components located at approximately 532, 533, 534.5,
and 535.2 eV, which could be attributed to –C=O, –C–O–, –O–C=O, –SO3- type groups,
respectively [102]. Although the signal-to-noise ratio was low at the S 2p region, at least two
main contributions were identified: the main one at 164.7 eV and other at 170.4 eV. The
signal has been fitted to Gaussian line shapes. For the resolution of each S 2p1/2-3/2 doublet it
was required the intensity ratio of the two components to be 1:2 and their widths to be the
same. Poleunis et al.[56] have attributed the most intense S 2p signal at 164.7 eV to thiolate
groups (–SH) on Vulcan XC-72. The contribution of sulfur atoms with double bonds to
carbon (S=C=S) with typical binding energies at 164 eV cannot be excluded [103]. It is well
known that vulcanization processes in carbon blacks involve reactions with sulfur leading to
the formation of S=C=S species.
Copyright © 2011. Nova Science Publishers, Incorporated. All rights reserved. 14 Paloma Ferreira-Aparicio
Figure 9. XPS spectra of the Vulcan XC-72 CB in the C 1s, O 1s,and S 2p regions.
The signal at 170.4 eV can be assigned to sulfonic groups (–SO2OH) [77,104,105]. For
the best fit of the S 2p1/2-3/2 doublets, a third contribution was found at a binding energy of
166.2 eV, which could be associated to a sulfite state. It has been reported that sulfur mutates
from the sulfonic acid group configuration to a sulfite state induced by irradiation, by X-ray,
or ions [104].
Surface Chemistry of the Catalyst: Pt/Vulcan XC-72
The species resulting from the decomposition of the CB surface groups in the presence of
Pt nanoparticles have been analyzed by mass spectrometry in an analogous way. The
desorption takes place in at least four well defined processes (peaks C-I – C-IV) between 370
and 740 K as revealed in the pressure variation profile in Figure 10a. The most defined and
intense peak is the third one (C-III) centered at ca. 610 K. The most significantcontributions
to the TPD curve is from the result of the catalyst, as revealed by mass spectrometry, and
presented in Figure 10b.
Figure 10. Temperature programmed desorption profile for the Pt/Vulcan XC-72 catalyst under
dynamic vacuum: a) pressure increase in the analysis chamber; b) ion current profiles corresponding to
the mass spectrometric analysis of desorbed species.
A detailed analysis of a number of m/z ratios and their profiles can determine the nature
of the main chemical species released at each temperature: the C-I peak (Figure 10b) is
mainly due to the release of H2O (m/z =18); peaks C-II and C-III can be assigned to the
simultaneous evolution of CO2 (m/z =44, m/z =28), SO2 (m/z =64, m/z =32) and COS (m/z
=60, m/z =28), and finally, the broad C-IV peak corresponds to the formation of CFx (m/z
=31) and CHy (m/z =15) species, H2 (m/z =2) and CO (m/z =28). All these species have been
previously detected during the temperature programmed desorption of the support (Figure
7b), but their decomposition profiles differ substantially in the presence of Pt nanoparticles.
The IR features of the catalyst in its pristine form and after treatment in vacuum at 448 K
are presented in Figure 11. The main IR absorption bands present in the support are also
found in the IR spectrum of the catalyst. However, there is a general change in its profile,
which is probably the result of the change in the proportion of sulfur and fluorine containing
groups after Pt incorporation. This change is even more evident when treating the catalyst
under vacuum at 448 K. According to the thermal desorption curve in Figure 10, the
treatment of the catalyst at that temperature just leads to the release of most of the adsorbed
water without influencing the decomposition of other surface species. As a matter of fact, the
broad absorption band in the region ca. 3400 cm-1 due to the fundamental stretching vibration
of water becomes dramatically reduced after heating the catalyst at 448 K (spectrum b in
Figure 11). In the region 500-1650 cm-1 numerous absorption bands attributable to vibration
frequencies of fluorocarbon species, sulfonic and carbonyl groups can be observed.
Absorption modes attributable to –SO2OH groups with characteristic vibrations at ca. 970,
1150, 1230 and 1425 cm-1 are probably overlapped with other IR vibrations corresponding to
C-F and C-O-C bonds laying in the same range and leading to a broad absorption band in that
region [ 93−95].
Figure 11. FTIR spectra obtained for the pristine Pt/Vulcan XC-72 catalyst as received (a) and after its
treatment under vacuum at 448 K (b).
Adsorption-Exchange Properties of the Pt/Vulcan XC-72 Catalysts
The adsorption properties of the Pt/Vulcan XC-72 catalyst can be evaluated by means of
different procedures using H2 and CO as probe molecules. The influence of the support
surface groups on the adsorption processes can be analyzed on catalyst samples subjected to
different thermal treatments. Exchange experiments using isotopic labeled molecules allow
the discovery fordetermining the surface groups that support the adsorptive properties of the
catalyst.
A. H2 Chemisorption on Pt/Vulcan Xc72

The application of a static volumetric method of adsorption to a commercial Pt/Vulcan
XC72 catalyst (BASF) leads to variable hydrogen uptakes at 298 K, depending on the thermal
treatment of the sample. H2 uptakes obtained on the pristine catalyst after being treated under
vacuum at temperatures as low as 423 K correspond to atomic ratios H/Pt close to 2.0, where
Pt is referred to the total amount of Pt in the catalyst. This large ratio reveals that adsorption
phenomena induced by groups on the support surface are taking place simultaneously with
the hydrogen chemisorption on the metal surface. Those processes interfere with H2
chemisorption measurements and make the determination of the surface Pt difficult. The
contribution of parallel adsorption phenomena masking the authentic H2 chemisorption on the
surface Pt has been minimized by applying increasing pretreatment temperatures in pristine
samples and/or successive H2/O2 titration cycles to oxidize only Pt-chemisorbed H2. As
shown in Figure 12, both procedures are effective to reduce H2 uptakes to a constant value of
0.24 moles of H2 per mol of Pt in the catalyst. The Pt dispersion, defined as the percentage of
surface Pt related to the total Pt in the catalyst, is 48%. By assuming that the Pt particles have
a spherical geometry and that their surface is formed by equal proportions of the main low
index planes [106], an average Pt particle size of 2.4±0.2 nm has been estimated.
Figure 12. H2 uptake per mol of Pt for the Pt/Vulcan XC72 catalyst as a function of the number of
cycles of H2 adsorption/O2 adsorption and the temperature of treatment under vacuum before H2
adsorption.
In order to verify the validity of that measurement as the actual H2 chemisorption on Pt,
the average Pt particle size estimated from the H2 uptake could be compared with the values
obtained from the pristine catalyst using XRD and TEM techniques. Both, the analysis of the
broadening of the X-ray diffraction line corresponding to Pt (220) plane (2=65.7) and the
analysis of the particle size distribution from TEM micrographs, yield mean crystallite sizes
slightly above that estimated from the H2 chemisorbed amount. By analyzing the broadening
of the Pt X-ray diffraction lines, the estimated volume average diameter is 2.7±0.3 nm. For
the statistical determination of the mean Pt particle size from TEM micrographs; numerous
samples representative of the catalyst, accounting for several hundred of particles have been
examined. The mean particle size defined as the median (D50) of the distribution is close to
3.5 nm.The somewhat larger average particle size obtained by TEM is probably the
consequence of the poorer representation of the smallest particles in micrographs, which
usually leads to overestimate the average diameter (Figure 13). By using the XRD technique,
the estimated values can be affected by a significant error in catalysts with a large proportion
of very small Pt particles or where is ainhomogeneous particle size distribution. However, in
this case, there is a very good agreement among the three applied techniques for the Pt mean
diameter estimations.
Figure 13. Particle size distribution analysis for a commercial Pt/Vulcan XC-72 catalyst estimated for
TEM micrographs.
B. CO Chemisorption on Pt/Vulcan Xc72

CO uptakes can be also used to determine the surface area of fresh catalyst samples after
their thermal treatment under vacuum. Using different evacuation temperatures, a constant
value of 0.22 mol CO/molPt is obtained independently from the applied pretreatment.
According to the obtained values for the monolayer coverage using H2 and CO as
chemisorption probes, the resulting CO/H stoichiometry is close to 0.5. This ratio is lower
than the typical 0.7 saturation limit usually found in the literature for supported Pt particles
with low or no interaction with the supports showing adsorption surface properties of Pt(111)
[107].
Although the CO uptakes seem to be unaffected by the presence of the support surface
groups, the CO adsorption isotherms reveal the influence of the support surface chemistry on
the adsorption of CO on the Pt crystallites dispersed on it. A detailed analysis of the CO
adsorption isotherms on catalyst samples evacuated at different temperatures indicates that, as
far as the support surface is progressively modified at increasing pretreatment temperature
(mainly by dehydration), the CO isotherm profile changes (Figure 14). Although CO
adsorption on Pt does not meet the premises of the Langmuir‘s adsorption model (i.e.,
monolayer coverage, adsorption site equivalence and no interaction among adsorbate
molecules), its simplicity and strong theoretical reasoning makes it a good approach to
describe the obtained isotherms. By considering that the curves approach the ideal model of a
type-I Langmuir isotherm at low equilibrium pressures, the CO adsorption strength related to
the adsorption constant in the Langmuir equation [CO= (·peq)/(1+·peq)] increases as far as
the support surface groups are dehydrated at increasing pre-treatment temperatures.
Figure 14. CO adsorption isotherms on the Pt/Vulcan XC-72 catalyst after its evacuation at (■) 423 K,
( ) 648 K.
C. The Role of Surface Groups in Adsorption on Pt/Vulcan Xc72

Adsorption results shown in Figure 12 indicate that a parallel H2 adsorption process takes
place simultaneously with H2 chemisorption on Pt when the catalyst has been evacuated at
temperatures as low as 423 K. To enlighten the nature of this process, its mechanism, and the
species involved in it, two types of experiments have been carried out: isotopic exchange
under steady-state conditions and temperature programmed desorption tests after D2
adsorption, CO adsorption and CO-D2 co-adsorption [108].
The ability of the catalyst thermally treated at 448 K under vacuum to exchange hydrogen
species from its surface with molecular hydrogen gas has been studied by mass spectrometry
using D2 as probe molecule for adsorption. The extent of the surface hydrogen mobility
process has been evaluated by analyzing the composition of the gas phase during the contact
time between pure D2 gas and the Pt/Vulcan XC-72 catalyst previously treated under high
vacuum at 448 K. The analysis of the gas phase composition reveals how the ion current for
D2 (m/z=4) decreases whereas those for HD (m/z=3) and H2 (m/z=2) ratios increase
progressively when D2 is circulated over the catalyst at 298 K. The observed hydrogen
exchange rate is presented in Figure 15 together with the ratio of exchanged atoms per surface
Pt center. The exchange rate has been expressed as a turnover number by referring the amount
of D exchanged atoms to the Pt surface centers in the catalyst. Pt surface centers have been
estimated from the H2 chemisorption measurements performed on the catalyst. As shown in
Figure 15, two processes taking place at different rates can be distinguished during the
exchange test. The exchange turnover frequency is very fast during the initial period of
contact (about 5 min) and then it reaches a steady-state with a constant value of 4.9 h-1. By
analyzing the molar ratio of exchanged D per surface Pt, it can be observed that this ratio
approaches the unity during the first step. This indicates that the catalyst exchanges
practically the whole monolayer of initially Pt-chemisorbed deuterium with the closest
surface groups able to exchange hydrogen species. Therefore, the first process after
contacting the catalyst with D2 gas can be attributed to a relatively fast exchange between the
firstly chemisorbed deuterium monolayer on nanometricPt particles and the proton acceptor
species on the support located closely at their periphery. After that first step, the exchange
rate is observed to decrease to a value which probably corresponds to the proton diffusion rate
on the carbon black surface at 298 K.
Figure 15. Deuterium-hydrogen exchange frequency (exch) (solid line) and amount of moles of
exchanged D atoms per mol of surface Pt (dashed line) in the Pt/CB catalyst as a function of contact
time between the gas and the sample at 298 K. The catalyst has been previously treated under dynamic
vacuum at 448 K for 1 h.
This deuterium-hydrogen exchange process is often observed on catalysts with proton

acceptor groups on the support surface. It has been previously shown that hydrogen uptakes
measured on this catalyst after vacuum treatment at soft temperatures largely surpass the Pt
monolayer coverage. This enhanced hydrogen adsorption is usually known as a spill-over,
and is usually ascribed to surface diffusion phenomena by hydrogen species on the support
surface [61]. This effect has already been reported for fuel cell catalysts [61,109,110].
Ramirez-Cuesta et al. have provided evidence of this phenomenon by means of inelastic

neutron scattering spectroscopy on Pt/C, Ru/C, and PtRu/C [110,111]. The contribution of
spilt-over hydrogen to adsorption measurements can be eliminated by applying successive
adsorption cycles of H2 and O2 until reaching steady-state H2 coverage. This procedure allows
saturating surface sites promoting spill-over and just evaluating surface Pt centers. The
particular adsorption properties of Pt/Vulcan XC72 are induced by surface functional groups
in the carbon black promoting hydrophilic and hydrophobic characteristics in its surface
[61,112,113].
The adsorption of D2 and CO as probe molecules has been carried out on catalyst aliquots
previously evacuated at 448 K in order to analyze their desorption profiles. After treatment in
vacuum at that temperature, the D2 adsorption at 298 K includes a large contribution of spilt-
over species. D2 uptake increases from 1.24 mmol·gPt-1 (when no surface diffusion
phenomena are involved in the measurement) to 3.95 mmol·gPt-1 for a pristine sample treated
under dynamic vacuum at 448 K for 1 h. On the other hand, the CO uptake for identical
conditions is 1.08 mmol·gPt-1, which corresponds to a coverage close to 50% of a monolayer.
An additional adsorption test was carried out on a CO-equilibrated sample. After saturating its
surface with CO at 298 K, the gas phase was removed and then, D2 was dosed. Under these
conditions, the measured D2 uptake corresponded to 2.05 mmol·gPt-1, and indicate that the
presence of CO does not block the hydrogen diffusion pathways between the metal and the
support surface groups.
Following each adsorption test, a temperature programmed desorption experiment was
performed at 10 K/min while analyzing the desorbed species. The pressure in the system was
registered during the experiments. Figure 16 presents the global desorption profiles obtained
from the catalyst after D2 adsorption, after CO adsorption and after CO-D2 co-adsorption. The
curves resulting from the temperature programmed heating of pristine samples of the catalyst
and its CB support under vacuum (without any chemisorbed probe) are also included as
references. Several striking features can be appreciated in the resulting profiles. The broad
desorption bands obtained for the D2-equilibrated sample evidences that only a part of the
adsorbed hydrogen is on the Pt surface. The Pt-chemisorbed hydrogen originates a low
temperature desorption peak (below 373 K). Large differences can be also found between the
profile obtained from the sample in which CO and D2 are co-adsorbed and the profiles for the
sample equilibrated with CO or D2 separately. The main desorption peak in the co-adsorption
curve appears at much lower temperature and the peak corresponding to the Pt-chemisorbed
hydrogen/deuterium disappears.
Figure 16. Chamber pressure due to desorbed products during temperature programmed desorption tests
in: a) a pristine sample of Vulcan XC72, b) a pristine sample of the Pt/Vulcan XC72 catalyst, c) D2-
equilibrated sample, d) CO- equilibrated sample, e) D2 adsorbed over a CO-equilibrated sample.
Adsorption of probes has been always performed on samples previously evacuated at 448 K.
The mass spectrometric analysis of the desorbed species during the TPD tests renders a
clearer picture of the surface phenomena taking place in the catalyst after the adsorption of
these probes. Figure 17 compiles the ionic current curves obtained in each case for the
formation of labeled water and SO2 (Figure 17A), labeled molecular hydrogen (Figure 17B)
and carbon oxides (CO and CO2) (Figure 17C). It can be observed that water desorption
above 373 K is in all cases associated to the release of SO2, which proceeds from the
decomposition of sulfonic groups. It must be noted that, when no adsorbed probe is present
on the catalyst, the SO2 release curve presents three contributions above 448 K with a
predominant maximum at ca. 600 K (Figure 17). This profile is drastically modified after
adsorbing CO, D2 or both. Adsorbed CO causes sulfonic groups to reduce their main
decomposition maximum to 507 K (Figure 17A-III). This process is also associated to the
formation of large amounts of CO2 (Figure 17C-III) instead of the reversible release of the
adsorbed probe (CO). This evidence of interaction by the adsorbed CO molecules with the
support hydrophilic sulfonic groups, contribute to oxidize them before being desorbed. Just a
small amount of H2 resulting from the decomposition of some CHx species in the support is
detected at temperatures above 500 K (Figure 17B-III). A similar H2 evolution profile can be
observed in the TPD test for the pristine catalyst (Figure 10).
The analyses of the labeled species desorbed from the D2- and the D2-CO-equilibrated
samples reveal several important details on the interaction of the adsorbates with the catalyst
surface.
In the D2-equilibrated sample, the release of molecular hydrogen isotopes confirms the
spill-over phenomenon (Figure 17B-II): three main desorption bands are observed, being the
main contribution that of H2 (m/z=2). Hydrogen desorption taking place at low temperature
(below 373 K) is usually associated to dissociated hydrogen species chemisorbed on the Pt
surface: the most weakly adsorbed species are released as D2 (m/z=4) and HD(m/z=3),
whereas H2 is also formed from Pt-adsorbed species resulting from the exchange with
hydrogen from the support surface groups. The desorption peak appearing within the 400-500
K range arises only from H2, showing no contribution of the heavier isotopes. It probably
results from the recombination of hydrogen species in direct interaction with sulfonic groups,
which are released simultaneously with water and SO2. The third peak appearing above 600 K
is typical from hydrogen spilt-over species in interaction with the support surface in
supported metals. Although the ionic current for mass 2 (H2) is the main contribution to that
peak, the ionic current increase for mass 3 in that temperature range reveals the presence of
labeled species remaining on the support, that are recombined at high temperature to be
released as HD.
The water desorption profiles for the D2-equilibrated sample indicate that the spill-over
phenomenon and the presence of water as proton acceptor are intimately related, since most
of the adsorbed deuterium atoms are finally released in two main peaks in the form of isotopic
labeled water (Figure 17A-II). These peaks concur with the molecular hydrogen desorption
processes at low and medium temperatures, being D2 and HD their main contributions. It
must be noted that there is some CO and CO2 desorption (Figure 17C-II) resulting from the
decomposition of surface groups, as previously seen in Fig. 4 for the TPD test in the pristine
catalyst. Although the CO2 release takes place simultaneously with that of SO2 in the absence
of adsorbates, these processes are decoupled after adsorbing D2 on the sample.
The TPD test on the catalyst where D2 has been adsorbed over the CO-equilibrated
sample provides new evidence on the hydrogen spill-over process. The profiles for molecular
hydrogen isotopes indicate that the Pt surface is able to catalyze the D2 dissociation and
diffusion towards the support, even when the Pt surface sites are blocked for hydrogen
adsorption on it (Figure 17B-I). Thus, molecular hydrogen evolution is just observed above
373 K. Only H2 is observed in the intermediate range 373-500 K, whereas H2 and HD appear
above 600 K. The absence of any molecular hydrogen formation below 373 K indicates that
the Pt surface is occupied by adsorbed CO at those temperatures. Regarding the competitive
adsorption of H2 and CO, Meland and Kjelstrup[114] have found similar results in a study
about the influence of CO poisoning of the anode in a PEMFC using electrochemical
impedance spectroscopy. They observed that although CO hinders hydrogen access to the
surface, by occupying it, and by making it more polarizable, the proton hydration step to
diffuse towards the membrane is relatively unaffected by its presence.
Figure 17. Ionic currents obtained for different masses during the temperature programmed desorption
tests in samples of the Pt/Vulcan XC72 catalyst equilibrated with: I) CO and D2 , II) D2, and III) CO.
Curves in A: ionic currents for m/z 20 (D2O (_____)), 19 (HDO (_ _ _ _ )), 18 (H2 (· · · ·)) and 64 (SO2 (·-·-·-·-
·-·-
)). Curves in B: ionic currents for m/z 4 (D2 (_____)), 3 (HD (_ _ _ _ )) and 2 (H2 (· · · ·)). Curves in C:
ionic currents for m/z 28 (CO (_____)) and 44 (CO2 (_ _ _ _ )).
In the TPD obtained after co-adsorption, HDO, D2O, and H2O are formed simultaneously
to H2 at intermediate temperatures. This indicates that most of the adsorbed D2 is finally
released as water (Figure 17A-I). Adsorbed CO is released mainly as CO2 in a peak with a
maximum at 460 K, which concurs with the most intense contribution for water and SO2
formation. At temperatures above 530 K water desorption is practically depleted and CO2
formation decreases in favor of CO [61].
An issue requiring special attention is the lability of the Vulcan XC72 surface sulfur
species, which experiences a significant change depending on the adsorbates on the catalyst.
It is worthy to note that at least three types of sulfur species with different stability are
observed to contribute to the ion current curves for mass 64 in the several TPD tests
performed for the pristine sample and those equilibrated with CO, D2, or both. A comparison
of the SO2 release curve in the D2-CO-equilibrated sample (Figure 17A-I) with those
corresponding to the tests after D2 or CO adsorption (Figure 17A II and III) evidences the
modification of the stability of the surface sulfur species formed. The main difference lies in
the decrease of the SO2 release temperature. Although its formation remains always
associated to water removal, the SO2 appearance begins at temperatures below 373 K when
D2 and CO are co-adsorbed.
It is clear from the results that the adsorbed probes have a major interaction with the
sulfur surface groups. They also probably interact with the fluorine containing species
attached to the Vulcan XC-72. By analyzing the ion current for mass 31, attributable to the
CF+ fragment (see Figure 10), the fluoride species release could be also followed. In the case
of the D2/CO co-adsorption, the release temperature of those fluorinated groups is observed to
decrease by 245 K yielding a peak for the CF+ fragment at 440 K (not shown).
The low decomposition temperature for sulfur surface groups in the presence of hydrogen
and CO has several implications in the stability of catalytic layers during fuel cell operation.
CO contamination of the electrocatalyst is a potential cause of degradation that can be easily
avoidable in most cases. The impact of the presence of CO in the PEMFC anode feeding is
fairly well known and studied and is considered to be most likely reversible[115]. However, it
can be inferred from the TPD results that the presence of CO in a H2 stream fed to a fuel cell
anode may accelerate the degradation of catalysts containing some surface groups on its
surface such as hydrophilic sulfur species. As a matter of fact, surface groups in Vulcan XC-
72 resemble those present in the perfluorosulfonic acid ionomer commonly used in catalytic
layers. The effect of CO contamination on the ionomer sulfonic groups close to Pt particles
could possibly be very similar to those observed in the Pt/Vulcan XC-72 catalyst surface
groups, but verifying this assumption needs further research.
H2 Adsorption and Proton Exchange Rate on Gas Diffusion Electrodes with

Pt/Vulcan XC72
Additional tests were carried out with gas diffusion electrodes (GDE) containing
Pt/Vulcan XC-72 in the catalytic layer for comparison purposes. Two GDEs were prepared
with the standard commercial Pt(20wt%)/Vulcan XC-72 catalyst from BASF. Two different
inks containing a Nafionperfluorinated ion exchange resin (Aldrich, 5 wt. % solution) were
prepared with distinct solventsfor the deposition of the catalytic layers. One of them was
dissolved in isopropanol and the other in a mixture of butylacetate, ethanol, glycerol in
proportions (45:50:5). The percentage of resin in the catalytic layer was 30%. The third
electrode was a commercial GDE from BASF (LT-140E-W ELAT).
The GDEs and a catalyst loading of 0.5 mgPt·cm-2, pretreated under vacuum at 448 K
before the adsorption or the exchange at 298 K, in the same way as the catalyst. H2 adsorption
isotherms on the GDEs showed at least two distinguishable plateaus at increasing equilibrium
pressures as it can be noted in Figure 18. The isotherms profile variation probably depends on
the coverage of the Pt surface by the perfluorosulfonic ion exchange resin and the interaction
between them. The two plateaus could be ascribed to the different hydrogen adsorption/
diffusion rates over the free Pt particles on the support or over Pt particles on Vulcan XC-72
which are covered by the resin or in close interaction with it. By considering that the two
homemade GDEs have been prepared with the previously analyzed Pt/Vulcan XC72 catalyst,
it is clear that the presence of the ion exchange resin introduces additional difficulties to the
determination of the exposed Pt surface area by means of H2 chemisorption. A previous study
has been shown the influence of using catalytic inks with different solvents on the catalytic
layer microstructure and the performance of the prepared electrodes [116]. During the
catalytic layer deposition process, the Nafion dispersion recasts in different configurations
which depend on the solvent composition and its evaporation rate. Thus, the Pt/Nafion
interface, the size of the Nafion aggregates and the catalyst coverage will also determine the
effective perimeter in the Pt particles for hydrogen surface diffusion.
Figure 18. H2 adsorption isotherms obtained for different gas diffusion electrodes (0.5 mgPt/cm²)
containing Pt/Vulcan XC72: (···○····) homemade GDE prepared by manual impregnation of an
isopropanol based ink on a woven gas diffusion medium; ( - - □ - -) homemade GDE prepared by
manual impregnation of a glycerol containing ink on a woven gas diffusion medium; (__▲__) a
commercial LT-140E-W ELAT GDE.
The hydrogen adsorption results in relation to Pt surface area suggest that, in general,
widely used data on the electrochemically active surface area and the Pt utilization in catalyst
layers should be corrected for the effects of the surface groups of the carbon black support,
which may store a significant amount of adsorbed hydrogen, and the ionomer. Paulus et al.
reported a fundamental investigation regarding to the catalyst utilization at the
electrode/membrane interface [117]. They compared GDEs (Pt black on carbon paper and
Pt/CB on a woven gas diffusion medium) with model electrodes designed by covering glassy
carbon with continuous or discontinuous Pt films. In agreement with our results, their study
reveals that the hydrogen adsorption/desorption characteristics and the catalyst surface
utilization depend on the nature of the catalyst in the electroactive layer and the pretreatment
applied to the GDEs. In all those cases, the degree of Pt utilization is observed to decrease
when increasing the sweep rate during cyclic voltammetry. This phenomena is explained in
terms of the diffusion of adsorbed species on the Pt surface and surface conductivity in the
electrolyte films. Accounting for this effect, Neyerlinget al. developed an analytical model to
describe the effective proton resistance in the porous cathode electrode of a PEMFC based on
a quick and accurate evaluation of cathode proton resistance by using in situ perturbation
measurements [118]. The model they proposed serves as a guideline for experimental design
parameters such that catalyst utilization is kept above 90%, which is a prerequisite for
measuring the oxygen reduction reaction kinetics.
The deuterium exchange rate has been also analyzed in the commercial GDE after heat
treatment under vacuum at 448 K. Figure 19 shows the deuterium exchange rate and the
moles of exchanged D atoms in the GDE as a function of time. In this case, the proportion the
surface Pt in the catalyst has not been determined. Therefore, the exchange rate is referred to
the total amount of Pt in the electrode.
Three processes occurring at different rates can be distinguished during the deuterium
exchange with the GDE, while only the two slower ones were observed during the exchange
with the bare catalyst. The occurrence of a very fast exchange at short times can be ascribed
to the presence of the proton exchange resin in the vicinity of some Pt crystallites. The second
and third exchange processes can be assigned to those previously seen for the catalyst itself
with the support surface groups, although their rate referred to the Pt (or surface Pt) in the
electrode is probably influenced by the presence of the ion exchange resin.
Figure 19. Deuterium-hydrogen exchange frequency (exch) (solid line) and amount of moles of
exchanged D atoms per mol of Pt (dotted line) in the commercial GDE as a function of contact time
between the gas and the sample at 298 K. The catalyst has been previously treated under dynamic
vacuum at 448 K for 1 h.
The mass spectrometric analysis of the isotopic composition of the gas phase during the
exchange process allows calculating the surface diffusion coefficient of deuterium in the
samples by representing the evolution of the exchanged atoms ( N et ) as a function of t .
When the surface migration is the rate determining step of the exchange, the measured rate
depends both upon the coefficient of surface diffusion (Ds) and the specific perimeter (Io) of
the metal particles, which are the source of dissociated deuterium species. By considering the
Pt particles to have a semi-spherical geometry and applying the model proposed by Kramer
and Andre[119], which has also been used by Cavanagh and Yates [120], and by Duprez and
Miloudi[121], the number of atoms diffused ( N et )at the beginning of exchange reaction
(when the concentration of labeled species is constant) can be estimated according to Eq. 1:
2
N et  CD  Io  Ds  t withIo = Np(2 π r) (1)

whereCD, is the atomic concentration of the labeled species (at·m-2), r is the average radius of
the metal particles (m), and Io is the length of the metal-support interface, i.e., the total
perimeter of the metal particle per m² of catalyst (m·m-2). By assuming that the
adsorption/desorption of D2 is very fast, and that the direct exchange of D2 with the support is
negligible at the experiment temperature, the coefficient of surface diffusion could be
calculated by the following Eq. (2):
    S1  dN et
Ds      with S  (2)
 4   C D  I 0 
1
d t
whereS1 is the initial slope of the curve representing the variation of N et as a function of t.
7 -2
The fitting of the experimental data to the model yields values of 7.77·10 m·m for the
metal-support interface (Io) in the catalyst and a surface diffusion coefficient (Ds) of 1.63 · 10-
19
m²·s-1. In the gas diffusion electrode the surface diffusion coefficient increases by three
orders of magnitude up to 1.83·10-16 m²·s-1 with a particle perimeter length (Io) of 12.37·107
m·m-2. It must be taken into consideration that the isotopic exchange has been performed in
the samples after their treatment at a temperature high enough to remove practically all the
adsorbed water without decomposition of the support surface groups. In that way, those
groups containing in their structure exchangeable hydrogen can be evaluated without the
contribution of the deuterium exchange with water molecules. A rough estimation of the
amount of exchanged hydrogen associated to surface groups in the studied catalyst within a
period of 0.4 h yields approximately a value of 5·10-6 mol·m-². This amount is reduced to
3.5·10-6 mol·m-² in the case of the commercial GDE. The addition of the proton exchange
resin to the catalytic layer increases the proton exchange rate in the vicinity of Pt particles,
but blocks some groups of the support which could participate in the proton surface diffusion.
A challenging breakthrough for improving the proton transfer pathways between the
electrodes and the ion exchange membrane consists in designing tailor-made supports that are
chemically modified with adequate proton acceptor groups to provide high hydrogen surface
diffusion coefficients [68,122,123].
CARBON BLACKS IN PEMFCFLOW FIELD PLATES

Flow field plates or bipolar plates (BPs) for PEMFC applications are usually designed to
accomplish many functions, such as distribute reactants uniformly over the active areas,
remove heat from the active areas, carry current from cell to cell and prevent leakage of
reactants and coolant. They have been traditionallymade of graphite.Both natural as well as
synthetic forms of graphite have very low resistivity, resulting in high electrochemical power
output, and excellent chemical stability to survive the fuel cell environment. However, the
machining process ofgraphite sheets, which were usually impregnated with polymer resin to
reduce their porosity, is very expensive and the separator plates obtained in that way comprise
nearly 80% of the mass and 45% of the cost in conventional PEMFC stacks [124]. The US
Department of Energy has established the following target values for composite bipolar
plates[125]:
• low weight <0.4 kg kW-1

• high flexural strength >25 MPa
• high flexibility: 3–5% deflection at mid-span
• high electrical conductivity >100 S cm-1
• high thermal conductivity >10 W (m K) -1
• low gas permeability <2·10-6 cm3 s-1 cm-2 at 353 K and 3 atm, and
• high corrosion resistance <1 mA cm-2.
In order to diminish the BPs cost and weight, developers are turning to eithermetal or
carbon composite materials. Metals, as sheets, are potential candidates for BPs material since
they have good mechanical stability, electrical conductivity and thermal conductivity, and can
be easily stamped to desired shape to accommodate the flow channels in a low cost process.
Metals investigated usually include aluminum, stainless steel, titanium, and nickel. However,
as they are exposed to an operating environment with a low pH (2–3) at temperatures close to
80 ºC, metal plates are prone to corrosion or dissolution. The dissolved metal ions may lead to
poisoning of PEM membrane and hence lowering of ionic conductivity. Moreover, a
corrosion layer on the surface of a BP increases the electrical resistance and decreases the
output of the cell.
In the light of these issues, two types of metallic plates have been studied, non-coated and
coated with a protective layer. Coatings should be conductive and adhere to the base metal
without exposing it. Further the coefficient of thermal expansion of the base metal and the
coating should be as close as possible to eliminate the formation of micro-pores and micro-
cracks in coatings due to unequal expansion [126,127]. Two types of coatings, metal-based
and carbon-based, have been investigated [14,15]. Noble metals, metal nitrides and metal
carbides are some of the metal-based coatings. Carbon-based coatings include graphite,
conductive polymers, diamond-like carbon and organic self-assembled monopolymers.
Conducting polymers (such as polyaniline or polypyrrole) or conducting paints containing
carbon blacks can be a good approach in terms of productivity and cost reduction, if suitable
structures, materials and fabrication procedures could be developed [128]. Even though there
has been much effort to develop metal (non-coated and coated) bipolar plates, mostly for
vehicular applications, there is no commercial product yet due to issues pertaining to
corrosion and contact resistance [15].
BPs can also be fabricated bymoulding carbon composite materials. Carbon–polymer
composites are promising alternatives to both metal and pure graphite bipolar plates, and have
the advantages of low-cost, light weight,ease in machining or in situmoulding of complex
flow fields during processing, and good corrosion resistance [129].The polymer or resin used
to bind the carbon in compositeplate material is usually thermoplastic or thermosetting,
whichimplies that the plates can be fabricated either by injectionmoulding [19,21] or by hot
pressing [28], respectively. The most common resins used to develop bipolar plates include
polyvinylidene fluoride (PVDF), polypropylene (PP), polyethylene terephthalate (PET) and
phenol formaldehyde (PF), vinyl ester resin (VER), polyphenylene sulfide (PPS), polyether
sulfone (PES), and epoxy resins [130−132]. Most polymer resins are intrinsically insulating,
and their conductivity values are approximately 10-14 ~ 10-17 S·cm-1, but their electrical
conductivity can be increased by the addition of conductive fillers. Conductive carbon fillers
such as natural graphite (NG), expanded graphite (EG), carbon fibers (CF), and carbon blacks
(CBs) have been used to prepare electrically conductive blends.
These mixtures, however, often result in poor mechanical properties of bipolar plates and,
compared to isotropic high-quality graphite plates, carbon-filled polymer composites have
generally lower conductivity. When conductive carbon fillers (conductivity 102 ~ 105 S/m)
are mixed with polymers, the corresponding composite might have higher conductivity than
that of pure, electrically insulating polymer matrix, but the conductivity of composites will
depend on the shape, particle size, and properties of conductive fillers applied. The dispersion
of the particles and the formation of a continuous network of the conductive fill are critical to
conductivity. Whatever the nature of conductive filler particles, current circulation is obtained
through ‗percolation‘ of the filler through the polymer resin, forming conductive pathways
throughout the material. The electrical conductivity of a composite is generally characterized
by its dependence on the fill volume fraction. At low filler loadings, the conductivity of the
composite is very close to that of electrically insulating pure polymer matrix. However, at
some critical loading, the conductivity increases many orders of magnitude with very little
increase in the filler loading, which is called the ―percolation threshold.‖ Many studies have
been conducted with the intent of reducing the ―percolation threshold‖ so that high material
toughness and high conductivity can be achieved. After the region of significant increase, the
conductivity of composite levels off and approaches to that of the filler material. At the
percolation threshold, enough filler has been added so that it begins to form a continuous
conductive network through the composite [133].
Carbon composites have been used industrially for several decades and generally
comprise carbon fibers to provide strength reinforcement for organic polymers. To meet the
required electronic conductivity, manufacturers have been using quite high loadings of carbon
in the composite material, typically 60–90% by volume [134]. Unfortunately, this makesthe
plates brittle, resulting in high scrap rates and an inability tomake thin plates, required for
high stack power densities.
In the case of the use of carbon blacks as filler in polyvinyl chloride, for example, the
surfacearea and mesoporous volume have been found to affect significantlythe rheology and
conductivity of the composite [135]. To enablelow loadings of carbon to be used, researchers
have been developingspecific forms of carbon for use in composite materials[136−139]. In
producing the composite material, the proportionof carbon filler to polymer is found to affect
not onlythe electronic conductivity but also the mechanical propertiessuch as the flexural
strength, density, water absorption and gaspermeability of the final plate. Good mechanical
properties areafforded by keeping the carbon content low and the polymercontent relatively
high. Heinzelet al. [134], for example, haveshown that additive loadings of 50 wt.% can
achieve bulk conductivitiesof 50 S cm−1 for injection-molded material. Theyhave also
reported conductivities of up to 150 S·cm−1 for somesamples although the nature of the
carbon additives was not disclosed.
Recent improvements in BPs development relay on their hydrophilic surface
modification. These surface treatments have been proved to be an efficient way of improving
water management in PEMFCs [140]. Hydrophilic carbon black aggregates have been
developed for use in the production of a fuelcell bipolar plate with improved electrical
conductivity and hydrophilicity[141]. Thehydrophilization of bipolar plates induces the
formation of a thin water-film on the surface of the flow channel, andthus prevents the water
slugs from occurring. In the hydrophilized bipolar plates, moisture introduced from
thepositive electrode is formed into water drops on the negative electrode, thereby inhibiting a
waterdrop effectobstructing the flow of oxidizing gas. Also, in the hydrophilized bipolar
plates, water can be favorablydischarged through the gas flow channel in the negative bipolar
plate due to the water-film formation. The corrosion of carbon in the electrochemical
environment is a matter of concern and cannot be neglected in the bipolar plate of PEMFC.
The carbon–polymer composite bipolar plates generally show good corrosion resistance in the
PEMFC environment [127,128].
CONCLUSION
Carbon materials, and in particular carbon blacks,have many desirable properties that
have attracted their use in the manufacture ofseveral components for electrochemical systems.
In particular, they are widely used in many PEMFCs components: catalysts, gas diffusion
layers, and bipolar plates.
The surface chemistry of the carbon black is shown to be an important factor in all these
applications, in particular in PEMFC electrocatalysts. The adsorption and the exchange
properties of a Pt/Vulcan XC72 catalyst have been studied by applying adsorption, desorption
and exchange techniques with H2, D2 and CO as probes. The obtained results indicate that the
presence of hydrophilic sulfonic groups associated to the carbon black induces a spill-over
process that favors hydrogen adsorption in large amounts on the catalyst. The chemisorbed
deuterium is susceptible of being exchanged with labile hydrogen species associated to some
support surface groups. This deuterium exchange process seems to take place in two steps
under isothermal conditions. The first one can be attributed to the initial chemisorbed
monolayer, which is readily exchanged with carbon black surface species in a fast process. In
a second step, the exchange reaches a steady state whose rate probably depends on a slower
hydrogen surface diffusion process on the carbon black surface.
The interaction of adsorbates such as D2 or CO with the sulfur-containing surface species
has been evidenced by means of temperature programmed desorption tests of adsorbed
probes. Coadsorption of both CO/D2 has revealed that pre-adsorbed CO blocks Pt surface
sites for D2 chemisorption on them, but the pathways for surface diffusion of deuterium
towards the carbon black support remain operative.
The sulfur-containing groups in the CB are thermally stable under an inert atmosphere at
temperatures up to 448 K in the absence of adsorbates such as H2 or CO. Above
thistemperature, they decompose by releasing H2O and SO2 as main degradation products. In
the presence of adsorbates, the thermal stability of those species is reduced. In particular, co-
adsorption of both CO and D2 reduces the decomposition temperature for sulfonic groups
below 373 K. This may lead to an irreversible degradation of the catalyst properties regarding
to proton mobility.
By comparing the hydrogen adsorption processes taking place in the Pt/Vulcan XC-72
catalyst with those occupying in a gas diffusion electrode containing that type of catalyst, it
has been observed that the presence of an ion exchange resin distributed within the catalytic
layer modifies the H2 adsorption behavior of the sample. The observed changes seem to
depend on the amount and distribution of the resin, inducing a faster exchange process with
deuterium and partially modifying the slower exchange with the surface groups of the catalyst
support.
The participation of the surface chemistry of PEMFC catalyst supports can be analyzed in
the light of these results. The surface modification of carbon materials as catalytic supports
may provide an effective pathway to develop new catalysts for enhanced performance of gas
diffusion electrodes providing faster proton mobility and better stability of surface groups
throughout the catalytic layer while reducing the amount of ion exchange resin in it.
Carbon black surface groups are also relevant in other PEMFC components such as gas
diffusion layers and carbon composite flow field plates. The development of carbon black
aggregates with improved electrical conductivity and hydrophilicity are promising strategies
to enhance the performance of those elements.
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Chapter 2
STUDY AND APPLICATION OF CARBON

BLACK VULCAN XC-72R IN POLYMERIC
ELECTROLYTE FUEL CELLS
M. J. Lázaro1, L. Calvillo1, V. Celorrio1,

J. I. Pardo2, S. Perathoner3 and R. Moliner1
1
Instituto de Carboquímica (CSIC),
Miguel Luesma Castán 4, 50018 Zaragoza, Spain.
2
Group of Applied Thermodynamics and Surfaces (GATHERS),
Aragon Institute for Engineering Research (I3A),
Universidad de Zaragoza, 50009 Zaragoza, Spain.
3
Dipartimento di Chimica Industriale ed Ingegneria dei Materiali,
Università di Messina, Viale Ferdinando Stagno d‘Alcontres 31, 98166 Messina, Italy.
ABSTRACT
The most developed fuel cells are those working at low temperature using a
polymeric electrolyte, PEMFC and DAFC, the latter making use of different alcohols
directly as fuel. At present, the most effective fuel cell catalysts, both in cathode and
anode, are highly dispersed platinum-based nanoparticles. These Pt nanoparticles are
normally supported on carbon materials in order to increase the active surface area of Pt
and improve the catalyst utilization. Among other factors, the performance of metal
nanoparticles supported on carbon materials depends strongly on the properties of the
support. For fuel cell applications, carbon supports should have several characteristics
such as high surface area for dispersing catalytic metal particles, high electrical
conductivity for providing electrical pathways, and mesoporous structure for the facile
diffusion of reactants and by-products. Moreover, the interaction between the carbon
support and the Pt plays an important role in the properties of the Pt/C catalyst. This
interaction can be improved through the surface modification of the support in order to
form proper functional groups and chemical links at the Pt/C interface. These functional
groups can significantly affect the manufacture and performance of electrocatalysts, and
they are responsible for both the acid-base and the redox properties of the carbon
supports.
42 M. J. Lázaro, L. Calvillo, V. Celorrio et al.
Nowadays, among all kinds of carbon supports, carbon blacks are the most
commonly used due to their high mesoporous distribution and their graphite
characteristics. Vulcan XC-72(R) is the most frequently used in the preparation of
commercial electrocatalysts because of its good compromise between electrical
conductivity and high surface area.
In this chapter, a detailed analysis about the properties of Vulcan XC-72R and the
effect that different functionalization treatments have on them will be reported.
Subsequently, the influence of the properties of the support on platinum supported
catalysts will be established. The results of the use of these catalysts at the anode side of a
PEM fuel cell will be presented in order to demonstrate the effective application of this
carbon material in low temperature fuel cells and to establish the effect of the
functionalization of the support on the fuel cell performance.
1. INTRODUCTION
The world‘s energy sector is currently in a period of transition. The utilization of
hydrogen as an energy carrier rather than liquid hydrocarbons through the use of fuel cells,
instead of the traditional internal combustion engines, is one of the most promising energetic
policies to solve the lack of petroleum and the issue of climate change, which is associated to
the emission of greenhouse gases.
Fuel cells are electrochemical devices that continuously convert the chemical energy of a
fuel and an oxidant directly into electrical energy. The fuel cell process has the major
advantage of not being Carnot-limited, thus allowing for a theoretical efficiency that is higher
than a heat engine.
Among the different types of fuel cells, polymer electrolyte fuel cells (PEMFCs and
DAFCs) are the most promising for both portable and stationary applications due to its
advantageous features such as high power density at lower temperatures (55–95 ºC), low
weight, compactness, and suitability for discontinuous operation [Liu 2006, McNicol 1999].
However, cost reduction of the stack components such as electrocatalysts, ionomer
membranes, membrane-electrode assemblies and bipolar plates is an important task to be
solved for the commercial application of this technology in the future. The development of
high performance electrocatalysts plays a vital role in this context. Therefore, the major task
in moving toward fuel cell commercialization is the development of breakthrough catalysts,
improvement of catalyst activity, stability and durability, and the reduction of catalyst cost.
At present, the most effective fuel cell catalysts, both in cathode and anode, are highly
dispersed platinum-based nanoparticles. The high cost of noble metals used as electrode
catalysts is one of the significant obstacles for the commercialization of PEMFCs. Therefore,
the metal nanoparticles are normally supported on carbon materials in order to maximize their
surface area and decrease the total amount of metal employed. Thus, the fraction of metal
particles (active sites) exposed to the reactants increases, improving the catalysts utilization
[Acres 1997]. Among other factors, the performance of metal nanoparticles supported on
carbon materials depends strongly on the properties of the support. For fuel cell applications,
carbon supports should have several characteristics such as high surface area, high electrical
conductivity, and mesoporous structure. Moreover, the interaction between the carbon
support and the Pt plays an important role in the properties of the Pt/C catalyst. This
Study and Application of Carbon Black Vulcan XC-72R ... 43
interaction can be improved through the surface modification of the support in order to form
proper functional groups and chemical links at the Pt/C interface.
Carbon materials are generally used as catalysts supports because of their stability in both
acidic and basic media, good electrical conductivity, high corrosion resistance, surface
properties and high specific surface area. Carbon has been used for many years as a support
for industrial precious metal catalysts [Auer 1998]. Activated carbon, carbon black, graphite
and graphitized materials have been applied in various catalytic processes. Carbon materials
have a strong influence on the properties of supported noble metal catalysts, such as metal
particle size, morphology, size distribution, stability, and dispersion [Kim 2006, Yu and Ye
2007]. On the other hand, carbon supports can also affect the performance of fuel cell
catalysts by altering mass transport, catalyst layer electrical conductivity, active
electrochemical area, and metal nanoparticle stability during the operation [Hall 2004, Inoue
2009]. Hence, the optimization of carbon supports is very important in PEMFC technology
development. In this sense, a carbon support with suitable properties must be selected in order
to obtain an active catalyst, since its properties have strong effects on the preparation and
performance of synthesised supported catalysts.
The ideal properties of a carbon support for their use in fuel cells are [Liu 2006, Dicks
2006]: i) high specific surface area for a high level of catalyst dispersion; ii) suitable pore
structure for the adequate diffusion of reactant and by-products; iii) electrical conductivity in
order to facilitate electron transfer during the electrochemical reactions; iv) suitable surface
chemistry for a good interaction between the catalyst nanoparticles and the carbon support;
and v) high corrosion resistance. Apart from these requirements, supports must be low cost
materials and permit the metal recycling process at the end of the catalyst life.
Respect to the suitable pore structure of the carbon support, a mesopore structure is
preferred. Generally, a high performance anode requires an efficient three-phase reaction
zone (gas-electrode-electrolyte) at nanoscale, where the electrochemical reactions occur,
which formation is favoured by a mesopore structure of the support [Joo 2006]. In addition,
the provision of an efficient transport of reactants and products is also required. The catalyst
utilization decreases with the presence of too many small micropores in the carbon structure
because the mass transport of reactants and products is poor in these micropores. When
macroporous size is larger than 50 nm, the surface area will become small and the electrical
resistance will increase. Therefore, mesoporous carbons are attractive for their use as catalyst
supports and have the potential to enhance both the dispersion and utilization of metal
catalysts. In recent years, some mesoporous carbon materials are being studied as alternative
supports for preparing electrocatalysts. The use of mesoporous carbons as catalyst support is a
new area that is of great interest for the development of the PEMFC technology.
The metal-support interaction has also attracted more and more attention [Yu and Ye
2007, Prado-Burguete 1989]. This interaction has been considered to affect the growth, the
structure, and the dispersion of platinum particles on the carbon support, thus providing the
potential benefits to the improvement of catalytic properties and stability of the
electrocatalysts. In addition, this interaction can also affect the electron transfer from metal
particles to the carbon support during the electrochemical reactions, thus affecting the catalyst
performance in the fuel cell. This effect is attributed to the change of platinum electronic
structure by the presence of the platinum-carbon interaction.
The electronic interaction at the metal-support interface can be modified by the presence
of functional groups on the carbon surface. The surface functional groups can significantly
affect the manufacture and performance of the electrocatalysts, and they are responsible for
both the acid-base and the redox properties of the carbon supports. The surface chemistry of
carbon materials can be modified by oxidation treatments, both in gas and liquid phase,
and/or thermal treatments [Moreno-Castilla 1995, Figueiredo 1999, Noh 1990, Darmstadt
2002].
In the Pt/C preparation, the platinum precursor-carbon interaction is favoured by the
presence of surface oxygen groups, which make the carbon surface more hydrophilic. Thus, it
is expected to achieve a better dispersion of the platinum. But, some surface oxygen groups
may not be stable under the reduction conditions involved in catalyst preparation, and their
decomposition would cause a negative effect on the catalyst. For these reasons the effect of
these groups on the dispersion and anchoring of the platinum is not well established. Some
authors have determined that the presence of surface oxygen groups is necessary to achieve a
good dispersion of Pt [Aksoylu 2001, Prado-Burguete 1989], whereas others argue that they
do not influence or have a negative effect on the dispersion of the active phase [Fraga 2002,
Guerrero-Ruiz 1998].
Regards to the controversy about the effect of the support functionalization on the
physico-chemical properties of catalysts, it must be remembered that their properties depends
not only on the surface chemistry of the support, but also on other factors including the
textural properties of the support, the catalyst synthesis method, or the nature of the metal
precursor. Therefore, it is necessary to carry out an exhaustive study to determine the effect
that the surface chemistry of the support has on the catalyst preparation.
However, the effect of the surface chemistry of the support on the electrocatalyst
performance has not been studied to a large extent. Carbon supports are not inert materials.
During the electrochemical reactions, the metal-support interaction is attributed to the
presence of a platinum-support electronic effect. The specific metal-support interaction
involves electron transfer from platinum clusters to oxygen atoms on the support surface [Yu
and Ye 2007]. This interaction is considered to be beneficial to the enhancement of the
catalytic properties and to improve electrocatalyst‘s stability. However, the functionalization

of the support results in a decrease of its electrical conductivity. Since the functionalization
process seems to have opposite effects on the performance of catalysts, further study is
needed. On the other hand, it has been observed that both methanol and CO electrooxidation
can be influenced by the surface state of the support [Calvillo 2007, Salgado 2008]. It will be
explained in more detail in section 3.1.2.
Among all types of carbon materials, carbon blacks are the most used as electrocatalyst
support for polymeric electrolyte fuel cells, due to their high electrical conductivity and
corrosion resistance, their porous structure and specific surface area [Bezerra 2007]. There are
many types of carbon blacks, such as acetylene black, Ketjen Black, Black Pearl, or Vulcan
XC-72. These materials show different properties, such as porosity, electrical conductivity,
surface functionalities and specific surface area, which depend on the manufacturing process.
Among these properties, specific surface area has an important effect on the preparation and
performance of the electrocatalyst. Catalysts supported on carbon blacks with low specific
surface area (e.g. acetylene black) usually show a very low dispersion. Carbon blacks with a
high specific surface area, such as Ketjen black, have also been studied in order to obtain
highly dispersed catalyst particles [Inoue 2009, Carmo 2007, Kim 2006]. However, these
materials show high ohmic resistance and problems of mass transfer in fuel cell applications.
Vulcan XC-72, which has a specific surface area around 250 m2 g-1 and is formed by an
aggregation of 30-60 nm size-particles, is extensively used as electrocatalyst support,
especially in polymeric electrolyte fuel cells [Shao 2006, Wikander 2006]. In this moment,
this material is used as support in commercial electrocatalysts (E-TEK and Johnson Matthey).
However, although a high and accessible specific surface area is necessary, it is not enough
for obtaining an efficient catalyst. Other factors, such as the pore size and pore size
distribution, or the surface chemistry, also affect the properties and activity of carbon black
supported catalysts [Zhou 2008a, Grolleau 2008, Carmo 2007].
Our research group has modified the surface chemistry of Vulcan XC-72R in order to
study its effect on the properties of electrocatalysts. In this chapter, a review of the properties
and use of Vulcan XC-72R as electrocatalyst support for low temperature fuel cells will be
presented.
2. CHARACTERIZATION AND MODIFICATION OF

PROPERTIES OF VULCAN XC-72R
Vulcan XC-72R, supplied by Cabot Corporation, was subjected to different oxidation
treatments in order to modify its surface chemistry, creating surface oxygen groups. The
oxidation treatments were carried out at room (Ta) and boiling temperature (Tb) for 0.5 and 2
h, using diluted (Nd) and concentrated (Nc) nitric acid or a mixture of nitric and sulphuric
acid (NS) as oxidizing agents. Nomenclature and oxidation conditions used for Vulcan are
presented in Table 1.
Table 1. Nomenclature and oxidation conditions of Vulcan XC-72R
Temperature Time
Sample Oxidizing agent

(°C) (h)
Vulcan --- --- ---
Vulcan NdTa0.5 Diluted HNO3 (2M) 25 0.5
Vulcan NdTa2 Diluted HNO3 (2M) 25 2
Vulcan NcTa0.5 Concentrated HNO3 (65%) 25 0.5
Vulcan NcTa2 Concentrated HNO3 (65%) 25 2
Vulcan NSTa0.5 HNO3-H2SO4 1:1 (v/v) 25 0.5
Vulcan NSTa2 HNO3-H2SO4 1:1 (v/v) 25 2
Vulcan NdTb0.5 Diluted HNO3 (2M) 115 0.5
Vulcan NdTb2 Diluted HNO3 (2M) 115 2
Vulcan NcTb0.5 Concentrated HNO3 (65%) 115 0.5
Vulcan NcTb2 Concentrated HNO3 (65%) 115 2
Vulcan NSTb0.5 HNO3-H2SO4 1:1 (v/v) 115 0.5
Vulcan NSTb2 HNO3-H2SO4 1:1 (v/v) 115 2
These oxidation treatments not only modified the surface chemistry of Vulcan, but also
affected its morphological and textural properties. These results are presented in the following
sections.
2.1. Morphology
The morphology of carbon blacks has been extensively studied by a large number of
authors due to it has a significant importance on their physicochemical properties. The terms
―primary particle‖ and ―aggregate‖ are used to describe the morphology of Vulcan [Hess and
Herd 1993]. An ―aggregate‖ is a rigid and discrete colloidal entity that consists of a group of
particles. An aggregate is the smallest unity. On the other hand, a ―primary particle‖ is the
non-discrete component of an aggregate and has a spherical shape. It consists of several small
crystals, formed of several graphene-like layers with an interplanar spacing of 0.35-0.38 nm,
which are disordered grouped to form spherical particles. Primary particles combine to form
aggregates of different size and structure.
Morphology was studied by scanning electron microscopy (SEM) and X-ray diffraction
(XRD). Figure 1 shows two SEM images of Vulcan XC-72R. It can be seen that Vulcan
consists of an aggregation of spherical particles, primary particles, with size in the range of 30
to 60 nm. The aggregation grade of particles is known as structure of the carbon black.
Figure 1. SEM images of Vulcan XC-72R.
Vulcan was also analyzed by XRD. The XRD pattern is presented in Figure 2. A peak
around 2θ = 24.85º, characteristic of graphite, can be observed, confirming that Vulcan has an
intermediate structure between amorphous and graphitic, called turbostratic structure.
Graphite (002)
Intensity (cps)
10 20 30 40 50 60 70 80
2-Theta (degree)
Figure 2. XRD pattern of Vulcan XC-72R.
The less severe oxidation treatments did not modify significantly the morphology of
Vulcan, since the SEM images obtained for those samples (see Figures 3A and 3B) were very
similar to those obtained for the original material (Figure 1). However, the most severe
treatments (at boiling temperature for 2 h) resulted in a partial destruction of its morphology.
In Figures 3C and 3D, it can be observed that primary particles had not a spherical shape and
the morphology of these materials was denser.
Figure 3. SEM images of Vulcan XC-72R treated with (A and B) HNO3-H2SO4 1:1 (v/v) at room
temperature for 0.5 h (Vulcan NSTa0.5); and (C and D) concentrated HNO3 at boiling temperature for 2
h (Vulcan NcTb2).
2.2. Thermal Stability
The thermal stability of Vulcan XC-72R, as well as the effect of the oxidation treatments,
was determined by temperature programmed oxidation (TPO) experiments. The thermal
stability (or resistance to the corrosion) of the material used as support in the PEM fuel cell
catalysts is an important characteristic that have to be taken into account because it affects the
catalyst durability. Due to its structure, Vulcan exhibits a high resistance to air oxidation. The
oxidation of untreated Vulcan took place at around 660 ºC, as can be seen in Figure 4. The
oxidation of functionalized Vulcan occurred at lower temperatures than that of the untreated
material, indicating that they were slightly less resistant to air oxidation. This can be
attributed to the partial destruction of its morphology during the oxidation treatments. Figure
4 also shows a slight weight loss before the oxidation of carbon materials treated with
concentrated HNO3 and HNO3-H2SO4 at boiling temperature, which is attributed to the
desorption of functional groups created during the oxidation treatments.
100
80 Vulcan
Vulcan NdTa0.5
Vulcan NcTa0.5
Weight (%)
60 Vulcan NSTa0.5
Vulcan NdTb0.5
Vulcan NcTb0.5
Vulcan NSTb0.5
40
Vulcan NdTa2
Vulcan NcTa2
Vulcan NSTa2
20 Vulcan NdTb2
Vulcan NcTb2
Vulcan NSTb2
0
0 200 400 600 800
Temperature (ºC)
Figure 4. Oxidation curves of Vulcan, before and after the oxidation treatments, obtained by TPO
experiments. Experiments were carried out under air atmosphere using a heating rate of 5 ºC min-1.
2.3. Textural Properties
The effect of the oxidation treatments on the textural properties of Vulcan was analyzed
by N2-physisorption. Table 2 shows the textural parameters obtained from this technique.
Vulcan had a relatively large specific surface area (SBET) of 218 m2 g-1 and a total pore
volume (VTotal) of 0.41 cm3 g-1. It had a mesoporous structure, but contained a large number
of micropores (30 % of total surface area). Micropores are non suitable for the application of
this material as electrocatalyst support. It is possible that an important portion of
nanoparticles may be sunken into these micropores, resulting in little or no electrochemical
activity because of the difficulty of reactant accessibility [Liu 2006, Antolini 2009].
After the oxidation treatments, a decrease of the specific surface area was observed. This
was associated to the destruction of the morphology observed by SEM. The decrease was
more significant as the severity of oxidation conditions increased, that is, as the concentration
of the oxidizing agent, and the oxidation temperature and time increased. However, the effect
of the oxidation treatment on the pore volume was the contrary. An increase of the total pore
volume was observed, although there was not a relationship between this effect and the
oxidation conditions.
The textural parameters obtained for the most oxidized sample (Vulcan NSTb2) indicated
a total destruction of the original Vulcan during this treatment. These results explain the
significant decrease of the thermal stability of this sample, as observed by TPO experiments.
Table 2. Textural parameters of Vulcan obtained by nitrogen physisorption at 77 k
SBET a VTotal b VMicropore c VMesopore d SMicropore c SMesopore d

Sample
(m2 g-1) (cm3 g-1) (cm3 g-1) (cm3 g-1) (m2 g-1) (m2 g-1)
Vulcan 218 0.41 0.03 0.38 65 153
Vulcan NdTa0.5 205 0.55 0.03 0.52 51 154
Vulcan NcTa0.5 224 0.45 0.04 0.41 66 158
Vulcan NSTa0.5 218 0.58 0.04 0.54 65 153
Vulcan NdTb0.5 206 0.51 0.03 0.48 56 150
Vulcan NcTb0.5 168 0.50 0.03 0.47 51 117
Vulcan NSTb0.5 132 0.44 0.02 0.42 37 95
Vulcan NdTa2 222 0.57 0.03 0.54 66 156
Vulcan NcTa2 225 0.60 0.04 0.56 70 155
Vulcan NSTa2 141 0.48 0.01 0.47 24 117

Vulcan NdTb2 177 0.50 0.02 0.48 41 136
Vulcan NcTb2 163 0.45 0.03 0.42 49 114
Vulcan NSTb2 0.06 0.001 0.001 0.000 0.06 0.00
a
Determined by the BET (Brunauer, Emmett and Teller) equation.
b
Determined by the single point method at P/P0=0.99.
c
Determined by the t-plot method.
d
Calculated from the difference between the total and micropore values.
2.4. Surface Chemistry
The surface chemistry of carbon blacks is another property that has been extensively
studied, since it has a strong influence on their physicochemical properties, such as the
electrical conductivity and the chemical and catalytic reactivity. The nature and amount of
surface groups depend on the synthesis process of the carbon black, its specific surface area
and the treatment conditions [Bansal and Donnet 1993]. These groups can increase the
wettability of the carbon surface, thereby facilitating metal precursor distribution throughout
the support surface during the impregnation and reduction steps of the catalyst synthesis.
The surface chemistry of Vulcan, before and after the oxidation treatments, was studied
using temperature programmed desorption (TPD) experiments. These experiments give
information about the surface oxygen groups created during the oxidation treatments. Acidic
groups are decomposed into CO2 at lower temperatures and basic and neutral groups are
decomposed into CO at higher temperatures [Figueiredo 1999]. CO and CO2 profiles can be
analyzed and obtained peaks can be related to the different functional groups depending on
their decomposition temperature [Aksoylu 2001, Samant 2004, Figuiredo 1999].
An estimation of the oxygen groups of the different samples is presented in Table 3. It
can be observed that an increase in the severity of oxidation treatments resulted in an increase
of the number of surface oxygen groups. Treatment with HNO3-H2SO4 at boiling temperature
was the most effective at creating functional groups, even though it resulted in the destruction
of the Vulcan structure.
From the CO2 evolution peaks, it was observed that mainly carboxylic groups, which are
stable at low temperatures, were created, whereas the CO evolution peaks suggested the
formation of phenol groups, which are stable at high temperatures (Table 3). It is expected
that not all types of oxygen surface groups have the same effect on platinum anchorage and
dispersion. The more stable the surface group is, the more effective the anchorage of the Pt
and the larger the metal dispersion become.
Table 3. Estimation of the type and number of the oxygen groups created during the
oxidation treatments from the deconvolution of TPD profiles. TPD experiments were
carried out in an inert atmosphere using a heating rate of 10 ºC min-1 up to 1050ºC. The
amounts of CO and CO2 desorbed were analysed by gas chromatography
CO2 Peak areas CO Peak areas

(μmol/g) (μmol/g) CO+CO2

Sample
Anhydride (μmol/g)
Carboxylic Anhydride Phenol Quinone
Lactone
Vulcan 0 0 0 0 317 317
Vulcan NdTa0,5 74 33 0 181 142 430
Vulcan NcTa0,5 105 74 33 491 168 871
Vulcan NSTa0,5 464 286 55 1144 140 2089
Vulcan NdTb0,5 101 79 0 321 201 702
Vulcan NcTb0,5 695 577 41 1226 778 3317
Vulcan NSTb0,5 1068 954 63 1929 236 4250
Vulcan NdTa2 80 49 0 267 210 606
Vulcan NcTa2 308 70 48 602 228 1256
Vulcan NSTa2 720 169 74 1152 364 2479
Vulcan NdTb2 293 272 25 569 522 1681
Vulcan NcTb2 1725 496 155 1366 900 4642
Vulcan NSTb2 2777 2084 110 3111 927 9009
3. USE OF VULCAN XC-72R AS ELECTROCATALYST SUPPORT

From the results obtained in section 2, the original Vulcan and some oxidized samples
were selected in order to study the effect of different synthesis methods and the surface
chemistry of the support on the catalysts properties.
3.1. Effect of the Functionalization of the Support
In order to study the effect of the functionalization of the support on the physicochemical
and electrochemical properties of catalysts, some oxidized Vulcan samples were selected to
prepare platinum-supported catalysts. Catalysts were prepared by the incipient wetness
impregnation method [Calvillo 2009]. It must be remembered that catalyst properties depends
not only on the surface chemistry of the support, but also on other factors including the
catalyst synthesis method and the nature of the metal precursor. Therefore, conclusions
extracted from this study are only valid for this catalyst synthesis method.
3.1.1. Physicochemical Properties

The incipient-wetness impregnation method was chosen to study the effect of the
functionalization of the support on the catalyst properties. Thus, Pt-supported catalysts were
prepared on different oxidized Vulcan XC-72R. Considering that the synthesis method and
the metal loading were the same for all catalysts (the metal content was obtained by EDX and
is shown in Table 4), it is expected that the surface chemistry of the support affects the
formation of metal particles with different size and morphology.
Table 4. Pt content and physical characteristics of catalysts

db Lattice parameterb Metal surface area

Electrocatalyst % Pta
(nm) (Ǻ) (m2 g-1)
Pt/Vulcan 12.9 5.6 3.9184 50
Pt/Vulcan NSTa0.5 13.2 8.6 3.9184 33
Pt/Vulcan NcTb0.5 13.3 15.1 3.9261 19
Pt/Vulcan NcTb2 13.3 16.5 3.9235 17
a
Obtained by SEM-EDX.
b
Calculated from XRD diffractograms.
The morphological and crystallographic properties of Pt catalysts were studied by X-ray

diffraction (XRD, Bruker AXS D8 Advance). XRD patterns of Pt nanoparticles supported on
Vulcan with different functionalization grade are reported in Figure 5. All samples exhibited
three peaks at around 2θ = 40, 47 and 67 º, which correspond to the (111), (200) and (220)
diffractions of the fcc structure of Pt, respectively. This indicates the effective reduction of
the metal precursor. Furthermore, a broad diffraction peak at 26.2º was observed, which is
attributed to the carbon support.
As can be seen in Figure 5, the intensity and width of the XRD peaks, which are related
with the Pt crystallite size, depended on the functionalization grade of the carbon support. A
decrease in the Pt reflections width was observed as the severity of the oxidation treatments
of Vulcan increased. This indicated that Pt crystallites became larger as the number of oxygen
surface groups of the support increased. Table 4 shows the average Pt crystallite size (d) that
was calculated from the XRD diffractograms using the Scherrer‘s equation. The average
crystallite size of Pt supported on non-oxidized Vulcan was about 5.6 nm. An increase in the
platinum crystallite size was observed as the number of surface oxygen groups increased. A
directly proportional relationship between the Pt size and the number of oxygen groups was
observed (see Figure 6). For catalysts supported on the most oxidized supports (Pt/Vulcan
NcTb0.5 and Pt/Vulcan NcTb2), Pt crystallite size of 15.1 and 16.5 nm were obtained,
indicating a possible agglomeration of Pt particles. This is attributed to both the partially
destroyed morphology and the high number of surface oxygen groups of the support.
Pt(111)
Pt(200)
Pt(220)
Intensity (A.U.)
Pt/Vulcan NcTb2
Pt/Vulcan NcTb0.5
Pt/Vulcan NSTa0.5
Pt/Vulcan
20 30 40 50 60 70 80
2-Theta (degree)
Figure 5. XRD diffractograms for the Pt electrocatalysts.
The surface area (SA) of the metal particles was calculated by the equation SA (m2 g-1) =
6 x 103/ρd, where ρ is the Pt density (21.4 g cm-3) and d is the mean metal crystallite size (in
nm). These values are also reported in Table 4. For Pt/Vulcan catalyst a surface area around
50 m2 g-1 was obtained. For the rest of catalysts, the surface are was lower due to its higher
crystallite size.
The lattice parameter was also calculated from XRD patterns and the results are
summarized in Table 4. The value of the lattice parameter of the Pt/C electrocatalysts
decreased as the crystallite size increased. The dependence of the lattice parameter on the
crystallite size was described before in the literature [Salgado 2008, Antolini 2006, Salgado
2005]. In this case, the results agree with those founded in the literature, since all catalysts
were synthesised by the same method. These values were close to 3.92 Å, which is the value
correspondent to pure platinum.
7 25
6 Oxygen groups
Oxygen groups (mmol g-1)

20
Pt crystallite size (nm)

Pt crystallite size
5
15
4
3
10
2
5
1
0 0
Vulcan Vulcan Vulcan Vulcan
NSTa0.5 NcTb0.5 NcTb2
Figure 6. Effect of the surface chemistry of the support on the properties of the catalysts: Relation
between the number of surface oxygen groups and the average Pt particle size (obtained by XRD).
Figure 7. TEM images of platinum catalysts supported on non-oxidized Vulcan (A, B) and the most
oxidized support (Vulcan NcTb2) (C, D).
The size and distribution of platinum nanoparticles were also studied by transmission
electron microscopy (TEM). A uniform distribution of platinum particles was achieved by the
incipient wetness impregnation method, as seen in Figure 7A. Platinum particles supported on
non-oxidized Vulcan were around 5 nm (Figures 7A and 7B). For catalysts supported on
oxidized Vulcan, the formation of some Pt agglomerates was observed (Figure 7C and 7D),
although platinum particles had a similar size when compared to the particles deposited on the
non-oxidized Vulcan. Hence, the increase of crystallite size detected by XRD was due to the
formation of agglomerates. These increase in the platinum crystallite size, or agglomeration
grade, can be attributed to the decomposition of less stable surface oxygen groups during the
reduction stage of the metal precursor, facilitating the mobility of platinum on the support
surface and favouring the agglomeration of platinum particles [Sepúlveda-Escribano 1998,
Román-Martínez 1995, Coloma 1994].
3.1.2. Electrochemical Properties

The activity of catalysts and the effect of the surface chemistry of the support were
determined by cyclic voltammetry and chronoamperometry. Electrochemical measurements
were carried out in a three-electrode cell using a MicroAutolab potentiostat. The counter
electrode was a pyrolitic graphite bar and a reversible hydrogen electrode (RHE) placed
inside a Luggin capillary was used as reference one. All potentials in the text are referred to
this electrode. Working electrodes were prepared depositing a thin-layer of the
electrocatalysts over a pyrolitic graphite disk (7 mm diameter, 1.54 cm2 geometric area). A
catalyst ink was prepared by mixing 2 mg of the catalyst and 10 μl of Nafion dispersion (5
wt.%, Aldrich) in 500 μl of ultrapure water (Millipore Milli-Q system). A 40 μl aliquot of the
suspension was deposited onto the graphite disk and dried. A 0.5 M H2SO4 solution, prepared
from high purity reagents (Merck) and deareated with nitrogen gas, was used as electrolyte.
The presence of CO in the anode of polymeric electrolyte fuel cells is a problem in the
development and subsequent operation of this type of devices. CO is strongly adsorbed on the
platinum surface, which disable the active sites for further reduction of the fuel, causing the
rapid loss of activity (poisoning) of the catalyst. In order to establish the CO tolerance of
catalysts, the electro-oxidation of a CO monolayer adsorbed on the catalyst surface was

studied. CO (99.99 %) was adsorbed onto the metal surface by bubbling this gas at 1 atm
through the electrolyte to achieve a full monolayer coverage of CO on Pt. The CO adsorption
process was carried out at 0.20 V. Subsequently, N2 gas was used to purge out the CO from
the solution, leaving only the CO adsorbed on the surface of Pt. Moreover, from these results,
the electroactive area of catalysts was determined by the integration of the COad oxidation
region, assuming a charge of 420 μC cm-2 involved in the oxidation of a monolayer of
linearly adsorbed CO. This electroactive area was used to normalize the current densities
given in the text.
Figure 8 shows the first and second voltammograms during the stripping of a CO
monolayer formed at 0.20 V for catalysts supported on Vulcan carbons with different surface
chemistry. The second cycle after oxidation corresponds to the voltammogram in the base
electrolyte for the clean surface. The peak potential for the COad oxidation was attained at
0.86 V for the catalyst supported on the original Vulcan. This is the common behaviour
described in the literature for these materials [Salgado 2008, Salgado 2010]. It was observed
that a great part of the COad was oxidized at higher potentials (E > 0.86 V). However, a shift
of the peak potential to more negative potentials was observed as the number of surface
oxygen groups of the support increased, indicating faster charge transfer kinetics of the CO
oxidation process. In addition, the oxidation peak was narrower, indicating that practically all
COad was oxidized at lower potentials on these catalysts than on Pt/Vulcan. It is know that the
carbon support can alter the electronic structure of the metal. This metal-carbon interaction
may strongly influence the electrochemical properties of catalysts. Moreover, the interaction
metal-support can be improved through the surface modification of the carbon support to
form proper functional groups and chemical links at the Pt/C interface [Antolini 2009, Yu and
Ye 2007]. Taking into account that all catalysts were obtained by the same synthesis method
and with similar metal loading, the shift of the peak potential can be attributed to the different
properties of the supports, mainly to their surface chemistry. It is known that
quinone/hydroquinone groups constitute a redox pair which is electrochemically active. The
presence of these groups on the surface of the support could help to oxidize the CO adsorbed
on Pt nanoparticles.
0.08 0.86 V 0.08

(a) (b)
0.83 V
-2
Current density / mA cm
0.04 0.04
0.00 0.00
-0.04 -0.04
-0.08 -0.08
0.0 0.2 0.4 0.6 0.8 1.0 1.2 0.0 0.2 0.4 0.6 0.8 1.0 1.2
0.08 0.08
(c) 0.81 V (d) 0.82 V
-2
0.04 0.04
0.00 0.00
-0.04 -0.04
-0.08 -0.08
0.0 0.2 0.4 0.6 0.8 1.0 1.2 0.0 0.2 0.4 0.6 0.8 1.0 1.2
Potential / VRHE Potential / VRHE
Figure 8. CO-stripping voltammograms for Pt/Vulcan (a);Pt/Vulcan NSTa0.5 (b); Pt/Vulcan NcTb0.5
(c); and Pt/Vulcan NcTb2 (d) electrocatalysts in 0.5 M H2SO4. Ead = 0.20 V; υ = 20 mV s-1; T = 25 ºC.
The activity of Pt catalysts towards the electrooxidation of methanol was studied by

cyclic voltammetry and chronoamperometry. Figure 9 shows the cyclic voltammograms
recorded in 2 M CH3OH + 0.5 M H2SO4 at room temperature. All the voltammograms
exhibited the irreversible nature of the methanol electrooxidation. The onset of methanol
electrooxidation occurred between 0.47 and 0.60 V. The highest current densities were
achieved by the Pt/Vulcan during the positive potential scan at potentials around 0.93 V. It
was also observed that, in the same potential scan direction, this catalyst presented the highest
activity for the methanol oxidation when compared with the other catalysts at potentials lower
than 0.70 V. The specific activities of these catalysts at 0.60 V vs. RHE are shown in Table 5.
This result could be attributed to the higher utilization of the Pt nanoparticles on original
Vulcan carbon, taking into account that the size of Pt crystallites supported on this carbon
material was smaller than those supported on oxidized carbon materials. Taking into account
that an improvement of the methanol electrooxidation was not observed for Pt catalysts
supported on oxidized Vulcan carbons, although the oxygen groups of the support facilitated
the CO oxidation (see Figure 8), it may be conclude that the support has an effect on the CO
oxidation but not improves the methanol deprotonation, which would be the limiting stage of
the process.
1.2 1.2
1.0
(a) 0.93 V
1.0
(b)
-2
0.8 0.8
0.6 0.6
0.4 0.4 0.91 V
0.2 0.2
0.0 0.0
-0.2 -0.2
-0.4 -0.4
0.0 0.2 0.4 0.6 0.8 1.0 1.2 0.0 0.2 0.4 0.6 0.8 1.0 1.2
1.2 1.2
1.0 (c) 1.0 (d) 0.91 V

-2
0.91 V
0.8 0.8
0.6 0.6
0.4 0.4
0.2 0.2
0.0 0.0
-0.2 -0.2
-0.4 -0.4
0.0 0.2 0.4 0.6 0.8 1.0 1.2 0.0 0.2 0.4 0.6 0.8 1.0 1.2
Potential /VRHE Potential /VRHE
Figure 9. Cyclic voltammograms for Pt/Vulcan (a); Pt/Vulcan NSTa0.5 (b); Pt/Vulcan NcTb0.5 (c); and
Pt/Vulcan NcTb2 (d) electrocatalysts in 2 M CH3OH + 0.5 M H2SO4. υ = 20 mV s-1; T = 25 ºC.
To further assess steady state catalyst performance with respect to methanol

electrooxidation, chronoamperometry tests at steady potential were carried out. Figure 10
shows the potentiostatic methanol oxidation currents as a function of time for the Pt based
catalysts at 0.60 V. Generally, the curves feature a sharper decrease during the earlier
minutes. Afterwards, the current diminishes much more slowly. This behaviour has been
ascribed to the accumulation of poisoning species, mainly CO, on the Pt surface during the
methanol oxidation as the cause of the initial rapid decay [Sivakumar and Tricoli 2006]. The
subsequent slow current decrease could be tentatively ascribed to the presence of surface
active impurities or anions in the electrolyte solution that may slowly adsorb onto the catalyst
surface during long-term experiments, thereby determining loss of activity [Gasteiger 1994,
Jiang and Kucernak 2003]. However, a stable performance of all catalysts was obtained in a
short time. Quasi-stationary current densities from chronoamperometric curves increased in
the order Pt/Vulcan NcTb2 < Pt/Vulcan NSTa0.5 < Pt/ Vulcan NcTb0.5 < Pt/ Vulcan as can
be seen in Table 5. Therefore, we can conclude that the functionalization of the support do not
improve the performance of Pt/Vulcan based catalysts in the methanol electrooxidation,
although it facilitates the electrooxidation of CO adsorbed on Pt nanoparticles.
0.06
Pt/Vulcan
Pt/Vulcan NSTa0.5
Pt/Vulcan NcTb0.5
-2
Pt/Vulcan NcTb2
0.04
0.02
0.00
0 100 200 300 400 500 600 700 800 900
Time / s
Figure 10. Chronoamperometric curves for Pt/Vulcan, Pt/Vulcan NSTa0.5, Pt/Vulcan NcTb0.5, and
Pt/Vulcan NcTb2 electrocatalysts recorded in 2 M CH3OH + 0.5 M H2SO4 solution at E = 0.60 V and
room temperature.
Table 5. Current densities obtained from cyclic voltammetry

(CV) and chronoamperometric (CR) curves for Pt/C catalysts in

2 M CH3OH + 0.5 M H2SO4 solution at 0.60 V
CV0.60 CR0.60
Electrocatalyst
(µA cm-2) (µA cm-2)
Pt/Vulcan 21 29
Pt/Vulcan NSTa0.5 15 22
Pt/Vulcan NcTb0.5 18 24
Pt/Vulcan NcTb2 14 20
3.2. Effect of the Synthesis Method
In the literature, different synthesis methods have been used to prepare platinum
electrocatalysts. Mainly, five general methods are usually employed such as impregnation,
ion exchange, precipitation, colloidal, and vapour phase methods. However, scarce works
about the comparison of catalysts synthesised by different methods can be found in the
literature [Salgado 2008, Lázaro 2010].
In this section, five Pt catalysts supported on the original Vulcan have been synthesised
by different methods in order to study the influence of the synthesis method on the
physicochemical and electrochemical properties of catalysts. Catalysts have been prepared by
the incipient wetness impregnation method (IWIM) [Calvillo 2009], the impregnation and
subsequent reduction with sodium borohydride (BM) [Calvillo 2007] and formic acid (FM)
[Álvarez 2010] methods, and the alcohol-reduction method using methanol (MM) [Gangeri
2006] or ethylene glycol (EGM) [Lázaro 2010].
For the incipient wetness impregnation method, the volume of the metal precursor
solution was chosen to match the pore volume of the carbon support. Subsequently, the metal
precursor was reduced in H2 atmosphere at 300 ºC for 2 h.
The impregnation-reduction method is one of the most commonly methods used to
fabricate catalysts. In this method, a solution of the metal salt precursor is prepared and mixed
with the carbon support. After the impregnation step, a reduction step is required to reduce
the catalyst precursor to its metallic state. Sodium borohydride (NaBH4) and formic acid
(CH2O2) were used as reducing agents. Syntheses were carried out at room temperature and
80 ºC, respectively.
Finally, two catalysts were prepared by the alcohol-reduction method. In these methods,
the solvent used to dissolve the metal precursor and carbon support acts also as reducing
agent. Methanol (CH3OH) and ethylene glycol (C2H6O2) were used as reducing agents.
Syntheses were carried out at 90 and 195 ºC, respectively.
In all cases, H2PtCl6 (8 % vol., Sigma-Aldrich) was used as metal precursor, and catalysts
with a metal loading of 20 wt. % were prepared.
3.2.1. Physicochemical Properties

The crystal structure of prepared catalysts was determined by X-ray powder diffraction
and X-ray diffractograms are shown in Figure 11. All Pt catalysts showed the characteristic
peaks of the fcc structure of Pt, indicating that the metal precursor was effectively reduced in
all cases. However, the intensity and width of these peaks depended on the synthesis method.
The width of these peaks is related to the Pt crystallite size: the wider the peak, the smaller
the Pt crystallite. The average Pt crystallite size was calculated by the Debye-Scherrer‘s
equation using the (220) peak of the Pt fcc structure (Table 6). As can be observed, the
smallest Pt crystallite size was obtained by the FAM method (3.7 nm), whereas the largest Pt
crystals were obtained by the EGM and IWIM methods (5.6 nm). Therefore, from these
results is deduced that the synthesis method has an important influence on the Pt crystallite
size.
According to the literature, the size and morphology of metal particles supported on
carbon materials depend on the metal-carbon interaction [Bessel 2001, Serp 2003, Ismagilov
2005]. The lattice parameter was also calculated from the XRD, considering the peak position
for Pt signals (Table 6). All the values were close to that for the pure platinum (3.92 Ǻ). In the
literature, it has been described that, for one synthesis method, the lattice parameter decreases
as the metal crystallite size increases [Salgado 2008, Antolini 2006, Salgado 2005]. However,
in this case, no relationship between the crystallite size and the lattice parameter was found,
since all catalysts were prepared by different methods.
Pt (111)
Pt (200)
Pt (220)
Pt/Vulcan-EGM
Intensty (a.u.)
Pt/Vulcan-MM
Pt/Vulcan-FAM
Pt/Vulcan-BM
Pt/Vulcan-IWIM
20 30 40 50 60 70 80
2-Theta (degree)
Figure 11. XRD diffractograms for Pt/Vulcan electrocatalysts synthesised by different methods.
Table 6. Pt content and physical characteristics of catalysts
Db Latticce parameterb Metal surface area

Electrocatalyst % Pt a
(nm) (Ǻ) (m2 g-1)
Pt/Vulcan-IWIM 12.9 5.6 3.9184 50
Pt/Vulcan-BM 17.3 4.2 3.9146 67
Pt/Vulcan-FAM 19.2 3.7 3.9155 76
Pt/Vulcan-MM 15.3 4.6 3.9079 61
Pt/Vulcan-EGM 20.0 5.6 3.9199 50

a
Obtained by SEM-EDX.
b
Calculated from XRD diffractograms.
The surface area of the Pt particles can be calculated by the equation (assuming spherical
particles): SA (m2 g-1) = 6 x 103/ρd; where ρ is the Pt density (21.4 g cm-3) and d is the mean
metal crystallite size in nm. The SA values are also summarized in Table 6. Values between
50 and 76 m2 g-1 were obtained. The maximum Pt surface area was achieved with the FAM
method, due to this method resulted in the smallest Pt crystallites. Therefore, to achieve the
maximum available Pt area, the Pt particles need to be dispersed as finely as possible.
3.2.2. Electrochemical Properties

The activity of Pt/Vulcan catalysts and the effect of the different synthesis methods were
determined by cyclic voltammetry and chronoamperometry. Electrochemical measurements
were carried out using the same methodology described in section 3.1.2.
Figure 12 shows the CO-stripping voltammograms for all catalysts, as well as the second
cycle after oxidation, which corresponds to the voltammogram in the base electrolyte for the
clean surface. No significant differences were observed for the catalysts synthesised by
different methods. The peak potential for the COad oxidation occurred at the same potential
for all catalysts (0.82 V). However, for Pt/Vulcan-BM, Pt/Vulcan FAM and Pt/Vulcan IWIM,
the electrooxidation of CO started at around 0.70 V, whereas for Pt/Vulcan-EGM and
Pt/Vulcan-MM, it started at more negative potentials. For the last two catalysts, also a
shoulder centred at 0.72 V was apparent, which implies that for these catalysts part of the
adsorbed CO is oxidized at more negative potentials. From these results, it is deduced that CO
is easily oxidized on Pt/Vulcan-EGM and Pt/Vulcan-MM catalysts.
0.82 V
0.10 0.10 0.82 V
(a) (b)
0.08 0.08
-2
0.06 0.06
0.73 V
0.04 0.04
0.02 0.02
0.00 0.00
-0.02 -0.02
-0.04 -0.04
0.0 0.2 0.4 0.6 0.8 1.0 1.2 0.0 0.2 0.4 0.6 0.8 1.0 1.2
0.10 0.82 V 0.10 0.82 V

(c) (d)
0.08 0.08
-2
0.06 0.06
0.04 0.04 0.72 V
0.02 0.02
0.00 0.00
-0.02 -0.02
-0.04 -0.04
0.0 0.2 0.4 0.6 0.8 1.0 1.2 0.0 0.2 0.4 0.6 0.8 1.0 1.2
0.10
(e)
0.08 0.85 V
0.06
-2
0.04
0.02
0.00
-0.02
-0.04
-0.06
-0.08
-0.10
-0.12
0.0 0.2 0.4 0.6 0.8 1.0 1.2
Potential / VRHE
Figure 12. CO-stripping voltammograms for Pt/Vulcan-BM (a); Pt/Vulcan-EGM (b); Pt/Vulcan-FAM
(c); Pt/Vulcan-MM (d); and Pt/Vulcan-IWIM (e) electrocatalysts in 0.5 M H2SO4. Ead = 0.20 V; υ = 20
mV s-1; T = 25 ºC.
The activity of Pt catalysts towards the electrochemical oxidation of methanol was

studied in order to determine their viability as electrocatalysts for direct methanol fuel cells
(DMFCs). Methanol electrooxidation was characterized by cyclic voltammetry and

chronoamperometry. Cyclic voltammograms (CVs) were recorded in 2 M CH3OH + 0.5 M
H2SO4 between 0.05 and 1.10 V at a scan rate of 0.02 V s-1.
1.6 1.6
0.94 V
1.4
(a) 1.4
(b)
Current density / mA cm -2
1.2 1.2
0.92 V
1.0 1.0
1.01 V
0.84 V 1.04 V
0.8 0.8
0.6 0.6
0.4 0.4
0.2 0.2
0.0 0.0
0.0 0.2 0.4 0.6 0.8 1.0 1.2 0.0 0.2 0.4 0.6 0.8 1.0 1.2
1.6 1.6
1.4 (c) 1.4 (d)

Current density / mA cm -2
1.2 1.2
1.0 0.87 V 1.0 0.92 V

1.04 V
0.8 0.8
0.6 0.6
0.93 V
0.4 0.4
0.2 0.2
0.0 0.0
0.0 0.2 0.4 0.6 0.8 1.0 1.2 0.0 0.2 0.4 0.6 0.8 1.0 1.2
1.6
1.4
(e)
Current density / mA cm-2
1.2
0.93 V
1.0
0.8
0.6
0.4
0.2
0.0
0.0 0.2 0.4 0.6 0.8 1.0 1.2

Potential / VRHE
Figure 13. Cyclic voltammograms for Pt/Vulcan-BM (a); Pt/Vulcan-EGM (b); Pt/Vulcan-FAM (c);
Pt/Vulcan-MM (d); and Pt/Vulcan-IWIM (e) electrocatalysts in 2 M CH3OH + 0.5 M H2SO4.. υ = 20
mV s-1; T = 25 ºC.
Figure 13 illustrates cyclic voltammograms recorded at room temperature. All catalysts

showed a similar catalytic activity towards the methanol electrooxidation. All the voltammo-
grams exhibited the irreversible nature of the methanol electrooxidation. The onset potential
for methanol electro-oxidation occurred between 0.50 and 0.62 V for all catalysts.
The highest current densities were achieved with the Pt/Vulcan-EGM catalyst during the
positive potential scan at potentials around 1.01 V. However, the highest current density at
the working potential of a DMFC (0.60 V) was obtained with the Pt/Vulcan-FAM sample
(Table 7), which can be attributed to the smaller size of the Pt particles and, therefore, to its
higher surface area.
Table 7. Current densities obtained from cyclic voltammetry

(CV) and chronoamperometric (CR) curves for Pt/C catalysts in
2 M CH3OH + 0.5 M H2SO4 solution at 0.60 V
CV0.60 CR0.60
Electrocatalyst
(µA cm-2) (µA cm-2)
Pt/Vulcan-IWIM 21 29
Pt/Vulcan-BM 31 43
Pt/Vulcan-FAM 39 52
Pt/Vulcan-MM 22 31
Pt/Vulcan-EGM 35 48
Potenciostatic current density- time (j-t) curves were also recorded in a 2 M CH3OH + 0.5
M H2SO4 solution at 0.60 V for 900 s, in order to determine the performance of the catalysts
towards methanol electrooxidation under potentiostatic conditions. Figure 14 shows such
curves for the Pt-supported catalysts. In all cases, a stable performance was achieved in a
short time. The values of the current densities increased in the order Pt/Vulcan-IWIM <
Pt/Vulcan-MM < Pt/Vulcan-BM < Pt/Vulcan-EGM < Pt/Vulcan- FAM, as observed in Table
7. These values are in agreement with those obtained by cyclic voltammetry.
0.10 Pt/Vulcan-IWIM
Pt/Vulcan-BM
Pt/Vulcan-EG
-2
0.08
Pt/Vulcan-FAM
Pt/Vulcan-MM
0.06
0.04
0.02
0.00
0 100 200 300 400 500 600 700 800 900
Time / s
Figure 14. Chronoamperometric curves for Pt/Vulcan-BM, Pt/Vulcan-EGM, Pt/Vulcan-FAM,

Pt/Vulcan-MM and Pt/Vulcan-IWIM electrocatalysts recorded in 2 M CH3OH + 0.5 M H2SO4 solution
at E = 0.60 V and room temperature.
4. TESTS IN A PEM SINGLE CELL

Catalysts supported on the original and oxidized Vulcan, synthesised by the incipient
wetness impregnation method, were also tested at the anode side in a home-made PEM fuel
cell (1 cm2 geometric area). Tests were carried out at room temperature and atmospheric
pressure. Pure hydrogen and oxygen (purity > 99.9 %) were passed through humidifiers and
fed at the anode and cathode sides, respectively.
In order to carry out the electrochemical measurements, several MEAs were prepared
using different electrodes for the anode, and a commercial 20 % Pt/C on GDM (Gas Diffusion
Membrane) electrode (E-TEK Inc.) for the cathode (Pt, 0.4 - 0.6 mg/cm2). The anode
electrodes were prepared by depositing a suspension of Nafion solution (10% wt.) and the
synthesised electrocatalyst (Nafion content in the suspension = 32 % wt) on pieces of E-TEK
ELAT carbon cloth. The final amount of metal active phase in all the prepared electrodes was
0.5 mg/cm2, for their comparison with the commercial electrode E-TEK. The commercial
electrode from E-TEK was based on Pt deposited on Vulcan XC-72, which was then
deposited on the carbon cloth gas diffusion membrane (Pt, 0.4-0.6 mg cm-2). The final
assembly of the electrodes and the Nafion membrane was hot pressed between two metallic
plates and heated at 120 ºC, with a pressure of 20 Kg/cm2 for 90 s.
1.0
0.9 E-TEK
Pt/Vulcan
0.8
0.7
Cell potential (V)
0.6
0.5
0.4
0.3
0.2
0.1 A
30
0.0
0 20 40 60 80 100 120 140 160 180
25
)
-2
Power density (mW cm
20
15
10
B
0
0 20 40 60 80 100 120 140 160 180
-2
Current density (mA cm )
Figure 15. Polarization (A) and power density (B) curves for Pt/Vulcan based electrode and the
commercial one at the anode side in a PEM fuel cell working at room temperature and atmospheric
pressure.
Figure 15 shows the polarization (cell potential versus current density) and power density
curves obtained for the Pt/Vulcan based electrode and the commercial gas diffusion electrode
(E-TEK Inc.). Comparing the obtained results, it was observed a better fuel cell performance
when the Pt/Vulcan based electrode was used, since less polarization losses were obtained
than those obtained with the commercial electrode. Both electrodes were based on Pt
supported on Vulcan XC-72 (E-TEK) and Vulcan XC-72R (our catalyst). The only difference
between both materials is their morphology: Vulcan XC-72 is formed by pellets, whereas
Vulcan XC-72R is a powder. However, even this morphological difference could
considerably influences the performance of the fuel cell. Carmo et al. published a
comparative study about both supports [Carmo 2007]. They obtained a higher catalytic
activity using Vulcan XC-72 than Vulcan XC-72R due to the higher electrical conductivity of
the first one. On the contrary, we obtained better results with the catalyst supported on Vulcan
XC-72R. Taking into account that both electrodes contained the same Pt loading, this result
can be attributed to the preparation of the electrodes. According to the literature, there must
be an optimum Nafion content in the electrode in order to obtain a satisfactory cell
performance [Sasikumar 2004, Litster 2004]. This result demonstrates that it is necessary not
only to optimize the properties of the catalyst but also the properties of the electrode in order
to obtain a good fuel cell performance.
1.0
E-TEK
0.9
Pt/Vulcan
0.8 Pt/Vulcan NSTa0.5
0.7 Pt/Vulcan NcTb0.5
Pt/Vulcan NcTb2
Cell potential (V)
0.6
0.5
0.4
0.3
0.2
0.1 A
30
0.0
0 20 40 60 80 100 120 140 160 180 200
25 B
)
-2
Power density (mW cm
20
15
10
0
0 20 40 60 80 100 120 140 160 180 200
-2
Current density (mA cm )
Figure 16. Polarization (A) and power density (B) curves for Pt electrocatalysts supported on Vulcan
with different surface chemistry at the anode side in a PEM fuel cell working at room temperature and
atmospheric pressure.
Catalysts supported on different oxidized Vulcan carbons were also tested in the fuel cell
in order to study the effect of the surface chemistry on their performance. The characteristic
curves obtained for these catalysts are showed in Figure 16. For all catalysts, the open circuit
potential (OCV) was lower than the reversible potential (1.23 V), which is attributed to
irreversible losses during the fuel cell operation. These losses result from three types of
polarization effects: activation, ohmic and concentration polarizations. The OCV was about
0.9 V for all catalysts except for Pt/Vulcan NcTb2, which is attributed to the higher
agglomeration of platinum nanoparticles.
At lower current densities (0 – 10 mA), a sharp drop in the cell potential was observed,
associated to the activation polarization. Losses obtained for Pt/Vulcan based electrodes were
around 17-36 %, whereas those obtained for the commercial electrode were about 43 %.
These losses depend both on the electrode composition and the interaction between hydrogen
and the surface of the electrode. Therefore, the lower losses obtained for Pt/Vulcan electrodes
are associated to the preparation of the electrode, as was mentioned above.
Losses in the second region of the curve are related to the ohmic resistance of the cell
components, such as the electric and contact resistances of electrodes, membrane and current
collecting components. Taking into account that all experiments were carried out in the same
experimental system and all electrodes were prepared by the same method and using the same
membrane, differences in the performance of electrodes can be attributed to the electron
transport through electrodes during the electrochemical reactions. The electron transport
depends on the electrical conductivity of the support and the Pt-support interaction, since an
electron transfer from Pt nanoparticles to the conductive gas diffusion layer through the
carbon support takes place during the electrochemical reactions. According to the literature,
this transfer takes place through the oxygen atoms of the surface of the support [Antolini
2009, Yu and Ye 2007a], therefore, the metal-support interaction can be improved through
the surface modification of the carbon support to form proper functional groups and chemical
links at the Pt/C interface. Probably, oxygen groups share Pt electron density favouring the
electron transfer from catalytic sites to the conductive carbon electrode. However, the
functionalization of the support decreases its electrical conductivity. Therefore, it is necessary
to establish a compromise between the two effects in order to optimize the cell performance.
In Figure 16 can be observed that the functionalization of the support did not improve the fuel
cell performance. However, similar ohmic losses were obtained for all Pt/Vulcan based
electrodes, despite the differences in the Pt particle size.
Finally, the voltage drop in the third region of the polarization curve (high current
densities) is associated with mass transport resistance of protons through the membrane and
the gas phase through the porous structure of the electrodes. Due to the same membrane was
used for preparing all MEAs, differences in the performance of electrodes can be attributed to
the diffusion of hydrogen through the electrodes. As can be seen in Figure 16, lower mass
transport losses were obtained with electrodes based on oxidized Vulcan. This can be
attributed to the higher pore volume of oxidized supports than the original Vulcan, which
results in a more effective diffusion of hydrogen through their porous structure.
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Chapter 3
A REVIEW OF CURRENT ANALYTICAL APPLICATIONS

EMPLOYING GRAPHITIZED CARBON BLACK
Christine M. Karbiwnyk*1 and Keith E. Miller2

1
Animal Drugs Research Center U.S. Food and Drug Administration,
Denver, Colorado, USA
2
University of Denver, Department of Chemistry and Biochemistry,
Denver, CO, USA
ABSTRACT
Graphitized carbon black (GCB) is a non-porous form of amorphous carbon. GCB
materials are hydrophobic. They are often used to effectively trap organic compounds
from water or under high humidity conditions; conditions where the performance of other
sorbents is reduced. While activated carbon relies on its high surface-area-to-volume ratio
to adsorb organic compounds, the surface interactions of GCB depend solely on
dispersion (London) forces. GCB materials have been used to trap a wide range of
organic compounds from C4 hydrocarbons to polychlorinated biphenyls (PCBs).
Typically, compounds are adsorbed on the GCB surface from large volumes of air or
water, and then subsequently released either by solvent desorption or thermal desorption
resulting in either a concentration of the analytes, solvent exchange or combination of
both. This review presents analytical applications of GCBs over the last decade. It
includes air monitoring, solid-phase extraction (SPE), purge traps for purification or low-
flow air sampling, and chromatography columns utilizing GCB packing material.
Keywords: Review; Graphitized carbon black; Solid-phase extraction; Polar compounds
* Corresponding Author: Animal Drugs Research Center U.S. Food and Drug Administration, P.O. Box 25087,
Denver, Colorado 80225-0087, USA
.
70 Christine M. Karbiwnyk and Keith E. Miller
1. INTRODUCTION
Carbon-based adsorbents have several advantages over silica-based adsorbents, including
high chemical inertness and thermal stability. Compared to polymer-based adsorbents, carbon
adsorbents tolerate a wider pH range, and they can withstand higher desorption temperatures.
The use of graphitized carbon blacks in gas chromatography began 40 years ago in packed
column gas chromatography (GC), and is still used today for the analysis of alcohols, ketones
and esters. Porous layer open tubular (PLOT) columns are capillary columns where the inner
surface is coated with a layer of solid porous material. PLOT columns coated with graphitized
carbon black (CarbographTM, Alltech Associates) can be used to separate both polar and non-
polar compounds. One advantage of some of the carbon-based columns over alumina-coated
columns is that they are generally less affected by water in the sample, which can cause
degradation in separation performance (such as changes in retention, selectivity, efficiency,
and peak area). The GCB PLOT stationary phase has been applied to gas chromatography of
polar compounds such as alcohols, free fatty acids and phenols, and to environmental
analyses. Restek™ produces micro-packed GC columns using 0.75mm ID deactivated
stainless steel tubing. The coiled tube can be several centimeters up to several meters in
length [1]. This represents a future application for GCB materials with the potential for higher
capacity compared to PLOT columns and increased efficiency over traditional packed
columns. GCBs are not sufficiently pressure resistant to be used in HPLC columns; instead,
porous graphitic carbon columns are used [2].
The use of carbonaceous sorbents for solid-phase extraction (SPE) began in the 1980s.
Initial applications included the extraction of non-polar analytes such as organochlorinated
insecticides [3,4] and then of moderately polar analytes such as triazines and phenoxy acids
[5,6]. Interest in GCBs increased when it was found to solve the difficult extraction problem
of isolating polar molecules, which have a low affinity for most reversed-phase sorbents,
from aqueous samples [7-11].
2. CHARACTERISTICS OF GRAPHITIZED CARBON BLACK

Carbon black is produced by the incomplete combustion of hydrocarbons. Graphitized
carbon black (GCB) materials are made by heating carbon black at > 2600 ○C in a furnace
with a reduced oxygen atmosphere. This process results in a material that is hydrophobic and
non-porous form of amorphous carbon with a particle size of 80–100 μm, and surface area of
approximately 200 m2/g [2].
The Carbotrap and Carbopack Graphitized Carbon Black (GCB) product lines from
Supelco are very similar, differing only in whether the particle size is larger or smaller than
40 mesh. The GCB materials 40 mesh and larger (e.g. 20/40) belong in the Carbotrap product
line, whereas the GCB materials 40 mesh and smaller (e.g. 40/60, 60/80, 80/100, etc.) belong
in the Carbopack product line. The larger 20/40 Carbotrap materials are typically used in 4
mm and larger internal diameter (ID) air monitoring tubes, permitting high flow rates without
excessive pressure drops. Carbopack 40/60 materials are typically used in <4 mm ID air
monitoring tubes, to prevent the channeling that would occur if a large 20/40 material was
used in a small-bore tube. The smaller (60/80, 80/100, etc.) Carbopack materials are typically
A Review of Current Analytical Applications … 71
used for all other applications (e.g. GC columns, SPE tubes, purge traps, purification, low-
flow air sampling, etc.). As a general rule, it is recommended that the smallest available
particle size is used as long as the application can accommodate the pressure drop [12]. The
relative adsorptive strength of Supelco‘s Carbotrap/Carbopack materials from weakest to
strongest is F, C, Y, B, Z, and X. The absorptive strength trends with the surface area of each
material. Surface area for the Carbotrap/Carbopack GCB materials are 5, 10, 24, 100 and 240
m2/g for F, C, Y, B and X, respectively [12]. LARA (Rome, Italy) produces 5 types of
graphitized carbon black (GCB) at present, best known as Carbograph. Surface area for the
Carbograph materials are 5, 10, 100, 130 and 240 m2/g for Carbograph 3, 2, 1, 4 and 5
respectively [13]. Carbotrap C (Supelco, Bellefonte, PA, USA) and Carbograph 2 (LARA,
Rome, Italy) selectively adsorbs C12 – C20 VOCs, Carbopack B (Supelco) and Carbograph 1
(LARA) adsorbs C5 – C12 VOCs. Carbograph 4 (LARA) has a surface area of 130 m2/g
overlaps the Carbograph 1 absorption characteristics with C4 – C12 VOCs.
Carbotrap/Carbopack F (Supelco) and Carbograph 3 (LARA) selectively adsorb molecules
greater than C20. Carbograph 5 (LARA) is said to be equivalent to Carbotrap X (Supelco) and
used for the adsorption of C3 – C5 compounds [12,13]. It is important to note here that some
materials have similar names, but should not be confused with GCB materials, Carboxen and
Carbosieve materials are molecular sieves with surface areas ranging from 75 – 1500 m2/g.
GCBs are also differentiated from activated carbon where by carbon undergoes a process to
make it extremely porous. The surface area of activated carbon exceeds 500 m2/g. The high
porosity of activated carbon results in high chemical adsorption, but it is sometimes difficult
to desorb analytes.
There are several properties contributing to the sorbent behavior of GCB. First, it is
carbon and works as a reversed-phase adsorbent. Second, due to its flat surface, GCB has a
particular affinity for aromatic compounds with respect to aliphatic ones [14]. Additionally,
the GCB surface is contaminated with positively charged chemical impurities similar to
benzpyrylium salts. This results in GCB acting as an anion exchanger as well as a non
specific adsorbent. Because of the double nature of GCB, this material offers the advantage
over conventional ion exchangers in the extraction of both charged and uncharged analytes
from a complex matrix. Complete desorption of acidic compounds from a GCB extraction
cartridge can then be achieved only by adding either an acidic or a basic agent to the eluent
phase [15]. Thus, when dealing with a range of compounds, elution into different fractions
can be accomplished, provided that a careful choice of washings and elution solvents is made
[14]. A complete review of the structure and adsorption properties of graphite-like carbons
can be found by Zheivot [16]. Phospholipids may partially saturate both specific and
nonspecific adsorptive sites of the GCB surface [14] so clean-up or dilution prior to the GCB
sorbent may be required with fatty sample matrices.
3. ANALYTICAL APPLICATIONS
3.1. Air Monitoring and Low-Flow Air Sampling
The Clean Air Act was enacted in 1970 because air pollution was resulting in mounting
dangers to public health and welfare, including injury to agricultural crops and livestock,
property damage, and hazards to air and ground transportation [17]. Regulating priority
pollutants and evaluating emerging pollutants requires air monitoring procedures with part
per trillion detection levels. Solid adsorbents that concentrate the analytes of interest from
large volume air samples are part of numerous standard procedures.
Multi-bed sampling tubes allow a wider range of compounds to be sampled, and many
are offered pre-packed from the manufacturer. The AirToxics (Supelco) tubes contain two
adsorbent beds. This allows for the analysis of a wide range of compounds, non-methane
hydrocarbons (C3 – C12), chlorofluorocarbons (CFCs) and aromatic hydrocarbons. The first
bed is a Carbotrap (Supelco) permeable to polar compounds, graphitic adsorbent, and the
second bed is a proprietary molecular sieve adsorbent for the collection of C3 – C5
compounds. Molecular sieve adsorbents suffer from water vapor interference. Carbopack and
Carbotrap graphitic carbons are relatively unaffected by atmospheric humidity. Because the
adsorption of water vapor from humid air can affect the sampling and analysis of VOCs,
several groups have evaluated selected carbon adsorbents under these conditions [18,19]. It is
typical to desorb the analytes in the back flush direction when multi-bed sampling tubes are
utilized.
3.1.1. VOCs
Volatile organic compounds (VOCs) refers to organic chemical compounds which have
significant vapor pressures and which can affect the environment and human health. VOCs
are numerous, varied, and ubiquitous. Although VOCs include both man-made and naturally
occurring chemical compounds, it is the anthropogenic VOCs that are regulated. VOCs are
typically not acutely toxic, but have chronic effects. A common sampling technique involves
pumping several liters of air through a solid adsorbent cartridge to concentrate the compounds
before analysis.
Solid adsorbents have proven useful for determining the vertical profiles of volatile
organic compounds (VOCs) using sampling platforms such as balloons, kites, and light
aircraft, and those profiles provide valuable information about the sources, sinks,
transformations, and transport of atmospheric VOCs. Sampling systems can also be set up at
ground level as a stationary site (busy intersection) or as a backpack (personal exposure
monitoring). Depending on the sampling site, compounds may be anthropogenic (e.g. toluene,
isobutene) indicating fuel exhaust or biogenic emissions (e.g. pinene, limonene) from trees.
The majority of ambient air sampling is performed on multibed GCB adsorbent tubes
which undergo thermal desorption prior to GC-MS analysis. Bahrami et al. [20], pumped 2.4
– 3.6 L of air through Carbotrap 300® adsorption tubes. The group identified 54 hydrocarbons
in the air of Tehran dominated by aliphatic and aromatic hydrocarbons. Gallego et al. [21],
found multi-sorbent bed tubes of Carbotrap, Carbopack X and Carboxen 569 show better
performance than Tenax TA tubes for very volatile organic compounds in ambient air
samples. Twenty-seven compounds in indoor and outdoor air had less breakthrough on the
carbonaceous multi-sorbent tube compared to the Tenax TA. Karbiwnyk et al. [22] used
multi-sorbent tubes (Carbotraps plus a molecular sieve adsorbent) to sample VOCs and CFCs
from vertical profiles of ambient air. Several Carbotrap adsorbent tubes were evaluated by
Donaldson et al. [23] in developing a method to determine aromatic hydrocarbons,
chlorinated aromatic hydrocarbons and 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) present
in combustion emissions. However, some research groups used a single type of GCB
adsorbent to collect and analyze specific target analytes, such as, BTEX [24], low boiling
hydrocarbons [25], PAHs [26], tobacco smoke [27], CFCs [28], and benzenes [29]. Fernandez
et al. [30] used Carbotrap B sampling tubes to measure 23 VOCs from the gaseous emissions
of coal-fired power stations. GCB materials have alternative desorption methods.
Supercritical CO2 with methanol modifier was used by Hong et al. [31], to desorb volatile
organic peroxides collected from indoor air onto Carbotrap adsorbent tubes. In addition to
thermal stability, GCB materials are also chemically stable. Thus methods employing solvent
desorption of analytes may be found in the literature. Cao and Zhu [32] used an ORBO-101
(20/40 mesh Carbotrap) sampling cartridge to measure the emission of oxygenated chemicals
(e.g. triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, 2-methoxyethanol,
and 2-ethoxyethanol and their acetates) from diesel fuel exhaust in order to conduct a human
exposure assessment. After sample collection, the two bed GCB adsorbent (Bed A 100 mg,
Bed B 50 mg) was transferred to two 4 mL amber vials. Target compounds were desorbed
with a 95/5 (v/v) mixture of methylene chloride and methanol with 85% recovery.
3.1.2. Aldehydes
Volatile aldehydes and ketones are widely used as solvents and are involved in several
industrial processes, e. g. reduction of plastics. Aldehydes and ketones are, furthermore,
formed by incomplete combustion of fossil fuels, and carbonyl compounds are also emitted
into the atmosphere by biogenic sources, e. g. vegetation. Volatile aldehydes and ketones are
also formed in the atmosphere as intermediates in the photochemical degradation of
hydrocarbons [33]. The degradation of carbonyl compounds in the atmosphere contributes to
the formation of ozone and other oxidants, e.g. peroxyacetylnitrate (PAN). Exposure to some
of these compounds is known to affect human, animal, and plant life. There is substantial
interest in the determination of these polar constituents of the atmosphere due to their
atmospheric importance and the well known toxicity of some of the compounds. Whereas
several techniques have been established for the analysis of hydrocarbons [34,35] the reliable
determination of polar compounds, e.g. airborne aldehydes and ketones, is still a challenge.
Dettmer et al. [36] concluded that the adsorptive enrichment of low-boiling carbonyl
compounds on Carbograph 5, thermal desorption, and GC analysis is a promising method for
the trace analysis of these compounds, without derivitization, in humid atmospheres. The
group found another GCB adsorbent, Carbotrap X, unsuitable for the sampling of low
molecular weight carbonyl compounds.
3.1.3. Headspace Sampling

Borusiewicz and Zięba-Palus [37] found the multi-bed adsorbent cartridges, Carbotrap
®
300 , to be effective in headspace passive sampling of trace levels of flammable liquid
compounds from fire debris. Carbotrap 300® turned out to be especially useful for isolation
and concentration of volatile oxygenated compounds e.g. ethanol or acetone. Jurjevic et al.
[38] investigated microbial volatile organic compounds (MVOCs) from Aflatoxigenic and
non-toxigenic Aspergillus flavus strains grown on corn and on peanut substrates. Analytes
were collected by trapping headspace volatiles using thermal desorption tubes (TDT) packed
with Tenax® TA and Carbotrap™ B. Trapped compounds were thermally desorbed from the
adsorbent tubes, separated by gas chromatography, and identified by mass spectrometry.
Volatiles that were associated with both the aflatoxigenic A. flavus strain and the
nontoxigenic strain on both substrates included: ethanol, 1-propanol, butanal, 2-methyl-1-

propanol, 3-methylfuran, ethyl acetate, 1-butanol, 3-methylbutanal, 3-methyl-1-butanol,
propanoic acid-2-methyl-ethyl-ester, 2-methyl-1-butanol, 1-pentanol, 2-pentanol, 3-methyl-3-
buten-1-ol, benzaldehyde, 3-octanone, 2-ethyl-1-hexanol and octane. Volatiles that were
associated only with the aflatoxigenic A. flavus strain included: dimethyl disulfide and
nonanal. Volatiles that were associated only with the nontoxigenic A. flavus strain included:
hexanal, 1- hexanol, 1-octene-3-ol, 1-octen-3-one and 2-pentyl furan.
3.2. Solid-Phase Extraction
Solid-phase extraction (SPE) utilizes carbon-based adsorbents to concentrate and purify

analytes from different sample matrices. SPE is a separation process by which compounds
that are dissolved or suspended in a liquid mixture are separated from other compounds in the
mixture according to their physical and chemical properties. Solid-phase extraction can be
used to isolate analytes of interest from a wide variety of matrices, including urine, blood,
water, beverages, soil, and animal tissue. This sample preparation technique uses a solid-
phase packing contained in a small plastic cartridge. The process, as most often practiced,
requires four steps: conditioning the sorbent, adding the liquid sample, washing away
impurities, and eluting the sample in as small a volume as possible with a strong solvent [39].
Filippov et al. [40] performed an extensive review of the preconcentration of organic
substances from aqueous solutions with non-polar adsorbents from the viewpoint of the
thermodynamics and kinetics of occurring processes, in addition to the effect of the chemical
nature and structure of an adsorbent and an organic trace component on the efficiency of
extraction.
Matrix solid phase dispersion (MSPD) is a sample preparation technique for use with
solid sample matrices. It was first developed to extract veterinary residues from complex
biological matrices such as liver, muscle and meat. More recent work has demonstrated the
applicability of the technique to extract organic analytes from fruit and vegetable material.
The technique involves homogenization of a small amount of sample tissue with bulk sorbent
in a mortar and pestle. The mechanical shearing forces produced by the grinding process
disrupt the structure of the tissue, dispersing the sample over the surface of the support
sorbent by hydrophilic and hydrophobic interactions. The process causes the mixture to
become semi-dry and free-flowing, and a homogenous blend of sample and sorbent is the
result. This blend is then packed into a pre-fritted SPE column, and elution of interference
compounds and analytes of interest can then take place using suitable solvents [41].
In 2003, Anastassiades et al. [42] introduced a novel approach to SPE sample prep called
―dispersive SPE‖. In this method, a food sample (10-20 g) is initially extracted with
acetonitrile. Gram levels of salt (magnesium sulfate, sodium chloride, and/or sodium sulfate)
are then added to drive partitioning between the aqueous residues and the acetonitrile layer.
Unlike most methods using conventional SPE tubes, in dispersive SPE, residual water and
cleanup are performed simultaneously by mixing bulk SPE materials and magnesium sulfate
with the acetonitrile extract. The bulk SPE sorbent adsorbs matrix interferences, and after a
simple vortex and centrifugation step, the supernatant is ready for further analysis using GC-
MS or LC-MS [43]. This procedure is often referred to as QuEChERS (Quick, Easy, Cheap,
Effective, Rugged and Safe).
3.2.1. Pesticides
Graphitized carbon black (GCB), commercially referred to as ENVI-Carb, Carbograph or
Carbopack, has been a popular adsorbent for sample clean-up and extraction of polar
pesticides that are difficult to recover from other adsorbent materials. Matrices vary from soil
[44-49] and water [50-62] to fruits and vegetables [49,63-67] to grains [68,69], eggs [70],
beverages [71,72], oils [73,74] and additional agricultural products [71,75-79]. Dispersive
solid-phase extraction (DSPE) or QuEChERS using GCB is gaining in popularity as a way to
clean-up matrix compounds that might otherwise interfere with analysis [80-89]. Walorczyk
[90] also used DSPE to determine pesticide residues in honey bees. Matrix solid phase
dispersion (MSPD) was used by Ye [91] as part of an extraction/clean-up procedure for
pesticides in tobacco.
A unique property of the GCB adsorbent is that isolation of acidic compounds from
neutral compounds can be easily achieved by differential elution. When analyzing acidic
compounds in complex aqueous environmental matrices, this class fractionation offers the
advantages of making the analytical method more selective. The presence of active centers
bearing a positive charge enables GCBs to behave as both nonspecific and anion exchange
sorbents. It follows that anionic organic compounds are specifically adsorbed on GCB surface
via electrostatics forces, and they can be desorbed only by adding a displacing agent to an
organic solution. Recently, trifluoroacetic acid, acetic acid and formic acid have been used as
displacing agents [53]. Research groups are also using multiple elution solvent systems to
improve recoveries from multi-residue extraction procedures. Akiyama et al.[92], used the
SupelClean ENVI-Carb GCB cartridge to extract 10 sulfonyl urea herbicides from rice before
LC-DAD analysis. The solid-phase extraction of five triazines (atrazine, deethylatrazine,
deisopropylatrazine, ametryne and prometryne) from breast milk samples was developed by
Balduini et al. [93]. Conrad et al. [94] found that higher recovery rates and reproducibility
values in the analysis of terbumeton and its major metabolites by SPE and DAD-HPLC in soil
bulk water were obtained with the graphitized carbon black sorbent than with other
conventional adsorbent materials like C-18. SPE allowed a 1000 times concentration factor
without interference from the dissolved natural organic components from soil samples with
good limit of detections for the four compounds studied: 0.009 μg/L for terbumeton,
0.100 μg/L for terbumeton-desethyl, 0.550 and 0.480 μg/L for terbumeton-2-hydroxy and
terbumeton-deisopropyl. Fifty-two base-neutral and acid herbicides were simultaneously
extracted by a Carbograph 4 cartridge from water samples without any sample pretreatment
by Curini et al. [95]. Brennan et al. [96], used a dual layer cartridge containing 300 mg GCB
in combination with 600 mg of primary/secondary amine (PSA) as an SPE cleanup technique
for fipronil (e.g. Frontline®, Icon®) and its degradation products from sediment samples. A
multiresidue method for 27 herbicides and 3 fungicides in bovine milk was developed by
Bogialli et al. [97], using an SPE cartridge filled with Carbograph 4. The GCB cartridge was
found to be more efficient in retaining the acidic analytes compared to an Oasis HLB sorbent
(Waters). Blasco et al. [98], found GCB to work best in the cleanup and extraction of
dithiocarbamates and metobolites from fruits and vegetables before LC-MS analysis.
Banerjee et al. [99], found that dispersive solid phase extraction (DSPE) with 25 mg of GCB
could remove more than 90% of the co-eluting interference of β-carotene. Along with PSA
and Na2SO4, sufficient cleanup and extraction of 87 pesticides from mango was achieved
before LC-MS/MS analysis. Di Corcia et al., [100] used Carbograph 4 cartridges in the
extraction and clean-up of 26 base/neutral pesticides and 13 acidic pesticides from aqueous
samples eluted together from the SPE cartridge with a suitably acidified eluent phase. Back
eluting the analytes by passing through the cartridge 1.5 mL of methanol followed by 8 mL of
a methylene chloride–methanol (80:20, v/v) solution acidified with formic acid, 50 mmol/L
resulted in recoveries equal to or better than 80%, except for carbendazim (67%),
butocarboxim (73%), aldicarb (75%) and molinate (77%). Ding et al., [101] used ENVI-Carb
(Supelco, USA) GCB cartridges to extract chlorophenoxy acid herbicide residues from
aqueous samples. Fernandez et al. [102], describes a method for analyzing aldicarb and their
metabolites (aldicarb sulphoxide and aldicarb sulphone) and carbofuran with its metabolite 3-
hydroxycarbofuran extracted from human urine samples with disposable 3 mL SPE cartridges
containing 500 mg of graphite carbon obtained from Supelco and further cleanup on NH2
cartridges from Waters. Lagana et al. [53] developed a method for the identification and
quantification of neutral diphenyl-ether (DPhE) (aclonifen, bifenox, fluoroglycofen, lactofen,
oxyfluorfen) and acid metabolites (acifluorfen, bifenox acid, fomesafen) at low nanogram per
liter concentration levels in natural water samples. The analytes were isolated from drinking
water, groundwater, and river water samples by SPE on Carbograph-1 cartridges. The acidic
DPhE compounds were separated from neutral DPhE during the elution from Carbograph-1
cartridge using dichloromethane:methanol (80:20, v/v) for neutral compounds and
dichloromethane:methanol (80:20, v/v) acidified with 25 mmol/L of formic acid for the
anionic metabolites. Zhang et al. [103] developed and validated a multiresidue procedure for
the analysis of 72 pesticides in wines using a modified QuEChERS procedure that added
GCB adsorbent to reduce matrix co-extractives in the final extract. Gilbert-Lopez et al. [104]
tested a modified QuEChERS procedure against an MSPD extraction procedure for 105
pesticides from olive oil. The fatty matrix required both C-18 and GCB adsorbents in addition
to the QuEChERS magnesium sulfate and PSA DSPE adsorbents. The MSPD procedure used
aminopropyl sorbent and Florisil SPE cleanup. In general, Gilbert-Lopez et al. found better
recoveries were achieved using the QuEChERS method for the studied pesticides. Using this
extraction protocol, 72% of the analytes are recovered in the range 70–130%, while using the
MSPD extraction procedure, the percentage of analytes was 57%. Hayward et al. [105]
describe a procedure for the analysis of milk fortified with 34 pesticides in which SPE
cleanup using PSA (500 mg)/GCB (250 mg) SPE columns (United Chemical Technologies,
Bristol, PA) help overcome the high fat content of the matrix. Ettiene et al. [106] used GCB
in their cleanup procedure to determine organophosphorus insecticides in the leaves and
stems of guava. Song et al. [107] used ENVI-Carb (Supelco) SPEs in the extraction and
cleanup of 100 pesticides (including organophosphorus, organochlorine, carbamate, and
pyrethrines) in vegetables (Chinese cabbage, cole, cucumber, and tomato) with a 35 min GC-
MS analysis procedure. Dopico et al. [108] evaluated the recovery of eight triazine herbicides
from water samples using carbograph and polymeric sorbents when they developed their LC-
UV method. Although the polymeric SPE had slightly higher recoveries (79 – 100%
compared to 80 – 97% from the GCB SPE), the group preferred the GCB SPE because it
resulted in lower relative standard deviations and permitted a high sample flow rate.
Famiglini et al. [109] chose Carbograph 4 (LARA) for their SPE procedure because the GCB
material allows good recoveries for both organochlorine and phenoxy acidic pesticides from
water samples in a single extraction step. Garcia-Rodriguez et al. [110] evaluated a one-step
pressurized liquid extraction and cleanup for pyrethroid, organophosphorus and carbamate
pesticides in seaweeds using a mixture of Florisil® and GCB. In 2008, Gonzalez-Rodriguez et
al. [111] found ENVI-Carb II/PSA dual layer SPE cartridges (Supelco) worked well to
cleanup matrix co-extractants when determining 23 pesticide residues in leafy vegetables by
GC-MS. The GCB layer has a strong affinity towards planar molecules and has also a unique
ability for the isolation/removal of pigments (e.g. chlorophyll and carotenoids) and sterols
commonly present in fruits, vegetables and other natural products. The PSA layer is a
polymerically bonded ethylenediamine-N-propyl phase that contains both primary and
secondary amines having a strong affinity and high capacity for removing up to 99% of fatty
acids (oleic, palmitic and linoleic acid), organic acids and some polar pigments and sugars
when conducting multiresidue pesticide analysis in foods. Gonzalez-Rodriguez et al. [112]
also found ENVI-Carb II/PSA dual layer SPE cartridges (Supelco) effective in their
extraction and cleanup of 11 new fungicides from grapes and wines before GC-MS analysis.
3.2.2. Mycotoxins
Mycotoxins are secondary metabolites of molds, contaminating a wide range of crop
plants and fruits before or after harvest. There are more than 200 currently known mycotoxins
belonging to different groups of chemical structures; the most important mycotoxins being:
aflatoxins, deoxynivalenol, ochratoxin A, fumonisins, zearalenone, patulin and T-2 toxin.
Since the discovery of the aflatoxins in 1960 and subsequent recognition that mycotoxins are
of significant health concern to both humans and animals, regulations gradually developed for
mycotoxins in food and feed [113]. Determining the level of mycotoxin contamination in
food and feed includes a wide array of in-laboratory testing which includes extracting, clean-
up and separation techniques.
A liquid chromatography/tandem mass spectrometry (LC-MS/MS) method was
developed by Lagana [114] to determine four trichothecene mycotoxins (nivalenol,
deoxynivalenol, fusarenon X and 3-acetyldeoxynivalenol) in maize. Sample preparation was
performed by extracting the analytes with a mixture of acetonitrile and water, followed by a
solid-phase extraction with Carbograph-4 cartridges as the purification step. The extraction
procedure resulted in recovery rates from the maize samples above 81%. Investigation of a set
of maize samples collected from farms located in different areas of northern and central Italy
revealed primarily deoxynivalenol contamination. Cavaliere et al. [115] used Carbograph-4
(LARA, Rome, Italy) for the extraction of fusarium mycotoxins (trichothecens B,
macrocyclic lactones (zeranols) and fumonisins B) from maize. This graphitized carbon black
is similar to Carboprep 200 (Restek), and ENVI-Carb (Supelco). Its surface area is 210 m2/g
and the particle size range is 120–400 μm. Carbograph-4 cartridges were prepared by filling
6 × 1.3 cm ID polypropylene tubes (Supelco, Milan, Italy) with 500 mg of adsorbent material,
placed between two polyethylene frits (Supelco). By taking advantage of GCBs ability to
behave as both reversed-phase and ion-exchange sorbent, in addition to an affinity for
aromatic compounds with respect to aliphatic compounds, Cavaliere et al. [115] found it was
possible to separate trichothecenes B in the methanol fraction from zeranols in the
dichloromethane/methanol (80:20, v/v) fraction, whereas acidic compounds were retained.
This clean-up procedure resulted in cleaner extracts than collecting a single fraction, and it
drastically reduced ion suppression during ESI ionization. Later, Cavaliere et al., [116,117]
expanded the method to include 19 mycotoxins produced by Fusarium genus in maize.
Samples were extracted in 2 fractions from Carbograph for the screening method and 3
fractions for the confirmation method.
Aflatoxins (AFs) are another class of mycotoxins produced mainly by the fungal species
Aspergillus flavus and A. parasiticus. AFs may occur on maize before or during harvesting, or
because of improper feed storage. AFs are biologically active compounds that, even in small
amounts, have powerful hepatotoxic, immunosuppressive, mutagenic, carcinogenic, and
teratogenic effects. AFB1 is the most common and potent of the four major AFs. Based on
epidemiological evidence, AFs have been classified as potential carcinogenic agents to
humans (group 1) by the World Health Organization [113]. Cavaliere et al. [118] developed 2
procedures to determine Aflatoxin M1 in cheese by LC-MS/MS. Carbograph 4 was used as a
clean-up cartridge in both procedures, however, procedure I (solvent extraction/MSPD/
Carbograph-4 clean-up) performed better than procedure II (hot water extraction/Carbograph-
4 cleanup) in terms of matrix effects, recovery and detection limits. In the determination of
aflatoxin M1 in cow‘s milk, Cavaliere et al. [119] sought an alternative to the expensive
immunoaffinity columns for sample preparation. The group found a two-step isolation
procedure (proteins precipitation and SPE by a Carbograph-4 cartridge) produced milk
sample extracts amenable to accurate and precise determination by LC-MS/MS with external
calibration of AFM1 levels in compliance with current EU regulations. Faberi et al. [120]
describe a sensitive LC-MS/MS method for determining type B fumonisin mycotoxins in
corn-based foodstuffs. Extracts were defatted by C-18 SPE then applied to Carbograph-4
cartridges. Base-neutral compounds were washed off the cartridge with 12 mL of
dichloromethane/methanol (80:20, v/v). Fumonisins were then eluted from the cartridge with
8 mL of dichloromethane/methanol (80:20, v/v) containing 50 mmol/L formic acid.
3.2.3. Hormones
An important issue which has emerged over the last several years in environmental
science is concern regarding the potential risks to humans and wildlife derived from exposure
to both natural and synthetic chemicals that may interfere with reproduction and
development. Therefore, much research has been directed toward the occurrence, effects and
risks of these compounds. In general, excreted human pharmaceuticals (e.g. birth control
pills) and natural hormones, have to pass through a sewage treatment works (STW) before
reaching rivers or streams. Many suspicions have been raised concerning the environmental
impact of endogenous (estrone, E1; 17β-estradiol, E2; Estriol, E3) and synthetic (17α-
ethynylestradiol, EE2) estrogens excreted by humans and animals that enter environmental
waters. A possible contribution to the EE2 found in sewage water, in addition to that from use
as a component of birth control pills, is derived from the potential conversion of other drugs
such as norethisterone/norethisterone acetate to EE2 [121].
Concern over the weakly estrogenic nature of nonylphenol ethoxylate (A9PE)
biotransformation products led Di Corcia et al., [122] to monitor these surfactants and their
metabolites in treated and untreated sewages. Extraction and clean-up was performed using
Carbograph 4 cartridges (LARA, Rome, Italy). The group exploited the GCB materials
characteristic of adsorbing anionic organics by electrostatic interactions, and used a stepwise
desorption procedure to isolate neutral analytes from acidic ones extracted from treated
sewages. Houde et al., [123] also developed a procedure to monitor nonylphenol ethoxylates
(NPEOs) and nonylphenol carboxylic acids (NPECs) in surface and drinking water utilizing
ENVI-Carb SPE followed by LC-MS/MS analysis. Shao et al. [124] describe the
determination of NPEOs in the aquatic environment by normal-phase LC-MS. Extraction and

cleanup of samples were performed on GCB solid-phase extraction cartridges with recoveries
for NPEOs between 91.9 and 117.5%. The limits of detection ranged between 0.5 and 2 ng/L
for individual NPEOs and between 5 and 0.5 μg/L for NP1EO and NP2EO. Ding and Wu
[125] describe the analysis of two well known hormonally active agents (nonylphenol (NP)
and bisphenol A (BPA)), in river water samples. The researchers achieved 80% to 85%
recovery with a graphitized carbon black SPE procedure and determination by ion-trap GC-
MS. A multiresidue analytical method for the determination of the most common and
biologically active natural and synthetic steroids (four estrogens: estriol, 17β-estradiol, 17α-
ethynylestradiol, estrone; one progestagen: progesterone and six androgens: trenbolone,
boldenone, nandrolone, testosterone, 17α-methyltestosterone, stanozolol) in environmental
waters was developed by Lagana et al. [126]. The analytes were isolated from water samples
by SPE using a graphitized carbon black adsorbent (Carbograph-1) resulting in recoveries
greater than 82%. The final samples were analyzed by reversed-phase LC-MS/MS using
atmospheric pressure chemical ionization (APCI). Esperanza et al. [127] developed and
refined two analytical methods for the detection and quantitation of two groups of endocrine-
disrupting chemicals in the liquid matrixes of two pilot-scale municipal wastewater treatment
plants. The group used C-18 SPE targeting seven sex hormones (estradiol, ethinylestradiol,
estrone, estriol, testosterone, progesterone, and androstenedione), and graphitized carbon
black for a group of nonionic surfactants (nonylphenol polyethoxylates), and their
biodegradation byproducts nonylphenol and nonylphenol ethoxylates with one, two, and three
ethoxylates. Baronti et al. [128] determined sub-part per trillion levels of estrogen compounds
from different aqueous environmental samples using 0.5 g of Carbograph 4 solid-phase
extraction cartridges. With respect to this work by Baronti et al. [128] on the analysis of free
estrogens, D‘Ascenzo [129] modified the extraction/purification procedure such that, after
elution of the free estrogens, the Carbograph 4 SPE cartridge was reversed and conjugated
estrogens were back eluted with 20 mL of a methylene chloride/methanol (60:40, v/v)
solution containing 10 mM sodium acetate. This procedure was used to investigate the fate of
the conjugated forms of the three most common natural estrogens in the municipal aqueous
environment. Lagana et al. [121] report on the development of an analytical method adequate
for determining four estrogen chemicals (estriol, 17β-estradiol, estrone and 17α-
ethynylestradiol) in sewage samples with a recovery of > 84% and a limit of detection of 0.5
– 1 ng/L, using ENVI-Carb (Supelco) SPE cartridges for extraction and cleanup before LC-
MS/MS analysis. Hanselman et al. [130] developed a sample preparation method that permits
the quantification of four natural steroidal estrogens (17α-estradiol, 17β-estradiol, estrone,
and estriol) in flushed dairy manure wastewater (FDMW) by GC-MS. Solid-phase extraction
with graphitized carbon black was used for the bulk extraction of estrogens from FDMW and
additional sample purification was accomplished with C-18. The sample preparation method
allowed estrogens to be detected accurately by GC-MS with average recovery of > 90%
measured by spiked recovery experiments. Yang et al. [131] describe a C-18 MSPD and
ENVI-Carb SPE cleanup method followed by very high pressure LC–MS/MS technique that
was developed to assay trace levels of unconjugated progestogens in eggs. Using the GCB-
NH2 SPE sample preparation, Yang et al. [132] validated a simple and sensitive method for
the simultaneous determination of 50 anabolic hormones with a wide range of polarity and
classification in samples of beef, pork, milk and shrimp. The group found the GCB-NH2 SPE
extraction resulted in higher recoveries and excellent matrix cleanup for the majority of
analytes tested compared to C-18 and HLB cartridges. An LC-MS/MS method for the
determination of free and conjugated estrogens in complex aqueous matrixes was developed
by Gentili et al. [133]. The group used a single Carbograph cartridge in their extraction
procedure that enabled differential elution, without derivatization, of the two fractions of the
analytes, for the best sensitivity in LC-MS analysis. This also enabled a reduction in the
required volume of environmental water needed for extraction. A sensitive analytical method
was developed and validated by Shao et al. [134] for simultaneous determination of 16
glucocorticoid (fluorometholone, flumethasone, triamcinolone, aldosterone, clobetasol
propionate, methylprednisolone, fluocinolone acetonide, hydrocortisone, prednisone,
dexamethasone, beclomethasone, prednisolone, budesonide, triamcinolone acetonide,
fludrocortisone acetate, and cortisone) residues in pig tissues (muscle, liver, and kidney).
Samples were hydrolyzed with beta-glucuronidase/arylsulfatase enzyme and passed through a
Supelclean ENVI-Carb graphitized carbon black solid-phase extraction cartridge, followed by
further purification using aminopropyl cartridges. Analytes were separated on an ultra-
performance liquid chromatography BEH C-18 column followed by tandem mass
spectrometry (MS) with an electrospray ion source in negative ion mode.
3.2.4. Antibiotics
Anthropogenic and ubiquitous use of antibiotics in agriculture (applications to fish ponds,
cattle, hogs, etc) and failure of water treatment plants to breakdown or remove these
compounds has resulted in the occurrence of antibiotic compounds in lakes and streams [135].
Concern also continues regarding exposure to antibiotics in the food supply [136,137].
Bruno et al. [138] made use of GCB‘s hydrophobic nature and its ability to adsorb acid
compounds in the extraction of trace level penicillins from water samples. Sample treatment
methods for the analysis of contaminants in food are usually based on deproteinization/
extraction by various solvents followed by a sequence of cleanup steps, which often involve
the use of SPE cartridges filled with a variety of sorbent materials. However, several research
groups have found that GCB sorbent materials allow one step clean up and extraction without
deproteinating the sample matrix. In some cases, sample dilution ensures the proteins won‘t
interfere with analyte recovery and additional sorbent materials may be utilized to reduce
fatty acid and phospholipid levels from the sample matrix. Thus, a milk matrix required only
a slight modification in sample preparation for Bruno et al. [139] to extract 10 β-lactam
antibiotics from bovine milk using Carbograph 4 SPE cartridges. Cavaliere et al. [140]
extended the method to the analysis of 14 sulfonamide (SAs) residues in milk and eggs. The
method uses a single SPE Carbograph 4 cartridge for simultaneous extraction and purification
of SAs in the above matrices. After analyte desorption, an aliquot of the final extract is
injected into an LC-MS instrument. Recovery of SAs in milk at the 5 ppb level ranged
between 76 and 112% with relative standard deviations (RSDs) of ≤13%. Recovery of SAs in
egg at the 50 ppb level ranged between 68 and 106% with RSDs of ≤12%. Estimated limits of
quantification (S/N = 10) of the method were 1−6 ppb of SAs in whole milk and 5−13 ppb of
SAs in eggs. Tetracycline antibiotics (TCAs) have a broad range of activity against gram-
positive and gram-negative bacteria and are inexpensive. For these reasons, TCAs are widely
used in veterinary medicine to prevent and treat several diseases as well as for promoting
growth in cattle and poultry. However, the ability of TCAs to form complexes with Ca2+ and
Mg2+ ions, which are species abundantly present in both milk and egg, makes them difficult
to analyze. Bruno et al. [141] found that dilution of milk and egg samples with water
containing respectively 10 and 1 mmol/L Na2EDTA succeeded in giving satisfactory analyte
recovery from Carbograph 4 cartridges.
3.2.5. Mercury
Due to the health risks associated with elemental mercury, methyl mercury, and dimethyl
mercury, quantification of these species in a variety of matrices is necessary to determine
total mercury concentrations. Dimethyl mercury ((CH3)2Hg) has been found in municipal
waste landfill gas, sub-thermocline waters of the Pacific Ocean, sediment cores, soils, and
urban air. The highly volatile nature of (CH3)2Hg makes analysis of this compound
problematic. Bloom et al. [142], found Carbotrap to be a superior adsorbent for (CH3)2Hg
compared to Tenax, a non-polar synthetic polymer often used for semi-volatile compound
collection, and several pure carbon-based molecular sieves (Carbosieve S-III, Carboxen-563,
Carboxen-564 and Carboxen-569). Bloom et al. [142], estimated recoveries of (CH3)2Hg from
Carbotrap sampling cartridges to be 98.9 ± 5.1%, with potentially a worst case scenario of
121.6 ± 6.2% if all flow measurement errors are included. The researchers concluded that
Tenax is unsuitable due to its small breakthrough capacity, and that all of the carbon
molecular sieves are unsuitable due to the lack of quantitative recovery of (CH3)2Hg. Bloom
et al., maintain the observation of very rapid breakthrough of (CH3)2Hg through Tenax is not
surprising, and serves to explain the failure of previous Tenax based analytical methods for
determining (CH3)2Hg in air.
3.2.6. Food Contaminants

In addition to pesticides and mycotoxins, food undergoes analysis for other toxins and
contaminants. Some compounds are the result of environmental contamination (e.g. dioxins
and paralytic shellfish toxins). Food safety analysis sometimes addresses an immediate threat
to public health, such as illness and renal failure resulting from the consumption of food
adulterated with melamine and cyanuric acid [143,144]. The presence of biogenic amines,
like putrucine and cadaverine, may be a sign of food spoilage. Fish, shellfish and other food
matrices can present challenges in residue analysis. Several research groups have found
success using graphitized carbon black adsorbent materials as part of the isolation and
cleanup procedures.
Dioxins are by-products of various industrial processes, and are commonly regarded as
likely human carcinogens that are persistent organic pollutants in the environment. The
tolerable daily intake of dioxin has been set very low, 1-4 pg/Kg body weight per day, to
allow for uncertainty in the dose response to different toxicity levels of the dioxin compounds
and to ensure public safety as far as possible [145]. Hoh et al. [146] developed a relatively
fast and easy analytical screening method to monitor fish oil potentially contaminated with
dioxin and dioxin-like PCBs at or above current food safety limits. A 2 g cod liver oil sample
required only gel permeation chromatography and SPE cleanup with graphitized carbon black
before direct sample introduction coupled to 2D gas chromatography time of flight mass
spectrometry analysis.
Paralytic shellfish poisoning (PSP) is caused by a group of 26 naturally occurring potent
neurotoxins. Symptoms begin anywhere from 15 minutes to 10 hours after eating the
contaminated shellfish, although they are usually observed within 2 hours. Symptoms are
generally mild, and begin with numbness or tingling of the face, arms, and legs. This is
followed by headache, dizziness, nausea, and muscular uncoordination. In cases of severe
poisoning, muscle paralysis and respiratory failure occur, and in these cases death may occur
in 2 to 25 hours [147]. Regulatory bodies are recommending lower limits to protect public
health. Sayfritz et al. [148] developed an improved LC–MS/MS method, which can be used
for the routine regulatory determinations of PSP toxins in shellfish samples in a single
chromatographic analysis. The group combined a novel extraction method, improved the
sample clean-up with GCB SPE and used gradient elution to lower the overall LOD of
saxitoxin (the most potent PSP) to 313 μg/kg.
Cyanuric acid (CYA) is a microbicide and disinfectant in water treatment applications as
a chlorine stabilizer, but might also be found in the environment from degradation of s-
triazine pesticides. This compound was implicated in renal failure when melamine and CYA
were added to dog and cat food ingredients to boost the apparent protein content of certain
food commodities [144]. These same contaminated food commodites were used in the
production of animal and fish feeds. Karbiwnyk et al. [149] describes an LC–MS/MS method
for the analysis of CYA residues in fish and shrimp muscle. CYA was extracted from ground
fish or shrimp with an acetic acid solution, defatted with hexane, and isolated with a graphitic
carbon black SPE column. Residues were separated from matrix components using a porous
graphitic carbon LC column, and then analyzed with electrospray ionization in negative ion
mode on a triple quadrupole mass spectrometer.
Biogenic amines in fish, cheese and meat products are the result of microbial
decarboxylation and, as such, their presence is indicative of spoilage and compromised food
safety. Adsorbent tubes filled with 70 mg of Tenax TA 60/80 mesh and Carbotrap 20/40
mesh (Supelco) were prepared by Awan et al. [150] to sample the headspace of stored
chicken meat for putrescine and cadaverine spoilage markers. The adsorbent tubes underwent
thermal desorption GC- differential mobility spectrometry analysis.
3.2.7. SPME
Solid-phase microextraction (SPME) is a solvent free method of analyte extraction. In
general, analytes are extracted into a polymetric phase (e.g. poly dimethylsiloxane)
immobilized onto a fused silica fiber. Typical applications include passive sampling ambient
air, headspace sampling, or placing the fiber into an environmental water sample. After
exposing the SPME fiber to the sample, the fiber is introduced into the GC injector where the
analytes are thermally desorbed, separated on the column, and identified by a detector.
Potter and Pawlizyn [151] created an SPME fiber with a Carbopack B stationary phase
and tested the extraction characteristics of a polycyclic aromatic hydrocarbon (PAH) and
polychlorinated biphenyl (PCB) mixed standard. The Carbopack B fibers produced virtually
zero bleed when desorbed at 300 ◦C for 10 min. The analytes tested (naphthalene, anthracene,
benz [a]anthracene, and benzo-[a]pyrene plus two polychlorinated biphenyls, 2,2',5-
trichlorobiphenyl (PCB3) and 2,2',3,4,5'-pentachlorobiphenyl (PCB5)) had excellent
sensitivity and were linear from 10 pg/mL to 2.5 ng/mL. Detection limits were estimated to
range from 7 pg/mL for naphthalene to 1 pg/mL for benzo[a]pyrene. Gierak et al. [152],
created carbon fibers for SPME by methylene chloride pyrolysis. Results of testing the fibers
with benzene, toluene, xylenes, trichloromethane and tetrachloromethane indicated that the
fibers can be used for the analysis of organic substances occurring in trace amounts in air or
liquid matrices. Maeoka et al. [153] quantified PCDDs/PCDFs and co-planar PCBs in soil
samples using an SPME carbon-coated fiber and GC-MS. Best results gave an extraction time
of 40 min under at 25-30 °C. A desorption temperature of 300 °C of SPME fibers coated with
Carbopack B showed the highest response for co-planar PCBs and PCDDs/PCDFs. Until
graphitic carbon black SPME fibers become commercially available, significant method
development in this area is not anticipated. However, work is being done with activated
carbon fibers [154-160], carbon tape SPME fibers [161], Carboxen (carbon molecular sieve)
plus polymer fibers [162, 163], and carbon nanotubes [164-172].
4. NOVEL APPLICATIONS
4.1. SALDI
Surface assisted laser desorption/ionisation (SALDI) is a derivation of matrix-assisted

laser desorption/ionization (MALDI). MALDI frequently relies on light-absorbing
compounds called matrices that are co-crystallized with the analyte to achieve high ionization
and desorption efficiencies. Although this approach offers numerous advantages and is an
indispensable tool in macromolecule analysis, the presence of the matrix also produces a high
chemical background in the region below m/z 700 in the mass spectrum. SALDI substitutes
the chemical matrix of MALDI for an active surface, eliminating matrix interference that is
seen in the m/z region below 700. SALDI mass spectrometry has evolved in recent years into
a technique with great potential to provide insight into many of the challenges faced in
modern research [173]. A great variety of substrates have been reported to work in SALDI
including graphitic carbon black materials. Han et al. [174] developed a method to obtain
laser desorption/ionization mass spectra of organic compounds by depositing sample
solutions onto a carbon substrate surface consisting of a thin layer of activated carbon
particles immobilized on an aluminum support. In common with the porous carbon

suspension samples used in previous SALDI work, the mass spectra contain only a few
―matrix‖ background ion peaks, minimizing interference with analyte ion peaks. A
suspension of glycerol, plus 5% – 10% by weight of sucrose, ensured that the ion signals
were stable over hundreds of laser shots.
Shariatgorji et al. [175] demonstrated that small GCB 4 particles provide a suitable
medium for both the solid-phase extraction of diverse compounds with widely varying
polarities from liquid samples and SALDI analysis of the compounds. The GCB particles
provide a clean spectral background, with no requirements for additives, high SALDI
efficiency, and both reversed-phase and ion-exchange SPE capabilities. The group developed
a GCB-μ-trap to extract three types of compounds (sulfonamides, human medicines, and
organophosphate esters) from water and urine samples. A few particles were removed from
all of the GCB-μ-traps for SALDI screening. Negative samples were discarded, whereas the
rest were extracted and quantified using LC-MS/MS. Chen et al. [176] combined the use of
GCB as an SPE adsorbent and SALDI matrix. Graphitic carbon black SPE tubes were used to
extract trace compounds from aqueous solutions. The GCB particles were then directly
analyzed by SALDI-MS. The group applied this technique to trace levels of phenolic
compounds [176] and quaternary ammonium surfactants [177] in water achieving detection
limits for these compounds in the ppt range. Chen et al. [178,179] also found that surfactants
can be used to enhance the SALDI signal from GCB materials. Amin et al. [180] significantly
enhanced the signal intensity of low-molecular weight compounds analyzed using surface-
assisted laser desorption/ionization time-of-flight mass spectrometry (SALDI-TOF-MS) when
oxidized graphitized carbon black (GCB) particles were used as the desorption/ionization
surface. Using this technique, the group successfully extracted and quantified a common
pharmaceutical compound, propranolol, from Baltic Sea blue mussels using deuterated
propranolol as the internal standard. The calibration curve showed a linear dynamic range of
response (0.1-20 μg/mL) and good reproducibility (RSD <10%). Later Amin et al. [181]
streamlined solid-phase extraction and SALDI-MS by creating GCB extraction disks. In the
same fashion as Empore Extraction Disks, GCB 4 particles (LARA, Rome Italy) were
embedded in a network of polytetrafluoroethylene (PTFE, 3M). The SPE and SALDI
properties of the GCB-4 disks were characterized for 15 pesticides with varying chemical
properties, and the screening strategy was applied to the analysis of pesticides in agricultural
drainage water.
CONCLUSIONS
The advantages of carbon-based adsorbents include high chemical inertness and thermal
stability. It acts as a reversed-phase adsorbent with a particular affinity for aromatic
compounds from aqueous solutions. Thus, the majority of GCB use in sample extractions has
been pesticide analysis. Because the GCB surface is contaminated with positively charged
chemical impurities similar to benzpyrylium salts, GCB also acts as an anion exchanger. This
double nature of GCB offers the advantage over conventional ion exchangers in the extraction
of both charged and uncharged analytes from a complex matrix. Elution of acidic compounds
into different fractions from a GCB extraction cartridge allows for cleaner extracts of a wide
range of compounds.
This allows the application of GCB to more complex sample matrices such as food to be
analyzed for mycotoxins, antibiotics, hormones, dioxins and other contaminants. Surface
assisted laser desorption/ionisation (SALDI) is an innovative use of GCB in sample
extraction (e.g. SPE) and analysis of analytes that will continue to mature, providing
increased mass spectral analysis options of compounds.
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Chapter 4
INTERMOLECULAR AND INTRAMOLECULAR

INTERACTION AT ADSORPTION ON THE SURFACE
OF GRAPHITIZED THERMAL CARBON BLACK
V. V. Varfolomeeva* and A. V. Terent’ev

Samara State Aerospace University named after academician S.P. Korolyov
(National Research University)
ABSTRACT
The display of intermolecular interaction at adsorption on the surface of graphitized
thermal carbon black (GTCB) is not enough described even in theoretical researches.
Scientific literature almost lacks the data about the influence of the intermolecular
H-bond on adsorption of molecules of different classes. Intermolecular H-bond was not

examined as one of the types of intermolecular interaction of adsorbate molecules with
the surface of GTCB. It was considered that physically and mathematically
(energetically) the homogeneous surface of GTCB is not inclined to this specific
interaction. However, the intermolecular H-bond is in fact one of the reasons which
hardens the examination of the intramolecular interaction at adsorption.
At present the only method to calculate the thermodynamic characteristics of
adsorption (TCA), based on the information about the structure of molecules and
allowing predicting this structure is the semiempirical molecular-statistical theory of
adsorbtion for quasi-rigid molecule, proposed by A.V. Kiselev and D.P. Poshkus. This
theory is based on the principle of additivity of the parameters of the intermolecular
interaction adsorbate-adsorbent. On the TCA basis it is possible to predict the interaction
of which conformational isomer with the surface of GTCB will be stronger. However, the
semiempirical molecular-statistical theory of adsorbtion does not take into consideration
the influence of the intramolecular H-bond, intermolecular H-bond and the sorbent force
field on the adsorbate geometry. The solution of this question will be possible if the
approaches are found allowing calculating the TCA taking into account the specific
interactions (intra- and intermolecular H-bond) under the influence of the sorbent force
field. Such calculations will allow explaining on the molecular level the reasons of
difference of the TCA of structural conformers of the compounds, stable in the gas phase
*
443086, Russia, Samara, Moskovskoye Shosse, 34; e-mail: varf2@ssau.ru
94 V. V. Varfolomeeva and A. V. Terent‘ev
and in the adsorbed state. Not using the quantum-chemical methods with minimum
permissible level of the calculations of the hydrogen-bonded molecular systems (for
example, MP2/6-311++G(d,p) and B3LYP/6-311++G(d,p)), it is not possible to obtain
the structural-energetic parameters of the conformational isomers to calculate their TCA.
The presented chapter shows the possibility of using the ab initio and DFT methods
in combination with the semiempirical molecular-statistical theory of adsorbtion for TCA
calculations of the conformation isomers of molecules taking as the example the aromatic
alcohols, amines and thiols. The detailed examination of adsorption of these compounds
on the GTCB taking into account the hydrogen bond, its exact qualitative characteristics
and quantative specification is important for clarifying the specific features of the
separate class of compounds. It is interesting to show how the situation of lone electron
pair, increase of the chain length by the -CH2 group, differentiation in electron-donor,
electron-accepting and repulsive possibilities of oxygen, nitrogen and sulfur atoms affect
hydrogen bond formation. The difficulty of the examination of the chosen object is
determined by the comparability of the values of the barriers of internal rotation with the
benefit in the heat of adsorption at the expense of the change of molecule conformation
while getting into in the GTCB force field. The results of the optimization of the
adsorbate molecules on the model fragment of the GTCB by the DFT method have
confirmed the forecast about the possibility to form the intermolecular H-bond by -OH,
-NH2, -SH groups together with graphite π electrons, which was of made by us earlier
To calculate the TCA of the molecules the automotized system is proposed in the
new version of which the integration of all the stages of the calculation in one and the
same program system is the necessary demand to provide the TCA calculation: the initial
data input, carrying on the TCA calculations, visualization of the results, saving the final
results in the data base. The analysis of the initial and calculating data is possible with the
help of the graphic module which allows to visualize the 3D molecule model on the
GTCB surface, create the 2D and 3D diagrams of the dependence of the TCA on the
torsion angles, draw the contour maps of the potential energy surface. The modules are
also worked out with the help of which it is possible to carry on the variation of the atom-
atom potential (AAP) parameters and examine all the possible ways of conformational
transfers (variation of the torsion angles). The special attention is paid to the preparation
of the geometric parameters of the molecule in the gas phase and adsorbed state.
The results of the search can form the fundamental basis for qualitative and
quantitative examination of the display of intermolecular interaction at adsorption on the
surface of GTCB.
INTRODUCTION
Within a framework of our research we put a problem of studying the influence of the
hydrogen bonds on the conformations of flexible molecules in the adsorption field of the
graphitized thermal carbon black (GTCB). The aromatic alcohols, amines and thiols with
several internal rotation angles are of a great interest here. The presence in the molecule of
several internal rotation angles leads to the molecule existing as set of conformers. While
experimentally defining the adsorption equilibrium constant (Henry constant К1) the average
value of all the conformations is found taking into account their mole ratio. The Henry
constant К1 characterizes the intermolecular interactions ‗adsorbate-adsorbent‘. At the
adsorption on the GTCB these interactions depend much on the geometry of the molecule of
adsorbate. In view of this fact the theoretical calculations of the thermodynamic
characteristics of adsorption (TCA) in many cases are the only means to single out the table
Intermolecular and Intramolecular Interaction at Adsorption … 95
conformational isomers in the adsorption state. However, nowadays the calculations of the
TCA for the flexible molecules of the aromatic hydrocarbons are complicated and not much
reproducible. The complexity of the research of the chosen objects is determined by the
comparability of the values of the internal rotation barriers with the heat of adsorption gain at
cost of the conformation of the molecule change when it gets into the GTCB force field.
Besides, the intermolecular H-bond is one of the reasons which complicate the study of the
intramolecular interaction at adsorption.
The display of the intramolecular interactions at adsorption on the surface of the GTCB is
not described in detail even in the theoretical researches. The literature almost lacks the data
about the influence of the intramolecular H-bond on the adsorption of molecules of different
classes. As a rule there are no serious problems defining the geometry of molecule in the gas
phase. A contemporary computer and the relevant software in the laboratory is sufficient for
this. At the concrete choice of the computational method the theoretical and experimental
results agree well. The systematized methodological basis for finding the geometry of the
flexible molecules in the adsorbed state does not exist. In this case in this case while
calculating the TCA sometimes the force field of the sorbent influence is neglected and the
data obtained for the gas phase is used. For the flexible molecules with several internal
rotation angles this can become the reason of an error.
In the present chapter we propose a complex of the complementary computational
calculation methods for the TCA of the flexible molecules definition with regard to their
geometry change at the adsorption. In terms of the task of the present chapter the
intermolecular interaction adsorbate-adsorbate was not taken into account, the calculations
were conducted for the Henry region. For the TCA calculations the semiempirical molecular-
statistical theory of adsorption was used [1, 2]. For the aromatic alcohols and amines the
calculated TCA are close to the experimental values.
SEMIEMPIRICAL MOLECULAR-STATISTICAL THEORY OF

ADSORBTION FOR QUASI-RIGID MOLECULE.
ASSUMPTIONS AND LIMITS OF APPLICATION
Semiempirical molecular-statistical theory of adsorption [1, 2] allows to calculate the
TCA, including the retention characteristics of the organic molecules of different classes. The
advantage of this theory is that in the calculation it uses the real geometrical structure of
molecule, defined either by different methods, such as electron diffraction, molecular
spectrum analysis, X-ray diffraction analysis or modeled on the base of regularities in valence
angles and bond lengths change. However, the reliable parameters of molecular structure are
defined for the limited number of compounds and usually are absent for the majority of
isomers. In case of isomers only with the help of the calculation of the TCA based on the real
data it is possible to identify them reliably [3]. But here while calculating the Henry constants
К1 great difficulties occur, first of all because the calculation based on the atom-atom
approximation cannot take into account the differences in the polarizability of isomers [4]. To
consider these differences various allowances are used [5-7]. Introduction of the allowances
in the polarizability often does not permit to archive the satisfactory correspondence of the
experiment and the calculation. In the science paper [1] it is noted that the К1 considerably
depends on the form of the atom-atom potential (AAP). That is why in calculation of the TCA
in is necessary to use a more theoretically proved form of the AAP. But numerous
parameters, laid in the calculations of the semiempirical molecular-statistical theory of
adsorption are the adjustable coefficients which do not have the strict physical sense and are
often selected on the base of trials and errors. For this reason such methods do not permit to
conduct the a priori calculations based only on the molecule characteristics data, which were
obtained by the independent methods. Moreover, molecular-statistical theory of adsorption at
the present time does not take into account the influence of the intra- and intermolecular
H-bond on the molecule adsorption as well as of the sorbent force field on the adsorbate
geometry. Such approach does not give the exact information about the structure of
compounds able to create hydrogen bonds in the gas phase and in the adsorbed state.
Consequently while defining their TCA the assumptions are used which can affect the
accuracy of the calculation.
By the present time the molecular-statistical calculation of the TCA have been conducted
for the large number of the adsorbents and adsorbates [8-21]. Extensive experimental material
about the adsorption of the organic compounds of different classes is accumulated [1, 4,
22-29]. Analyzing the scientific literature it becomes clear that comparing with all the known
carbon sorbents the GTCB characterized by the greatest homogeneity of the surface and the
geometry and chemistry of which is quite well studied is of the special interest. Adsorption on
such surface takes place mostly at the expanse of dispersion (nonspecific) interaction of
sorbate molecules with this surface [1, 2, 30]. In case of the GTCB the predominant
dependence of the nonspecific interaction energy on the distance between the adsorbent flat
surface and molecule force centers displays to the fullest extent. In other words, the spatial
arrangement of atoms in the adsorbate molecule in many cases becomes the determinative
factor in the separation of the compound mixtures of the structural and geometrical isomers
on the GTCB. The examples of such separations obtained by different authors are to be found
in the following works [31-34]. However it is necessary to point to the certain limits in the
GTCB definition only as the nonspecific adsorbent. Traditionally it was considered that this
sorbent is not inclined to the intermolecular specific interactions with adsorbate molecules.
But with the ambient temperature the display of the weak specific interaction with the sorbent
π electrons is possible. However, if the adsorbates the inert gases, cyclanes, n-alkanes,
n-alkenes, n-alkynes or the molecules with rigid carcass are incapable of the specific
interactions, then it is not necessary to take into account the intermolecular H-bond with the
GTCB surface. It is on these objects was the semiempirical molecular-statistical theory of
adsorption for quasi-rigid molecule created and tested. In the calculation of the TCA the
assumption is made that the molecules are quasi-rigid as the majority of molecules have quite
small amplitude of nuclear motions in comparison with the internuclear distance. This is one
of the theory restrictions which is connected with the incapability of the molecules of internal
rotation, internal rearrangement and preservation of their configuration at adsorption. For
known reasons the intramolecular effects and the intermolecular specific interactions at
adsorption under the influence of the force field of the sorbent were not studied. The
maximum development the molecular-statistical calculations archived for the system ―the
GTCB – hydrocarbons and their derivatives‖.
We should note that the nature of the intra- and intermolecular forces in general and that
of the specific interactions (intra- and intermolecular H-bond) in particular is not simple.
They are determined by the simultaneous impact of a great number of factors, so it is not
possible to narrow down these forces to elementary interactions. Relying on the energy
additivity of the intermolecular interaction with the GTCB in separate fragments or atoms of
these molecules and taking into account that the sorbent surface is extremely sensitive to the
structure of molecule, it is possible to examine the influence of the force field of the
GTCB on the geometry of the flexible molecules of adsorbate. Thus, the aromatic alcohols,
amines and thiols studied in this paper belong to the typical class of flexible molecules
[35-39]. They can exist in several conformations connected with the geometry of the inner-
rotating -OH, -NH2 and -SH groups and the examination of these compounds always attract
special attention [39-45]. In [46] with the example of the benzyl alcohol the possible
intramolecular CH···O interaction was shown, to which the force field of the GTCB
contributes. The explanation of intramolecular effect is the uniqueness of origin of the
molecule own conformational transitions for each stable conformer. Moreover, the
intermolecular H-bond formed with the GTCB π electrons stabilizes the conformation with
intramolecular CH···O H-bond. These peculiarities of adsorbates behavior on the surface of
the GTCB with participation of the intermolecular H-bond were used by us in the description
of the intramolecular interactions at adsorption of the aromatic alcohols, amines and thiols.
In [2] A.V. Kiselev writes: ―The direction of further studies on the GTCB depends on the
problems we will set‖. Within the framework of our research we have set the task to study the
hydrogen bonds influence on the conformation of the flexible molecules with several internal
rotation angles in the adsorption GTCB field. To fulfill this task it is necessary to find the
approaches which permit to calculate the TCA taking into account the intra- and
intermolecular H-bond under the influence of the force field of the sorbent for different
classes of organic compounds. Such calculations will allow the explaining on the molecular
level the reasons of difference of the TCA of compounds structural conformers stable in the
gas phase and in the adsorbed state. On the base of the calculation of the TCA it is possible to
forecast the interaction of what conformational isomers with the surface of the GTCB will be
stronger. With this viewpoint the study of the intermolecular H-bond at adsorption on the
GTCB is of the great interest both for the molecular theory of adsorption itself and for the
theory of the intermolecular interactions in general.
The use of basic molecules as well as the lack of regard of the molecule conformation
change in the force field of the GTCB is one more assumption at the calculations of the TCA.
The use of basic molecules does not allow taking into account the influence of the specific
interactions such as hydrogen bond and conjugation, alteration of the inner strain at the
substituent introduction, alteration of the chain mobility under the influence of the
intramolecular forces and the outer field of the sorbent. With the example of the o-
phenylenediamine quasi-rigid at adsorption we showed the necessity to regard all these
interactions at the calculation of the TCA, as well as the particular influence of the
intramolecular NH···N H-bond on the retention characteristics [33]. In some cases the
researchers suppose that the diversity in the calculated values and the experiment results are
connected with lack of the regard of the specifics the concrete compound specifity [16].
However, in many cases the weak specific interactions can be veiled. The nonobviousness of
these effects while using the basic fragments leads to the necessity to introduce the
allowances for the AAP not only for each atom sort but also it can lead to the correction of
the potentials values within the narrow classes of compounds. Moreover, after the empirical
specification of the AAP the borderlines of its application often are not exactly defined. All
the abovementioned factors create additional difficulties for the AAP choice and can become
the reason for the incorrect calculation not only for the molecules with the strained structure,
voluminous substituents, several heteroatoms and their uncommon combinations, but also for
quite simple molecules. Accumulating the experimental material and extending the circle of
the compounds studied we encounter more and more molecules the TCA of which cannot be
forecast with the satisfactory exactness. Thus, the promiscuous use of the basic molecules and
no regard of the influence of the force field of the sorbent on the conformation of the
compounds studied may lead not only to the loss of the physic of the process understanding,
but also it can lessen to the great extent the theory value [47].
MOLECULAR-STATISTICAL CALCULATION METHODS

We calculated the TCA for benzyl alcohol (BA), 1-phenylethanol (1-PE), benzylamine
(BAm), 1-phenylethylamine (1-PEAm), benzylmercaptan (BM), and 1-phenylethylmercaptan
(1-PM) using the molecular-statistical method.
In this method, the Henry constant K1 for the adsorption of quasi-rigid molecules is
calculated by the equation [1, 2]:
1 2
1 2𝜋𝑘𝑇 Φ0
𝐾1 = exp − sin 𝜃 𝑑𝜃 𝑑𝜓,
4𝜋 Φ"𝑧 𝑘𝑇
where Φ0 and Φ𝑧" are the potential function  for the interaction between adsorbate and
adsorbent molecules at the potential minimum and its second derivative with respect to the
distance z between the center of mass of the adsorbate molecule and the surface of the
adsorbent in the equilibrium distance z0;  and  are the Euler angles which determine the
orientation of the molecule with respect to the surface of the adsorbent.

To define the potential energy of interaction of the adsorbate molecule with GTCB the
atom–atom approximation is used:
Φ= υ𝐴 𝑀 …𝐶(𝐺𝑇𝐶𝐵)
,
𝐴(𝑀) C(GTCB )
where A(M) and C(GTCB) – atom of the adsorbate molecule and the adsorbent atom
correspondingly.
To define the AAP of the intermolecular interaction the Buckingham–Corner potential is
used
υ𝐴 𝑀 …𝐶(𝐺𝑇𝐶𝐵)
= −𝐶1 𝑟 −6 − 𝐶2 𝑟 −8 + 𝐵 exp −𝑞𝑟 ,
where C1 and C2 are parameters of the attraction, B and q are the repulsion parameters and r is
the interatomic distance. The atom-atom potential parameters were taken from [3]; they are
listed in the Table 1.
Table 1. AAP parameters for interactions of various atoms

with the carbon atom of the GTCB
C1, C2, B,
Atom
kJ m6/mol kJ m8/mol kJ/mol
C (sp3) -1.5750 -0.14530 8491.00
C (sp2) -1.6853 -0.15547 9085.37
H -0.5672 -0.06400 5214.40
O -1.1194 -0.11005 3250.02
N -1.6318 -0.26445 6194.36
S -3.8672 -0.45069 26759.81
This method allows the TCA of molecules on the GTCB to be calculated for various
conformations and temperatures. The results can be used to predict the interaction energies
between the GTCB surface and various conformers.
The variation of torsional angles in all possible conformational transitions and
calculations of TCA were performed using the automatic system [48] intended for studying
the adsorption and chromatographic behavior of compounds of different types. In the renewed
version of the automated system there exists the possibility to choose exactly the angle for the
observation of the molecule and its separate fragments position regarding the sorbent surface.
This is important for the establishment of the fact of the intermolecular interaction on the base
of not only the calculated distances XH···πGTCB but also considering the orientation of the
-XH group (figure 1).
Figure 1. The window of the TCA automated calculation system. In the picture there is the BA I′a
conformer of benzyl alcohol with intramolecular CH···O and OH···πGTCB H-bonds.
In order to specify the geometry of the molecules under consideration in the gas phase
and in the adsorbed state, we conducted a series of quantum-chemical calculations.
QUANTUM-CHEMICAL CALCULATIONS OF THE MOLECULAR

STRUCTURE AT ADSORPTION ON THE GRAPHITIZED THERMAL
CARBON BLACK
To obtain the exact the TCA within the quasi-rigid molecule approach it is necessary to
know the conformations of molecules in the adsorbed state. The quantum-chemical methods
of calculations can become the additional instrument to define the stable conformers on the
sorbent surface. They permit to simultaneously obtain all the range of the molecular
characteristics, which is impossible to do using any experimental method, and for some cases
they are the only information source about their structure. In the presented chapter using the
example of the aromatic alcohols, amines and thiols, we show the possible application the
ab initio and the density functional theory (DFT) methods together with the semiempirical
molecular-statistical theory of adsorption to find the TCA of the molecules conformational
isomers. Conduction of the detailed examination of these compound adsorption on the GTCB
with the account of the hydrogen bond, its reliable qualitative characteristics and quantitative
specification is of a great importance for clear out the particularities of a separate class of
compounds. Without the quantum-chemical methods application with the minimum
recommended calculation level of the molecular systems with hydrogen bond (for example,
МР2/6-31+G(d,p) or B3LYP/6-31+G(d,p) [49]) it is not possible to obtain the structure-
energy parameters of conformational isomers for calculation of their TCA.
The specifics of the objects studied consists in the considerable influence of the weak
hydrogen bonds on the compounds structure-energy characteristics. The hypothesis was made
that the most stable forms of the molecules in the gas phase can be stabilized by the
intramolecular interaction between hydrogen, connected with nitrogen, sulfur or oxygen and
π electron cloud of the aromatic ring, to which the flexible side chain contributes. In [36, 38,
41, 43, 45, 50, 51] results of the spectroscopic method research showed that two conformers
of the benzyl alcohol: gosh-conformer with intramolecular OH∙∙∙π H-bond and anti-conformer
with free -OH group exist in the gas phase. The calculations at the HF/6-31G(d), МР2/6-
31G(d), МР2/6-31G(d,p) and etc. levels qualitatively proved the existence of these structures
[36, 41-44]. However, the calculated values of the angle Cortho-Cipso-Cα-O for conformers with
intramolecular H-bond, depending on the method, can be equal τ1 = 22–57. The minimum
recommended calculation level for the systems with hydrogen bonds [49] presupposes the use
of diffusion functions. In the flexible benzyl alcohol molecule weak intramolecular H-bonds
influence considerably its geometry of the molecule, that is why it is reasonable to use two
diffusion and two polarization functions, as well as the split-valence basis sets 6-311G.
Parameters τ1 = 58.3, r(O…Cipso) = 2.44 Å and r(H…Cipso) = 2.54 Å calculated at the
MP2/6-311++G(d,p) level [46] agree well with the electron diffraction results [52]: τ1 = 54,
r(O…Cipso) = 2.45 Å и r(H…Cipso) = 2.53 Å.
The calculation of the potential energy surface (PES) of the benzyl alcohol and
1-phenylethanol was conducted at the B3LYP/6-311++G(d,p) level. At that the Cortho–Cipso–
Cα–O and Cipso–Cα–O–H angles were verified at 10 interval. Two stable conformers of
benzyl alcohol were obtained: gosh-conformer BAI with intramolecular OH∙∙∙π H-bond and
anti-conformer BAII (figure 2a, 2b). Despite the energetic preference of the gosh-conformer,
anti-conformer possesses a better population [46]. It is connected with a greater mobility
around the Cipso–Cα bond, to which the CH···O interaction in the range of 1 ≈ 30 contributes.
Such interaction compensates the hydroxyl group repulsion from the benzene ring, decreasing
the rotation barrier.
Figure 2. Stable conformers of benzyl alcohol in the gas phase (a – BAI, b – BAII) and in the adsorbed
state (c – BAIIa).
The formation of the intramolecular OH∙∙∙π H-bond in gosh-position of the

1-phenylethanol molecule is analogical to the benzyl alcohol (figure 3a). In the anti-
conformer the -CH3 group repulsion from the benzene ring and the possible formation of the
CH···O hydrogen bond (figure 3b) leads to the reduction of the 1 angle declension from the
benzene ring plane is 34.2 (table 2). The PES of the 1-phenylethanol molecule obtained
(figure 3I) agrees well with the results of [53]. In BAI, 1-PEI and 1-PEIII conformers the
distance between the hydrogen hydroxyl group and the nearest carbon aromatic ring equals
2.54 Å, and the O-H…Cipso angle ≈ 73. In 1-PEIII simultaneous formation of two
intramolecular H-bonds is possible (figure 3c) [53]. However, the intramolecular OH∙∙∙π
H-bond weakens the CH···O interaction. In case of 1-PEII r2 is less at 0.10 Å, whereas the
declension of the oxygen from the benzene ring plane is more at 10.6. Despite the existence
of two intramolecular H-bonds 1-PEIII loses in the energy quantity to 1-PEI and 1-PEII
conformers. This is connected with the methyl group repulsion the benzene ring.
Copyright © 2011. Nova Science Publishers, Incorporated. All rights reserved. 102 V. V. Varfolomeeva and A. V. Terent‘ev
Figure 3. Stable conformers of the 1-phenylethylamine in the gas phase (a – PEAI, b – PEAII, c –
PEAIII) and in the adsorbed state (d – PEAIa), as well as the PES of the 1-phenylethylamine (I) and the
difference in the adsorption heat at T = 413 K and the electronic energy in all the possible diapason of
the conformer transactions (II).
Scheme.
Table 2. The structural and energetic characteristics of the aromatic alcohols, amines and thiols in the gas phase, calculated by the
MP2/6-311++G(d,p) method, and the retention values calculated for them (lnK1 [K1, cm3/m2])
lnK1
τ1 τ′1 τ2 τ′2 ΔE0 r1 α1 r2 α2
T = 413 T = 463
BAI 58.3 --- 52.8 --- 0 2.54 73.4 2.85 88.1 0.87 -0.51
BAII 60.6 --- -173.3 --- 5.0 --- --- 2.81 86.3 1.43 -0.02
BAmI 87.3 --- 57.8 -57.8 0.4 2.71 67.8 --- --- 1.44 -0.03
BAmII 51.0 --- 62.7 -179.6 0 2.66 66.4 2.72 90.7 1.23 -0.17
BMI 82.2 --- 52.2 --- 0 2.80 75.4 3.47 83.1 1.74 0.24
BMII 92.0 --- 179.9 --- 1.6 --- --- 3.58 78.6 1.77 0.26
1-PEI 42.4 -76.5 53.0 --- 0 2.54 73.2 2.67 92.5 1.03 0.33
1-PEII 34.2 -87.4 -170.3 --- 5.8 --- --- 2.49 94.4 2.37 0.75
1-PEIII 135.2 9.8 -57.5 --- 9.8 2.54 72.1 2.59 93.2 2.45 0.84
1-PEAmI 43.1 -76.6 62.1 179.8 0 2.66 66.3 2.60 93.8 1.45 0.05
1-PEAmII 55.7 -68.0 48.4 -68.3 3.6 2.66 70.9 --- --- 1.26 -0.11
1-PEAmIII 122.0 -5.2 -61.4 -178.4 10.1 2.61 67.6 2.73 89.0 2.69 1.05
1-PEMI 62.6 -58.6 47.7 --- 0 2.77 76.6 3.11 91.3 1.41 0.04
1-PEMII 69.7 -54.0 -177.2 --- 1.5 --- --- 3.16 86.6 1.51 0.13
1-PEMIII 78.9 -48.7 -62.5 --- 3.2 2.89 71.5 3.81 75.6 1.59 0.18
Torsion angles, deg.: τ1 – Cortho-Cipso-Cα-X; τ′1 – Cortho-Cipso-Cα-Cβ; τ2 – Cipso-Cα-X-H; τ′2 – Cipso-Cα-N-H′ (see scheme). ΔE0 – the value of the electronic energy
related to the most stable conformer, kJ/mol. r1 – the distance between the hydrogen of -XH group and the closest atom of the carbon of the benzene ring
Cipso, Å; r2 – the distance between the hydrogen connected to the Cortho of the benzene ring and the atom X, Å. α1 – valence angle XH…Cipso, deg.; α2 –
valence angle CorthoH…X, deg. The distances and the valence angles at the evident impossibility to form the hydrogen bond are not pointed out. T –
temperature, K. X – O, N or S atoms.
21009.
To find out the PES of benzylamine, benzyl mercaptan, 1-phenylethylamine and

1-phenylethyl mercaptan the rotation of Cortho–Cipso–Cα–X, Cipso–Cα–X–H angles (X = N, S)
at the PBE0/6-311++G(d,p) level with 10 interval and the optimization of the geometry at
every point was carried out. The obtained stable conformers of aromatic amines and
mercaptans were optimized at the MP2/6-311++G(d,p) level.
In benzylamine case the existence of two hydrogen atoms, connected with nitrogen atom
makes possible the formation of the bifurcated NH···π hydrogen bond in gosh-position (figure
4a). At this the symmetrical molecule conformer with 1 = 87.3 stabilizes. One hydrogen
atom of the amino group being in anti-position, the second oriented to the benzene ring, the
intramolecular H-bond also forms (figure 4b). These stable conformers almost do not differ in
energy. To formation of the bifurcated hydrogen bond the contribution of each component
decreases because of the steric factor. Thay is why such bifurcated interaction can
compensate the drawbacks of the gosh-form and the formation of the intramolecular H-bond
in the anti-conformer, but it does not leade to the energy gain. Whereas in the beveled
conformer of benzyl alcohol (1 = 58.3), the energy of the hydrogen bond is enough not only
to compensate the steric drawbacks of the gosh-form , but also to gain in the energy quantity
in comparison with the anti-conformer в 5.0 kJ/mol (table 2).
Figure 4. Stable conformers of the benzylamine in the 1-phenylethylamine (a – BAmI, b – BAmII) and
in the adsorbed state (c – BAmIa, d – BAmIIa).
In 1-phenylethylamine molecule NH···π interaction competes with the intramolecular

CH···N H-bond. Like in the benzylamine case hydrogen atoms of the amino group 1-PEAm
interact with π electrons of the benzene ring forming gosh- and anti-conformers. That is why
in all stable conformers of 1-phenylethylamine the intramolecular NH···π H-bond forms.
Compatible values of r2, α2 and τ1 in the 1-PEAmI and 1-PEIII conformers (table 2) speak well
for the weak CH···N interaction in amine.
In the stable conformers of benzyl mercaptan and 1-phenylethyl mercaptan (table 2)
compared to alcohols analogical in structure one can observe a considerable declension from
the plane of -SH group. Energy values of anti- and gosh-conformers are alike, which
witnesses a weaker force of the intramolecular H-bond with aromatic π conjugated system.
This is connected with a strong sulfur atom repulsion from the benzene ring. In aromatic
alcohols, amines and thiols the hydrogen bond energy the more stronger the more is the
electronegativity of the partner atom and the less are its sizes. In thiols the sulfur atom big
size makes the formation of the intramolecular CH···S H-bond unprofitable.
Quantum-chemical calculations of the derivative aromatic hydrocarbons are carried on in
different directions. To single out the preferable conformers at adsorption on the GTCB we
used two methods. The first one is concluded in the comparison of the molecule potential
energy of the molecule which takes into account the intramolecular interactions, with the heat
of adsorption which takes into account the influence of the GTCB force field in all the
possible diapason of conformational transitions [33, 46, 54, 55]. The difference of the
adsorption heats in all the possible diapason of conformational transitions was defined with
the help of the automated system of the TCA calculations [48]. The rotation was carried on
with the same angles and intervals, as those used to calculate the PES. The AAP parameters
used for the calculations are to be found in the table 1. After the comparison of the difference
of the adsorption heats with the PES the preferable conformers at adsorption were singled out
(table 3). In the table and in the text such conformers are defined be the bottom index ―a‖.
In our research paper [55] we noted that in some cases one should find not only the
molecule energetic minimums at adsorption but also the possibility to overcome the potential
barrier on the way of the transaction of the stable conformers in the gas phase to the
conformers preferable at adsorption. For the compounds under consideration from the PES
calculated it is clear that the barrier of the rotation around any mobile connection is
considerably lower 30 kJ/mol (figure 3I). The heats of adsorption are considerably higher 40
kJ/mol. Thus we can suppose that the time of the elementary adsorption act surpasses
considerably the time of the conformational transactions of the adsorbate molecules
themselves. In this case the greater majority of the elementary adsorption acts will be
accompanied by the adsorbate molecule transaction to a state more preferable energetically.
Then the additional study of the possibility to overcome the potential barrier is not necessary.
The second method was used to define more exactly the geometry of the molecules in the
adsorption state. To reach this the optimization of the compounds under investigation on the
GTCB structural fragment [46]. By the way of the gradual increase of the hexagonal aromatic
rings quantity the optimum (from the computational costs viewpoint) size of the carbon
fragment was found. In our opinion to obtain the reliable structural characteristics it is
sufficient to choose a fragment that is bigger than the projection of the molecule at 1.5-2.5
hexagonal aromatic rings on each side. For the objects under investigation a fragment of the
grapheme was chosen, consisting of 112 carbon atoms, forming 44 hexagonal aromatic rings,
with 26 hydrogen end atoms. Optimization of the objects on such a fragment requires
considerable computational resources. Opposed to the energetic characteristics, the definition
of the geometrical parameters does not depend so much on the basis set choice [56]. That is
why while optimizing the molecules under investigation on the GTCB fragment we agrees to
the decrease of the basis set chose the PBE0/6-31G(d) method. From scientific researches
[57, 58] it is known that the use of the PBE0 functional is one of the most efficient methods
of calculating the structural and energetic properties of large systems. The correct data about
the molecule in the adsorbed geometry obtained by this method permit to prove the prognosis
made by us in [46], which consists in the possibility of formation of the intermolecular H-
bond with π electros of the GTCB by -OH, -NH2 and -SH groups. Conformers obtained at
optimization on the GTCB fragment are defined by the bottom index «a» in this chapter.
The calculations were performed using the PC GAMESS software for quantum chemical
calculations [59].
THE RESULTS DISCUSSION

To find out the molecule geometry in the GTCB force field there were proposed two
methods described in the previous part. On the base of the conducted experiment in the same
diapason of temperatures we attempted to evaluate the application limits of these methods
aiming at the determination of the further researches direction.
First Method
Two conformers stabilize in benzyl alcohol at adsorption. The first one (figure 1) is
similar to the gosh-conformer (figure 2a) in the gas phase. However, because of the GTCB
force field gravitation the -OH group comes closer to the benzene ring the forming the
intramolecular CH···O H-bond in such position there appear a possibility of the
intermolecular H-bond between the –OH group and the π electrons of the GTCB [46, 54]. The
formation of the intermolecular H-bond in the BAI′a conformer and the decrease of the
Cipso-Cα angle lead to the weakening of the intramolecular OH···π H-bond. Compared to the
BAI the r1 increases at 0.1 Å (table 2, 4), and the angle α1 decreases to 68.4º (the angle of
alteration from the right line increases). It has to be noted that in the 413-463 К temperature
diapason the contribution of the intermolecular H-bond is not considerable that is why in is
not taken into account in the calculations. Hereinafter under the term ―intermolecular H-
bond‖ the potential possibility to form this very bond is meant.
In the BAII the mobility around the Cipso-Cα, bond connected with the absence of the
intramolecular OH···π H-bond allows the structure with the intramolecular CH···O H-bond to
stabilize without any energetic difficulties. This leads to the fact that the less preferable anti-
conformer becomes preferable at adsorption (figure 2c). The calculated values of the Henry
constant of the BAIIa and BAII′a (table 3 and 4, correspondently) conformers well agree with
the experiment results(figure 5a).
For the benzylmercaptan molecule two structures stable at adsorption were singled out
(table 3): the gosh-conformer with the perpendicular related to the benzene ring plane
position of the –SH group and the plane conformer. The difference in the energy of these
conformers is not that considerable as compared to analogous alcohols. Unlike the BAIIa, the
BMIIa is not stabilized be the intramolecular CH···S H-bond. In connection with this in the
experiment conditions the Henry constant can turns out to be much less than the value
calculated for the BMIIa (lnK1 = 3.10).
Table 3. TCA of the aromatic alcohols, amines and thiols calculated for the stable conformer at adsorption on the GTCB, found by the
difference in the adsorption heat for different temperatures (Δq(T), kJ/mol) with the electronic energy difference (ΔE0, kJ/mol), and the
comparison with the experiment results
Δq(T)-ΔE0 Δq(T)-ΔE0 lnK1

τ1 τ′1 τ2 τ′2 T = 413 T = 463
T = 413 T = 463
calc exp calc exp
BAIa 80 --- 50 --- 1.5 1.3 1.06 -0.36
2.12 0.60
BAIIa 20 --- -170 --- 3.9 4.0 2.04 0.47
BAmIa 10 --- 70 -170 3.9 4.0 2.27 0.70
2.29 0.77
BAmIIa 0 --- 60 -60 4.5 4.5 2.37 0.77
BMIa 80 --- 60 --- 1.4 1.3 1.69 0.20
--- ---
BMIIa 0 --- 70 --- 2.0 2.2 3.10 1.39
1-PEIa 20 -100 190 --- 5.71 5.37 2.53 0.89
2.63 1.04
1-PEIIa 20 -100 60 --- 2.75 2.49 1.63 0.16
1-PEAmIa 10 -110 60 180 4.9 3.9 2.52 0.91
1-PEAmIIa 10 -110 170 -70 3.4 2.0 3.11 2.64 1.40 1.09
1-PEAmIIIa 10 -110 -70 50 3.2 3.5 2.55 0.93
1-PEMIa 110 -10 -60 --- 7.7 7.1 3.05 1.34
1-PEMIIa 110 -10 170 --- 6.0 5.6 3.24 --- 1.53 ---
1-PEMIIIa 110 -10 50 --- 4.3 3.9 3.25 1.54

Torsion angles, deg.: τ1 – Cortho-Cipso-Cα-X; τ′1 – Cortho-Cipso-Cα-Cβ; τ2 – Cipso-Cα-X-H; τ′2 – Cipso-Cα-N-H′ (see scheme). K1 – the Henry constant, cm3/m2. T –
temperature, K.
21009.
1-phenylethanol, 1-phenylethylamine and 1-phenylethylmercaptan on the GTCB surface

tend to situate one of the groups in the benzene ring plane (table 3, 4). This is connected with
the fact that the energy gain at adsorption with such a position surpasses the energy of this
group repulsion from the adsorbate benzene ring. At adsorption in 1-phenylethanol anti-
conformer 1-PEIa with intramolecular CH···O H-bond stabilizes. Whereas -OH group is
closely situated to the benzene ring plane (figure 3d). The calculated retention values for
1-phenylethanol well agree with the experiment results (figure 5a). In 1-phenylethyl-
mercaptan the intramolecular CH·S H-bond is not preferable because of the voluminous S
atom. At adsorption the conformer 1-PEMIa with the -CH3 group position in the benzene ring
plane and stabilized by the intramolecular SH···π H-bond is more preferable.
In benzylamine like the benzyl alcohol the plane conformer with intramolecular CH···N
H-bond (figure 4c) stabilizes at adsorption. However beside it one observes the conformer
without the intramolecular H-bond (figure 4d). In this conformer the aminogroup H atoms are
in the gosh-position symmetrically as related to the benzene ring plane (figure 4d′). I such
stagnated position the first H atom repulsion counteracts the second H atom declension from
the benzene ring plane and vice versa. The symmetrical position at adsorption on the GTCB
results in the conformer BAmIIa being a little more profitable than the conformer BAmIa with
the intramolecular CH···N H-bond. The retention values calculated while comparing the
difference in the heat of adsorption and the PES well agree with the experiment results
(table 3, figure 5b). It is worth mentioning that both conformers can contribute considerably
to the retention values. However, because of the proximity of their Henry constants within the
framework of the research it is not possible to unambiguously define how much the
population of the conformer BAmIa at adsorption is.
Figure 5. The values of the Henry constant lnK1 [K1, cm3/m2] depending on the reverse temperature T,
K. Thin and dotted lines are the retention values, calculated for stable in the gas phase conformers; fat
lines are the retention values calculated with the account the conformation change under the influence
of the GTCB force field; the dots are the experimental values. On the figure 5a: the rounded dots and
the uninterrupted lines belong to the benzyl alcohol; the lozenges and dotted lines – to the
1-phenylethanol. On the figure 5b: rounded dots and the uninterrupted lines belong to the benzylamine;
the lozenges and dotted lines – to the 1-phenylethylamine.
The 1-phenylethylamine conformer 1-PEAmIIIa, analogous to the conformer BAmIIa, is

the competitor of the conformer 1-PEAmIa with the intramolecular CH···N H-bond (table 3).
But it is not that much energetically profitable because of the methyl group which destructs
the symmetry. That is why the the conformer 1-PEAmIa with the aminogroup in the benzene
ring plane is the most stable in the adsorbed state like that of the 1-phenylethanol. This
conformer is stabilized by the intramolecular CH···N H-bond and is able to form the
intermolecular H-bond π electrons of the GTCB.
Thus, using the first method it is possible to obtain the retention values comparable with
the experiment results (figure 5). There are however some drawbacks in this method which
are to be taken into consideration. These are the possible inaccuracies connected with the
variation interval, with the incomplete correspondence of the states in which the heats of
adsorption and the electronic energies are calculated as well as neglection of the
intermolecular H-bond formation.
Second Method
While defining the stable conformers in the adsorbed state using the second method we
oriented on the results obtained by the first method (table 3). We got a good agreement of
structural characteristics and retention values for the conformers unable to form the
intermolecular H-bond. Consequently, the second method can be used for the specification of
the geometrical parameters of the adsorbate molecules, as well as torsional angles and
parameters, characterizing the intramolecular H-bond in particular.
While optimizing on the GTCB fragment the plane conformer BMIIa, we got the structure
BMII′a in which the -SH group is situated perpendicularly to the benzene ring (table 4). As
was noted in the calculation part, the GTCB structural fragment was chosen in such a way so
as the following increase of its bidimensional surface did not lead to a considerable change of
the adsorbate geometry. However, at optimization only the fragment of graphene is used
whereas the tridimensional structure of carbon black is not taken into account. In other words,
we neglected the gravitation of the adsorbate atoms to the second and the following adsorbent
layers. On the one hand, their contribution is not considerable. On the other, it is possible that
this very little energy was lacking for the definition of the minimum at the plane position of
the -SH group as related to the benzene ring.
At optimization on the GTCB fragment of the conformers BAI′a, BAmI′a and 1-PEAmI′a
able to form the intermolecular H-bond with sorbent π electrons, we observed a considerable
deviation from the values obtained by the first method. This can be connected with the
overestimation of the influence of the intermolecular H-bond at optimization which in its turn
is the consequence of the imperfection of the basis used 6-31G(d) as well as of the
tridimensional GTCB structure neglection and the temperature influence neglection.
However, there is no undisputable confirmation of the fact that the parameters of the
conformers BAIa, BAmIa and 1-PEAmIa is defined more exactly as in the first method the
intermolecular H-bond influence was not taken into account. In the objects under research in
the chosen temperature diapason it seems that it is the conformations of the adsorbate
molecules having no specific intermolecular interaction with the adsorbent that mostly
contribute to the experimental retention values. That is why it is necessary to conduct the
additional researches on the objects able to form the H-bond for the purpose of finding out the
extent of the intermolecular H-bond with the GTCB π electrons influence on the TCA values;
also for the purpose of clearing out the precise application limits of the studied methods of
molecules in the adsorbed state conformations definition.
Table 4. Structural characteristics of the adsorberbed molecules, found by the

optimization of the aromatic alcohols, amines and thiols on the GTCB fragment, and the
retention values calculated for them (lnK1 [K1, cm3/m2])
lnK1
τ1 τ′1 τ2 τ′2 r1 r2 r3
T = 413 T = 463
BAI′a 23 --- 63 --- 2.64 2.49 2.56 1.22 -0.20
BAII′a 18 --- 179 --- - 2.36 - 2.04 0.48
BAmI′a 25 --- 67 -176 2.72 2.47 2.94 1.74 0.25
BAmII′a -4 --- -56 61 - - - 2.35 0.74
BMI′a 60 --- 55 --- 2.90 3.13 2.95 1.61 0.15
BMII′a 92 --- 179 --- - - - 1.77 0.27
1-PEI′a 22 -100 180 --- - 2.36 - 2.54 0.89
1-PEAmI′a 28 -92 63 179 2.67 2.47 2.95 1.93 0.43
1-PEMI′a 111 -16 56 --- 2.85 3.19 - 2.65 1.02
Torsion angles, deg.: τ1 – Cortho-Cipso-Cα-X; τ′1 – Cortho-Cipso-Cα-Cβ; τ2 – Cipso-Cα-X-H; τ′2 – Cipso-Cα-N-H′
(see scheme). r1 – the distance between the hydrogen of the -XH group and the closest the closest
atom of the carbon of the benzene ring Cipso, Å; r2 – the distance between the hydrogen connected
to the Cortho of the benzene ring and the X atom, Å; r3 – the distance between the hydrogen of the
-XH group and the closest the closest atom of the carbon of the GTCB fragment, Å. At the evident
impossibility to form the hydrogen bond the distances are not pointed out. T – temperature, K. X –
O, N or S atoms.
It is obvious that the analysis of the results cited here does not allow to state that the
proposed approaches solve all the problems. However, they can help in cases when the
conclusions about the comparison of the experimental and calculated data are not satisfactory.
CONCLUSION
The research of the flexible molecules of the aromatic alcohols, amines and thiols showed
that the intramolecular H-bond influence contributes much to the TCA values. The
intramolecular H-bond influence on the geometry of these compounds is connected with the
rotation of the adsorbate tops and with the energy of the intermolecular interaction with the
sorbent surface. The structural characteristics of the stable molecule conformers in the
adsorbed state which were found by us do not follow any simple regularity, but are
determined by the combined activities of different intramolecular effects in the sorbent force
field. The preparation of the molecule geometrical parameters in the gas phase and the PES
calculation using the quantum-chemical calculation methods allowed us to define the
permissible calculation levels of the molecules inclined to the formation of the hydrogen
bonds. For the gas phase this is the MP2/6-311++G(d,p) method, for the PES definition -
B3LYP/6-311++G(d,p) or PBE0/6-311++G(d,p) methods.
In the present chapter we proved the importance of the definition of the real
conformational structure for the aromatic molecules with flexible side chains. Calculating the
TCA for the class of compounds under consideration the use of the basic molecules (even
optimized in the gas phase) neglecting the sorbent force field influence leads to the total
disagreement of the calculation and experiment results. We proposed two methods for the
definition of the molecule conformation in the adsorbed state. The first one defines the
structures for which the retention values well agree with the experiment results. Nevertheless
there are the restrictions of the method that do not allow observing the delicate energetic
effects. The use of the second method which is based on the structural adsorbate
characteristics definition as the result of the molecule optimization on the sorbent fragment is
quite promising from our viewpoint. Applying this method it is possible to single out the
exact geometric parameters of the adsorbate molecule. The data correctness will depend on
the basic set choice, the GTCB fragment structure and the method of temperature account.
The results obtained by the two methods provide the opportunity to solve the counter
problem – to obtain the molecule the AAP parameters by the TCA known on the basis of the
theoretical calculations and the experiment without the basic molecules and their fragments
use. To develop and widen the application of the first and the second methods the detailed
research of the intermolecular H-bond and its reliable qualitative characteristics and
quantitative description is necessary. The definition of the potential characterizing the
intermolecular H-bond with the adsorbent with the regard of the directionality will allow
increasing the predictive ability of the molecular-statistical theory of the TCA calculation.
EXPERIMENTAL PART
The experimental definition of the Henry constant was conducted on the chromatograph
―Model 3700‖ with the flame ionization detection, produced by the ―Chromatograph‖
company licensed by the ―Varian‖ company. The U-shaped packed column made of lead
glass with the inner diameter of 2.7 mm and 0.4 m column length was used. As the sorbent
the GTCB Carbopack C 60/80 mesh of the ―Supelco‖ company was used. The carrier gas is
helium. The measurements were conducted in the isothermal mode with the temperature
diapason of 413-463 K with the 10 K interval.
As the adsorbates the benzyl alcohol (analytical reagent grade, AR) of the ―Volga-
Reactive‖ company, (+/-)-1-phenylethanol (97 %), benzylamine (98+ %) and
(+/-)-1-phenylethylamine (98+ %) of the ―Alfa-Aesar‖ company were used. The solvent is the
carbon tetrachloride (chemically pure, CP). The standards are n-hexane (CP) and n-octane
(CP) of the ―Volga-Reactive‖ company.
The Henry constant calculation was carried on by the taken K1 values obtained in the
Kiselev‘s laboratory for the n-C6H14 [1]. The correctness of the calculations conducted was
verified by the results for the n-C8H18. The lnK1values obtained by us for the n-octane
differed from those from [1] at not more than 0.1.
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Editors: I. J. Sanders, T. L. Peeten, pp. 115-132 © 2011 Nova Science Publishers, Inc.
Chapter 5
HEAT TRANSFER AND GROWTH OF PRIMARY

BLACK CARBON PARTICLES IN GAS MIXTURE
Y. A. Baranyshyn, S. P. Fisenko and O. G. Penyazkov

A.V. Luikov Heat and Mass Transfer Institute,
National Academy of Sciences, 15 P. Brovka St., 220072, Minsk, Belarus.
ABSTRACT
Results of the experimental and theoretical study of the interference between heat
transfer and growth of primary black carbon particles are presented. Experimental study
was performed in shock tube with length about 7 m and inner diameter 50 mm. Black
carbon nanoparticles have been formed during the pyrolysis of ethylene, diluted with
argon, behind the reflected shock wave. The pyrolysis temperature was in the range 2000
– 3500 K, total pressure was 7.5 - 11 bars. Home-made pulsed photoemission pyrometer
with a temporal resolution of 1 μs was used for measurements of temperature of black
carbon particles during their growth. Substantial difference (about 900 K) in temperature
of black carbon particles and the temperature of gas mixture was discovered.
For simulation of nonisothermal growth of black carbon nanoparticles the
mathematical model was developed, which considers the heat transfer and growth of
black carbon nanoparticles in the supersaturated carbon vapor in the free molecular
approximation (the Knudsen number Kn > 103). It was established that due to very high
supersaturation of carbon vapor and the release of the latent heat of sublimation
temperature of the particles can exceed the temperature of the gas phase more than one
thousand degree. Heat transfer between the carrier gas and black carbon nanoparticle
significantly affects on the value of this temperature difference.
For determining parameters of growth of primary black carbon nanoparticles the
inverse problem was solved using the data of electron microscopy and gasdynamic
measurements. It was obtained that in order to reach to final diameter the growth time of
primary black carbon particles been less 10 μs and the temperature difference been above
1000 K. The final diameter of primary black carbon particles is in the range 27 - 55 nm.
116 Y. A. Baranyshyn, S. P. Fisenko and O. G. Penyazkov
NOMENCLATURE
c, heat capacity per an atom, J/K;
Dc, diameter of carbon particle, m;
g, number of atoms;
k, Boltzmann coefficient, J/K;
kc, coagulation constant, m3/sec;
m, atomic mass, kg;
mc, particle mass, kg;
Nc, number density of particles, m−3;
Ndc number density of double particles, m−3; n, numerical density of carbon vapour, m−3;
ns, numerical density of the saturated carbon vapor, m−3;
p, pressure of gas, Pa;
ps, pressure of the saturated carbon vapor, Pa;
Rc, radius of a particle, m;
S, supersaturation of the carbon vapor;
t, time, sec;
T, temperature of gas, K;
va, volume per carbon atom in the condensed phase, m3
v , mean thermal velocity of particle, m/sec;
u, latent heat of a phase transition per an atom, J;
U, photomultiplier voltage, V.
Greek Symbols
ε, particle-to-circumscribed sphere volume ratio;

λ, wavelength, m;
ρc, carbon density, kg/m3;
Π, energy flux from the gas to a particle, J/(m2·sec);
σ, surface tension of the condensed carbon, N/m;
σSB, Stefan–Boltzmann coefficient, W/(m2·K4);
σSB*, effective Stefan–Boltzmann coefficient, W/(m2·K4).
Subscripts:
*, effective;
5, behind the reflected shock wave;
a, atom;
c, carbon particle;
car, carrier gas;
C2H4, ethylene;
max, maximum value;
s, saturated;
st, steady-state value.
Heat Transfer and Growth of Primary Black Carbon Particles … 117
INTRODUCTION
Black carbon particles are formed in various transformations of hydrocarbon fuels at
relatively high temperature conditions. These conditions create some difficulties in
experimental studies of black carbon formation. Nevertheless, there are a lot of works of
experimental study and theoretical modeling of black carbon formation ([1-6] and references
therein). The main reason of such activity is that black carbon is widely used industrial
product. It is now well established that black carbon particles affect the functioning of power
plants and engines, on the climate changes, and human being health ([7-11] and references
therein).
Kinetics of the formation of black carbon nanoparticles and their subsequent growth are
challenging scientific problem at present. Unfortunately, the modern level of measurement
technique does not meet all the requirements of such studies and cannot directly support
theoretical researches. But the basic problem for experimental studies is that primary black
carbon particles are actually nanoparticles. Additionally, a short growth time of primary
nanoparticles is a serious obstacle for experimental registration of parameters of heat and
mass processes during the particles growth.
The deviation of the temperature of black carbon nanoparticles from the gas temperature
during their formation and growth is the subject of growing interest of scientists, e.g. [12-14].
This deviation is the result of the release of the latent heat of phase transition at desublimation
(we also use the term condensation) of carbon atoms. It also depends on a heat transfer rate of
primary carbon nanoparticles with carrier gas in the nonequilibrium gas mixture. Obviously,
the temperature of primary black carbon nanoparticles is a substantial parameter that affects
many aspects of the growth and, no doubts, the pyrolysis kinetics of hydrocarbon vapor in its
vicinity.
The aim of this chapter is to present results of our experimental and computational study
of the interference of heat transfer and the growth of primary black carbon particles in
supersaturated carbon vapor. In experiments this supersaturated carbon vapor has been
formed due to ethylene pyrolysis in the shock tube. Some preliminary results have recently
been published in [15]. It is worthy to note that in our experiments we used home-made the
photoemission pyrometer with microsecond temporal resolution [16, 17].
The structure of the chapter is the following. First, we describe out experimental setup.
Then we analyze our experimental results about temperature of black carbon particles
obtained in the shock tube during ethylene pyrolysis and subsequent condensation of carbon
vapor. Next, we discuss our simulation results on the formation of primary soot particles and
simulation of energy transfer of black carbon nanoparticles. The inverse problem of primary
black carbon particles is analyzed also.
EXPERIMENTAL SETUP
To provide information of black carbon formation was performed the experimental study
of the pyrolysis of the manometric prepared ethylene – argon mixture (5% С2H4 – 95% Ar)
behind the reflected shock wave in the shock tube. For these purposes the stainless steel shock
tube with the length of the driven section 7.1 m and the inner diameter 50 mm was used. The
schematic of test section of shock tube is sketched in Figure 1.
Figure 1. Sketch of test section of shock tube for soot formation study. 1 – high-frequency pressure
sensors; 2 – photomultipliers with color filters; 3 – pulse photoemission pyrometer; 4 – laser.
The study was carried out behind the reflected shock wave for the following conditions:
temperature was 2000 – 3400 K, gas pressure was 7.0 – 11.5 bars and the gas density was
1.61 – 1.63 kg/m3. The parameters of gas were calculated by the shock adiabatic curve,
assuming the ―frozen‖ chemistry, and by the temperature dependence of the heat capacity
from shock wave velocity measurements at different locations along the tube. To justify this
approach we use only diluted mixture of ethylene. Four high-frequency piezoelectric pressure
sensors were installed along the tube wall and in the reflected plane for pressure monitoring
and the incident wave velocity measurements (Figure 1).
To provide spectroscopic observations, two quartz rods 8 mm in diameter were mounted
opposite to each other in the shock tube. Radiation impinged through one rod on a registering
photomultiplier tube of the pulse photoemission pyrometer. The last registered the radiation
of hot carbon particles (Figure 2). The fundamentals of the photoemission method for
temperature measurement were detailed in [18]. In particular, in our experiments the
accelerating voltage of the pulse photoemission pyrometer was 1100 V and the retarding
voltage realizing the separation of photoelectrons was -0.6 V.
Figure 2. Emission signal of carbon black particles detected by the pulse photoemission pyrometer (1)
and measured particles temperature (2) at T5 = 2150 K.
Another rod was used to detect the radiation of C2 radicals (transitions A3П – Х3П) at the
wavelength of  = 516.5 nm and of hydrogen atoms (transitions Hα) at the wavelength of  =
656.3 nm. For this purposes, two photomultipliers having doubled narrowband
monochromatic filters with max = 516.2 nm (0.5 = 4.6 nm) and max = 656.2 nm (0.5 =
2.6 nm), respectively, were used. Thus we can measure the induction time of the mixture,
which is the time difference between shock arrival to the measuring section of the tube and
the radiation appearance there.
Also we carried out additional research of laser absorption in the shock tube during the
pyrolysis and black carbon formation. For this purposes we used a laser with working
wavelength 645 nm and output power 3 mV. The photomultiplier having doubled narrowband
monochromatic filter with max = 646.7 nm (0.5 = 2.2 nm) was used to detect its radiation.
Stainless steel plates were attached to the reflected wall to collect deposited carbon
particles produced in experiments. After each experiment we extracted plate with black
carbon from the tube and examined it under a bitmapped electron microscope Carl Zeiss
Supra 55.
The analysis of our experiments showed that the measurement error of the incident shock
wave velocity was of the order of 1 %. When combined with the error associated with
preparing a test mixture, this resulted in the 1.5 % error in determining parameters behind a
reflected shock wave. The temperature measurement error by the photoemission method did
not exceed 5 %. Accuracy of the determination of the induction time could result in the 10 %
measurement error.
EXPERIMENTAL RESULTS
The advanced homemade photoemission pyrometer was used to measure a temperature of
black carbon particles and to research nonisothermal effects. The range of sensitivity of the
pyrometer was limited (0.0 – 4.0 V), therefore two series of experiments under the same
initial conditions were carried out. In the first experiments, neutral color filters with the
transmitting efficiency 3.0 – 70.0 % were located in front of the pyrometer. Thus we detected
carbon particle radiation without signal pining. Under the same conditions additionally we
carried out experiments without neutral color filters (or using filters with higher transmitting
efficiency) for exact temperature measurement at the initial detecting stage.
We found that at the initial detecting stage temperature of carbon particles was
significantly higher then the gas temperature. In different experiments the temperature
difference between gas and maximum carbon particles temperature was about 550 – 900 K
(Fig. 3), but it dropped fast to the value that was lower than the gas temperature by 400 – 550
K and finally reached the quasi-steady state (Figure 3). The rate of temperature change was
about 106 K/s. For temperature of pyrolysis lower than 2400 K temperature of black carbon
particles did not exceed gas temperature significantly.
Figure 3. Difference temperatures between carbon particles and gas : 1- stage of growth, 2- steady-state
temperature of carbon particles.
Interesting experimental results are displayed in Figure 4. For practically the same initial
conditions we carried out black carbon temperature measurements using the neutral color
filter in front of the photoemission pyrometer and without last one. As can be seen, the
temperature of carbon particles is initially higher than the gas one but then due to fast cooling
it has become lower than the gas temperature and, finally, reached its quasi –steady state
value.
Figure 4. Carbon particles temperature measured with various neutral color filters at similar pyrolysis
conditions. 1 – T5 = 2850 K; 2 – T5 = 2880 K; 3 – T5 = 2900 K.
The measurements of absorption of laser radiation in the shock tube during carbon black
formation are displayed in Figure 5. We found that in our experiments during the temperature
measurement we can consider the gas as optically transparent one (optical density of gas no
more than 3 m-1).
Figure 5. Signal of laser radiation absorption in the shock tube during carbon black formation at T5 =
2840 K. 1 – absorption; 2, 3 – the beginning and the end of particles temperature measurement.
Additionally, we detected the radiation of C2 radicals ( = 516.5 nm) and hydrogen atoms
( = 656.3 nm) in the course of our experiments and use these measurements for determining
of the induction time. Dependence of the induction time versus T5 is presented in Figure 6.
When the gas temperature was increased in the range 2000 – 3400 K the induction time
decreased from 1.54 to 0.03 ms for C2 and from 1.76 to 0.25 ms for radical H. Such nonlinear
dependence of the induction time is associated with change of kinetics of pyrolysis during
growth of primary black carbon particles.
Figure 6. Induction time versus the inverse temperature at pyrolysis of ethylene – argon mixture (5%
С2H4 – 95% Ar). 1 – C2 radicals, 2 – H atoms.
It is important to emphasize here that the temperature of carbon particles reaches its
steady-state value long before the end of the pyrolysis process. To our mind, it is a clear
indication of the fact that the black carbon formation and the slow chemical processes are
separated in time.
As already mentioned above, the black carbon produced in our experiments were
collected and examined under a bitmapped electron microscope. The example of the obtained
electron picture is shown in Figure 7. By analyzing the electron pictures we found that the
mean diameter, D, of primary carbon nanoparticles decreased from 55 to 27 nm if the
pyrolysis temperature T5 was varied from 2100 to 2800 K (Figure 8). The standard deviation
is about 6 nm.
Simulation of growth of primary carbon particles in supersaturated carbon vapor [19]
clarifies some details of this process, which cannot be measured directly now. These results
are presented in the next chapter.
Figure 7. Electron picture of black carbon particles produced at pyrolysis temperature. T5 = 2350 К.
Figure 8. Mean diameter of black carbon particles at different pyrolysis temperatures.
SIMULATION
Mathematical Model and Results
For the sake of convenience of readers, we briefly present here our mathematical model
for the nonisothermal growth of primary carbon nanoparticles in supersaturated carbon vapor
[18]. There is a relationship between a particle radius R and a number of carbon atoms g in it
R( g,  )  (3gva / 4 )1/ 3 , (1)

where  is the particle-to-circumscribed sphere volume ratio, va is the volume per carbon atom
in the condensed phase.
Growing carbon nanoparticles may have different geometrical shapes, slightly differing
from sphere, and also have some pores. In particular, pores can be formed during
condensation of carbon dimers and trimers at the cluster surface. Carbon dimers and trimers
are formed quite often in equilibrium carbon vapor [20]. Thus, the use of the particle-to-
circumscribed sphere volume ratio  in our equations owes us to take into account partially
the real particle geometry. Also we assume that while growing this ratio preserves its value. It
is worth to note that a preferable nanoparticle shape has to be close to a spherical one in order
to minimize a contribution of the surface free energy of a nanoparticle. We restrict our
consideration here only to the typical case  = 0.9. Different values of  are investigated in
[18].
To describe the nonisothermal growth of the nanoparticle we use the idea of thermal
motion of preserved carbon atoms in the nanoparticle as the motion in the potential hole. The
depth of this potential hole is equal to the sublimation energy per carbon atom. This value is
well known from numerous scientific handbooks.
Supersaturation S of carbon vapor is determined as
S  n / ns (T ) , (2)
where n and ns(T) are the number density of carbon vapor and saturated vapor at the
temperature T, respectively.
Typically, we will consider all processes of growth and heat transfer only for one
millisecond. This duration is the characteristic time of the nanoparticle growth in many
experiments in shock tubes. In our mathematical model, we also neglect the impact of the
particles coagulation during this period. Indeed, the rate of change in the number Ndc of
―double‖ particles due to inelastic collisions of two smaller particles is [21]:
dN dc
 kc N c2 . (3)
dt
In Eq. (3) we neglected the decay rate of the ―double‖ particles. If we consider particles to be
uncharged, the coagulation constant kc is:
kc  4 Rc 2v , (4)
where Nc is the number density of black carbon nanoparticles, and the mean thermal velocity,
v , of the particle is expressed with a good accuracy by the formula:
v  kTc / mc , (5)
where mc is the particle mass. Let us make a numerical estimation. For a black carbon
nanoparticle with the radius Rc = 10 nm and Тc = 2000 К, we have that kc  10 -14. It then
follows from expressions (3-5) that we can neglect coagulation of primary nanoparticles
during one millisecond if Nc1016 m-3. Thus we consider only the growth in the supersaturated
carbon vapor and do not take into account their coagulation. Coagulation is a very important
player in the soot formation but for larger times, or for larger number density of particles (see
Fig.5).
It is worth to emphasize that for particles with Rc = 10 nm and Nc  1016 m-3 we have to
consider the gas mixture with such particles to be an optically thick medium [22]. This
circumstance drastically changes the efficiency of radiation cooling of the carbon
nanoparticles.
The mean free path of carbon atoms is much larger than diameters of primary
nanoparticles of black carbon, therefore we use the free molecular approximation of transfer
processes in the gas phase.
It should also be noted that for relatively high supersaturation of carbon vapor the critical
radius of the carbon particle is smaller than the size of a single atom. Actually any ternary
collisions lead to the formation of stable carbon clusters. Below we analyzes only the growth
of the nanoparticles with an initial radius equals to one nanometer and with the temperature
equals to that of the gas mixture of the supersaturated carbon vapor, consisting only of carbon
atoms, and carrier gas. The nonisothermal growth of the particle and its temperature change is
described by the following system of the ordinary differential equations (more simplified
form of them have been presented in [18]):
dRc m  nkT ps (Tc ) 

   , (6)
dt c 2 mk  T Tc 
dTc 3  dRc 3va  SB* (Tc4  T 4 )va 

 (cTc  u)  
dt Rcc  , (7)
dt   
where ps(T) is the equilibrium carbon vapor saturated pressure at the temperature T; c the
mass density of the carbon particle (~ 2000 kg/m3); m the mass of the carbon atom, c the heat
capacity per carbon atom in the condensed phase, and SB* the effective Stefan–Boltzmann
coefficient. An expression for energy fluxes in the gas phase to particle  can be written as
follows:
1  nkT (cT  u  0.5kT ) ps (Tc )(cTc  u  0.5kTc ) 

   
2 mk  T Tc 
. (8)
kncar  2kT 2 2kTc 2 
   
2 mcar k  T Tc 
It is clear from the equations that in our model the growth of carbon particles can be
associated only with desublimation of carbon atoms.
We also take into account a feedback between the growth of particles and the carbon
vapor state. The first additional equation is for the change in the carbon vapor number density
n(t) due to condensation:
dn Nc  nkT ps (Tc ) 
 4 Rc 2   . (9)
dt 2 mk  T Tc 
We can thus describe the carbon vapor depletion during the growth of black carbon
nanoparticles.
The change in the gas mixture temperature due to energy exchange with nanoparticles is
governed by Eq. (10) that represents the specific form of the energy conservation law:
dT Nc
 4 Rc 2 . (10)
dt nc  ncar ccar
It is worthy to emphasize that optical properties and especially radiative emittance of carbon
nanoparticles drastically differs from the thermal radiative emittance of a macroscopic black
body [23, 24].
We use the following expression for the effective Stefan–Boltzmann coefficient SB* in
Eq. (7):
 RcTc 
 SB
*
  SB  ISB  , (11)
 b 
where the function ISB(RTc/b) is plotted in [18].

The system of ordinary differential equations (6-11) was solved by means of the software
Mathcad 14. We used the Runge – Kutta method of the fourth order. Simulation results are
presented below.
It was already mentioned that the physical reason for the nonisothermal growth of carbon
nanoparticles in the gas mixture is the condensation of the supersaturated carbon vapor on
them and the release of the latent heat of phase transition. It is clear that if the partial pressure
of carrier gas is high enough, then the growth is practically isothermal one.
It has been established in our simulation that the temperature of particles is reached the
steady-state value in about one microsecond of growth. For high supersaturations of carbon
vapor some numerical results of the temperature difference between the particle and the gas
phase are shown in Figure 9.
For different supersaturations after the growth during one millisecond the dependence of
the particle radius on S is displayed in Figure 10. For a gas temperature 2500 K, the growth
rate increases but it still is very low. The reasons for such a low growth are obvious when we
are considering this figure together with Figure 9. We see that a significant increasing of the
particle temperature enhances the evaporation of carbon atoms and the effective growth rate
is smaller.
Figure 9. Difference of the steady-state temperature and initial one versus supersaturation carbon vapor.
1 – T = 2500 K; 2 – T = 2000K.
Figure 10. Particles radius versus supersaturation of carbon vapor. 1 – T = 2500 K; 2 – T = 2000K.
The temperature difference between the steady-state particle and the gas depending on
the number density of particles is shown in Figure 11. The number density of particles is an
important parameter for many aspects of the carbon nanoparticles growth. Nevertheless, for N
< 1016 m-3 it is obvious that the temperature difference does not depend on the number density
of particles. For the below simulations the number density of particles is therefore chosen
equal to Nc = 1015 m-3, so we can use the approximation of an optically thick layer. We see
that for higher supersaturation we have a higher growth rate of the particle and,
correspondingly, a higher temperature difference between the particle and the gas mixture.
Figure 11. Particles steady-state and initial temperature difference versus the number density of
particles. T = 2000 K; ncar = 51022 m-3; 1 – S = 107; 2 – S = 106; 3 – S = 105.
For N < 1016 m-3 we did not observe the depletion of carbon vapor during the time less
than one millisecond.
In our mathematical model, the increasing of the carrier gas number density ncar in the
range 51021 – 51023 m-3 decreases the steady-state particle temperature (Figure 12). As a
result, we have a much lower evaporation rate that leads to a higher growth rate of the particle
(Figure 13). The characteristic time of the particle growth is much larger than that for
reaching the steady-state particle temperature.
Figure 12. Particles steady-state and initial temperature difference versus the time. S = 107; T = 2000
K; 1 – ncar = 51021; 2 – ncar = 51022; 3 – ncar = 51023 m-3.
Figure 13. Particles radii versus the time. S = 107; T = 2000 K; 1 – ncar = 51021; 2 – ncar = 51022; 3 – ncar
= 51023 m-3.
Inverse Problem of Primary Particles Growth
On the base of our model and experimental data on particle size and parameters of gas in
the shock tube we solved the inverse problem of particle heat and mass transfer to calculate
their temperature and time of growth. Experimental values of the temperature and pressure of
the gas mixture behind the reflected shock wave were used as the gaseous-phase parameters
in the calculations. The initial radius of carbon particle was taken to be one nanometer, and its
initial temperature was assumed to be equal to the temperature of the gas medium. Under the
assumption of the first stage of decomposition of an ethylene molecule into a stable methane
molecule and a carbon atom C2 H4  C+CH 4 , the carbon supersaturation in experiments
can be evaluated by the formula:
pC 2 H 4  T5
S  0,5 . (12)
T5  ps (T5 )
Table 1 gives experimental conditions of growth of primary black carbon particles in the
shock tube. Also results of solving of inverse problem based on from our mathematical
model. As is seen, in the case of such high supersaturations the growth time of primary
carbon particles is about 7–10 μsec. A strong heating of the particles up to temperatures much
higher than the gas-medium temperature is obtained. The steady-state value of the
temperature on this time interval is held by energy exchange with the atoms of the gaseous
phase argon and evaporation of carbon atoms from the particles. As our calculations have
shown, a change of 10% in the degree of supersaturation exerts virtually no influence on the
temperature and rate of growth of particles, all other parameters being constant. The growth
time in this case changes by less than 1 μsec, whereas the carbon particles temperature
changes by approximately 50 K. Thus, the accuracy of determination of the degree of
supersaturation of the carbon vapor S, which is dependent on the adopted kinetic scheme of
pyrolysis, has an insignificant effect on calculation of the growth time and of steady-state
temperature of primary carbon particles. To note that obtained results on the temperature of
primary particle are confirmed by a recorded data from pulse photoemission pyrometer, see
Figure 3.
Table 1. Parameters of black carbon particles at different pyrolysis conditions
Tc, Dc,
T5, K pAr, Pa pC2H4, Pa S tc, μs
K nm
2150 7,2 10ּ5 0,36 10ּ5 7,310ּ8 7,2 4321 53
2350 8,010ּ5 0,39 10ּ5 7,410ּ6 8,2 3653 35
2510 8,510ּ5 0,42 10ּ5 6,510ּ5 8,6 3707 34
2680 9,010ּ5 0,45 10ּ5 6,910ּ4 6,5 3780 28
CONCLUSION
Black carbon particles were obtained at the pyrolysis of ethylene – argon mixture (5%
С2H4 – 95% Ar) during experiments in the shock tube. It was established that temperature of
carbon particles at some moments exceeds the temperature of the gas mixture by about 550 –
900 К, but it falls fast enough and reaches quasi-steady state value. For different experiments,
the measured temperature excess of carbon particles over gas temperature is very impressive,
see data in Figure 3. According to our simulations the physical reason of this excess is the
release of latent heat of phase transition during condensation (desublimation) of carbon
atoms. We expect that smaller nanoparticles have even a larger temperature that is in
accordance with our simulation results.
Measurements of diameter of primary black carbon particles made by means of the
electron microscope showed that diameter of primary particles decreases from 55 to 28 nm if
pyrolysis temperature increases (2000 – 2800 K). High temperature of particles leads to
higher rate of carbon evaporation from them and decreasing of final radii of carbon particles.
We have developed the mathematical model for simulation of carbon particle heat and
mass transfer in the supersaturated carbon vapor within the free molecular regime
approximation. Our mathematical model permits studying the nonisothermal growth of
nanoparticles. We found that after a very fast growth of carbon particles with a characteristic
time of about 1 s, their temperature reaches steady-state value. This value can be
significantly higher than the gas temperature. There are some values in our experimental data
that support this conclusion (Figure 3 and Table 1).
Additionally we have solved the inverse problem on determination of the growth time
and temperature of primary carbon particles using the experimental parameters of the gaseous
phase and the data of electron microscopy. We found that of the growth time is about 7–10
μsec. Over this period, the carbon nanoparticles reach a steady-state temperature 1000–2000
K higher than the gas temperature as a result of the release of the latent phase-transition heat.
It is clear that carbon particles with a substantially elevated temperature can drastically
change a pyrolysis rate of hydrocarbon gases. Thus, for high supersaturation of carbon vapor
and, therefore large condensation rate special investigations for pyrolysis kinetics should be
made. Our experimental data presented in Figure 6 gives some details of pyrolysis kinetics.
Pyrolysis experiments with different hydrocarbon gases in our shock tube are under
consideration now. We expect to receive similar results relatively nonisothermal growth of
primary black carbon nanoparticles.
It is worthy to emphasize that obtained results and developed approach could be used also
for studies of heat and mass transfer during pyrolysis of metalorganic vapors behind a shock
wave and formation of metal nanoparticles. In the mixture of argon and metalorganic vapors
behind a shock wave a huge supersaturation of metallic vapor are created [25, 26], and we
expect manifestation of strong nonisothermal effects in such systems also.
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Clusters 1991, 20, 449-451.
Chapter 6
WHAT DOES CARBON NANOMATERIAL

CAUSE IN HUMAN HEALTH?
Masakazu Umezawaa and Ken Takedaa,b

a
Department of Hygienic Chemistry, Faculty of Pharmaceutical Sciences,
Tokyo University of Science, Chiba 278-8510, Japan.
b
Research Center for Health Sciences of Nanoparticles, Research Institute for
Science and Technology, Tokyo University of Science, Chiba 278-8510, Japan.
Previous studies have shown that exposure to nano-sized particles through the airway
affects both the respiratory and extrapulmonary organs. The potential health risks of inhaling
nanomaterials are of great concern because of their high specific activity and their unique
property of translocation [1, 2]. Inhaled nanoparticles with a diameter of less than 100 nm are
the main particles that reach and are deposited in the alveolar region. Furthermore, they can
enter the circulatory system and translocate to extrapulmonary tissue [3].

As the core of airborne combustion-derived particle matter is composed of carbon
nanoparticles [4], research into the health effects of exposure to carbon black nanoparticles
has started from a focus on the effects of ambient particle matter on human health [5, 6]. It
was reported that exposure to ultrafine carbon black through the airway affects the respiratory
system [7–13], the cardiovascular system [7, 8], the central nervous system [7, 14] and other
organs [7]. Intratracheal instillation of suspension of ultrafine carbon black causes an increase
in the counts of macrophages, lymphocytes and neutrophils, and an increase in the level of
lactate dehydrogenase (LDH) and nitric oxide (NO), and in the expression of
proinflammatory cytokines such as interleukin (IL)-1, IL-6 and tumor necrosis factor (TNF)
in bronchoalveolar fluid and chemokine macrophage inflammatory protein (MIP)-1/CCL-3
[9, 10]. The instillation of ultrafine carbon black suspension also enhances pulmonary damage
and inflammation induced by antigen and bacterial components such as lipoteichoic acid
(LTA) [11], lipopolysaccharide (LPS) [12] and ovalbumin (OVA) [13]. In the brain,
intranasal instillation of the carbon black suspension induces cytokines IL-1 and TNF,
chemokines such as MCP-1/CCL2, MIP-1/CCL-3 and monokine induced interferon-/CXC
chemokine ligand 9 in the olfactory bulb [14]. Another report showed that inhaled carbon
nanomaterials, especially carbon black, are deposited in the lungs and activate local and
134 Masakazu Umezawa and Ken Takeda
systemic responses with an expression change of genes and proteins in the blood cells and
lung tissue [8].
Since inhaled airborne particles can enter the circulatory system [3], maternal exposure to
airborne carbon particles also has the potential to cause damage to the developing fetus. It is
well known that environmental particle matter containing elemental and organic carbons
affects fetuses and future offspring when inhaled by pregnant mothers [15]. Previous studies
have shown abnormality of the male reproductive system in the offspring of pregnant mice
exposed to carbon black nanoparticles [16]. An increase in partial vacuolation of seminiferous
tubules and a decrease in cellular adhesion of seminiferous epithelia and the level of sperm
production were observed in the maternal carbon nanomaterial-exposed mice. An in vitro
study using a human placental perfusion model showed that nanoparticles (<240nm,
polystyrene beads) can cross the placental barrier [17]. The translocation depends on the
characteristics of the particle; however, carbon nanomaterials, especially nano-sized carbon
black particles, may also affect the fetus when inhaled by pregnant mother. Research into the
effects of carbon black nanoparticles on the development of the fetus and future offspring is
currently in progress.
At the present time, there is a limitation that disturbs research into the health effects of
carbon nanomaterials. The information on the health effects is limited by current technology,
which does not allow for the complete analysis of the biokinetics of carbon nanomaterials
including carbon black and carbon nanotubes. The carbon atoms constituting carbon materials
are hardly detectable in biological tissue. A method based on detection of impurities of
metals, such as nickel, present in carbon nanotube was proposed previously [18]. However, at
present there is no method for detecting carbon nanomaterials in biological organs. The
development of a method for detecting or visualizing carbon black is required both for the
understanding of its health effects and for determining how it may be used safely.
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[1] Oberdörster G., Oberdörster E., Oberdörster J. (2005). Nanotoxicology: an emerging
discipline evolving from studies of ultrafine particles. Environ. Health Perspect., 113,
823-839.
[2] Nel A., Xia T., Mädler L., Li N. (2006). Toxic potential of materials at the nanolevel.
Science, 311, 622-627.
[3] Oberdörster G., Sharp Z., Atudorei V., Elder A., Gelein R., Lunts A., Kreyling W., Cox
C. (2002). Extrapulmonary translocation of ultrafine carbon particles following whole-
body inhalation exposure of rats. J. Toxicol. Environ. Health Part A, 65, 1531-1543.
[4] BéruBé K., Balharry D., Sexton K., Koshy L., Jones T. (2007). Combustion-derived
nanoparticles: mechanisms of pulmonary toxicity. Clin. Exp. Pharmacol. Physiol., 34,
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pollution and mortality in nine California counties: results from CALFINE. Environ.
Health Perspect., 114, 29-33.
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What Does Carbon Nanomaterial Cause in Human Health? 135
air pollution: epidemiological evidence of general pathophysiological pathways of

disease. Circulation, 109, 71-77.
[7] Donaldson K., Tran L., Jimenez L. A., Duffin R., Newby D. E., Mills N, MacNee W,
Stone V. (2005). Combustion-derived nanoparticles: a review of their toxicology
following inhalation exposure. Part. Fibre Toxicol., 2:10.
[8] Erdely A., Hulderman T., Salmen R., Liston A., Zeidler-Erdely P. C., Schwegler-Berry
D., Castranova V., Koyama S., Kim Y. A., Endo M., Simeonova P. P. (2009). Cross-
talk between lung and systemic circulation during carbon nanotube respiratory
exposure. Potential biomarkers. Nano Lett., 9, 36-43.
[9] Li X. Y., Brown D., Smith S., MacNee W., Donaldson K. (1999). Short-term
inflammatory responses following intratracheal instillation of fine and ultrafine carbon
black in rats. Inhal. Toxicol., 11, 709-731.
[10] Tin-Tin-Win-Shwe, Yamamoto S., Kakeyama M., Kobayashi T., Fujimaki H. (2005).
Effect of intratracheal instillation of ultrafine carbon black on proinflammatory
cytokine and chemokine release and mRNA expression in lung and lymph nodes of
mice. Toxicol. Appl. Pharmacol., 209, 51-61.
[11] Yamamoto S., Tin-Tin-Win-Shwe, Ahmed S., Kobayashi T., Fujimaki H. (2006). Effect
of ultrafine carbon black particles on lipoteichoic acid-induced early pulmonary
inflammation in BALB/c mice. Toxicol. Appl. Pharmacol., 213, 256-266.
[12] Inoue K., Takano H., Yanagisawa R., Hirano S., Sakurai M., Shimada A., Yoshikawa
T. (2006). Effects of airway exposure to nanoparticles on lung inflammation induced by
bacterial endotoxin in mice. Environ. Health Perspect., 114, 1325-1330.
[13] Koike E., Takano H., Inoue K., Yanagisawa R., Sakurai M., Aoyagi H., Shinohara R.,
Kobayashi T. (2008). Pulmonary exposure to carbon black nanoparticles increases the
number of antigen-presenting cells in murine lung. Int. J. Immunopathol. Pharmacol.,
21, 35-42.
[14] Tin-Tin-Win-Shwe, Yamamoto S., Ahmed S., Kakeyama M., Kobayashi T., Fujimaki
H. (2006). Brain cytokine and chemokine mRNA expression in mice induced by

intranasal instillation with ultrafine carbon black. Toxicol. Lett., 63, 153-160.
[15] Xu G., Umezawa M., Takeda K. (2009). Early development origins of adult disease
caused by malnutrition and environmental chemical substances. J. Health Sci., 55, 11-
19.
[16] Yoshida S., Hiyoshi K., Oshio S., Takano H., Takeda K., Ichinose T. (2010). Effects of
fetal exposure to carbon nanoparticles on reproductive function in male offspring.
Fertil. Steril. 93, 1695-1699.
[17] Wick P., Malek A., Manser P., Meili D., Maeder-Althaus X., Diener L., Diener P. A.,
Zisch A., Krug H. F., von Mandach U. (2010). Barrier capacity of human placenta for
nanosized materials. Environ. Health Perspect., 118. 432-436.
[18] Elgrabli D., Floriani M., Abella-Gallart S., Meunier L., Gamez C., Delalain P.,
Rogerieux F., Boczkowski J., Lacroix G. (2008). Biodistribution and clearance of
instilled carbon nanotubes in rat lung. Part. Fibre Toxicol. 5:20.
Chapter 7
EFFECT OF CARBON BLACK FILLERS ON THE

TRIBOLOGICAL PROPERTIES OF PTFE
Yoshinori Takeichi
Toyohashi University of Technology
ABSTRACT
Polymer materials are widely used as the sliding surface materials because of their
excellent low frictional properties and chemical inertness. However, the wear amount of
polymer material after long period of friction is relatively larger than that of metal or
ceramic. Therefore, polymer materials are actually used in the form of composites by
adding various kinds of filler materials to enhance their wear resistance. Carbon fiber,
glass fiber, graphite, molybdenum disulfide and fine bronze powder are the typical fillers
used for reducing wear of the polymer material.

Carbon black is well known as a filler of the rubber products such as automobile tires
in the field of tribology. On the other hand, in case of polymer material, the general
purpose of adding carbon black is giving electrical conductivity to polymer materials or
reducing degradation of polymer materials caused by ultraviolet light. There is little
report on the wear reducing effect of carbon black filler for the polymer materials. We
used carbon black as a filler of polytetrafluoroethylene (PTFE) in order to reduce the
wear of it. PTFE is widely used as a tribomaterial because it shows excellently low
friction coefficient comparing with other polymer materials. The wear and frictional
properties of PTFE filled with twelve kinds of carbon black were studied using ring-on-
disk tribometer. The effects of the average particle diameter, the nitrogen surface area
and the DBP absorption of carbon black on the friction coefficient and specific wear rate
were studied.
The friction coefficient of PTFE composites decreased linearly with the decrease of
the nitrogen surface area and specific wear rate of PTFE composites decreased with the
decrease of the average particle diameter. We discussed wear reducing mechanisms of
PTFE composites filled with carbon black by assuming simple model of carbon black. It
was considered that the wear reducing action of carbon black is to make it difficult to
extract the PTFE fibre from the composite by getting caught in the carbon black.
138 Yoshinori Takeichi
INTRODUCTION
Tribology
Tribology is defined as follows. "Tribology is the science and technology of interacting

surfaces in relative motion and of related subjects and practices." When two surfaces in
contact slide each other, the mechanical interactions and chemical interactions take place at
the interface and they generate friction and wear of materials.
People have been making an effort to reduce the frictional resistance from the ancient
times [1]. In the modern industrial society in particular, it is very important to reduce the
frictional resistance which occurs at many sliding parts of machine for running machine
stably and safely with good efficiency, and it makes great contribution to the energy
conservation. Moreover, it is also important to reduce the wear of materials which sliding
each other for long-term reliability of machine. The wear of sliding parts used in the machine
sometimes causes the trouble of the machine, and it occasionally causes a very dangerous
accident.
Solving the problems of friction and wear is meaningful not only to industry but also to
our healthy life. For example, reducing the wear of material used in the artificial hip / knee
joints is crucial issue for the patient who received joint replacement surgery. The wear and
friction in an artificial heart valve, the friction between human blood vessel and the stent
inserted into a blood vessel to keep it open and improve blood flow to the heart, these are the
biotribological issues. When we see our daily lives we can see that a lot of actions such as
writing with a pencil, combing hair, shaving, etc. are related to tribological problem. In this
way, tribology concerns various filed ranging from industry to our day-to-day life.
In practice, the lubricants such as oil or grease are widely used to effectively reduce the
friction between sliding surfaces and then reduce the wear of materials. However, oil and
grease are difficult to be used as lubricant under some conditions, for example, at high
temperature, in high vacuum, in clean environment, in human body and so on. Oil cannot
lubricate sliding surface at high temperature or in vacuum because it is easily evaporated
under these conditions. In clean environment such as food-processing plant or electronic
device factory, the dispersion of oil-mist from the lubricant used in the factory machine is
strongly restricted. In these situations, using "solid lubricants" is one of the solutions for
reducing the friction. Various kinds of materials actually act as solid lubricant, for example,
soft metal such as tin or copper, lamellar material such as graphite or molybdenum disulfide
(MoS2), polymer materials such as polytetrafluoroethylene and so on. Solid lubricants are
applied to the sliding surfaces in several ways. They are used in the form of film or coating,
used as one of additives for oil or grease, or one of constitutional materials of sliding parts.
Polymer materials are used as not only solid lubricants but also self-lubricating materials
because they shows very low friction coefficient comparing with the conventional metal
materials used at the mechanical sliding surface. The polymer materials are lightweight and
many of them are easily to mold. Recently, various kinds of polymer materials are improved
and replacing metal materials used for the sliding parts in order to reduce the weight and cost
of production. However, the polymer materials have a disadvantage that they usually show
poor mechanical properties and larger wear amount than metal materials. A number of great
Effect of Carbon Black Fillers on the Tribological Properties of PTFE 139
efforts have been made to reduce the wear of polymer materials by many tribology
researchers.
Polytetrafluoroethylene and Carbon Black Filler
Polytetrafluoroethylene (PTFE) is well known by the DuPont brand name "Teflon".

PTFE consisting of carbon and fluorine atoms is a synthetic polymer of tetrafluoroethylene. It
is a chemically stable crystalline polymer with a melting point of 327 ºC and it has superior
heat-resistant and chemical-resistant. As a tribomaterial, which means a material used for
reducing friction, PTFE is widely used because it shows excellently low friction coefficient
when it slides against any kinds of solid surface. The wear rate of PTFE, however, is
unacceptably high in comparison with other polymer materials. The mechanisms of low
friction and poor wear resistance of PTFE have been studied until now.
Speerschneider and Li [2] proposed a structural model of PTFE that was described as a
banded structure composed of crystalline slices. Where the crystalline slices, the thickness of
each slice was about 20 nm, separated from each other by a thin layer of non-crystalline or
disorder matrix. The low friction property of PTFE was explained with the easiness of
relative slip between the slices. Tanaka et al. [3] explained that the slip between slices caused
large-scale destruction of banded structures of PTFE and the PTFE fibers made of destructed
banded structures transferred on the counterface. As the results, the slippage occurs between
the PTFE and transferred PTFE film, and this PTFE-PTFE contact results in the low friction
coefficient. They concluded that PTFE showed poor wear resistance because the transfer film
could be easily detached from counterface. Briscoe and Stolarski [4] investigated the effect of
rotating and liner motion on the wear amount in pin-on-disk configuration. They pointed out
that the combination of rotating motion made thick and strongly adhering film on the
counterface and then reduce the wear of PTFE.
Several methods to reduce the wear of various kinds of polymer materials have been
studied. One of the most practical and promising methods to reduce wear is using polymer
material in the form of polymer based composite by adding adequate filler materials into
polymer matrix. Graphite, molybdenum disulfide, bronze fine powder, glass fiber and carbon
fiber are widely used as the filler materials in the commercially available PTFE composites.
The wear reduction effects of filler and its mechanism have been studied for PTFE. Lancaster
[5] studied the mechanism of wear reduction in polymers for carbon fiber reinforcement and
proposed two factors. Firstly, the fibers were exposed at the sliding surface and supported part
of the applied load; secondly, the fibers smoothed the surface of the counterface and thus
reduce the localized stresses at the asperity contact. Tanaka and Kawakami [6] studied the
effects of the filler's shape and size on the wear resistance of PTFE composites and concluded
that the action of fillers to prevent the banded structures from large-scale destruction was a
factor in the reduction of wear, including the load supporting action of fillers. They also
pointed out that the very small fillers could not prevent the large-scale destruction of the
banded structure effectively. Blanchet and Kennedy [7] studied the wear properties of PTFE
and PTFE composites and discussed the wear mechanism of them. They proposed that the
role of the fillers is interrupting subsurface deformation and crack propagation which produce
large wear sheets. On the other hand, Kawamura et al [8] investigated the effect of lamella
solid lubricant reinforcement on the wear resistance of the fibrillated PTFE based composites
and pointed out that the wear resistance of PTFE composites can be improved by reducing
wear debris in size. Gong et al. [9] pointed out that the PTFE composite filled with metallic
net incorporating with graphite improve the wear resistance of composite. The wear debris of
the composite was far smaller than those of pure PTFE. They concluded that these fine wear
debris were formed by the extrusion and smearing of the metallic net in the composite.
Khedkar et al. [10] pointed out that wear rate of PTFE composite can be reduced by adding
the fillers that are effective in impeding large-scale fragmentation of PTFE and produces the
smaller size of wear debris. Wang and Yan [11] investigated wear properties of the PTFE
films formed by transferring from the PTFE composites and concluded that some inorganic
filler materials could effectively prolong the wear life of transfer film of PTFE-based
composite.
The mechanisms mentioned above show that the action of fillers to reduce wear is
categorized into 3 types. These are the formation of a thick and strongly adhering transfer
film, the load supporting action and the prevention the large-scale destruction of banded
structures, and the reduction of wear debris in size. In these mechanisms, the formation of a
thick and strongly adhering transfer film is commonly accepted. However when the friction
process is at a steady state, where the thickness of the transfer film is constant, wear rate of
the PTFE composite must be controlled by the extraction process of the PTFE fibre from the
composite, even if the wear debris were made of the removed transfer film. Then the basic
wear reducing action of the fillers seem either the load supporting action and the prevention
of the large-scale destruction of banded structure or the reduction of the wear debris size. It is
possible to ascertain these mechanisms by the friction test of the PTFE compound filled with
very small particles such as carbon black.
From a more practical point of view, carbon black is one of the low-cost materials in
comparison with the cost of various kinds of materials as the filler of polymer composites
used in the tribogical components. It is widely used commercially in some industries as filler
material of rubber products, as pigment for paint and ink products and as conductor material
of plastic products. Although carbon black is well-known as a filler of rubber such as

automobile tire within the field of tribology, the application of carbon black as a filler
material for polymer composite is seldom reported. It is necessary to investigate the effect of
carbon black filler on the tribological properties of polymer material.
Because of these backgrounds mentioned above, a series of the friction tests were
conducted on the PTFE composite filled with carbon black, the effect of carbon black filler on
the wear and frictional properties of PTFE were investigated, and then the wear reducing
mechanisms of PTFE composites are discussed PTFE in in this chapter.
EXPERIMENT
PTFE Composite Specimens Filled with Carbon Black
Most of thermoplastic resin products are formed by injection molding. On the contrary,
injection molding method cannot be applied for PTFE because PTFE has very high viscosity
at the temperature of over its melting point and it doesn't show fluidity. Thus, PTFE products
are formed with PTFE molding powder by the compression molding, isostatic pressing or ram
extrusion. PTFE molding powder with the diameter ranging from several tens to a few
hundred of micrometer are produced by various chemical manufacturers. PTFE composites
are also formed in the same methods mentioned above by using mixture of PTFE powder and
filler. PTFE powder and filler are mixed quite well in the mixing process of them because a
uniform dispersion of filler in the PTFE matrix is strongly required in order to obtain
favorable tribological properties as well as mechanical properties. In general, fillers are easily
agglomerated and it is hard to uniformly disperse filler materials in the PTFE matrix.
In the sample preparation mentioned in this chaper, a PTFE aqueous dispersion, Fluon
AD911 (Asahi Glass Co., Ltd.) are used as matrix material of PTFE composite specimen.
This product contains 60 mass % of small negatively charged PTFE particles whose median
particle size is 0.25 µm and some polymer dispersant. Carbon black powder is well dispersed
in the PTFE aqueous dispersion with the aid of dispersant in the liquid.
It is considered that one of the most important factors affecting mechanical strength
among the various characteristics of the carbon black is considered to be average particle size.
It is also considered that particle size of carbon black is one of significant factors in the
mechanisms as explained earlier. Therefore several kinds of carbon black were selected as
filler based on its average particle diameter as shown in the Table 1. The values of
representative properties of carbon black, that is, average particle diameter, nitrogen surface
area and DBP absorption can be referred to the manufacturer's data sheets and shown in this
table. For the selected 12 kinds of carbon blacks, the average particle diameter ranges from 13
to 122 nm, nitrogen surface area ranges from 12 to 370 m2/g and the DBP absorption ranges
from 41 to 158 cm2/100g. The carbon black and the PTFE composite filled with each carbon
black are labeled as CB1 to CB12.
Table 1. Average particle diameter, nitrogen surface area and DBP absorption of the
carbon blacks used in the friction test (obtained from the manufacturer's data sheet)
Symbol for carbon black CB13 CB14 CB18 CB22 CB24 CB25
Average particle
13 14 18 22 24 25
diameter, nm
Nitrogen surface
370 290 142 115 125 225
area, m2/g
DBP absorption,
73 98 130 113 165 155
cm3/100g
Symbol for carbon black CB38 CB43 CB62A CB62B CB122A CB122B
Average particle
38 43 62 62 122 122
diameter, nm
Nitrogen surface
56 42 27 32 12 19
area, m2/g
DBP absorption,
158 115 87 140 41 42
cm3/100g
The PTFE dispersion and one of the carbon blacks were mixed and kneaded well in a
mortar and pestle machine for 50,000 times rotating of twin pestles. During this mixing and
kneading process, the liquid mixture of the PTFE dispersion and the carbon black was
changed into a lump. Then the appropriate quantities of lump was put in the metal mold and
pressed into a disk at about 37 MPa for 20 minutes. The thickness of the pressed PTFE
composite disk specimen was about 2 mm. The disk was heated in a vacuum of 10-4 Pa at 380
ºC for 2 hours. Finally, it was naturally-cooled to room temperature.
Friction Test
Most of the tribological investigations, i.e. friction tests are conducted with an apparatus
called "tribometer" which can measure the friction coefficient of the target specimens. Wear
amount of specimen is measured during or after the friction test. A large number of different
tribometers have been developed and are available, for example, Timken tester (ring surface
against disk), four-ball tester (balls against balls), Falex tester (cylindrical surface against V-
block), pin-on-disk tester and so on [12]. Although various types of tribometers have been
practically used to understanding tribological properties of specimens, choosing appropriate
type of tribometer is still one of the big experimental issues for many tribology researchers.
The experimental results of friction and wear are often different from the phenomena
occurring in real machinery unless the appropriate tribometer and experimental conditions are
chosen in the friction test.
A pin-on-disk configuration, that is, a combination of polymer pin against steel disk is
widely used to understanding fundamental tribological properties of polymer material.
However, the tribometer with a ring-on-disk configuration as shown in Fig. 1 was used in the
friction test for the PTFE composite filled with carbon black because it is possible that the pin
specimen scrapes the transfer film and the scraped counterface promotes the wear of the
compound. The ring and disk specimen are mounted on the motor-driven rotating shaft and
the free-rotating shaft respectively. A normal load pressing ring specimen against disk
specimen is transmitted through the motor-driven rotating shaft. If the ring specimen rotates,
the disk specimen rotates together with the free-rotating shaft because of the friction between
the ring and disk specimens. But actually, the rotation of free-rotating shaft is blocked by the
load cell which is mounted to be subjected to frictional force. So the frictional force can be
measured with the load cell.
Ring specimen
Disk specimen
Figure 1. Schematic figure of the ring-on-disk configuration for the friction test.
The disk specimen was PTFE or PTFE composite filled with carbon black. The material
used as the ring specimen was stainless steel (SUS304, the Japanese Industrial Standards) and
its Vickers hardness was 170 HV. The ring specimen is in the shape of a cylinder and its
height, inner diameter and outer diameter are 10 mm, 12 mm and 16 mm respectively. The
sliding surface of the ring specimen, which is the cylindrical section of cylinder, was polished
with the waterproof abrasive paper to provide the controlled surface roughness of less than
0.03 μm (Ra) because a surface roughness strongly affect the wear. The ring specimens were
cleaned ultrasonically with acetone before testing because a contamination on the sliding
surface strongly influences the frictional properties.
The normal applied load was 980 N then the applied pressure was 11.14 MPa. The ring
specimen was rotated with a rotational speed of 300 r.p.m. then the sliding speed was 0.22
m/sec at the mean diameter of the ring. The sliding distance was 2,200 m which corresponds
to the sliding period of about 2.8 h. The temperature of the atmosphere environment was
room temperature. The relative humidity was controlled to be 30 % by flowing dried air into
the sliding test chamber. Sliding test was conducted 3 times for each composite specimen.
The wear amount was obtained by measuring the wear depth at 4 points on the wear track of
disk specimen by contact probe displacement sensor, and then converted into wear volume by
multiplying contact area.
RESULTS AND DISCUSSIONS

Morphology of Carbon Black
Before discussing the results of friction test, we discuss the morphology of carbon black
because the morphology of filler material strongly affects mechanical properties including
tribological properties of polymer composite.
d
bd α
D/2
(a) (b)
Figure 2. Models of (a) the fused junction of carbon black particles and (b) the branch structure of
carbon black aggregate.
Unit of carbon black referred to as an aggregate is a conglomerate of near-spherical

particles that are inseparably fused together making a branched structure [13-16]. Table 1
shows the values of representative properties of twelve kinds of carbon blacks obtained from
the manufacturer's data sheets. The nitrogen surface area is the specific surface area
calculated using the amount of nitrogen gas adsorbed on the surface of the carbon black of
mass 1 g. The DBP absorption is the volume of the dibutyl phthalate (DBP) kneaded into the
carbon black of mass 100 g. It can be considered that the DBP absorption value corresponds
to the volume of the opening space (or the void volume) of the aggregates where the dibutyl
phthalate will be absorbed. These 3 kinds of properties of carbon black mentioned above
closely associated with the morphology of carbon black.
In order to examine the relation among the average diameter of the particles, the specific
surface area and the value of DBP absorption, the specific surface area of a particle and the
relation between the particle diameter and the DBP absorption value were calculated by
assuming a model of carbon black aggregate. Figure 2 (a) shows a model of the fused
junctions of particles thought on the TEM image of carbon black [13, 16]. Where d is the
diameter of particle and bd ( 0  b  1) is the diameter of joint. Then the surface area, A ,
of a particle with n ( n  2 ) joints can be calculated as follows:
A  d 2 
n
2

1  1 b 2 d 2  (1)
Because the value of b can be estimated to be about 0.6 [13, 16], 1  b 2 can be
approximated at 1  b 2 2 ; thus for b  0.6 , 1  b 2  0.8 and 1  b 2 2  0.82 . Then
 d 2 (4  n b 2 )
A (2)
4
For the weight, W , of a carbon particle with n joints, it can be calculated as follow:
 4
   1  1  b 2   d 3 
3
d  2
W     n 1 1 b
2
1     (3)
 3  
2  3   2  
Here  is the density of the carbon black. Using the above approximation, equation (3)
can be written as:
 4 n b 4 (6  b 2 )    d 3
3
d 
W         (4)
2 3 24  6
Then the specific surface area, Asp , or nitrogen surface area of a carbon particle with n
joints can be written as follows:
A 3(4  n b 2 ) g (n, b)
Asp    (5)
W 2 d d
3(4  n b 2 )
g (n, b)  (6)
2
Here g n, b is a function named "g-factor" which was introduced for the convenience
of discussion. The specific surface area, Asp , is inversely proportional to the particle size, d,
if n and b are independent of d , because the density of carbon blacks,  , is assumed to be
constant. Though Asp is a specific surface area of one carbon particle with n joints, it is
considered to be about the same as the nitrogen surface area of the carbon black of which
particle has n joints. Thus Asp can be regarded as the value of nitrogen surface area. In
addition, equation (5) shows that g-factor value corresponds to the product of the average
particle diameter and the nitrogen surface area which is the specific surface area.
In regard to DBP absorption, it was assumed that the shape of an opening space of the
aggregate to be a cone as shown in Fig. 2 (b). In this case, the volume of a conical opening
space per the weight of the particles forming the opening space, VDBP , which corresponds to
the value of DBP absorption, is given by
 ( Nd sin ) 2 Nd cos  N 2 (sin ) 2 cos

VDBP   (7)
3 lNd 3 3 l
Here N is the number of the particles forming each branch of the aggregate,  is semi-
apex angle of the conical opening space,  is the ratio of the particle's volume contained in
the cone and l is the number of the branches forming a conical space. Equation (7) shows the
value of VDBP is independent of the particle size.
Figure 3 shows the relation between the nitrogen surface area and the average particle
diameter. In this figure, a dotted line and a broken line show the relations of Asp  1936 / d
and Asp  3922 / d , respectively. Because all the filled marks fit well with the dotted line of
Asp  1936 / d , the large carbon blacks of d  38 nm have about the same g-factor. On the
other hand, all the unfilled marks are located on the right side of the dotted line. As the
broken line of which g-factor is 3922 nm·m2/g is located on the right side of the dotted line of
which the g-factor is 1936 nm·m2/g, the small carbon blacks of d  25 nm shown with the
unfilled marks have larger g-factors than the large carbon blacks shown with the filled marks.
Thus, the carbon blacks used in this experiment can be categorised into two groups, that is,
the small carbon blacks and the large carbon blacks.
400
Nitrogen surface area Asp, m /g

CB13 CB38
2
CB14 CB43
CB18 CB62A
300 CB22 CB62B
CB24 CB122A
CB25 CB122B
200
2
g1 /d g1 = 3922 nm·m /g
2
100 g2 = 1936 nm·m /g
g2 /d
0
0 20 40 60 80 100 120 140
Average particle diameter d, nm
Figure 3. Relation between specific surface area (i.e. nitrogen surface area) Asp and average particle
diameter d.
200
CB13 CB38
DBP absorption, cm /100g
CB14 CB43
CB18 CB62A
150 CB22 CB62B
3
CB24 CB122A
CB25 CB122B
100
50
0
0 20 40 60 80 100 120 140
Average particle diameter d, nm
Figure 4. Relation between DBP absorption and average particle diameter d.
Figure 4 shows the relation between the DBP absorption and the average particle
diameter. Though the value of VDBP is independent of the particle size as shown in equation
(7), the value of DBP absorption increases with the increase of average particle diameter for
the small carbon blacks (unfilled marks) and decreases with the increase of average particle
diameter for the large carbon blacks (filled marks). For the large carbon blacks, it is possible
to say that the number of particles forming each branch of the aggregates increases with the
decrease of particle size, because the number of particles per unit weight increases with the
decrease of particle size. On the other hand, the same idea cannot be applied for the small
carbon blacks. Then it is satisfactory to consider that the structure of aggregate is broken
during DBP kneading process, because of the small diameter of the fusing point between
particles or small b . Then the small carbon black has a large g-factor because of its small b .
Friction Test Results
A typical effect of the concentration of carbon black filler on the specific wear rate of the
PTFE composite is shown in Fig. 5. The bars and the filled circles show the specific wear rate
and friction coefficient, respectively. Here, the specific wear rate is defined as the value
which divided wear amount in volume by sliding distance and normal load, and it is
expressed in the unit of mm3/(N·m). The best concentration is around 10 mass % for the
highest wear resistance and is around 20 mass % for the lowest friction coefficient. As the
purpose of this experiment was to improve the wear resistance, we conducted the following
experiments at a constant concentration of 10 mass %.
Specific wear rate, ( 10 ) mm /N·m
30 0.10
3
Friction coefficient
-6
20
0.05
10
0 0.00
2.5%
5%
10%
15%
20%
25%
Concentration of carbon black
Figure 5. Specific wear rate and friction coefficient of PTFE composite filled with carbon black (CB13)
in various concentrations.
Figure 6 shows the specific wear rate and friction coefficient of PTFE without filler
(PTFE) and three kinds of PTFE composite filled with carbon black (CB), graphite (Gr),
carbon fiber (CF), tungsten disulfide (WS2) and molybdenum disulfide (MoS2) in their
optimum concentration for reducing wear. These fillers except carbon black are widely used
as the filler materials in the commercially available PTFE composites as previously
mentioned. The wear rate of PTFE composite filled with carbon black filler and that of MoS2
filler are shown in almost the same level. Both of them show lower wear rate than the other
fillers. Although the addition of the filler material to PTFE generally makes friction
coefficient to be increased, the PTFE composite filled with carbon black tends to show lower
friction coefficient than PTFE without filler.
0.15
180
3
-6
20 0.10
10 0.05
0 0.00
PTFE CB Gr CF WS2 MoS2
Figure 6. Specific wear rate and friction coefficient of PTFE without filler (PTFE) and PTFE composite
filled with carbon black (CB), graphite (Gr), carbon fiber (CF), tungsten disulfide (WS2) and
molybdenum disulfide (MoS2).
The specific wear rates and friction coefficients for a pure PTFE and the PTFE
composites filled with twelve kinds of carbon blacks are shown in Fig. 7. The composites
filled with large carbon blacks as CB38, CB62 and CB122B show lower friction coefficient
than the pure PTFE. For the specific wear rate, small carbon blacks are apt to decrease the
specific wear rate and the lowest specific wear rate is about 50 times lower than that of the
pure PTFE obtained by the friction test of the composite filled with CB22.
Figure 8 shows scanning electron microscopic images of the wear debris for the large
carbon blacks. In case of wear debris formed during the sliding test of the composite that
shows low specific wear rate, long and narrow ribbons or short and wide ribbons are observed
as shown in Fig. 8 (a), (b), (c) and (d). On the other hand, the wear debris formed by the
friction test of the composites that show high specific wear rate are long and wide as shown in
Fig. 8 (e) and (f). These results correspond with the interpretation [8] that the wear resistance
of PTFE can be improved by reducing the wear debris in size.

180
3
0.10
-6 20
0.05
10
0 0.00
Pure
CB13
CB14
CB18
CB22
CB24
CB25
CB38
CB43
CB62A
CB62B
CB122A
CB122B
Figure 7. Specific wear rate and friction coefficient of PTFE without filler (Pure) and PTFE composites
filled with 10 mass % of carbon black.
(c) (d)
(e) (f)
Figure 8. SEM images of wear debris of PTFE composite filled with carbon black. (a) CB38, (b) CB43,
(c) CB62A, (d) CB62B, (e) CB122A and (f) CB122B.
Figure 9, 10 and 11 show the variation in the friction coefficient and the specific wear
rate with the average particle diameter, the nitrogen surface area and the DBP absorption of
the carbon black used as the filler, respectively. As shown in Fig. 9 (a), though the friction
coefficient for the composites filled with small carbon blacks (unfilled marks) is higher than
that for the composites filled with large carbon blacks (filled marks), the friction coefficient is
independent of the particle size. On the other hand, the specific wear rate decreases with the
decrease of particle size as shown in Fig. 9 (b).

20
CB13 CB38
3
CB14 CB43
0.10 CB18 CB62A
15 CB22 CB62B
CB24 CB122A
-6
CB25 CB122B
10
0.05
CB13 CB38
CB14 CB43 5
CB18 CB62A
CB22 CB62B
CB24 CB122A
CB25 CB122B
0.00 0
0 50 100 0 50 100
Average particle diameter d, nm Average particle diameter d, nm
(a) (b)
Figure 9. Relations between (a) the friction coefficient and the average particle diameter d, (b) the
specific wear rate and the average particle diameter d.
The friction coefficient decreases linearly with the decrease of nitrogen surface area of
the carbon black as shown in Fig. 10 (a). In case of specific wear rate, though the increasing
rate of the specific wear rate is different to a large extent from the small carbon blacks
(unfilled marks) to the large carbon blacks (filled marks), the specific wear rate decreases
with the increase of the nitrogen surface area as shown in Fig. 10 (b).
Fig. 11 (a) shows that the value of friction coefficient of the composite filled with small
carbon blacks (unfilled marks) decreases slightly with increase in the DBP absorption value.
The friction coefficient for the composites filled with small carbon blacks show higher
friction coefficient than the composites filled with large carbon blacks (filled marks). The
specific wear rate of composite increases linearly with the increase of the DBP absorption
value of the carbon black filled for the small carbon blacks and decreases with the increase of
the DBP absorption value for the large carbon blacks as shown in Fig. 11 (b).

20
CB13 CB38
3
CB14 CB43
0.10 CB18 CB62A
Friction coefficient 15 CB22 CB62B
CB24 CB122A
-6
CB25 CB122B
10
0.05
CB13 CB38
CB14 CB43 5
CB18 CB62A
CB22 CB62B
CB24 CB122A
CB25 CB122B
0.00 0
0 100 200 300 400 0 100 200 300 400
2 2
Nitrogen surface area A sp, m /g Nitrogen surface area Asp, m /g
(a) (b)
Figure 10. Relations between (a) the friction coefficient and the nitrogen surface area Asp, (b) the
specific wear rate and the nitrogen surface area Asp. Specific wear rate, ( 10 ) mm /N·m
20
CB13 CB38
3
CB14 CB43
0.10 CB18 CB62A
15 CB22 CB62B
CB24 CB122A
-6
CB25 CB122B
10
0.05
CB13 CB38
CB14 CB43 5
CB18 CB62A
CB22 CB62B
CB24 CB122A
CB25 CB122B
0.00 0
0 50 100 150 200 0 50 100 150 200
3 3
DBP absorption, cm /100g DBP absorption, cm /100g
(a) (b)
Figure 11. Relations between (a) the friction coefficient and the DBP absorption value, (b) the specific
wear rate and the DBP absorption value.
Effect of Carbon Black on the Friction Coefficient
Though Asp is a function of d as shown in equation (5), the friction coefficient of the
PTFE composite was directly proportional to Asp as shown in Fig. 10 (a) and was
independent of d as shown in Fig. 9 (a). This inconsistency was caused by the difference of
the range changing between Asp and d , that is, Asp changes widely for small carbon blacks
and d changes widely for large carbon blacks.
Therefore the relation between the friction coefficient and the g-factor was obtained as
shown in Fig. 12. The friction coefficient decreases almost linearly with the decrease of g-
factor. This result means that the friction resistance originates in the mechanical interaction
between aggregates, because the g-factor increases with the decrease of n and/or b as shown
in equation (6) and the decrease of n or b makes the profile of the aggregates rough by
reducing the number of branches for n and by reducing the diameter of joints for b as shown
in Fig. 13. When the profiles of the aggregates is smooth, the shearing resistance between the
PTFE composite and PTFE transfer film on the counterface become same as that between
pure PTFE and PTFE transfer film.
0.10
0.05
CB13 CB38
CB14 CB43
CB18 CB62A
CB22 CB62B
CB24 CB122A
CB25 CB122B
0.00
0 1000 2000 3000

g-factor
Figure 12. Relation between friction coefficient and g-factor value.
b·d n=2 b·d n=3
(a) (b)
Figure 13. Models of the profile of carbon black aggregate for (a) small b and n (n=2) and (b) large b
and n (n=3).
Furthermore, the hard aggregates heighten the pressure in the real contact areas. Then the
friction coefficient,  , of the PTFE composites which is lower than that of pure PTFE will
be obtained by obeying the following equation [17].

 (8)
p
Here  is the shear strength of pure PTFE and p is the pressure in the real contact area.
Effect of Carbon Black on the Wear
Though it was reported [6] that the large filler was more effective at reducing wear rate
than the small filler, the specific wear rate increased with the increase of average particle size
as shown in Fig. 9 (b). In case of carbon black filler, however, it is possible that the
aggregate, not particle, acts as the size of filler. Therefore the size of the aggregate was
estimated as follows.
When the number of particles forming each branch of the aggregates increases m pieces (
 as the following equation.
N  m ), the DBP absorption, VDBP (equation (7)), become VDBP
 ( N  m) 2 (sin  ) 2 cos
 
VDBP (9)
3 l
  VDBP . Then the increasing rate of the DBP absorption is given by

Here, VDBP
 VDBP ( N  m) 2  N 2 2m
VDBP
  (10)
VDBP N2 N
When the number of particles forming each branch of the aggregates increases m pieces,
the diameter of the aggregate increases by m d . Then the ratio of the diameters of aggregates
can be estimated, using equation (10), by the following equation.
D2 2 N 2 d 2 ( N 1  m)d 2 (VDBP 2  V DBP 1 )d 2

   (11)
D1 2 N 1 d1 N 1 d1 2V DBP 1 d1
Here D1 and D2 are the diameters of aggregates for two kinds of carbon blacks and N1
and N 2 are the number of particles forming the branches of their aggregates and d1 , d 2 and
VDBP1 , VDBP 2 are their particle diameters and DBP absorption values, respectively.
Table 2 shows the ratios between the estimated diameters of aggregate of carbon blacks
and that of CB122B, D / DCB122B . As D / DCB122B increases with the increase of particle
size, we can say that the small aggregate reduces the specific wear rate.
Table 2. Ratio of the aggregate diameter referring to the diameter of CB122B
Symbol for carbon

CB13 CB14 CB18 CB22 CB24 CB25
black
D/DCB122B 0.15 0.19 0.30 0.33 0.48 0.48
Symbol for carbon
CB38 CB43 CB62A CB62B CB122A CB122B
black
D/DCB122B 0.74 0.66 0.78 1.10 0.99 1.00
These results show that the reduction of wear debris in size should be the main action of
fillers to reduce wear rate of composite, though it is probable that the aggregate‘s diameters of
small carbon blacks are underestimated by breaking during the DBP kneading process.
On the other hand, it is possible that the friction force control the extracting speed of the
wear debris. Therefore, we obtained the relation between the specific wear rate and the
product of the average particle diameter and friction coefficient as shown in Fig. 14.
20
CB13 CB38
3
CB14 CB43
CB18 CB62A
15 CB22 CB62B
CB24 CB122A
-6
CB25 CB122B
10
0
0 2 4 6 8 10
Friction coefficient  Particle diameter
Figure 14. Relation between the specific wear rate and the product of friction coefficient and average
particle diameter.
As the standard deviation of the line fitting 1.54 for Fig. 14 is less than that of 1.80 for
Fig. 9 (b), it is satisfactory to consider the wear mechanism of PTFE-carbon black composite
as the extraction of the molecular chain. The wear reducing action of carbon black is to make
it difficult to extract the PTFE fibre from the composite by getting caught in the carbon black.
In this way, the excessive filler content or large filler would promote the inter-winding
between the fibre and the carbon black to a large degree, and result in high wear rate.
CONCLUSION
Effect of carbon black as a filler of PTFE composite was investigated and the wear
reducing capability of carbon black was revealed. Addition of carbon black drastically
decreased the wear amount of PTFE and its wear reducing effect was comparable or better
comparing with the conventional filler materials. The relation between the tribological
properties of PTFE composite filled with the twelve kinds of carbon black and the
morphological properties of carbon black were studied, and then the following conclusions
were obtained.
1) The friction coefficient of the PTFE composites filled with carbon black decreased
linearly with the decrease of the nitrogen surface area of the carbon black filler and
with the decrease of product of the nitrogen surface area and the average particle
diameter, g-factor.
2) The PTFE composites filled with large carbon blacks show lower friction coefficient
than that of the pure PTFE.
3) The specific wear rate of the PTFE composites filled with carbon blacks decreased
with the decrease of the product of the average particle diameter and friction
coefficient.
4) The wear reducing action of carbon black is considered to be the prevention of
extracting the PTFE fiber from the PTFE composite.
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[14] Ungár, T.; Gubicza, J.; Ribárik, G.; Pantea, C.; Zerda, T. W. Carbon 2002, 40, 929-937.
[15] Medalia, A. I. J. Colloid and Interface Sci. 1970, 32, 115-131.
[16] Hess, W. M.; Herd, C. R. In Carbon black: science and technology; Donnet, J. B.;
Bansal, R. C.; Wang, M. J.; Ed.; Marcel Dekker. Ins.: New York, US, 1993; pp. 89-173.
[17] Bowden, F. P.; Tabor, D. The Friction and Lubrication of Solids; Oxford University
Press: Oxford, UK, 1958; pp 90-121.
Chapter 8
THE ROLE OF CARBON BLACK IN THE

RHEOLOGY OF RUBBER COMPOUNDS:
DYNAMIC PROPERTIES, NONLINEAR
BEHAVIOR AND MODELING
Fabio Bacchelli* and Salvatore Coppola

Polimeri Europa, Centro Ricerche Elastomeri, Ravenna, Italy
ABSTRACT
Rubber compounds, even when reinforced with approximately spherical particles,
represent highly concentrated suspensions characterized by complex interactions between
filler particles and between particles and polymer. Unlike a concentrated suspensions
with low viscosity matrix, the rheological behavior of a rubber compounds can be
described using a single medium approach. In comparison with the rheology of polymer
melts and solutions, these filled systems display yield-like behavior and very long
relaxation phenomena which reflect the processes of flocculation and aggregation of
particles as well as disruption of particle aggregates in the medium. Long memory of the
deformation history is also observed and related to slow restructuring phenomena.
Additionally, rubber compounds display highly nonlinear viscoelastic behavior and
viscoelastic parameters depending on concentration and structure of particles.
Rheological properties are assessed for polybutadiene based rubber compounds and
advanced investigative techniques are used to characterize the filler network as well as
the state-of-mix. The role of filler interactions in shear and extension is investigated. It is
shown that reinforcement is due to hydrodynamic effects together with the build-up of a
secondary particulate structure within the rubber matrix and the consequent amount of
immobilized polymer. In terms of compound processability, this study attempts to point
out the effect of state-of-mix on the transient elongational response of uncured systems.
The K-BKZ model is implemented in order to describe and predict the transient
rheological response of the investigated rubber compounds in the linear and nonlinear
regime. The behavior of uncured systems is also described by means of the semi-
* Polimeri Europa, Centro Ricerche Elastomeri, Ravenna, Italy, Via Baiona 107, I-48123 Ravenna, Italy,
fabio.bacchelli@polimerieuropa.com
158 Fabio Bacchelli and Salvatore Coppola
empirical Leonov‘s model starting form the linear viscoelastic response of the polymer
matrix.
INTRODUCTION
Whatever the chemical nature and composition, rubber compounds are reinforced system
of complex heterogeneous nature. They are consisting of several phases and at least one phase
is a viscoelastic material. As a consequence, particular morphologies are observed, arising
from interactions between the polymer matrix and the reinforcing network. The resulting
structure strongly affects flow properties and rheological response.
Addition of fillers into polymers is a common industrial practice and carbon black is
widely used to reinforce elastomers. Among factors that basically determine the behavior of
filled polymers, like the structure of the filler, the viscoelasticity of the polymer matrix and
the interfacial interactions, the state of dispersion is known to be extremely important. Rubber
compounds are obtained by melt blending because of the large amount of dispersive mixing
that can be achieved by this way, due to the high viscosity of the molten polymer [1].
Active fillers, such as high surface area carbon blacks, interact both with the polymer
matrix and with each other. Physical adsorption of rubber molecules takes place on the filler
surface [2], occluding part of the polymer in internal voids. This results in a partial
immobilization of the elastomer and an apparent increase of the filler volume fraction [3, 4].
Moreover, filler particles form aggregates and agglomerates resulting in a secondary structure
represented by a filler-filler network [5].
Rheology is the science of deformation and flow of matter, whose investigation tools
essentially result from continuum mechanics considerations. The presence of a reinforcing
filler is known to induce dramatic changes in the rheological behavior of a polymer and this
effect is generally attributed to three main contributions: the hydrodynamic effect of the filler
in the molten polymer, the change of the relaxation times of the matrix and the building of a
filler network. Strong nonlinear viscoelastic behavior are observed both in shear and
extension.
EXPERIMENTAL
A commercial high-cis-polybutadiene (high-cis-BR) characterized by a cis content of
97% was investigated (Neocis BR40, Polimeri Europa). The polymer, nearly linear, has an
average molecular weight of 420000 g/mol and a polydispersity index of 3.8. Two series of
compounds were prepared in a laboratory Brabender Plasticorder using different mixing
procedures. The first was obtained by adding a nearly spherical carbon black (N990) and
other high structure grades (N330, N121). The second was obtained with the N330 at two
different times of mixing. The added volume fraction of filler was 0.21 for all compounds.
The linear viscoelasticity of high-cis-BR was investigated by means of a stress controlled
Anton Paar Physica MCR 501 and a strain controlled Rheometrics Ares A11. Frequency
sweep measurements were performed with a cone-plate configuration (25 mm, 0.1 rad) in the
range 30÷110°C and curves were shifted by TTS to 23°C. The dynamic modulus of carbon-
The Role of Carbon Black in the Rheology of Rubber Compounds 159
black-filled polybutadiene was determined at 23 °C using grooved parallel plates (20 mm, 2
mm gap). To avoid slippage, a 10 N load for 30 min was applied before starting the
measurement. Frequency sweep was performed in stress-controlled mode, with a resulting
strain amplitude always below 0.03 strain units. The investigated frequency range was
extended by performing stress relaxation and creep experiments and by converting data by
means of Schwarzl formulas [6]. The software used for the calculation of relaxation spectra
was the Anton Paar Rheoplus/32 v. 2.62. Large amplitude strain sweep experiments were
performed using an Alpha Technologies RPA2000 closed chamber rheometer, equipped with
serrated biconical geometry.
Stress growth experiments on unfilled and filled polybutadiene were performed in
uniaxial extension at constant deformation rate using two different extensional platforms. A
home made assembly [7] based on a four wheels Rheotens 71.97 tensile tester produced by
Göttfert was employed for testing compounds at different mixing times (first series of
compounds). Elongational measurements reported in the modeling section (second series of
compounds) were performed using a SER-HV-P01 commercial fixture [8] hosted by the cited
Anton Paar Physica MCR 501 rotational rheometer. Extruded cylindrical specimens for
extensional measurements were prepared by means of a Göttfert Rheograph 6000 capillary
rheometer and relaxed for at least three days before measurement.
RESULTS AND DISCUSSION

The presence of a filler results in a hydrodynamic increase in viscosity. This concept,
developed by Einstein [9], is based on the flow disturbance and energy dissipation around a
spherical particle in laminar flow of a Newtonian medium. The ratio of the suspension‘s and
the solvent's viscosities, η and η0, is found to be dependent on the filler volume fraction υ:

f   1  2.5 (1)
0
This ratio, a relative viscosity, may be referred to as a hydrodynamic reinforcement factor

f. Guth and Gold [10] extended this relationship to higher concentrations of filler taking
interparticular interactions into account:
f  1  2.5  14.1 2 (2)
The Guth-Gold equation is usually valid for the case of elastomer-filler reinforcement.
Considering frequencies and durations of two-body collisions, Manley and Mason [11]
determined the second coefficient as 10.05. In the present paper an empirical extension of the
previous equation as suggested by Thomas [12] will be used:
f  1  2.5  10.05 2  AeB (3)
where A = 0.00273 and B = 16.6 are found to be valid for various systems.
This description is in line with the assumption that in a polymer network the relaxation
times remain unchanged while the filler particles hydrodynamically affect the modulus. Then,
in viscoelastic systems both the steady-state viscosities at a given shear rate and the dynamic
moduli at a given frequency are connected by a hydrodynamic reinforcement factor. Systems
with inactive fillers only show hydrodynamic reinforcement. The shift factor required for this
operation can be identified with the hydrodynamic reinforcement factor f.
In systems filled with interacting particles a further reinforcement is observed to be
associated with a secondary filler structure. Particles or aggregates may interact directly by
van der Waals or hydrogen bonds or indirectly via the polymer. This is generally termed filler
network, even though the structure is not comparable to a continuous three-dimensional
polymer network structure.
Moreover, for high structure blacks reinforcement no longer depends on the theoretical
filler volume fraction but on some effective filler concentration, which takes the polymer
immobilized or occluded into account. It can be assumed that the effective filler volume
fraction is linearly related to the actual value by an effectiveness factor β as proposed by
Kraus [13]:
eff f   (4)
As the amount of polymer immobilized by the filler is assumed to enhance viscosity and
dynamic moduli, it must be independent of stress in the linear viscoelastic range. Therefore,
no effect of flow kinematics is to be expected and the hydrodynamic reinforcement factor f of
the dynamic moduli in this region is constant with respect to both amplitude and frequency.
Fillers, when added to polymer systems, are known to cause a considerable change in
dynamic properties. It is also known that the dynamic properties of compounds, dynamic
hysteresis in particular, can to a great extent be influenced by filler morphology, namely
surface area and particle size distribution. Since the secondary network is not a perfectly
elastic body but exhibits loss mechanism through particles rearrangement, a contribution is
observed to both storage modulus and loss modulus. Assuming that the stresses in this
secondary structure and in the polymer network may be superimposed, the linear dynamic
moduli of the filled systems may be written as [14]:
G' ( )  f (eff )  G'0 ( )  G'S ( )  f (eff )  G'0 ( )  GS

(5)
G" ( )  f (eff )  G"0 ( )  G"S ( )  f (eff )  G"0 ( )
where the index 0 represents the pure elastomer and the index S the secondary structure.
Low strain oscillating techniques are widely used for investigating the linear viscoelastic
rheological response of polymer systems. Figure 1 represents the dynamic shear moduli of the
investigated high-cis-BR together with the response of carbon black filled compounds in the
linear viscoelastic range. Data of compounds based on carbon blacks with different surface
areas are reported. The filler volume fraction is above the percolation threshold. As expected,
the reinforcing effect of N330 is much larger than that of the low surface area N990, which
qualitatively also shows a moduli trend comparable to that of the pure elastomer. The dashed
lines represent the prediction of equation (5), with the reinforcing factor calculated on the
basis of equation (3) and the effective volume fraction estimated according to equation (4)
with values of βfrom Eggers and Schümmer [14].
Figure 1. Linear viscoelastic behavior of polybutadiene and related carbon black compounds. Dashed
lines represent the prediction of equation (5), with the combination of hydrodynamic reinforcement and
secondary structure.
The reinforcing action of carbon black can also be described by analyzing the relaxation
dynamics of the filled systems. In Figure 2 the relaxation spectra of carbon black compounds
are reported and compared to that of the pure elastomer. Large differences are observed at
longer times, were the filler contribution in slowing down the terminal relaxation is
particularly effective. The spectrum of the N990 based compound is qualitatively similar to
that of the polymer matrix, accounting for a dominant effect of hydrodynamic reinforcement.
The introduction of the high surface area N330, with his important secondary structure,
completely changes the shape of the relaxation spectrum, moving the characteristic maximum
of the pure elastomer to shorter times and enlarging the range of very long relaxation
dynamics. This result should be discussed in terms of transient rheological response, a
concept very close to the compound processability. Dimensionless parameters, as for example
the Deborah and Weissenberg numbers [15], commonly used to compare the characteristic
time of the material with the characteristic times of experimental practice, are obviously
governed by the reported relaxation behavior.
Figure 2. Relaxation spectra of high-cis-polybutadiene and related carbon black compounds. Dashed
lines help to point out differences and similarities among spectra.
While performing strain sweep experiments in oscillation, the linear viscoelastic behavior
is usually achieved below a shear strain of 0.1%, and the modulus is observed to fall off with
increasing amplitude beyond a sort of yield point strain whose magnitude decreases with
increasing proportion of filler. At high strains, the drop in modulus is large, and all the
compounds appear to approach the unfilled pure gum whose modulus is low throughout the
amplitude scale.
Figure 3. Schematic representation of the Payne effect.
The modulus of filled elastomers arises, according to Payne [16, 17], from several
contributing factors which can be classified as follows (Figure 3):
 pure gum contribution which depends on the kind of elastomer used (and on the
crosslink density in the case of cured systems)
 hydrodynamic or strain amplification effect which is based upon the concept that the
local strain in between the filler particles is amplified over the externally applied
macroscopic strain
 polymer-filler interactions: elastomer-carbon black bonds acting as crosslinks
 filler-filler interactions: the carbon black structure is believed to be responsible
for the increases in the dynamic modulus at low strains.
The decrease in elastic modulus upon increasing strain amplitude, attributed by Payne
[16, 17] to the structure of the carbon black, may be visualized as filler–filler linkages of
physical nature which are broken down by straining. The breakdown of the filler network by
increasing strain amplitude would release the immobilized rubber so that the effective filler
volume fraction and hence, the modulus would decrease. This mechanism suggests that the
Payne effect can serve as a measure of filler networking which originates from filler–filler
interaction as well as polymer–filler interaction.
Figure 4. Strain dependence of the normalized shear modulus for polybutadiene and related compounds
obtained with carbon black of different surface area.
A typical graph showing the shear modulus variation with strain amplitude of filled high-
cis-polybutadiene (normalized using the plateau modulus of the pure polymer) is shown in
Figure 4 and compared with the contribution of the pure elastomer. As expected, the
normalized shear modulus decreases with increasing the amplitude of oscillation. The effect
is more pronounced with carbon black of high surface area and is then associated with the
properties of filler particles. The normalized shear modulus has been found to have a limiting
value both at low strains and at high strains, when further changes of modulus with strain are
negligible. The quantity at very high strains represents the dynamic shear modulus when all
the carbon black structure has been broken down. This is higher than the gum modulus due to
hydrodynamic effects plus the filler-polymer contribution.
The differences in filler networking associated with the filler structure are depicted in
Figure 5, where the AFM technique has been used [18] to produce the reported images of
polybutadiene/carbon black compounds. Isolated nearly spherical particles of N990 are
clearly visible, while aggregates are observed in the case of N330.
Figure 5. AFM images of polybutadiene compounds with different filler structure, BR/N990 (left) and
BR/N330 (right). Image size is 20 μm.
Simple shear is the customary mode of deformation for the study of rheology. However,
simple shear experiments do not provide all the information necessary to describe
processability of rubber compounds. The milling behavior of gum elastomers and filled
rubber was first studied by Tokita and White [19] who distinguished four characteristic
milling regions that can be readily interpreted in terms of extensional flow properties of
rubbers associated with convergent flows such as that at the approach to the nip. Similar
arguments can be used to describe milling in an internal mixer: as the rotor advances, the
rubber passes successively through extensional flow and high shear regions to reach the void
behind the rotor. In general the mixing process involves both extensional and shear flows,
where the extensional flow is more efficient in the dispersion and break-up of rigid aggregates
during filler dispersion. The significance and importance of the extensional flow investigation
in the processing of rubber was discussed by Nakajima [20], who pointed out that the
elongational behavior plays an important role in mixing elastomers with carbon-black. Cotten
and Thiele [21], working on extensional behavior of carbon black filled SBR rubber at
constant deformation rate, found that the composite curve showed no tendency to reach a
steady state viscosity even at the lowest strain rate of 1.8·10-4 s-1 and some upward curvature
continued to persist. In analogy with shear behavior, they observed a viscosity decrease with
increasing the strain rate and with decreasing the carbon black loading. They also reported
that, while higher carbon black loading or different carbon black structure caused an increase
in viscosity without changing the transient plot shape, an increase in carbon black surface
area was responsible of both an increase in viscosity and in the upward curvature of the
transient stress growth.
The amplification factor previously described in terms of shear modulus according to
Payne‘s representation can be extended to extensional data. In Figure 6, the ratio between the
tensile stress of a polybutadiene carbon black compound and that of the pure elastomer is
reported for various fillers. A strong dependence on the strain rate is observed for all systems,
accounting for the high sensitivity of complex systems to the extensional flow. The simple
hydrodynamic contribution predicted by equation (1) and (2) results to be only valid for the
nearly spherical, low surface area N990 at low stretch ratios.
Figure 6. Amplification factors in uniaxial extension for polybutadiene/carbon black compounds at two
deformation rates and various stretch ratios.
According to Medalia [22, 23] and Tokita and Pliskin [24], the dependence of the
compound rheology on the state-of-mix can be related to the presence of immobilized
polymer in the form of occluded rubber. Occluded rubber is a geometrical concept and refers
to rubber, which is situated within the irregular contours of a filler aggregate and it is thus
shielded from stress. In the well-dispersed stage, the carbon black particles are individually
isolated or grouped in small aggregates while at an earlier stage of mixing the particles at the
same filler loading are not well dispersed and can be found to be agglomerated with one
another. Each agglomerate contains not only filler particles, but also has rubber occluded
between the particles. When stress is applied, the entire filler agglomerate with its occluded
rubber behaves as a single filler particle so that the effective filler volume fraction in the early
stages of mixing is always larger than that of the well-mixed compound. The effective
volume fraction φE(t), in the early stages of mixing is always larger than that of the well-
mixed compound. Namely
 E (t )    OR (t ) (6)
where φOR(t) is the occluded rubber volume fraction at time t. The effective volume fraction
decreases with mixing time. Accordingly, the poorly dispersed compound always shows
higher viscosity.
Figure 7 concerns with the transient extensional response of polybutadiene/carbon black
composites obtained at different mixing time. The hydrodynamic effect can be deduced from
the difference between the linear viscoelastic envelope of the compounds and three time the
transient shear viscosity of the pure elastomer, according to the Trouton rule [15]. Both
systems exhibit strong nonlinearities and a pronounced strain hardening is observed, to be
intended as the upward detachment from the linear viscoelastic response. At shorter mixing
time, a less efficient carbon black dispersion is expected together with a higher effective filler
volume fraction and, consequently, a more pronounced strain hardening is observed. This is
particularly true at low deformation rates, where the filler network disruption due to the
extensional flow is less effective.
Figure 7. Transient extensional behavior of polybutadiene/N330 compounds at different state-of-mix

and various deformation rates. The linear viscoelastic response of the pure elastomer according to
Trouton rule is also reported.
Plots of the engineering stress versus stretch ratio are reported in Figure 8 showing in
detail the contribution of carbon black loading on the extensional response of the polymer
matrix, together with the effect of a different filler dispersion. According to Nakajima [20]
and Cotten and Thiele [21], the stress growth curve shows no tendency to reach steady state
even at the lowest investigated deformation rate. Some upward curvature continues to persist
and a limiting strain (rupture strain) was reached in every measurement. Comparable s-like
courses of the engineering stress were previously reported by Dreval‘and Borisenkova [25].
The stress-strain plot of a rubber compound shows a more complex behavior respect to that of
the polymer matrix, as a consequence of the already discussed interaction with the filler.
Phenomena associated to stretch ratios higher than 3 are clearly due to filler networking and
related reassessment upon deformation. According to the response of the pure elastomer, a
clear strain dependence is only observed in the case of well-mixed compound.
Figure 8. Stress growth in uniaxial extension for the pure polybutadiene (a) and polybutadiene/N330
compounds obtained at different mixing time (b, c).
The amplification factor in uniaxial extension, already shown in Figure 6 for various
fillers, can be used to represent the variation in occluded rubber as a function of carbon black
dispersion. In Figure 9, the ratio between the tensile stress of pure polybutadiene and that of
the N330 compound is reported for the two investigated times of mixing. As expected, the
optimization of carbon black dispersion leads to a strong decrease of the amplification factor,
accounting for a large decrease of the effective filler volume fraction. Amplification factors
are not comparable to those reported in Figure 6 for N330, due to a different mixing
procedure.
Figure 9. Amplification factors in uniaxial extension for polybutadiene/carbon black compounds

obtained at two different mixing times.
The variation of the effective volume fraction upon mixing can be further investigated by
analyzing the relaxation behavior after cessation of extensional flow. Measurements at
deformation rate 0.04 s-1 were performed on polybutadiene/carbon black compounds. The
extensional deformation was stopped after stretching times of 10 and 30 s and the results
superposed with the tensile stress growth curve of an uninterrupted steady extension
performed at the same deformation rate. The results are shown in Figure 10 where the effect
of the different mixing time on the composite rheology is clearly observed in terms of
different strain hardening and stress relaxation. Data are in agreement with the previously
reported concept of occluded rubber and its effect on the effective filler volume fraction. The
retarded relaxation of the filled polymer characterized by incomplete mixing (3 min, higher
effective filler volume fraction) is also in qualitative agreement with previously published
results obtained by shear stress relaxation experiments [26], where a decrease in the rate of
stress relaxation is reported at higher carbon black load.
Figure 10. Relaxation after cessation of steady extension for polybutadiene/N330 compounds at
different state-of-mix. Stretch ratios reached before starting relaxation are reported.
As a confirmation of the previously discussed findings, the compound morphology as a

function of the state-of-mix can be accounted for by direct observation through Atomic Force
Microscopy (Figure 11). In the well dispersed state, uniformly distributed aggregates with an
average aggregate size of about 100 nm are visible, according to the literature [1]. At shorter
mixing time, large filler clusters or agglomerates of about 1 μm in size are observed together
with unfilled areas and aggregates.
Figure 11. AFM images of polybutadiene/N330 compounds at different state-of-mix, 3 min mixing
(left) and 10 min mixing (right). Image size is 5 μm.
MODELING
In this section, first we briefly recall some fundamentals on the rheological modeling of
viscoelastic liquids then we compare the predictions of few selected models with the results
of stress growth experiments in uniaxial extensional flow carried out on the above-mentioned
samples of high cis-BR and its compounds with N990 and N330, respectively.
The displacement of two points inside a continuous body in the period between a time t‟
in the past and the current time t, can be described by means of the displacement gradient
tensor E, which in cartesian components can be expressed such as:
xi (t ')
E(t , t ')  (7)
x j (t )
where the common Einstein‘s convention has been used for the repeated indexes (this
convention will be further used in following).
If a deformation in a continuous body of material has to be considered alone, excluding
any contribution from rigid body motion, the Cauchy strain tensor [27, 28] has to be used:
C(t, t ')  ET (t, t ')  E(t, t ') (8)
The Cartesian components of the Cauchy strain tensor are readily determined to be:
xk (t ') xk (t ')

C(t , t ')  (9)
xi (t ) x j (t )
It is often convenient, when dealing with viscoelastic liquids, to take the current time t as
the ―reference‖ state and the past time t‟ as the ―deformed‖ state. The relevant tensor then
becomes the inverse of the Cauchy strain tensor, better known as the Finger strain tensor. Its
Cartesian components are given by:
xi (t ) x j (t )
C1 (t , t ')  (10)
xk (t ') xk (t ')
Considering the two important particular cases of shear flow and uniaxial extensional
flow we thus obtain the following expressions for the Finger strain tensor:
Shear flow
 t 
2 t 
1      x  dx     x  dx 0 
 t'  t' 
 t

 
C1 (t , t ')      x  dx 1 0 (11)
 t' 
 0 0 1
 
 
 
Uniaxial extensional flow
  t  
 exp  2    x  dx  0 0 
  t'  
 
  t
 
1
C (t , t ')  0 exp      x  dx  0 (12)
 
  t'  
  t 
 0 0 exp      x  dx  

  t' 
where x is a dummy variable, and integrands represent the arbitrary shear rate and Hencky
strain rate for shear and uniaxial extensional flow, respectively.
Now that we have the strain measure ready, we can turn our attention towards the
determination of the stress tensor which is of course dependent on the model we choose for
the description of the viscoelastic liquid.
The basic model for viscoelastic liquids is with no doubt the so called Lodge model [28].
It intends to describe the mechanical behavior of a temporary network of Gaussian strands
connecting junctions that move affinely with deformation (rubberlike liquid). It is here worth
recalling that permanent (cross-linked) networks are well describe in first approximation by
the neo-Hookean expression [15], which gives for the stress tensor the following expression:
τ  kTC1 (13)
where  is the number concentration per unit volume of elastic strands, k is the Boltzmann
constant, T is the absolute temperature.
Unlike the case of a permanent network, in Lodge‘s model:
1) The strands are connected by temporary junctions

2) The strands are ―alive‖ (i.e. mechanically active) only while their junctions are still
―alive‖.
3) The active strands are created at a constant rate and have a life-time distribution
which is independent of the deformation.
If  is the number concentration per unit volume of mechanically active elastic strands,
b the rate of ―birth‖ of strands per unit volume, and f(t-t‟) is the strands life-time distribution
(i.e. the fraction of strands born in the interval between t‟ and t‟ + dt‟ and that are still ―alive‖
at time t) then the time-independent number concentration of mechanically active strands is
given by:
t
    b f  t  t ' dt ' (14)

It is now possible to compute the stress in the material analogously to the case of
permanent networks. In particular, the stress according to Lodge‘s model is carried only by
the strands that are still ―alive‖ at time t:
t
τ    b f  t  t ' kTC1  t , t ' dt ' (15)

or, which is the same:
t
 kT  f  t  t 'C1  t , t ' dt '
τ 
t
(16)
 f  t  t 'dt '

In the last expression, there is a function of t-t‟ only, represented by:
 kT f  t  t '
t
(17)
 f  t  t 'dt '

The latter represents the memory of the material exactly as the ―memory function‖ m(t-t‟)
from the theory of Linear Viscoelasticity [29]:
G  t  t ' dG  x  
H  
m  t  t '     exp   x /   d ln  (18)
t ' dx 

where x=t-t‟, G(x) is the relaxation modulus and H() is the relaxation time spectrum [29].
According to Lodge‘s model, the stress tensor can therefore be expressed more generally
such as:
 m t  t 'C t, t ' dt '

1
τ (19)

As already pointed out above, a key assumption of Lodge‘s model is that network
junctions are not affected by deformation. It is possible to actually remove this hypothesis
adopting the so called K-BKZ model [28]:
 m  I , I , t  t ' C t, t '  m  I , I , t  t ' C t, t 'dt '

1 1
τ 1 1 2 2 1 2
(20)

where m1 and m2 are two time and strain-dependent memory functions, I1 and I2 are the first
and second invariant [27] of the Finger strain tensor. In order to achieve proper reduction in
the limit of small deformations and, based on the experimental results that demonstrated the
factorization of time and strain [30, 31], Wagner derived the following modified expression
for the K-BKZ model [32]:
 m t  t ' h  I t, t ' , I t, t ' C t, t 'dt '

1
τ 1 2
(21)

The latter equation is the most commonly known version of the K-BKZ model. The
 
kernel function inside the integral, h I1  t , t ' , I 2  t , t ' , represents the ―damping function‖
and can be derived from experimental results in shear and in extension.

Doi and Edwards [33], through a microrheological approach obtained a simple integral
constitutive equation, similar to that of the K-BKZ model. Doi-Edwards theory proved to be
very successful in predicting many features of the non-linear viscoelastic behavior in shear
flow but does not predict any strain-hardening in extensional flow [33]. However, this model
successfully predicts a universal damping function in shear deformation for entangled
polymers, approximated by [34]:

h    (22)
  2
where =3.63 gives the best fit to the original Doi-Edwards prediction.
In this work, we have therefore chosen to introduce the Doi-Edwards damping function into
the K-BKZ constitutive equation (21) with the aim of predicting both shear and extensional
behavior. For extensional flow, according to Papanastasiou et al. [34], the damping function
can be conveniently expressed as:

h  I1 , I 2   (23)
  3   I1  (1   ) I 2
In the present work, we use a zero value for the  parameter, while retaining the same
value determined in shear flow for the  parameter.
Here it is worth noting that damping functions values lower than the Doi-Edwards
function are always likely to be affected by experimental artifacts (such as slip at the
polymer/tool interface) [28]. For this reason, K-BKZ equation (Doi-Edwards damping
function) and Lodge‘s model (constant damping function equal to unity) represent two
limiting cases of the integral constitutive models.
In the figures below, we report the stress growth experimental results for the high cis-BR
used in this study as well as for its related compounds with N990 and N330, respectively. In
figures 12-14, the predictions of Lodge‘s model and K-BKZ model with Doi-Edwards
original damping function (=3.63) are reported for a direct comparison with experimental
results.
It is evident that in all cases Lodge‘s model overestimates the strain hardening behavior
of the investigated materials. K-BKZ model is able to make satisfactory quantitative
predictions for the raw polymer sample, especially at high Hencky strain rates (figure 12). It
is almost needless to say that the use of Lodge‘s and K-BKZ model has to be considered with
care in the case of filled materials but a comparison has been shown nevertheless in figures
13-14. Significant disagreement with experimental results is indeed obtained for both models
in the case of filled polymers. Moreover, in the case of high cis-BR / N330 compound, the
stress is overestimated even in the linear viscoelastic limit. This will be further discussed
below. It is worth recalling here that all other physically relevant choices for the damping
function parameters would have falled in between Lodge‘s and K-BKZ predictions.
It is evident from the discussion reported above that the viscoelastic behavior of the
investigated unfilled and filled elastomers is not very satisfactorily predicted by Lodge‘s and
K-BKZ models.
We now focus our attention onto a differential model proposed by Leonov [35, 36, 37]
for the prediction of unfilled and filled polymers where polymer-filler interactions are
prevalent. In this model, the polymer chains are viewed as ―trapped‖ and ―free‖ depending if
they are connected to the filler surface or not. The deformation evolution of the ―free‖ chains
is described by the following tensorial differential equation:

2 c b  I1 , I 2  c2  c  I 2  I1  / 3  δ   0 (24)
where  is the relaxation time, c is the Finger tensor,  is the unit matrix and the down
triangle represents the upper convected time derivative [27]. Clearly, the function b(I1, I2) is
phenomenological and provides to the model the necessary flexibility to predict the behavior
of polymers with different structure. The latter function works actually as a deformation
history dependent scaling factor for the relaxation time . In the present work this function
takes the form:
b  I1 , I 2    I 2 / I1 
m
(25)
The differential tensorial equation for the deformation of trapped chains is expressed such
as:

2 s  f   s 2  s  J 2  J1  / 3  δ   0 (26)
Where f() is the mobility factor, i.e. a deformation history dependent scaling factor for
the relaxation time of trapped chains. J1 and J2 are the first and second invariant of the Finger
tensor for the trapped chains,  is the fraction of initially trapped chains that are debonded
from the particles. Its evolution is described by the following scalar equation:
2
d  v   v T  1   
     2  tr   (27)
dt  2  *
 
where v is the velocity vector and * is the strain at which yielding occurs. The elastic
potentials for free an trapped chains are given by the following expressions:
W f  I1 , I 2  
3G
2  n  1

1     I1 / 3  1    I 2 / 3  1
n 1 n 1
 (28)
Wt  J1 , J 2  
3G
2  n  1

1     J1 / 3  1    J 2 / 3  1
n 1 n 1
 (29)
From these expressions the stress tensor for free and trapped chains can calculated:
a    W f W f 
σf  2 c  c1  (30)
1  a  I1 I 2 
1    Wt 1 Wt 
σt  2 s s  (31)
1  a  J1 J 2 
where a is the initial ratio of free to trapped chains.

The above illustrated model can be easily extended to a multimode version, accounting
for the usual polydispersity of polymeric materials. The details of this extension can be found
in the original paper by Joshi and Leonov [35]. The input data of the model are the above
mentioned material parameters and the linear viscoelastic moduli of the materials (Figure 1).
In figures 15-17, the comparison between the experimental results and Leonov‘s model
predictions is depicted. The parameters adopted for implementing Leonov‘s model are m=1.6,
n=0, =0.8 for all samples. Different values have been of course chosen for the structural
parameters *, a and in particular *=30%, a=500 for high cis BR / N990 compound,
*=0.5%, a=50 for high cis BR / N330 compound. It has been assumed that the mobility
factor is given by f()=. The values for the critical yielding strains have been approximately
determined by means of Payne effect experiments (Figure 4).
A much better agreement is found with experimental results for the raw polymer (Figure
15) and for the high cis BR/N990 compound (Figure 16). The shape of the stress growth
curve is well captured by the model in the strain hardening region at all Hencky strain rates.
Slight differences for the high cis BR/N990 compound are evidenced at the lowest Hencky
strain rate but this is probably related to the naturally incomplete knowledge of the relaxation
spectrum fitted with the multimode version of the model. A more significant difference is
instead observed for the high cis-BR/N330 compound (Figure 17). Even if the strain
hardening behavior is qualitatively well predicted, we find again a significant deviation in the
prediction of the response a low strains, i.e. in the so called linear viscoelastic limit.
Figure 12. Transient extensional viscosity of high cis-BR at four different Hencky strain rates. Lines are
predictions of K-BKZ (continuous) and Lodge‘s (dashed) model (see text for details).
This deviation is found either using a viscoelastic spectrum determined from Small
Amplitude Oscillatory Extension (SAOE) or from Small Amplitude Oscillatory Shear
(SAOS) experiments. As the SAOS experiments have been carried out checking that the
response was inside the linear viscoelastic range, the failure in matching the mechanical
response at low strains (Figure 17) can be related with the failure of Cox-Merz rule [15]. Such
failure has already been reported in the literature [38, 39, 40] and a modified Cox-Merz rule
has been proposed by Gleissle and Hochstein [39] to take into account the effect of
hydrodynamic forces in suspensions. This modified Cox-Merz rule fails as well when
polymer-filler and filler-filler interactions become dominant. Therefore it cannot work for our
high cis-BR / N330 compound as the frequency dependence of the complex modulus is very
different from that of the raw polymer (Figure 1). For all the above mentioned reasons, the
difference observed in Figure 17 is most probably related to the fact that the filler-filler
interactions are not negligible [39] in contrast with the main assumptions of the implemented
version of Leonov‘s model. This aspect certainly deserves further investigation, also
considering the relevance of high Surface Area fillers for actual applications.
Figure 13. Transient extensional viscosity of high cis-BR / N990 compound at four different Hencky
strain rates. Lines are predictions of K-BKZ (continuous) and Lodge‘s (dashed) model (see text for
details).
strain rates. Lines are predictions of K-BKZ (continuous) and Lodge‘s (dashed) model (see text for
details).
Figure 15. Transient extensional viscosity of high cis-BR at four different Hencky strain rates. Lines are
predictions of Leonov‘s model (see text for details).
strain rates. Lines are predictions of Leonov‘s model (see text for details).
strain rates. Lines are predictions of Leonov‘s model (see text for details).
CONCLUSION
Rubber compounds represent highly concentrated suspensions characterized by complex

interactions between filler particles and between particles and polymer. A very long memory
of the deformation history together with a strong nonlinear viscoelastic response is observed
as a consequence of restructuring phenomena. It is shown that reinforcement in a carbon
black filled polybutadiene is due to hydrodynamic effects together with the build-up of a
secondary particulate structure within the rubber matrix and a consequent amount of occluded
and immobilized polymer. In this frame, rheology proves to be a powerful tool for
investigating the complex behavior of rubber compounds. Among rheological techniques, the
transient extensional response results to be very sensitive to the filler network as a function of
the state-of-mix. The K-BKZ and Lodge strain dependent models were implemented in order
to describe and predict the transient rheological response of the polybutadiene compounds in
the linear and nonlinear regime. It has been confirmed that this class of simple models do not
represent the best choice for the description of such complex systems. Experimental results
were also described by means of the semi-empirical Leonov‘s model starting form the linear
viscoelastic response of polymer matrix and filled compound. While a satisfactory agreement
was found for polybutadiene filled with a low surface area carbon black (N990), model
failure is observed in the case of high structure N330, also in the linear viscoelastic limit,
accounting for a large and complex filler-filler interaction.
ACKNOWLEDGMENTS
The authors wish to thank Polimeri Europa for the permission to publish this paper. The
authors are also indebted to Dr. Maria Francesca Pirini for the AFM contribution. Alberto
Abbondanzieri, Pier Dante Tavolazzi and Danilo Visani are acknowledged for their technical
support.
REFERENCES
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[22] Medalia, A. I. Rubber Chem Technol 1972, 45, 1171-1194.
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Chapter 9
CARBON BLACKS FOR ENERGY

STORAGE AND CONVERSION
Gui-xin Wang* and Kang-ping Yan‡

College of Chemical Engineering, Sichuan University, Chengdu, China
ABSTRACT
The key physicochemical properties related to energy storage and conversion of
carbon blacks, such as structure, accessible specific surface area, texture, morphology,
and surface chemistry, are summarized. The status of the applications of carbon blacks
for energy storage and conversion, including primary batteries, rechargeable batteries,
supercapacitors, air batteries, fuel cells, solar cells, hydrogen energy, biomass energy,
and nuclear energy, has been reviewed. The applications of carbon blacks as conductive
additives, electrode materials, current collectors, catalysts, catalyst supports, high

efficient fuel, and reducing agents, are described systematically. The main factors
affecting the state-of the-art performance are analyzed. The existed issues and challenges
of carbon blacks for energy storage and conversion are discussed. Besides the
conventional applications of carbon blacks in batteries and supercapacitors, it is
considerably promising and competitive for the following perspectives: green catalysts to
decompose hydrocarbon, catalyst supports, electrode materials of solar cells, accelerant
of biomass energy, reductive of nuclear fuel, and high efficient fuels for direct carbon
fuel cells. Some aspects, including feedstock, manufacturing conditions, post treatments
* Gui-xin Wang received his Ph.D. degree in Applied Chemistry from the Graduate University of the Chinese
Academy of Sciences in 2006, and then joined the State Key Laboratory of Materials-Oriented Chemical
Engineering and the College of Chemistry and Chemical Engineering, Nanjing University of Technology. He
joined the faculty of the College of Chemical Engineering, Sichuan University in 2007. He has more than 20
refereed publications, several book chapters and numerous patents, several of which have been licensed. His
recent work focuses on the synthesis and characterization of novel materials for possible energy
storage/conversion and sensor applications, and corrosion protection for materials and equipments. E-mail:
guixin66@scu.edu.cn, guixin68@yahoo.com, Tel.: +86-28-85406192
‡ Kang-ping Yan is a professor at the College of Chemical Engineering, Sichuan University. He has more than 70
refereed publications, and numerous patents, several of which have been licensed. He is also the editor in chief
for several ―China National 11th 5-year Plan Teaching Materials‖ published by the Chemical Industry Press.
His research focuses on the electrochemical engineering, energy materials, and aluminium foil for electrolytic
capacitors. E-mail: ykp@scu.edu.cn, Tel.: +86-28-85406192
184 Gui-xin Wang and Kang-ping Yan
and good dispersion, should be paid attention to further improve the performance. Carbon
blacks or carbon black composites with specific function will become more important
and more competitive for energy storage and conversion.
1. INTRODUCTION
As an attractive function material, carbon black has gained considerable attentions from
fundamental research to applications. According to the International Carbon Black
Association [1], carbon black [C.A.S. No. 1333-86-4] is high-pure elemental carbon in the
form of colloidal particles and produced by incomplete combustion or thermal decomposition
of gaseous or liquid hydrocarbons under controlled conditions. The coalesced colloidal sized
quasi-spheroidal particles have a paracrystalline graphitic microstructure and partially
contribute to the formation of smallest primary units (i.e. aggregates) of carbon blacks.
Carbon black generally contains greater than 97 wt.% elemental carbon arranged as aciniform
(grape-like cluster) particulate, and is chemically and physically district from soot or black
carbon which are commonly refer to various unwanted carbonaceous by-products resulting
from the incomplete combustion of carbon-containing materials, such as oil, fuel oils or
gasoline, coal, paper, rubber, plastics and waste material. Furthermore, soot and black carbon
typically contain less than 60 wt.% carbon and large quantities of dichloromethane and
toluene extractable materials, and can exhibit an ash content of 50 wt.% or more [1]. In fact,
carbon blacks are generally a generic term for a family of carbon products which have a great
variety of types and diverse trade names according to different standards. As one of the top 50
industrial chemicals manufactured worldwide based on annual tonnage, current worldwide
production of carbon blacks is about 18 billion pounds (8.1 million metric tons) per year, and
approximately 90% is used in rubber industry [1].
Various grades of carbon blacks can be compartmentalized according to the
characteristics like structure, morphology (shape, particle or pore size distribution, pore or
void volume, degree of aggregation or agglomeration), surface chemistry, and a number of
other properties which depend on specific applications. Based on the manufacturing process,
carbon blacks can be categorized as lampblack, channel black, furnace black and thermal
black [1-3]. These carbon blacks are different greatly in their chemical composition, structure,
texture and surface chemistry. Each kind of carbon black has its own advantages: Lampblack,
first produced by the Chinese over 3,500 years ago, is the primogenitor of modern carbon
black and has been used as a pigment for centuries [1]; Channel black produced from natural
gas was the major carbon black used worldwide in the early twentieth century for rubber and
pigment applications and the exception of a special product made in Germany; Furnace black
and thermal black have been produced since the early twentieth century, and occupy the main
market of current carbon blacks [2,3]. Thereinto, furnace black and thermal black produce
nearly all of the world's carbon blacks, with the furnace black produced by the furnace
process using heavy aromatic oils as feedstock being over 90% of all current carbon blacks.
The thermal black process uses natural gas (consisting primarily of methane or heavy
aromatic oils) as feedstock material to be decomposed into carbon black and hydrogen in a
hot refractory lined furnace without air. The by-produced hydrogen gas is recycled to burn in
air to preheat the reaction precursor. The produced carbon blacks will be further processed to
remove impurities, pelletized, screened, and then packaged for shipment. Currently, more
Carbon Blacks for Energy Storage and Conversion 185
than 99% carbon blacks are produced by partial combustion processes using natural gas or
heavy aromatic oils, and temperature has a strong influence on the carbon black yield. At the
same time, the environmental and energy consumption issues are greatly serious.
Consequently, production with green clean technology and low cost is a big challenge to the
sustainable development of carbon blacks. Besides reducing or eliminating carbon oxide
emissions during the producing process, choice of raw materials, new technique or
sustainable energy is promising and competitive to produce carbon blacks. For example,
decomposition of renewable materials like vegetable or straw by plasma treatment is an
innovative technology for producing carbon blacks, while thermal decomposition of natural
gas using solar energy is an ideal alternative method to produce carbon blacks and hydrogen
as solar energy is steady enough to satisfy the continuous production [4].
2. PHYSICOCHEMICAL PROPERTIES
2.1. General Properties
Carbon blacks possess unique physicochemical properties including mass density, surface
area, structure, morphology, texture, surface chemistry, solubility, electrical properties,
optical properties, and so on. As one of common carbon materials, they are light (mass
density is usually no more than 2.3 g cm-3) and insoluble in water. The physical appearance is
black and finely divided pellet or powder shapes [1]. Electrical properties are closely related
to the efficiency of energy storage and conversion, and will be discussed separately in another
section. Typical index parameters utilized to describe the general physicochemical properties
of carbon blacks are as follows: specific gravity, adsorbed iodine value, dibutyl phthalate
(DBP) oil absorption, vapor pressure, relative vapor density, flash point, pour point,
kinematic viscosity, sieve retaining, appearance, carbon content, ash content, impurity (like
sulfur, lithium, and other elements) content, and so on. Of these factors, structure [5-8],
texture and surface morphology [5-14], and surface chemistry [5-7,9-12,14-16] have an
important influence on the performance of carbon blacks for energy storage and conversion.
These parameters are strongly affected by the carbon sources, manufacturing technics,
operational conditions and post treatment.
As a fundamental characteristic of carbon black, structure is used to describe chain or
clustered aggregate formation and can be high or low depending on the intended applications
[13]. So structure is a measure of the complexity of the carbon black aggregate particle and
reflects how the constituent primary particles are connected. It is essentially related to the
graphitic characteristics which dominate the electrical conductivity of carbon blacks.
However, it is also used to refer to the topology and the pore distribution [9]. Carbon black
has a dominating paracrystal graphitic microstructure, and some regions have amorphous and
regular graphitic-like arrangement. Furthermore, amorphous structure of carbon black can
also be rearranged to form discrete layer planes indicative of graphite structure after being
heated at 2800 oC (5072 oF) in an inert environment for 2 hours, and the distance between the
layer planes near the surface of the particle approaches the theoretical value of 0.3354 nm of
graphite [22]. The structure of carbon black particles is strongly affected by both carbon
sources and synthesis conditions.
The structure of carbon blacks is always analyzed with XRD, high resolution
transmission electron microscope (HRTEM) and Raman spectrograph. A microstructure
model based on an XRD investigation showed that small crystallites within a single carbon
black particle were randomly oriented, and a white mist formed in huge furnaces for the
industrial production of carbon black showed that a condensed phase of precursor soot (a high
temperature stable form of hydrocarbon) existed in the formation process of carbon black
(mature soot) [23]. XRD patterns for carbon blacks are constituted of (001) three-dimensional
and (hk) two-dimensional reflections, so a type of turbostratic structure where the graphene
layers (graphitic planes) are parallel but rotated around c-direction can be identified. The
degree of crystallinity differs appreciably from particle to particle even for the same carbon
black sample. Whether one nucleus or multiple nuclei can form one individual particle of
carbon black, while the particles containing multiple nucleation sites are more inclined to be
poorly ―graphitized‖ [24]. The interior region of one particular usually shows more abnormity
than the exterior one [6,24]. Transmission electron microscope (TEM, especially HRTEM), a
intuitionistic technique to investigate the microstructure of carbon blacks, can detect the
graphene layer structure with arrangement [13,24,25]. In Raman spectra, carbon black has the
characteristics for sp2 carbon disorder-induced (D) and graphite (G) bands, and the integrate
intensity ratio of the D to G band (ID/IG) reflects the texture ordering and degree of
graphitization [26,27]. The D band and G band locate at around 1330 and 1590 cm-1,
respectively. The relative intensity ratio of ID/IG is related to the structural properties of
carbon [28]. This ratio can reflect the perfection of the graphitic-layer structure and the
properties of the edge planes or boundaries of graphite crystal faces. As the value of ID/IG
increases, the defect structure generally gains, while the degree of graphitization becomes
smaller, so the electronic conductivity declines [29]. Ball milling will affect the surface
structure, and the value of ID/IG increased from 1.6 to 2.1 after ball milling, indicating the
original partial graphitization was damaged significantly and the defect structure increased
[30].
Surface morphology and texture concerns more the physical characteristics, such as
shape, fractal dimension, surface roughness, specific surface area, particle size and
distribution, pore size and distribution, average diameter, pore volume, void volume,
aggregation and agglomeration [9,11,13,14]. Carbon black is essentially consisted of
elemental carbon in the form of nearly spherical colloidal size particles (primary particles
with average particle sizes ranging from several to ~100 nm), and the fundamental
inseparable units of carbon black are aggregates comprised of particles which seem to be
virtually continuous on the lattice scale. These carbon black particles are mainly constructed
of parallel graphene layers arranged in a concentric fashion [24]. The structure inside these
primary particles is complex enough to be explained by an atomic scale and a mesoscopic
scale (short-range order as well as medium-range order). According to the different
preparation conditions, the internal structure of the carbon black is various, such as
amorphous, bent layers with concentrically arranged, bent layers with paracrystalline
structure, bent layers with statistically arranged, plane crystallites with statistically oriented
and onion-like structure. Of all types of internal structures, bent three-dimensional subunits or
single bent graphene layers dominate the primary carbon black particles which are generated
by resistive heating of graphite electrodes or condensation in a quenching gas atmosphere of
He, Ar, Ar/H2 and pure H2, and these bent carbon aggregates are composed of disordered
three-dimensional arrangements of about 3 ~ 5 layers. Carbon atoms are able to form three
different basic types of hybridization (i.e. sp, sp2 and sp3) to determine the kind of bondings
between the C-atoms and the possible heteroatoms like oxygen, nitrogen and sulfur. The
strength of the curvature is affected by the hybridization state of carbon atoms which is
related to the type of bonding, and the deviation from the plane structure results in a
combined effects of lower electron density of graphitic bonding and higher number of
intermediate hybridization states located between sp2 and sp3. Furthermore, the total
hybridization state of the carbon blacks represents an integral dimension to quantify the
various sizes and curvature radii of bent graphene layers present in one primary particle [25].
The internal structure of carbon black particles on a mesoscopic scale is described by
different models [6,31] according to the assumption that that the structure-forming units of
carbon black particles are mainly consisted of basic structural units (BSUs) like
nanocrystalline or turbostratic graphitic regions. In these substructures, many graphene layers
are stacked together, and the distances between the layers are larger than 0.3348 nm (expected
for pure graphite) and the graphene sheets are shifted against each other [32]. The sizes of the
BSUs in the plane (La) range from a few to 2 ~ 3 nm, and the extent of the graphitic
crystallites is limited by the incorporation of oxygen or tetrahedrally coordinated carbon
atoms. The BSUs in the primary carbon black particles will be arranged concentrically or
randomly [33]. The BSU oriented randomly may form carbon black, while the one oriented to
a plane, axis or point, may result in planar graphite, a whisker or a spherule. The
paracrystalline model [6] considered that the disturbed and bent graphene layers arranged
concentrically, and the deviation from the plane structure of the graphene layers is associated
with the formation of mixed hybridization states.
Figure 1. Internal structure of carbon black particles produced in Ar: (a) statistical arrangement of plane
graphite crystallites (100 mbar Ar) with corresponding model; (b) paracrystalline structure in particles
(10 mbar Ar) with corresponding model. Reproduced from ref. [25].
Surface morphology or internal microstructure is often determined by techniques like

microscopy (including TEM, SEM, AFM, STM), X-ray diffraction (XRD), BET (Brunauer
Emmett Teller), BJH (Barrett Joyner Halenda), t-plot, dibutyl phthalate (DBP) absorption,
and so on. The fractal dimension of carbon blacks is markedly affected by the pyrolysis
conditions, and surface fractal dimension (Ds) decreases with increasing pyrolysis pressure
and temperature, while the low Ds indicates a low surface roughness [13]. Under different
cooling gas pressure, the internal structure and the corresponding model of carbon black are
different (Fig. 1) [25]. As far as current most commercially produced carbon black, average
primary particle diameter generally ranges from 10 to 400 nm, while average aggregate
diameter usually ranges from 100 to 800 nm. In addition, particle or pore size distribution will
frequently affect the surface area, pore volume, average particle size of carbon blacks, so does
their performance. Graphitization treatment will usually decline the surface area of carbon
blacks because of improved graphene arrangement orders.
Carbon black is usually consisted of primary particles whose basic building blocks are
individual graphene layers instead of crystallites, which has been demonstrated by
transmission electron microscope results [23,25,34]. These graphene layers exhibit numerous
distortions and discontinuities to form various types of carbon black. Though some carbon
atoms are present in graphite-like layer, there is no long range three-dimensional order as in
graphite. The dimensions of these graphitic domains are characterized by the average stacking
height of the parallel layers in the ―c‖ axis (Lc) and the average diameter of the parallel layers
in the ―ab‖ plane (La), which can be determined by X-ray diffraction. The dimensions of the
crystalline regions, especially Lc, increase in general with specific surface area decreasing or
radius of the spherical primary carbon black particles increasing [6]. Variation in the stacking
of the poorly developed graphene layers leads to the measured broad distribution of
interplanar spacings, and the level of crystalline development is obviously different from
particle to particle. XRD analysis results indicated that the stacking height (Lc) of the
graphene layers of carbon black particles initially scales with its average particle size, and
then levels off beyond a certain value in spite of increasing particle size, while the diameter of
the graphene layers (La) is little dependent on the particle size. As expected, the overall pore
surface area correlates inversely with particle size [24]. If the carbon blacks have more
amorphous structure, the number of stacked layers and condensed rings in the plane will
decrease, indicating the crystallite sizes in c- and in a-direction decline [25]. Determined from
radial distribution function (RDF) data [35], the interatomic distances and number of
neighbors which are essential for graphite monolayers (as shown in Fig. 2) in commercial
carbon blacks and the carbon blacks from vacuum pyrolysis have small difference, indicating
the graphene layers within the same graphitic domain are not arranged in a crystal-like
structure. The distance between the layers in carbon black is 0.36 ~ 0.37 nm, and the location
of the neighbouring carbon atoms in the adjacent layers distribute randomly to yield a various
changes of carbon-carbon distances, agreeing with the accepted turbostratic structure of
carbon black. The change may be related to the radius of curvature because a larger radius of
the carbon black particle will allow a more undisturbed arrangement of the graphene layer in
an ordered graphite-like structure.
Figure 2. Number of neighbors and the interatomic distances in a single layer of graphite. Reproduced
from ref. [35].
Surface chemistry is another important property of carbon blacks, and mainly refers to
defects and chemisorbed complexes like surface function groups or other hetero atoms. Apart
from influencing the conductivity [16,19], surface chemistry plays a decisive role in well
dispersing carbon blacks [18], improving surface activity and enhancing the efficiency of
energy storage and conversion. The varying degrees of surface chemistry mostly depend on
the conditions of manufacturing process [10] or post treatments (such as surface modifying,
oxidizing, halogenating, nitrifying, and sulphonating) [18].
The anomalous arrangement of carbon atoms will lead to the defects on the surface and
the heterogeneously distributed surface energy of carbon blacks. The surface defects, as well
as the extent of the disorder of graphene layer structure, are always associated with the
surface activity of carbon blacks. Higher concentration of surface defects will usually lead to
higher surface reaction activity, which closely links the surface chemistry. Removing carbon
atoms from the first and the second graphite layer will create pit shaped defects on the
surface. The concentration of surface defects can be determined effectively by either the area
between the isotherms of a carbon black and defect-free graphitized carbon black or the area
of the first layer formation peak of the adsorption potential distribution (APD), and thermal
carbon blacks produced from natural gas have a higher concentration of surface defects than
furnace blacks and thermal blacks produced from oil feedstock [36].
There are various acid and basic properties on the surface of carbon blacks. Acid
properties are originated from surface oxygen functional groups [37], while basic properties
are related to the basal planes of the graphene layers and the π electrons of these layers can
act as Lewis bases [38,39]. The concentration of the basic sites at the graphene planes can be
estimated from X-ray photoelectron spectroscopy (XPS) analysis, while the combined
concentration of basic sites and basic oxygen groups at graphene planes can be obtained by
titration with a hydrochloric acid [39]. Typical oxygen-reach functional groups on carbon
surface are as follows: carboxyl, carboxylate, ether, quinine, phenol, aldehyde, lactone, nitryl,
sulfonate, and so on [40]. These functional groups will modify the surface characteristics and
the behavior of carbon blacks [41,42]. It is reported that incorporation of oxygen into
graphene sheet layers will lead to the formation of heterocyclic ring systems [43]. O and S
will make the graphene arrays distort to produce a fairly broad distribution of d-spacings
(0.35 ~ 0.41 nm) despite of particle size and structure [22]. The carbon atoms located at the
edges of the graphene layers may possess unsaturated valences and have a tendency to reduce
their potential energy by forming bonds with oxygen [23]. Typical classes of chemicals
adsorbed onto the carbon black surface are polycyclic aromatic hydrocarbons (PAHs), nitro
derivatives of PAHs and sulfur-containing PAHs. In the case of commercial carbon black,
organic contaminants such as polycyclic aromatic hydrocarbons (PAHs) can only be extracted
under very rigorous laboratory analytical procedures using organic solvents or high
temperatures [1].
These functional groups and adsorbed complexes are always associated with the volatile
content and conductivity of carbon black. What‘s more, they will become active sites during
reactions and greatly influence the wettability of the electrode materials to electrolyte which
is very important for the electrochemical performance. Thus, the surface chemistry will do
good or harm to batteries. It is not difficult to understand the advantages of surface chemistry
for enhancing the performance of carbon blacks because the complexes can become active
sites, store electrolyte, and improve dispersion. At the same time, the high activity will also
lead to key self-discharge reactions in batteries. In order to improve the dispersion and the
performance characteristics of carbon blacks, specific surface chemistry should be carefully
designed and performed in especial solution by manufacturing or post treatment process.
2.2. Electronic Properties
The electronic properties play a significantly role in the applications of carbon blacks for
energy storage and conversion, and they are greatly affected by some factors, such as carbon
source [5-8,45], structure (such as degree of graphitization, graphene layer distance, topology,
pore distribution, pore volume, void volume) [5-7,9], average size [5,7], compression
pressure [7,14,17], impurities [12], and surface chemistry [5,10,12,15-17]. In nature, these
multiform factors will ultimately influence the electron tunneling which is by far the most
important for conductivity because electron tunneling involves the ability of electrons to jump
the gaps between closely spaced carbon black aggregates, and measures including narrowing
the gaps and increasing interaggregate contact should have key effects in increasing the
electrical conductivity [16]. Carbon black has a combined structure of amorphism and
graphite, and the electronic structure is mixed sp2/sp3 forms. [5]. The conductivity of carbon
blacks is originated from the graphene layer, and high degree of graphitization will generally
produce high conductivity. In addition, high microstructure including high specific area and
pore volume presents a good conductivity at very low mass density or high volume fraction of
carbon blacks [6]. Greater amount of chain-like structure of carbon blacks will shorten the
distance between particles or aggregation to allow electrical flow to pass easily through along
the molecular chains. Therefore, carbon blacks with good structure generally have high
conductivity together with high surface area. Carbon black produced from acetylene is
regarded as a highest degree of aggregation and crystalline orientation in comparison with all
types of carbon black [8]. The electrical conductivity of the carbon blacks with small surface
area generally increased with the graphitic character of the surface, and the surface graphitic
character has a determining influence on the conductivity [5]. The specific conductivity of
carbon blacks is typically in the range from 0.1 to 100 (Ω∙cm)-1, and is affected by graphitic
conduction via touching aggregates and by the relative ability of electrons to jump the gap
between closely spaced aggregates (electron tunneling) [6].
Compression pressure will greatly affect the electrical conductivity and the mechanical
work [6,15]. The conductivity usually increases with increasing pressure because aggregates
of carbon blacks will be rearranged into more dense packing and much closer contacts
between different aggregates under compression [12,46,47]. In addition, pressure has close
relation with the mechanical work, and he patterns of dependence of the conductivity on
pressure and mechanical work were similar. Of the opposing effects involved in the influence
of mechanical work on the conductivity, pressure effect appeared to be more important than
volume effect. Both the conductivity and its variation under compression were closely
associated with the density of the carbon blacks: the increase in conductivity with decreasing
volume was more distinct for the carbon black whose volume under compression was smaller,
and the total increase in conductivity was more marked for the densest carbons and least for
the lightest one [15]. However, the electrical conductivity will change at very high pressures
because of the reorientation of carbon black graphene layers [12,48].
Surface chemistry will also influence the electrical conductivity of thermal and
conductive carbon blacks, and the conductivity generally increases with decreasing
concentration of surface oxygen and sulphur functional groups. Based on tight-binding
approximation (TBA) and density functional theory (DFT), Chutia [19] found that the
presence of organic functional groups (OFGs) such as –OH and –CHO groups in the
periphery of the graphene layers of the carbon black basic structural units (BSUs) affected the
electronic properties of carbon black. According to the various types of topological
associations such as C-H∙∙∙C, O-H∙∙∙C, C-H∙∙∙O, O-H∙∙∙O, the two different sets of models
including plane arrangements and stacking arrangements of OFGs are shown in Fig. 3. With
the substitution of such OFGs in the pristine graphene layers, the energy gaps obtained by the
difference of the energy of highest occupied molecular orbital (HOMO) and lowest
unoccupied molecular orbital (LUMO) of the systems decreased, which can be attributed to
the increase in the number of π and lone pair electrons due to the OFGs. The change of
energy gaps associated with the topological association among the OFGs and with the
graphene moieties was seen to be marginal, and the chemical topology of the BSUs plays a
key role in the electrical properties of carbon black aggregates. However, Pantea [12] found
some carbon blacks with similar concentration of surface oxygen and sulphur functional
groups had different conductivities, and the conductivity was correlated best with the
polyaromatic character of the carbon black surface characterized by the C2H-/C2- peak ratio of
the static secondary ion mass spectroscopy analysis. They also found that the surface probed
by secondary ion mass spectroscopy (SIMS) is more important for the conductivity than the
surface-near region probed by the asymmetry of the electron spectroscopy for chemical
analysis (ESCA) carbon peak, and the electrical conductivity had no correlation with bulk
structure of carbon black. Furthermore, the surface chemistry of oxygen- and sulphur-
containing functional groups has only a very limited influence on the conductivity [5,14].
Copyright © 2011. Nova Science Publishers, Incorporated. All rights reserved. 192 Gui-xin Wang and Kang-ping Yan
Figure 3. (Color online) (a) (G–G)σ, (b) (SG–SG)CCσ, (c) (SG–SG)OCσ, (d) (SG–SG)OOσ carbon black
models of in plane arrangements (above); and (a) (G–G)π, (b) (SG–SG)OCπ, (c) (SG–SG)OOπ carbon
black models of stacking arrangements (below). Reproduced from ref. [19].
In addition, heating treatment, especially graphitization treatment which is carried out by

annealing at high temperatures in an inert atmosphere, will greatly influence the degree of
graphitization, structure, porosity, surface chemistry and volatile content, so does the
electrical conductivity of carbon blacks. With similar particle size and structure, the electrical
conductivity of carbon blacks depends on the polyaromatic character of the first atomic layer,
and heat treatment at temperatures ranging from 670 to 870 ºC can desorb the surface
carbonaceous deposits or transform the deposits into more polyaromatic structures to enhance
the electrical conductivity [14]. Carbon black annealed at above 2000 ºC showed a higher
degree of ordering, as suggested by the very strong intensity of G band [25] and the TEM
analysis results [19]. Graphitization heat treatment of a precursor carbon black could
effectively produce a wide variety of forms (unusual parallel stacking of graphene sheets
along with increased crystallographic order in the c-direction) of partially graphitized
nanosized carbonaceous materials with a set of unique properties, and the thickness of
graphite shell was at least a factor of 2 higher than that typical of acetylene black. At the same
time, graphitization heat treatment will also change the constitution and improve the purity of
carbon black [19].
2.3. Characterization
As far as the various properties of carbon blacks, plenty of methods and techniques are
utilized to characterize qualitatively or quantitatively, and the usually adopted tools with their
corresponding testing function are summarized in Table 1.
Table 1. Typical tools for the characterization of carbon blacks
Techniques Testing contents

XRD (X-ray diffraction) Bulk structure, grain size, unit cell parameters,
degree of graphitization and composition
SAXS (small-angle X-ray scattering) Structural features, surface fractal dimension
Raman spectrum Using D band, G band and intensity ratio ID/IG to
determine the degree of graphitization and surface
structural characteristics
IR (infrared) or FT-IR (Fourier transform infrared) Surface functional groups
spectra
XPS (X-ray photoelectron spectroscopy) Elemental analysis, surface chemical states, surface
defects, atom binding energy
XRF (X-ray fluorescence) Elemental analysis (half-quantitative)

MS (mass spectrometry), SIMS (secondary ion mass Elemental analysis of impurities in carbon
spectroscopy) (quantitative), Surface chemistry, surface defect
Potentiometric titration, pKa spectra, Boehm chemical Identification and quantification of acid-base groups
titration method of surface functionalities
Thermal analysis, TG (thermal gravity), DTA Content of carbon, volatile, impurity, oxidization or
(differential thermal analysis), DSC (differential graphitization temperature
scanning calorimetry)
BET (Brunauer Emmett Teller), BJH (Barrett Joyner Specific surface area, surface defect, pore size
Halenda), t-plot distribution, average pore diameter, pore volume
Laser particle size analyzer Particle size distribution
SEM (Scanning electron microscopy), TEM Morphology, aggregate shape, texture, defect,
(Transmission electron microscopy), AFM (Atomic forceprimary particle size, pore wall, graphitization,
microscopy), STM (Scanning tunnel microscopy) crystal lattice
EDS (energy dispersive X-ray spectroscopy) Elemental analysis (composition, content)
ESCA (Electron spectroscopy for chemical analysis) Surface chemistry
C-NMR spectroscopy Quantitative analysis of bonding relations, detection
of carbon atoms, bulk chemistry
EELS (electron energy loss spectra) Hybridization state, bonding types of carbon atoms
IGC (Inverse gas chromatography) Surface energy, structural defects
Soft x-ray absorption spectra Local structure/chemical-states information of the
primary particles or crystallites
EIS (electrochemical impedance spectroscopy) Electrical conductivity
3. CARBON BLACKS VS. ENERGY

Energy and environment are regarded as typical central societal issues and have attracted
extensive attentions from governments to individuals nowadays. Rapid depletion of fossil
fuels (mainly from energy production, transport, and industry), growing environmental
problems and extreme climate changes pose serious scientific and technological challenges to
address the increasing global demand for energy [49]. Energy economy and energy
technology are highlighted to solve the global energy crisis and related issues to keep the
sustainable development of humankind and society. Development of high efficient methods
and technologies for energy storage and conversion is necessary to address the inevitable
challenge. Currently, alternative renewable energies such as solar cells, fuel cells, green
batteries, supercapacitors, biomass, and clean fuels are becoming appealing. Among them,
solar cells and fuel cells are energy conversion devices, while batteries and supercapacitors
are energy storage devices. A widespread commercialization of such energies and energy
technologies is hampered by cyclability, durability, operability problems, safe concerns and
high cost, which is needed to further develop materials with good performance and low cost.
For instance, various fields (such as electric vehicles (EV) or hybrid electric vehicles (HEV),
street lamp, spare power supply, electric machines, communication and transportation) using
lithium ion batteries, nickel metal hydrate, fuel cells, solar cells, supercapacitors and related
materials are becoming more and more popular nowadays to decline the consumption of
conventional fossil fuel and the emission of greenhouse gas.
Materials, especially carbon materials, play a considerable important role in both the
sustainable development of new clean technologies for energy storage and conversion and the
harmonious development of society and environment. Due to the excellent properties (unique
electronic structure, chemical stability, high accessible electrochemical surface, conductivity,
diathermancy, corrosion resistance, particle size distribution, environmental compatibility and
low cost), carbon blacks have extensive applications in a variety of common and specialty
high performance fields, such as tires, rubber and plastic fillers, pigmentation, ultraviolet
(UV) stabilization, marine, aerospace, carbon paper, printing inks and dyeing, paints or
coatings, lacquers, enamels, radar absorbent, food coloring, and so on. Furthermore, carbon
blacks with specific morphology and surface chemistry are also utilized to adsorb and store
CO2 to decrease the greenhouse effect. As for energy storage and conversion, carbon blacks
have been abundantly adopted to enhance the performance by using as conductive additives,
electrode materials, catalyst and catalyst support, current collector, high efficient fuel, fuel
accelerant (carbon blacks are added biomass or fuel oil to improve burning efficiency),
nuclear fuel reducing agent, and so on. Though many types of carbon black have been utilized
in various fields, carbon blacks continue to play an important role in energy storage and
conversion to meet enormous energy market and sustainable energy economy. In order to
satisfy the different application requirements, carbon blacks with specific structure,
morphology and surface chemistry are designed and developed. In addition, carbon paste,
carbon papers or carbon clothes that are made from carbon blacks are also explored to allow
for convenient applications.
4. APPLICATIONS FOR ENERGY STORAGE AAND CONVERSION

With the quick advancement of energy economy and environment, carbon blacks are
playing a more and more important role in energy storage and conversion. Closely linked
with the renewable energy to form an enormous subject area, carbon blacks have become a
very interesting topic and draw tremendous perspectives from fundamental research to many
potential applications. Because of the advantages of chemically inert, high electrical and
thermal conductivity nature, wide potential window, various morphologies, good corrosion
resistance, good dispersibility and reasonable cost, carbon blacks have drawn special
attentions in various energy storage and conversion fields such as primary batteries,
rechargeable batteries, solar cells, fuel cells, supercapacitors, and fuel oil. According to the
role of carbon black for energy storage or conversion, carbon blacks typically serve as:
hydrogen storage, conductive additive, conducting heat, electrochemical component, current
collector, catalyst carrier, and fuel oil blending component. There are considerable differences
in carbon black formulations and characteristics, and the properties of carbon blacks will vary
depending on the manufacture process and the desired performance characteristics for
specific applications.
4.1. Hydrogen Storage
Hydrogen is one of the ideal green renewable sources for the sustainable development of
society and environment, and has a very attractive alternative for a future sustainable energy
system with low-CO2 emissions. It can be obtained from various resources (such as water,
biomass, natural gas), and utilized as a green fuel in high-efficiency power generation
systems like fuel cells and internal combustion engines. Currently, efficient safe storage of
hydrogen becomes a key factor for the extensive applications, and it is an interesting
alternative to develop storage technologies (such as hydrogen adsorption storage, hydrogen

reaction storage, compressed hydrogen or cryogenic liquid hydrogen) for fuel cells or
hydrogen-driven combustion engines in vehicles. Therefore, various lightweight materials
with high reversible hydrogen storage capacity at moderate temperatures and pressures are
designed and synthesized for the demand [50,51 ]. The physical storage of hydrogen is
affected by the geometry and the surface chemistry of adsorbent, together with the
temperature and the pressure of adsorption. The interaction force from the first layer adsorbed
molecules is different from that from the second and subsequent layers, which can be
reflected in the heat of adsorption of different layers (the heat of adsorption of the first layer
of carbon black is 11~12 kJ mol-1 (0.11~0.12 eV) and drops to the latent heat of condensation
of 5.56 kJ mol-1 (0.058 eV) in the subsequent layers) [50,52]. Appropriate carbon black
materials can be used as matrixes for hydrogen storage, and the electrochemical response is
more dependent on the presence of doping agents (foreign metals like lithium) and the surface
structure than the carbon black surface area. Furthermore, C-MA21 carbon black had a
similar electrochemical response with carbon nanotubes and was a promising candidate for a
high reversible electrochemical storage of hydrogen [53]. Apart from storage hydrogen
directly, carbon black is also added the magnesium powder in hydrogen to show catalytic
effect during hydrogen absorption and prevent the particle growth of Mg and MgH2 to
improve the storage performance of hydrogen [29]. Carbon black nanoparticles can surface
modification of Ti-30V-15Mn-15Cr alloy to improve the electrochemical kinetics properties
to release more hydrogen, and initial discharge capacity can reach 930 mAh g-1 (3.55 wt%) at
45 mA g-1 discharge current at 353 K [54]. Because of the limited hydrogen charge/discharge
capability and poor cycle stability, only carbon blacks for hydrogen storage are not paid many
attentions nowadays. On the contrary, carbon blacks used as an effective additive for other
materials like metal or alloy are promising candidates for hydrogen storage.
4.2. Conductive Additives
4.2.1. Conductive Additives for Batteries

Electrode materials including anodes and cathodes, especially high-voltage cathodes
generally have low electronic conductivities, so that a conductive additive must be admixed to
form electrodes and to improve electrochemical performance [55,56]. Especially for cycle
performance and high rate performance or power characteristics, conductive additives are
significantly important. Currently, various conductive additives, such as acetylene black,
graphite, graphene, carbon nanotubes and vapor grown carbon fibers, have been utilized as
popular conductive additives for energy storage and conversion.
Carbon blacks are now usually used to improve the electrical and the mechanical
properties of electrode materials including inorganic materials and conductive polymers, and
play an important role in current conductive additive market and are usually adopted to
improve the electrochemical performance of electrode materials. In conductive polymers,
carbon black particles exist in the amorphous regions and they occupy and jostle into the free
volume of the amorphous regions [57], and cause the number of the free volume hole and the
fraction of the free volume to decline with the carbon black content increasing [58]. ―High
structure‖ carbon blacks are required to satisfy the conductive applications in energy and
multiple nano-sized ―branches‖ consisting of individual carbon nano-particles are believed to

create additional contact points with active material in electrode matrixes to enhance the
efficient conductivity with low concentrations of carbon black additives [19]. Besides electric
conductivity enhancement in electrode materials, carbon blacks also conduct heat, store
electrolyte and have reinforce effect to prevent the materials from volume swelling or falling
off during cycles. Although the reinforcing effect of carbon black particles is inferior to that
of the fiber conductive additives (like vapor grown carbon fibers (VGCFs) or carbon
nanotubes (CNTs)) or sheet conductive additives (like graphene), carbon blacks generally
have particle morphology so that they can be dispersed easily. Therefore, various carbon
blacks are carefully designed and widely used for improving the electrochemical performance
from traditional dry-cells to lithium-ion batteries and supercapacitors. As typical zero-
dimensional small particles with high conductivity and high surface area, carbon blacks are
the popular conductive additives because they are cheap and easy to be dispersed in contrast
with fiber or sheet conductive additives. The conductive route is aciniform (grape-like
cluster) particle chain transfer, and the conductive mechanism of carbon black particles in
particle electrode materials is shown in Fig. 4.
------ carbon black particles

------ electrode active materials
Figure 4. Conductive mechanism of carbon black particles in particle electrode materials.
As conductive additives, some key factors, such as electrical conductivity, electrolyte

absorption, porosity, surface area, surface activity, surface function groups, particle size
distribution, good adherence and mechanical properties, will greatly affect the
electrochemical performance of electrode materials. The basic demand of carbon black for
conductive additive is good conductivity, good electrolyte absorption, proper particle size
distribution, good adherence, beneficial surface function groups and accessible surface area.
Among various kinds of carbon black, acetylene black produced from acetylene gas has
relatively high electrical conductivity. As for different devices for energy storage or
conversion, special catalysis and matching should also be considered.
Besides considering the physical parameters like structure, morphology, particle size and
surface area, good distribution of carbon blacks in electrodes also play an important role in
improving performance. Carbon black is always consisted of grain particles, and it is much
easier to be dispersed in electrode materials in comparison with fiber conductive additives
like carbon nanotubes (CNTs), vapor grown fibers (VGCFs) or metal fiber. However, carbon
black particles have the trend to aggregate because of the high surface energy originating
from the small grain size. It is essential to well disperse carbon blacks for effective
applications. Texture is a complex measure of the carbon black aggregate particle and reflects
how the constituent primary particles are connected. Both are used to selectively modify the
surface chemistry, size and complexity of the aggregate particle. In order to increase the
surface accessibility and the utilization efficiency, aggregated chunks have to be broken into
submicron or nano-sized particles for effectively being dispersed and coated on electrode
materials. Specially, carbon blacks are treated with various methods like oxidization or
etching to produce specific functional groups and texture to change the surface state.
Furthermore, surfactants are usually adopted to well disperse carbon blacks to coat on
electrode materials. These surfactants must not deteriorate the electrochemical properties of
the batteries besides being completely dissolved in a solvent, so those with Na+ or K+ ions are
not the suitable one. Amphoteric surfactants with high electrochemically stability are
promising for use in batteries [59,60].
Among various conductive carbon blacks, acetylene black produced by decomposing
acetylene gas and Super P are two kinds of popular conductive additives for batteries or
supercapacitors because of the high electronic conductivity. Acetylene black, a special type of
carbon black formed by an exothermic decomposition of acetylene gas, has highest degree of
aggregation and crystalline orientation in comparison with all types of carbon black [44], as
well as wide surface range; while Super P is the commercial trade name of a conductive
carbon black with high void volume allowing the retention of a carbon network at low filler
content, and the void volume can originate from the interstices between carbon black particles
and the porosity, similar to furnace black [61]. Besides the in-situ produced carbon black or
the calcined carbon black during the synthesizing process of electrode materials, most carbon
black conductive additives are always added to the electrode active materials as an
independent composition via blending with appropriate binder to form slurry to coat a current
collector.
Primary Batteries
Among various primary batteries including carbon-Zn, alkaline cell, Zn-air, Ag-Zn, Li-
manganese dioxide, Li-carbon fluoride, and Li-iron sulfide, Zn-Mn batteries dominate the
primary market segment. Since the original carbon-zinc cell consisted of a natural manganese
dioxide-carbon black core cathode with aqueous ZnCl2-NH4Cl electrolyte was invented by
Leclanché in 1860, carbon-zinc cells have evolved greatly and still have a wide use all over
the world [62].
As important electrode materials for primary batteries, manganese dioxide is a poor
electrical conductor, so chemically inert carbons or carbon blacks are added to the cathode
material mix to enhance conductivity for forming electrode. Thus, the cathode (also called
bobbin, black mix, depolarizer, or positive electrode) is consisted of a wet powder mixture of
MnO2, powdered carbon black, and electrolyte (NH4Cl and/or ZnCl2, and water), and the
carbon black serves the multiple purposes, including increasing the cathode electrical
conductivity, holding the electrolyte, and providing compressibility and elasticity, to the
cathode mix during processing [56]. Though graphite was once used as the principal
conductive media and is still used to some extent, acetylene carbon black has displaced
graphite in this role for both Leclanché and zinc chloride cells because of its unique
properties and high ability to hold more electrolytes in the electrode mix. Therefore, intense
shearing of the black particles during the mixing process must be careful as this reduces its
ability to hold electrolyte. This is critical for zinc-chloride cells because they contain much
higher electrolyte levels than the Leclanché cells. Cells containing acetylene carbon black
usually give superior intermittent service, which is the way most zinc-carbon batteries are
used. Graphite, on the other hand, serves well for high flash currents or for continuous drains.
[56,63]. In a Li/MnO2 cell, addition of carbon black to MnO2 can not only improve the
conductivity and the ability of the electrode to absorb and hold electrolyte, but provide
compressibility and elasticity to the electrode [64]. As a conductive additive for the MnO 2
cathode, it was reported that carbon black was more effective than submicron carbon
filaments. The volume resistivity of the MnO2 composite cathode was higher using carbon
filaments instead of carbon black in spite of the lower volume electrical resistivity of the
filament compact than that of the carbon black compact, which is due to the good
spreadability of carbon black between the MnO2 particles. Surface treatment of carbon black
with pluronic was found to be effective to improve electrolyte absorptivity, rate of absorption,
the discharge capacity, open- and closed-circuit voltages (OCV and CCV), cathode packing
density, and gravimetric and volumetric energy densities [65]. In comparison with other
conductive additives of graphitized mesophase pitch, natural graphite, graphitized carbon
filaments and carbon filaments without graphitization, the dispersion of carbon black is
related to the spreadability of carbon black between MnO2 particles and spread upon
squeezing, so binder content will not affect the dispersion of carbon black and the electrical
resistivity of MnO2 cathodes. Adding 5 wt% of carbon black could make the resistivity and
the density of the MnO2 cathode with 6 wt% polyvinylidenefluoride (PVDF) binder reached
~8.9 Ω cm and ~1.65 g cm-3 [66].
In magnesium primary batteries, acetylene carbon black is utilized for conductivity and
moisture retention and mixed with MnO2, barium chromate (an inhibitor), and magnesium
hydroxide (a pH buffer) to form cathode [67]. In lithium/thionyl chloride batteries, a carbon
black electrode is also used as the conductor at the cathode of thionyl chloride [68].
In spite of the improved electrochemical performance, acetylene black will do harm to
the storage performance by the self-discharge reaction originating from the thermodynamic
decomposition of MnO2 by the acetylene black and the surface chemistry serves as a site of
initiation of the unwanted reaction upon storage to produce short shelf life of alkaline primary
batteries or zinc chloride cells. Therefore, only minute amounts of acetylene black now may
be added to the MnO2 cathodes in very special cases that demand an immediate boost of
performance. Graphitization treatment can significantly improve the purity and the shelf life
to greatly enhance the discharge capacity of energy devices like alkaline batteries, zinc-
carbon batteries and Li/MnO2 primary batteries, and the performance of the treated carbon
black is even better than that of the composite conductive additive of acetylene black and
graphite in a Li/MnO2 primary battery using organic electrolyte of LiClO4 dissolved in PC
and DME solvents [19].
Rechargeable Batteries
Plentiful rechargeable batteries such as lead-acid, nickel metal hydrate and lithium ion
are demanded by the rapid development of portable electronic equipments, 4C (computer,
communication, consumer electronic, control) technologies, electric machines, electric bikes,
and electric vehicles or hybrid electric vehicles. In order to improve the electrochemical
performances, various additives like conductivity and anti-combustion are added. It was
reported that adding carbon black can effectively increase the cycle life and decrease the
polarization of electrode [69]. In comparison with mesocarbon microbeads (MCMB) and
activated carbon, carbon black particles have a poor effect for diminishing the supercooling
by providing nucleation seeds and promoting the primary crystallization of ethylene
carbonate (EC) at or near its liquidus temperature, indicating carbon black has a good low-
temperature performance in EC solvent [70,71]. Carbon blacks are always added to lead-acid
batteries to increase the conductivity of the negative active-material to assist in the initial
charging of the battery (formation) and high levels have a beneficial effect on battery life [72-
76]. Typical composition of lead-acid battery paste usually contains no more than ~4% of
carbon black [68]. In addition, various carbon blacks have also been utilized in Ni-MH as a
support electronic conductor-binder materials (additives) [77-79] or Ni-Cd batteries to decline
the contact resistance and improve the electrochemical behavior.
Lithium rechargeable batteries are very attractive because of their high energy densities,
high efficiency and long cycle life [56]. There are many systems of lithium rechargeable
batteries, such as lithium/molybdenum disulfide (Li/MoS2), lithium/manganese dioxide
(Li/MnO2), lithium/titanium disulfide (Li/TiS2), lithium/niobium selenide (Li/NbSe3),
lithium/lithiated cobalt dioxide (Li/LixCoO2), lithium/lithiated nickel dioxide (Li/LixNiO2),
and lithium/vanadium pentoxide (Li/V2O5). Carbon blacks are usually added to the electrode
materials of these lithium rechargeable batteries to improve conductivity for the better
performance.
Another enormous market for the applications of carbon black conductive additives in
rechargeable batteries is Li-ion batteries that are key components of the portable electronic
equipments with impressive growth requirements. The common electrochemically active
electrode materials in Li-ion batteries are a lithium metal oxide for the positive electrode and
lithiated carbon for the negative electrode [80]. These materials are firstly adhered to a metal
foil current collector using a binder (such as polyvinylidene fluoride, the copolymer
polyvinylidene fluoride-hexafluroropropylene (PVDF-HFP), or polytetrafluoroethylene
(PTFE) and a conductive additive (typically carbon blacks, carbon nanotubes, vapor grown
fibers, graphite, graphene, metal particles or fibers) to form electrodes. Then, the positive
electrode and the negative electrode are sandwiched by a microporous polyethylene or
polypropylene separator film which is electrically isolated in a can to make electrons flow in
external circuit to form current no matter what type of the adopted electrolyte (liquid, gel-
polymer or solid) [81]. Conductive additives will effectively improve the capacity, rate
performance and cyclability of electrode materials via reduction of internal resistance.
Therefore, carbon blacks with a proper amount are necessary to improve the electronic
conductivity of electrode materials, but more carbon will reduce the volume capacity or
volume energy because carbon has a low mass density (usually no more than 2.0 g cm-3), so
metal or alloy with high conductivity and high mass density will also be adopted to improve
the volume capacity. Minimum volume of carbon conductive additives or organic binder
should be critically used in the low-density electrode like LiFePO4 to reduce the cost of
volumetric energy density [82]. In order to optimize and improve the electrochemical
behavior, numerous studies including carbon sources, carbon amount, carbon adding method,
surface chemistry, graphitization technics, dispersion approaches, and carbon composites
have been carried out. On the other hand, multiple measures, including composite conductive
additive, current collector coating and electrode material particle coating, have been utilized
to improve the performance, and the schematic diagrams of possible ways of incorporating
conductive additives have been summarized in Fig. 5 [83].
Conductive coatings have a strong influence on overall conductivity by substantially
reducing contact resistance and greatly improve the electrochemical performance of cathode
materials including spinel LiMn2O4 (low cost, high rate), LiFePO4 (low cost, high energy),
Li(Ni0.8Co0.15Al0.05)O2 (―Gen 2‖ material, high energy, high power) and LiNi1/3Co1/3Mn1/3O2
(high capacity, high energy, good cycle performance) [84]. Due to the volume fraction of
active material, percolation was achieved and the percolation threshold (i.e. critical loading)
is no less than 30%, larger than the theoretical value (29%) for 3D spherical particulate
system. Adoption of carbon black/PVDF composite coatings is generally more advantageous
than addition of conductors to composite cathodes for all baseline materials, and the
schematic diagram and the changes of conductivity of carbon black conductive additive and
PVDF binder are provided in Fig. 6. Even with only 10% conductive coatings containing
4.51% carbon black and 5.49% PVDF can increase the overall conductivity by at least 14.9 S
m-1, a value 25 times larger than the bulk conductivity of the active material [84].
Figure 5. Possible ways of incorporating conductive additives: (a) addition of large (graphite) and small
particles (carbon black), (b) current collector coating, and (c) coating of the cathode particles. Using
multiple schema for loading with conductive additives has been achieved to improve the performance,
Reproduced from ref. [83].
Figure 6. Schematic diagram of coating of carbon black/PVDF (left), and conductivities of different
combinations of carbon black and PVDF (right) [84].
Carbon black conductive additives can incoordinately improve the performance of

different electrode materials. The influence of carbon black on the electrical conductivity and
discharge capacity in LiMn2O4-based composites prepared by cold pressing physical mixtures
of LiMn2O4, carbon black and polyvinylidenefluoride (PVDF) was investigated, and the
electrical conductivity and the change in capacity followed a percolating process, and the
percolation threshold was 3 vol.% of carbon black [85]. The decrease of specific resistance
and the increase of specific capacity are not linear with the addition content of carbon black,
and the specific resistance and the specific capacity will change little when a proper amount is
reached. In other words, carbon blacks have a percolation threshold for enhancing the
performance of electrode materials, and more or less content of carbon blacks is not
beneficial to maximize the performance, which is similar to that of polymer added with
carbon blacks. As far as the LiFePO4 cathode is considered, the resistivity of LiFePO4
measured using four-point probe method dropped from 176 to 67 Ω cm as carbon black
increased from 3 to 10 wt%, and homogeneous electronic resistivity could be observed when
the concentrations of the carbon black were above 6 wt%. It was found that the addition of ~3
wt% carbon black significantly improved the electronic conductivity of LiFePO4 composite
cathodes [86]. The electrochemical behavior of LiFePO4 has little change for carbon black
loadings from 6 to 15 wt%, except that the polarization was slightly higher at 6 wt% [82].
Nanofilm coating including 7.5% graphite, 10.15% carbon black and 12.35% PVdF can
improve the bulk conductivity of LiFePO4 from 10-9 to 0.591 S m-1, and carbon black was
added to enhance the conductivity because of the relatively low conductivity of the binder
[84]. In addition, the graphitic compound on the LiFePO4 surface is important to improve the
performance, and sp2 carbon was found to be much more effective than sp3 carbon [87],
consisting with the electronic structure of carbon blacks.
Figure 7. Mechanism sketch indicating the possible influence of carbon black on the kinetics of
Li+/electron electrochemical insertion into active particles, (a) poor distribution (part of active material
is not in contact with carbon black electronic conductor), and (b) good distribution (Li+ and electron
are available at the same spot). Reproduced from ref. [88].
Dispersion of the carbon blacks is also the key to improve the electrochemical
performance of electrode materials. The uniformity of carbon black distribution significantly
affects the cathode kinetics no matter what type of LiMn2O4-spinel, LiCoO2 and LiFePO4,
and gives better kinetics even at a lower content of carbon black. The possible mechanism
sketch of the influence of carbon black particle distribution on the kinetics of Li+/electron
electrochemical insertion into active particles is shown in Fig. 7, and good distribution will
leave Li+ and electron available at the same spot to enhance the rate characteristics [88].
Carbon blacks generally consist of many small particles and the powders tend to
aggregate chunks during usage process, but they can be dispersed well using orotan®
polyacrylate dispersant. LiCoO2 cathode directly coated with 1 wt.% as-dispersed carbon
black using amphoteric-gelatin surfactant exhibits excellent capacity characteristics and
restricted expansion of the cell thickness compared with a bare cathode during storage at 85
ºC. In comparison with a conventional cell using bare LiCoO2, the volumetric density and rate
capability have been improved without sacrificing electrochemical performance. The
discharge capacity has been improved ~10%, but greatly diminishes the reactivity between
the charged cathode and the electrolyte to enhance the cycle life and rate capability whether at
high temperature or at high working potential. The carbon black can decline the dissolved Co
concentration from 1050 to 320 ppm after storage for 96 h at 85 ºC and suppress the
electrolyte decomposition. Because of the low mass density of carbon blacks, high carbon
content in an electrode will lead to a low volumetric capacity, as shown in Table 2. [59].
Besides the improved cathode performance, adding carbon black to current anode of graphite
can also improve the capacity retention in spite of allowing for a lower lithium intercalation
[89].
In the iron/carbon black composite electrode material for a paste type rechargeable
alkaline battery [90], carbon black not only forms an enhanced electronic conductive network
to improve the reduction/oxidation reactions of iron despite that iron is discharged as the
insulator species such as Fe(OH)2 and Fe3O4, but also functions as the nucleation cores for the
deposition of dissolved iron intermediate to form core-shell iron composite nanometer
particles. Furthermore, carbon black subsequently prevents the iron particle size from
growing during the charge/discharge cycles and maintains the ability of a high rate discharge.
The influence of carbon black on the discharge curves, cyclic voltammetry and cycle
performance is shown in Fig. 8, and carbon black can greatly improve the electrochemical
performance of iron [90].
Figure 8. Discharge curves of the nickel–iron battery at a constant current density of 200 mA g−1 (a)
pure iron nanoparticle and (b) iron/carbon-black composite nanoparticle;(c) Cyclic voltammetry of iron
electrode materials in 8 M KOH + 1M LiOH solution; and (d) Cycling stability curves of various iron
electrode materials at a current density of 200 mA g−1 between 1.65 and 0.8 V. Reproduced from ref.
[90].
Besides the improved electronic conductivity and electrochemical performance of other

electrode materials, carbon black conductive additives are also electrochemically active at 57
ºC and at potentials above 3.8 V, and undergo significant changes of structure, electronic
properties and surface morphology upon cycling in LiPF6 electrolyte. A potential role of
carbon retreat/redistribution in composite cathodes for cathode impedance rise and capacity
loss has been demonstrated in diagnostic studies of LiNi0.8Co0.15Al0.05O2, LiFePO4 and 123
material cathodes from tested cells [86]. Carbon structure considerably affects the
electrochemical performance of battery. In Raman spectrum, carbons with low ID/IG ratios
(disordered/graphene) have higher electronic conductivities, so even small amount as low as
≤1 wt.% will contribute to improve the electrochemical performance of electrode materials. It
is reported that iron nitrate will improve carbon structure [86]. On the other hand, carbon
black with high surface area is also relevant to the electrolyte reactions occurring at the
cathode [91]. The content of added carbon black was found to strongly affect the irreversible
capacity of LiMn2O4 cathodes originating in oxidation reactions [92], and manganese
dissolution increased for larger surface-area carbon, while the polarization was greater for
smaller surface-area carbon [93].
Consequently, carbon blacks are widely adopted to increase the electrical conductivity
between the active particles in the rechargeable battery systems including lead-acid, Ni-Cd,
Ni-MH, lithium and lithium ion. The detailed reasons for the influence of the
physicochemical properties of carbon black conductive additives on the conductivity, rate
characteristics and cycle performance of electrode materials are still not very clear. So
selection of carbon blacks and optimal combinations of different conductive additives remain
challenging. Choices of materials and architectures, as well as dispersion method, play a key
role in improving the performance of electrode materials for batteries and supercapacitors.
More in-situ techniques for investigating the changes of carbon blacks in the electrode
materials are needed to analyze the mechanism.
4.2.2. Conductive Additives for Supercapacitors

As intermediate power and energy sources between conventional electrolytic capacitors
and batteries, supercapacitors, also called ultracapacitors or electrochemical capacitors (ECs),

have gained considerable interests in many fields, such as hybrid power sources, back-up
power storage, peak power sources, portable electronic devices, electric vehicles and other
related markets [94,95]. Supercapacitors are a class of electrochemical energy storage devices
with unique advantages such as rapid storage and release of energy, high columbic efficiency,
good cycle performance, and good adaptability. A supercapacitor is typically constituted of
positive electrode, separator, negative electrode, can, lead, seal and electrolyte [96]. When the
positive electrode is same with the negative electrode, a symmetrical supercapacitor can be
obtained, for example, typical carbon-based supercapacitors. However, when the positive
electrode is different from the negative electrode, a nonsymmetrical supercapacitor, also
named hybrid supercapacitor, can be obtained. Therefore, according to the capacitor
configure and the energy storage mechanism of electric double-layer principle and faradic
pseudocapacitance principle, there are three types of supercapacitors, i.e. electronic double-
layer capacitors, pseudocapacitors and hybrid supercapacitors. Electronic double-layer
capacitors store energy mainly by utilizing the electronic double-layer (also called Helmholtz
layer) capacitance arising from the static charge separation at the electrode–electrolyte
interface, while pseudocapacitors store energy mainly by utilizing the pseudocapacitance
arising from the fast and reversible Faradic reactions. As for a similar electrode area, the
specific capacitance of pseudocapacitor is generally higher than that of electronic double-

layer capacitor. Hybrid supercapacitors combine the advantages of electronic double-layer
capacitors and pseudocapacitors by simultaneously utilizing the electronic double-layer
capacitance from one electrode and the pseudocapacitance from another electrode, so their
specific capacitance and energy densities are more close to lithium ion batteries. Lithium ion
supercapacitors are a kind of supercapacitors using lithium ions to store energy, which is
labeled based on the energy storage medium, similar to lithium ion batteries. However, the
energy storage principle of lithium ion supercapacitors is still electric double-layer and
faradic pseudocapacitance, so the power density and cycle performance are better than
lithium ion batteries. Electronic double-layer capacitance is originated from the electronic
double-layer electrode materials, like various carbon materials with high surface area and
specific morphology. Pseudocapacitance is originated from redox electrode materials
including any materials that can take redox reaction, like numerous electrode materials for
batteries, CoOx, V2O5, RuO2, and so on [97,98]. As for one electrode material, electronic
double-layer capacitance and pseudocapacitance always appear together, and the question is
which is dominate. Furthermore, these capacitances are closely related to the adopted
electrolyte, and aqueous electrolyte always has a higher capacitance than organic or ionic
liquid electrolyte. In order to take full advantage of double-layer capacitance and
pseudocapacitance, many redox materials/carbon composite electrodes have also been
extensively investigated for supercapacitors besides adopting nonsymmetrical hybrid
configuration.
No matter what kind of redox electrode materials or electrical double-layer electrode
materials, carbon black conductive additives are effective to improve the electrochemical
performance. Carbon blacks with high conductivity generally have a specific structure (i.e.
aggregates with a highly branched, open structure), high porosity, small particle size, and
chemically clean (oxygen free) surface [99]. Thus, various types of carbon blacks, including
acetylene black and Super P, are significantly utilized as conductive additives in
supercapacitors. In contrast with fiber carbon materials like carbon nanotubes (CNTs) or
vapor grown fibers (VGCFs) under a good dispersion condition, acetylene black particles
have relatively poor function to enhance the electrochemical performance in spite of the
improved capacity [99-101]. However, acetylene black particles are much easier to be
dispersed than fiber conductive additives and appropriate carbon black particles are also
adopted to compensate the interspace of fibers to form a good effective conductive network.
The electronic conductivities of different multi-walled carbon nanotubes (MWNTs)
synthesized by chemical vapor deposition (CVD) method are different. In order to compare
the electrochemical performance of various MWNTs under the similar conductivity
atmosphere, acetylene black particles are always added to decrease the conductivity
difference between various MWNTs [102,103]. The influence of the acetylene black content
on the specific resistivity of MWNTs/acetylene black composite is provided in Fig. 9, and the
specific resistivity is obtained as follows: around 3 g MWNTs/acetylene black composites
dried at 100 ºC for 10 h was compressed in a hollow stainless steel cylinder inner-lined with 5
mm polytetrafluoroethylene (PTFE) loop with an inner diameter of 10 mm between two metal
plungers using an oil hydraulic press, and the adopted pressure was 5 MPa [103]. The
sample height l (cm) was obtained by the difference between before and after compression.
The resistance R (Ω) was measured at room temperature by electrochemical impedance
spectroscopy over the frequency range of 10 ~ 1000 Hz with a voltage of 1 V using an

electrochemical working station combining PAR 273A potentiostat/galvanostat and signal
recovery model 5210 lock-in-amplifier which was controlled by a Powersuit software. After
an initial steady step for 1 min, the values were recorded. According to the ohmic rule, the
specific resistances ρ (Ω·cm) of the MWNTs/acetylene black composites were calculated
RA
using the formula   (where, A is the area of the plunger transect, cm2). Because
l
acetylene black is good particle conductive agent and MWNTs are fiber materials, a good
conductive network can form by adding appropriate acetylene black to MWNTs. Less
acetylene black particles will not benefit the formation of good even conductive network,
while more acetylene black particles will aggregate to do harm to the conductive network.
From the experimental results, 10 wt.% acetylene black was enough to decline the
conductivity difference and improve the specific capacitance of multi-walled carbon
nanotubes [103].
80 55.0
75
54.5
Speciifc resistivity (m cm
Specific capacitance (F/g)

70
65 54.0
60
53.5
55
50 53.0
0 2 4 6 8 10 12 14 16 0 2 4 6 8 10 12 14 16 18 20
Content of acetylene black (wt.%) Content of acetylene black (wt.%)
Figure 9. Effect of the acetylene black content on the specific resistivity of MWNTs/acetylene black
composite and the specific capacitance of MWNTs. Reproduced from ref. [103].
Typical carbon black materials including acetylene black and Super P are always utilized
as conductive additives or coatings on electrode particles or current collectors to improve the
electrochemical performance of electrode materials such as activated carbon
[99,100,103,104], LiNi0.8Co0.2O2 [101], Ni(OH)2 [105], NiO [106], MnO2 [107], RuO2 [108],
FexP [109,110], V2O5 [111], polymer [112], graphene [113], graphene-MnO2 composites
[114], and so on. In order to further improve the electrochemical performance of electrode
materials, fiber conductive additives like carbon nanotubes and vapor grown carbon fibers are
also widely adopted. As for activated carbon particles, the conductive mechanisms of
different conductive additives including carbon black, carbon nanotubes (CNTs) and vapor
grown carbon fibers (VGCFs) are shown in Fig. 8. Acetylene black has relatively poor
performance to improve the capacitance and rate performance under the same conditions.
Furthermore, the percolation threshold of acetylene black is higher than that of carbon
nanotubes or vapor grown carbon fibers [100]. In addition, acetylene black particles have
relatively poor mechanical performance that is related to the cycle performance.
Copyright © 2011. Nova Science Publishers, Incorporated. All rights reserved. Carbon Blacks for Energy Storage and Conversion 207
Figure 10. Upper: schemes of conductive mechanism for different conductive additives; Below: Cyclic
voltammograms of AC-based supercapacitors with different conductive additives at 20 mV s−1 sweep
rate (left), Specific capacitance of AC with different conductive additives at various current densities
(middle), Effect of the content of conductive additives on the specific capacitance of AC at 5.0 mA
cm−2 current density (right). Reproduced from ref. [100].
In order to increase the capacitance using pseudocapacitance effect, oxidization

treatment, halogenation treatment, or redox additives (such as metals, metal oxides or
hydrates, alloys, conductive polymers) are always utilized whether in organic or aqueous
electrolytes. Pseudocapacitance effect from the functional group on the surface of carbon
blacks will be much more obvious in an aqueous electrolyte. Furthermore, oxidization
treatment of carbon blacks will increase the surface redox functional group to enhance the
wettability and binding energy of the interface, which is beneficial to the electrochemical
performance and the interface interaction in composite. Hydrous RuO2/carbon black

nanocomposite, prepared by a novel incipient wetness method using a fumed silica
nanoparticle, is composed of RuO2 nanoparticles (20–60 nm) dispersed on a high-surface-area
Ketijen black (KB, 1180 m2 g–1) and has 3D porous structure at high loading of 60 wt% RuO2
(Ru content is 46 wt%). The hydrous RuO2/KB nanocomposite electrode exhibited a specific
capacitance of 647 F g–1 with high charge utilization of RuO2 (72%), much higher than the
reported values at similar loading of RuO2 [108]. Using ultrasonication and in situ reduction
methods, acetylene carbon black particles were deposited on the edge and basal surfaces of
graphene nanosheets, and improved the electrochemical performances of pure graphene
material. The specific capacitance of the graphene nanosheets/carbon black composite
synthesized by ultrasonication method can reach 175.0 F g-1 at 10 mV s-1, higher than that of
the pure graphene (122.6 F g-1). Furthermore, ultrasonication is better than in-situ reduction to
prepare graphene nanosheets/carbon black composite for improving the electrochemical
performances of pure graphene. The incorporation of carbon black into graphene can inhibit
the nanosheet agglomeration and improve the electrolyte/electrode accessibility as well as the
electrode conductivity. [113].
Besides carbon blacks, other conductive additives like carbon fibers, carbon nanotubes,
metal particles or fibers, have been exploited to further improve the electrochemical
performance. In comparison with fiber-like conductive additives like vapor grown carbon
fibers (VGCFs) or multi-walled carbon nanotubes (MWNTs), acetylene black has relatively
poor effect for improving the electrochemical performance of activated carbon, but acetylene
black has advantages in being dispersed evenly because of the non-one-dimensional particle
morphology [100]. Currently, different types of conductive additives no matter what kind of
morphology are combined to form composite conductive additive to enhance the performance
by coupling the multifarious functions of individual conductive additive. It is expected that
synergy effects can produce in such composite conductive additive. According to the
morphology of the conductive additives, generally adopted composite conductive additives
currently include the combination of particle/particle, particle/panel, particle/fiber, and

particle/fiber/mat. For instance, carbon black-1/carbon black-2 composite, carbon
black/graphite composite, carbon black/graphene composite, carbon black/carbon filament
composite, carbon black/carbon nanotubes composite, carbon black/vapor grown fibers
composite, carbon black/metal fiber (with high conductivity and high density, such as Ag
silk, Cu silk, steel silk, Al silk) composite, carbon black/polymer, and so on. Carbon
black/fiber conductive additives can combine the advantages of particle carbon blacks and
fiber conductive additives to form an effective conductive network and have been
investigated extensively to enhance the electrochemical performance. Furthermore, these
fiber additives will also improve the mechanical properties of the electrode that is beneficial
to the cyclability. Therefore, composite conductive additives, such as carbon black/graphite,
carbon black/carbon nanotubes, carbon black/vapor grown fiber, carbon black/metal fiber,
carbon black/graphite/carbon nanotubes, have become an interesting topic for developing an
efficient conductive network with low content of carbon blacks. However, the even dispersion
of these conductive additives will become more difficult after adding fiber additives, and poor
dispersion do harm to the function of the composite conductive additives (even worse than
that of an individual composition).
Table 2. Performance comparison of carbon black conductive additives for various

electrode materials
Type of carbon Electrode materials + Electrochemical performance Reference

black electrolyte
Degussa, Printex LiCoO2 + 1 M LiPF6 2 wt.% of uniformly distributed carbon 88
XE2 in EC:DMC (1:1 ratio black gives better kinetics than 10 wt.% of
by volume, Merck) non-uniformly distributed carbon black.
LiMn2O4-spinel + 1 At 10 C-rate, the reversible capacity of
M LiPF6 in EC:DMC LiMn2O4 with 2 wt.% of uniformly
(1:1 ratio by volume, distributed carbon black is close to that
Merck) with 10 wt.% of non-uniformly distributed
carbon black.
Super P carbon LiCoO2 + 1 M LiPF6 The volumetric capacity of the bare 59
black, average in EC:DEC (1:1 ratio LiCoO2 (2 wt% carbon content), 2 wt%
particle size: ~10 by volume) carbon-coated LiCoO2 and 1 wt% carbon-
μm, BET surface coated LiCoO2 could reach 508, 537 and
area: 0.2 m2 g-1 566 mAh cm-3, respectively.
nanosized The resistivity dropped from 176 to 67 86

Ωcm as carbon black increased from 3 to
LiFePO4 + 1.2 M
LiPF6 in EC:EMC
10 wt%, and homogeneous electronic
(3:7) resistivity could be observed when the
concentrations of the carbon black were
above 6 wt%.
Addition of ~3 wt% carbon black
significantly improved the electronic
conductivity of LiFePO4 composite
cathodes.
Carbon black MnO2, MnO2/Ni, The resistance decreases continuously, 107

(Black pearls 2000, MnO2/Pb, + 1 M while the specific capacitance increases
Cabot Corp) Na2SO4 solution. until the carbon loading becomes 20 wt %
and starts to decrease for loading higher
than 20 wt %
40 nm, Timcal, Fe + 8M KOH + 1M Carbon black could strongly improve the 90
Switzerland LiOH aqueous discharge capacity and the cycle
solution performance. When Fe : Carbon = 3:1 in
weight, the stable capacity was 600 mAh g-
1
in the voltage window ranging from 0.8
to 1.65 V
The conductivity of an electrode will be influenced by many factors, such as inherent

conductivity of electrode material, type of conductive additives, level of dispersion achieved
for conductive additive, interaction mode between conductive additive and electrode material,
intrinsic conductivity of other additive like binder or flammable inhibitor, assembling
method, and applied electric potential. For example, the overall conductivity of electrode
materials is strongly affected by the conductive coatings and the carbon black/PVdF
composite coatings are more advantageous than addition of conductors to composite cathodes
for all baseline materials [115]. Currently, various conductive additives are commonly
dispersed by multifarious methods like intensive mechanical shearing, ultrasonication, and

using surfactant solvent which may do harm to the electrochemical performance. For
instance, acetylene black (specific resistance 0.320 Ω cm) mixed 12.5 wt% mesoporous
carbon (average pore size 3 nm, pore volume 1.08 cm3 g-1, mesopore specific surface area
1230.8 m2 g-1, specific resistance 0.678 Ω cm) using ultrasonic treatment and ethanol
dispersant could improve the initial specific discharge capacity of LiCoO2 cathode from
145.20 to 155.80 mAh g-1 at a rate of 0.5 C, and from 123.30 to 139.20 mAh g-1 at a rate of
2.0 C [116]. Acetylene black (average diameter of 30 nm, specific conductivity 3.13 S cm-1)
mixed 40 wt% multi-walled carbon nanotubes (MWCNTs, 10 ~ 30 nm in diameter, 10 ~ 20
µm in length, specific conductivity 10.25 S cm-1) using ultrasonic treatment and
polyvinypyrrolidone (PVP) dispersant could improve the initial specific capacity of LiCoO2
cathode from 134.4 to 147.2 mAh g-1 at a rate of 0.5 C, and the cycle performance and rate
performance have been enhanced [117]. In addition, carbon blacks are occasionally surface
treated using oxidization or halogenation to change surface active states for good dispersion
[18].
In order to eliminate the difficulty for even dispersion and form carbon coated electrodes,
carbon black and carbon black composite can form in situ on the surface of electrode
materials by pyrolyzing hydrocarbon (such as methane, acetylene, benzene, pitch) and
carbohydrate (such as sugars, starches, celluloses, gums, urea) in an inert atmosphere. Carbon
blacks synthesized in situ have become an important method to improve the electrochemical
performance of electrode materials and current many carbon coated composite electrode
materials are mostly prepared by this method via pyrolyzing hydrocarbon or carbohydrate.
For instance, the charge transfer resistances of the Li4Ti5O12, the Li4Ti5O12/C composite using
carbon black in-situ prepared from pitch and the Li4Ti5O12/C/CNTs composite using carbon
black in-situ prepared from pitch and CNTs (20 ~ 30 nm in diameter, 1 ~ 2 µm in length)
prepared by chemical vapor deposition (CVD) were 203.86, 155.28 and 68.83 Ω,
respectively. Simultaneously, the rate performance and the cycle performance have been
greatly improved [118]. The charge transfer resistances of the Li2FeSiO4/C composite using
carbon black in-situ prepared from high soften point coal pitch and the Li2FeSiO4/C/CNTs
composite using carbon black in-situ prepared from high soften point coal pitch and CNTs
(30 ~ 70 nm in diameter, 1 ~ 2 µm in length) prepared by CVD method were 175 and 135 Ω,
respectively. Simultaneously, the discharge capacities at various current rates and the
cyclability have been largely enhanced [119].
In summary, loading is of critical importance for carbon black conductive additives, and
the loading should be optimized to form a good conductive mat. On the other hand, some
basic physicochemical properties, such as structure (especially degree of graphitization),
particle size, the void space between particles, accessible surface area, porosity, pore size
distribution, surface chemistry and dispersion, will also greatly affect the performance of
carbon black conductive additives. High porosity, small particle size and high degree of
chain-like structure, as well as less void space between particles or aggregates, are necessary
to improve the conductivity. In addition, the structure and surface chemistry will also
influence the dispersancy of carbon blacks in electrode materials, electrical conductivity and
to some degree the color of the finished article. Though surface chemistry will achieve good
dispersion, the conductivity will decrease when carbon blacks have plenty of oxygen function
groups [16,19]. As a conductive additive, the percolation threshold of carbon black varies in
different electrode materials. Furthermore, the values of the specific resistance and cyclability
are also related with the particle size distribution, form or structure of aggregation and pore
ratios. In addition, carbon blacks in the electrodes also have electrochemical activity. It is
advantageous to increase the conductivity, specific area and pore ratios while to decline the
content of carbon blacks as conductive additives for improved performance. Besides the
conductivity and the electrochemical activity, carbon blacks will also improve the mechanical
properties of the electrode which are very important to the cyclability, similar to the strength
function of carbon blacks in polymers or tires. However, the mechanical properties of carbon
blacks in electrodes have few reports up to now. Generally speaking, microstructure of carbon
blacks as conductive additives should be further optimized to match the electrodes, and
proper additives like other carbon blacks or graphite and proper mixed method and
temperature are beneficial to improve the function of carbon blacks by forming composite
conductive additives. Carbon blacks with specific structure, morphology and surface
chemistry should be designed to improve the electrochemical performance (especially rate or
power performance, kinetic characteristics, cycle and calendar life) of these advanced energy
devices. At the same time, the post treatments, including oxidization, halogenation, calcining,
ball milling or sonication, are necessary to improve the performance of carbon black
conductive additives.
4.3. Electrode Materials
Besides the extensive applications as conductive additives, carbon blacks are also utilized
as electrode materials separately. Besides electrolyte, binder, current collector, match of
electrode with electrolyte, device configuration and assembly, the electrochemical
performance of carbon blacks are interrelated with many factors such as structure, structure
defect, morphological properties (accessible electrochemical surface area, shape, texture, pore
size distribution), compatibility, surface chemistry, conductivity, electrolyte, binder, and
assemble method.
4.3.1. Primary Batteries

Of the practical battery systems, lithium/thionyl chloride (Li/SOCl2) batteries have one of
the highest cell voltages (nominal voltage 3.6 V) and energy densities (about 590 Wh kg-1 or
1100 Wh L-1, the highest values being achieved with the low-rate batteries), and have been
commercially for a long history for memory backup and other applications requiring a long
operating life [56]. Li/SOCl2 cell is typically consisted of a lithium anode, a porous carbon
cathode, and a nonaqueous electrolyte like SOCl2:LiAlCl4 or SOCl2:LiGaCl4. Carbon blacks
are always used to form cathode because of the advantages of high conductivity, good
mechanical performance, anticorrosion and low cost, while thionyl chloride is both the
electrolyte solvent and the active cathode material. Electrolyte formulations and electrode
characteristics are different greatly, and the proportions of anode, cathode, and thionyl
chloride will vary depending on the manufacturer and the desired performance characteristics.
In the carbon cathode or in the electrolyte, catalysts, metallic powders, or other substances
have been utilized to enhance performance. In the overall reaction process of 4Li +2SOCl2 →
4LiCl↓+ S +SO2, the produced sulfur and sulfur dioxide are initially soluble in the excess
thionyl chloride electrolyte, and a moderate buildup of pressure appears due to the generation
of sulfur dioxide during the discharge. However, the lithium chloride is not soluble and
precipitates within the porous carbon black cathode as it is formed. Furthermore, sulfur may
also precipitate in the carbon black cathode at the end of discharge. Therefore, the blocking of
the carbon black cathode becomes the factor that limits the cell‘s service or capacity in most
cell designs and discharge conditions [56]. Thus, optimized microstructure of carbon blacks
to prevent the precipitation of lithium chloride and sulfur while holding good conductivity is
one of perspective method to improve performance.
Lithium/polycarbon fluorides (Li/(CFx)n) batteries have a high achieved specific energy
density of 2600 Wh kg-1, so various forms have been manufactured commercially [120].
Varieties of carbons, especially carbon blacks, are directly fluoridated at high temperatures to
form polycarbon fluorides of the general formula (CFx)n as the cathodes. According to the
composition of the cathode materials, the open-circuit voltage of lithium/polycarbon fluorides
cells ranges from 2.8 to 3.3 V [120]. Carbon blacks are used to be fluoridated to form
cathodes, so the interaction between carbon and fluorin is important for the performance.
4.3.2. Metal/Air Batteries

Metal/air batteries are a type of high energy devices using oxygen from ambient
atmosphere to produce electricity via an electrochemical process. Their energy densities are
much higher than most currently available primary and rechargeable batteries [56,121]. Many
multivalent metals such as lithium, magnesium, aluminium, zinc, and iron, have been
investigated as the potential candidates for the applications of such air batteries. In the cell,
metal is used as anode, and oxygen as cathode reactant (i.e. depolarizing agent) diffuses into
the interior cathode active surface in contact with electrolyte to be reduced to either oxide or
peroxide ions that further react with cationic species. In the presence of an aqueous alkaline
electrolyte, the air cathode catalytically promotes the reaction of oxygen, while catalytic air
electrode has no changes or consumption in this process [56]. Because air battery
technologies have many advantages such as high available energy density, safety, flat
discharge voltage, long shelf life, low energy cost, and ecological benefits, they have gained
considerable attentions for extensive applications.
Among various air batteries, zinc/air battery technology is relatively mature and has been
applied for many fields ranging from portable military to medical, telecommunication and
electronic products. Nowadays, zinc/air batteries are the leading power source for miniature
hearing aids. In a zinc/zir cell, cathode structure including separator, catalyst layer, metallic
mesh, hydrophobic membrane, diffusion membrane, and air-distribution layer, has been
improved by introduction of a dual layer approach [56]. In such dual layer structure, different
standards of carbon black have been added to form dual layer cathode: low surface area
carbon black is used to produce a hydrophobic cathode layer with good electrical contact to
the screen current collector to prevent electrolyte penetration and to slow water evaporation
loss, while high surface area carbon black is used to promote better access to the electrolyte
and to facilitate better oxygen catalysis [56].
Lithium is the lightest, lowest potential metal with high chemical activity, so lithium/air
battery is especially attractive due to the potential for the highest specific energy among all
known electrochemical couples. In contrast with other carbon source like DARCO G-60,
Ketjenblack (KB, one type of carbon blacks) is better to improve the performance, and the
lithium/air batteries using such carbon-based air electrodes exhibited the highest specific
capacity of 2340 mAh g-1 based on the weight of carbon alone. However, KB-based air
electrodes expanded significantly after being soaked with electrolyte and absorbed much
more electrolyte than electrodes made from other carbon materials to produce a large increase
in battery weight and a corresponding decrease in the specific energy of the lithium/air
battery. Among 4 generations of Li/air cells, G4 cell is a double-sided pouch cell using a heat-
sealable polymer with low permeability window as both the packaging and oxygen diffusion
membrane, and the schematic diagram is shown in Fig. 11 [121]. In the weight distribution of
a complete G4 Li/air battery, ~70% is attributed to electrolyte, and lithium metal anodes and
KB-carbon account for only 5.12% and 5.78%, respectively. In order to further enhance the
specific capacity of Li/air battery, nanostructured carbons with a large mesopore volume and
optimized pore size are needed to decline the electrolyte absorption while still holding
significant amounts of reaction products to maintain capability [121].
Figure 11. Schematic of a typical G4 cell with polymer membranes. Reproduced from ref. [121]
In these air batteries, the interface reaction between metal and oxygen is the central
problem to improve performance, so diffusion or distribution of oxygen and catalytic function
of cathode or electrolyte are vital to design the products. Certainly, leakage of electrolyte, as
well as corrosion of electrode, collector and lead, has to be considered for applications.
In contrast with the above primary metal/air batteries, rechargeable metal/air batteries
have an advantage of potentially low life-cycle costs because only one reactant (i.e. the anode
material) is needed to be contained within the battery. Iron/air cells are a type of such
rechargeable air batteries, and the iron anodes do not suffer the fatal problems of zinc/air
batteries like a severe redistribution of active materials or gross shape change upon prolonged
electrical cycling. In spite of the lower energy densities of electrically rechargeable iron/air
cells than mechanically rechargeable cells, iron/air batteries are another candidate as a motive
power source, especially for electric vehicles or hybrid electric vehicles, and navigation. In
such rechargeable air batteries, carbon black was bonded with Teflon (PTFE) and catalyst of
silver to form a hydrophobic layer for partial cathode on the air side for oxygen reduction
[56]. In these rechargeable air batteries, carbon blacks are usually adopted to form cathode by
using the conductivity and the surface area to promote the performance. Therefore, structure,
particle size, surface area, surface chemistry, and good dispersion should be optimized for
further development.
4.3.3. Solar cells

As one of promising renewable energy devices, solar cells have gained considerable
attentions because of the advantages of sustainability and cleanness for light-to electricity
conversion. Among various types of solar cells, dye-sensitized solar cells (DSSCs) are
attractive because of simple fabrication process and low cost. In DSSCs, counter electrode
serves as electrocatalyst for triiodide reduction and to transfer electrons from external circuit
to triiodide and iodine in the redox electrolyte. Thus, cheap carbon black can be used as
conductive additives or electrode materials to form carbon counter electrode to replace the
conventional counter electrode comprising of expensive platinum coated conductive oxide to
decline the cost because the advantages of high electronic conductivity, high reaction activity
for triiodide reduction, and good anticorrosion. In the dried carbon electrode, 20 wt.% carbon
black is adopted as conductive additive, and the overall conversion efficiencies of the DSSCs
using various carbon materials are close to that using Pt [122]. Of course, it is necessary to
optimize the microstructure parameters (i.e. conductivity, mesopore volume, particle size, and
accessible surface area) of carbon blacks to increase the performance.
4.3.4. Li-ion Batteries

Various carbon blacks have been investigated as a potential anode material for the Li-ion
batteries, but the charge/discharge capacity is low and the first-cycle irreversible capacity is
high. The partial amorphous structure and high surface area may contribute to the low
reversible capacity and high first-cycle irreversible capacity by forming a solid electrolyte
interphase (SEI) membrane [91,123-126]. In the low-potential region of 0.01 ~ 1.5 V vs.
Li+/Li, the carbon black shows a large irreversible capacity. The thermal stability of the SEI-
layer on carbon black was found to be similar to that formed on graphite, and the onset
temperature for degradation of the SEI-layer was higher for LiPF6 than LiBF4. However,
carbon black has stronger reactions involving SEI-layer decomposition than graphite.
Furthermore, the electrode composed of the same carbon black with different binders
(ethylene propylene diene terpolymer in cyclohexane, polyvinylidene fluoride in 1-methyl-2-
pyrrolidinone, a starblock-copolymer with polyisopropene and poly((ethane-co-buten)-block-
styrene)) in cyclohexane) has different oxidation reaction potentials in an EC/DMC (2:1 in
volume) electrolyte using 1 M LiPF6 or LiBF4 salt [91]. Because of the combined
characteristics of amorphous and graphite forms, carbon blacks have higher irreversible
capacity and poorer cycling performance in comparison with graphite that has good degree of
graphitization. Therefore, pure carbon blacks have few individual applications in Li ion
batteries. On the contrary, carbon black conductive additives have a dominate advantage for
lithium ion batteries.
4.3.5. Supercapacitors
The BET specific surface area of carbon blacks has a wide distribution, typically ranging
from several to greater than 1500 m2 g-1, and is more accessible than other forms of high
surface area carbons, so carbon blacks with high surface area have been used to form the
electrodes or the binders for supercapacitors [26,99,127-132]. The specific capacitance of

carbon blacks varies considerably depending on the adopted electrolyte and the operating
temperature. The gravimetric capacitance of various carbon blacks does not increase linearly
with the surface area, and the capacitance limitation for the surface areas above 1200 m2 g-1
can be ascribed to a space constriction for charge accommodation inside the pore walls [127].
Carbon blacks with high graphitization degree have a very strong intensity of G band, but the
specific capacitance is as low as 2.0 F g-1, indicating conductivity is not the only key factor
for capacitance. It was found that both pore size and the defects in the carbon structure
affected the ion adsorption and migration of electrolyte within the electrodes. The small value
of ~0.1 s of the relaxation time constant made the frequency behavior of the carbon black
supercapacitor to approach the one of an electrolytic capacitor [25,128], suggesting a high
power densities can be obtained using carbon black with high conductivity. Carbon paste
electrodes (CPEs) are of great interest to prepare various geometric configurations of
electrodes. The specific capacitance of the CPE prepared from carbon black powder is
drastically affected by the binder and electrolyte, and surface modification using a potential
pulse can produce carbon-oxygen (C-O) species to improve the capacitance via enhance
pseudocapacitive effect [129]. Attributed to the different solved ions, the anion capacitance is
always different from the cation capacitance of the same carbon materials under the same
conditions. The graphitic microstructure with structural defects where the anion intercalation
takes place can improve the anion adsorption capacitance of carbon black, so the blockage of
the structural defects by modifying with urea and melamine have generally a detrimental
effect on the anion adsorption capacitance at low current load of 0.05 A g-1. However, this
phenomenon of electrochemical intercalation of anions becomes less pronounced due to the
possible kinetic limitations at high current load of 1.0 A g-1. Furthermore, carbon blacks are
more difficult to be electrochemical oxidized than amorphous activated carbons because of
the graphitic nature [130]. Using 2M NaOH aqueous solution as the electrolyte, the specific
capacitance of the nanostructured mesoporous nongraphitized carbon black with a BET
surface area of ~469.2 m2 g-1 (micropore area of ~145.7 m2 g-1) decreases from ~44 to ~39 F
g-1 when the current density increases from 3 to 32 mA cm-2, and the specific power has a
great improvement (from 98.84 to 782.42 W kg-1) [131]. In conclusion, the size of the solved
ion of organic electrolyte is generally larger than that of aqueous electrolyte, and the
accessible electrochemical surface area with suitable porosity morphology for solved ion of
electrolyte plays an important role in improving the electrochemical performance of carbon
black electrode materials for supercapacitors.
Besides improving the electrical contact between particles, fine carbon blacks with highly
branched structure are ideally suited to fill inter-particle voids produced between coarse
particles, and addition of carbon blacks can allow some manipulation of the inter-particle void
volume existing in carbon electrodes for accounting for ~25-40% of the total electrode
volume [99]. Some voidage in electrode is essential to act as ―electrolyte reservoir‖ and to
provide access to the internal porosity of carbon particles, but voids will decline both the
volumetric and the gravimetric energy density of supercapacitors. Therefore, porous carbon
black is adopted to partially fill the voids to displace excess electrolyte that would otherwise
completely fill the voids and increase the wet electrode weight and ultimately the cell cost
while providing additional capacitance [99].
Table 3. Electrochemical performance comparison of different carbon black electrodes

for supercapacitors
Type of carbon black Binder + Electrochemical performance Reference

electrolyte
Vulcan XC72 (Cabat, SBET = PTFE + 1 M Specific capacitance 12.6 F g-1 (9.57 µF 127
2 -1
240 m g ) (C2H5)4NBF4 in cm-2)
Black Pearl 2000 (Cabat, SBET acetonitrile, Specific capacitance 70.5 F g-1 (8.48 µF
2 -1
= 1405 m g ) scan rate 20 mV cm-2)
-1
MM192 (Timcal, SBET = 1875 s Specific capacitance 66.5 F g-1 (7.31 µF
2 -1
m g , high-temperature post- cm-2)
treatment)
Particle size ~390 nm, SBET = Silicon oil + Increased from 14.09 to 37.26 µF cm-2 129
2 -1
6.6 m g , Adsorption HClO4 after being modified
DibutilFtalato 42 mL/100 g, Silicon oil + Increased from 8.51 to 17.96 µF cm-2
0.35% Sulfur, <1 ppm LiClO4 after being modified
lithium, CPE, carbon black: Nujol + HClO4 Increased from 2.13 to 12.36 µF cm-2
Silicon oil = 72 : 28, carbon after being modified
black: Nujol = 73 : 27 (in Nujol + LiClO4 Increased from 4.28 to 8.16 µF cm-2
weight) after being modified
Carbon black (CB): Black PVdF The reversible intercalation of anions 130
Pearls 2000, (polyvinylidene in-between the graphene layers takes
CB oxidized with 50% HNO3 fluoride) in place at potentials higher than 0.75 V
to form oxidized CB of CB-O NMP (N- vs. Ag/AgCl and at moderately low
CB or oxidized CB treated methyl-2- current loads, while the deintercalation
with urea or melamine to pyrrolidone) + occurs at approximately 0.4 V vs.
form nitrogen-containing 1.0 M H2SO4 Ag/AgCl during the cathodic reduction;
species As for the melamine treated carbon
black, the anion adsorption capacitance
is more than four times higher than the
capacitance for cation adsorption;

As for the urea treated carbon black, the
anion adsorption capacitance is
approximate two times their adsorption
capacitance for cations
Highly graphitized powder of PTFE + 1.5 M Specific capacitance 2.0 F g-1 (4.0 µF 26
~40 nm in diameter (C2H5)4NBF4 in cm-2), relatively small resistance, small
(PureBlack 205, Superior acetonitrile relaxation time constant (~0.1 s),
Graphite, SBET = 50 m2 g-1 ) frequency behavior was close to an
electrolytic capacitor
In order to improve the electrochemical performance of supercapacitors, carbon blacks as

well as redox materials like metal oxides or hydrates and conducting polymers are frequently
adopted to form composite electrodes to enhance pseduocapacitnace. For example, carbon
blacks (commercial Black Pearls 2000® and Vulcan® XC-72 R) are impregnated by
differently aged inorganic RuO2 sols (i.e. of different particle size) to form hydrous ruthenium
oxide/carbon black nanocomposite electrodes for supercapacitors, and their capacitive
performance is influenced by the aging time (particle size) of Ru oxide sol as well as the
concentration of the oxide solid phase in the impregnating medium. In deaerated 0.50 mol
dm-3 H2SO4 electroltye, the RuO2/carbon black composite with high surface area carbon
(Black Pearls 2000®) has a higher capacitance than that with low surface area carbon
(Vulcan® XC-72 R). Furthermore, the inner surface of the high surface area carbon is hardly
accessible to the electrolyte and rather inactive because of the pore blocking by the oxide
particles at the top of the carbon grains with prolonged aging of the oxide sol, while low
surface area carbon has low impregnation efficiency of small oxide particles [133]. Therefore,
accessible surface area and pore size distribution of carbon blacks for forming different
composite electrodes to satisfy various rate performances. On the other hand,
MnFe2O4/carbon black composites prepared by a co-precipitation method using VULCAN®
XC72 carbon black in alkaline aqueous solutions have pseudocapacitance in electrolytes of
alkali and alkaline chlorides, sulfates and sulfites, and the content of carbon black has a
strong influence on the electrochemical performance. When the weight content of carbon
black in the MnFe2O4/carbon black composite is 0.3, the optimum capacitance occurs (70
wt.% ferrite electrode calcined at 350 ºC exhibited a capacitance of ~55 F g-1 at a scan rate of
200 mV s-1, with corresponding specific energy of 7.6 Wh kg-1 at a power density of 11 kW
kg-1) and the self-discharge rate reduces (After the ferrite loading of 70 wt.%, the specific
capacitance started to drop quickly) [134]. The reported electrochemical performances of
different carbon black electrodes are summarized in Table 3. In composite electrodes, carbon
blacks not only prevent the particles from aggregation and disperse the active materials so as
to enhance the active surface area, but also provide a good conduction path and store
electrolyte in the electrode. In addition, carbon blacks also have electrochemical activities to
contribution to the whole performances of supercapacitors.
4.4. Current Collectors
In order to reduce current paths and contact resistance in electrodes, highly conductive
carbon blacks are adopted as the current collectors for electrode materials and electrolyte. For
instance, carbon black structure can be molded into the shape of a cup which serves as the
battery container and an integral center rod to serve as cathode current collector. The cathode
mix consisting of manganese dioxide, carbon black, and inhibitors is packed into the spaces
on both sides of the anode of magnesium and is in intimate contact with the inside and outside
surfaces of the anode, the center rod, and the inside surfaces of the cup, and such
configuration provides larger electrode surface areas [56]. In order to handy usage, carbon
blacks are made into specific shapes. For example, carbon black is made into carbon paper
that has porous structure and definite strength to be used as the current collector of Pt
particles in fuel cells; carbon blacks are made into carbon clothes that have porous structure,
flexibility and mechanical properties to be used as the current collector of supercapacitors,
and spraying aluminium in inert atmosphere can further improve the conductivity. In addition,
carbon black nanoparticles can also act as both a microcurrent collector and an electrocatalyst
to improve the electrochemical kinetics properties of the Ti-30V-15Mn-15Cr alloy to release
more hydrogen [135]. In this context, the physicochemical properties (i.e. conductivity,
particle size, mechanical properties like strength and toughness, anticorrosion, homogeneous)
of carbon blacks as current collector should be considered to improve the performance and
the life.
4.5. Catalyst and Catalyst Supports
The excellent properties (good chemical/electrochemical stability, good electrical

conductivity, high accessible surface area, suitable pore size distribution, facile dispersion and
good environmental compatibility) make carbon blacks one of the promising high efficient
non-metal catalysts and catalyst support or loader materials for the best performance. In other
words, carbon blacks act as not only a catalyst, but also a support for other catalyst particles
distribution to form an active layer. Porosity, morphology and conductivity of the carbon
blacks will considerably influence the catalysis results. The characteristics of carbon blacks
for catalysts or catalyst supports are summarized as follows.
Because of the above unique properties, carbon blacks have been investigated as an
attractive high effective and stable catalyst for the decomposition of methane [136-148],
natural gas [149], ethane [150] or other hydrocarbons for hydrogen production without CO or
CO2 emissions, which will significantly simplify the technics and save energy and sources by
eliminating the need for water gas shift reaction and the removal stages for CO or CO2
required by conventional hydrogen production in the steam reforming process. Different
carbon blacks have different catalytic activities. In contrast with another popular carbon
catalyst of activated carbon, carbon black catalyst is not rapidly deactivated, and carbon black
with an open porosity has a lower reaction rate and a much higher catalytic sustainability
[139,144-146]. Carbon blacks are more effective than activated carbon for the activation of
methane because the activation energies over the representative commercial carbon blacks of
DCC-N330 and BP-2000 were respectively 183 and 143 kJ mol-1 (lower than those over
activated carbons (ca. 200 kJ mol-1)). Simultaneously, the carbon black produced by the
decomposition of methane can also act as the catalyst for the reaction for CO2-free hydrogen
production [138]. Texture properties and surface chemistry will considerably affect the
catalytic activity of carbon blacks. The catalytic performance of three types of carbon black
with different texture properties (specific surface area, pore volume, bulk density) and oxygen
surface groups for decomposition of methane in a laboratory scale fixed-bed quartz reactor
showed that oxygen surface groups would enhance the initial methane reaction rate and
hydrogen yield, indicating these oxygenated groups can generate active radicals that are
capable of attacking methane molecules at high temperature with the formation of methyl
radicals which initiates the chain of consecutive reactions leading to production of carbon.
The stable period of activity in which both the amount of groups desorbed as CO and the
surface area fell slowly, might be related to constant surface concentration of the active sites
that originated from the carbon black crystallites produced by decomposition of methane. The
quasi-steady state in the activity led to similar methane conversion rate and hydrogen yield
over the three kind s of carbon black catalysts. As the run progressed, the total pore volume
decreased because of the deposited carbon, while the degree of graphitization increased [143].
Specific morphology and surface chemistry are beneficial to improve the catalytic
performance of carbon blacks. The decomposition of the oxygen-containing groups formed
on the surface of carbon black will produce the active sites of carbon atoms for methane
decomposition reaction. Increasing surface defects will improve the catalytic activity of
nanosized carbon black catalyst for methane decomposition to produce hydrogen in a
fluidized-bed reactor, but decrease the catalytic stability. Loadings of appropriate amounts of
Ni or Co could greatly improve the initial activity of carbon black with poor stability, while
doping of Pd to Ni or Co could enhance the stability without further increasing the activity
[147].
In order to investigate the influence of morphology on the catalytic performance, various
types of carbon black synthesized from coal tar or heavy petroleum oil with different surface
areas and primary particle size, were used as the catalysts with respect to methane
decomposition under atmospheric pressure from 1123 to 1223 K. These carbon blacks all
exhibited stable catalytic behavior in spite of carbon deposition. The produced carbon black
from the decomposition of methane did not deposit evenly on the surface and formed
protrusions in several places on the surface of pristine carbon black, which would lead to the
―regeneration‖ of the covered surface area by the creation of a new one to keep stable
catalytic activity. As the primary particle size decreased, the activation energy almost
decreased, while the activity, the specific surface area and the number of active sites
including the corners of crystallites with higher activity almost increased, which led to a high
catalytic activity. In contrast with the fluffy carbon black, the pelletized carbon black with the
same primary particle size showed lower activity and lower activation energy. In spite of the
primary particle size, the reaction orders of the pelletized carbon blacks were almost all
around 0.67, lower than that of fluffy carbon blacks (near 1) [141]. Besides the above
significant catalytic function for methane, carbon blacks are also effective catalysts for
dehydrogenation of ethane to hydrogen and ethylene, as well as subsequent decomposition of
ethylene to hydrogen and solid carbon, so high hydrogen yields can be obtained. In
comparison with non-catalytic decomposition, higher ethane conversion, higher stability for
hydrogen production and lower ethylene selectivity could be obtained using carbon blacks (no
matter what types of rubber, color or conductive carbon black) as the catalysts. Temperature,
structure and texture would greatly influence the catalytic conversion, selectivity, hydrogen
yield and stability. The catalytic conversion, selectivity and hydrogen yield increased with
surface area increasing to ca. 100 m2 g-1, but had no proportional relationship with the
specific surface area. Representative carbon black catalysts like N330F and BP2000 exhibited
stable activity for ethane decomposition and hydrogen production for 36 h in spite of carbon
deposition [150]. Commercial carbon black catalysts with pellet form can be used for the
production of H2-CH4 mixtures in a fluidized bed reactor (FBR), and the H2/CH4 ratio can be
adjusted by simply varying the operating conditions including the carbon black catalyst,
temperature, pressure, and space velocity, which makes it possible to couple the gas stream
from the catalytic decomposition of methane (CDM) reactor to a conventional combustion
engine for significant reductions in CO2 emissions. From the investigation results, it can be
concluded that texture morphology (specific surface area, pore size and pore volume) is more
important than surface chemistry for a carbon black catalyst [148]. Although many good
results have been reported using carbon black catalysts, it is notable that the detailed
influence of specific surface area and primary particle size on the catalytic activity of carbon
blacks are not clear: Lee [138] thought that no trend could be induced between the catalytic
activity and the surface area of fresh carbon blacks, but Ryu [141] and Lee [150] considered
that catalytic activity almost increased with increased specific surface area within a limited
range. Typical catalytic characteristics of various carbon black catalysts are summarized as
the following table.
Table 4. Performance comparison of different carbon black catalysts
Carbon black Catalysts Electrochemical performance Reference

All furnace black No trend could be induced between the activity and the surface 138
DCC-N330: 79 m2 g-1, 0.75 % ash area;
V-PA90: 140 m2 g-1, 2 % ash The catalytic activity of carbon blacks was maintained nearly
BP-450: 76 m2 g-1, 2 % ash constant during the reaction in spite of large variations of the
BP-1100: 240 m2 g-1, 2 % ash total surface area, marked changes of the morphology and the
BP-2000: 1475 m2 g-1, 2 % ash carbon deposition;
With a volumetric hourly space velocity (VHSV) of 15.0 l (h
gcarbon black catalyst) -1 at 1123 K, the catalytic stability is in
sequence: BP-2000 > DCC-N330 > V-PA90 > BP-1100 > BP-
450.
Various carbon blacks synthesized Activity: number of activation sites remains almost constant 141
from coal tar or heavy petroleum during the reaction
oil, Activation energy: 165 ~ 246 kJ mol-1, almost increased with
Primary particle size: 11-19 ~ 61- primary particle size increasing, but not absolutely depending
100 nm on the particle size
Specific surface area: 140 ~ 29 m2 Reaction order: the pelletized carbon blacks regardless of the
g-1 primary particle size nearly all ~0.67, fluffy carbon blacks ~1
Commercial carbon blacks The performance of the carbon black catalysts at the early stage 143
XC72: Bulk density 0.46 g cm-3 of the runs differs significantly, but the performance is close in
specific surface area 223 m2 g-1, the quasi-steady state.
pore volume 0.68 cm3 g-1 The initial hydrogen concentration and the corresponding
CO+CO2 6.81 cm3 g-1 methane conversion: BP1300: 41% vol. H2, 26%; BP2000:
BP1300: Bulk density 0.72 g cm-3 17% vol. H2, 9%; XC72: 12% vol. H2, 6%;
specific surface area 395 m2 g-1, After ca. 100 min time on stream, a quasi-steady H2 percentage
pore volume 0.92 cm3 g-1 could be obtained in sequence: BP1300 > BP2000 > XC72;
CO+CO2 23.66 cm3 g-1 The rate of methane decomposition per unit of carbon black
BP2000: Bulk density 0.24 g cm-3 catalyst in the quasi-steady state: BP2000 > BP1300 > XC72;
specific surface area 1337 m2 g-1, Initial reaction rate: BP1300 > BP2000 > XC72, consistent
pore volume 3.06 cm3 g-1 with the amount of oxygen surface groups;
CO+CO2 11.98 cm3 g-1
nanosized carbon black produced nitric acid treatment can obviously increase the oxygen- 147
from the thermal cracking of containing groups, and these groups would be decomposed at
heavy petroleum; high temperature to form the surface defects to improve the
Pristine: C 98%, H 0.1%, O 0.9%, catalytic performance;
N 0.5%, S 0.5%; In contrast with the untreated carbon black catalyst, the initial
Loading contents of Ni, Co, Pd- conversion of methane on treated carbon black increased from
Ni, and Pd-Co were 0.16 wt.%, 1.7 to 2.5%, while the time for decreasing to half of the initial
0.63 wt.%, 0.22 wt.% and 0.22 conversion deceased from 40 to 12 min;
wt.%, respectively Loadings of Ni or Co could increase the initial conversion to
6.6 and 5.6 %, respectively. However, the stability became
much poorer.
Doping of Pd to Ni or Co did not good to promote the catalytic
activity, but slightly enhanced the stability.
Rubber black: 5 types, particle The catalytic activities including conversion, selectivity, 150
diameter ranges from 11-19 to 61- stability and hydrogen yield are greatly affected by the
100 nm, surface area ranges from performed temperature;
160 to 29 m2 g-1 With a volumetric hourly space velocity (VHSV) of 15,000
Color black: 3 types, particle cm3 (h gcarbon black catalyst) -1 at 1023 K, the C2H6 conversion, C2H4
diameter ranges from 15 to 58 nm, selectivity and H2 yield almost increased with the specific
surface area ranges from 256 to 23 surface area increasing from 29 to ca. 100 m2 g-1, and would
m2 g-1 decrease differently with specific surface area higher than 100
Conductive black: 2 types, particle m2 g-1. Though the hydrogen yield was almost linear with the
diameter both ~15 nm, surface specific surface area increasing from ca. 150 to 1475 m2 g-1, the
2
area ranges from 1369 to 1475 m maximum hydrogen yield is close to the that using carbon
g-1 black with 85 m2 g-1.
Table 4. (continued)
Carbon black Catalysts Electrochemical performance Reference

BP1300: C 83.7%, O 15.4%, BP2000 showed higher catalytic activity and more stable than 148
specific surface area 495 m2 g-1,BP1300. For the similar hydrogen concentration (balanced with
apparent density 0.369 g cm-3 methane) production, the catalytic results of 60 g BP2000 are
pore volume 0.92 cm3 g-1 nearly same with 140.1 g BP1300.
BP2000: a slight initial decay in the hydrogen concentration
BP2000: C 97.1%, O 2.7%,
2 -1 from 36 to 30% and a quasi-steady state that lasted for
specific surface area 1337 m g ,
approximately 1200 min on stream;
apparent density 0.155 g cm-3
3 -1 BP1300: a constant hydrogen concentration of 30% after 800
pore volume 3.06 cm g
min
Besides the above decomposition of hydrocarbons, carbon blacks are also used as the
catalysts to decompose hydrogen molecules into hydrogen atoms [151] and improve
electrochemical hydrogen release capacities and cyclability of body-centred –cubic (bcc)
phase Ti-30V-15Mn-15Cr alloy [54].
Based on the current reported results, we can conclude that the number of active sites on
the carbon black catalysts plays a very important role in determining the catalytic results,
while this number is related to structure (amorphous or graphite), texture (open porosity,
specific surface area, pore size distribution, pore volume), morphology (particle, fiber, pellet,
fluffy) and surface chemistry (defects, active functional groups like carboxyl, hydroxyl,
nitryl, sulfonic, halogen). Active sites can form on the carbon materials where disrupting
regular array of carbon bonds, forming free valences, discontinuities (edges or corners),
energetic abnormalities (surface defects or dislocations) [139,141] and oxygen surface groups
[143]. Therefore, only considering the specific surface area and pore size is not enough to
obtain good carbon black catalysts. As a specific high effective catalyst, carbon blacks should
be designed and synthesized from combining factors (like carbon sources, pyrogenation
technics, surface treatment and preparation method) to increase the number of active sites and
match the catalytic technics (temperature, pressure, space velocity or flow rate, reactor,
catalyst position) to improve the catalytic performance.
Besides as a novel non-metal catalyst with high efficiency and high stability, carbon
blacks also act as a good support for other catalysts (like Pt, C) for high catalytic results. In
fact, the pristine carbon black acts as the support for the new produced carbon black catalysts
in the above investigation [141,143]. The most used carbon support for catalysts is the
commercial carbon black material like Vulcan XC72 and Vulcan XC72R (Cabat), and
different types will produce different results. In contrast with XC72R (SBET = 241 m2 g-1) and
Black Pearl (SBET = 1485 m2 g-1), Vulcan XC72 (SBET = 232 m2 g-1) has higher conductivity
properties. The morphologies of the various PtRu/carbon black support materials are
compared in Fig 12. In the range of 0.6~1.0 V for methanol oxidation, Black Pearl was the
best Pt support, while Vulcan XC72 was the best PtRu support [152]. Carbon blacks with
good conductivity will enhance the stability against corrosion of platinum-titanium dioxide
nanocomposite electrocatalysts for fuel cell application [153,154]. Carbon black (Vulcan
XC72R) supported CoPd3 electrocatalysts as oxygen cathodes showed high catalytic activity
for oxygen reduction in a 5 cm2 fuel cell [155]. Carbon black is treated by hydrogen peroxide
can introduce oxygen-bearing functional groups on the surface and enhance the
electrochemical stability of Pt/C catalysts. The as-formed functional groups connect with
1
metal nanoparticles via O atoms so as to alleviate the agglomeration of supported
2 nanocatalysts and to improve the cycle performance [156].
Figure 12. TEM images of the (a) PtRu/XC72R, (b) PtRu/XC72, and (c) PtRu/Black Pearl. Reproduced
8
from ref. [152]
Figure 13. The electrochemical surface area values of the catalyst samples measured during the
potential scan test (left), Pt oxidation/reduction peaks recorded before and after the potential scan test:
(a) Pt/XC; (b) Pt/XC-O (right). Reproduced from ref. [156].
In Proton Exchange Membrane (PEM) fuel cells, the electrodes always employ an
electrocatalyst layer with a porous, carbonaceous, electronically-conductive, and hydrophobic
substrate. Carbon black support is usually adopted for the catalysts like platinum or a
platinum-containing alloy, as well as dispersed ionomeric material similar in constituency to
the electrolyte membrane, and dispersed hydrophobic polymer such as polytetra-
fluoroethylene, to form catalyst layer. The substrate can be a carbon paper or a woven or non-
woven cloth to serves as a reactant-gas diffusion layer. The catalyst layer may be deposited
directly onto the electrolyte membrane or onto the substrate and later placed in contact with
the membrane, and the catalyst layer structure is sometimes altered between anodes and
cathodes to adjust their respective hydrophobicity and reactant diffusion properties. The
thickness of the catalyst layer typically ranges from 10 to 20 µm, that of the substrate from
0.1 to 0.5 mm (uncompressed) [56,152-156]. In order to decline the contact resistance
between catalyst and carbon black support, catalyst can be synthesized in situ on carbon black
support. For example, TiN/carbon black composites formed by direct synthesis of TiN
nanoparticles on carbon black via a mpg-C3N4/carbon black composite template have

improved the contact between TiN and carbon black, functioning as an efficient cathode
catalyst for oxygen reduction reaction (ORR) in polymer electrolyte fuel cells (PEFCs) [157].
In spite of the different function of catalysts and catalyst supports, carbon blacks with high
conductivity, accessible electrochemical surface area and proper pore size distribution are
expected to be the ideal catalyst or catalyst supports.
4.6. Biomass Energy Accelerant (Microbial Fuel Cells)
As a noble clean energy technology that can directly convert biomass to electricity,
microbial fuel cells (MFCs) have attracted extensive attentions for energy sustainable
development and environmental protection. Carbon blacks can improve the performance of
both anode and cathode of MFCs. In order to improve the power density of the renewable
energy source, carbon black or polypyrrole has been used to coat the anode of carbon paper.
Function of the carbon black has been demonstrated by comparing the power density plots
from both polypyrrole/carbon black-coated anode and only polypyrrole-coated anode. The
maximum power densities of the carbon paper, the polypyrrole-coated carbon paper, and the
polypyrrole/carbon black-coated carbon paper can reach 151, 303, and 452 mW m-2,
indicating both carbon black and polypyrrole are present on the anode with a synergistic
effect [158]. On the other hand, a polypyrrole/carbon black (Ppy/C) composite has been
employed as an electrocatalyst for the oxygen reduction reaction (ORR) in an air-cathode
microbial fuel cell (MFC), and the tested results using cyclic voltammogram and linear sweep
voltammogram methods show that the Ppy/C is well suitable to fully substitute the traditional
cathode materials in MFCs. The maximum power density of the MFC with a Ppy/C cathode
can reach 401.8 mW m−2, higher than either that with a carbon black cathode (90.9 mW m−2)
or that with a non-pyrolysed FePc cathode (336.6 mW m−2). The power output with a Ppy/C
cathode is lower than that with a commercial Pt cathode, but the power per cost of a Ppy/C
cathode is 15 times greater than that of a Pt cathode [159]. Conductive carbon blacks are
adopted to enhance the electron transfer properties between microorganism and electrode in
these MFCs, so conductivity and accessible surface area for wettability of carbon blacks
should be the key to improve performance. As for the carbon black composites, surface
functional groups will be considered to obtain a good dispersion. Therefore, surface chemistry
and particle size should be optimized to keep high conductivity and good dispersion.
4.7. Nuclear Fuel Formation Reagent
As a high efficient clean energy, nuclear energy has attracted special attentions and is
developed step by step to decrease the serious energy crisis and environmental problems.
Nuclear fuel composed of Uranium oxide (UO2) and uranium carbide (UC2, formed by direct
reduction of UO2 with carbon) kernels coated with carbon black and silicon carbide represent
a significant improvement in efficiency, longevity, and safety of nuclear fuels for the next
generation of nuclear power systems. Many factors, such as types, surface area, morphology,
purity, volatile content, dispersion and adding method of carbon black, will greatly influence
the quality of UO2-UC2 fuel kernels for the generation IV high temperature gas reactor
program. Uniform distribution of carbon black in the UO2 gel before the thermochemical step
(the gel forming step) plays a very important role in improving the performance of the nuclear
fuel. Surface chemistry with suitable chemical groups is closely related with the good
dispersability. Suitable surface modification can bring properly selected chemical groups
bonded to the surface and make carbon blacks self-disperse without other treatments like
additions of surfactants, intensive mechanical shearing, or prolonged sonication. Carbon
black modified with sodium sulfonate groups (~2 wt% content of sulfur) was found the best
candidate for good self-dispersion. Carbon blacks modified through proprietary diazonium
salt chemistry offer many advantages over traditional dispersions, and are easy to be well
dispersed without intensive mechanical shearing or sonication. The particle size of the
dispersed carbon black aggregates is suitable (in the target range of 0.15~0.20 µm), and the
stability is high (for at least 30 days in water and hexamethylenetetramine/urea solutions, for
at least 6 hours in the simulated broth of carbon-containing (UO2∙H2O) gel spheres). The use
of surface-modified carbon blacks in the uranium-containing broth will disperse well and not
adversely impact the chemistry of the gelation process, so high quality uranium oxicarbide
(UCO) kernels will be obtained by calcining the precursor using the as-modified carbon black
[18]. Besides the above surface chemistry, other factors like carbon sources, particle size and
dispersion method should also be considered to improve the efficiency of carbon blacks as
reductive agents.
4.8. Direct Carbon Fuel Cells (DCFCs)
Although the renewable energy technologies such as solar, wind, wave, geothermal,
hydro, biomass and nuclear energy in the overall energy portfolio are significantly attractive,
traditional fossil fuels like oil and coal are still dominant players in current energy
consumption. Therefore, upgrading current technologies to improve utilizable efficiency and
decline environmental pollution becomes the critical point and the low hanging fruit towards
the harmonious development of energy and environment. In this context, Direct Carbon Fuel
Cell (DCFCs) offers the potential of significantly higher conversion efficiencies than
conventional technologies of today.
A DCFC is a fuel cell using a carbon rich material as a fuel via an electrochemical
process to directly generate electricity [160-162]. DCFC technologies have gained extensive
interests because of its many advantages such as safety, remarkably efficiency, environmental
friendly, low cost, abundant raw materials, medium operating temperature, convenient waste
heat cycle, simple system (internal reforming, reduced cooling requirement, no need for
traditional equipments like steam-reforming reactors, boilers, turbines), operation and
maintenance economy, no noble catalysts, no sulphur sensitive catalysts, negligible NOx and
SOx emissions, and broad capabilities (H2 and coal gas generating internally as by-products
power the hydrogen fuel cells) [160-169]. The efficiency of conversion of the chemical
energy in the DCFC using a molten carbonate electrolyte and solid elemental carbon with
atmospheric oxygen contained in ambient air at a temperature of 650 ~ 800ºC can reach
75~80%, about twice as efficient as other forms of power production processes utilizing solid
fuels like petroleum coke or coal (from 30~40% for coal fired conventional subcritical or
supercritical boilers to 30~40% for integrated gasification combined cycle power plants)
[162]. In comparison with currently available power generation systems like NGCC (Natural
Gas Fired Combined Cycle), SCPC (Supercritical Pulverized Coal) and IGCC (Integrated
Gasification Combined Cycle), DCFC has a high efficiency with a low cost [162]. Fuel cells
use electrochemical process to produce electricity and are generally much more efficient than
burning fossil fuels. However, even contrasted with other fuel cells using hydrogen and
simple hydrocarbons such as methane, the efficiency of DCFC is still very attractive (close to
the theoretical value) because of the favorable thermodynamics of the carbon-oxygen reaction
(Table 5, [163]). Therefore, DCFC technologies are strongly competitive for future electrical
production systems and will make it possible to cleaner, more efficient power generation for
various markets including bulk power, personal power, distributed generation, and remote
locations. Nowadays, many types of DCFC systems, including molten hydroxides (William
W. Jacques obtained an US Patent 555,511 in this type of fuel cell in 1896), molten carbonate
(William W. Jacques obtained a Canadian patent in this type of fuel cell in 1897, molten tin
and tin oxide (utilizing molten tin and tin oxide as an inter stage reaction between oxidation
of the carbon dissolving in the anode and reduction of oxygen at the solid oxide cathode
[164]), solid oxide, and alkaline, are under investigation to push the electrochemical
conversion of carbon.
Table 5. Comparison of efficiencies of various fuel cells, Reproduced from ref. [163]
Fuel Theoretical Fraction of fuel used in Fraction of voltage Total efficiency

limit practical operation available at practical rate (higher heating value)
Carbon 1.01 1.0 0.8 0.80
Hydrogen 0.69 0.75 to 0.85 0.8 0.41 to 0.47
Methane 0.90 0.75 to 0.85 0.8 0.54 to 0.61
(Operating temperature of 750°C. Energy cost of fuel synthesis is excluded.)
The schematic diagram of a DCFC is presented in Fig. 14 [163]. The total reaction of the
DCFC is C + O2 → CO2, and the half cell reactions are C + 2 O2- → CO2 + 4 e- (anode) and
O2 + 4 e- → 2 O2- (cathode), respectively. There are 4 molar electron transfers when 1 molar
carbon black is oxidized, and the net electrochemical reaction is the same as the complete
chemical reaction for carbon combustion, so the DCFC using air as oxidant is also called
―Carbon/Air Fuel cell‖ [165]. However, the efficiency of using fuel for generating electricity
close to theoretical limits, and the produced carbon dioxide has high purity to be recycled
directly, which will improve the environment by substantially declining the amount of
emitted pollutants and is beneficial to reach low-carbon economy. On the other hand, the
exhaust CO2 and sulfur oxides can also be captured and sequestered leaving the process as
environmentally constructive because of the concentrated waste gases from DCFC systems
[160-164]. The potential advantages of DCFC technology and the attitudes of
commercialization as a function of a methodical development program place it in the high-
probability future as a promising and competitive power in the next generation of power
generation [160-169].
Figure 14. Schematic diagram of a DCFC. Reproduced from ref. [163].
Carbon anode materials are plentiful and facile. In principle, any types of carbon, fossil
fuel, hydrocarbon, biomass or organic wastes can be converted to electric power using direct
carbon conversion. For natural gas and oil, pyrolysis (thermal decomposition) yields
hydrogen and carbon. For dirtier resources (coals, biomass, organic wastes), the carbon may
have to be extracted by reaction with hydrogen, followed by pyrolysis [163]. Of any tested
carbon fuel, carbon black has the highest electrochemical reactivity and becomes the focused
carbon fuel in DCFC research [161-163,166-169]. 0.02~0.05% residual ash in most carbon
blacks has little effect on system performance, cost, or cell lifespan because of the low rate of
ash accumulation [163]. The reactivities of carbon blacks are affected by microstructure and
surface chemistry, and the best one can yield energy at about 100 mW cm-2 and 100 mW at
0.8 V, sufficient for many fuel cell or battery applications [163]. In a tubular solid oxide fuel
cell which consisted of a NiO–YSZ anode support tube, a NiO–ScSZ anode functional layer,
a ScSZ electrolyte film, and a LSM–ScSZ cathode, carbon black can directly convert to
electricity, and the maximum power densities are 104, 75, and 47 mW cm-2 at 850, 800, and
750 ºC, respectively [166]. Catalytic gasification can significantly improve the performance
of solid oxide electrolyte DCFC, and decline the operation temperature to the medium
temperature range (600 ~ 800 ºC). The catalytic effects for carbon black gasification with
CO2 are in sequence: K>Ni>Ca, and the power densities of 0.7 V discharge are 1477, 1034
and 1123 W m-2 for the carbon black with K, Ca and Ni additives at 750 ºC [167].
Because DCFC is an electrochemical process and electrochemical reactions are restricted

to electrode/electrolyte interfaces, the incompatibility in the dimensional scale between the
size of the reaction site at interface and the size of carbon electrode particles becomes the
major problem for the conversion of solid fuels. Consequently, how to overcome the wide
dimensional gap and decline the resistance to bring fuel and oxidant together becomes vital to
enhance the conversion of carbon. In other words, an effective delivery mechanism or a
―vehicle‖ to make fuel particles and oxidant contact fully should be devised to facilitate the
oxidation reaction. Carbon particles are generally in the order of micron or submicron, several
orders of magnitude larger than the width of triple phase boundary (about tens of nanometers
by estimation [168]). In order to decrease the influence of dimensional incompatibility,
various approaches such as stream gasification, catalytic gasification [167], and fluidized bed
[169,170] to improve the conversion efficiency. In addition, the corrosion problems in the
industrial system have to be considered. Thus, in spite of the inspiring laboratory results and
widespread researches, the scale-up applications of DCFCs from laboratory to prototypes and
then systems are still hindered by some factors such as construction design (transport and
utilization of carbon fuel, oxidant, exhaust gas, fly ash within the cell), anode and cathode
materials, electrolyte, fuel form relating to interaction with electrodes and electrolytes,
corrosion or spallation limits of materials used for current collection, humid atmosphere
above electrode, additives, waste gases and fly ash treatment. As far as only carbon blacks are
considered, the particle size, morphology and conductivity should be paid attention to
enhance the performance of DCFC.
SUMMARY AND OUTLOOK

Due to the unique advantages of structure, morphology, surface chemistry, conductivity
and dispersivity, carbon blacks, one class of carbon materials, are considerable attractive for
energy storage and conversion for a wide variety of applications. Among various
physicochemical properties, structure, morphology, electronic properties, and surface
chemistry, are critical factors in selecting carbon blacks for a specific application. On the other
hand, distribution of carbon black particles will also affect the performance (especially used
as conductive additives), which is a combined result of structure, surface chemistry, blending
ways (stirring, ultrasonication, ball milling) and dispersing system (solvent, surfactant).
The most significant advances in carbon black applications for energy storage and
conversion include hydrogen storage, conductive additive, electrode materials, current
collector, catalysts, catalyst supports, solar cells, biomass energy, nuclear energy, and high
efficient fuels for direct carbon fuel cells. Only carbon blacks for hydrogen storage are
hindered by the limited hydrogen charge/discharge capability and poor cycle stability, but
carbon blacks used as an effective additive for other materials like metal or alloy are
interesting for hydrogen storage. Besides the extensively conventional applications as
conductive additives and electrode materials for batteries or supercapacitors, carbon blacks
are significantly promising and competitive for the perspective fields including green
catalysts to decompose hydrocarbon, catalyst supports, electrode materials of solar cells,
accelerant of biomass energy, reductive of nuclear fuel, and high efficient fuels for direct
carbon fuel cells.
In spite of the widespread applications of carbon blacks for energy storage or conversion,
there are still several issues needed to be paid attention in the future. In other words, more
work is needed to further applications by considering the following problems: 1) Green clean
route to synthesize carbon blacks with special properties, including conductivity, structure,
porosity, and surface chemistry; 2) Good even dispersion of carbon black particles to improve
the performance and to solve the fast aggregation problem during and after the production or
usage; 3) Influence of the synthesis and the physicochemical properties including
microstructure, morphology, particle size and distribution of carbon blacks on the electrode
conductivity, the electrochemical performance and the working efficiency; 4) Reactions of
carbon blacks with electrode and electrolyte under various conditions, especially the
worthless reactions for the performance fade at high or low temperatures; 5) Post treatment or
modification of carbon blacks, mainly concentrating on the microstructure and surface
chemistry, should be selected carefully to enhance the performance; 6) Synthesis of carbon
black composite materials with special structure, morphology, and surface chemistry for a
special application, especially in-situ synthesis technique for forming composite materials to
improve the contact and homogeneity.
In summary, comprehensive understandings of the structure (especially microstructure),
morphology, accessible surface area, particle size, porosity, and surface chemistry, are
beneficial to boost the further applications of carbon blacks for energy storage and
conversion. As for the current shortcomings of carbon blacks for applications, measures,
including structure design, surface treatment (such as chemical, electrochemical, heat,
plasma, laser, polishing), graphitization treatment, grafting, inner filling, coating, modifying,
composing with other complexes to form composites, and matching, should be considered to
further improve the performance characteristics for energy storage and conversion.
ACKNOWLEDGMENTS
This work is financially supported by the Youth Foundation of Sichuan University
(07046). Helps from the Analytical & Testing Center of Sichuan University is greatly
acknowledged. The reviewers for their insightful comments are highly appreciated.
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Chapter 10
CARBON BLACK TREATED IN LOW PRESSURE

PLASMA: A NEW CLASS OF GRANULAR
ADSORBENTS FOR ACID AND BASIC COMPOUNDS
Nicoletta De Vietro*
University Aldo Moro, Bari, Italy
ABSTRACT
The surface chemical composition and morphology of carbon black play a crucial
role in its adsorption properties. To improve the adsorption ability for acid and basic
compounds in liquid and in gas phases, carbon black granules can be treated in low
pressure 13,56 MHz radio frequency glow discharges, generated in suitable special
reactors which allow homogeneous processing of powders and granules. In this chapter it
is shown that the surface acid or basic character of the granules can be increased by
grafting acid or basic chemical groups utilizing glow discharges fed with different gas
mixtures: e.g. oxygen/ammonia, acrylic acid/argon and allylamine/argon.
The chemical and morphological characterization of treated carbon black was
performed by means of X-ray photoelectron spectroscopy, water contact angle
measurements, Brunauer-Hemmett-Teller specific surface area evaluations and scanning
electron microscopy observations.
The study of the adsorption ability for basic and acid compounds in liquid and gas
phases was accomplished with Boehm‘s titrations, in basic and acid water solutions, and
vapour adsorption tests with ammonia, hydrochloric, acetic and propanoic acids.
The results show that plasma treatments significantly improve the adsorption ability
of carbon black granules and this effect is mainly due to the surface grafting of acid/basic
groups and not to a surface morphological modification.
Keywords: carbon black granules, plasma treatment and deposition, acid/base surface
properties.
*
*Corresponding author: fax: +39.080.5443405. e-mail address: n.devietro@chimica.uniba.it (N. De Vietro)
238 Nicoletta De Vietro
1. INTRODUCTION
Microcrystalline carbon, often called ―amorphous‖ carbon, is known in many varieties:
active carbon (AC), carbon black (CB), coke, etc. [1]. Its structure derives from graphite, as
shown by Hofmann and Wilm [2] using X-ray diffraction. Carbon black is the generic
accepted name for a wide variety of finely divided carbonaceous granules or powders
(particle size from 100 Å to 2 mm) produced by the partial combustion of liquid or gaseous
hydrocarbons under controlled conditions [1].
Since the diffuse applications of carbon black as adsorbent and filter for substances in
liquid and gas phase involve interfacial interactions, its morphology, surface area (ranging
from about 6 to 1100 m2/g) and composition are extremely important [3]. Carbon black, for
example, is usually used in cigarette filters with the aim of reducing the content of toxic
substances (acids, bases, organic compounds) in the inhaled smoke produced during the
combustion of tobacco. The chemical functionalities on carbon surface have been
traditionally split into two families according with their acid or basic character in aqueous
solution [4].
In spite of the fact that the homogeneous treatment of powders and granules, both under
low and atmospheric pressure conditions, requires special reactor designs, many examples
have been published on the surface modification of organic and inorganic powders [5-26].
Few studies have been reported, however, on the possibility of tuning the surface acid/base
character of carbon-based materials through plasma processes. This approach is extensively
utilized, instead, for flat polymers. Arefi-Khonsari et al. [27-28], for example, investigated the
possibility of tuning, by means of plasma treatments, the work of adhesion of
poly(propylene), which is related to the contact angle of solutions at different pH values
through the Fowkes equation [29-30]. Whitesides et al. [31] used ‗‗contact angle titrations‘‘,
among other diagnostics, to investigate the behaviour of acid and basic functional groups
grafted on the surface of low density polyethylene. The relationship between water contact
angle (WCA) values and density of surface groups was studied.

The basic character of NH3-plasma treated polymers was explored by means of
derivatization-aided X-ray photoelectron spectroscopy (XPS) analysis [32-34], using vapours
of a Lewis molecular probe [33].
On the other hand, most approaches, with the aim of changing the surface properties of
carbon black by low pressure plasma processes [35-43], deal with surface treatments in
oxygen containing glow discharges with the purpose of increasing the surface density of the
acid functionalities. Only few studies report on carbon black surface modification by plasma
enhanced-chemical vapour deposition (PE-CVD) [11, 25, 41], in order to increase the acid or
the basic character of the granule surface, with the purpose of improving the adsorption of
basic or acid compounds, respectively. For this reason, we decided to perform a systematic
study on the plasma grafting, etching and deposition, with the aim of improving the acid
and/or the basic surface properties of granular carbon black.
Plasma processes, in fact, as well described in the next, are able to alter the surface
chemistry and morphology of solid substrates, to some extent, depending on experimental
conditions such as: feed composition, input power, pressure, treatment time, field frequency
and plasma mode (e.g., low pressure vs high pressure, continuous vs modulated, etc.). As it
will be discussed in the next section, plasma processes are often preferred to other more
Carbon Black Treated in Low Pressure Plasma 239
conventional methods (wet processes, thermal treatments, etc.) because they allow very
shallow surface treatments (even at nanometric scale) at room temperature, are ‗‗dry‘‘, i.e.
they do not need solvent, and, therefore, their impact on the environment is generally very
low.
We evaluate the modification of carbon black surface after: i) treatment in O2 containing
plasma as well as after PE-CVD with acrylic acid (AA) containing feed (increase of surface
acidity); ii) after treatment in NH3 fed glow discharge and after PE-CVD with allylamine (Aa)
containing feed (increase of surface basicity).
2. THE PLASMOCHEMICAL APPROACH: AN OVERVIEW

Plasma, which can be regarded as the fourth state of the matter, is composed of highly
excited atomic, molecular, ionic and radical species. It is typically obtained when gases are
excited into energetic states for instance by radio frequency (RF), microwave (MW) or hot
electrons from an external source, etc.. It is a highly unusual and reactive chemical
environment in which many surface reactions can occur.
Low pressure plasmas, often called ―glow discharges‖ (even if these two terms have
different meaning, they are generally utilized as synonyms), are media in thermodynamic
non-equilibrium characterized by a large variety of processes which can be utilized for unique
modifications of conventional surfaces. The excitation of low pressure gases (10-3-1 torr) with
radio frequency is the most diffuse and easy low pressure plasma generation.
Among the principal positive features of glow discharge technology, which are
contributing to its growing study and utilization in different fields, it is worth mentioning:
 due to the non thermodynamic equilibrium, it is possible to generate highly reactive

species in a cold environment (the translational temperature can be few degrees or
tents of degree higher than room temperature) and, therefore, treating also
temperature sensitive materials;
 since the medium is rich of ions and every substrate immersed in the plasma becomes
negatively charged, by modifying the working conditions and the reactor geometry, it
is possible to superimpose, tune and control the positive ion bombardment to a
chemical process;
 the non conventional and non equilibrium conditions allow to prepare a completely
new class of materials (in form of thin films) with unique properties;
 The high versatility, which enables to easily vary in a broad range the chemical
composition and properties of treated surfaces (e.g. wettability, adhesivity, dyebility,
refractive index, hardness, gas barrier characteristics, chemical inertness,
biocompatibility, acid/base character, etc.);
 the possibility of in situ process control to improve reproducibility, by means of
suitable non intrusive diagnostics.
The low pressure plasma surface modifications can be grouped into three main classes:
treatments, etching and plasma enhanced-chemical vapour deposition.
Under most experimental conditions, neutrals species (radicals) are the main reactants,
charged particles play a synergistic effect making the surface to be treated more reactive
through momentum transfer for ion bombardment. In particular, since all surfaces exposed to
the plasma are charged negatively with respect to the plasma itself, only positive ions
bombardment must be considered.
2.1. Plasma Treatments
Plasma treatments consist in the change of the chemical composition of the uppermost
surface layers, without appreciably removing or adding layers, by ―grafting‖ chemical
functionalities and/or by inducing ―cross-linking‖ and ―branching‖ through positive ion
bombardment. In the first case, the plasma is fed with a non-depositing reactive feed (NH3,
O2, CO2, H2O; N2, etc.) while, to obtain only cross-linking and branching, the feed gas must
contain only inert gases (Ar, He, etc.).
Treatment processes based on ammonia containing feed are extensively utilized and
studied for several applications, which require the grafting of basic functional groups. Plasma
stimulated NH3 decomposition initiates several gas phase and gas-surface reactions with the
involvement of photodissociation by Vacuum Ultra Violet (VUV)/Ultra Violet (UV)
radiation, electron and heavy particle collisions [44-51]. According to Nicholas et al. [47], the
primary decomposition of NH3 by electron impact dissociation involves mainly the reactions:
NH3 + e- → NH2 + H + e- (a)
NH3 + e- → NH + 2H + e- (b)
While, in VUV photodissociation of NH3 the major role is believed to be played by the
reaction:
NH3 + γ → NH + 2H (c)
According to d‘Agostino et al. [46], the importance of reaction a or b (i.e. the extent of
NH2 or NH radicals) depends on the vibrational excitation of NH3 .
Albeit many different transient species can be produced in NH3 containing plasmas, the
only stable products are H2, N2, NH3 and N2H4, while the most important radicals are NH,
NH2, H and N produced directly from NH3 dissociation or as products of secondary reactions.
When the concentration of N-containing active species is high, the grafting of various
N-containing groups onto the substrate surface such as primary, secondary and tertiary amino,
as well as imino and nitrile groups, can occurs [32].
Treatment processes in oxygen containing plasmas are also well studied. O-containing
groups such as –OH, –COOH and –C=O are formed on the surface of organic substrates
exposed to oxygen fed glow discharges [52-54]. CO2, CO and other partially oxidized volatile
moieties can be also produced, resulting in a continuous ablation of the substrate surface
exposed to the plasma (dry etching) which competes with the treatment process.
2.2. Dry Etching
As already mentioned above, the dry etching is the ablation of materials (semiconductors,
metals, polymers, etc.) through reactions between thier surface and the reactive species
generated in the plasma.
The most important requirement for a etching process is the presence in the feed gas of
chemical species (O2, CF4/O2, Cl2, etc.) able to react with the substrate surface to form
volatile or partially volatile products.
Etching processes have been deeply investigated since 70‘s and then they found wide
application in microelectronics manufacturing for the production of integrated circuits. A
particular case of dry etching is the plasma cleaning in which surface contaminations, in
particular due to organic residual layers, are removed mostly in oxygen plasma to obtain a
clean surface.
2.3. Plasma Enhanced-Chemical Vapour Deposition
Plasma enhanced-chemical vapour deposition, also known as plasma polymerization,

deals with the deposition of organic or inorganic thin films (100 - 10000 Å) [55].
The film precursors, the building block of the growing coating, are formed from the
fragmentation of an organic compound in jargon called ―monomer‖. They react in the plasma
phase as well as on the surfaces exposed to the plasma, modifying their chemical nature,
forming oligomers and contributing to film growth. The overall process is affected by several
experimental factors such as gas feed composition, reactor geometry, pressure, input power,
ion bombardment dose and energy, additive or contaminant concentration, etc. and this allows
to vary the chemical composition and the properties of the deposit in a wide range.
3. EXPERIMENTAL
Carbon black granules can be easily treated in rotating low pressure plasma reactors such
as depicted in Figure 1.
The reactor is composed by a 53 cm long pyrex glass tube (13 cm diameter), sealed with
viton o-rings and equipped with 5 internal glass longitudinal bars fixed to the glass chamber.
During the plasma processes the glass tube rotates (up to 100 rpm) to keep the granular
material stirred for homogeneous treatment and to reduce the agglomeration of the granules at
the bottom of the pyrex chamber. The discharge is ignited between two powered external
copper electrodes, conformal to the cylindrical chamber, and a steel grounded internal tubular
one. This tubular electrode is open at the end inside the reactor for pumping, while the
opposite side is connected to a rotative pump through a butterfly valve for pressure control.
The two external electrodes are connected to a radio frequency (13.56 MHz) power supply by
means of a L-type matching network. Feed gas enters the vacuum chamber through a drilled
tube fixed under the grounded electrode.
enters the vacuum chamber

The plasma through
processes a drilled
described in thistube fixed
chapter wereunder the atgrounded
conducted the rotationelectrode.
speed of
25 rpm, on as received 10.00 g of granular carbon black (0.1–2 mm, DC W60 16x25,
Filtrona) after one hour of degassing in the reactor.
A B
Figure 1. Rotating low pressure plasma reactor for homogeneous granules treatment. (A) process
chamber and electrode assembly; (B) section: 1) RF external electrodes; 2) internal glass bars; 3)
internal ground electrode.
The grafting/etching processes were performed with feed gas containing O2 and NH3,
while PE-CVD with acrylic acid (99%, Sigma Aldrich) or allylamine vapours (99%, Sigma
Aldrich) mixed with argon.
In order to vary the fragmentation of acrylic acid or allylamine and, therefore, the
grafting extent of acid (carboxylic) or basic (e.g. amine) functionalities, both continuous and
modulated RF operation were utilized. In continuous way the discharge was on for the whole
experiment duration while, in modulated mode, the experiment time was divided in intervals
of 100 ms (period) and, within a period, the discharge was on only for part of the time (ton)
and off for the rest of the period (ton + toff =100 ms). The extent of fragmentation is related to
the so called ―duty cycle‖ (DC) defined as: DC = ton/(ton + toff).
The various plasma processes were optimized under the experimental conditions reported
in Table 1.
Table 1. Optimized experimental conditions
treatments PE-CVD with AA PE-CVD with Aa

AA 5 sccm Aa 5 sccm
gas feed NH3/O2 10 sccm
Ar 20 sccm Ar 20 sccm
20 W
20 W 20 W
power 100 W
100 W 100 W
100 W, DC 3 %
pressure 0.250 mbar 0.300 mbar 0.300 mbar
The surface chemical composition of carbon black, before and after plasma processing,
was determined by X-Ray Photoelectron Spectroscopy analyses, with AlKα radiation at an
electron take-off angle of 45° (sampling depth of ~ 7 nm). C1s fitting spectra was performed
utilizing the components of Table 2.
Table 2. XPS C1s fitting components
PE-CVD with AA PE-CVD with Aa

1 C-H; C-C 285.0 ± 0.2 eV 1 C-H; C-C 285.0 ± 0.2 eV
2 C-OH; C-O-C 286.6 ± 0.2 eV 2 C-NH2; C-NH; C-NC; COH; C-O-C 286.6 ± 0.2 eV
3 O-C-O; C=O 288.2 ± 0.2 eV 3 C≡N; C=N; O-C-O; C=O 288.2 ± 0.2 eV
4 COOH; COOR 289.1 ± 0.2 eV
The characterization of the treated surfaces was also accomplished with water contact
angle measurements on flat graphite substrates, treated as the carbon black granules. 2 µL
drops of acid/base solutions, at different pH values, were utilized and the measurements were
performed within 12 h from plasma processes. As reported in ref. [27], the reduction of the
water contact angle measurement at acid pH values is due to the presence of basic grafted
groups, while the reduction at basic pH is due to the grafting of acid functionalities.
Since the adsorption properties can be influenced also by the surface porosity and
morphology, Brunauer-Hemmett-Teller (BET) surface area measurements and scanning
electron microscopy (SEM) observations on carbon black granules, before and after plasma
processing, were performed. In particular, the BET measurements, realized with N2
physisorption on a Micrometrics ASAP 2010 instrument, were utilized to detect variation of
Specific Surface Area (SSA) induced on carbon black granules (out-gassed at 40 °C for 4 h)
by plasma processes [56]. Mean values of five different measurements and relative error bars
were considered. SEM observations (Cambridge stereoscan 360 instrument), on the other
hand, allow to visually evaluate morphology modifications; due to the high morphological
non-homogeneity of carbon black, SEM observations were acquired at the same point of the
same granule, before and after different treatments. An image processing software (Imagel,
NIH) was utilized to evaluate the porosity of the samples. Some observations with a phase
contrast light microscope (Leica DM IL) were also performed.
3.1. Evaluation of the Surface Adsorption Properties
The ability of plasma processed carbon black to adsorb acids and bases in water solution
was evaluated according to the method proposed by Boehm [57]. 20 ml of HCl 0.02 N or
NaOH 0.02 N were added to a vial contained 1.00 g of carbon black granules. After 24 h of
stirring at 180 rpm, the granules were separated from the solution and the excess of
unadsorbed acid or base was titrated with NaOH or HCl, respectively. The difference between
the acid (base) equivalents contained in the solutions, before and after the adsorption, allows
to evaluate the amount of acid (base) adsorbed by the granules, corresponding to the
equivalents of basic (acid) functional groups plasma-grafted at the surface of carbon black.
The ability of carbon black granules to adsorb acid/base compounds in gas/vapour phase
can be tested employing the pyrex glass system schematized in Figure 2.
It consists of two flasks sealed with steel clamps to a central vial containing 0.10 g of
carbon black granules between two fiberglass septa.
T=25 °C
CB
NH3
fiberglass
septum
N2
A B
T=50 °C
Figure 2. Scheme of the pyrex glass system utilized to test the ability of carbon black granules to
adsorb acid and basic compounds in gas/vapour phase.
Fig. 2: scheme of the pyrex glass system utilized to test the ability of carbon
To evaluate the adsorption of acids, the flask A is filled with 100 ml of HCl 12 N or
acetic (CH3COOH) acid or propanonic (CH3CH2COOH) acid. 60 sccm of N2 are bubbled in
this flask for 20 min to strip the acid vapours, then the N2/acid mixture flows through the
carbon black granules and finally bubbles in 100 ml of bi-distilled water in flask B, to trap
unadsorbed acid. At the end of the experiment, the solution in flask B is titrated with NaOH.
Experiments performed with and without carbon black in the vial allowed to evaluate the
adsorption property of carbon black.
The adsorption of basic compounds can be evaluated by flowing through the vial 15 sccm
of NH3 for 20 min. The unadsorbed NH3 is trapped in 100 ml of HCl 0.15 N, in flask B, and
then titrated with NaOH 0.2 N.
4. RESULTS
4.1. Treatments in NH3/O2 Containing Plasmas
The XPS surface composition of carbon black granules, after treatment in NH3/O2
containing glow discharge powered at 20 W, is reported in Figure 3, as a function of the feed
composition along with that of untreated granules.
The surface composition is affected by the plasma treatment since the oxygen and nitrogen
content varies for the grafting of O- and N-containing chemical functionalities. The oxygen
percent is always higher than that of nitrogen, also when the feed gas contains 100 %
ammonia.
At 100 W the trends are not significantly different, only an increased grafting efficiency
of O- and N-containing groups is detected.
In addition to carbon (89.8 %) and oxygen (7.4 %) the surface of untreated carbon black
granules contains also other elements such as: Na, K, and Cl, each in concentration less than
1 %, which lightly increases after treatment in O2/NH3 containing plasmas, in particular at
100 % O2 likely for the partial removal of surface carbon due to dry etching reactions.
that of untreated granules.
100
C
O
90 N
XPS atomic %
80
20
10
0 20 40 60 80 100
untreated O2 % in NH3/O2-plasma
Figure 3. XPS atomic percent of treated carbon black granules as a function of the O2 percent in NH3/O2
fed plasmas at 20 W.
Fig. 3: XPS atomic percent of treated carbon black granules as a function of the
The increase of XPS oxygen percent after treatment in 100 % NH3-plasma is reasonably
due to oxygen uptake from air after the treatment itself.
Treatments in pure oxygen plasma causes pores enlargement and roughening increase of
the carbon black granules, reasonably for etching reactions between the carbon surface and
the oxygen atoms formed in the plasma phase.
The modification of the surface morphology is much less evident if the treatment is
performed in 100 % NH3 glow discharge. In fact, the SEM images of Figure 4, taken at the
enlargedsame point of
of treated a carbon
carbon blackblack granule before and after a prolonged NH3-plasma treatment
pores.
(1 hour), show a slight enlarged of treated carbon black pores.
A B
5000x 5000x
Figure 4. SEM image of an untreated carbon black granule (A ) and after 1 h of treatment in 100% NH3
Fig. 4: SEM
plasmaimage
at 100 of an untreated
W (B). All imagescarbon blackat 5000x of magnification.
were acquired
The modification of the surface morphology of carbon black granules is more important
in oxygen than in ammonia plasma for the higher etching ability of oxygen. In the field of
polymer treatment, in fact, NH3 plasmas are well known for surface functionalization, while
O2 plasmas both for functionalising and etching.
Since morphological modifications affect the surface area, which in turn influences the
adsorption properties, evaluations of the specific surface area of untreated and treated carbon
black were performed with BET measurements. The SSA increases for all fed composition in
the ranges 70 – 95 % at 20 W and 95 – 115 % at 100 W.
To investigate the acid and basic character of the carbon black surface after plasma
treatment, WCA measurement vs pH were performed on flat graphite substrates treated under
the same experimental conditions of carbon black granules. Of course, since the two substrate
are different, the results obtained on graphite must be carefully extended to carbon black,
even though XPS analyses showed that the surface chemical modifications induced by the
plasma treatments on graphite and carbon black are quite similar [39], it is possible to assume
that also the acid/base properties are similar for the two substrates. Figures 5 shows the trend
of WCA vs pH for graphite, before and after plasma treatment at 20 W.
The WCA values of the untreated graphite, reported as reference, indicate the absence of
both acid and basic groups on the sample surface, since the contact angle is not affected by
N-containing polarthegroups.
pH. The hydrophilic character of the surface increases for all feed compositions, for the
grafting of O- and/or N-containing polar groups.
100
untreated
80 NH3 100%
NH3 50% - O2 50%
contact angle (°)
60
O2 100%
40
20
0
0 2 4 6 8 10 12 14
pH
Figure 5. Contact angle measured with solutions at different pH on flat graphite substrates treated in
Fig. 5: contact angle
NH3measured
/O2-plasmas with solutions
at 20 W. at different
Measurements pH on flat
were performed graphite
within 12 h from the plasma treatment.
The lowest contact angles are obtained after treatment in 100 % O2: since the contact
angle decreases at basic pH, acid groups are grafted on the graphite surface. With 100 % NH3,
the behaviour is amphoteric because the water contact angle decreases both at pH lower than
4 and higher than 12, indicating the grafting of both basic and acid groups, respectively. Since
the feed gas does not contain oxygen but only ammonia, this effect could be due to reactions
with atmospheric oxygen or humidity of the free radicals survived on the surface after the
plasma treatment.
At higher input power (100 W) the same trends are obtained, the only important
difference is that all WCA values are lower, indicating an increased grafting efficiency of
O- and N-polar groups, likely due to the increased feed fragmentation and consequent higher
density of active species, in agreement with XPS data previously shown.
These experimental results allow to conclude that, since it is possible to vary the
chemical composition and morphology of carbon black granules, plasma technology can be
considered a promising tool to improve the utilization of carbon black granules for several
practical applications.
Figure 6 reports the Boehm‘s titration results for carbon black, before and after NH3/O2-
plasma treatment at 20 W. The equivalents of H3O+ and OH- ions trapped on the surface basic
and acid sites are reported as a function the feed composition.
It is important to stress that untreated carbon black gives basic reaction in water and
releases about 1.5x10-5 equivalents of OH- per gram. This basic behaviour is probably due to
Na and K oxides formed as ashes during the production of carbon black.
No acid behaviour was measured for untreated carbon black.
Figure 6. Boehm‘s titrations results for carbon black granules, before and after treatment in NH3/O2 fed
plasmas at 20 W.
Figure 6 clearly shows that, in addition to the basic character (adsorption of H3O+), also
the acid character (adsorption of OH-) increases after treatment in 100 % NH3-plasma. The
increase of the acidity for carbon black, modified in a 100 % NH3 glow discharge, is likely
due to surface acid functionalities created during air exposure for the reaction of atmospheric
oxygen with the residual reactive sites left on the carbon black surface (see XPS results of
Figure 3). Oxygen addition to the feed increases the acid properties of carbon black and
reduces the basic character. It is worth noticing that the basic character is always higher than
the acid one, likely for the intrinsic basic behaviour of untreated carbon black. The
comparison of Figures 6 and 3 reveals that the acid behaviour of treated granules is correlated
with XPS oxygen content and, reasonably, to the density of grafted O-containing groups. The
basic behaviour, on the other hand, seems related to the XPS N percent and, therefore, to the
grafted N-containing groups.
Increasing the treatment power to 100 W results in a slight decrease of the ability to
adsorb acid and basic compounds.
The results of the tests of adsorption of acids and basics in gas phase for treatments at
20 W are reported in Figures 7, as a function of the feed composition, utilizing HCl and NH3
with the apparatus described in Figure 2.
-3
2.5x10
HCl
NH3
Adsorbed equivalentes 2.0x10
-3
-3
1.5x10
-3
1.0x10
-4
5.0x10
0.0
-2
untreated 00 2
20 4 50 6 880 10
100
OO2 2%
%ininONH
2
3/Oplasma
-NH 3
2-plasma
Figure 7. HCl and NH3 equivalents adsorbed by carbon black granules, before and after treatment in
NH3/O2 fed plasmas at 20 W.
The adsorption extent of NH3 and HCl is low and almost identical on untreated carbon
black and increases significantly after the plasma treatment. In agreement with the adsorption
results obtained in solution (Figure 6), the adsorption of NH3 on carbon black (i.e. the acid
character) increases with the O2 content in the feed and, therefore, with the XPS oxygen
content (i.e. density of grafted oxygen containing groups), while the adsorption of HCl
vapours (basic character) increases with the NH3 level in the feed and, so, with the XPS
nitrogen percent (density of grafted N-groups). The carbon black treated at 20 W in 100 %
NH3 plasma, in fact, adsorbs up to 35 % of the total HCl vapours which flow in the system.
The same trend is obtained if the input power is increased at 100 W with only a
somewhat lower general adsorption ability.
An important distinction between the adsorption in solution and in gas phase consists in
the fact that, while in liquid the carbon black treated in 100 % NH3 absorbs bases for
treatments at both 20 and 100 W, in gas phase the adsorption of bases is registered only at
20 W. Another relevant difference is that untreated carbon black adsorbes both acids and
bases in gas phase. In solution, in fact, only acids are adsorbed while basics are released.
Since any nitrogen was detected by XPS, it is possible to explain this phenomena ipotizing
that basic species (e.g., Na and K oxides) decompose in solution but are stable during the gas
adsorption experiments.
4.2. PE-CVD by Acrylic Acid Vapours
Since it has been reported that, by changing and/or modulating the input power in a glow
discharge fed with acrylic acid it is possible to obtain coatings with different content of acid
groups [58-63], we studied the deposition processes at 20, 100 W and at 100 W with
modulation (DC 3 %), in order to obtain films with the highest density of carboxylic groups.
The modulation below 100 W was not possible for plasma instabilities. Figure 8 reports the
chemical charatcterization, in terms of XPS results, of the obtained coatings.
Figure 8. XPS C1s spectra of thin films deposited in acrylic acid fed plasmas at: 20 W (A); 100 W (B)
and 100 W, DC 3 % (C).
As it can be appreciated observing Figure 8, where the XPS C1s regions of the films
deposited under the selected experimental conditions are reported, despite the lower oxygen
percent (~ 19.7 % ), the content of carboxylic groups is higher at 20 W (~ 9.9 %).
WCA measurements are in agreement with XPS data, since the coating deposited at 20 W
is characterized by the lowest contact angle value (20° ± 2°), i.e. the highest hydrophilicity,
while at 100 W the highest hydrophobicity (WCA = 62° ± 2°) is obtained. As a consequence,
the study was addressed to the deposition performed at 20 W.
In order to evaluate the utilization of coated carbon black granules as adsorbent material
in gas phase, in solution and for hot fumes, coated carbon black were aged in air, in water and
by thermal treatments. After the ageing, the samples were observed with the optical
microscope to exclude delamination, then analyzed with the XPS and with the goniometer for
WCA evaluations. The results after ageing in air are reported in Figure 9.
1.4 45
O/C
1.2 WCA (°)
40
1.0
35
WCA (°)
0.8
O/C
30
0.6
0.4 25
0.2
20
0.0
-5 0 5 10 15 20 25 30
as deposited
time (days)
Figure 9. XPS O/C and WCA values vs time of ageing in air of thin films deposited in acrylic acid fed
plasmas at 20 W.
Both the WCA and the oxygen–to–carbon ratio increase with ageing, in particular during
the first 15 days. The exhamination of the XPS C1s region indicates that the ageing causes the
reduction of carboxylic groups and the increase of the carbonyls.
The thermal stability after one month of air ageing was tested after heating at 100 and
150 °C. The water contact angle did not change even after 180 min at 100 °C while, after
5 min at 150 °C, it increased from 20 to 50° indicating that, at this high temperature, the
coating suffers significant modifications which preclude its utilization.
In order to test the water stability of the thin film deposited at 20 W, it was covered a
silicon substrate which was then immersed in bi-distilled water. After one day a complete
delamination was observed, indicating that it is not compatible with utilization in water. For
the film deposited at 100 W in modulated mode (DC 3%), the delamination started after one
week of immersion and was completed after 1 month while, for the coating deposited at 100
W in continuos mode, no delamination or variation of WCA and XPS data, also after one
month of immersion, was detected. So, the water stability seems to be inversely proportional
to the content of carboxylic groups which is the highest for deposition at 20 W (9.9 %) and
the lowest at 100 W in continuous mode (1.8 %).
In conclusion, the experimental results indicate that carbon black granules, when coated
with thin films obtained for PE-CVD of acrylic acid at 20 W, can be evaluated as
gases/vapors adsorber for applications up to 100 °C while, if the the PE-CVD of acrylic acid
is performed at 100 W, can be considered as adsorbers in water.
In order to test the adsorption properties of carbon black for basic molecules in gas phase,
the extent of ammonia adsorption of 10.00 g of carbon black, coated with PE-CVD of acrylic
acid at 20 W for 60 min, was tested with the system described in Figure 2. The results are
compared in Figure 10 with that of untreated carbon black. The percent of ammonia adsorbed
per gram of carbon black were calculated respect to the total ammonia which fed the system
during each experiment. The measurements were performed at 50 °C after 15 days of ageing
in air when, according to Figure 9, the chemical composition of the surface is stable.
The same results were obtained also after six months of ageing in air.
10 100
% of NH3 adsorbed equiavelents/CBg

NH3 adsorbed equivalents*10 /CBg
untreated CB 90
pdAA CB
-3
8 80
70
6 60
50
4 40
30
2 20
10
0 0
untreated pdAA
Figure 10. NH3 adsorption per gram of carbon black coated with thin film deposited by acrylic acid fed
plasma at 20 W. Data are reported as absolute equivalents and in percent of the total amount of NH 3
which fed the system.
The adsorption ability for basic compounds of coated carbon black granules was about
the 70 % of the total ammonia equivalent utilized for the measurements while, for the
untreated carbon black, it was only the 5 %.
Figure 11 reports the OH- equivalents adsorbed in water per gram of carbon black
granules (Boehm‘s titrations) coated with PE-CVD of acrylic acid at 100 W (the best
conditions for adsorption in water), after 15 days of ageing in air. The adsorption ability of
coated granules increases more than four times respect the untreated sample.
Also in this case, the same results were obtained after 6 months of ageing.
1.0
/CBg g)
untreated CB
equivalents (*10/CB
pdAA CB
-4 -4
0.8
adsorbed equivalents*10
0.6
0.4
OH- relesed
OH adsorbed
equivalents
0.2
--
OH
0.0
untreated pdAA
Figure 11. Boehm‘s titrations results for carbon black granules untreated and coated with thin film
deposited by acrylic acid fed plasma at 20 W.
In order to evaluate the effect of the acrylic acid coating on the carbon black morphology,
a granule was observed with SEM, before and after the plasma deposition at 20 W (Figure
12). The observation was carefully made at the same point.
A B
400x 400x
C D
2000x 2000x
Figure 12. SEM images of a carbon black granule, untreated (A, C) and coated (B, D) with thin film
deposited by acrylic acid fed plasma at 20 W. Images A and B are acquired at 400x magnification,
while images C and D at 2000x.
The observation at low magnification (400x) does not show macroscopic morphological
modifications before and after the plasma treatment but, at greater magnification, it is clearly
evident that the plasma deposition of the acrylic acid coating causes pore obstruction. BET
specific surface area measurements showed that, although the SSA of carbon black granules
is not macroscopically changed by PE-CVD (untreated carbon black = 1100 ± 60 m2/g;
coated carbon black =1170 ± 60 m2/g), the plasma deposition reduces the surface area of
micro-pores of about 43 %, passing from 700 ± 50 m2/g, for untreated carbon black, to 400 ±
70 m2/g for the coated sample. The total pores volume is also reduced by plasma process
(about 32 %): 0.88 ± 0.05 cm3/g for virgin granules; 0.60 ± 0.03 cm3/g for coated carbon
black.
These results indicate that the improvement of the adsorption properties of carbon black
granules after PE-CVD of acrylic acid can be ascribed to an increase of the surface
concentration of acid groups, which chemically bond the NH3 molecules or the OH- ions, and
not to a morphological modifications (i.e. increase of the specific surface area).
4.3. PE-CVD by Allylamine Vapours
The deposition of thin films in plasmas fed with allylamine was studied to obtain carbon
black granules with a high surface density of basic (i.e. aminic) groups to be utilized for acid
compounds adsorption. The PE-CVD processes were performed at 20 and 100 W only in
continuous mode since, unlike glow discharges fed with acrylic acid vapours, with allylamine
vapours input power modulation never resulted in stable plasmas.
Figure 13. XPS C1s spectra of thin films deposited by allylamine fed plasmas at: 20 W (A) and 100
W (B).
The XPS C1s region of coatings are reported in Figure 13.

The area of the peak No. 2 at 286,6 eV and the nitrogen percent is higher for the film
deposited at low input power, which probably contains the highest concentration of basic
groups. The small oxygen percent is reasonably due to uptake after air exposure. Also the
water contact angle values indicate that the coating deposited at 20 W is characterized by the
highest density of polar groups, since the WCA is lower at 20 W (45° ± 2°). As a
consequence, as for acrylic acid, also in this case, the attention was focused on thin films
obtained at 20 W.
In order to consider the possible utilization of coated carbon black granules as adsorbent
for acid vapors, the ageing in air was followed for thirty days. Any delamination was not
detected with optical microscopy. The evolutions of XPS chemical composition and WCA
values are reported in Figure 14.
The water contact angle increases markedly during the first 15 days of ageing, while the
atomic chemical composition stabilizes after the first days. The exhamination of the detailed
C1s region indicates an increase of the area of the peak at 288.2 eV and a reduction of the
contribution at 286.6 eV which, after one month, passes from 22 to 19 % indicating a
reduction of the surface basic gropus conteining nitrogen atoms.
25 80
20 70
XPS atomic %
15 60
WCA (°)
10 WCA 50
O%
N%
5 40
0 30
0 5 10 15 20 25 30
as deposited
time (days)
Figure 14. XPS O %, N % and WCA values vs time of ageing in air of thin films deposited by
allylamine fed plasmas at 20 W.
The thermal stability of the coating was evaluated after heating at 100 and 150 °C. While
in the first case the film is stable since any XPS or WCA variation was not detected also after
180 min, 5 min heating at 150 °C results in a WCA increase from 45° to 65° and in a
reduction of the XPS nitrogen content of about 15 %, indicating that coated carbon black
granules cannot be utilized at high temperature.
Test of water stability showed that the film is unstable in water, also at room temperature,
since, after 1 h of immersion, it was totally delaminated.
In conclusion, the results indicate that carbon black granules coated with plasma
deposited allylamine thin films at 20 W can be evaluated as gas/vapour adsorber for
applications up to 100 °C and not for utilization in water.
The adsorption results, obtained with the system of Figure 2 fed with HCl vapours, are
compared, in Figure 15, with that obtained for untreated carbon black sample. The
measurements were performed at 50 °C on granules aged for 15 days in air when, according
to Figure 14, the chemical composition of the surface is stable.
It can be observed that the adsorption ability increases, after the PE-CVD in allylamine
containing plasmas, passing from the 5 % to the 55 % of the total hydrochloric acid
equivalents which flowed through the system.
Figure 15. HCl adsorption per gram of carbon black coated with thin film deposited by allylamine fed
plasmas at 20W. Data are reported as absolute equivalents and in percent of the total amount of HCl
Also in this case, as for acrylic acid PE-CVD, the modification of surface morphology
was evaluated by means of SEM observations at the same point of a carbon black granule,
before and after the plasma deposition process (Figure 16).
At low magnification (200x), any macroscopic morphological modification due to plasma
deposition is detected while, at higher magnification (5000x), it clearly appears that the
deposition causes pores obstruction with a consequent reduction of the surface area. This is
supported by BET specific surface area measurements, from which it emerges that the SSA of
carbon black granules is macroscopically reduced by plasma treatment (virgin carbon black =
1100 ± 60 m2/g; coated carbon black = 350 ± 50 m2/g). Coating deposition also reduces the
surface area of micro-pores of about 53 %, passing from 700 ± 50 m2/g for untreated
2
carbon black to 328 ± 40 m /g for the coated sample. The total pores volume is also reduced
by plasma process (about 69 %), passing from 0.88 ± 0.05 cm3/g to 0.27 ± 0.03 cm3/g.
Figure 16. SEM images of a carbon black granule, untreated (A, C) and coated (B, D) with thin film
deposited by allylamine fed plasma at 20 W. Images A and B are acquired at 200x magnification while
images C and D at 5000x.
These experimental evidences, allow us to conclude that the improvement of the surface
adsorption properties of carbon black granules, induced by PE-CVD in allylamine containing
glow discharges, is not due to a morphological modification (an increase of pores area would
be necessary) but to the basic groups contained in the plasma deposited thin films.
In order to test the possible utilization of the carbon black granules coated in allylamine
containing plasma as adsorbers, the ability to retain acid vapours was evaluated utilizing
hydrochloric, acetic and propionic acid. Acetic and propionic acids are well known pollutants
which can be produced, for instance, during olive oil production and are responsible of the
unpleasant odours diffused in the atmosphere by olive oil factories. The results of adsorption
at 50 °C are reported in Figure 17 for granules aged for 15 days in air.
It can be observed that the adsorption ability increases after plasma treatment and that it
is function of the probe acid. The adsorption ability of the coated carbon black granules was
about the 55 %, 60 % and 73 % of the total equivalents of hydrochloric, acetic and propanoic
acid flowed through the system, respectively, while for the untreated carbon black it was in
the range 5 – 32%.
Figure 17. Acid adsorption per gram of carbon black coated with thin film deposited by allylamine fed
plasmas at 20W. Data are reported as absolute equivalents and in percent of the total amount of acid
CONCLUSIONS
In this contribution it has been shown that low pressure plasma processes are suitable to
modify the surface composition of carbon black granules, improving their adsorption ability
for acid and basic compounds in liquid and in gas phase.
Glow discharges fed with O2/NH3 gas mixtures allow the grafting of acid and/or basic
functional groups and the increase of the specific surface area of carbon black granules. As
expected, the surface concentration of acid groups rises with the O2 content of the feed gas,
while basic functionalities are better implanted in NH3 rich plasmas. An amphoteric
behaviour, i.e. the ability to adsorb both acids and bases, has been also detected.
When the discharge is fed with acrylic acid or allylamine the deposition occurs.
With plasma fed with acrylic acid vapours, the amount of carboxylic groups on the
carbon black granules is not related to the oxygen content in fact, while the highest surface
oxygen atomic percentage is shown at 100 W in modulate mode, the highest carboxyl
functionalities content is obtained at 20 W in continuous mode. The films show marked
ageing in air with a reduction of the surface concentration of carboxylic groups which levels
in 15 days. The gas phase adsorption ability of carbon black granules after plasma deposition
in acrylic acid at low input power increases up to 70 %. The coating is stable at high
temperature (max 100 °C), but it quickly delaminates after immersion in water. The water
resistance increases at higher input power (100 W) and, therefore, despite the concentration of
carboxylic groups is not maximum, this deposit can be utilized to improve the carbon black
adsorption of basic substances in water solution.
Plasmas fed with allylamine vapours can be utilized to deposit thin film with basic
properties and, so, able to absorb acid compounds in gas/vapour phase. The amount of basic
groups is related to the nitrogen content in the deposit, in fact, under the experimental
condition explored, the highest basic groups content is obtained at 20 W, in continuous mode,
when the XPS nitrogen percent is highest. Plasma deposition of allylamine at low input power
can increase the gas phase adsorption ability of carbon black granules towards acid
compounds and the improvement depends on the particular acid compounds considered.
ACKNOWLEDGMENTS
Dr. Akihiro Tanaka (ULVAC-PHI, Chigasaki, Japan) is acknowledged for XPS small
spot analyses.
The author are also grateful to Prof. Giammario Martra and Dr. Chiara Bisio (University
of Torino, Italy) for BET specific surface area measurements.
Finally, Mr. Vincenzo Bonasia and Mr Savino Cosmai are acknowledged for their
precious technical support.
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Chapter 11
PRODUCTION, PROPERTIES AND APPLICATIONS OF

CARBON BLACKS IN RECHARGEABLE
LITHIUM-ION BATTERIES
B. Jin*
Key Laboratory of Automobile Materials (Jilin University), Ministry of Education, and
School of Materials Science and Engineering, Jilin University, Changchun, China
1. INTRODUCTION
Carbon black is a family of small particle size carbon pigments, which are formed in the
gas phase by the thermal decomposition of hydrocarbons, and has been used widely in lithium
secondary batteries, inks, coatings, rubbers and plastics. This chapter is to provide an
introduction as to how the carbon blacks are manufactured and their most important physical
and electrochemical properties. Primary emphasis is given to introducing the electrochemical
properties and the applications in rechargeable lithium-ion batteries. Here we will also draw
the electrochemical properties from examples taken from our own work. This contribution
consists of four sections. Section 1 is entitled Introduction. The following section (Section 2)
describes the manufacturing method. Section 3 focuses on the physical and electrochemical
properties and the applications. Section 4 provides summary and future prospects.
2. MANUFACTURING METHOD
Carbon blacks can be manufactured by five major methods, such as Lampblack process,
the oil furnace process, acetylene process, thermal process and the impingement process.
* Corresponding author. Tel.: +86-431-85095170; E-mail: jinbo@jlu.edu.cn (B. Jin)

264 B. Jin
2.1. Lampblack Process
The lampblack process is the oldest among five processes, and its application is very
limited. Lampblacks have historically been made by burning aromatic oils in shallow pans
with limited air supply [1]. The carbon black formed is drawn off into settling areas and
periodically collected. Generally, lampblacks have great average particle size of about 70-100
nm and a large number of particles per aggregate. Because of relatively low blackness and
easy dispersion, lampblacks are widely used in tint colorant for coatings.
2.2. Oil Furnace Process
The oil furnace process involves the production of carbon black from highly aromatic
feedstock oil in a burning gas circumstance. It is very rapid and continuous process in which
the oil is converted to carbon black aggregates at high temperature.
In the oil furnace process, a flame is established in the reactor with oil or natural gas and
excess air [1]. The carbon black forms where the feedstock oil is injected into this flame. The
reaction products are then cooled with a water spray immediately after carbon black
formation and further cooled as it passes through a heat exchanger and onto the collector.
A large number of furnace carbon black products are pelletized (beaded) to provide a
more easily handled and less dusty form. Carbon blacks used in rubber and plastic
applications are most typically beaded with water and dried.
2.3. ACETYLENE PROCESS
As a special grade of carbon black, acetylene black can be manufactured by the thermal
decomposition of acetylene gas under pressure or incomplete burning similar to channel and
lampblacks.
The Shawinigan process was first used in 1933 and is still utilized today. In this process,
acetylene gas is introduced at the top of a cylindrical reactor with several meters height. The
reactor is preheated to about 800 ℃ prior to introducing the acetylene. This reaction produces
temperatures at the carbon black surface in excess of 2500 ℃. The formation of carbon black
most likely takes place in the 800-2000 ℃ zone by mechanisms similar to other carbon
blacks, followed by partial graphitization in the higher temperature region [1].
Acetylene black displays low reactivity due to its highly graphitic surface, and is widely
used in the applications requiring chemical inertness or high electrical/thermal conductivity.
2.4. Thermal Process
As a kind of carbon black, thermal black is manufactured by the decomposition of oil and
natural gas. They are made in the absence of air by means of a cyclic type process which is
based on pairs of furnaces (generators). The generators are lined with open checker brickwork
which is preheated prior to charging with the gas or oil feedstock. The respective heat and
Production, Properties and Applications of Carbon Blacks … 265
carbon black production cycles require about 2.5 minutes each. Following the production
cycle, there is about a one-minute steam purge process to remove the carbon black and
hydrogen gas from the generators. The product is then subjected to a water spray for cooling,
passed through a collection filter and conveyed to a beader, dryer and bulk storage tank. The
average particle size of thermal black is about 250-500 nm, and larger than that of all other
types of carbon black [1].
2.5. The Impingement Process
The impingement or channel process is now essentially obsolete, but is initially the most
important methods of carbon black manufacture in the United States. In this process, natural
gas is burned from slotted ceramic tips to produce fan type flames in evenly spaced rows.
These flames are set to impinge on channel irons on to which the carbon black is deposited
and subsequently collected. The impingement carbon blacks were first produced during the
1870's and reached their peak production in the 1920's and 1930's [1].
The channel process suffers from poor carbon conversion of the natural gas feedstock and
poor collection efficiency due to the rising cost of the natural gas. As a result, this kind of
carbon black process is no longer utilized in the United States.
In above-mentioned five manufacturing methods, acetylene process is widely in
rechargeable lithium-ion batteries industry because acetylene black produced by this process
is often used as carbon conductive additive in the electrode manufacture. The following
section will describe the physical and electrochemical properties and applications of carbon
black in rechargeable lithium-ion batteries.
3. PHYSICAL AND ELECTROCHEMICAL

PROPERTIES AND THE APPLICATIONS

3.1. Carbon Black-Based Composite Cathodes
3.1.1. Sulfur/Carbon Black Composite Cathodes

It is well-known that the elemental sulfur is an attractive cathode active material due to
low cost, low equivalent weight, no toxicity and high theoretical specific capacity of 1675
mAh/g-sulfur [2], assuming the complete reaction of lithium with sulfur to Li2S. Although the
sulfur has these advantages, the lithium-sulfur batteries can not discharge fully at low
temperature because the sulfur is an insulator. Therefore, the composite cathodes of the sulfur
(active cathode) and the carbon black (conductive additive) are widely investigated in order to
improve the sulfur utilization [3-6]. We also report the electrochemical properties of
sulfur/carbon black composite cathodes [7]. The composite cathodes are made from mixtures
of elemental sulfur powder, carbon black powder, carboxymethyl cellulose binder,
polytetrafluoroethylene binder and Brij35P [Poly (ethyleneglycol) dodecyl ether] dispersant
in a weight ratio of 51.6:26.7:18:2:1.7, the mixture of distilled water and alcohol (90:10, vol.)
is used as solvent. The elemental sulfur and carbon black powder are mixed in a blender,
agitated for 30 seconds at high speed each time, and it is carried out for ten times. The slurry
266 B. Jin
is ball-milled for 10 hours, and then coated onto Al foil. The resulting electrode films are
pressed with a twin roller, cut into rectangle plate with an area of 84.42 cm2 and disc with an
area of 4 cm2, followed by drying at 60 ℃ for 12 hours under vacuum prior to use. Lithium
cells are constructed with a separator made from Celgard2500 membrane, the cathode
composite with an area of 84.42 cm2, and anode of lithium metal. The cells are laminated and
sealed in a pouch under vacuum, and filled with 0.5 g of electrolyte. Figure 1 demonstrates
that the average particle size of plate-like carbon black is around 1 m. As shown in Fig. 2,
the sulfur and carbon black powder are mixed evenly and proved useful to increase the
reaction area between two types of particles. Figure 3 shows cycle characteristics of lithium-
sulfur batteries with different electrolytes. The initial discharge capacity of cells with four
electrolytes ELS1, ELS2, ELS3 and ELS4 is 48.994, 46.925, 48.918 and 36.995 mAh,
respectively. On the second cycle, the corresponding discharge capacity of cells is 67.531,
64.16, 60.03 and 50.393 mAh. The cell with electrolyte ELS1 has the best cycle performance.
Its discharge capacity after 10 cycles is almost the same as the initial discharge capacity, and
is the highest for the four cells.
Jeon et al. [3] report the preparation and electrochemical properties of lithium-sulfur
polymer batteries with a composite, a polymer electrolyte and a lithium anode. The composite
cathode is made from elemental sulfur, carbon black, polyethylene oxide (PEO), LiClO4, and
acetonitrile. Sulfur powder is prepared by ball-milling in a dry condition. A mixture
containing 50 wt.% ball-milled sulfur, 15 wt.% carbon black (Super P black, dried at 140 ℃
under vacuum for 12 h), and 35 wt.% PEO with LiClO4 is ball-milled for 30 min. Acetonitrile
is poured into this mixture and the slurry is ball-milled again to achieve uniform mixing. A
thin film is cast directly on to a stainless steel current-collector, and the solvent (acetonitrile)
is allowed to evaporate at room temperature. It is found that the open-circuit voltage is about
2.5 V. As the current load increases, the discharge capacity decreases. A composite cathode
with sulfur can not maintain well-distributed morphology and loses reactive sites between
sulfur and lithium during charge-discharge cycling. Therefore, lithium-sulfur batteries have a
poor cycling life and low utilization of sulfur.
Figure 1. FE-SEM image of carbon black.
Figure 2. SEM image of sulfur and carbon black powder after blending at high speed for 10 times.
100
ELS1
ELS2
80 ELS3
Discharge Capacity(mAh)
ELS4
60
40
20
0
0 2 4 6 8 10 12
Cycle Number
Figure 3. Cycle performance of lithium-sulfur batteries with different electrolytes.
Jung et al. [4] find new approaches to improve cycle life characteristics of lithium-sulfur
batteries. Two different methods are tried for an improvement in the cycling performance of
lithium-sulfur batteries: (1) A mixed polymer binder system of polyvinyl pyrrolidone (PVP)
and polyethyleneimine (PEI) is developed to maintain the initial morphology of the carbon
electrodes, the positive electrode of lithium-sulfur batteries during charge-discharge cycles;
(2) a tetrabutylammonium (TBA)-based mixed salt system is applied to an organic liquid
electrolyte of the lithium-sulfur batteries to change certain chemical reactions of polysulfides
in the electrolyte solutions. Super-P (2 g) carbon black and 16 g of elemental sulfur are
dispersed in the mixed binder solution by the ball milling method to prepare composite slurry
268 B. Jin
for the positive electrode of lithium-sulfur batteries. The slurry is coated onto a carbon-coated
Al current collector with a doctor blade. To examine the effect of PEI on the performance of
the positive electrode, two composite slurries with the composition of Sulfur/Super-P/PVP
(16:2:1.0 and 16:2:2) and the corresponding electrodes are prepared.
The lithium-sulfur batteries with PEI show a remarkable improvement in cycling
performance as well as in discharge capacity, compared with the lithium-sulfur batteries with
PVP only. The discharge capacity at the 50th cycle is found to be ~580 mAh/g-sulfur, 83% of
an initial capacity (~720 mAh/g-sulfur), at a high current density of 2.0 mA/cm2. The lithium-
sulfur batteries with a mixed electrolyte of 0.5 M LiCF3SO3/0.5 M TBAPF6 does not show a
distinct improvement in the aspect of discharge capacity. In the mixed electrolyte of 0.5 M
LiCF3SO3/0.5 M TBAPF6, however, the lithium-sulfur batteries show a significant
enhancement in the cycling life characteristics, compared to the lithium-sulfur batteries with
imidazolium salts and much better than that of lithium-sulfur batteries with 1.0 M LiCF3SO3.
Kim et al. [5] report the cycling performance of rechargeable lithium-sulfur batteries with
dimethoxyethane (DME)/dioxolane (DOX) (4/1) solvent systems. The supporting electrolyte
systems used are classified into the two groups: (1) conventional lithium salts and (2) mixed
salts composed of lithium salt and imidazolium salt. To analyze the effect of the imidazolium
cation on the cycling life characteristics of secondary lithium-sulfur batteries, they use the
following three kinds of immidazolium salts, with the same anion, to the mixed-salt systems:
1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (EMITFSI); 1-butyl-3-
methyl-imidazolium bis(trifluoromethylsulfonyl)imide (BMITFSI); 1,2-dimethyl-3-
propylimidazolium bis(trifluoromethylsulfony)imide (DMPITFSI). 67.5 wt.% elemental
sulfur, 11.4 wt.% carbon black as a conductive material, and 21.1 wt.% polyethylene oxide as
a binder are mixed in an acetonitrile solvent to prepare a positive active material slurry for a
lithium-sulfur battery. The slurry is coated onto a carbon-coated Al current collector.
Even after 100 cycles, the EMI- and BMI-added lithium-sulfur batteries show much
larger capacities, 721 and 642 mAh/g-sulfur, respectively, when compared to that (534
mAh/g-sulfur) of the LiTFSI-based lithium-sulfur batteries. By contrast, the DMPI-added

lithium-sulfur batteries show poor cycling life performance where their capacity decreases to
below 200 mAh/g-sulfur even before 10 cycles. It is probable that this phenomenon is due
mainly to the deactivation of the carbon cathode caused by coating of non-conductive and
insoluble materials, which might result from side reactions between DMPI and lithium
polysulfides.
Choi et al. [6] demonstrate that the effect of the carbon black types and the sulfur particle
size on the discharge capacity or the utilization of sulfur. They use the test cell for evaluating
the effect of several factors on the utilization. The test cell is composed of a cathode with an
approximate dimension of 2.5 cm × 5 cm and an anode of 200 m thick lithium foil. The
cathode is prepared by coating the mixture containing elemental sulfur (83%), carbon black
(12%) for electrical conductivity and binder (5%) on a carbon-coated Al current collector. Six
different carbon blacks are used. The loading quantity of the cathode mixture is about 3.0
mg/cm2 for the one side layer. The electrolyte is based on dimethoxyethane and dioxolane
solvent (4:1). The supporting salt is LiCF3SO3.
The DBP (dibutyl phthalate) absorption number of the used carbon black has a strong
effect on the utilization while the specific surface area is not so critical to it. It is also found
that the sulfur particle size is a factor having an effect on the utilization. The authors improve
the cathode component and achieve the utilization of about 50%. By using that cathode, the
volumetric energy density of about 330 Wh/l is obtained for the full size lithium-sulfur
battery (3.8 mm thickness, 35 mm width and 62 mm height).
3.1.2. LiFePO4/Carbon Black Composite Cathodes

Recently, lithium transition metal phosphates proposed by Goodenough and co-
workers with ordered olivine-type structures, LiMPO4 (where M = Fe, Mn, Ni, or Co), have
attracted extensive attention as lithium insertion cathode materials for the next generation of
rechargeable lithium-ion batteries [8-18]. Among these phosphates, LiFePO4 is the most
attractive because of its high stability, low cost and high compatibility with environment.
However, it is difficult to attain its full capacity because its electronic conductivity is very
low, which leads to initial capacity loss and poor rate capability, and diffusion of Li+ ion
across the LiFePO4/FePO4 boundary is slow due to its intrinsic character [8]. The electronic
conductivity of LiFePO4 is only 10-9 S cm-1, as demonstrated previously by us [19], which is
much lower than those of LiCoO2 (~10-3 S cm-1) [20] and LiMn2O4 (2×10-5-5×10-5 S cm-1)
[21]. There are two methods to improve the electronic conductivity. One is to introduce
conductive additives including carbon coating [22] and supervalent cation doping [23]. The
other is to control particle size by optimizing synthesis conditions [24, 25]. Thus,
LiFePO4/carbon black composite cathodes have been investigated to improve the
electrochemical performance of LiFePO4 [26-27].
In the meantime, we also investigate the effect of carbon black on electrochemical
properties of LiFePO4/carbon black composite cathodes [28]. LiFePO4-C nanoparticles are
prepared from starting materials of LiOH·H2O, FeSO4·7H2O, (NH4)3PO4·3H2O, C6H8O6,
nano-sized acetylene black (Chevron Chemical Co., average particle size: 50 nm) or multi-
walled carbon nanotube (ILJIN CNT Co., purity  95%, length: 10-50 m, diameter: 10-25
nm). After LiOH·H2O is dissolved in distilled water to obtain 1 M solution, (NH4)3PO4 ·3H2O
and FeSO4·7H2O powders are added to LiOH solution. C6H8O6 is subsequently added to the
above mixture. The resulting mixture is heated at 170 ℃ for 12 h. After being cooled to room
temperature, the solution is filtered to separate the precipitate powders; the powders are
washed with distilled water. The obtained powders are dried at 110 ℃ for 1 h under vacuum.
In order to improve low electronic conductivity of LiFePO4, 5 wt.% nano-sized acetylene
black (AB) or 5 wt.% multi-walled carbon nanotube (MWCNT) is added. The mixtures of
LiFePO4 nanoparticles and 5 wt.% AB or 5 wt.% MWCNT in N-methylpyrrolidinone (NMP)
are ball-milled for 10 h using a shaker type of ball mill (Planetary Mono Mill) that rotated at
300 rpm. After being dried at 90 ℃ for 12 h, the powders are further heated at 500 ℃ for 1 h
in nitrogen atmosphere. After being cooled to room temperature, the mixtures of NMP and
LiFePO4-C nanoparticles are again ball-milled for 10 h. At last, the mixtures are dried at 90
℃ for 12 h. A composite electrode is prepared by mixing LiFePO4-C with carbon black and
polyvinylidenefluoride in NMP in a weight ratio of 70:25:5. The mixture is coated onto an
aluminum foil, cut into 2×2 cm sections and heated at 110 ℃ for 24 h under vacuum.
Figure 4 demonstrates that the average particle size of plate-like carbon black is around
0.5 m. As shown in Fig. 5, as for LiFePO4-C with 5 wt.% AB (LiFePO4-AB5), the average
grain size is around 100-300 nm in the length and around 20-100 nm in the width; LiFePO4
nanoparticles are connected each other by AB, and the dispersed AB provides pathways for electron
transference. The electronic conductivity of LiFePO4-AB5 and LiFePO4-MWCNT5 is
270 B. Jin
improved; 8.00×10-5 S/cm for LiFePO4-AB5, 1.08×10-1 S/cm for LiFePO4-MWCNT5,

compared to 5.86×10-9 S/cm for LiFePO4. Cycling performance of pure LiFePO4, LiFePO4-AB5
and LiFePO4-MWCNT5 at discharge rate of C/4 is shown in Fig. 6. As shown from Fig. 6, the discharge
capacity of pure LiFePO4 is 143 mAh/g at the first cycle, and decreases to 130 mAh/g after 30
cycles; it is obvious that the discharge capacity decreases upon cycling. As for LiFePO4-AB5,
the initial discharge capacity is 132 mAh/g; after 30 cycles, the discharge capacity is also 132
mAh/g. LiFePO4-MWCNT5 exhibits the best cycling performance with discharge capacity of
142 mAh/g after 30 cycles.
Figure 4. SEM image of acetylene black.

Figure 5. SEM image of LiFePO4-AB5.
160
Discharge capacity (mAh g-1)

140
120
100
80
60
40 LiFePO4-AB5
LiFePO4
20
LiFePO4-MWCNT5
0
0 5 10 15 20 25 30
Cycle number
Figure 6. The cycling performance of pure LiFePO4, LiFePO4-AB5 and LiFePO4-MWCNT5.
Jin et al. [26] investigate the electrochemical characteristics of LiFePO4/carbon black

composite cathodes in solid polymer electrolyte (SPE). In their study, carbon black is added
to enhance the electronic conductivity of LiFePO4. LiFePO4 is prepared with the starting
materials of LiOH·H2O, FeSO4·7H2O, H3PO4 and ascorbic acid. After LiOH·H2O is dissolved
in distilled water to obtain 1 M solution, H3PO4 and FeSO4·7H2O powders are added to LiOH
solution. A Telflon obturation vessel filled with the mixture is sealed in a stainless steel
autoclave and heated at 150 ℃ for 3 h. Carbon black (3, 5 and 10 wt.%) is added into the
solution of N-methylpyrrolidone (NMP) and LiFePO4, the mixture is ball-milled for 10 h. The
obtained powders are further dried at 400 ℃ for 1 h in nitrogen atmosphere. Cathodes are
made from mixtures of LiFePO4-C powders, carbon black (SP270) and polyvinylidene
fluoride binder dissolved in NMP in a weight ratio of 70:25:5. The obtained slurry is ball-
milled for 1 h, and coated onto an Al foil. The resulting electrode films are pressed with a
twin roller, cut into a round plate (Φ = 15.958 mm) and dried at 110 ℃ for 24 h under
vacuum.
The charge/discharge results show that initial discharge capacity of LiFePO4 is 104
mAh/g. The discharge capacity of LiFePO4-C/SPE/Li battery with 5 wt.% carbon black is 128
mAh/g at the first cycle and 127 mAh/g after 30 cycles, respectively. It is demonstrated that
cycling performance of LiFePO4-C/SPE/Li batteries is better than that of LiFePO4/SPE/Li
batteries.
Shin et al. [27] investigate the electrochemical properties of carbon-coated LiFePO4
cathode using graphite, carbon black, and acetylene black. For the preparation of LiFePO4, a
mixture containing 0.5 mol Li2CO3, 1 mol FeC2O4·2H2O, and 1 mol (NH4)2H·PO4 is placed in
a zirconia bowl and the mechanochemical activation is carried out using a planetary mill in
the air. The activated powders after the mechanochemical processing are heat-treated at 700
℃ in an Ar + 5% H2 atmosphere for 10 h. For carbon-coated LiFePO4, 5 wt.% carbon
powders are added to the mixture. The graphite, carbon black, and acetylene black are used as
272 B. Jin
a carbon sources. Cathodes are prepared by mixing 85 wt.% LiFePO4, 10 wt.% acetylene
black, and 5 wt.% polyvinylidene difluoride. The mixture slurry is coated on an Al foil and
dried at 80 ℃ for 24 h.
The electrochemical performance of carbon-coated LiFePO4 demonstrates higher specific
capacity and better capacity retention compared to pure LiFePO4. The improved
electrochemical properties are attributed to the reduced LiFePO4 particle size and enhanced
electrical contacts by carbon. Among carbon-coated LiFePO4 particles, the particles coated
with graphite exhibit better electrochemical performance than others coated with carbon black
or acetylene black. The carbon-coated cathode with graphite shows stable discharge capacity
of 120 mAh/g even at 2 C at room temperature. Equivalent circuit analysis from impedance
measurement suggests the improved electrochemical performance of carbon-coated cathodes
using graphite are attributed to the low charge transfer resistance and low Li-ion migration
resistance.
3.2. Carbon Black-Based Composite Anodes
Graphite is an anode material used commonly for rechargeable lithium-ion batteries.

Recently, silicon as an attractive alternative has been studied extensively [29-33]. Si has a
theoretic specific capacity of 3579 mAh/g [34], compared to only 372 mAh/g of C [35].
Gómez Cámer et al. [36] report a simple method for obtaining nanosized silicon (n-Si)
with promising electrochemical properties as an anode material for lithium-ion batteries. The
method involves the formation of a composite electrode with cellulose fibers. Super P
(TIMCAL) and Printex XE2 (Degussa) are used as the conductive carbon black (CCB). The
particles of Printex XE2 are submicronic in size with a tendency to form loosely bound
agglomerates. By contrast, Super P carbon possesses bigger particles, with less tendency to
agglomerate (based on manufacturer data, the particle size of Super P is 40 nm and hence
larger than the 30nm of Printex XE2). Cellulose fibers are added to a suspension of n-Si, or n-
Si and carbon, in isopropanol and are then mildly heated (～363 K) to dryness. Three
composites are prepared with the following composition in weight %: composite A (50 n-
Si/50 cellulose fibers); composite B (50 n-Si/40 cellulose fibers/10 Printex XE2); composite C
(50 n-Si/40 cellulose fibers/10 Super P). All composites are dried at 353 K under vacuum for
1 h.
It is demonstrated that the performance of these electrodes can be enhanced by the
addition of CCB. This beneficial effect is not only a result of the improvement in electrical
conductivity and inter-particle contacts, but also due to a reduction of the expansion and
shrinkage undergone by the electrode when Li is inserted into Si or extracted from LixSi, as
revealed by in situ electrochemical dilatometry measurements. The best results are obtained
with a CCB of high surface area and porosity. The Si/cellulose fiber/carbon electrodes
obtained deliver charge capacities as high as 1800 mAh/g and exhibit good capacity retention
on cycling. These electrodes also exhibit lower expansion/shrinkage compared to carbon-free
electrodes on discharging and charging the cell, respectively.
3.3. Carbon Black-Based Electrode Binders
In rechargeable lithium-ion batteries, carbon black-filled polymer composites are widely

used as electrode binders [37-39].
Chen et al. [39] investigate the mechanical and electrical properties of poly(vinylidene
fluoride-tetrafluoroethylene-propylene) (PVDF-TFE-P) and carbon black-filled PVDF-TFE-P
composites. The carbon black is used for its electrolyte absorption properties in addition to
boosting the conductivity. Preparation of TETA-crosslinked BRE-7131X and BRE-
7131X/carbon black films, and bisphenol-crosslinked BRE-7131X and BRE-7131X/SS films
is as follows. A PVDF-TFE-P polymer (BRE-7131X, 60% fluorine; Dyneon, Co., Oakdale,
MN) slab obtained from the manufacturer is cut into small pieces and dissolved in methyl
ethyl ketone (MEK) to make a solution containing 20% BRE-7131X by weight. Then 3 pph
(parts per hundred mass of BRE-7131X) 1,4-diazabicyclo[2.2.2]octane, 4 pph CaO, a
determined amount of triethylenetetramine, and 25 pph Super-S carbon black (SS; MMM
Carbon, Brussels, Belgium), if desired, are added to the BRE-7131X solution and mixed for 1
h. The final mixture is then cast onto a piece of Teflon release film using a spreader bar with a
gap of 0.016 inch, and dried in air overnight. A BRE-7131X slab is cut into small pieces and
dissolved in MEK to make a solution containing 20% BRE-7131X by weight. Then 6 pph
MgO, 2 pph CaO, bisphenol, and 25 pph SS, if desired, are added to the BRE-7131X solution
and mixed. Films are cast as above and dried in air, and then heated under a flow of argon in a
tube furnace at 110 ℃.
Uncrosslinked PVDF-TFE-P uptakes about 140% solvent by mass and swells
significantly. The amount of solvent absorbed can be reduced and the mechanical properties
improved by crosslinking the polymer. Compared to the bisphenol-based crosslinking recipe,
the proposed TETA-based crosslinking recipe gives films with a higher degree of crosslinking
and better mechanical properties. The TETA-crosslinked composites have very good
mechanical and electrical reversibility even during cyclic deformation to 100% strain. The
cycling results of amorphous Si0.64Sn0.36 electrodes show that the capacity retention of the
electrodes can be significantly improved by using the proposed elastomeric binder.
3.4. Carbon Blacks Used as Electrode Conductive Additives
Carbon black has been extensively used as a conductive additive in the electrode
manufacture for rechargeable lithium-ion batteries [40-50].
We investigate the effect of different conductive additives including acetylene black
(AB) and carbon black (SP270) on charge/discharge properties of LiCoPO4/Li batteries [51].
LiCoPO4 nanoparticles are synthesized from a stoichiometric mixture of LiOH·H2O, CoO,
and (NH4)2HPO4 using a solid-state reaction method and subsequent high-energy ball-
milling process. Firstly, the mixture is ground in an agate mortar and pressed into a pellet at a
pressure of 650 kgf/cm2, and then fired in air at 750 ℃ for 8 h. After cooling, the resulting
material is again calcined slowly at 350 ℃ for 6 h. Finally, the material is cooled and ground
into powder, and a pellet is again made by pressing at a pressure of 650 kgf/cm2 before being
heated at 750 ℃ for 36 h. After cooling, the resulting material is again ground into powder.
The resulting LiCoPO4 nanoparticles are prepared by the high-energy ball-milling process for
274 B. Jin
10 h using a shaker type of ball mill (Planetary Mono Mill) that rotated at 300 rpm. The
cathodes are made from mixtures of LiCoPO4, AB or SP270, and polyvinylidene fluoride
binder dissolved in N-methylpyrrolidinone in a weight ratio of 70:25:5. The slurry is ball-
milled for 1 h, and then coated onto an Al foil. The resulting electrode film is pressed with a
twin roller, cut into a rectangle plate (area = 4 cm2) and dried at 110 ℃ for 24 h under
vacuum. Lithium cells are constructed with a separator made from Celgard2500 membrane,
the cathode, and anode of lithium metal.
Figure 7. FE-SEM images of the electrodes with different conductive additives (a) AB and (b) SP270.
120
AB
Discharge capacity (mAh g-1)
100 SP270
80
60
40
20
0
0 5 10 15 20 25 30
Cycle number
Figure 8. Cycling performance of LiCoPO4/Li batteries with different conductive additives.
FE-SEM images of the electrodes with different conductive additives are shown in Fig. 7.
As can be seen from Fig. 7a, the distribution of LiCoPO4 nanoparticles in AB nanoparticles is
generally homogeneous and the contact between LiCoPO4 nanoparticles and AB
nanoparticles is fairly intimate. As shown from Fig. 7b, the distribution of LiCoPO4
nanoparticles in SP270 is inhomogeneous and the contact between LiCoPO4 nanoparticles
and SP270 is poor. Figure 8 demonstrates that LiCoPO4/Li battery with AB has the best
electrochemical properties, and exhibits a discharge plateau at aound 4.7 V with an initial
discharge capacity of 110 mAh/g at a discharge current density of 0.05 mA/cm2 at room
temperature.
SUMMARY AND FUTURE PROSPECTS

Carbon blacks can be manufactured by five major methods, such as Lampblack process,
the oil furnace process, acetylene process, thermal process and the impingement process. In
five manufacturing methods, acetylene process is widely in rechargeable lithium-ion batteries
industry because acetylene black produced by this process is often used as carbon conductive
additive in the electrode manufacture. The composite cathodes of the sulfur as an active
cathode and the carbon black as a conductive additive can improve the sulfur utilization in
lithium-sulfur batteries. Carbon black as a conductive additive can increase the electronic
conductivity of LiFePO4 as a cathode and Si as an anode, and improve the electrochemical
performance of LiFePO4 and Si in rechargeable lithium-ion batteries. In the meantime, carbon
black-filled polymer composites are used as electrode binders, the filled carbon black is used
for its electrolyte absorption properties in addition to boosting the conductivity.
Although carbon black has fewer amounts than that of other components including
cathode and anode in recharge lithium-ion batteries, however, it plays a key role in improving
the electrochemical performance. In order to improve the cycling life of lithium-ion batteries,
the development of novel carbon black and carbon black-based composites with other carbon
conductive additives such as graphite, carbon fiber and carbon nanotube is a key factor.
ACKNOWLEDGMENTS
The author acknowledges the financial supports from National Key Basic Research and
Development Program of China (Grant No. 2010CB631001) and the China Postdoctoral
Science Foundation Funded Project (Grant No. 20090451124).
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INDEX
112, 158, 189, 195, 215, 216, 230, 237, 238, 243,
A 244, 246, 247, 248, 251, 253, 255, 256, 257, 258,
260
Abraham, 113
adsorption isotherms, 18, 19, 24, 25
absorption spectra, 193
advancement, 195
acceptable corrosion resistance, vii, 1, 2
aerogels, 10, 33
access, 5, 22, 212, 215
aerosols, 131
accessibility, 9, 48, 197, 208
aerospace, 194
accommodation, 215
AFB1, 78
accounting, 17, 161, 165, 168, 175, 179, 215
aflatoxin, 78
acetic acid, 75, 82
AFM, 164, 169, 180, 188, 193
acetone, 73, 143
aggregation, x, 45, 46, 157, 184, 186, 190, 197, 211,
acetonitrile, 74, 77, 216, 266, 268
217, 227
acetylene gas, 197, 264
agriculture, 80
acid, viii, xi, 4, 5, 14, 24, 31, 35, 38, 41, 44, 45, 58,
air batteries, xi, 183, 212, 213
74, 75, 78, 80, 81, 82, 133, 135, 189, 193, 199,
airborne particles, 134
204, 220, 231, 237, 238, 239, 242, 243, 244, 246,
alcohols, vii, ix, 41, 70, 94, 95, 97, 100, 103, 104,
247, 248, 249, 250, 251, 252, 253, 254, 255, 256,
106, 107, 110
257, 260, 261, 271
aldehydes, 73
acidic, 43, 71, 75, 77, 78, 84, 260
aldosterone, 80
acidity, 239, 247
aliphatic compounds, 77
acrylic acid, xi, 237, 239, 242, 249, 250, 251, 252,
alkenes, 96
253, 254, 255, 257, 260, 261
allylamine, xi, 237, 239, 242, 253, 254, 255, 256,
activated carbon, viii, 69, 71, 83, 199, 206, 208, 215,
257, 259
218, 232, 234, 260
aluminium, 183, 212, 217
activation energy, 219
ambient air, 72, 82, 224
active centers, 75
amine, 75, 104, 242, 259, 260
active compound, 78
amine group, 259
active radicals, 218
amines, ix, 77, 81, 82, 94, 95, 97, 100, 103, 104, 105,
active site, 42, 54, 190, 218, 219, 221
107, 110
adamantane, 113
amino, 104, 240
adaptability, 204
ammonia, xi, 237, 240, 244, 245, 246, 251
additives, xi, 29, 83, 138, 183, 194, 196, 197, 198,
ammonium, 83
199, 200, 201, 203, 204, 205, 206, 207, 208, 209,
amorphous carbon, viii, 36, 69, 70
210, 211, 214, 226, 227, 229, 232, 233, 269, 273,
amplitude, 96, 159, 160, 162, 163
274, 275
anchorage, 50
adhesion, 134, 238
anchoring, 44
adsorption, viii, xi, 10, 16, 17, 18, 19, 20, 21, 22, 23,
androgens, 79
24, 25, 26, 30, 34, 37, 54, 71, 72, 93, 94, 95, 96,
annealing, 192
97, 98, 99, 100, 102, 105, 106, 107, 108, 109,
280 Index
anode, vii, 2, 4, 7, 9, 22, 24, 38, 41, 42, 43, 54, 63, binding energy, 13, 14, 193, 207
64, 203, 211, 212, 213, 214, 217, 223, 225, 226, biocompatibility, 239
266, 268, 272, 274, 275 biodegradation, 79
antibiotic, 80 biokinetics, 134
antigen, 133, 135 biologically active compounds, 78
antigen-presenting cell, 135 biomarkers, 135
apex, 145 biomass, xi, 183, 194, 195, 223, 224, 226, 227
aqueous solutions, 74, 83, 84, 217 biomass energy, xi, 183, 227
argon, ix, xi, 115, 117, 122, 129, 130, 237, 242, 273 birth control, 78
aromatic compounds, 71, 77, 84 bisphenol, 79, 273
aromatic hydrocarbons, 72, 95, 105, 190 black carbon nanoparticles, ix, 115, 117, 124, 125,
aromatic rings, 11, 105 130
artificial heart valve, 138 blacks, v, vi, 1, 8, 27, 183, 194, 263, 273
ascorbic acid, 271 blends, 28, 39
assessment, 73 blood, 74, 134, 138
asymmetry, 191 blood flow, 138
atmosphere, 4, 30, 48, 50, 58, 70, 73, 143, 186, 192, BMI, 103, 110, 268
205, 210, 212, 217, 227, 256, 269, 271 body weight, 81
atmospheric pressure, 36, 63, 64, 79, 219, 238, 258, boilers, 224
259 Boltzmann constant, 171
atom-atom potential (AAP), ix, 94, 96 bonding, 4, 187, 193
atoms, ix, 4, 13, 19, 20, 22, 25, 26, 44, 65, 94, 96, bonds, 11, 13, 16, 94, 96, 97, 99, 100, 101, 110, 160,
97, 99, 103, 104, 105, 108, 109, 110, 116, 117, 163, 190, 221
119, 121, 122, 123, 124, 125, 126, 129, 130, 134, bone, 261
139, 186, 188, 189, 190, 193, 218, 221, 222, 245, brain, 133
254 branching, 240
attachment, 261 breakdown, 80, 163
automobile, 263 breast milk, 75
automobile tires, x, 137 bromine, 4
building blocks, 188
burn, 184
B by-products, vii, 41, 43, 81, 184, 224
bacteria, 80
barium, 199 C
barriers, ix, 94, 95
base, viii, ix, 5, 7, 10, 28, 41, 42, 44, 54, 59, 70, 74, cabbage, 76
75, 81, 84, 94, 95, 97, 99, 106, 128, 193, 204, calibration, 78, 84
231, 237, 238, 239, 243, 246, 260 calorimetry, 193
basicity, 239 candidates, 27, 196, 212
batteries, xi, xii, 1, 2, 3, 4, 8, 31, 183, 190, 194, 195, capillary, 54, 70, 159
196, 197, 198, 199, 200, 204, 211, 212, 213, 214, carbides, 28
227, 231, 232, 233, 234, 263, 265, 266, 267, 268, carbohydrate, 210
269, 271, 272, 273, 274, 275 carbon atoms, 105, 117, 123, 124, 125, 126, 129,
beef, 79 130, 134, 187, 188, 189, 190, 193, 218
Beijing, 258 carbon dioxide, 225
Belarus, 115 carbon film, 36
Belgium, 273 carbon materials, vii, 10, 11, 30, 32, 41, 42, 43, 44,
benchmarks, 33 48, 56, 58, 134, 185, 194, 205, 213, 214, 215,
bending, 12 221, 227, 234
beneficial effect, 10, 199, 272 carbon nanotubes, 10, 32, 83, 134, 135, 195, 196,
benefits, 4, 43, 212 197, 200, 205, 206, 208, 210, 233
benzene, 82, 101, 103, 104, 106, 108, 109, 110, 210 carbon tetrachloride, 111
beverages, 74, 75 carbonyl groups, 16
Index 281
carboxyl, 189, 221, 257 China, 183, 258, 263, 275

carboxylic acid, 78 chlorine, 3, 82
carboxylic groups, 50, 249, 250, 251, 257, 261 chlorophyll, 77
carboxymethyl cellulose, 265 chromatography, viii, 50, 69, 70, 73, 77, 80, 81, 85,
cardiovascular system, 133 112, 193
carotene, 75 chromium, 4
carotenoids, 77 circulation, 28, 135
catalysis, 32, 131, 197, 212, 218 classes, viii, 93, 95, 96, 97, 190, 239
catalyst, vii, xi, 5, 6, 10, 15, 16, 17, 18, 19, 20, 21, classification, 79
22, 23, 24, 25, 26, 27, 30, 32, 33, 34, 35, 37, 38, Clean Air Act, 71
41, 42, 43, 44, 45, 48, 50, 51, 52, 54, 55, 56, 58, clean energy, 223
62, 64, 183, 194, 195, 212, 213, 218, 219, 220, clean technology, 185
221, 222, 227, 235, 236 cleaning, 241
catalytic activity, 61, 64, 218, 219, 220, 221 cleanup, 74, 75, 78, 79, 80, 81
catalytic effect, 195, 226 climate, 42, 117, 194
catalytic properties, 43, 44 climate change, 42, 117, 194
cathode, vii, 2, 4, 9, 25, 32, 33, 34, 41, 42, 63, 198, clusters, 44, 124, 169
199, 200, 201, 202, 203, 204, 210, 211, 212, 213, coal, 4, 73, 184, 210, 219, 220, 224
217, 223, 225, 226, 231, 232, 233, 259, 265, 266, coal tar, 219, 220
268, 269, 271, 272, 274, 275 coatings, xii, 28, 38, 194, 200, 206, 209, 249, 254,
cathode materials, 200, 212, 223, 226, 232, 269 261, 263, 264
cation, 215, 216, 234, 268, 269 cobalt, 199
cattle, 80 coke, 7, 224, 238
cell culture, 261 collisions, 124, 159, 240
cell line, 261 color, 118, 120, 121, 210, 219
cellulose, 265, 272 combined effect, 187
central nervous system, 133 combustion, vii, 4, 42, 70, 72, 73, 133, 184, 185,
ceramic, x, 4, 137, 265 195, 199, 219, 225, 235, 238
cerium, 4 combustion processes, 185
chain mobility, 97 commercial, viii, 16, 18, 24, 25, 26, 27, 28, 42, 45,
chain transfer, 196 63, 64, 65, 158, 159, 188, 190, 198, 216, 218,
challenges, xi, 5, 31, 35, 81, 83, 183, 194, 231, 232 221, 223, 228, 229, 230, 235
cheese, 78, 82 communication, 194, 199

chemical, vii, ix, x, xi, 1, 3, 5, 7, 15, 27, 32, 35, 41, compatibility, 194, 211, 218, 269
42, 43, 44, 49, 55, 65, 70, 71, 72, 74, 77, 79, 83, complex interactions, x, 157, 179
84, 94, 100, 105, 106, 110, 122, 135, 137, 138, complexity, 95, 185, 197
139, 141, 158, 184, 191, 193, 194, 205, 210, 212, compliance, 78
218, 224, 225, 228, 237, 238, 239, 240, 241, 242, composites, vii, x, xi, 1, 7, 10, 28, 29, 39, 137, 139,
244, 246, 247, 249, 251, 254, 255, 259, 260, 264, 140, 141, 148, 149, 150, 152, 155, 166, 184, 200,
267 201, 205, 206, 217, 222, 223, 228, 232, 233, 272,
chemical inertness, x, 3, 70, 84, 137, 239, 264 273, 275
chemical interaction, 138 composition, xi, 3, 9, 13, 19, 24, 26, 65, 158, 184,
chemical properties, 44, 74, 84 193, 198, 199, 208, 212, 237, 238, 239, 240, 241,
chemical reactions, 267 242, 244, 246, 247, 248, 251, 254, 255, 257, 268,
chemical stability, 1, 27, 194 272
chemical structures, 77 compounds, viii, ix, x, xi, 11, 13, 69, 70, 71, 72, 73,
chemical vapor deposition, 205, 210 74, 75, 77, 78, 79, 80, 81, 83, 84, 93, 94, 95, 96,
chemical vapour deposition (CVD), 205, 210, 238, 97, 99, 100, 105, 110, 111, 112, 113, 157, 158,
239, 242, 243, 249, 251, 253, 255, 256, 261 159, 160, 161, 162, 163, 164, 165, 166, 167, 168,
chemicals, 73, 78, 79, 184, 190 169, 170, 174, 179, 237, 238, 243, 244, 247, 251,
chemisorption, 17, 18, 19, 24, 30 253, 257
chemokines, 133 compressibility, 2, 198
chicken, 82 compression, 6, 140, 190, 191, 205, 229
282 Index
computer, 95, 199 cycling, 204, 213, 214, 266, 267, 268, 270, 271, 272,
conception, 39 273, 275
condensation, 117, 123, 125, 126, 130, 186, 195 cylindrical reactor, 264
conditioning, 74 cytokines, 133
conductivity, vii, viii, x, 1, 2, 3, 4, 5, 7, 9, 10, 25, 27,
28, 29, 31, 41, 42, 43, 44, 49, 64, 65, 137, 185,
186, 189, 190, 191, 192, 193, 194, 195, 196, 197, D
198, 199, 200, 202, 203, 204, 205, 208, 209, 210,
damping, 173, 174
211, 213, 214, 215, 217, 218, 221, 223, 227, 228,
DBP, x, 137, 141, 144, 145, 146, 150, 151, 153, 154,
229, 264, 268, 269, 271, 272, 273, 275
185, 188, 268
conductor, 140, 198, 199, 202
decay, 56, 124, 221
conductors, 200, 209
decomposition, xii, 11, 14, 15, 16, 21, 22, 24, 27, 30,
configuration, 5, 14, 33, 96, 139, 142, 158, 205, 211,
44, 50, 54, 129, 184, 185, 197, 199, 203, 214,
217
218, 219, 220, 221, 226, 228, 234, 235, 240, 260,
congress, 32
263, 264
conjugation, 97
decomposition temperature, 24, 30, 50
conservation, 125, 138
deconvolution, 50
constant rate, 172
defects, 189, 193, 215, 218, 220, 221, 230
constituents, 73
deformation, xi, 139, 157, 158, 159, 164, 165, 166,
construction, 226
167, 168, 170, 171, 172, 173, 174, 175, 179, 273
consumption, 81, 185, 194, 212, 224
degradation, x, 5, 7, 10, 24, 30, 35, 36, 37, 38, 70,
contact time, 19, 20, 26
73, 75, 82, 137, 214
contaminant, 241
degradation mechanism, 10
contaminated food, 82
degree of crystallinity, 186
contamination, 24, 36, 77, 81, 143
Degussa, 209, 272
contour, ix, 94
dehydration, 18
convention, 170
density functional theory (DFT), ix, 94, 100, 191
conversion rate, 218
Department of Energy, 27
COOH, 13, 240, 243
deposition, 24, 203, 205, 210, 219, 220, 237, 238,
cooling, 120, 124, 188, 224, 265, 273
239, 241, 249, 250, 251, 252, 253, 255, 257, 258,
copolymer, 200, 214
259, 260, 261
copper, 138, 241
deposits, 192
correlation, 9, 191
depth, 123, 143, 242
corrosion, vii, 1, 7, 9, 27, 28, 29, 38, 43, 44, 48, 183,
derivatives, 96, 112, 113, 190
194, 195, 213, 221, 226, 259
desorption, viii, 10, 11, 12, 14, 15, 16, 19, 20, 21, 22,
cost, vii, 1, 2, 3, 7, 10, 27, 28, 38, 39, 42, 43, 95,
23, 25, 26, 30, 48, 50, 69, 70, 71, 72, 73, 78, 80,
138, 140, 185, 194, 195, 200, 211, 212, 214, 215,
82, 83, 84
223, 224, 225, 226, 265, 269
destruction, 47, 48, 49, 50, 139, 140
covering, 25
detachment, 166
cracks, 28
detectable, 134
creep, 159
detection, 13, 72, 78, 79, 83, 111, 134, 193
crop, 77
developed fuel cell, vii, 41
crops, 71
deviation, 109, 117, 122, 154, 176, 187
crystal structure, 58
diesel fuel, 73
crystalline, 139, 188, 190, 197
differential equations, 125, 126
crystallinity, 3, 186
differential scanning, 193
crystallites, 18, 25, 52, 56, 59, 186, 187, 188, 193,
differential scanning calorimetry, 193
218, 219
diffraction, 17, 46, 51, 58, 95, 100, 188, 193, 238
crystallization, 199
diffusion, vii, 1, 5, 7, 8, 9, 20, 22, 24, 25, 26, 27, 30,
crystals, 46, 58
31, 32, 34, 35, 37, 41, 43, 63, 64, 65, 100, 212,
culture, 261
213, 222, 269
cycles, 17, 20, 196, 203, 265, 266, 267, 268, 270,
diffusion process, 30, 35
271
diffusion rates, 24
Index 283
dioxin, 72, 81 electrode/electrolyte interfaces, 226

dioxin-like PCBs, 81 electrodes, vii, 1, 2, 3, 4, 5, 7, 8, 9, 10, 24, 25, 27, 30,
direct observation, 169 31, 33, 34, 37, 54, 63, 64, 65, 186, 196, 197, 200,
directionality, 111 205, 210, 211, 212, 215, 216, 217, 222, 226, 232,
discharges, xi, 237, 238, 239, 240, 253, 256, 257, 233, 234, 241, 242, 267, 272, 273, 274
259, 260 electrolysis, 4
diseases, 80 electrolyte, vii, 2, 3, 4, 5, 7, 25, 33, 34, 35, 38, 39,
disorder, 7, 139, 186, 189 41, 42, 43, 44, 45, 54, 56, 59, 190, 196, 197, 198,
dispersion, viii, xi, 17, 24, 28, 43, 44, 50, 54, 69, 74, 199, 200, 203, 204, 207, 209, 211, 212, 213, 214,
75, 96, 138, 141, 158, 164, 166, 167, 184, 190, 215, 216, 217, 222, 224, 226, 227, 233, 266, 267,
198, 200, 204, 205, 208, 209, 210, 214, 218, 223, 268, 271, 273, 275
227, 264 electron, ix, x, xi, 5, 6, 9, 43, 44, 46, 53, 65, 94, 95,
displacement, 143, 170 100, 115, 119, 122, 130, 148, 186, 187, 188, 190,
dissociation, 4, 22, 240 191, 193, 202, 203, 223, 225, 237, 240, 242, 243,
distilled water, 244, 250, 265, 269, 271 269
distortions, 188 electron diffraction, 95, 100
distribution, viii, 17, 18, 30, 34, 42, 43, 45, 50, 53, electron microscopy, x, xi, 5, 6, 46, 53, 115, 130,
160, 172, 184, 185, 186, 188, 189, 190, 193, 194, 193, 237, 243
197, 202, 210, 211, 212, 213, 214, 217, 218, 221, electronic structure, 43, 55, 190, 194, 202
223, 224, 227, 232, 274 electrons, ix, 94, 96, 97, 104, 106, 109, 189, 190,
distribution function, 188 191, 200, 214, 239
diversity, vii, 1, 97 e-mail, 93, 237
dizziness, 82 emission, 36, 42, 73, 194
doping, 195, 219, 269 endocrine, 79
double bonds, 13 endocrine-disrupting chemicals, 79
drainage, 84 energetic characteristics, 103, 105
drinking water, 76, 78 energetic parameters, ix, 94
drugs, 78 energy, vii, ix, xi, 1, 3, 4, 5, 7, 8, 13, 14, 31, 37, 42,
drying, 266 94, 96, 97, 98, 100, 101, 102, 103, 104, 105, 106,
durability, 10, 32, 34, 35, 42, 48, 194 107, 108, 109, 110, 116, 117, 123, 125, 129, 138,
dyeing, 194, 260 159, 183, 185, 189, 190, 191, 193, 194, 195, 196,
197, 198, 199, 200, 204, 207, 211, 212, 213, 214,
215, 217, 218, 219, 220, 223, 224, 226, 227, 228,
E 230, 231, 234, 241, 269, 273
energy consumption, 185, 224
economics, 228
energy density, 3, 200, 212, 215, 231, 269
editors, 228, 230
energy parameters, 100
egg, 80
energy transfer, 117
elastomers, 158, 163, 164, 174
engineering, 166, 183
electric conductivity, 196
enlargement, 245
electric current, 4
entropy, 7
electrical conductivity, vii, x, 1, 2, 7, 27, 28, 29, 31,
environment, 27, 28, 29, 72, 79, 81, 82, 138, 143,
41, 42, 43, 44, 49, 64, 65, 137, 185, 190, 191,
185, 194, 195, 224, 225, 239, 269
192, 197, 198, 201, 204, 210, 218, 228, 268, 272
environmental contamination, 81
electrical properties, 185, 191, 228, 229, 273
environmental impact, 78
electrical resistance, 28, 43
environmental protection, 223
electricity, 4, 5, 7, 212, 214, 223, 224, 225, 226, 236
enzyme, 80
electrocatalysis, 34
epithelia, 134
electrocatalyst, 5, 6, 24, 32, 38, 44, 45, 48, 63, 214,
epoxy resins, 28
217, 222, 223, 236
equilibrium, 18, 24, 94, 98, 123, 125, 239
electrochemical behavior, 199, 200, 202
ester, 28, 74
electrochemical impedance, 22, 193, 205, 234
estriol, 79
electrochemistry, 2, 7, 33, 258
estrogen, 79
electrode surface, 217
284 Index
etching, 197, 238, 239, 240, 241, 242, 244, 245, 261 flame, 111, 264
ethanol, 24, 73, 210 flexibility, 27, 174, 217
ethyl acetate, 74 flight, 81, 84
ethylene, ix, 58, 115, 116, 117, 118, 122, 129, 199, flocculation, x, 157
214, 219 flooding, 6, 9, 31
ethylene glycol, 58 flour, 2
evacuation, 18, 19 flow field, vii, 1, 5, 6, 28, 30, 39
evaporation, 24, 38, 126, 128, 129, 130, 212 fluid, 133
evidence, 20, 22, 78, 135 fluidized bed, 219, 226, 236, 258, 259
evolution, 15, 22, 26, 36, 50, 174, 175 fluorescence, 193, 260
exchange rate, 19, 25, 27 fluoride ions, 11
excitation, 239, 240 fluorine, 11, 16, 23, 139, 273
experimental condition, 129, 142, 238, 240, 242, fluorine atoms, 139
246, 250, 258 fluoropolymers, 11
experimental design, 25, 259 food, 74, 77, 80, 81, 82, 84, 138, 194
exposure, x, 13, 72, 73, 78, 80, 133, 134, 135, 247, food safety, 81, 82
254 food spoilage, 81
extraction, viii, 69, 70, 71, 74, 75, 77, 78, 79, 80, 82, force, viii, 4, 93, 94, 95, 96, 97, 104, 105, 106, 108,
83, 84, 140, 154 110, 111, 142, 154, 193, 195
extracts, 77, 78, 84 formaldehyde, 28
extrusion, 140, 141 formation, ix, 11, 13, 15, 21, 22, 23, 28, 29, 43, 50,
51, 54, 73, 94, 101, 104, 105, 106, 109, 110, 117,
118, 119, 121, 122, 124, 130, 140, 184, 185, 186,
F 187, 189, 190, 193, 199, 206, 218, 264, 272
formula, 124, 129, 206, 212
fabrication, vii, 1, 9, 28, 33, 36, 214
fractal dimension, 186, 188, 193
factories, 256
fragments, 97, 99, 111
families, 238
France, 3, 33, 36, 39
farms, 77
free energy, 123
fat, 76, 108
free radicals, 246
fatty acids, 70, 77
free volume, 196
feedstock, xi, 183, 184, 189, 264, 265
friction, x, 137, 138, 139, 140, 141, 142, 143, 147,
ferrite, 217
148, 149, 150, 151, 152, 154, 155
fetus, 134
fruits, 75, 77
fiber, x, 6, 9, 82, 137, 139, 147, 148, 155, 196, 197,
fuel cell, vii, xi, 1, 3, 4, 5, 6, 7, 8, 9, 20, 24, 27, 31,
205, 206, 208, 221, 272, 275
32, 33, 34, 35, 36, 37, 38, 39, 41, 42, 43, 44, 45,
fibers, 4, 28, 29, 82, 139, 196, 197, 200, 205, 206,
48, 54, 60, 63, 64, 65, 183, 194, 195, 217, 221,
208, 272
222, 223, 224, 225, 226, 227, 231, 236
fibroblasts, 261
full capacity, 269
filament, 198, 208
functionalization, viii, 42, 44, 51, 57, 65, 245
filled polymers, 158, 174
furan, 74
filler particles, x, 28, 157, 158, 160, 163, 164, 165,
179
filler surface, 158, 174 G
fillers, x, 28, 38, 137, 139, 140, 141, 148, 154, 158,
160, 165, 167, 177, 194, 258 gas diffusion, vii, 1, 5, 7, 8, 9, 24, 25, 27, 30, 32, 37,
film formation, 29 63, 64, 65, 222
films, 25, 36, 140, 239, 241, 249, 250, 251, 253, 254, gasification, 224, 226, 236
255, 256, 257, 259, 260, 261, 266, 271, 273 gel, 2, 81, 200, 224, 234, 259
filters, 118, 119, 120, 121, 238 gel permeation chromatography, 81
financial, 275 gelation, 224
financial support, 275 General Motors, 39
fish, 80, 81, 82 genes, 134
fish oil, 81 genus, 77
Index 285
geometrical parameters, 105, 109, 110 heavy particle, 240

geometry, viii, 17, 26, 93, 94, 95, 96, 97, 100, 104, height, 143, 188, 205, 264, 269
105, 106, 109, 110, 123, 159, 195, 239, 241 helium, 111
Germany, 184 herbicide, 76
global demand, 194 hexane, 82, 111
glow discharge, xi, 36, 237, 238, 239, 240, 244, 245, high fat, 76
247, 249, 253, 256, 259, 260 high resolution transmission electron microscope
glycerol, 24, 25, 83 (HRTEM), 186, 229
glycol, 58, 73 high thermal conductivity, vii, 1, 27
governments, 194 history, xi, 157, 174, 175, 179, 211
grades, 158, 184 homogeneity, 96, 227, 243
grain size, 193, 197, 269 honey bees, 75
granules, xi, 237, 238, 241, 242, 243, 244, 245, 246, hormones, 78, 79, 84
247, 248, 250, 251, 252, 253, 254, 255, 256, 257, hot pressing, 28
258, 259, 260 human, 72, 73, 76, 78, 81, 83, 117, 133, 134, 135,
graph, 163 138
graphene sheet, 187, 190, 193 human body, 138
graphite, viii, ix, x, 2, 4, 27, 28, 32, 37, 38, 39, 42, human exposure, 73
43, 46, 54, 71, 76, 94, 112, 137, 138, 140, 147, human health, 72, 133
148, 185, 186, 187, 188, 189, 190, 193, 196, 198, humidity, viii, 36, 69, 72, 143, 246
199, 200, 201, 202, 203, 208, 211, 214, 221, 229, hybrid, 39, 194, 199, 204, 213, 231
238, 243, 246, 271, 272, 275 hybridization, 187
Graphitized carbon black (GCB), viii, 69, 70, 75 hydrocarbons, viii, xii, 42, 69, 70, 72, 73, 95, 96,
graphitized thermal carbon black (GTCB), viii, 93, 105, 184, 190, 218, 221, 225, 238, 263
94 hydrocortisone, 80
gravitation, 106, 109 hydrogen, ix, xi, 4, 5, 7, 16, 19, 20, 21, 22, 24, 25,
gravity, 185, 193 26, 27, 30, 32, 37, 38, 42, 54, 63, 65, 94, 96, 97,
greenhouse, 42, 194 100, 101, 103, 104, 105, 110, 119, 121, 160, 183,
greenhouse gases, 42 184, 195, 217, 218, 219, 220, 221, 224, 226, 227,
groundwater, 76 228, 229, 230, 234, 235, 236, 265
growth, vii, ix, 43, 80, 115, 117, 120, 121, 122, 123, hydrogen atoms, 104, 119, 121, 221
124, 125, 126, 127, 128, 129, 130, 159, 165, 167, hydrogen bonds, 94, 96, 97, 100, 110, 160
168, 170, 174, 176, 195, 200, 241 hydrogen gas, 19, 184, 265
growth rate, 126, 127, 128 hydrogen peroxide, 221, 236
growth time, x, 115, 117, 129, 130 hydrophilicity, 10, 29, 31, 250
hydrophobic, viii, 5, 6, 9, 20, 38, 69, 70, 74, 80, 212,
213, 222, 260
H hydrophobic properties, 9
hydrophobicity, 9, 10, 222, 250
hair, 138
hydroquinone, 55
halogen, 13, 221
hydroxide, 199
halogenation, 207, 210, 211
hydroxyapatite, 258
hardness, 143, 239
hydroxyl, 101, 221
harvesting, 78
hypothesis, 100, 173
hazards, 72
hysteresis, 160
headache, 82
health, vii, x, 71, 72, 77, 81, 82, 117, 133, 134
health effects, 133, 134 I
health risks, vii, x, 81, 133
heat capacity, 116, 118, 125 ideal, 18, 43, 185, 195, 223
heat conductivity, 5 identification, 76
heat removal, 6 image, 5, 6, 9, 144, 243, 245, 266, 267, 270
heat transfer, vii, ix, 115, 117, 124 images, 46, 47, 53, 148, 149, 164, 169, 222, 245,
heating rate, 48, 50 252, 256, 274
286 Index
immersion, 250, 254, 257

immobilization, 158
J
impregnation, 25, 34, 50, 51, 54, 57, 58, 63, 217
Japan, 88, 133, 230, 258
improvements, 2, 9, 29
joints, 138, 144, 145, 152
impurities, 2, 56, 71, 74, 84, 134, 184, 190, 193
Jordan, 32
in vitro, 134, 261
incompatibility, 226
incomplete combustion, vii, 70, 73, 184 K
individuals, 194
induction, 119, 121, 259, 260 K-BKZ model, xi, 157, 173, 174
induction time, 119, 121 ketones, 70, 73
industrial chemicals, 184 kidney, 80
industries, 140 kinetics, 25, 54, 74, 117, 121, 130, 196, 202, 203,
industry, 138, 184, 194, 265, 275 209, 217
inflammation, 133, 135 KOH, 203, 209
inflammatory responses, 135
infrared spectroscopy, 38
infrastructure, 6 L
ingredients, 82
inhibitor, 199, 209 lactate dehydrogenase, 133
initiation, 199 lakes, 80
injury, 71 lamella, 139
insertion, 202, 203, 269 laminar, 159
integrated circuits, 241 laser radiation, 121
integration, ix, 54, 94, 236 lead, 9, 28, 30, 31, 97, 106, 109, 111, 124, 189, 190,
interface, vii, 24, 25, 26, 27, 37, 38, 41, 43, 55, 65, 199, 203, 204, 213, 219, 231
138, 174, 204, 207, 213, 226, 261 lead-acid battery, 31, 199, 231
interference, ix, 72, 74, 75, 83, 115, 117 leakage, 27, 213
interferon, 133 learning, 38
Intermolecular H-bond, viii, 93 legs, 82
intermolecular interaction adsorbate-adsorbent, viii, lending, 158
93 ligand, 133
intermolecular interactions, 94, 97 light, vii, x, 1, 2, 28, 30, 72, 83, 137, 185, 214, 243
internal structure, 187 linoleic acid, 77
interphase, 214 liquid chromatography, 77, 80
iodine, 185, 214 liquid phase, 44
ion adsorption, 215 liquids, 170, 171
ion bombardment, 239, 240, 241 lithium, xii, 185, 194, 195, 196, 199, 200, 203, 204,
ion exchangers, 71, 84 205, 211, 212, 214, 216, 231, 232, 233, 234, 263,
ion-exchange, 77, 83 265, 266, 267, 268, 269, 272, 273, 274, 275
ionization, 77, 79, 82, 83, 84, 111 lithium insertion, 269
ions, 3, 11, 14, 28, 80, 197, 205, 212, 215, 239, 240, lithium ion batteries, 194, 205, 214, 233
247, 253 liver, 74, 80, 81
iron, 4, 36, 198, 203, 204, 212, 213, 232 livestock, 71
irradiation, 14 longevity, 223
Islam, 276 low density polyethylene, 238
isolation, 73, 75, 78, 81 low temperatures, 50, 227, 259
isomers, ix, 94, 95, 96, 97, 100 lubricants, 138
isotherms, 18, 19, 24, 25, 189 Luo, 86, 234
issues, xi, 10, 28, 31, 35, 138, 142, 183, 185, 194, lying, 11
227, 234 lymph, 135
Italy, 41, 71, 77, 78, 84, 157, 237, 258, 259, 261 lymph node, 135
lymphocytes, 133
Index 287
membranes, 9, 35, 36, 37, 42, 213, 259

M memory, xi, 157, 172, 173, 179, 211
memory function, 172, 173
machinery, 142
mercury, 81
macrophage inflammatory protein, 133
metabolites, 75, 77, 78
macrophages, 133
metal carbides, 28
magnesium, 74, 76, 195, 199, 212, 217, 229
metal electrocatalysts, vii, 1
magnitude, 27, 29, 162, 226
metal ion, 28
majority, 72, 79, 84, 95, 96, 105
metal nanoparticles, vii, 5, 10, 41, 42, 130, 222
malnutrition, 135
metal oxides, 2, 207, 216
man, 72
metals, 9, 22, 28, 42, 134, 195, 207, 212, 241
management, vii, 1, 4, 9, 29
methanol, 33, 35, 44, 55, 56, 58, 60, 61, 62, 73, 76,
manganese, 2, 3, 198, 199, 204, 217, 231
77, 78, 79, 221
manipulation, 215
methodology, 59
manufacturing, xi, xii, 31, 39, 44, 183, 184, 185,
methyl group, 101, 109
189, 190, 241, 263, 265, 275
methylene chloride, 73, 76, 79, 82
manure, 79
methylprednisolone, 80
market segment, 198
mice, 134, 135
masking, 17
microelectronics, 241
mass, 2, 11, 12, 14, 15, 19, 21, 22, 23, 24, 26, 27, 43,
micrometer, 141
44, 65, 73, 77, 80, 81, 82, 83, 84, 98, 112, 116,
microorganism, 223
117, 124, 125, 128, 130, 141, 144, 147, 149, 185,
microscope, 119, 122, 130, 186, 188, 243, 250
190, 191, 193, 200, 203, 273
microscopy, x, 6, 115, 130, 188, 193, 254
mass spectrometry, 11, 14, 19, 73, 77, 80, 81, 83, 84,
microstructure, 24, 36, 38, 184, 185, 186, 188, 190,
193
211, 212, 214, 215, 226, 227
materials, vii, viii, x, xi, 1, 2, 3, 4, 6, 7, 10, 11, 27,
microstructures, 259
28, 29, 30, 32, 33, 35, 41, 42, 43, 44, 47, 48, 54,
migration, 26, 215, 272
56, 58, 64, 69, 70, 73, 74, 75, 78, 80, 81, 83, 84,
military, 212
134, 135, 137, 138, 139, 140, 141, 148, 155, 174,
miniature, 212
175, 183, 184, 185, 190, 193, 194, 195, 196, 197,
Ministry of Education, 263
198, 199, 200, 201, 202, 203, 204, 205, 206, 209,
missions, 4, 72, 195, 218, 219, 235
210, 211, 212, 213, 214, 215, 216, 217, 218, 221,
mixing, 2, 3, 54, 74, 141, 158, 159, 164, 165, 166,
223, 224, 226, 227, 229, 230, 232, 234, 235, 238,
167, 168, 169, 198, 266, 269, 272
239, 241, 260, 268, 269, 271
model system, 38
materials science, 7
modelling, 34
matrix, x, 29, 71, 74, 75, 76, 78, 79, 80, 82, 83, 84,
models, 170, 174, 179, 187, 191, 192
139, 141, 157, 158, 161, 167, 174, 179
modifications, 239, 243, 246, 250, 253
matrixes, 79, 195, 196
modules, ix, 94
matter, 10, 16, 24, 29, 133, 134, 158, 200, 203, 205,
modulus, 158, 160, 162, 163, 165, 172, 176
208, 219, 239
moisture, 29, 199
MCP-1, 133
mold, 138, 141
measurements, ix, xi, 17, 19, 20, 25, 34, 54, 59, 63,
molds, 77
111, 115, 118, 120, 121, 158, 159, 237, 243, 246,
mole, 94
250, 251, 253, 255, 258, 272
molecular structure, 95
meat, 74, 82
molecular weight, 73, 84, 158
mechanical properties, 2, 28, 29, 138, 141, 143, 196,
molecules, viii, 4, 16, 18, 20, 22, 27, 70, 71, 77, 93,
197, 208, 211, 217, 273
94, 95, 96, 97, 98, 99, 100, 105, 109, 110, 111,
media, 43, 198, 239
158, 195, 218, 221, 251, 253
median, 17, 141
molybdenum, x, 137, 138, 139, 147, 148, 199
medical, 212
momentum, 240
medicine, 80
monolayer, 18, 19, 20, 30, 54
melt, 158
morphology, xi, 2, 8, 31, 39, 43, 46, 47, 48, 49, 51,
melting, 139, 140
52, 58, 64, 143, 144, 160, 169, 183, 184, 185,
melts, x, 157
288 Index
186, 188, 194, 196, 197, 204, 205, 208, 211, 215,
218, 219, 220, 221, 223, 227, 228, 229, 237, 238,
O
243, 245, 247, 252, 255, 266, 267
obstacles, 42
mortality, 134
obstruction, 253, 255
Moscow, 112, 113
octane, 74, 111, 273
moulding, 259
oil, 74, 76, 81, 138, 183, 184, 185, 189, 194, 195,
mussels, 84
205, 216, 219, 220, 224, 226, 256, 263, 264, 268,
mycotoxins, 77, 78, 81, 84
275
oil production, 256
N oligomers, 241
olive oil, 76, 256
nafion, 34 optical density, 121
nanocomposites, 233 optical microscopy, 254
nanofibers, 10 optical properties, 125, 185
nanohorns, 10, 32 optimization, ix, 43, 94, 104, 105, 109, 110, 111, 168
nanomaterials, vii, x, 133, 134, 233 ordinary differential equations, 125, 126
nanometer, 124, 129, 203 ores, 81, 203
nanometers, 3, 226 organic compounds, viii, 69, 72, 73, 75, 83, 96, 97,
nanoparticles, vii, ix, x, 5, 9, 10, 14, 15, 41, 42, 43, 112, 238
48, 51, 53, 55, 56, 57, 65, 115, 117, 122, 123, organic peroxides, 73
124, 125, 126, 127, 130, 133, 134, 135, 196, 208, organic polymers, 29
217, 222, 223, 230, 232, 234, 269, 273, 274 organic solvents, 190
nanotube, 32, 33, 35, 134, 135, 229, 269, 275 organs, x, 133, 134
naphthalene, 11, 82 oscillation, 162, 163
natural gas, 184, 189, 195, 218, 226, 228, 235, 264, oxidation, 3, 7, 32, 34, 44, 45, 47, 48, 49, 50, 51, 54,
265 55, 56, 59, 60, 62, 203, 204, 214, 221, 222, 225,
nausea, 82 226
necrosis, 133 oxygen, ix, xi, 4, 5, 10, 11, 25, 33, 34, 35, 37, 44, 45,
neglect, 124 50, 52, 53, 54, 56, 63, 65, 70, 94, 100, 101, 187,
nervous system, 133 189, 191, 205, 210, 212, 213, 215, 218, 220, 221,
networking, 163, 164, 167 223, 224, 236, 237, 238, 240, 241, 244, 245, 246,
neutral, 50, 75, 78, 120, 121 247, 248, 250, 254, 257, 260
neutrophils, 133 oxygen plasma, 241, 245, 260
next generation, 223, 225, 269 ozone, 73
nickel, 28, 134, 194, 199, 203, 233
niobium, 199
nitric oxide, 133
P
nitrides, 28
Pacific, 81
nitrogen, ix, x, 36, 37, 49, 54, 94, 100, 104, 112, 137,
paints, 28, 194
141, 144, 145, 146, 150, 151, 155, 187, 216, 230,
PAN, 73
244, 248, 254, 258, 259, 269, 271
parallel, 17, 19, 159, 186, 188, 193
nitrogen gas, 54, 144
paralysis, 82
NMR, 193, 230
particle collisions, 240
noble metals, 42
particle mass, 116, 124
nodes, 135, 213
particle morphology, 2, 196, 208
nonequilibrium, 117
patents, 183
nonionic surfactants, 79
pathophysiological, 135
non-polar, 70, 74, 81
pathways, vii, 21, 27, 28, 30, 41, 135, 269
novel materials, 183
percolation, 28, 160, 200, 202, 206, 210
nucleation, 186, 199, 203
perfusion, 134
nuclei, 186
permeability, 5, 7, 9, 27, 213
permeation, 5, 81
Index 289
permission, 180 polymer materials, x, 137, 138, 139

permit, 5, 43, 95, 97, 100, 105 polymer matrix, xi, 28, 139, 158, 161, 166, 179
peroxide, 212, 221, 236 polymer melts, x, 157
PES, 28, 100, 101, 102, 104, 105, 108, 110 polymer systems, 160
pesticide, 75, 77, 84 polymeric electrolyte, vii, 41, 44, 45, 54
petroleum, vii, 42, 219, 220, 224 polymeric materials, 175
pharmaceutical, 84, 230 polymerization, 241, 259, 261
pharmaceuticals, 78 polymers, 10, 28, 29, 139, 158, 173, 174, 196, 207,
phenol, 28, 50, 189 211, 216, 238, 241, 260, 261
phenolic compounds, 83 polypropylene, 28, 31, 77, 200
phosphates, 269 polystyrene, 134
photochemical degradation, 73 polysulfides, 267, 268
photoelectron spectroscopy, xi, 189, 193, 237, 238 polytetrafluoroethylene (PTFE), v, x, 8, 9, 36, 37, 84,
photoemission, ix, 115, 117, 118, 119, 120, 129 137, 139, 140, 141, 142, 143, 147, 148, 149, 151,
photolysis, 260 152, 153, 154, 155, 200, 205, 213, 216, 261
physical characteristics, 51, 59, 186 polyvinyl chloride, 29
physical properties, 8, 31 polyvinylidene fluoride, 28, 200, 214, 216, 271, 274
physical structure, vii, 1 ponds, 80
physicochemical properties, xi, 46, 49, 183, 185, poor performance, 206
204, 210, 217, 227 population, 101, 108
pigmentation, 194 porosity, 27, 44, 71, 192, 197, 198, 205, 210, 215,
pitch, 198, 210 218, 221, 227, 228, 243, 272
placenta, 135 portfolio, 224
placental barrier, 134 potential benefits, 43
plants, 77, 79, 80, 117, 224 poultry, 80
plastic products, vii, 140 power generation, 5, 195, 224, 225
plastics, xii, 73, 184, 258, 263 power plants, 117, 224
platinum, vii, 4, 5, 10, 32, 33, 34, 35, 36, 37, 41, 42, precipitation, 57, 78, 212, 217
43, 44, 50, 51, 52, 53, 54, 57, 58, 65, 214, 221, prednisone, 80
222, 236 preparation, viii, ix, 32, 38, 39, 42, 43, 44, 64, 65,
playing, 195 74, 77, 78, 79, 80, 94, 110, 141, 186, 221, 266,
polar, 70, 72, 73, 74, 75, 77, 81, 246, 247, 254 271
polar groups, 246, 247, 254 preservation, 96

polarity, 79 prevention, 140, 155
polarizability, 95 probability, 225
polarization, 9, 64, 65, 100, 199, 202, 204 probe, 16, 19, 20, 21, 143, 202, 238, 256
pollutants, 72, 81, 225, 256 process control, 239
pollution, 71, 134, 135, 224 progesterone, 79
polybutadiene, xi, 157, 158, 159, 161, 162, 163, 164, prognosis, 105
165, 166, 167, 168, 169, 179 propagation, 139
polychlorinated biphenyls (PCBs), viii, 69, 81, 82, propranolol, 84
83 propylene, 214, 238, 273
polycyclic aromatic hydrocarbon, 82, 190 protection, 183, 223, 259
polydispersity, 158, 175 proteins, 78, 80, 134
polyether, 28 proton exchange membrane fuel cells (PEMFCs), vii,
polymer, x, 5, 7, 27, 28, 29, 32, 33, 34, 35, 36, 37, 1
38, 39, 42, 70, 81, 83, 137, 138, 139, 140, 141, protons, 65
142, 143, 157, 158, 160, 161, 163, 165, 166, 168, prototypes, 226
174, 176, 179, 181, 200, 202, 206, 208, 213, 222, public health, 71, 81, 82
245, 258, 259, 266, 267, 271, 273, 275 public safety, 81
polymer chain, 174 pulse discharge, 260
polymer composites, 28, 39, 140, 273, 275 purge traps, viii, 69, 71
polymer films, 36 purification, viii, 69, 71, 77, 79, 80
290 Index
purity, vii, 1, 2, 54, 63, 193, 199, 223, 225, 269 reinforcement, vii, xi, 29, 139, 157, 159, 160, 161,
PVP, 210, 267, 268 179
pyrolysis, ix, 82, 115, 117, 119, 120, 121, 122, 123, relaxation, x, 157, 158, 159, 160, 161, 168, 169, 172,
129, 130, 188, 226, 228, 229, 235 174, 175, 176, 215, 216
pyrolysis temperature, ix, 115, 122, 123, 130 relaxation times, 158, 160
pyrolytic graphite, 37 relevance, 177
reliability, 138
renal failure, 81, 82
Q renewable energy, 195, 214, 223, 224
reparation, 44
quantification, 76, 79, 80, 81, 193
reproduction, 78
quantum chemical calculations, 100, 106
repulsion, 98, 101, 104, 108
quantum-chemical methods, ix, 94, 100
requirements, 4, 7, 33, 43, 83, 117, 194, 200
quartz, 118, 218
researchers, 7, 29, 79, 81, 97, 139, 142
quasi-rigid molecule, viii, 93, 96, 98, 100
residues, 74, 75, 76, 80, 82
quaternary ammonium, 83
resins, 28
quinone, 11, 55
resistance, vii, x, 1, 2, 4, 7, 9, 25, 27, 28, 29, 43, 44,
quinones, 10
48, 65, 137, 138, 139, 147, 148, 152, 194, 195,
199, 200, 202, 205, 209, 210, 216, 217, 222, 226,
R 257, 272
resolution, ix, 13, 115, 117, 186
radar, 194 resources, 105, 195, 226
radial distribution, 188 respiratory failure, 82
radiation, 13, 36, 118, 119, 120, 121, 124, 240, 242 response, xi, 81, 83, 84, 157, 158, 160, 161, 166,
radicals, 119, 121, 122, 218, 240, 246, 260 176, 179, 195
radio, xi, 237, 239, 241, 260 restrictions, 96, 111
radius, 26, 116, 123, 124, 126, 127, 129, 188 restructuring, xi, 157, 179
Raman spectra, 186 rheology, x, 29, 157, 164, 165, 168, 179
Raman spectroscopy, 229 rings, 11, 105, 188, 241
raw materials, 185, 224 risks, vii, x, 78, 81, 133
reactant, 5, 6, 43, 48, 212, 213, 222 rods, 118
room temperature, 47, 55, 57, 58, 61, 62, 63, 64, 142,
reactants, vii, 3, 5, 27, 41, 42, 43, 240

reaction order, 219 143, 205, 239, 254, 266, 269, 272, 275
reaction rate, 218, 220 roughness, 143, 186, 188
reaction zone, 43 rowing, 194
reactions, 4, 5, 13, 34, 43, 44, 65, 190, 203, 204, 214, Royal Society, 230
218, 225, 226, 227, 239, 240, 241, 244, 245, 246, rubber, vii, x, 137, 140, 157, 158, 163, 164, 165,
260, 267, 268 166, 167, 168, 179, 184, 194, 219, 235, 264
reactive sites, 7, 247, 266 rubber compounds, x, 157, 158, 164, 179
reactivity, 49, 203, 226, 264 rubber products, x, 137, 140
reagents, 54 rubbers, xii, 164, 263
reasoning, 18 Russia, 93
recall, 170 ruthenium, 216, 234
recalling, 171, 174
recognition, 77
S
recombination, 22
reconstruction, 261
safety, 81, 82, 212, 223, 224
recovery, 73, 75, 77, 78, 79, 80, 81, 206
salts, 35, 71, 84, 268
recycling, 43
saturation, 18
redistribution, 204, 213
scaling, 174, 175
refractive index, 239
scanning calorimetry, 193
regeneration, 219
scanning electron microscopy, xi, 46, 237, 243
regulations, 77, 78
scattering, 20, 37, 193, 229
Index 291
schema, 201 specific surface, xi, 43, 44, 45, 48, 49, 144, 145, 146,
science, 7, 78, 95, 138, 156, 158, 236 183, 186, 188, 190, 210, 214, 218, 219, 220, 221,
sediment, 75, 81 237, 246, 253, 255, 257, 258, 268
selectivity, 70, 219, 220 specifications, 3
semiconductors, 241 spectroscopy, xi, 20, 22, 37, 38, 191, 193, 206, 229,
seminiferous tubules, 134 230, 234, 237
sensitivity, 80, 82, 120, 165 sperm, 134
sensors, 118 Spring, 233
sewage, 78, 79 SSA, 243, 246, 253, 255
sex, 79 stability, vii, 1, 2, 4, 7, 10, 23, 24, 27, 28, 30, 34, 35,
sex hormones, 79 42, 43, 44, 48, 49, 70, 73, 84, 194, 196, 197, 203,
shape, 7, 28, 46, 47, 123, 139, 143, 145, 161, 165, 214, 218, 219, 220, 221, 224, 227, 250, 254, 269
176, 184, 186, 193, 211, 213, 217 stabilization, 194
shear, xi, 153, 157, 158, 160, 162, 163, 164, 165, standard deviation, 76, 80, 122, 154
166, 168, 170, 171, 173, 174 standardization, 34
shear deformation, 173 state, ix, xi, 9, 14, 19, 20, 30, 36, 44, 56, 58, 94, 95,
shear strength, 153 96, 97, 100, 101, 102, 104, 105, 109, 110, 111,
shelf life, 199, 212 116, 120, 122, 125, 126, 127, 128, 129, 130, 140,
shellfish, 81 157, 158, 160, 164, 165, 166, 167, 169, 170, 179,
shock, ix, 115, 116, 117, 118, 119, 121, 124, 128, 183, 187, 193, 197, 218, 220, 221, 230, 239, 273
129, 130 steel, 28, 70, 117, 119, 142, 143, 205, 208, 241, 243,
showing, 4, 18, 22, 163, 166 266, 271
shrimp, 79, 82 stem cells, 261
side chain, 100, 110 stent, 138
signals, 13, 58, 83 steroids, 79
signal-to-noise ratio, 13 sterols, 77
silica, 37, 70, 82, 208, 259 STM, 188, 193
silicon, 223, 250, 272 stoichiometry, 18
silk, 208 storage, xi, 2, 3, 5, 37, 78, 160, 183, 185, 189, 190,
silver, 213 194, 195, 196, 197, 199, 203, 204, 227, 228, 229,
simulation, ix, 115, 117, 126, 130 230, 231, 234, 261, 265
simulations, 127, 130 stress, 35, 158, 160, 165, 166, 167, 168, 170, 171,
sintering, 9, 10 172, 173, 174, 175, 176, 247

society, 138, 194, 195 stretching, 11, 16, 168
Socrates, 37 structural characteristics, 105, 109, 110, 193
sodium, 58, 74, 79, 224 structural defects, 193, 215
software, 95, 106, 126, 159, 206, 243 structure, vii, viii, xi, 2, 3, 8, 27, 33, 41, 42, 43, 44,
solar cells, xi, 183, 194, 195, 214, 227, 234 46, 48, 50, 51, 55, 58, 65, 71, 74, 93, 95, 97, 98,
solid oxide fuel cells, 7, 236 100, 104, 106, 109, 110, 117, 139, 140, 143, 144,
solid phase, 74, 75, 216 147, 157, 158, 160, 161, 163, 164, 165, 174, 179,
solid-phase extraction (SPE), viii, 69, 70 183, 184, 185, 186, 187, 188, 189, 190, 191, 192,
solubility, 185 193, 194, 195, 196, 197, 202, 204, 205, 208, 210,
solution, viii, 24, 54, 56, 57, 58, 62, 63, 75, 79, 82, 211, 212, 213, 214, 215, 217, 219, 221, 222, 227,
93, 190, 203, 209, 215, 238, 243, 244, 248, 250, 233, 238
257, 267, 269, 271, 273 styrene, 36, 214
solvents, 24, 71, 73, 74, 80, 190, 199 substitutes, 83
sorption, 113, 230 substitution, 191
Spain, 41 substrate, 6, 8, 9, 83, 222, 239, 240, 241, 246, 250,
species, 3, 10, 11, 12, 13, 14, 15, 16, 19, 20, 21, 22, 260
23, 24, 25, 26, 30, 37, 56, 78, 80, 81, 203, 212, substrates, 73, 83, 238, 240, 243, 246, 260, 261
215, 216, 239, 240, 241, 247, 248 sucrose, 83
specific gravity, 185 sulfate, 35, 74, 76
sulfites, 217
292 Index
sulfonamide, 80 target, 27, 73, 142, 224

sulfonamides, 83 technical support, 180, 258
sulfur, ix, 11, 13, 14, 16, 23, 24, 30, 37, 94, 100, 104, techniques, xi, 17, 30, 73, 77, 157, 160, 179, 188,
185, 187, 190, 211, 224, 225, 265, 266, 267, 268, 193, 204
275 technologies, 194, 195, 212, 224
sulfur dioxide, 211 technology, vii, 1, 3, 7, 42, 43, 134, 138, 156, 185,
sulphur, 34, 191, 224 194, 212, 223, 225, 230, 231, 236, 239, 247, 261
Sun, 32, 36, 90, 91, 236, 276 temperature, vii, ix, 5, 7, 11, 15, 16, 17, 18, 19, 20,
supercapacitors, xi, 183, 194, 195, 196, 197, 204, 21, 22, 23, 24, 26, 27, 30, 32, 35, 39, 41, 42, 45,
205, 207, 215, 216, 217, 227, 231, 232, 233, 234 47, 48, 49, 50, 55, 57, 58, 61, 62, 63, 64, 83, 96,
supercooling, 199 103, 106, 107, 108, 109, 110, 111, 115, 116, 117,
suppression, 77 118, 119, 120, 121, 122, 124, 125, 126, 127, 128,
surface area, vii, x, xi, 2, 5, 10, 18, 24, 25, 34, 41, 42, 129, 130, 138, 140, 142, 143, 171, 185, 186, 188,
43, 44, 45, 48, 49, 51, 52, 59, 62, 70, 71, 77, 137, 193, 195, 199, 203, 205, 211, 214, 215, 216, 218,
141, 144, 145, 146, 150, 151, 155, 158, 160, 161, 219, 220, 221, 223, 224, 225, 226, 239, 250, 254,
163, 164, 165, 179, 183, 185, 186, 188, 190, 193, 257, 264, 265, 266, 269, 272, 275
195, 196, 197, 204, 205, 209, 210, 211, 212, 213, temperature dependence, 118
214, 216, 217, 218, 219, 220, 221, 222, 223, 227, tension, 116
234, 237, 238, 243, 246, 253, 255, 257, 258, 268, testing, 77, 82, 143, 159, 193
272 testosterone, 79
surface chemistry, vii, xi, 1, 8, 9, 10, 18, 30, 43, 44, tetrachlorodibenzo-p-dioxin, 72
45, 49, 50, 51, 53, 54, 64, 65, 183, 184, 185, 189, tetraethoxysilane, 259
190, 191, 192, 194, 195, 197, 199, 200, 210, 211, texture, xi, 183, 184, 185, 186, 193, 197, 211, 218,
214, 218, 219, 221, 223, 224, 226, 227, 228, 229, 219, 221
238, 260 TFE, 139, 141, 273
surface energy, 189, 197 thermal analysis, 193
surface layer, 240 thermal decomposition, xii, 184, 185, 226, 228, 235,
surface modification, vii, 1, 29, 30, 39, 41, 43, 55, 263, 264
65, 196, 215, 224, 238, 239, 261 thermal expansion, 7, 28
surface properties, 10, 18, 43, 237, 238, 260 thermal stability, 10, 30, 48, 49, 70, 73, 84, 214, 250,
surface reactions, 239, 240 254
surface structure, 186, 195 thermal treatment, 16, 18, 44, 239, 250
surface tension, 116 thermodynamic characteristics of adsorption (TCA),

surface treatment, 10, 29, 221, 228, 234, 238, 239, viii, 93, 94
259 thermodynamic equilibrium, 239
surfactant, 33, 203, 210, 227, 231 thermodynamics, 74, 225
surfactants, 78, 83, 197, 224, 229 thin films, 239, 241, 249, 250, 251, 253, 254, 255,
suspensions, x, 157, 176, 179 256, 259, 261
sustainability, 214, 218 tin, 82, 138, 225
sustainable development, 185, 194, 195, 223 tin oxide, 225
sustainable energy, 185, 194, 195 tissue, x, 74, 133, 134
swelling, 196 titanium, 28, 38, 199, 221, 236
Switzerland, 209 tobacco, 73, 75, 238
symmetry, 109 tobacco smoke, 73
synergistic effect, 223, 240 toluene, 72, 82, 184
synthesis, 9, 10, 32, 33, 35, 44, 49, 51, 55, 57, 58, topology, 185, 190, 191, 228
59, 183, 185, 222, 225, 227, 261, 269 torsion, ix, 94
synthesizing microporous layers, vii, 1 toxic substances, 238
toxicity, 73, 81, 134, 265
toxicology, 135
T toxin, 77
trade, 184, 198
tanks, 3
transactions, 102, 105, 260
tar, 219, 220
Index 293
transformation, 233 Vickers hardness, 143

transformations, 72, 117 vinylidene fluoride, 273
transition metal, 269 viscoelastic liquids, 170, 171
translocation, x, 133, 134 viscosity, x, 140, 157, 158, 159, 160, 164, 166, 176,
transmission, 5, 53, 186, 188 177, 178, 179, 185
transmission electron microscopy (TEM), 5, 17, 18, visualization, ix, 94
53, 144, 186, 188, 193, 222 volatile organic compounds, 72, 73
transport, 5, 10, 43, 65, 72, 194, 226 vulcanization, 13
transportation, 5, 72, 194
treatment, 9, 10, 15, 16, 17, 18, 20, 25, 27, 35, 36,
37, 49, 78, 79, 80, 82, 185, 188, 190, 192, 198, W
199, 207, 210, 216, 220, 221, 227, 228, 234, 237,
waste, 37, 81, 184, 224, 225, 227, 259
238, 239, 240, 241, 242, 244, 245, 246, 247, 248,
waste heat, 224
253, 255, 256, 258, 259, 260, 261
wastewater, 79
treatment methods, 80
water, vii, viii, xi, 1, 5, 6, 9, 10, 11, 16, 21, 22, 23,
tribology, x, 137, 138, 139, 140, 142
27, 29, 31, 54, 69, 70, 72, 74, 75, 77, 78, 79, 80,
trifluoroacetic acid, 75
82, 83, 185, 195, 198, 212, 218, 224, 237, 238,
tumor, 133
243, 244, 246, 247, 250, 251, 254, 255, 257, 264,
tumor necrosis factor, 133
265, 269, 271
tungsten, 147, 148
water absorption, 29
tunneling, 190
water desorption, 21, 22, 23
turnover, 19
water evaporation, 212
water vapor, 72
U wear, x, 137, 138, 139, 140, 142, 143, 147, 148, 149,
150, 151, 153, 154, 155
Ukraine, 230 weight loss, 48
uniform, 10, 33, 53, 141, 266 weight ratio, 265, 269, 271, 274
united, 76, 265 weight reduction, 7
United States, 265 wettability, 50, 190, 207, 223, 239, 258
uranium, 223, 229 wildlife, 78
urea, 75, 210, 215, 216, 224 working conditions, 7, 239
urine, 74, 76, 83 World Health Organization (WHO), 78, 90

USA, 69, 71, 76, 231 worldwide, 184
V X
vacuum, 11, 12, 15, 16, 17, 18, 19, 20, 21, 24, 25, x-ray diffraction, 17, 46, 51, 95, 188, 193, 238
26, 138, 142, 188, 228, 241, 260, 266, 269, 271, x-ray diffraction (XRD), 17, 46, 47, 51, 52, 53, 54,
272, 274 58, 59, 186, 188, 193, 230
valence, 95, 100, 103 x-ray photoelectron spectroscopy (XPS), 13, 14, 34,
valve, 6, 9, 138, 231, 241 36, 37, 189, 193, 238, 243, 244, 245, 246, 247,
vanadium, 4, 31, 199 248, 249, 250, 253, 254, 258
vapor, ix, 72, 115, 116, 117, 122, 123, 124, 125, 126,
127, 129, 130, 185, 196, 197, 200, 205, 206, 208,
210 Y
VDF, 28, 273
yield, x, 17, 157, 162, 185, 188, 218, 219, 220, 226
vegetables, 75
vegetation, 73
vehicles, 194, 195, 199, 204, 213, 231 Z
velocity, 116, 118, 119, 124, 175, 219, 220, 221
versatility, vii, 1, 239 zinc, 2, 3, 4, 198, 199, 212, 213
vibration, 11, 16 zirconia, 271

Carbon Black Production, Properties and Uses Production, Properties and Uses

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Copyright © 2011. Nova Science Publishers, Incorporated. All rights reserved.

CARBON BLACK: PRODUCTION,

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CHEMICAL ENGINEERING METHODS

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Nova Science Publishers, Inc.

NOTICE TO THE READER

DECLARATION OF PARTICIPANTS JOINTLY ADOPTED BY A COMMITTEE OF THE

Library of Congress Cataloging-in-Publication Data

Carbon black : production, properties, and uses / editors, Ian J. Sanders

V. V. Varfolomeeva and A. V. Terent‟ev

Chapter 10 Carbon Black Treated in Low Pressure Plasma: A New Class

CARBON BLACKS IN ELECTROCHEMICAL

INTRODUCTION: APPLICABILITY OF CARBON

Figure 1. Schematic representation of a zinc-carbon dry cell.

e. mechanical strength: providing mechanical support to the MEA.

CARBON BLACKS IN GAS DIFFUSION ELECTRODES FOR PEM FUEL

Surface Chemistry of the Vulcan XC-72 Carbon Black

XPS analysis of the CB indicates a surface composition corresponding to C, O, and S in

Surface Chemistry of the Catalyst: Pt/Vulcan XC-72

Adsorption-Exchange Properties of the Pt/Vulcan XC-72 Catalysts

A. H2 Chemisorption on Pt/Vulcan Xc72

B. CO Chemisorption on Pt/Vulcan Xc72

C. The Role of Surface Groups in Adsorption on Pt/Vulcan Xc72

This deuterium-hydrogen exchange process is often observed on catalysts with proton

Ramirez-Cuesta et al. have provided evidence of this phenomenon by means of inelastic

H2 Adsorption and Proton Exchange Rate on Gas Diffusion Electrodes with

CARBON BLACKS IN PEMFCFLOW FIELD PLATES

• low weight <0.4 kg kW-1

• high corrosion resistance <1 mA cm-2.

J. Electrochem. Soc.142 (5), 1726-1731.

of fine platinum catalystsupported on single-wall carbon nanohorns for fuel cell

(2002).Comparison of high surface Pt/C catalysts by cyclic voltammetry.J. Power

[79] Antolini, E. (2010). Composite materials: An emerging class of fuel cellcatalyst

M. (2006).Hydrophilic modification of expanded polytetrafluoroethylene (ePTFE) by

Patent No. WO 01/89013.

STUDY AND APPLICATION OF CARBON

M. J. Lázaro1, L. Calvillo1, V. Celorrio1,

catalytic properties and to improve electrocatalyst‘s stability. However, the functionalization

2. CHARACTERIZATION AND MODIFICATION OF

Table 1. Nomenclature and oxidation conditions of Vulcan XC-72R

Sample Oxidizing agent

Figure 1. SEM images of Vulcan XC-72R.

Figure 2. XRD pattern of Vulcan XC-72R.

2.2. Thermal Stability

2.3. Textural Properties

Table 2. Textural parameters of Vulcan obtained by nitrogen physisorption at 77 k

SBET a VTotal b VMicropore c VMesopore d SMicropore c SMesopore d

Vulcan NSTa2 141 0.48 0.01 0.47 24 117

2.4. Surface Chemistry

CO2 Peak areas CO Peak areas

(μmol/g) (μmol/g) CO+CO2

3. USE OF VULCAN XC-72R AS ELECTROCATALYST SUPPORT

3.1. Effect of the Functionalization of the Support

3.1.1. Physicochemical Properties

Table 4. Pt content and physical characteristics of catalysts

db Lattice parameterb Metal surface area

The morphological and crystallographic properties of Pt catalysts were studied by X-ray

Oxygen groups (mmol g-1)

Pt crystallite size (nm)

3.1.2. Electrochemical Properties

catalysts, the electro-oxidation of a CO monolayer adsorbed on the catalyst surface was