The Purpose of This Paper Is To Deal With The Solution of The Inverse Kinematics Problem in Robotic Arms

The purpose of this paper is to deal with the solution of the inverse kinematics problem in
Robotic arms. A two links, two degree of freedom (dof) planar robot arm (manipulator) is
simulated using a Multilayer Static Neural Network (MSNN) and animated. For the neural
learning scheme is used an iterative technique (Levenberg-Marquardt algorithm) that can be
thought of as a combination of steepest descent and the Gauss-Newton method. When we
changed the error goal, we observed an oscillation on the end-effector of the manipulator due
to increase of the error. Simulation and animation results for a two dof manipulator provide
evidence that this approach is indeed successful with respect to an ANFIS structure, in which
the main characteristic are the qualitative values versus the quantitative values of the static
structures.
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ELECTROCHEMICAL MACHINING (ECM)

Joseph McGeough
Institute for Integrated Micro and Nano Systems
University of Edinburgh
Edinburgh, EH9 3JL, United Kingdom
(July, 2005)
Michael Faraday’s early metallurgic researches, from 1818 to 1824, anticipated the
developments which have led to widespread use today of alloy steels. Much effort has been
expended to improve their performance for their service as cutting tools in machining. The aim
has always been to yield higher rates of machining and to tackle recently developed harder
materials on the principle that the tool material must be harder than the workpiece which is to be
machined. Much progress has been made; however, in recent years some alloys, which are
exceedingly difficult to machine by the conventional methods, have been produced to meet a
demand for very high-strength, heat resistant materials. Moreover, these new materials often
have to take a complex shape. A search has had to be made for alternative methods of machining
since the evolution of suitable tooling has not kept pace with these advances.
Electrochemical machining (ECM) has been developed initially to machine these hard to
machine alloys, although any metal can so be machined. ECM is an electrolytic process and its
basis is the phenomenon of electrolysis, whose laws were established by Faraday in 1833. The
first significant developments occurred in the 1950s, when ECM was investigated as a method
for shaping high strength alloys. As of the 1990s, ECM is employed in many ways, for example,
by automotive, offshore petroleum, and medical engineering industries, as well as by aerospace
firms, which are its principal user.
Metal removal is achieved by electrochemical dissolution of an anodically polarized workpiece
which is one part of an electrolytic cell in ECM. Hard metals can be shaped electrolytically by
using ECM and the rate of machining does not depend on their hardness. The tool electrode used
in the process does not wear, and therefore soft metals can be used as tools to form shapes on
harder workpieces, unlike conventional machining methods. The process is used to smooth
surfaces, drill holes, form complex shapes, and remove fatigue cracks in steel structures. Its
combination with other techniques yields fresh applications in diverse industries. Recent
advances lie in computer-aided tool design, and the use of pulsed power, which has led to greater
accuracy for ECM-produced components.
Theoretical background
Since electrolysis is the basis of ECM, it must be understood before going further through the
characteristics and other details of the process.
Electrolysis
Electrolysis is
the name
given to the
chemical
process which
occurs, for
example,
when an
electric
current is
passed
between two
conductors
dipped into a
liquid
solution. A
typical
example is Fig. 1. Electrolysis of copper sulphate solution.
that of two
copper wires
connected to a source of direct current and immersed in a solution of copper sulphate in water, as
shown in Figure 1. An ammeter, placed in the circuit, will register a flow of current; from this
indication, the electric circuit can be deduced to be complete. A significant conclusion that can
be made from an experiment of this sort is that the copper sulphate solution obviously has the
property that it could conduct electricity. Such solution is termed an electrolyte. The wires are
called electrodes, the one with positive polarity being the anode, and the one with negative
polarity the cathode. The system of electrodes and electrolyte is referred to as the electrolytic
cell, whilst the chemical reactions which occur at the electrodes are called the anodic or cathodic
reactions or processes.
Electrolytes
are different
from metallic
conductors of
electricity in
that the
current is
carried not by
electrons but
by atoms, or
group of
atoms, which
have either
lost or gained
electrons, thus
acquiring
either positive
or negative
charges. Such Fig. 2. Electrolytic dissolution of iron.
atoms are
called ions. Ions which carry positive charges move through the electrolyte in the direction of the
positive current, that is, toward the cathode, and are called cations. Similarly, the negatively
charged ions travel toward the anode and are called anions. The movement of the ions is
accompanied by the flow of electrons, in the opposite sense to the positive current in the
electrolyte, outside the cell, as shown also in Figure 2 and both reactions are a consequence of
the applied potential difference, that is, voltage, from the electric source.
A cation reaching the cathode is neutralized, or discharged, by the negative electrons on the
cathode. Since the cation is usually the positively charged atom of a metal, the result of this
reaction is the deposition of metal atoms.
To maintain the cathodic reaction, electrons are required to pass around the external circuit.
These are obtained from the atoms of the metal anode, and these atoms thus become the
positively charged cations which pass into solution. In this case, the reaction is the reverse of the
cathodic reaction.
The electrolyte in its bulk must be electrically neutral; that is, there must be equal numbers of
opposite charges within it, and thus there must be equal amounts of reaction at both electrodes.
Therefore, in the electrolysis of copper sulphate solution with copper electrodes, the overall cell
reaction is simply the transfer of copper metal from the anode to the cathode. When the wires are
weighted at the end of the experiment, the anodic wire will be found to have lost weight, whilst
the cathodic wire will have increased in weight by an amount equal to that lost by the other wire.
Some examples of the reactions occurring in these processes are shown in the Appendix.
These results are embodied in Faraday’s two laws of electrolysis:
1. The amount of any substance dissolved or deposited is directly proportional to the
amount of electricity which has flowed.
2. The amounts of different substances deposited or dissolved by the same quantity of
electricity are proportional to their chemical equivalent weights.
A popular application of electrolysis is the electroplating process in which metal coatings are
deposited upon the surface of a cathodically polarized metal. An example of an anodic
dissolution operation is electropolishing. Here, the item which is to be polished is made the
anode in an electrolytic cell. Irregularities on its surface are dissolved preferentially so that, on
their removal, the surface becomes flat and polished.
ECM is similar to electropolishing in that it also is an anodic dissolution process. But the rates of
metal removal offered by the polishing process are considerably less than those needed in metal
machining practice.
Some observations relevant to ECM can be made:
• Since the anode metal dissolves electrochemically, its rate of dissolution depends only
upon the atomic weight and the ionic charge, the current which is passed, and the time for
which the current passes. The dissolution rate is not influenced by the hardness or other
characteristics of the metal.
• Since only hydrogen gas is evolved at the cathode, the shape that electrode remains
unaltered during the electrolysis. This feature is perhaps the most relevant in the use of
ECM as a metal shaping process.
Characteristics of ECM
In ECM, electrolytes serve as conductors of electricity and Ohm’s law also applies to this type of
conductor. The resistance of electrolytes may amount to hundreds of ohms.
Accumulation within the small machining gap of the metallic and gaseous products of the
electrolysis is undesirable. If growth were left uncontrolled, eventually a short circuit would
occur between the two electrodes. To avoid this crisis, the electrolyte is pumped through the
interelectrode gap so that the products of the electrolysis are carried away. The forced movement
of the electrolyte is also essential in diminishing the effects both of electrical heating of the
electrolyte, resulting from the passage of current and hydrogen gas, which respectively increase
and decrease the effective conductivity.
Working principles
Fig. 3. Working principles of ECM.
Electrochemical machining is founded on the principles outlined. As shown in Figure 3, the
workpiece and tool are the anode and cathode, respectively, of an electrolytic cell, and a constant
potential difference, usually at about 10 V, is applied across them. A suitable electrolyte, for
example, aqueous sodium chloride (table salt) solution, is chosen so that the cathode shape
remains unchanged during electrolysis. The electrolyte is also pumped at a rate 3 to 30
meter/second, through the gap between the electrodes to remove the products of machining and
to diminish unwanted effects, such as those that arise with cathodic gas generation and electrical
heating. The rate at which metal is then removed from the anode is approximately in inverse
proportion to the distance between the electrodes. As machining proceeds, and with the
simultaneous movement of the cathode at a typical rate, for example, 0.02 millimeter/second
toward the anode, the gap width along the electrode length will gradually tend to a steady-state
value. Under these conditions, a shape, roughly complementary to that of the cathode, will be
reproduced on the anode. A typical gap width then should be about 0.4 millimeter. Being
understood the characteristics and working principles of ECM, its advantages should be stated in
short before going further through machining processes:
• the rate of metal machining does not depend on the hardness of the material,
• complicated shapes can be machined on hard metals,
• there is no tool wear.
The schematic of an industrial “electrochemical machine” is shown in Figure 4, and an actual
example of a cathode tool and anode workpiece are shown in Figure 5.
Fig. 4. Industrial electrochemical machine.
Electrochemical
machining
Machine
components
Industrial
electrochemical
machines work on
the principles
outlined. Particular
attention has to be
paid to the stability
of the
electrochemical
machine tool frame,
and to the machining
table which should
also be stable and
firm. The electrolyte
has to be filtered
carefully to remove
the products of
machining and often
has to be heated in
its reservoir to a
fixed temperature, Fig. 5. Example of cathode tool (above) and anode
for instance 30oC workpiece (below).
(86oF), before
entering the machining apparatus. This procedure is used to provide constant operating
conditions. During machining the electrolyte heats up from the passage of current. Precautions
must be taken to avoid a high electrolyte temperature which can cause changes in the electrolyte
specific conductivity and subsequent undesirable effects on machining accuracy.
Rates of machining
The rates at which metals can be electrochemically machined is in proportion to the current
passed through the electrolyte and the elapsed time for that operation, and is in inverse
proportion to the electrochemical equivalent of the anode-metal which corresponds to the atomic
weight of the dissolving ions over the ionic charge times the Faraday’s constant. See the
Appendix for more details.
Many factors other than current influence the rate of machining. These involve electrolyte type,
rate of electrolyte flow, and some other process conditions. For example current efficiency
decreases when current density is increased for a certain metal, for example, for nickel.
If the ECM of titanium is attempted in sodium chloride electrolyte, usually very low (10–20%)
current efficiencies are obtained. When this solution is replaced by some mixture of fluoride-
based electrolytes, to achieve greater efficiencies (>60%), a higher voltage is used.
If the rates of the flow are kept too low, the current efficiency of even the most easily
electrochemically machined metal is reduced. Insufficient flow does not allow the products of
machining to be so readily flushed from the machining gap. When complex shapes have to be
produced the design of tooling incorporating the right kind of flow ports becomes a considerable
problem.
Surface finish
Type of electrolytes used in the process affects the quality of surface finish obtained in ECM.
Depending on the material, some electrolytes leave an etched finish. This finish results from the
nonspecular reflection of light from crystal faces electrochemically dissolved at different rates.
Sodium chloride electrolyte tends to produce an etched, matte finish with steels and nickel
alloys.
The production of an electrochemically-polished surface is usually associated with the random
removal of atoms from the anode workpiece, whose surface has become covered with an oxide
film. This is governed by the metal-electrolyte combination used. Nonetheless, the mechanisms
controlling high-current density electropolishing in ECM are still not completely understood. For
example, with nickel-based alloys, the formation of a nickel oxide film seems to be a prerequisite
for obtaining a polished surface; a finish of this quality, of 0.2 µm, has been claimed for Nimonic
(a nickel alloy) machined in saturated sodium chloride solution. Surface finishes as fine as 0.1
µm have been reported when nickel-chromium steels are machined in sodium chlorate solution.
The formation of an oxide film on the metal surface is considered the key to these conditions of
polishing.
Sometimes the formation of oxide film on the metal surface hinders efficient ECM and leads to
poor surface finish. For example, the ECM of titanium is rendered difficult in chloride and
nitrate electrolytes because the oxide film formed is so passive. Even when higher voltages about
50 V are applied to break the oxide film, its disruption is so non-uniform that deep grain
boundary attack of the metal surface can occur.
Occasionally, metals that have undergone ECM have a pitted surface while the remaining area is
polished or matte. Pitting normally stems from gas evolution at the anode; the gas bubbles
rupture the oxide film.
Process variables also affect surface finish. For example, as the current density is raised the
finish generally becomes smoother on the workpiece surface. A similar effect is achieved when
the electrolyte velocity is increased. In tests with nickel machined in hydrochloric acid solution
the surface finish has been noted to improve from an etched to a polished appearance when the
current density is increased from about 8 to 19 A/square centimeter with constant flow velocity.
Accuracy and dimensional control
Electrolyte selection plays an important role in ECM. Sodium chloride, for example, yields much
less accurate components than sodium nitrate. The latter electrolyte has far better dimensional
control owing to its current efficiency - current density characteristics. Using sodium nitrate
electrolyte, the current efficiency is greatest at the highest current densities. In hole drilling these
high current densities occur between the leading edge of the drilling tool and the workpiece. In
the side gap there is no direct movement between the tool and workpiece surface, so the gap
widens and the current densities are lower. The current efficiencies are consequently lower in the
side gap and much less metal than predicted from Faraday’s law is removed. Thus the overcut in
the side gap is reduced with this type of electrolyte. If another electrolyte such as sodium
chloride solution was used instead, then the overcut could be much greater. Using sodium
chloride solutions, its current efficiency remains steady at almost 100% for a wide range of
current densities. Thus, even in the side gap, metal removal proceeds at a rate which is mainly
determined by current density, in accordance with Faraday’s law. A wider overcut then ensues.
Shaping
Most metal-shaping operations in ECM utilize the same inherent feature of the process whereby
one electrode, generally the cathode tool, is driven toward the other at a constant rate when a
fixed voltage is applied between them. Under these conditions, the gap width between the tool
and the workpiece becomes constant. The rate of forward movement between the tool and the
workpiece becomes constant. The rate of forward movement of the tool is matched by the rate of
recession of the workpiece surface resulting from electrochemical dissolution.
Three practical cases are of interest in considering some equations derived for the variation of
the interelectrode gap width:
1. When there is no tool movement, the gap width increases indefinitely with the square
root of machining time. This condition is often used in deburring by ECM when surface
irregularities are removed from components in a few seconds, without the need for
mechanical movement of the electrode.
2. When the tool is moved mechanically at a fixed rate toward the workpiece, the gap width
tends to a steady value. This inherent feature of ECM, whereby an equilibrium gap width
is obtained, is used widely in ECM for reproducing the shape of the cathode tool on the
workpiece.
3. Under short-circuit conditions the gap width goes to zero. If some process conditions,
such as too small equilibrium gap width caused by a too high movement of the tool
toward the workpiece, occur, contact between the two electrodes ensues. This causes a
short circuit between the electrodes and hence premature termination of machining.
The equilibrium gap is applied widely in the shaping process. Studies of ECM shaping are
usually concerned with three distinct problems:
1. The design of the cathode tool shape needed to produce a required profile geometry of
the anode workpiece.
2. For a given cathode tool shape, prediction of the resultant anode workpiece geometry, for
example, hole drilling by ECM.
3. Specification of the shape of the anode workpiece, as machining proceeds. This is most
readily predicted for the smoothing of surfaces, although for actual shaping of
components by ECM, estimates of the machining times as the shape develops provide
useful information about the process.
Applications
Smoothing of rough surfaces
Deburring, or
smoothing, of
surfaces
(Figure 6), is
the simplest
and a
common use
of ECM. A
plane-faced
cathode tool is
placed
opposite a
workpiece
that has an
irregular
surface. The
current
densities at
the peaks of
the surface
irregularities
are higher
than those in
the valleys.
The former Fig. 6. Smoothing of rough surfaces.
are, therefore,
removed
preferentially and the workpiece becomes smooth, admittedly at the expense of stock metal
(which is still machined from the valleys of the irregularities, even though at a lower rate).
Electrochemical smoothing is the only type of ECM in which the final anode shape may match
precisely that of the cathode tool.
Electrochemical deburring is a fast process; typical times for smoothing the surfaces of
manufactured components are 5 to 30 seconds. Owing to its speed and simplicity of operation,
electrochemical deburring can be performed with a fixed, stationary cathode tool. The process is
used in many industries.
Hole drilling
Hole drilling
is another
principal way
of using ECM
(Figure 7).
The cathode-
tool is usually
made in the
form of a
tubular
electrode.
Electrolyte is
pumped down
the central
bore of the
tool, across
the main
machining
gap, and out
between the
sidegap that
forms
between the
wall of the
tool and the Fig. 7. Electrochemical hole drilling.
hole. Reversal
of the electrolyte flow can often produce considerable improvement in machining accuracy.
The main machining action is carried out in the gap formed between the leading edge of the drill
tool and the base of the hole in the workpiece. ECM also proceeds laterally between the side
walls of the tool and component, where the current density is lower than at the leading edge of
the advancing tool. Since the lateral gap width becomes progressively larger than that at the
leading edge, the side-ECM rate is lower. The overall effect of the side-ECM is to increase the
diameter of the hole produced. The distance between the side wall of the workpiece and the
central axis of the cathode tool is larger than the external radius of the cathode. This difference is
known as the "overcut". The amount of overcut can be reduced by several methods. A common
procedure involves the insulation of the external walls of the tool (Figure 7), which inhibits side-
current flow. Another practice lies in the choice of an electrolyte such as sodium nitrate, which
has the greatest current efficiency at the highest current densities. In hole drilling these high
current densities occur between the leading edge of the drill and the base of the workpiece. If
another electrolyte such as sodium chloride were used the overcut could be much greater. The
current efficiency for sodium chloride remains steady at almost 100% for a wide range of current
densities. Thus, even in the side gap, metal removal proceeds at a rate that is mainly determined
by the current density, in accordance with Faraday's law.
Holes with diameters of 0.05 to 75 millimeter have been achieved with ECM. For holes of 0.5 to
1.0 millimeter diameter, depths of up to 110 millimeter have been produced. Drilling by ECM is
not restricted to round holes; the shape of the workpiece is determined by that of the tool
electrode.
Full-form shaping
Full-form shaping utilizes a constant gap across the entire workpiece and the tool is moved
mechanically at a fixed rate toward the workpiece in order to produce the type of shape used for
the production of compressor and turbine blades. In this procedure, current densities as high as
100 A/square centimeter are used, and across the entire face of the workpiece, the current density
remains high.
Electrolyte flow plays an even more influential role in full-form shaping than in drilling and
smoothing of surfaces. The entire large cross-sectional area of the workpiece has to be supplied
by the electrolyte as it flows between electrodes. The larger areas of electrodes involved mean
that comparatively higher pumping pressures and volumetric flow rates are needed.
Electrochemical grinding
The main feature of electrochemical grinding (ECG) is the use of a grinding wheel in which an
insulating abrasive, such as diamond particles, is set in a conducting material. This wheel
becomes the cathode tool. The nonconducting particles act as a spacer between the wheel and
workpiece, providing a constant interelectrode gap, through which electrolyte is flushed.
Accuracies achieved by ECG are usually about 0.125 millimeter. A drawback of ECG is the loss
of accuracy when inside corners are ground. Because of the electric field effects, radii better than
0.25 – 0.375 millimeter can seldom be achieved.
A wide application of electrochemical grinding is the production of tungsten carbide cutting
tools. ECG is also useful in the grinding of fragile parts such as hypodermic needles.
Electrochemical arc machining
A process that relies on electrical discharges in electrolytes, thereby permitting metal erosion as
well as ECM in that medium, has been developed. Because this process relies on the onset of
arcs rather than sparks, it has been named electrochemical arc machining (ECAM). A spark has
been defined as a sudden transient and noisy discharge between two electrodes; an arc is a stable
thermionic phenomenon. Duration discharges of approximately 1 second to 1 millisecond are
described as sparks, whereas for durations of about 0.1 second said discharges can be considered
arcs. Because in the ECAM process duration, energy, and time of ignition of sparks are under
control, it is valid to regard them as arcs.
An attraction of the ECAM technique is the very fast rates of metal removal attainable by the
combined effects of sparking and ECM. The ECAM technique can be applied in all the ways
discussed for ECM, thus surfaces can be smoothed and drilled. Turning is also possible, as is
wire machining.
One form of this process relies on a pulsed direct current, that is, full-wave rectified ac power
supply that is locked in phase with a vibrating tool head. The oscillation of the tool gives rise to a
set of conditions whereby ECM occurs over each wave cycle. The interelectrode gap narrows as
the tool vibrates over one cycle. During the same period the current rises until sparking takes
place by breakdown of the electrolyte and/or generation of electrolytic gas or steam bubbles in
the gap, the production of which aids the discharge process.
For drilling, the discharge action occurs at the leading edge of the tool, whereas ECM takes place
on the side walls between the tool and the workpiece. The combined spark erosion and ECM
action yields fast rates of metal removal. Because ECM is still possible, any metallurgical
damage to the components caused by the sparking action can be removed by a short period of
ECM after the main ECAM action. Currents of 250 A at 30 V are typically used in the process.
Economic aspects
The industrial sectors utilizing ECM technology fall into five main categories: tool and die,
automotive, aerospace, power generation, and oil and gas industries. Leading the world’s
principle machine tool manufacturing nations in production and export of tools in the 1980s were
Japan followed by the former West Germany. The United States led in imports and consumption;
consumption was high for both Japan and W. Germany as well. Unconventional machine tools
including ECM are generally considered to account for only 1% of total production.
Electrodischarge machining (EDM) holds the largest share, possibly as much as 50% and ECM
about 15% lagging behind laser processes which are 20%.
Manufacturing engineers wishing to use ECM processes in industry need to address the
challenge of proper tool design. The cost of design can be as much as 20% of the cost of an
electrochemical machine for complex components. Predictability of overcuts obtained for
specific applications and the particular electrolytes to be used for the alloy metals that have to be
machined must also be considered along with specific controls and limits on the ECM equipment
needed.
Computer-controlled equipment and sensors are available for electrochemical machining
systems. However in the 1990s practical ECM systems are often favored because the amount of
control and/or monitoring of the process is far less than that which was required in the 1970s.
Thus machines are used successfully in which electrical spark detection is eliminated and
machining products control, for example, pH monitoring, is nonexistent.
The present and future status of ECM
High-rate anodic electrochemical dissolution is a practical method of smoothing and shaping
hard metals by employment of simple aqueous electrolyte solutions without wear of the cathodic
tool. ECM can offer substantial advantages in a wide range of cavity-sinking and shaped-hole
production operations.
Control of the ECM process is improving all the time, with more sophisticated servo-systems,
and better insulating coatings. However there is still a need for basic information on electrode
phenomena at both high current densities and electrolyte flow-rates.
Tool design continues to be of paramount importance in any ECM operation. The use of
computer-aided design to predict cathode tool profiles will continue to advance.
Recently developments in ECM practice have dwelt on the replacement of constant dc by pulsed
currents (PECM). Significant improvements in surface quality have been claimed. Much smaller
electrode gaps may be obtained, for example, below 0.1 millimeter leading to improved control
of accuracy, for example to 0.02 to 0.10 millimeter, with dies, turbine blades, and precision
electronic components. The key to further advancement in PECM lies in development of a low
cost power supply. Successful development of technique will enable on-line monitoring of the
gap size, enabling closer process control.
Despite these attractions, PECM should be regarded as complementary to, and not a substitute
for, established ECM technology; the former is expensive and metal removal rates can be lower
than these of the latter.
The advent of new technology for controlling the ECM process and the development of new and
improved metal alloys, which are difficult to machine by conventional means, will assure the
future of electrochemical machining.
Appendix
Electrolysis
Reactions that occur during the electrolysis of copper sulphate (Figure 1) are as follows. The
anodic reaction is ionizing of copper:
Cu ==> Cu2+(aq) + 2e-
While at the cathode the copper ions are discharged to form copper metal:
Cu2+(aq) + 2e- ==> Cu
Reactions that occur during the electrolysis of iron (Figure 2) are as follows. The anodic reaction
is ionizing of iron:
Fe ==> Fe2+(aq) + 2e-
At the cathode, the reaction is likely to be the generation of hydrogen gas and the production of
hydroxyl ions:
H2O + 2e- ==> H2 + 2OH-
The net reaction is thus:
Fe + 2H2O ==> Fe(OH)2(s) + H2
The ferrous hydroxide may react to form ferric hydroxide:
4Fe(OH)2 + 2H2O + O2 ==> 4Fe(OH)3
Characteristics of ECM
By use of Faraday’s laws, if “md” (kg) is the mass of metal dissolved, and because “md = vd”
where “v” (m3) is the corresponding volume and “d” (kg/m3) the density of the anode metal, the
volumetric removal rate of anode metal (m3/second) is given by:
Where “a” (kg/mol) is the atomic weight of the anode metal, “I” (ampere) is the current flowing,
“z” is the ionic charge of the anode metal, and the Faraday constant “F” equals 96,487
coulombs/mol. If a machining operation has to be carried out on an iron workpiece at a typical
rate of 2.6 × 10-8 kg/C, for this removal rate to be achieved by ECM, the current in the cell must
be about 700 A, because “a/zF” = 29 × 10-8 and “d”= 7,860 kg/m3 for iron.
Rates of machining
By use of Faraday’s laws the rates at which metals can be electrochemically machined can be
calculated.
Where “md” (kg) is the mass of metal electrochemically machined by current “I” (ampere)
passed for a time “t” (second). The quantity “a/zF” is called the electrochemical equivalent of the
anode metal as mentioned before.
Table I shows the metal machining rates that can be obtained when a current of 1000 A is used in
ECM. Metal removal rates in terms of volumetric machining are often more useful than mass
removal rates, and both quantities are included. (It is assumed that the anodic current efficiency
is 100%, that is all the current is used to remove metal, which is not always the case.)
Table I. Metal machining rates
Metal Atomic Ionic Density Removal rate

weight charge 103 kg/m3 -3
10 kg/s 10-6 m3/s
Aluminum 26.97 3 2.67 0.093 0.035

Beryllium 9.0 2 1.85 0.047 0.025
Chromium 51.99 2 7.19 0.269 0.038
3 0.180 0.025
6 0.090 0.013
Cobalt 58.93 2 8.85 0.306 0.035
3 0.204 0.023
Niobium 92.91 3 9.57 0.321 0.034
(Columbium) 4 0.241 0.025
5 0.193 0.020
Copper 63.57 1 8.96 0.660 0.074
2 0.329 0.037
Iron 55.85 2 7.86 0.289 0.037
3 0.193 0.025
Magnesium 24.31 2 1.74 0.126 0.072
Manganese 54.94 2 7.43 0.285 0.038
4 0.142 0.019
6 0.095 0.013
7 0.081 0.011
Molybdenum 95.94 3 10.22 0.331 0.032
4 0.248 0.024
6 0.166 0.016
Nickel 58.71 2 8.90 0.304 0.034
3 0.203 0.023
Silicon 28.09 4 2.33 0.073 0.031
Tin 118.69 2 7.30 0.615 0.084
4 0.307 0.042
Titanium 47.9 3 4.51 0.165 0.037
4 0.124 0.028
Tungsten 183.85 6 19.3 0.317 0.016
8 0.238 0.012
Uranium 238.03 4 19.1 0.618 0.032
6 0.412 0.022
Zinc 65.37 2 7.13 0.339 0.048
Bibliography
• Electrochemical machining, J. A. McGeough, in “Kirk-Othmer Encyclopedia of
Chemical Technology” (5th edition), Vol. 9, pp 590-606, J. I. Kroschwitz (editor), Wiley-
Interscience, NY 2005.
• Machining methods: electrochemical, J. A. McGeough and X. K. Chen, in “Kirk-Othmer
Encyclopedia of Chemical Technology” (4th edition), Vol. 15, pp 608-622, J. I.
Kroschwitz and M. Howe-Grant (editors), Wiley-Interscience, NY 1995.
• A Study of Electrical Discharges in Electrolyte by High-Speed Photography, X. Ni, J. A.
McGeough, and C. A. Greated, “Journal of Electrochemical Society” Vol. 140, pp 3505-
3512, 1993.
• Study of Pulse Electrochemical Machining Characteristics, K. P. Rajurkar, J. Kozak, and
B. Wei, “Annals International College for Production Research” Vol. 42, pp 231-234,
1993.
• Jet and Laser-Jet Electrochemical Micromachining of Nickel and Steel, M. Datta, L. T.
Romankiw, D. R. Vigliotti, and R. J. Von Gutfeld, “Journal of Electrochemical Society”
Vol. 136, pp 2251-2256, 1989.
• Advanced Methods of Machining, J. A. McGeough, Chapman and Hall, London, 1988.
• Analysis of Electrochemical Arc Machining by Stochastic and Experimental Methods, A.
B. M. Khayry and J. A. McGeough, “Proceedings of the Royal Society of London” Vol.
A412, pp 403-429, 1987.
• An Electrochemical Machining Method for Removal of Samples and Defective Zones in
Metal Pipes, Vessels and Structures, D. Clifton, J. W. Midgley, and J. A. McGeough,
“Proceedings of the Institution of Mechanical Engineers, Part B, Journal of Engineering
Manufacture” Vol 201, pp 229-231, 1987.
• Surface Effects on Alloys Drilled by Electrochemical Arc Machining, A. DeSilva and J.
A. McGeough, “Proceedings of the Institution of Mechanical Engineers, Part B, Journal
of Engineering Manufacture” Vol. 200, pp 237-246, 1986.
• Analysis of Taper Produced on Side Zone During ECD, V. K. Jain and V. N. Nanda,
“Precision Engineering, Journal of the American Society for Precision Engineering” Vol.
8, No. 1, pp 27-33, 1986.
• Electrochemical Wirecutting, S. R. Ghabrail and C. F. Noble, in “Proceedings of the 24th
International Machine Tool Design and Research Conference” pp 323-328, B. J. Davies
(editor), Macmillan, Manchester, UK 1984.
• Drilling Without Drills, G. Bellows and J. D. Kohls, “American Machinist” pp 178-183,
1982.
• Deburring-2: Electrochemical Machining, D. Graham, “The Production Engineering”
Vol. 61, No. 6, pp 27-30, 1982.
• Comparative Studies of ECM, EDM and ECAM, I. M. Crichton, J. A. McGeough, W.
Munro, and C. White, “Precision Engineering” Vol. 3, pp 155-160, 1981.
• Aspects of Drilling by Electrochemical Arc Machining, T. Drake and J. A. McGeough, in
“Proceedings of the 21th Machine and Tool Design and Research Conference” pp 362-
369, J. M. Alexander (editor), Macmillan, New York, 1981.
• Basic Study of ECDM-II, M. Kubota, Y. Tamura, H. Takahahi, and T. Sugaya, “Journal
Association Electro-Machining” Vol. 13, No. 26, pp 42-57, 1980.
• Basic Study of ECDM-I, M. Kubota, Y. Tamura, J. Omori, and Y. Hirano, “Journal
Association Electro-Machining” Vol. 12, No. 23, pp 24-33, 1978.
• Newcomers for Production, G. Bellows, in “Non-Traditional Machining Guide 26” pp
28-29, Metcut Research Associates Inc., Cincinnati, Ohio, 1976.
• Electrochemical machining, J. Kaczmarek, in “Principles of Machining by Cutting,
Abrasion and Erosion” pp 487-513, Peregrinus, Stevenage UK, 1976.
• Principles of Electrochemical Machining, J. A. McGeough, Chapman and Hall, London,
1974.
Listings of electrochemistry books, review chapters, and proceedings volumes are also available
in the Electrochemistry Science and Technology Information Resource (ESTIR).
(http://electrochem.cwru.edu/estir/)
The Encyclopedia is hosted by the Ernest B. Yeager Center for Electrochemical Sciences (YCES) and the
Chemical Engineering Department , Case Western Reserve University , Cleveland, Ohio.
Copyright Notice.
Edited by Zoltan Nagy ( nagyz@email.unc.edu ), Department of Chemistry , The University of North
Carolina at Chapel Hill .
Return to: Top – Encyclopedia Home Page – Table of Contents – Author Index – Subject Index
– Search – Dictionary – ESTIR Home Page – YCES Home Page
Fig. 1. Operating principle of a fuel cell. (Copied from an article on

solid oxide fuel cells.)
As illustrated in Figure 1, the hydrogen and the oxygen gases are n

Ot
CORROSION INHIBITION
Corrosion reactions involve a metal or metal alloy and its fluid surroundings. All metals and
alloys are susceptible to corrosion by one or more naturally available or man-made fluids.
These reactions may cause a uniform loss of metal with consequent loss of cohesive strength or
simply an unacceptable change in appearance, for example tarnishing of gold or silver. There can
be local losses involving much less metal but leading to diminished whole piece strength.
Localized corrosion is exemplified by pitting or stress corrosion cracking.
Control of the corrosion rate can be affected by reducing the tendency of the metal to oxidize, by
reducing the aggressiveness of the medium, or by isolating the metal from the fluid. The latter
can be done by coating the metal with a millimeter thick impervious non-corroding coating.
These have wide spread use, but their effect may not be permanent because of breaks in the
coating over time. Also in some systems coating might interfere with the process for which the
equipment is used because they might change the heat transfer properties for example.
In cases where a fairly thick coating is not acceptable, the use of corrosion inhibitors comes into
play. These chemicals are continually fed into the fluid with the objective of having them move
to the metal-fluid interface. There the intact inhibitor molecule attaches to the metal, or it reacts
with the surface to form a thin adherent compound. In the first case they act by adsorption (Toth,
2002). In either case, the films are only one to a few molecules thick, that is nanometer
thickness.
Some inorganic (non-carbon) chemicals like the chromates function in both ways and do so very
well. However they are hazardous to human and animal health and are not normally used now.
Other inorganics like phosphates, borates, nitrites, and silicates function by reaction to form
micrometer thick films. They are used for some metals in near neutral (pH ~ 7) aqueous
solutions, for instance, in water treatment plants.
For many aqueous systems, for elevated temperature equipment, for crude oil production, etc.
organic (carbon based) chemicals find more use. These materials are likely to function by
adsorption. Here the organic molecule, which orients itself suitably, becomes attached to the
solid surface often via a less than total reaction between the inhibitor molecule and the solid
surface. The attachment does not require a total electron transfer in either direction. A coulumbic
force, for example ion-dipole attraction, suffices to attach the inhibitor molecule to the solid
surface. This in turn interferes with access of the corrosive entity to the surface.
The adsorbed layer can be formed all over the surface either in a single layer or as a multilayer or
a mixture of both. The more complete the coverage the better. This process has the advantage of
being molecularly thin and thus not too intrusive in heat conduction for example.
But there are problems. The amount of a given material adsorbed from a mixture depends on its
concentration, temperature, fluid flow rate, as well as on the nature of the adsorbent that is, the
solid surface. The film has to be kept intact by continually adding inhibitor to the medium to
maintain a predetermined concentration of inhibitor. The continuing concentration is generally
lower than that used initially, but both are at the milli-molar level.
That is not all. If temperature or flow rate of the system changes, the amount adsorbed is apt to
change. For temperature, the change is energetic, a basic change in the amount adsorbed. For
fluid flow, the change is dynamic, that is a change of fluid movement at the interface. This may
affect the amount left at the interface. Faster flow generally causes removal of some of the
physically adsorbed material from the solid surface.
To this point the object was to get you to visualize the system. The point now is to get some
insight into how the efficiency of inhibition is determined. Corrosion rates can be measured in a
variety of ways. In fact, corrosion rates can be determined from any measurable change
available. Examples are metal weight loss, rate of gaseous production, and changes in solution
composition. The basic approach is to expose small pieces of the metal in question to the fluid
environment, preferably under flow conditions. Measurement of the corrosion rate can be carried
out electrochemically or chemically. It is best to acquire not only the initial rate but also the
steady rate. The latter is more useful for practical purposes.
For weight
loss, plot the
change in
weight of each
cleaned
coupon (metal
sample) both
before and
after exposure
using multiple
samples. Each
one of these
can be
removed at
predetermined
times, see the
representative
curve Figure 1. Fig. 1. Weight loss of coupons.
The slope of
the curve at any point is the corrosion rate at that time. Note that the rate past point A is not quite
flat. The bottom curve shows the corrosion rate for the inhibited system. The weight loss of the
inhibited coupon divided by the loss of the uninhibited coupon provides a measure of inhibition
efficiency.
To repeat, the rates can be determined from any quantity which changes regularly as a function
of time. Thus, change in solution concentration of iron (for steels), pH of the solution, or weight
of metal coupon can be used.
There are some caveats. Laboratory experiments are useful in screening candidate inhibitors.
Following that, they should be subjected to a lab system that emulates conditions in the field,
composition of the fluid, temperature and its changes, flow rates and their changes, time, and so
on. Then there should be tests in the real system itself, at least long enough to cover any
condition cycles the system may have. However, continuous exposure with ongoing data output
is best.
To repeat, inhibitors are useless if they do not reach the metal surface intact. They can be lost by
reaction with chemicals in the stream or to “thieves” in the system, that is any other solid surface
exposed to the fluid stream like sand. Also, the inhibitor should not be detrimental to either
process or product. Further, since the system may change with time, so must the corrosion
control. Thus the control system must be monitored consistently.
The question may be asked, why go to all of the trouble that is entailed in using corrosion
inhibitors? There are two important reasons to do so.
First, there is the matter of safety. Industrial corrosion can lead to process breakdowns that
culminate in explosions or the venting of chemicals dangerous to health. In either case the ounce
of prevention looms large over the pound of cure.
Second, there is the matter of cost. An article in 1995 (Battelle) estimated the cost of corrosion in
the United States per year was $300 billion, an appreciable portion of the Gross Domestic
Product. It also estimated that 30% of that amount could be saved by corrosion control, which of
course includes corrosion inhibition.
Related articles
Anodizing
Electrochemistry of corrosion
Bibliography
• Fundamental Behavior of Model Corrosion Inhibitors, M. Knag, "Journal of Dispersion
Science and Technology" Vol. 27, pp 587-597, 2005.
• Adsorption: Theory, Modeling, and Analysis, J. Toth (editor), Marcel Dekker, New York,
2002.
• Corrosion Inhibitors: Principles and Applications, V. Sastri, Wiley New York, 1998.
• Economic Effects of Metallic Corrosion in the United States, Battelle Columbus
Laboratories, Columbus OH, 1995.
• Corrosion Inhibitors: an Industrial Guide (2nd edition), E. Flick, Noyes, Park Ridge NJ,
1993.
• Chemical Inhibitors for Corrosion Control, B. G. Clubley (editor), Royal Society of
Chemistry, Cambridge, UK 1990.
• Organic-Compounds as Corrosion-Inhibitors in Different Environments - a Review, B.
Sanyal, "Progress in Organic Coatings" Vol. 9, pp 165-236, 1981.
DIELECTRICS
William D. Brown,1 Dennis Hess,2 Vimal Desai,3 and M. Jamal Deen4
1
Department of Electrical Engineering, University of Arkansas
3217 Bell Engineering Center, Fayetteville, AR 72701, USA
2
School of Chemical and Biomolecular Engineering, Georgia Institute of Technology
311 Ferst Drive, Atlanta, GA 30332, USA
3
Mechanical, Materials and Aerospace Engineering, University of Central Florida
4000 Central Florida Blvd., Orlando, FL 32816, USA
4
Electrical and Computer Engineering, McMaster University
1280 Main Street West, Hamilton, ON L8S 4K1, Canada
(May, 2006)
What is a dielectric? An historical perspective
The science of
dielectrics, which has
been pursued for well
over one hundred
years, is one of the
oldest branches of
physics and has close
links to chemistry,
materials, and
electrical engineering.
The term dielectric
was first coined by
Faraday to suggest
that there is
something analogous
to current flow
through a capacitor
structure during the
charging process
when current
introduced at one
plate (usually a metal)
flows through the
insulator to charge
another plate (usually
a metal). The
important
consequence of
imposing a static
external field across
the capacitor is that
the positively and
negatively charged
species in the Fig. 1. Schematic representation of different
dielectric become mechanisms of polarization.
polarized. Charging occurs only as the field within the insulator is changing. Maxwell
formulated equations for electromagnetic fields as they are generated from displacement of
electric charges and introduced dielectric and magnetic constants to characterize different media.
It is generally accepted that a dielectric reacts to an electric field differently, compared to free
space, because it contains charges that can he displaced. Figure 1 illustrates some of the charge
configurations and their response (polarization) under the influence of an external field. Because
almost all material systems are made up of charges (an exception being neutron stars!), it is
useful to characterize materials by their dielectric constant.
A schematic
representation of the
real part of the
dielectric constant is
shown in Figure 2. At
high frequencies
(>1014 Hz), the
contribution comes
solely from electronic
polarization, implying
that only free
electrons, as in
metals, can respond to
the electric field. That
is why metals are
such good optical
reflectors! Even the
various thermal and
mechanical Fig. 2. Contributions to the frequency-
properties, such as dependent dielectric constant from the different
thermal expansion, charge configurations.
bulk modulus,
thermal conductivity, specific heat, and refractive index, are related to the complex dielectric
constant, because they depend on the arrangement and mutual interaction of charges in the
material. Thus, the study of dielectrics is fundamental in nature and offers a unified
understanding of many other disciplines in materials science.
The scope of dielectric science and technology
In time, the focus on
dielectric science and Table I. Core Areas of Dielectric
technology has broadened Science and Technology
from the materials of the
traditional dielectric films Physics/Chemistry/Materials
used in semiconductor Science
devices and capacitors,
particularly oxides and
nitrides. More recently, • Polarizability, Relaxation,
materials of unique Ions, Breakdown Phenomena
dielectric responses have • Elementary Excitations:
been studied and utilized in Polaritons, Excitons, Polarons,
novel ways. Table I lists Phonons
many of the core
• Phase Transitions, Critical
technology areas of interest
Phenomena
to those involved in
dielectric science and • Bonding, Ionicity,
technology. Crystal/Ligand Fields,
Electronic Correlation
For instance, in the not too
distant past, polymer • Bonding, Reaction, Kinetics,
scientists and technologists Transport, Energetics,
expanded their horizons Thermodynamics
from consumer products to • Interfaces, Interphases
the high technology arena.
Particularly notable are
inventions in Properties of Dielectrics
telecommunications, where
plastic fibers are used for • Structural/Mechanical
short optical data links, and
polymeric films are used • Thermal
for nonlinear optics • Electrical
applications. In the field of • Optical
microelectronics, radiation
sensitive polymers • Magnetic
(photoresists) have been • Chemical
formulated for use with a
wide variety of exposure
systems, from the early Synthesis/Processing
ones using visible light to
those using near ultraviolet, • Deposition: Chemical Vapor
laser, e-beam, and x-ray Deposition CVD, Plasma-
sources, for the fabrication CVD, Room Temperature
of the sub-micrometer (RT)CVD, Physical Vapor
structures of high speed, Deposition (PVD), Sputtering.
high density integrated Evaporation, Dip/Spin/Spray
circuits. Steady progress Coating
has also been made in the
field of passivation, where • Growth: Thermal, Anodic,
Epitaxial
various polymeric films are applied to microscopic objects such as integrated circuits and the
packages that house them.
Ceramists have also extended the range of applications; ceramic materials are used in packages
for semiconductor integrated circuits, as well as in automobile engines, in composites for
aerospace vehicles, and in high efficiency power generation stations. A notable advance was the
discovery of high-temperature superconductivity, for which Bednorz and Muller were awarded
the Nobel Prize in Physics in 1987.
Electronic and optical engineers are pushing the limits of the material properties and applications
of organic and inorganic conductors, semiconductors, and insulators. One example is the revived
interest in diamond and diamond-like films. These recent efforts resulted in higher speed, higher
density devices and interconnection schemes, both electrical and optical, for computers and
telecommunication systems. Another example, the low-dimensional (d = 1, 2) nanostructures,
which could only be speculated about in the past, are now a reality. This allows researchers to
test some fundamental concepts in quantum mechanics. It is probable that more innovative
devices will follow.
Since the mid-1990s, the microelectronics industry has invested heavily, with some success, in
the development of high- and low-k dielectrics (“k” is the dielectric constant of a material).
These materials are required because of the continuing reduction of both horizontal and vertical
dimensions of integrated circuits (ICs), which results in an increase of the gate leakage current,
and consequently, an increase in heat dissipation. Therefore, high-k materials are needed for the
gate dielectric in complementary metal-oxide-semiconductor (CMOS) ICs, storage capacitors,
and nonvolatile static memory devices. Similarly, the reduction in spacing of metal interconnects
in both the vertical and horizontal dimensions has created the need for low-k materials that serve
as interlevel dielectrics to offset the increase in signal propagation time between transistors,
known as RC delay (“R” is metal wire resistance and “C” is interlevel dielectric capacitance). As
a result of these requirements for present and future sub-100 nm IC technologies, many new
dielectric materials and material combinations have been and must continue to be created and
characterized if the device density of ICs is to continue to increase as anticipated by Moore’s
Law.
The previous discussion is not intended to suggest that dielectric science and technology is only
important for electronic components. Far from it; dielectrics play important roles in applications
ranging from sensors, isolation for conductors in the power utility industry, to ceramic cookware.
Further, in the rapidly emerging field of biological systems, the dielectric constant is important
because electrostatic effects are used to link the structure and function of biological molecules. It
has been proposed that electrostatic effects play a major role in important biological activities
such as enzyme catalysis, electron transfer, proton transport, ion channels, and signal
transduction. The role of the science and technology of dielectrics is also important in existing
fields of sensors, nanotechnology, electronics, photonics, chemical and mechanical systems, and
in emerging fields of biology and biochemistry. Thus, it appears inevitable that the dielectric
properties of nanoscale materials and structures will be critical to developing novel devices for
current and future commercial applications. For example, large amounts of energy can be stored
in nanocomposites that show large polarizabilities. In addition, dielectric materials such as
ferroelectric and piezoelectric nanomaterials offer significant advantages for communication
devices and data storage systems. Recently, there have been investigations of nanoporous
composites formed by the incorporation of nanosize air bubbles, leading to a significant decrease
in the dielectric constant and the ability to vary the dielectric constant by controlling the
concentration of air bubbles. Furthermore, the continuing trend in miniaturization requires
increasingly thinner dielectric materials without nanoscale defects. An understanding of material
and interfacial properties at the nanoscale is often facilitated by materials modeling as well as the
development of innovative characterization tools. One such tool is the development of the
scanning nonlinear dielectric microscope (SNDM) that can be used to measure the microscopic
point-to-point variation of the linear and nonlinear dielectric properties of insulators.
Future requirements and achievements in the area of dielectrics can be realized only by the
further development and fundamental understanding of reliable material synthesis, processing,
and characterization technologies, making it possible to tailor dielectric materials, their thin film
structures, and their interfaces to specific applications. In the past, these technologies have been
successfully applied in the microelectronics and other industries that depend on the unique
mechanical, optical, chemical, and electrical properties of high performance dielectric materials.
The advent of nanoscale devices in recent years demands that scientists and engineers continue
to focus attention on dielectric material design, synthesis, and characterization for enhanced
performance, reliability, and manufacturability.
Figure 3 is an
attempt to
depict the
multitude of
interactions
among the
many and
diverse core
areas of
dielectric
science and
technology
that present
challenging
possibilities Fig. 3. Interactions among the core areas of dielectric science
for the and technology.
community of
scientists, engineers, and technologists in research, development, and manufacturing.
Acknowledgement
This article was reproduced from The Electrochemical Society Interface (Vol. 15, No. 1, Spring
2006) with permission of The Electrochemical Society, Inc. and the authors.
Bibliography
• Material Science and Engineering for the 1990s, National Academy of Science Press,
Washington, 1989.
• Introduction to Ceramics (2nd edition), W. D. Kingery, H. K. Bowen, and D. R. Uhlmann,
pp 918 et seq., Wiley, New York, 1976.
• Introduction to Solid State Physics (4th edition), C. Kittel, Wiley, New York, 1971.
• Solid State Physics, Advances in Research and Applications, F. Seitz, D. Turnbull, and
H. Ehrenreich, Academic Press, New York, 1969.
• Theory of Quantum Liquids, D. Pines and P. Nozieres, p. 280, Benjamin, New York,
1966.
Copyright Notice.
DIELECTRICS
William D. Brown,1 Dennis Hess,2 Vimal Desai,3 and M. Jamal Deen4
1
Department of Electrical Engineering, University of Arkansas
3217 Bell Engineering Center, Fayetteville, AR 72701, USA
2
School of Chemical and Biomolecular Engineering, Georgia Institute of Technology
311 Ferst Drive, Atlanta, GA 30332, USA
3
Mechanical, Materials and Aerospace Engineering, University of Central Florida
4000 Central Florida Blvd., Orlando, FL 32816, USA
4
Electrical and Computer Engineering, McMaster University
1280 Main Street West, Hamilton, ON L8S 4K1, Canada
(May, 2006)
What is a dielectric? An historical perspective
The science of
dielectrics, which has
been pursued for well
over one hundred
years, is one of the
oldest branches of
physics and has close
links to chemistry,
materials, and
electrical engineering.
The term dielectric
was first coined by
Faraday to suggest
that there is
something analogous
to current flow
through a capacitor
structure during the
charging process
when current
introduced at one
plate (usually a metal)
flows through the
insulator to charge
another plate (usually
a metal). The
important
consequence of
imposing a static
external field across
the capacitor is that
the positively and
negatively charged
species in the Fig. 1. Schematic representation of different
dielectric become mechanisms of polarization.
polarized. Charging
occurs only as the
field within the insulator is changing. Maxwell formulated equations for electromagnetic fields
as they are generated from displacement of electric charges and introduced dielectric and
magnetic constants to characterize different media. It is generally accepted that a dielectric reacts
to an electric field differently, compared to free space, because it contains charges that can he
displaced. Figure 1 illustrates some of the charge configurations and their response (polarization)
under the influence of an external field. Because almost all material systems are made up of
charges (an exception being neutron stars!), it is useful to characterize materials by their
dielectric constant.
A schematic
representation of the
real part of the
dielectric constant is
shown in Figure 2. At
high frequencies
(>1014 Hz), the
contribution comes
solely from electronic
polarization, implying
that only free
electrons, as in
metals, can respond to
the electric field. That
is why metals are
such good optical
reflectors! Even the
various thermal and
mechanical
properties, such as Fig. 2. Contributions to the frequency-
thermal expansion, dependent dielectric constant from the different
bulk modulus, charge configurations.
thermal conductivity,
specific heat, and refractive index, are related to the complex dielectric constant, because they
depend on the arrangement and mutual interaction of charges in the material. Thus, the study of
dielectrics is fundamental in nature and offers a unified understanding of many other disciplines
in materials science.
The scope of dielectric science and technology
In time, the focus on
dielectric science and Table I. Core Areas of Dielectric
technology has broadened Science and Technology
from the materials of the
traditional dielectric films Physics/Chemistry/Materials
used in semiconductor Science
devices and capacitors,
particularly oxides and
nitrides. More recently, • Polarizability, Relaxation,
materials of unique Ions, Breakdown Phenomena
dielectric responses have • Elementary Excitations:
been studied and utilized in Polaritons, Excitons, Polarons,
novel ways. Table I lists Phonons
many of the core
• Phase Transitions, Critical
technology areas of interest
Phenomena
to those involved in
dielectric science and • Bonding, Ionicity,
technology. Crystal/Ligand Fields,
Electronic Correlation
For instance, in the not too
distant past, polymer • Bonding, Reaction, Kinetics,
scientists and technologists Transport, Energetics,
expanded their horizons Thermodynamics
from consumer products to • Interfaces, Interphases
the high technology arena.
Particularly notable are
inventions in Properties of Dielectrics
telecommunications, where
plastic fibers are used for • Structural/Mechanical
short optical data links, and
polymeric films are used • Thermal
for nonlinear optics • Electrical
applications. In the field of • Optical
microelectronics, radiation
sensitive polymers • Magnetic
(photoresists) have been • Chemical
formulated for use with a
wide variety of exposure
systems, from the early Synthesis/Processing
ones using visible light to
those using near ultraviolet, • Deposition: Chemical Vapor
laser, e-beam, and x-ray Deposition CVD, Plasma-
sources, for the fabrication CVD, Room Temperature
of the sub-micrometer (RT)CVD, Physical Vapor
structures of high speed, Deposition (PVD), Sputtering.
high density integrated Evaporation, Dip/Spin/Spray
circuits. Steady progress Coating
has also been made in the
field of passivation, where • Growth: Thermal, Anodic,
Epitaxial
various polymeric films are applied to microscopic objects such as integrated circuits and the
packages that house them.
Ceramists have also extended the range of applications; ceramic materials are used in packages
for semiconductor integrated circuits, as well as in automobile engines, in composites for
aerospace vehicles, and in high efficiency power generation stations. A notable advance was the
discovery of high-temperature superconductivity, for which Bednorz and Muller were awarded
the Nobel Prize in Physics in 1987.
Electronic and optical engineers are pushing the limits of the material properties and applications
of organic and inorganic conductors, semiconductors, and insulators. One example is the revived
interest in diamond and diamond-like films. These recent efforts resulted in higher speed, higher
density devices and interconnection schemes, both electrical and optical, for computers and
telecommunication systems. Another example, the low-dimensional (d = 1, 2) nanostructures,
which could only be speculated about in the past, are now a reality. This allows researchers to
test some fundamental concepts in quantum mechanics. It is probable that more innovative
devices will follow.
Since the mid-1990s, the microelectronics industry has invested heavily, with some success, in
the development of high- and low-k dielectrics (“k” is the dielectric constant of a material).
These materials are required because of the continuing reduction of both horizontal and vertical
dimensions of integrated circuits (ICs), which results in an increase of the gate leakage current,
and consequently, an increase in heat dissipation. Therefore, high-k materials are needed for the
gate dielectric in complementary metal-oxide-semiconductor (CMOS) ICs, storage capacitors,
and nonvolatile static memory devices. Similarly, the reduction in spacing of metal interconnects
in both the vertical and horizontal dimensions has created the need for low-k materials that serve
as interlevel dielectrics to offset the increase in signal propagation time between transistors,
known as RC delay (“R” is metal wire resistance and “C” is interlevel dielectric capacitance). As
a result of these requirements for present and future sub-100 nm IC technologies, many new
dielectric materials and material combinations have been and must continue to be created and
characterized if the device density of ICs is to continue to increase as anticipated by Moore’s
Law.
The previous discussion is not intended to suggest that dielectric science and technology is only
important for electronic components. Far from it; dielectrics play important roles in applications
ranging from sensors, isolation for conductors in the power utility industry, to ceramic cookware.
Further, in the rapidly emerging field of biological systems, the dielectric constant is important
because electrostatic effects are used to link the structure and function of biological molecules. It
has been proposed that electrostatic effects play a major role in important biological activities
such as enzyme catalysis, electron transfer, proton transport, ion channels, and signal
transduction. The role of the science and technology of dielectrics is also important in existing
fields of sensors, nanotechnology, electronics, photonics, chemical and mechanical systems, and
in emerging fields of biology and biochemistry. Thus, it appears inevitable that the dielectric
properties of nanoscale materials and structures will be critical to developing novel devices for
current and future commercial applications. For example, large amounts of energy can be stored
in nanocomposites that show large polarizabilities. In addition, dielectric materials such as
ferroelectric and piezoelectric nanomaterials offer significant advantages for communication
devices and data storage systems. Recently, there have been investigations of nanoporous
composites formed by the incorporation of nanosize air bubbles, leading to a significant decrease
in the dielectric constant and the ability to vary the dielectric constant by controlling the
concentration of air bubbles. Furthermore, the continuing trend in miniaturization requires
increasingly thinner dielectric materials without nanoscale defects. An understanding of material
and interfacial properties at the nanoscale is often facilitated by materials modeling as well as the
development of innovative characterization tools. One such tool is the development of the
scanning nonlinear dielectric microscope (SNDM) that can be used to measure the microscopic
point-to-point variation of the linear and nonlinear dielectric properties of insulators.
Future requirements and achievements in the area of dielectrics can be realized only by the
further development and fundamental understanding of reliable material synthesis, processing,
and characterization technologies, making it possible to tailor dielectric materials, their thin film
structures, and their interfaces to specific applications. In the past, these technologies have been
successfully applied in the microelectronics and other industries that depend on the unique
mechanical, optical, chemical, and electrical properties of high performance dielectric materials.
The advent of nanoscale devices in recent years demands that scientists and engineers continue
to focus attention on dielectric material design, synthesis, and characterization for enhanced
performance, reliability, and manufacturability.
Figure 3 is an
attempt to
depict the
multitude of
interactions
among the
many and
diverse core
areas of
dielectric
science and
technology
that present
challenging
possibilities Fig. 3. Interactions among the core areas of dielectric science
for the and technology.
community of
scientists, engineers, and technologists in research, development, and manufacturing.
Acknowledgement
2006) with permission of The Electrochemical Society, Inc. and the authors.
Bibliography
• Material Science and Engineering for the 1990s, National Academy of Science Press,
Washington, 1989.
• Introduction to Ceramics (2nd edition), W. D. Kingery, H. K. Bowen, and D. R. Uhlmann,
pp 918 et seq., Wiley, New York, 1976.
• Introduction to Solid State Physics (4th edition), C. Kittel, Wiley, New York, 1971.
• Solid State Physics, Advances in Research and Applications, F. Seitz, D. Turnbull, and
H. Ehrenreich, Academic Press, New York, 1969.
• Theory of Quantum Liquids, D. Pines and P. Nozieres, p. 280, Benjamin, New York,
1966.
Copyright Notice.
ELECTROCHEMICAL CAPACITORS
Their Nature, Function, and Applications
Brian E. Conway
Chemistry Department, University of Ottawa
10 Marie Curie Street
Ottawa, Ontario K1N 6N5, Canada
(March, 2003)
Historical introduction
Electrochemical capacitors provide a mode of electrical charge- and energy-storage and delivery,
complementary to that by batteries. The first electrochemical capacitor device was disclosed in a
General Electric Co. patent in 1957 to Becker but was of a crude nature, employing porous
carbon. Later work by Sohio (1969) described a so-called "electrokinetic capacitor" utilizing
porous carbon in a non-aqueous electrolyte which enabled it to be charged up to about 3 V,
though the operation of the device was not "electrokinetic" in nature, a misnomer. In 1971,
Trasatti and Buzzanca recognized that the electrochemical charging behavior of ruthenium
dioxide films was like that of capacitors. Between 1975 and 1980, the present author and his co-
workers, under contract with the then Continental Group Inc., carried out extensive fundamental
and development work on the ruthenium oxide type of electrochemical capacitor (Conway,
1997) which behaves as a surface- redox pseudocapacitance (see below). The whole field has
burgeoned since about 1990 and is very active in fundamental, and R&D directions.
A great deal of scientific and technological research has been reported in the scientific literature
since about 1990. An extensive and detailed account of this has been given in the author's
monograph on "Electrochemical Supercapacitors: Scientific Fundamentals and Technological
Applications" (1999).
Scientific introduction
In order to describe "electrochemical capacitors" and to explain their function and applications, it
is necessary first to consider the nature of an ordinary electrostatic capacitor or a "condenser" as
it used to be called, and thence the meaning of the term electrical capacitance.
The nature of electricity took a long time to be understood, from the early experiments on
electrostatic electricity in the mid-18th century, for example by Galvani, through the time of the
invention of the first electric battery by Alessandro Volta (Volta's "Pile") in 1800, on to
Faradays's and Davy's monumental discoveries on the chemical origin of electricity generated by
Volta's pile. At first, two "kinds" of electricity were postulated: "animal electricity", as in the
works of Galvani on stimulation of the frog's leg nerve by contact between two dissimilar metals
and later, "Voltaic electricity" generated chemically from a Volta pile of zinc and silver or
copper plates separated by paper wetted with an acid or salt solution (Conway, 2000).
In parallel with these discoveries were extensive works on electrostatic electricity generated for
example by the rubbing of naturally occurring amber or by the so-called Wimshurst machine (a
rotating circular plate, containing insets of amber-like material, rubbing against charge-collector
plates connected overall to a Leyden Jar or a spark-gap). It was from this direction of research on
electricity that the invention of the electric condenser arose, referred to as the "Leyden Jar", and
capable of storing electric charge generated by a Wimshurst machine. Such a jar had the
"capacity", depending on its dimensions and materials of construction, of storing electric charge
by bringing it together in a condensed way (hence the term "condenser") on the surfaces of a
Leyden Jar at a certain two-dimensional charge density.
The principle of design and operation of the Leyden Jar and all subsequent regular condensers or
capacitor devices, is as follows. Two metal surfaces that constitute electrodes are separated at
some small distance either in air (or vacuum) or on each side of a liquid or solid film, referred to
as the "dielectric", a term first used by Michael Faraday . For a given separation of the electrode
plates, the capacitance developed per unit area of the two plates depends on the properties of the
dielectric between the plates characterized by its so-called dielectric constant.
In the case of the Leyden Jar (Figure
1), the material (glass) of the jar itself
serves a the dielectric medium and
the contact plates were metal foils
wrapped, inside and out, around the
cylindrical surfaces of the jar. The
electrical contact to the inner surface
foil was by means of a conducting
electrolyte solution (or originally by
ordinary water itself) in which was
immersed a conducting metal
electrode for electrical contact. The
device was charged by joining two
wires from the inside electrode and
the outside foil to an electrostatic
machine of the Wimshurst type. In Fig. 1. Leyden
later experimentation, the Leyden Jar Jar, the first
capacitor was connected to the capacitor or
electrodes of a Volta's pile or battery "condenser".
for charging. This was the first-
generation capacitor for storage of electric charge.
The nature of electric charge remained elusive until much later (1897) when J.J. Thomson
identified and characterized the fundamental entity of electric charge as the "electron", present
ubiquitously in all atoms of the Universe and identified, in his experiments, by means of
experiments on gases at low pressures in gas-discharge tubes (Crookes tubes or neon lights). The
electron charge was determined independently by Townsend and by Millikan (Glasstone, 1940),
and was shown to be equivalent to Faraday's constant for the relation between extent of passage
of charge and extent of chemical change (as related by Faraday's Laws) caused by electrolysis of
conducting solutions, when calculated on a "per gram-atom" or "gram-equivalent" basis.
Relation of capacitance to geometry and dielectric constant of a capacitor
The capacitance of a capacitor is proportional to the area of the contact plates and the dielectric
constant of the medium between the plates, and it is inversely proportional to the separation
between the plates (see the Appendix). In relation to electrochemical capacitors, to be discussed
below, the capacitance of small dielectric capacitors is very small being on the order of
microfarads or nanofarads (millionth or billionth of a farad, respectively) for small devices on
the order of mm or cm in dimensions. By having very thin insulating films, on the order of 10 to
100 nanometers, formed anodically on the plate of a two-electrode capacitor, substantially larger
specific capacitances (that is per cm2) can be attained. Such devices are called "electrolytic
capacitors" because the thin dielectric oxide films are formed on the plates by an anodic
electrolysis procedure applied at metals such as aluminum, tantalum, titanium, niobium, etc.
Such capacitors are still of the dielectric type (the dielectric medium being here the thin,
insulating oxide film, usually having a relatively high dielectric constant) and should not be
confused with the "electrochemical" capacitor type of device which is the topic of this article.
Electrochemical capacitors are a special kind of capacitor based on charging and discharging the
interfaces of high specific-area materials such as porous carbon materials or porous oxides of
some metals. They can store electric charge and corresponding energy at high densities in an
highly reversible way, as does a regular capacitor, and hence can be operated at specific power
densities (in watts/kg) substantially higher than can most batteries. Their capacitance for a given
size of the device is thus much higher, by a factor of 10,000 or so, than those achievable with
regular capacitors. For this reason proprietary names such as "Supercapacitors" or
"Ultracapacitors" have been coined to describe their performance.
While they function formally like rechargeable batteries in storing or delivering electric charge,
their mechanisms of charge storage are quite different, in most cases, from those operating in
batteries. Thus, electrochemical capacitors are not substitutes for batteries but rather are to be
regarded as complementary to them for charge storage or delivery. They can offer
advantageously fast charging or discharging rates over most batteries of comparable volume but
their energy density is usually less, by a factor of 3 to 4, than that of batteries. Their high power
or power densities, however, enables them to be employed in interesting complementary ways in
hybrid systems with batteries.
An important difference between charging a capacitor and charging a battery is that there is
always an intrinsic increase of voltage on charge (or decrease on discharge) of a capacitor as the
charge per cm2 is increased or decreased. In contrast, an ideal battery has a constant voltage
during discharge or recharge except as the state of charge approaches 0 or 100%. Although
practical batteries exhibit some dependence of cell voltage on state of charge, especially lithium-
intercalation batteries, the latter for fundamental reasons arising from intercalation. (See the
Appendix for further details.)
The double-layer capacitance at electrode interfaces
Nature of electrical double layers
An important
class of
electrochemical capacitors utilizes the co-called double-layer capacitance that arises at all
electrode interfaces with electrolyte solutions or ionic melts. The concept and model of the
double layer arose in the work of von Helmholtz (1853) on the interfaces of colloidal
suspensions and was subsequently extended to surfaces of metal electrodes by Gouy, Chapman,
and Stern, and later in the notable work of Grahame around 1947. Models of the double layer are
shown in Figure 2, with their capacitor-like structures.
Helmholtz envisaged a capacitor-like separation of anionic and cationic charges across the
interface of colloidal particles with an electrolyte. For electrode interfaces with an electrolyte
solution, this concept was extended to model the separation of "electronic" charges residing at
the metal electrode surfaces (manifested as an excess of negative charge densities under negative
polarization with respect to the electrolyte solution or as a deficiency of electron charge density
under positive polarization), depending in each case, on the corresponding potential difference
between the electrode and the solution boundary at the electrode. For zero net charge, the
corresponding potential is referred to as the "potential of zero charge".
In response to positive or negative electric polarization of the electrode relative accumulations of
cations or anions develop, respectively, at the solution side of the charged electrode. If, for
energetic reasons, the ions of the electrolyte are not faradaically dischargeable (that is no
electron transfer can occur across the interface ("ideally polarizable electrode", for example a
mercury electrode, Grahame 1947 and Parsons 1954), then an electrostatic electrical equilibrium
is established at the interface resulting in a "double layer" of separated charges (electrons or
electron deficiency at the metal side and cations or anions at the solution side of the interface
boundary), negative and positive, across the interface.
The difference of potential extends beyond the immediate layer of solvated ions in the compact,
capacitor-like (Helmholtz) region, out into solution, so that a further diffuse region capacitance
(the diffuse-layer capacitance "Cdiff") arises. It combines with that of Helmholtz's region "CH" in
series. (See the Appendix for further details.)
The Helmholtz region capacitance "CH" is of special significance for electrochemical capacitors
since it is directly dependent on accessible electrode area and has large values (relative to those
for regular dielectric capacitors) between about 16 µF/cm2 and about 40-50 µF/cm2, depending
on electrode potential, the chemical nature of the metal surface, chemical nature of the solvent,
and the types of ions (and their solvation by the solvent) present in the electrolyte solution.
The most extensively studied metal surface, with respect to its double-layer capacitance, is that
of mercury in various solvent media, especially water.
It was mentioned that the specific capacitances of electrode double layers are very large, some
10,000 times those of ordinary dielectric capacitors, per cm2 area. The reason for this is that the
separation of charges in electrochemical double layers is on the order of 0.3-0.5 nm instead of 10
to 100 nm with oxide-film dielectrics (electrolytic capacitors) or 1000 nm with very thin mica or
polystyrene dielectric-film hardware capacitors.
Hence, it is seen that with large specific-area porous electrodes, for example at carbons having
say 1000 m2/g of material and exhibiting, say, 15 µF/(real cm2) of double-layer capacitance in
some suitable electrolyte solution, the accessible capacitance "C" is 1000 (m2/g) × 10,000
(cm2/m2) × 15 (µF/cm2) = 150 million µF/g, that is 150 farads/g, a very large capacitance! Hence
the term "supercapacitors" or "ultracapacitors" for devices based on double-layer capacitance at
high-area substrates.
The high degree of reversibility of charge acceptance and delivery, and hence capability for
excellent operating power levels compared with batteries of comparable size arises because no
slow chemical processes or phase changes take place between charge and discharge as they do in
most battery-type electrical charge generating devices.
It is the essence of battery-type charge/discharge processes that faradaic processes take place
leading to major chemical and structural changes of the electrochemical reactive materials, for
example conversions of lead dioxide to lead sulfate and lead metal to lead sulfate in discharge of
the lead-acid battery which, as is well known, limits charge/discharge to a cycle life of 1000 to
3000, depending on rates of charge and discharge, and temperature. By contrast, electrochemical
double-layer and oxide-type (see below) capacitors can exhibit cycle lives up to one million
under suitable conditions. This is because, ideally at least, only storage and delivery of
electrostatic charge takes place at the extended two-dimensional interface of high-area materials
and no irreversible or slow chemical phase changes take place as they do between three-
dimensional chemical materials in rechargeable batteries. This is a fundamental difference
between the electrochemical behavior and properties of electrochemical capacitors relative to
those of batteries.
Electrical irreversibility in electrochemical capacitor charging and discharge:
rate effects
It was stated earlier in this article that charging and discharging of electrochemical capacitors has
commonly been perceived as a process much more reversible than that for batteries and hence
being capable of operation at high power densities. While, in practice, this is largely true,
charging of the high-area, porous-electrode structures that are required for achieving large
capacitance densities (farads/g or farads/cm3) encounters limitations of rate due to the distributed
electrolytic and contact resistances within the pore structure of such materials.
In the
simplest
analysis, any
practical
capacitor
device
behaves as if
an ohmic
resistance is
in series with
it, the so-
called
equivalent (or
real) series
resistance
(Figure 3).
The presence
of real or
equivalent
series
resistance in
the operating
equivalent
circuit of any
capacitor
introduces an
ir potential
drop in the
process of
charging or
discharging
and this drop
Fig. 3. Hierarchy of equivalent circuits for capacitors and
depends, of
electrochemical capacitors showing "transmission-line" circuit
course, on the
for the latter, in the case of a porous carbon electrode.
charging rate
(current)
leading to distortion of the charging curve of accumulated charge against voltage, in time. When
the distributed resistance effect also operates, as it normally does, the distortion effect becomes
more complex but has been experimentally and computationally evaluated (de Levie, 1963).
The above effect causes limitation of rates at which the capacitor can be charged or discharged
and, for ac modulated charging, it also introduces a frequency-dependent phase angle (normally
-90o) between the modulated applied voltage and the resultant charging current. This also applies
to other, non-constant charging modes.
In practice,
with a porous
electrode, the
situation is
much more
complex since
the matrix of
microscopic
pores within
the
macroscopic
electrode
structure
offers a
complex,
series/parallel
equivalent
circuit
comprised of
a distribution Fig. 4. de Levie transmission-line model for
of ohmic resistance/capacitance matrix in an high-area porous
(resistive) and electrode.
capacitive
elements which leads to the whole electrode having a non-uniform effective resistance and
capacitance, dependent on frequency (in ac modulation) or on the time-scale of pulsed or non-
constant rates of charging. As shown in the classical work of de Levie (1963), the equivalent
circuit for such electrodes is that of a transmission line (Figure 4) having a -45o phase angle
(Figure 5) characterizing its impedance behavior.
This situation leads to

limitation of the rates
of which charging or
discharging of porous
capacitor electrodes
can be conducted and
is additional to any
equivalent series
resistance effects a
practical cell may
experience due to cell
design and electrolyte
resistance.
Fig. 5. Complex-plane impedance plots
de Levie has pointed (imaginary capacitive component against real
out that the ohmic component) for a porous electrode
distributed R/C effect according to de Levie.
in porous electrodes
is equivalent to
restrictions of power due to ohmic ir drop (that is the potential drop due to current passing
through resistive elements in the matrix). Thus there is a "penetration effect" into the electrode
matrix due to attenuation of for example a modulation or time-dependent transient charging
voltage so that not all of the depth or width, or diameter of the electrode structure is subject to a
uniform charging rate. This introduces a non-chemical irreversibility in the charge/discharge
behavior of the electrochemical capacitor device which is electrically demonstrable.
It must be stated, however, that in state-of-the-art developments of electrochemical capacitors,
using aqueous-solution electrolytes, the above distributed-resistance effect has been substantially
minimized so that devices having high operating power have been successfully engineered and
marketed. Nevertheless, with non-aqueous electrolyte capacitors, which have higher operating
voltages up to 3.0 to 3.5 V (hence 9 to 12 times energy density which depends on the square of
maximum operating voltage), the distributed ohmic effects are more significant so that
achievable operating power levels are less than those attainable with aqueous electrolyte devices.
Electrochemical capacitors based on pseudocapacitance
A different kind of capacitance can arise at electrodes of certain kinds, for example ruthenium
dioxide, when the extent of faradaically admitted charge depends linearly, or approximately
linearly, on the applied voltage. For such a situation, the electrode behavior is equivalent to, and
measurable as, a capacitance. This capacitance can be large but it is faradaic and not electrostatic
(that is non-faradaic) in origin. This is hence an important difference from the nature of double-
layer capacitance, so it is called "pseudocapacitance". This kind of pseudocapacitance can
originate when an electrochemical charge-transfer process takes place to an extent limited by a
finite quantity of reagent or of available surface. Several examples of pseudocapacitance can
arise, but the capacitance function is usually not constant and, in fact, is usually appreciably
dependent on potential or state of charge.
However, when the process is surface limited, and is proceeding in several one-electron stages, a
broad range of significant capacitance values arises as is found with ruthenium dioxide
electrodes where the pseudocapacitance is almost constant (within 5%) over the full operating
voltage range. Some other metal oxides behave similarly but only over smaller operating voltage
ranges. The ruthenium dioxide pseudocapacitance provides one of the best examples of
electrochemical (pseudo)capacitance as, in addition to the almost constant capacitance over a
wide voltage range, its reversibility is excellent, with a cycle life over several hundred-thousand
cycles. Furthermore, the pseudocapacitance can increase the capacitance of an electrochemical
capacitor by as much as an order of magnitude over that of the double-layer capacitance.
However, its cost prevents its large-scale use so that it has been employed mainly in military
applications.
Another type of material exhibiting pseudocapacitive behavior that is highly reversible is the
family of conducting polymers such as polyaniline or derivatives of polythiophene. These are
cheaper than ruthenium dioxide but are less stable, giving only thousands of cycles (still quite
attractive) over a wide voltage range. (See the Appendix for a more detailed discussion of the
pseudocapacitance.)
Applications and technology
Fabrication of electrochemical capacitors
General industrial production of electrochemical capacitors follows that of battery cell
procedures with automatic production-line machinery. Cell designs are of various kinds
including cylindrical, prismatic, button, or coin types, with some larger embodiments being of
cake-tin sizes or larger, and some multi-cell series for higher voltage with bipolar electrodes
having edge seals. In series configurations for high-voltage applications, balancing of unit cell
performance and behavior is a technological challenge.
Hybrid systems
The high power-density capability of electrochemical capacitors has led them to be employed in
hybrid configurations with batteries and fuel cells in a load-leveling function, for example in
electric vehicles. The capacitor component, suitably coupled with a battery or fuel cell, provides
the necessary power density for up-hill or accelerative driving while regenerative braking
provides a certain extent of recharging.
Another type of hybrid system is where ruthenium dioxide is used as a second oxide component,
acting as a pseudocapacitance in electrolytic capacitors (the Evans Hybrid Capacitor). This gives
indirectly, an improved capacitance density for the overall two-electrode device.
Another interesting hybrid type, currently under investigation in our own and other laboratories,
is a combination of a double-layer carbon (electrochemical capacitor) electrode combined to
work against a rechargeable battery electrode, for example a lead-acid positive plate (acidic
solution) or a nickel battery positive plate (alkaline solution). This type of device (called an
asymmetric capacitor) enables almost all of the charge residing on the capacitor-type electrode to
be utilized on discharge in contrast to the battery-type electrode while, with a symmetrical
capacitor made with two similar double-layer capacitance electrodes, each electrode is only half
discharged from its initial voltage, relative to the other electrode, when the cell discharge voltage
reaches zero, therefore delivering less electrical energy than the hybrid.
Another application is in electrical research experiments where very high energy and high-rate
discharges are required, for example through gases for high-energy spark or arc generation.
A variety of other applications has been envisaged in the literature (Conway, 1999). Examples
are: cold-start assist for diesel locomotives; emergency back-up power for computer systems;
stationary power-system load leveling or bridging for short-period power outages; energy source
for initial heating of catalytic converter units; energy collection and storage from windmill
dynamos.
For society at large, the use of capacitor/battery hybrid systems for improvement of electric-
vehicle (EV) performance will assist the adoption of EV transportation systems with zero or
diminished nitrogen oxide and carbon dioxide atmospheric contamination. However, such a
transition to an "EV lifestyle" will probably not become substantial for another one to two
decades.
Appendix
The capacitance "C" of a capacitor depends on a) the area "A" of the contact plates, b) the
separation "d" between the plates (when parallel), and c) the dielectric constant "ε" of the
medium between the plates (limitingly vacuum, for which "ε" is taken as 1; for all other
materials, including gases, ε > 1). The relationship between "C" and the above quantities is given
by the simple equation (Conway 1999)
[1] C=Aε/4πd
or, in terms of so-called rationalized units,
[2] C = Aε εo / d
where εo (= 8.84 × 10-12 farads/m) is the dielectric permittivity of free space. The units of "C" are
in farads or coulombs per volt, that is coulombs stored by the capacitor per volt across its two
electrodes.
Some important differences between capacitors and batteries
always an intrinsic increase of voltage "V" on charge (or decrease on discharge) of a capacitor as
the charge per cm2 is increased or decreased, according to Equation [3] which defines the relation
between capacitance "C" and the inter-plate voltage "V" that arises from accumulation of a
charge "q":
[3] C = q/V or q = CV
In contrast, an ideal battery has a constant voltage during discharge or recharge except as the
state of charge approaches 0 or 100%. (Practically, most batteries exhibit some dependence of
cell voltage on state of charge, especially lithium-intercalation batteries, the latter for
fundamental reasons arising from intercalation).
The consequence of the above difference, based on Equation [3], is that the energy stored by a
capacitor is 1/2 CV2 or 1/2 qV while, for a battery, the corresponding stored energy (or energy
density) is qΔV, twice as much as that for a capacitor charged to the same cell voltage "ΔV".
Thus, the stored energy in a capacitor device increases as the square of the cell voltage "V" as
charge is accumulated. This is an important difference between capacitor and battery cell
behavior and affects the interfacing between such systems in hybrid devices.
It was noted above that the energy stored in a capacitor cell, charged to a voltage "V" is 1/2 CV2
and "V" increases as charge "q" accumulates on its plates determined by "C". The charging
energy 1/2 CV2 arises in the following way. For a capacitor being charged from an initial voltage
V = 0 to a final value "Vf" the energy "E" stored will be a free-energy "G" (charge times
voltage):
[4]
At any state of charge, q = CV (Equation [3]), so that
[5]
[6] G = 1/2CVf2
Double-layer capacitance
The charge density "q" (coulomb/cm2) of electrons and ions at the interface is dependent on the
potential difference, ΔΦ, across this double layer so that a differential capacitance "Cdl" arises
determined by
[7] Cdl = dq/d(ΔΦ) or Δq/ΔΦ
capacitor-like (Helmholtz) region, out into solution, so that a further diffuse-layer capacitance
"Cdiff" arises. It combines with the capacitance of Helmholtz region "CH" in series, electrically, so
that
[8]
Pseudocapacitance
dioxide, when the extent of faradaically admitted charge "q" depends linearly, or approximately
linearly, on the applied voltage "V". For such a situation, there is a mathematical derivative,
dq/dV that would be constant, which is equivalent to, and measurable as, a capacitance (see
Equation [3]). This capacitance, denoted by "CΦ", can be large but it is faradaic and not
electrostatic (that is non-faradaic) in origin. This is hence an important difference from the nature
of double-layer capacitance "C" or "Cdl" so it is called "pseudocapacitance". The
pseudocapacitance can increase the capacitance of an electrochemical capacitor by as much as an
order of magnitude over that of the double-layer capacitance.
This kind of pseudocapacitance can originate when an electrochemical charge-transfer process
takes place to an extent limited by a finite quantity of reagent or of available surface, the latter in
the case of adsorption (for example of hydrogen), with charge transfer. Several examples of
pseudocapacitance can arise as follows, but the "CΦ" function is usually not constant and, in fact,
is usually appreciably dependent on potential or state of charge.
a) When an electrochemical adsorption process, arising from charge transfer, takes place at an
electrode surface, for example in the process of electrosorption of H atoms discharged at Pt
electrode surfaces in aqueous acid solution by the process:
[9] H3O+ + Pt + e- ==> H2O + Pt/H
so-called underpotential deposition since the above reaction takes place over a potential range
"ΔV" of about 0.35 V positive to the equilibrium potential for H2 gas evolution in the electrolysis
of water.
Fractional H coverages "Θ" at Pt can increase continuously, over the above electrode potential
range, from 0 to 1, prior to evolution of H2 and each atom of H deposited requires passage of one
electron of electric charge. Hence, a pseudocapacitance "CΦ" arises from the relation between
charge passed "q" and "ΔV", and "q" is faradaically related to the coverage fraction "Θ" of
electrodeposited H. A full monolayer (Θ ==> 1) of H requires passage of about 210 µC of charge
"q1" per cm2 of a smooth Pt surface.
[10] CΦ = q1 dΘ/dΔV
"Θ" is related to electrode potential "V" by the relation
[11] Θ/(1 - Θ) = K exp (VF/RT)
b) A number of electrochemical reactions involving species in solution, such as Fe+++/Fe++ or
[Fe(CN)6]3-/[Fe(CN)6]4-, known as redox processes, take place at inert electrodes, for example Au
or Pt, with a logarithmic relation (the Nernst equation) between the extents of
oxidation/reduction between the redox couple pair of ions. Thus, for example
[12] E = Eo + (RT/F) ln a[Fe(CN)6]3-/a[Fe(CN)6]4-
where "a" represents the respective activities of the two ions of the redox couple. The above
Equation [11] can be rearranged in terms of the fractions of a given chemical quantity of the
redox ions in the reversible reaction
[13] [Fe(CN)6]3- + e- <==> [Fe(CN)6]4-
that exist in the course of reduction (or reoxidation) as a function of the potential "E" in relation
to its so-called standard value "Eo" in Equation [12]. E = Eo when the reagent ion activities
(concentrations) are equal so that the ln function is zero. The rearranged form of Equation [11] is
in terms of the molar quantities "Qox" and "Qred" in relation to the total reagents Qox + Qred (= Q)
and reads
[14]
with Qred/Q = 1 - Qox/Q. Then it is seen that Equation [14] has the same form as that of Equation
[11] (after taking logarithms) for electrosorption and its derivative is a capacitance quantity.
c) A similar logarithmic relation in X / (1 - X) applies to absorption of Li+ ions into Li-
intercalation hosts in Li-ion battery electrochemistry where "X" is the fractional occupancy of
available intercalation sites in the intercalation host material, for example TiS2, CoO2, etc.
Hence, Li+ ion intercalation formally exhibits a pseudocapacitance, though the Li+ ion systems
are normally referred to as battery devices.
In each of the three
types of
pseudocapacitance
systems, "CΦ" is
substantially
dependent on
potential, having a
large maximum of
about 2200 µF/cm2 at
"Θ", "Qox/Q", or "X"
equal to 0.5, but with
appreciable values of
"CΦ" arising only over
a potential range of
about 120 mV which
is too narrow to be of
value for practical
applications.
However, when the
redox process is a
surface one,
proceeding in several
one electron stages, a
much broader range
(1.4 V) of significant
Fig. 6. Comparison of cyclic voltammetry
"CΦ" values arises as
behavior of a reversibly chargeable
is found with RuO2
electrochemical capacitor material (RuO2) and
electrodes where "CΦ"
a battery-type (Pb/PbCl2) like in the lead-acid
is almost constant
battery.
within 5% over that
voltage range. Some
other transition-metal oxides behave similarly but only over smaller operating voltage ranges,
about 0.6 to 0.8 V (Conway, 1997).
The case of RuO2 pseudocapacitance provides one of the best examples of electrochemical
(pseudo)capacitance as its "CΦ" is almost constant over a 1.4 V voltage (Figure 6) range and its
reversibility is excellent, with a cycle life over several hundred-thousand cycles. However, its
cost prevents its large-scale use so that it has been employed mainly in military applications.
Another type of material exhibiting quasi-redox behavior that is highly reversible is the family of
conducting polymers such as polyaniline or derivatives of polythiophene. These are cheaper than
ruthenium dioxide but are less stable, giving only thousands of cycles (still quite attractive) over
a voltage range between 0.8 V and up to 3.0 V for some materials.
Figure 6 shows the contrast between a reversibly charged electrochemical capacitor material
(RuO2) and an irreversibly chargeable battery-type material (Pb/PbCl2).
Related articles
Electrolytic capacitors
Bibliography
• Power Limitations of Supercapacitor Operation Associated with Resistance and
Capacitance Distribution in porous Electrode Devices, W. G. Pell and B. E. Conway,
"Journal of Power Sources" Vol. 105, pp 169-181, 2002.
• Advances in Electrochemical Capacitors and Hybrid Power Systems, R. J. Brodd, D. H.
Doughty, K. Naoi, M. Morita, C. Nanjundiah, J. H. Kim, and G. Nagasubramanian
(editors), The Electrochemical Society Proceedings, Vol. 2002-7, Pennington, NJ, 2002.
• Bicentennial of Alessandro Volta's Invention of the "Electric Pile", B. E. Conway,
"Canadian Chemical News" Vol. 52, No. 1, pp 15-17, January 2000.
Available at: http://www.accn.ca/accn2000/january2000/pg12-22.pdf (the second article
in the file).
• Electrochemical Supercapacitors: Scientific Fundamentals and Technological
Applications, B. E. Conway, Kluwer Academic/Plenum Publishing, New York, 1999.
• The Role and Utilization of Pseudocapacitance for Energy Storage by Supercapacitors, B.
E. Conway, V. Birss, and J. Wojtowicz, "Journal of Power Sources" Vol. 66, pp 1-14,
1997.
• Ruthenium Dioxide: a New Interesting Electrode Material, Solid State Structure and
Electrochemical Behavior, S. Trasatti and G. Buzzanca, "Journal of Electroanalytical
Chemistry" Vol. 29, pp A1-A5, 1971.
• Michael Faraday, a Biography, L. Pearce Williams, Chapman and Hall, London, 1965.
• On Porous Electrodes in Electrolyte Solutions, R. de Levie, "Electrochimica Acta" Vol.
8, pp 751-780, 1963.
• Low Voltage Electrolytic Capacitor, H. L. Becker, U.S. Patent 2,800,616, 1957.
• Equilibrium Properties of Electrified Interfaces, R. Parsons, in "Modern Aspects of
Electrochemistry" Vol. 1, pp 103-179, J. O'M. Bockris (editor), Butterworths, London,
1954.
• The Electrical Double Layer and the Theory of Electrocapillarity, D. C. Grahame,
"Chemical Reviews" Vol. 41, pp 441-501, 1947.
• Physical Chemistry, (Chapter 1) S. Glasstone, MacMillan, London, 1940.
• Leyden Jar, "Encyclopaedia Britannica" Vol. 13, p 989, 1929.
• The Electron in Chemistry, J. J. Thomson, Chapman and Hall, London, 1923.
• On the Charge of Electricity Carried by Gaseous Ions, J. J. Thomson, "Philosophical
Magazine" Vol. 5, pp 346-355, 1903.
• Ueber einige Gesetze der Vertheilung elektrischer Ströme in körperlichen Leitern mit
Anwendung auf die thierisch-elektrischen Versuche (in German), H. von Helmholtz,
"Annalen der Physik und Chemie, Leipzig" Vol. 89, pp 211-233, 1853. Available on the
WWW.
Copyright Notice.
ELECTROCHEMICAL CAPACITORS
Their Nature, Function, and Applications
Brian E. Conway
Chemistry Department, University of Ottawa
10 Marie Curie Street
Ottawa, Ontario K1N 6N5, Canada
(March, 2003)
Historical introduction
Electrochemical capacitors provide a mode of electrical charge- and energy-storage and delivery,
complementary to that by batteries. The first electrochemical capacitor device was disclosed in a
General Electric Co. patent in 1957 to Becker but was of a crude nature, employing porous
carbon. Later work by Sohio (1969) described a so-called "electrokinetic capacitor" utilizing
porous carbon in a non-aqueous electrolyte which enabled it to be charged up to about 3 V,
though the operation of the device was not "electrokinetic" in nature, a misnomer. In 1971,
Trasatti and Buzzanca recognized that the electrochemical charging behavior of ruthenium
dioxide films was like that of capacitors. Between 1975 and 1980, the present author and his co-
workers, under contract with the then Continental Group Inc., carried out extensive fundamental
and development work on the ruthenium oxide type of electrochemical capacitor (Conway,
1997) which behaves as a surface- redox pseudocapacitance (see below). The whole field has
burgeoned since about 1990 and is very active in fundamental, and R&D directions.
A great deal of scientific and technological research has been reported in the scientific literature
since about 1990. An extensive and detailed account of this has been given in the author's
monograph on "Electrochemical Supercapacitors: Scientific Fundamentals and Technological
Applications" (1999).
Scientific introduction
In order to describe "electrochemical capacitors" and to explain their function and applications, it
is necessary first to consider the nature of an ordinary electrostatic capacitor or a "condenser" as
it used to be called, and thence the meaning of the term electrical capacitance.
The nature of electricity took a long time to be understood, from the early experiments on
electrostatic electricity in the mid-18th century, for example by Galvani, through the time of the
invention of the first electric battery by Alessandro Volta (Volta's "Pile") in 1800, on to
Faradays's and Davy's monumental discoveries on the chemical origin of electricity generated by
Volta's pile. At first, two "kinds" of electricity were postulated: "animal electricity", as in the
works of Galvani on stimulation of the frog's leg nerve by contact between two dissimilar metals
and later, "Voltaic electricity" generated chemically from a Volta pile of zinc and silver or
copper plates separated by paper wetted with an acid or salt solution (Conway, 2000).
In parallel with these discoveries were extensive works on electrostatic electricity generated for
example by the rubbing of naturally occurring amber or by the so-called Wimshurst machine (a
rotating circular plate, containing insets of amber-like material, rubbing against charge-collector
plates connected overall to a Leyden Jar or a spark-gap). It was from this direction of research on
electricity that the invention of the electric condenser arose, referred to as the "Leyden Jar", and
capable of storing electric charge generated by a Wimshurst machine. Such a jar had the
"capacity", depending on its dimensions and materials of construction, of storing electric charge
by bringing it together in a condensed way (hence the term "condenser") on the surfaces of a
Leyden Jar at a certain two-dimensional charge density.
The principle of design and operation of the Leyden Jar and all subsequent regular condensers or
capacitor devices, is as follows. Two metal surfaces that constitute electrodes are separated at
some small distance either in air (or vacuum) or on each side of a liquid or solid film, referred to
as the "dielectric", a term first used by Michael Faraday . For a given separation of the electrode
plates, the capacitance developed per unit area of the two plates depends on the properties of the
dielectric between the plates characterized by its so-called dielectric constant.
In the case of the Leyden Jar (Figure

1), the material (glass) of the jar itself
serves a the dielectric medium and
the contact plates were metal foils
wrapped, inside and out, around the
cylindrical surfaces of the jar. The
electrical contact to the inner surface
foil was by means of a conducting
electrolyte solution (or originally by
ordinary water itself) in which was
immersed a conducting metal
electrode for electrical contact. The
device was charged by joining two
wires from the inside electrode and
the outside foil to an electrostatic Fig. 1. Leyden
machine of the Wimshurst type. In Jar, the first
later experimentation, the Leyden Jar capacitor or
capacitor was connected to the "condenser".
electrodes of a Volta's pile or battery for charging. This was the first-generation capacitor for
storage of electric charge.
The nature of electric charge remained elusive until much later (1897) when J.J. Thomson
identified and characterized the fundamental entity of electric charge as the "electron", present
ubiquitously in all atoms of the Universe and identified, in his experiments, by means of
experiments on gases at low pressures in gas-discharge tubes (Crookes tubes or neon lights). The
electron charge was determined independently by Townsend and by Millikan (Glasstone, 1940),
and was shown to be equivalent to Faraday's constant for the relation between extent of passage
of charge and extent of chemical change (as related by Faraday's Laws) caused by electrolysis of
conducting solutions, when calculated on a "per gram-atom" or "gram-equivalent" basis.
The capacitance of a capacitor is proportional to the area of the contact plates and the dielectric
constant of the medium between the plates, and it is inversely proportional to the separation
between the plates (see the Appendix). In relation to electrochemical capacitors, to be discussed
below, the capacitance of small dielectric capacitors is very small being on the order of
microfarads or nanofarads (millionth or billionth of a farad, respectively) for small devices on
the order of mm or cm in dimensions. By having very thin insulating films, on the order of 10 to
100 nanometers, formed anodically on the plate of a two-electrode capacitor, substantially larger
specific capacitances (that is per cm2) can be attained. Such devices are called "electrolytic
capacitors" because the thin dielectric oxide films are formed on the plates by an anodic
electrolysis procedure applied at metals such as aluminum, tantalum, titanium, niobium, etc.
Such capacitors are still of the dielectric type (the dielectric medium being here the thin,
insulating oxide film, usually having a relatively high dielectric constant) and should not be
confused with the "electrochemical" capacitor type of device which is the topic of this article.
Electrochemical capacitors are a special kind of capacitor based on charging and discharging the
interfaces of high specific-area materials such as porous carbon materials or porous oxides of
some metals. They can store electric charge and corresponding energy at high densities in an
highly reversible way, as does a regular capacitor, and hence can be operated at specific power
densities (in watts/kg) substantially higher than can most batteries. Their capacitance for a given
size of the device is thus much higher, by a factor of 10,000 or so, than those achievable with
regular capacitors. For this reason proprietary names such as "Supercapacitors" or
"Ultracapacitors" have been coined to describe their performance.
While they function formally like rechargeable batteries in storing or delivering electric charge,
their mechanisms of charge storage are quite different, in most cases, from those operating in
batteries. Thus, electrochemical capacitors are not substitutes for batteries but rather are to be
regarded as complementary to them for charge storage or delivery. They can offer
advantageously fast charging or discharging rates over most batteries of comparable volume but
their energy density is usually less, by a factor of 3 to 4, than that of batteries. Their high power
or power densities, however, enables them to be employed in interesting complementary ways in
hybrid systems with batteries.
always an intrinsic increase of voltage on charge (or decrease on discharge) of a capacitor as the
charge per cm2 is increased or decreased. In contrast, an ideal battery has a constant voltage
during discharge or recharge except as the state of charge approaches 0 or 100%. Although
practical batteries exhibit some dependence of cell voltage on state of charge, especially lithium-
intercalation batteries, the latter for fundamental reasons arising from intercalation. (See the
Appendix for further details.)
The double-layer capacitance at electrode interfaces
Nature of electrical double layers
An important
class of
electrochemical capacitors utilizes the co-called double-layer capacitance that arises at all
electrode interfaces with electrolyte solutions or ionic melts. The concept and model of the
double layer arose in the work of von Helmholtz (1853) on the interfaces of colloidal
suspensions and was subsequently extended to surfaces of metal electrodes by Gouy, Chapman,
and Stern, and later in the notable work of Grahame around 1947. Models of the double layer are
shown in Figure 2, with their capacitor-like structures.
Helmholtz envisaged a capacitor-like separation of anionic and cationic charges across the
interface of colloidal particles with an electrolyte. For electrode interfaces with an electrolyte
solution, this concept was extended to model the separation of "electronic" charges residing at
the metal electrode surfaces (manifested as an excess of negative charge densities under negative
polarization with respect to the electrolyte solution or as a deficiency of electron charge density
under positive polarization), depending in each case, on the corresponding potential difference
between the electrode and the solution boundary at the electrode. For zero net charge, the
corresponding potential is referred to as the "potential of zero charge".
In response to positive or negative electric polarization of the electrode relative accumulations of
cations or anions develop, respectively, at the solution side of the charged electrode. If, for
energetic reasons, the ions of the electrolyte are not faradaically dischargeable (that is no
electron transfer can occur across the interface ("ideally polarizable electrode", for example a
mercury electrode, Grahame 1947 and Parsons 1954), then an electrostatic electrical equilibrium
is established at the interface resulting in a "double layer" of separated charges (electrons or
electron deficiency at the metal side and cations or anions at the solution side of the interface
boundary), negative and positive, across the interface.
capacitor-like (Helmholtz) region, out into solution, so that a further diffuse region capacitance
(the diffuse-layer capacitance "Cdiff") arises. It combines with that of Helmholtz's region "CH" in
series. (See the Appendix for further details.)
The Helmholtz region capacitance "CH" is of special significance for electrochemical capacitors
since it is directly dependent on accessible electrode area and has large values (relative to those
for regular dielectric capacitors) between about 16 µF/cm2 and about 40-50 µF/cm2, depending
on electrode potential, the chemical nature of the metal surface, chemical nature of the solvent,
and the types of ions (and their solvation by the solvent) present in the electrolyte solution.
The most extensively studied metal surface, with respect to its double-layer capacitance, is that
of mercury in various solvent media, especially water.
It was mentioned that the specific capacitances of electrode double layers are very large, some
10,000 times those of ordinary dielectric capacitors, per cm2 area. The reason for this is that the
separation of charges in electrochemical double layers is on the order of 0.3-0.5 nm instead of 10
to 100 nm with oxide-film dielectrics (electrolytic capacitors) or 1000 nm with very thin mica or
polystyrene dielectric-film hardware capacitors.
Hence, it is seen that with large specific-area porous electrodes, for example at carbons having
say 1000 m2/g of material and exhibiting, say, 15 µF/(real cm2) of double-layer capacitance in
some suitable electrolyte solution, the accessible capacitance "C" is 1000 (m2/g) × 10,000
(cm2/m2) × 15 (µF/cm2) = 150 million µF/g, that is 150 farads/g, a very large capacitance! Hence
the term "supercapacitors" or "ultracapacitors" for devices based on double-layer capacitance at
high-area substrates.
The high degree of reversibility of charge acceptance and delivery, and hence capability for
excellent operating power levels compared with batteries of comparable size arises because no
slow chemical processes or phase changes take place between charge and discharge as they do in
most battery-type electrical charge generating devices.
It is the essence of battery-type charge/discharge processes that faradaic processes take place
leading to major chemical and structural changes of the electrochemical reactive materials, for
example conversions of lead dioxide to lead sulfate and lead metal to lead sulfate in discharge of
the lead-acid battery which, as is well known, limits charge/discharge to a cycle life of 1000 to
3000, depending on rates of charge and discharge, and temperature. By contrast, electrochemical
double-layer and oxide-type (see below) capacitors can exhibit cycle lives up to one million
under suitable conditions. This is because, ideally at least, only storage and delivery of
electrostatic charge takes place at the extended two-dimensional interface of high-area materials
and no irreversible or slow chemical phase changes take place as they do between three-
dimensional chemical materials in rechargeable batteries. This is a fundamental difference
between the electrochemical behavior and properties of electrochemical capacitors relative to
those of batteries.
Electrical irreversibility in electrochemical capacitor charging and discharge:
rate effects
It was stated earlier in this article that charging and discharging of electrochemical capacitors has
commonly been perceived as a process much more reversible than that for batteries and hence
being capable of operation at high power densities. While, in practice, this is largely true,
charging of the high-area, porous-electrode structures that are required for achieving large
capacitance densities (farads/g or farads/cm3) encounters limitations of rate due to the distributed
electrolytic and contact resistances within the pore structure of such materials.
In the
simplest
analysis, any
practical
capacitor
device
behaves as if
an ohmic
resistance is
in series with
it, the so-
called
equivalent (or
real) series
resistance
(Figure 3).
The presence
of real or
equivalent
series
resistance in
the operating
equivalent
circuit of any
capacitor
introduces an
ir potential
drop in the
process of
charging or
discharging
and this drop
Fig. 3. Hierarchy of equivalent circuits for capacitors and
depends, of
electrochemical capacitors showing "transmission-line" circuit
course, on the
for the latter, in the case of a porous carbon electrode.
charging rate
(current)
leading to distortion of the charging curve of accumulated charge against voltage, in time. When
the distributed resistance effect also operates, as it normally does, the distortion effect becomes
more complex but has been experimentally and computationally evaluated (de Levie, 1963).
The above effect causes limitation of rates at which the capacitor can be charged or discharged
and, for ac modulated charging, it also introduces a frequency-dependent phase angle (normally
-90o) between the modulated applied voltage and the resultant charging current. This also applies
to other, non-constant charging modes.
In practice,
with a porous
electrode, the
situation is
much more
complex since
the matrix of
microscopic
pores within
the
macroscopic
electrode
structure
offers a
complex,
series/parallel
equivalent
circuit
comprised of
a distribution Fig. 4. de Levie transmission-line model for
of ohmic resistance/capacitance matrix in an high-area porous
(resistive) and electrode.
capacitive
elements which leads to the whole electrode having a non-uniform effective resistance and
capacitance, dependent on frequency (in ac modulation) or on the time-scale of pulsed or non-
constant rates of charging. As shown in the classical work of de Levie (1963), the equivalent
circuit for such electrodes is that of a transmission line (Figure 4) having a -45o phase angle
(Figure 5) characterizing its impedance behavior.
This situation leads to

limitation of the rates
of which charging or
discharging of porous
capacitor electrodes
can be conducted and
is additional to any
equivalent series
resistance effects a
practical cell may
experience due to cell
design and electrolyte
resistance.
Fig. 5. Complex-plane impedance plots
de Levie has pointed (imaginary capacitive component against real
out that the ohmic component) for a porous electrode
distributed R/C effect according to de Levie.
in porous electrodes
is equivalent to
restrictions of power due to ohmic ir drop (that is the potential drop due to current passing
through resistive elements in the matrix). Thus there is a "penetration effect" into the electrode
matrix due to attenuation of for example a modulation or time-dependent transient charging
voltage so that not all of the depth or width, or diameter of the electrode structure is subject to a
uniform charging rate. This introduces a non-chemical irreversibility in the charge/discharge
behavior of the electrochemical capacitor device which is electrically demonstrable.
It must be stated, however, that in state-of-the-art developments of electrochemical capacitors,
using aqueous-solution electrolytes, the above distributed-resistance effect has been substantially
minimized so that devices having high operating power have been successfully engineered and
marketed. Nevertheless, with non-aqueous electrolyte capacitors, which have higher operating
voltages up to 3.0 to 3.5 V (hence 9 to 12 times energy density which depends on the square of
maximum operating voltage), the distributed ohmic effects are more significant so that
achievable operating power levels are less than those attainable with aqueous electrolyte devices.
Electrochemical capacitors based on pseudocapacitance
dioxide, when the extent of faradaically admitted charge depends linearly, or approximately
linearly, on the applied voltage. For such a situation, the electrode behavior is equivalent to, and
measurable as, a capacitance. This capacitance can be large but it is faradaic and not electrostatic
(that is non-faradaic) in origin. This is hence an important difference from the nature of double-
layer capacitance, so it is called "pseudocapacitance". This kind of pseudocapacitance can
originate when an electrochemical charge-transfer process takes place to an extent limited by a
finite quantity of reagent or of available surface. Several examples of pseudocapacitance can
arise, but the capacitance function is usually not constant and, in fact, is usually appreciably
dependent on potential or state of charge.
However, when the process is surface limited, and is proceeding in several one-electron stages, a
broad range of significant capacitance values arises as is found with ruthenium dioxide
electrodes where the pseudocapacitance is almost constant (within 5%) over the full operating
voltage range. Some other metal oxides behave similarly but only over smaller operating voltage
ranges. The ruthenium dioxide pseudocapacitance provides one of the best examples of
electrochemical (pseudo)capacitance as, in addition to the almost constant capacitance over a
wide voltage range, its reversibility is excellent, with a cycle life over several hundred-thousand
cycles. Furthermore, the pseudocapacitance can increase the capacitance of an electrochemical
capacitor by as much as an order of magnitude over that of the double-layer capacitance.
However, its cost prevents its large-scale use so that it has been employed mainly in military
applications.
Another type of material exhibiting pseudocapacitive behavior that is highly reversible is the
family of conducting polymers such as polyaniline or derivatives of polythiophene. These are
cheaper than ruthenium dioxide but are less stable, giving only thousands of cycles (still quite
attractive) over a wide voltage range. (See the Appendix for a more detailed discussion of the
pseudocapacitance.)
Applications and technology
Fabrication of electrochemical capacitors
General industrial production of electrochemical capacitors follows that of battery cell
procedures with automatic production-line machinery. Cell designs are of various kinds
including cylindrical, prismatic, button, or coin types, with some larger embodiments being of
cake-tin sizes or larger, and some multi-cell series for higher voltage with bipolar electrodes
having edge seals. In series configurations for high-voltage applications, balancing of unit cell
performance and behavior is a technological challenge.
Hybrid systems
The high power-density capability of electrochemical capacitors has led them to be employed in
hybrid configurations with batteries and fuel cells in a load-leveling function, for example in
electric vehicles. The capacitor component, suitably coupled with a battery or fuel cell, provides
the necessary power density for up-hill or accelerative driving while regenerative braking
provides a certain extent of recharging.
Another type of hybrid system is where ruthenium dioxide is used as a second oxide component,
acting as a pseudocapacitance in electrolytic capacitors (the Evans Hybrid Capacitor). This gives
indirectly, an improved capacitance density for the overall two-electrode device.
Another interesting hybrid type, currently under investigation in our own and other laboratories,
is a combination of a double-layer carbon (electrochemical capacitor) electrode combined to
work against a rechargeable battery electrode, for example a lead-acid positive plate (acidic
solution) or a nickel battery positive plate (alkaline solution). This type of device (called an
asymmetric capacitor) enables almost all of the charge residing on the capacitor-type electrode to
be utilized on discharge in contrast to the battery-type electrode while, with a symmetrical
capacitor made with two similar double-layer capacitance electrodes, each electrode is only half
discharged from its initial voltage, relative to the other electrode, when the cell discharge voltage
reaches zero, therefore delivering less electrical energy than the hybrid.
Another application is in electrical research experiments where very high energy and high-rate
discharges are required, for example through gases for high-energy spark or arc generation.
A variety of other applications has been envisaged in the literature (Conway, 1999). Examples
are: cold-start assist for diesel locomotives; emergency back-up power for computer systems;
stationary power-system load leveling or bridging for short-period power outages; energy source
for initial heating of catalytic converter units; energy collection and storage from windmill
dynamos.
For society at large, the use of capacitor/battery hybrid systems for improvement of electric-
vehicle (EV) performance will assist the adoption of EV transportation systems with zero or
diminished nitrogen oxide and carbon dioxide atmospheric contamination. However, such a
transition to an "EV lifestyle" will probably not become substantial for another one to two
decades.
Appendix
The capacitance "C" of a capacitor depends on a) the area "A" of the contact plates, b) the
separation "d" between the plates (when parallel), and c) the dielectric constant "ε" of the
medium between the plates (limitingly vacuum, for which "ε" is taken as 1; for all other
materials, including gases, ε > 1). The relationship between "C" and the above quantities is given
by the simple equation (Conway 1999)
[1] C=Aε/4πd
or, in terms of so-called rationalized units,
[2] C = Aε εo / d
where εo (= 8.84 × 10-12 farads/m) is the dielectric permittivity of free space. The units of "C" are
in farads or coulombs per volt, that is coulombs stored by the capacitor per volt across its two
electrodes.
Some important differences between capacitors and batteries
always an intrinsic increase of voltage "V" on charge (or decrease on discharge) of a capacitor as
the charge per cm2 is increased or decreased, according to Equation [3] which defines the relation
between capacitance "C" and the inter-plate voltage "V" that arises from accumulation of a
charge "q":
[3] C = q/V or q = CV
In contrast, an ideal battery has a constant voltage during discharge or recharge except as the
state of charge approaches 0 or 100%. (Practically, most batteries exhibit some dependence of
cell voltage on state of charge, especially lithium-intercalation batteries, the latter for
fundamental reasons arising from intercalation).
The consequence of the above difference, based on Equation [3], is that the energy stored by a
capacitor is 1/2 CV2 or 1/2 qV while, for a battery, the corresponding stored energy (or energy
density) is qΔV, twice as much as that for a capacitor charged to the same cell voltage "ΔV".
Thus, the stored energy in a capacitor device increases as the square of the cell voltage "V" as
charge is accumulated. This is an important difference between capacitor and battery cell
behavior and affects the interfacing between such systems in hybrid devices.
It was noted above that the energy stored in a capacitor cell, charged to a voltage "V" is 1/2 CV2
and "V" increases as charge "q" accumulates on its plates determined by "C". The charging
energy 1/2 CV2 arises in the following way. For a capacitor being charged from an initial voltage
V = 0 to a final value "Vf" the energy "E" stored will be a free-energy "G" (charge times
voltage):
[4]
At any state of charge, q = CV (Equation [3]), so that
[5]
[6] G = 1/2CVf2
Double-layer capacitance
The charge density "q" (coulomb/cm2) of electrons and ions at the interface is dependent on the
potential difference, ΔΦ, across this double layer so that a differential capacitance "Cdl" arises
determined by
[7] Cdl = dq/d(ΔΦ) or Δq/ΔΦ
capacitor-like (Helmholtz) region, out into solution, so that a further diffuse-layer capacitance
"Cdiff" arises. It combines with the capacitance of Helmholtz region "CH" in series, electrically, so
that
[8]
Pseudocapacitance
dioxide, when the extent of faradaically admitted charge "q" depends linearly, or approximately
linearly, on the applied voltage "V". For such a situation, there is a mathematical derivative,
dq/dV that would be constant, which is equivalent to, and measurable as, a capacitance (see
Equation [3]). This capacitance, denoted by "CΦ", can be large but it is faradaic and not
electrostatic (that is non-faradaic) in origin. This is hence an important difference from the nature
of double-layer capacitance "C" or "Cdl" so it is called "pseudocapacitance". The
pseudocapacitance can increase the capacitance of an electrochemical capacitor by as much as an
order of magnitude over that of the double-layer capacitance.
This kind of pseudocapacitance can originate when an electrochemical charge-transfer process
takes place to an extent limited by a finite quantity of reagent or of available surface, the latter in
the case of adsorption (for example of hydrogen), with charge transfer. Several examples of
pseudocapacitance can arise as follows, but the "CΦ" function is usually not constant and, in fact,
is usually appreciably dependent on potential or state of charge.
a) When an electrochemical adsorption process, arising from charge transfer, takes place at an
electrode surface, for example in the process of electrosorption of H atoms discharged at Pt
electrode surfaces in aqueous acid solution by the process:
[9] H3O+ + Pt + e- ==> H2O + Pt/H
so-called underpotential deposition since the above reaction takes place over a potential range
"ΔV" of about 0.35 V positive to the equilibrium potential for H2 gas evolution in the electrolysis
of water.
Fractional H coverages "Θ" at Pt can increase continuously, over the above electrode potential
range, from 0 to 1, prior to evolution of H2 and each atom of H deposited requires passage of one
electron of electric charge. Hence, a pseudocapacitance "CΦ" arises from the relation between
charge passed "q" and "ΔV", and "q" is faradaically related to the coverage fraction "Θ" of
electrodeposited H. A full monolayer (Θ ==> 1) of H requires passage of about 210 µC of charge
"q1" per cm2 of a smooth Pt surface.
[10] CΦ = q1 dΘ/dΔV
"Θ" is related to electrode potential "V" by the relation
[11] Θ/(1 - Θ) = K exp (VF/RT)
b) A number of electrochemical reactions involving species in solution, such as Fe+++/Fe++ or
[Fe(CN)6]3-/[Fe(CN)6]4-, known as redox processes, take place at inert electrodes, for example Au
or Pt, with a logarithmic relation (the Nernst equation) between the extents of
oxidation/reduction between the redox couple pair of ions. Thus, for example
[12] E = Eo + (RT/F) ln a[Fe(CN)6]3-/a[Fe(CN)6]4-
where "a" represents the respective activities of the two ions of the redox couple. The above
Equation [11] can be rearranged in terms of the fractions of a given chemical quantity of the
redox ions in the reversible reaction
[13] [Fe(CN)6]3- + e- <==> [Fe(CN)6]4-
that exist in the course of reduction (or reoxidation) as a function of the potential "E" in relation
to its so-called standard value "Eo" in Equation [12]. E = Eo when the reagent ion activities
(concentrations) are equal so that the ln function is zero. The rearranged form of Equation [11] is
in terms of the molar quantities "Qox" and "Qred" in relation to the total reagents Qox + Qred (= Q)
and reads
[14]
with Qred/Q = 1 - Qox/Q. Then it is seen that Equation [14] has the same form as that of Equation
[11] (after taking logarithms) for electrosorption and its derivative is a capacitance quantity.
c) A similar logarithmic relation in X / (1 - X) applies to absorption of Li+ ions into Li-
intercalation hosts in Li-ion battery electrochemistry where "X" is the fractional occupancy of
available intercalation sites in the intercalation host material, for example TiS2, CoO2, etc.
Hence, Li+ ion intercalation formally exhibits a pseudocapacitance, though the Li+ ion systems
are normally referred to as battery devices.
In each of the three
types of
pseudocapacitance
systems, "CΦ" is
substantially
dependent on
potential, having a
large maximum of
about 2200 µF/cm2 at
"Θ", "Qox/Q", or "X"
equal to 0.5, but with
appreciable values of
"CΦ" arising only over
a potential range of
about 120 mV which
is too narrow to be of
value for practical
applications.
However, when the
redox process is a
surface one,
proceeding in several
one electron stages, a
much broader range
(1.4 V) of significant
Fig. 6. Comparison of cyclic voltammetry
"CΦ" values arises as
behavior of a reversibly chargeable
is found with RuO2
electrochemical capacitor material (RuO2) and
electrodes where "CΦ"
a battery-type (Pb/PbCl2) like in the lead-acid
is almost constant
battery.
within 5% over that
voltage range. Some
other transition-metal oxides behave similarly but only over smaller operating voltage ranges,
about 0.6 to 0.8 V (Conway, 1997).
The case of RuO2 pseudocapacitance provides one of the best examples of electrochemical
(pseudo)capacitance as its "CΦ" is almost constant over a 1.4 V voltage (Figure 6) range and its
reversibility is excellent, with a cycle life over several hundred-thousand cycles. However, its
cost prevents its large-scale use so that it has been employed mainly in military applications.
Another type of material exhibiting quasi-redox behavior that is highly reversible is the family of
conducting polymers such as polyaniline or derivatives of polythiophene. These are cheaper than
ruthenium dioxide but are less stable, giving only thousands of cycles (still quite attractive) over
a voltage range between 0.8 V and up to 3.0 V for some materials.
Figure 6 shows the contrast between a reversibly charged electrochemical capacitor material
(RuO2) and an irreversibly chargeable battery-type material (Pb/PbCl2).
Related articles
Electrolytic capacitors
Bibliography
• Power Limitations of Supercapacitor Operation Associated with Resistance and
Capacitance Distribution in porous Electrode Devices, W. G. Pell and B. E. Conway,
"Journal of Power Sources" Vol. 105, pp 169-181, 2002.
• Advances in Electrochemical Capacitors and Hybrid Power Systems, R. J. Brodd, D. H.
Doughty, K. Naoi, M. Morita, C. Nanjundiah, J. H. Kim, and G. Nagasubramanian
(editors), The Electrochemical Society Proceedings, Vol. 2002-7, Pennington, NJ, 2002.
• Bicentennial of Alessandro Volta's Invention of the "Electric Pile", B. E. Conway,
"Canadian Chemical News" Vol. 52, No. 1, pp 15-17, January 2000.
Available at: http://www.accn.ca/accn2000/january2000/pg12-22.pdf (the second article
in the file).
• Electrochemical Supercapacitors: Scientific Fundamentals and Technological
Applications, B. E. Conway, Kluwer Academic/Plenum Publishing, New York, 1999.
• The Role and Utilization of Pseudocapacitance for Energy Storage by Supercapacitors, B.
E. Conway, V. Birss, and J. Wojtowicz, "Journal of Power Sources" Vol. 66, pp 1-14,
1997.
• Ruthenium Dioxide: a New Interesting Electrode Material, Solid State Structure and
Electrochemical Behavior, S. Trasatti and G. Buzzanca, "Journal of Electroanalytical
Chemistry" Vol. 29, pp A1-A5, 1971.
• Michael Faraday, a Biography, L. Pearce Williams, Chapman and Hall, London, 1965.
• On Porous Electrodes in Electrolyte Solutions, R. de Levie, "Electrochimica Acta" Vol.
8, pp 751-780, 1963.
• Low Voltage Electrolytic Capacitor, H. L. Becker, U.S. Patent 2,800,616, 1957.
• Equilibrium Properties of Electrified Interfaces, R. Parsons, in "Modern Aspects of
Electrochemistry" Vol. 1, pp 103-179, J. O'M. Bockris (editor), Butterworths, London,
1954.
• The Electrical Double Layer and the Theory of Electrocapillarity, D. C. Grahame,
"Chemical Reviews" Vol. 41, pp 441-501, 1947.
• Physical Chemistry, (Chapter 1) S. Glasstone, MacMillan, London, 1940.
• Leyden Jar, "Encyclopaedia Britannica" Vol. 13, p 989, 1929.
• The Electron in Chemistry, J. J. Thomson, Chapman and Hall, London, 1923.
• On the Charge of Electricity Carried by Gaseous Ions, J. J. Thomson, "Philosophical
Magazine" Vol. 5, pp 346-355, 1903.
• Ueber einige Gesetze der Vertheilung elektrischer Ströme in körperlichen Leitern mit
Anwendung auf die thierisch-elektrischen Versuche (in German), H. von Helmholtz,
"Annalen der Physik und Chemie, Leipzig" Vol. 89, pp 211-233, 1853. Available on the
WWW.
Copyright Notice.
ELECTROCHEMISTRY OF CORROSION
Jerome Kruger
The Johns Hopkins University
Baltimore, MD 21218, USA
(April, 2001)
Ulick R. Evans, the British scientist who is considered the "Father of Corrosion Science", has
said that "Corrosion is largely an electrochemical phenomenon, [which] may be defined as
destruction by electrochemical or chemical agencies...". Corrosion in an aqueous environment
and in an atmospheric environment (which also involves thin aqueous layers) is an
electrochemical process because corrosion involves the transfer of electrons between a metal
surface and an aqueous electrolyte solution. It results from the overwhelming tendency of metals
to react electrochemically with oxygen, water, and other substances in the aqueous environment.
Fortunately, most useful metals react with the environment to form more or less protective films
of corrosion reaction products that prevent the metals from going into solution as ions.
While the term corrosion has in recent years been applied to all kinds of materials in all kinds of
environments, this article will only consider the electrochemistry of corrosion of metals and
alloys in aqueous solutions at ambient temperatures. Electrochemical corrosion occurring under
such conditions is a major destructive process that results in such costly, unsightly, and
destructive effects as the formation of rust and other corrosion products, the creation of the
gaping holes or cracks in aircraft, automobiles, boats, gutters, screens, plumbing, and many other
items constructed of every metal except gold.
Systems such as boiling water nuclear reactors involving aqueous solutions are also examples of
electrochemical corrosion but will not be covered. This article will also not cover the non-
electrochemical process termed high temperature oxidation, a destructive process which is the
exposure of a metal or alloy to high temperatures in a gaseous environment (usually including
oxygen or gases with sulfur containing compounds) where much thicker layers of corrosion
products are formed. However, it must be pointed out that if the high temperature oxidation
process results in the formation of salt layers that melt at the high temperatures used, a difference
in electrode potential between phases or heterogeneities in an alloy can lead to hot corrosion
which has electrochemical features similar to that of the condensed aqueous films involved in
atmospheric corrosion. This technologically important corrosion process leads to the failure of
such applications as gas turbines, heat exchangers, and many others that operate at high
temperatures.
Consequences of corrosion
Corrosion has many serious economic, health, safety, technological, and cultural consequences
to our society.
Economic effects
Studies in a number of countries have attempted to determine the national cost of corrosion. The
most extensive of these studies was the one carried out in the United States in 1976 which found
that the overall annual cost of metallic corrosion to the U.S. economy was $70 billion, or 4.2% of
the gross national product. To get a feeling for the seriousness of this loss, we may compare it to
another economic impact everyone is worried about – the importation of foreign crude oil, which
cost $45 billion in 1977.
Health effects
Recent years have seen an increasing use of metal prosthetic devices in the body, such as pins,
plates, hip joints, pacemakers, and other implants. New alloys and better techniques of
implantation have been developed, but corrosion continues to create problems. Examples include
failures through broken connections in pacemakers, inflammation caused by corrosion products
in the tissue around implants, and fracture of weight-bearing prosthetic devices. An example of
the latter is the use of metallic hip joints, which can alleviate some of the problems of arthritic
hips. The situation has improved in recent years, so that hip joints which were was at first limited
to persons over 60 are now being used in younger persons, because they will last longer.
Safety effects
An even more significant problem is corrosion of structures, which can result in severe injuries
or even loss of life. Safety is compromised by corrosion contributing to failures of bridges,
aircraft, automobiles, gas pipelines etc. – the whole complex of metal structures and devices that
make up the modern world.
Technological effects
The economic consequences of corrosion affect technology. A great deal of the development of
new technology is held back by corrosion problems because materials are required to withstand,
in many cases simultaneously, higher temperatures, higher pressures, and more highly corrosive
environments. Corrosion problems that are less difficult to solve affect solar energy systems,
which require alloys to withstand hot circulating heat transfer fluids for long periods of time, and
geothermal systems, which require materials to withstand highly concentrated solutions of
corrosive salts at high temperatures and pressures. Another example, the drilling for oil in the sea
and on land, involves overcoming such corrosion problems as sulfide stress corrosion,
microbiological corrosion, and the vast array of difficulties involved in working in the highly
corrosive marine environment. In many of these instances, corrosion is a limiting factor
preventing the development of economically or even technologically workable systems.
Cultural effects
International concern was aroused by the disclosure of the serious deterioration of the artistically
and culturally significant gilded bronze statues in Venice, Italy. Corrosive processes will
accelerate the deterioration of precious artifacts such as those in Venice by the highly polluted
environments that now are prevalent in most of the countries of the world. Likewise, inside the
world's museums conservators and restorers labor to protect cultural treasures against the ravages
of corrosion or to remove its traces from artistically or culturally important artifacts.
Electrochemistry of corrosion
The same metallic surface exposed to an aqueous electrolyte usually possesses sites for an
oxidation (or anodic chemical reaction) that produces electrons in the metal, and a reduction (or
cathodic reaction) that consumes the electrons produced by the anodic reaction. These "sites"
together make up a "corrosion cell". The anodic reaction is the dissolution of the metal to form
either soluble ionic products or an insoluble compound of the metal, usually an oxide. Several
cathodic reactions are possible depending on what reducible species are present in the solution.
Typical reactions are the reduction of dissolved oxygen gas, or the reduction of the solvent
(water) to produce hydrogen gas. Examples of these reactions are given in the Appendix.
Because these anodic and cathodic reactions occur simultaneously on a metal surface, they create
an electrochemical cell of the type shown in Figure 1.
The sites where the

anodic and cathodic
reactions take place,
the anodes and the
cathodes of the
corrosion cell, are
determined by many
factors: (i) they are
not necessarily fixed
in location; (ii) they
can be adjacent or
widely separated so
that, for example, if Fig. 1. The electrochemical cell set up between
two metals are in anodic and cathodic sites on an iron surface
contact, one metal can undergoing corrosion.
be the anode and the
other the cathode, leading to galvanic corrosion of the more anodic metal; (iii) there can exist
variations over the surface of oxygen concentration in the environment that result in the
establishment of an anode at those sites exposed to the environment containing the lower oxygen
content – differential aeration corrosion; (iv) or similarly, variations in the concentration of metal
ions or other species in the environment, arising because of the spatial orientation of the
corroding metal and gravity; or finally, (v) variations in the homogeneity of the metal surface,
due to the presence of inclusions, different phases, grain boundaries, disturbed metal, and other
causes, can lead to the establishment of anodic and cathodic sites.
The process occurring at the anodic sites is the dissolution of metal as metallic ions in the
electrolyte or the conversion of these ions to insoluble corrosion products such as rust. This is the
destructive process called corrosion. The flow of electrons between the corroding anodes and the
non-corroding cathodes forms the corrosion current, the value of which is determined by the rate
of production of electrons by the anodic reaction and their consumption by the cathodic reaction.
The rates of electron production and consumption, of course, must be equal or a buildup of
charge would occur.
Driving force, corrosion tendencies
A driving force is necessary for electrons to flow between the anodes and the cathodes. This
driving force is the difference in potential between the anodic and cathodic sites. This difference
exists because each oxidation or reduction reaction has associated with it a potential determined
by the tendency for the reaction to take place spontaneously. The potential is a measure of this
tendency.
Electrochemical equilibria: oxidation and reduction
Since most corrosion reactions occurring in the presence of a liquid, such as water, are not
chemical but are electrochemical, the use of chemical equilibria is of minimal use for studying
aqueous corrosion. A useful way to study the relation of potential to corrosion is through the use
of an electrochemical equilibrium diagram – called the "Pourbaix Diagram" – developed by M.
Pourbaix, it plots potential against pH, a parameter also of great importance to corrosion
processes.
The simplified
Pourbaix diagram for
iron is shown in
Figure 2. The
potential plotted is
that of iron as
measured against a
standard hydrogen
reference electrode.
The Pourbaix diagram
enables the
determination, by
means of potential
and pH
measurements,
whether (i) a metal
Fig. 2. The potential – pH (Pourbaix )
surface is in a region
equilibrium diagram for iron.
of immunity where
the tendency for
corrosion is nil, (ii) in a region where the tendency for corrosion is high, or (iii) in a region where
the tendency for corrosion may still exist but where there is also a tendency for a protective or
passive film to exist. Such a film can drastically affect the rate of corrosion, and, in some cases,
practically stop it (see Passivity and breakdown). Lines (a) and (b) on Figure 2 represent oxygen
reduction (Appendix, Equations [2] or [3]) and hydrogen evolution (Appendix, Equation [4]),
respectively. They are a measure of the concentration of oxygen or hydrogen in solution and
show the variation of potential with pH for solutions in equilibrium with one atmosphere of
either oxygen or hydrogen. Lines drawn parallel to (a), but lower, would give the variation of
potential with pH for a solution containing less oxygen than that represented by (a). Thus, the
potential of a specimen can give some indication of the oxygen concentration in the
environment. The differences in oxygen concentration between different sites on a metal lead to
the differential aeration corrosion mentioned above. By means of the Pourbaix diagram, through
potential and pH measurements, some idea can be gained about the tendency of a metal to be in
an immune, passive, or corroding regime and also to estimate the influence of limited or ready
access of oxygen on the corrosion process.
Kinetics, corrosion rates
While it is necessary to determine corrosion tendencies by measuring potentials, it will not be
sufficient to ascertain whether a given metal or alloy will suffer corrosion under a given set of
environmental conditions. Because even though the tendency for corrosion may be high, the rate
of corrosion may be very low, and thus corrosion may not be a problem.
Corrosion
rates are
determined by
applying a
current to
produce a
polarization
curve (the
degree of
potential
change as a
function of
the amount of
current
applied) for
the metal
surface whose
corrosion rate
is being
determined.
When the
potential of
the metal
surface is Fig. 3 Schematic illustration of plots of potential "E" against
polarized by the logarithm of the current density "i" (polarization curves)
the produced by making the investigated metal surface an anode
application of and then a cathode. Two cathodic reactions are shown, the one
the current in with the higher cathodic exchange density "i2o,c" giving the
a positive higher corrosion current "i2corr". The extrapolations of the
direction, it is anodic and cathodic curves produce the Evans diagrams (see
said to be Figure 4).
anodically
polarized; a negative direction signifies that it is cathodically polarized. The degree of
polarization is a measure of how the rates of the anodic and the cathodic reactions are retarded
by various environmental (concentration of metal ions, dissolved oxygen, etc. in solution) and/or
surface process (adsorption, film formation, ease of release of electrons, etc.) factors. The former
is called concentration polarization the latter activation polarization. The variation of potential as
a function of current (a polarization curve) allows one to study the effect of concentration and
activation processes on the rate at which anodic or cathodic reactions can give up or accept
electrons. Hence, polarization measurements can thereby determine the rate of the reactions that
are involved in the corrosion process – the corrosion rate.
Figure 3 shows anodic and cathodic polarization curves that represent anodic reactions (like
metal dissolution) or cathodic reactions (for example, oxygen reduction or hydrogen evolution).
In Figure 3 the potential "E" is plotted as a function of the logarithm of the current density "i".
When the corrosion reactions are controlled by activation polarization, as is frequently observed,
polarization behavior will be a straight line on this plot following the Tafel equation (see also the
Appendix). On this figure, "Eo,a" and "Eo,c" are the equilibrium potentials for the reactions under
consideration (anodic or cathodic). The "Tafel lines" are characterized by the "slope" of the
linear part of the polarization curve and by their "intercept" when extrapolated to the equilibrium
potential. The "intercept" is proportional to the logarithm of the exchange current density "io"
(that is expressing the inherent rate of the electrode reaction). The values of these characteristic
constants in the Tafel equation depend on the metal and the environment under consideration. It
is possible to extrapolate the anodic and cathodic linear portions of the polarization curves to the
corrosion potential "Ecorr", where, under ideal conditions, they should intersect. The value of the
current at their intersection will be the rate of corrosion "icorr" expressed in current density. The
values of the exchange current densities for the cathodic and anodic reactions have a profound
effect on the corrosion rate. This is illustrated with an example of using two values of "io,c" (but
assuming, for sake of simplicity, that "Eo,c" is constant): the larger the "io,c" – the larger the
corrosion rate, "icorr" (see Figure 3).
Parts of the
extrapolations shown
in Figure 3 produce
the diagrams (Evans
diagrams) shown in
Figure 4. The relative
values of the "slopes"
of the anodic or
cathodic polarization
curves, determine
whether the anodic,
cathodic, or both
reactions control the
rate of the corrosion
process. Evans
diagrams are used
extensively by
corrosion scientists
and engineers to Fig. 4. Evans diagrams (produced from the
evaluate the effect of extrapolation shown in Figure 3, illustrating
various factors on three main ways in which the corrosion rate can
corrosion rates. be mainly controlled: (a) control by the
Passivity and reactions on the anode; (b) control by the
the breakdown of reactions on the cathode; and (c) control by a
mixture of both.
passivity
Since both driving force (corrosion-tendency) and kinetic (corrosion-rate) considerations are
crucial in determining the extent of corrosion of a metal surface, a crucial factor controlling the
rate is the existence of the phenomenon of passivity for certain metals and alloys, such as
stainless steels and titanium. Considerable controversy still exists about what process is
responsible for the existence of the phenomenon of passivity, even though many studies were
carried out to develop a better understanding of it. For the purposes of this discussion, it is
sufficient to characterize passivity as the conditions existing on a metal surface, because of the
presence of a protective film whose nature is the source of the controversy, that markedly lower
the rate of corrosion, even though active corrosion would be expected from driving force
(corrosion-tendency) considerations.
To be effective, a passive film must provide a protective barrier that keeps the corrosion current
on a metallic surface at a low enough value so that the extent of corrosion damage is minimized.
An effective film is one that resists the breaching (called the breakdown) of the passive film.
Breakdown processes lead to the forms of localized corrosion that are some of the major sources
of corrosion failures, pitting, crevice, intergranular, and stress corrosion (see below). They cause
the disruption of the passive film and thus expose discrete bare sites on the metal surface to an
environment where the tendency for attack is very high. The many mechanisms proposed for
chemical breakdown are based on two models, each having many variations. They are (i)
Adsorbed Ion Displacement Models and (ii) Ion Migration or Penetration Models. Two types of
breakdown processes exist: electrochemical breakdown where many studies have found that
breakdown takes place at a potential above a specific "breakdown potential," and mechanical
breakdown which occurs when the passive film is ruptured as a result of stress or abrasive wear.
It should be noted that all breakdown mechanisms involve a damaging species. Unfortunately,
one of the major species causing breakdown of passivity is the chloride ion, a damaging species
abundantly available in nature.
Competing with the passive film breakdown process is the passive film repassivation process.
Thus, an effective alloy for resisting localized corrosion would be one whose surface not only
forms a passive film that resists the process leading to breakdown but also is capable of
repassivating at a rate sufficiently high so that, once breakdown has occurred, exposure to a
corrosive environment is minimal.
Types of corrosion
The breakdown and repair of passivity process just described is involved in many but not all of
the various types of corrosion.
Pitting corrosion
The initiation of a pit occurs when electrochemical or chemical breakdown exposes a small local
site on a metal surface to damaging species such as chloride ions. The sites where pits initiate are
not completely understood, but some possibilities are at scratches, surface compositional
heterogeneities (inclusions), or places where environmental variations exist. The pit grows if the
high current density – the area of breakdown initiation is exceedingly small – involved in the
repassivation process does not prevent the formation of a large local concentration of metal ions
produced by dissolution at the point of initiation. If the rate of repassivation is not sufficient to
choke off the pit growth, two new conditions develop. First, the metal ions produced by the
breakdown process are precipitated as solid corrosion products (such as the Fe(OH)2, Appendix,
Equation [7]) which usually cover the mouth of the pit. This covering traps the solution in the pit
and allows the buildup of positive hydrogen ions through a hydrolysis reaction (Appendix,
Equation [5]). Then, chloride or another damaging negative ions diffuse into the pit to maintain
charge neutrality. Consequently, the repassivation becomes considerably difficult because the
solution in the pit is highly acidic, contains a large concentration of damaging ions and metallic
ions, and contains a low oxygen concentration. Thereby the rate of pit growth accelerates.
The pit is the anode of an electrochemical corrosion cell, and the cathode of the cell is the non-
pitted surface. Since the surface area of the pit is a very small fraction of the cathodic surface
area, all of the anodic corrosion current flows to the extremely small surface area of the
breakdown initiation site. Thus, the anodic current density becomes very high, and penetration of
a metal structure bearing only a few pits can be rapid.
Crevice corrosion
Crevice corrosion
results when a portion
of a metal surface is
shielded in such a
way that the shielded
portion has limited
access to the
surrounding
environment. Such
surrounding
environments contain
damaging corrosion
species, usually
chloride ions. A
typical example of
crevice corrosion is Fig. 5. An idealized picture of the environment
the crevice formed at that develops in a crevice by the corrosion cell
the area between two produced on iron by an anode in a crevice and
metal surfaces in a cathode outside of the crevice.
close contact with a
gasket or another metal surface. The environment that eventually forms in the crevice is similar
to that formed under the precipitated corrosion product that covers a pit (Figure 5). Similarly, an
electrochemical corrosion cell is formed from the couple between the unshielded surface and the
crevice interior exposed to an environment with a lower oxygen concentration compared with the
surrounding medium. This combination of being the anode of a corrosion cell and existing in an
acidic, high-chloride environment where repassivation is difficult makes the crevice interior
subject to corrosive attack.
Stress corrosion cracking, hydrogen damage, and corrosion fatigue
Stress corrosion cracking (SCC) is a form of localized corrosion which produces cracks in metals
by the simultaneous action of a corrodent and tensile stress. The electrochemical cell between the
exterior and the interior environments of a crack is similar to that described above for a crevice.
Because of the necessity for the application of stress, the breakdown of the passive layer on a
metal surface in SCC is generally ascribed to mechanical causes but many suggest that
electrochemistry is a significant factor because it controls the rate of repair of the passive layer
ruptured by mechanical stress.
Corrosion fatigue has a somewhat similar mode of failure to SCC. It mainly differs from SCC in
that it involves situations where the stress is applied cyclically rather than as a static sustained
tensile stress. With both corrosion fatigue and SCC, the issues of film mechanical breakdown,
repassivation, adsorption of damaging species, hydrogen embrittlement, and electrochemical
dissolution are to greater or lesser extents involved in determining susceptibility.
Intergranular corrosion
With the exception of metallic glasses, the metals used in practical devices are made up of small
crystals (grains) whose surfaces join the surfaces of other grains to form grain boundaries. Such
boundaries or the small regions adjacent to these boundaries can under certain conditions be
considerably more reactive (by being more anodic) than the interior of the grains. The resulting
corrosion is called intergranular corrosion. It can result in a loss of strength of metal part or the
production of debris (grains that have fallen out).
Uniform corrosion
Uniform corrosion results from the sites, not necessarily fixed in location, that are distributed
over a metal surface where the anodic and cathodic reactions take place. Uniform corrosion
damage, sometimes called wastage, is usually manifested in the progressive thinning of a metal
part until it virtually dissolves away or becomes a delicate lace-like structure.
Galvanic (and thermogalvanic) corrosion
Two metals having different potentials in a conducting electrolyte result in the more anodic
metal usually being attacked by galvanic corrosion. Because of electrical contact between two
different metals, galvanic corrosion differs from the other forms of corrosion described
previously in that the anodic and cathodic sites of the corrosion cell reside separately on the two
coupled different metals comprising the corrosion cell, while for the other forms of corrosion, the
cathodes and anodes exist on the surface of the same metal.
The value for the differences in potential between two dissimilar metals is usually obtained from
a listing of the standard equilibrium potentials for the various metals (for reactions of the type
given in Appendix, Equation [1]). However, since the standard potentials assume bare metal
surfaces in a standard solution containing their ions at unit concentration (strictly speaking,
activity), while in practice metals invariably have films on their surfaces and are exposed to
nonstandard environments, these potentials are not always reliable guides to the corrosion
tendencies of the anodic member of a corrosion cell produced by two coupled dissimilar metals.
Another factor besides the coupling of two different metals that can lead to galvanic corrosion is
a difference in temperature at separated sites on the same metal surface. Such a situation leads to
thermogalvanic corrosion. This kind of corrosion can be encountered in heat exchanger systems
where temperature differences are common.
Selective leaching
When one component of an alloy is removed selectively by corrosion because there exist
differences in potential between different constituents of an alloy – a situation analogous to that
of the galvanic corrosion of coupled dissimilar metals. This results in an increase in the
concentration of the remaining components and selective leaching occurs. This type of corrosion
is also called parting and, after the most common example, the selective leaching out of zinc
from brass, dezincification.
Erosion corrosion
Erosion corrosion result from the disruption of protective passive films by erosive or abrasive
processes. Once the protective or passive film is removed in an aqueous electrolyte, the
electrochemical processes for the types of corrosion described above take place.
Corrosion prevention
The types of electrochemical corrosion just described can be prevented or controlled by utilizing
the current understanding of the principles underlying corrosion processes. This understanding
has been the basis for the development of a number of corrosion prevention measures.
Three corrosion
control measures are
based on
electrochemical
driving force as
shown in the
Pourbaix diagram
given in Figure 6: (i)
Cathodic protection –
proposed to the
British Admiralty for
corrosion protection
of copper-sheathed
ships by Sir Humphry
Davy in 1824 –
provides corrosion Fig. 6. Pourbaix diagram for iron showing how
control by making the corrosion protection can be achieved by using
structure to be measures that bring a corroding system into
protected the cathode either the immunity or the passivity region.
of a corrosion cell by
bringing the potential of the structure into or near the immunity region of the Pourbaix diagram;
(ii) Anodic protection makes the structure to be protected an anode and an applied current brings
the structure's potential into the passivity region of the Pourbaix diagram; and (iii) Environment
modification by changing the pH to bring the structure to be protected into either the immunity or
passivation regions.
Other measures used to control electrochemical corrosion processes are the following: (i)
Corrosion resistant alloys are developed to be corrosion resistant and contain constituents such
as chromium, which produce more effective protective films that resist breakdown and
repassivate rapidly. (ii) Coatings are an artificial barrier to the corrosive environment on a metal
surface as contrasted to the naturally formed barrier that a corrosion resistant alloy provides. The
most widely used organic coatings are paints. Other organic coatings include lacquers, waxes,
and greases. Some metallic coatings such as chrome plate provide a protective barrier because
they are more corrosion resistant than the metals they protect. Zinc coatings, however, act in the
opposite manner. This coating, because it has a greater tendency to corrode than the metal to
which it is applied, cathodically protects it. Finally, ceramic coatings such as porcelain enamels
and glasses are used to protect metal surfaces by providing chemically resistant barriers, usually
oxides, which are more stable than metals. (iii) Corrosion inhibitors are added to the
environment in which a given metal must be used to make the environment less corrosive. The
inhibitors act either by adsorbing on metal surfaces by providing barriers to the environment or
by keeping the environment from becoming more corrosive by providing a buffering action.
Appendix
Corrosion rections
Some examples of the anodic and cathodic reactions that occur simultaneously on a metal
surface in a "corrosion cell" are as follows.
A typical anodic oxidation that produces dissolved ionic product, for example for iron metal is:
[1] Fe ==> Fe2+ + 2e-
Examples of cathodic reductions involved in corrosion process are:
[2] O2 + 2H2O + 4e- ==> 4OH-
[3] O2 + 4H+ + 4e- ==> 2H2O
[4] 2H+ + 2e- ==> H2
The cathodic reaction represented by Equation [2] exemplifies corrosion in natural environments
where corrosion occurs at nearly neutral pH values. Equations [3] and [4] represent corrosion
processes taking place in the acidic environments encountered in industrial processes or for the
confined volumes (pits, crevices) where the pH can reach acidic values because of hydrolysis
reactions such as:
[5] Fe2+ + 2H2O ==> Fe(OH)2 + 2H+
This reaction produces H+ ions, the concentration of which can, uder certain conditions, become
large if the H+ ions cannot readily move out from a confined volume. The overall corrosion
reaction is, of course, the sum of the cathodic and anodic partial reactions. For example, for a
reaction producing dissolved ions (sum of reactions [1] and [4]):
[6] Fe + 2H+ ==> Fe2+ + H2
or, for a reaction producing insoluble hydroxide (sum of reactions [1] and [2]):
[7] 2Fe + O2 + 2H2O ==> 2Fe(OH)2
Tafel equation
The Tafel equation is an early (1905) empirical relation between the overpotential of the
electrode and the current density passing through the electrode:
"a" and "b" are characteristic constants of the electrode system. A plot of electrode potential
against the logarithm of the current density is called the "Tafel plot" and the resulting straight
line the "Tafel line". "b" is the "Tafel slope" that provides information about the mechanism of
the reaction, and "a" the intercept, provides information about the rate constant (and the
exchange current density) of the reaction.
Related articles
Anodizing
Corrosion inhibition
Bibliography
• Principles and Prevention of Corrosion (2nd edition), D. A. Jones, Prentice Hall, Upper
Saddle River NJ, 1996.
• Corrosion (two volumes), L. L. Shreir, R. A. Jarman, and G. T. Burstein (editors),
Butterworth-Heinemann, Oxford, Boston, 1994.
• Advances in Localized Corrosion: NACE-9, H. S. Isaacs, U. Bertocci, J. Kruger, and S.
Smialowska (editors), National Association of Corrosion Engineers, Houston TX, 1990.
• Passivity of Metals – a Materials Science Perspective, J. Kruger, "International Materials
Reviews" Vol. 33, pp 113-129, 1988.
• Corrosion Engineering (2nd edition), M. G. Fontana, McGraw-Hill, New York, 1986.
• Corrosion and Corrosion Control: An Introduction to Corrosion Science and Engineering
(3rd edition), H. H. Uhlig and R. W. Revie, Wiley, New York, 1985.
• Basic Corrosion and Oxidation, J. M. West, Ellis Horwood, Chichester UK, 1980.
• Passivity of Metals, R. P. Frankenthal and J. Kruger (editors), The Electrochemical
Society, Pennington NJ, 1978.
• Atlas of Electrochemical Equilibria in Aqueous Solutions (2nd edition), M. Pourbaix,
National Association of Corrosion Engineers, Houston TX, 1974.
Copyright Notice.
THE ELECTROCHEMICAL SOCIETY: THE FIRST

HUNDRED YEARS, 1902 - 2002
Mary Yess
The Electrochemical Society, Inc.
Pennington, NJ 08534-2839, USA
WWW Home Page: http://www.electrochem.org/
(September, 2008)
The Electrochemical
Society (ECS) has a
birthplace of historic
distinction – Philadelphia –
the home of Benjamin
Franklin (and his famous
kite) and the birthplace of
the United States. The
Society originally was
called the American
Electrochemical Society,
but, like the nation, it had its
roots in distant lands. ECS
was like the nation in other
respects. It was a melting
pot; in this case, a melting
pot of scientific and
technological disciplines,
and of their adherents, who
came from countries from
Australia to Mexico to
Russia and points in
between.
The following photo
essay is a distillation of the
Society’s history – the usual
dates, names, and
significant markers, but also some amusing anecdotes and intriguing photographs. We hope you
will enjoy this quick look at a society that has made its mark on the world of electrochemistry
and solid-state science and technology.
Beginnings...
The Society’s roots can be traced farther back in time than when our story begins. Relics
found in the Middle East suggest that, thousands of years ago, voltaic cells were being used.
Electroplating of some sort is known to have existed in those times as well.
1800 --- Alessandro Volta concluded that a “pile” of dissimilar metals provided the electricity
responsible for the twitching of frogs’ legs reported by Galvani.
1815 --- Humphry Davy used a group of these “piles” to discover and isolate the elements
potassium, sodium, and calcium. Davy also coined the term “electrochemical.”
1831 --- Michael Faraday was led to formulate the laws of electrolysis and was the first to use
the terms anode, cathode, electrode, ion, cation, anion, and electrolyte. He was the first to
propose that the passivation of iron in concentrated nitric acid was due to the formation of an
oxide film.
1856 --- William Perkin invented the first synthetic dye. The Society of Chemical Industry
instituted the Perkin Medal in his honor in 1906, and ECS is one of six societies able to nominate
candidates for the award.
1879 --- Thomas Edison patented the carbon-thread incandescent lamp. This man of many
talents (and patents!) joined ECS in 1903.
1886 --- Charles M. Hall in the United States and Paul L. T. Heroult in France (both became
ECS members) simultaneously inaugurated electrolytic processes that had great industrial
importance: the production of aluminum.
1888 --- Edward Weston

formed the Weston
Electrical Instrument Co.
Weston invented the
“Weston Cadmium Cell”,
which became the voltage
standard throughout the
world, and which is
depicted in the Society’s
official seal. In 1873,
Weston had adapted the A wonderful drawing of Edward
electric generator for Weston’s company in Newark, NJ,
electroplating, the first where the first dynamo was made.
important industrial
application of electrochemistry
1890 --- Herbert Dow started the Midland Chemical Co., the first to use electrolytic apparatus to
commercially manufacture a chemical other than metal; in this case, to extract bromine from
brine.
1891 --- Edward Acheson discovered silicon carbide, which he called carborundum, a better
abrasive than any other known substance except diamond.
1901 --- Edison formed a battery company and marketed a rechargeable nickel-iron battery. At
one time, Edison had a rather dim view of rechargeable batteries, judging from a quote attributed
to him: “The storage battery is… a mechanism for swindling the public by stock companies…
Scientifically, storage is all right, but, commercially, as absolute a failure as one can imagine.”
By the beginning of the 20th century, many talented individuals had invented and were
building the foundations and infrastructures for the communications, electronics, illumination,
and entertainment revolutions that would come to play such important roles in our lives and in
the yet-to-be formed ECS.
Founding... Faraday
Hall
Heroult
1902 Edison
• The first Tyrannosaurus
rex fossil was discovered by Dow
the famous fossil hunter
Barnum Brown.
• Feeling the need for a
forum at which
electrochemical matters could
be discussed and argued, some Reed
members of the American
Chemical Society (ACS)
proposed the formation of a
new section devoted to the
field of electrochemistry. ACS The Manufacturers’ Club –
demurred. One man, C. J. site of the founding meeting
Reed, was especially interested of The Electrochemical
in creating a new society as Society.
such a forum, and gained the
support of Joseph W. Richards, a
prominent professor of metallurgy at Richards
Lehigh University. A letter was sent
to about 30 engineers, chemists, and scientists, soliciting members for the new society. The
qualifications for membership were rather simple – express an interest in electrochemistry and
pay the $5 annual dues.
• The first meeting of the American Electrochemical Society was held at the
Manufacturers’ Club in Philadelphia on April 3, 1902; it was attended by 52 of the 337 charter
members. A motion to organize passed unanimously. Richards, the acting chairman, was elected
president; Reed as secretary; P. G. Salom as treasurer; and six vice-presidents and seven
“managers” also were elected. This leadership represented a good mix of scientific and
technological disciplines and indicated from the start that the term “electrochemistry” might
encompass a broader range of interests than the name implied.
• The original constitution called for publication of papers presented at the meetings and of
the discussions that ensued; this was accomplished in 1902 with the new publication,
Transactions of the American Electrochemical Society.
1903
• Marie and Pierre Curie shared the Nobel Prize in Physics and the Wright brothers made the
first powered flight.
1904
• John Ambrose Fleming invented the vacuum diode tube.
• The international ties were strengthened when the sixth Society meeting was jointly
sponsored with the Bunsen Gesellschaft and the Faraday Society. The Board discussed a request
from members at the University of Wisconsin, asking to form the Society’s first Local Section,
which would come to fruition in 1907. (The “Local” was dropped in 1998.)
1906
• J. J.
Thomson
discovered the
electron and Lee
de Forest invented
the triode vacuum
tube.
• The 10th
meeting was held
at Columbia
University.
Professor Charles Thomas Edison’s laboratory in Menlo Park, NJ. (From
F. Chandler, Vol. 54 of the Transactions.)
dean of American
chemists, welcomed the gathering:
“Mr. President and fellow members
of the youngest scientific organization Chandler
in this country, which, I think, may
prove the most important… You have already worked a revolution in many branches of chemical
industry and seem destined to change entirely the character of a large proportion of chemical
operations…” Chandler would later be named the first Honorary Member of the Society.
• One of the popular features of the 10th meeting was an “excursion” to Thomas Edison’s
Laboratory in West Orange, New Jersey. Edison had been approached earlier, but declined.
This time, Edison agreed, and in response to a letter confirming that the Society would schedule
an excursion, Edison noted to his secretary, “Say it will be all right but I have very little that will
be interesting.”
1907
• ECS member Leo Baekeland
developed Bakelite, the first synthetic
plastic that could be molded into
durable products. In 1995, the Jupiter
probe used a form of Baekeland’s
invention for its heat shield.
• The four-page monthly
American Electrochemical Society
Bulletin began circulation to the Baekeland
membership. It contained such things
as lists of individuals applying for membership, newly elected members, information on
meetings, situations wanted, positions available, and general news of interest to members. Many
issues contained listings of patents of interest to electrochemists, as well as book reviews. The
Bulletin was discontinued in 1948, with the appearance of the Journal of The Electrochemical
Society.
1908
• Henry Ford introduced the Model T car.
1910
• The agenda for the 1910 fall
meeting included an evening smoker
with entertainment by SECTION Q.
The special “section" was apparently
organized by the Canadian W. Lash
Miller to “promote intimacy and
friendship.” It seems that Miller
provided all members at the initial
meeting of Section Q with lighted Miller
candles and at the appropriate time
there was a lighted procession to visit a laboratory. This was reported to have resulted in much
joviality – one wonders why, but perhaps it was the bagpipers who led the procession. Lawrence
Addicks, in his Fiftieth Anniversary address, recounted a number of other Section Q
shenanigans. One was the bribing of two New York City policemen to accompany two hired
vaudeville actors in staging a mock raid on a technical session in the Chemists’ Club, to the
horror of Carl Hering, “the embodiment of gentlemanly reserve.”
1911
• The First Emblem Of The
Society, a handsome blue
enamel and gold pin (pictured
at left), was made by Tiffany of
New York.
1915
• At the spring meeting in
Atlantic City, Technical
Committees were established to
consider and report on topics
related to electrochemistry. The
first ten were: Primary Batteries,
Secondary Batteries, Electric
Furnaces, Electrolysis,
Electroanalysis, Electrometallurgy, Electroplating, Radioactivity, Chlorine and Caustic, and
Experimental and Theoretical Electrochemistry.
• At the invitation of the Panama-Pacific International Exposition, the Society journeyed
to San Francisco for its 28th meeting. The Society was welcomed officially by the management
and presented with a commemorative medal (pictured above).
1916
• Einstein published the general theory of relativity.
1917
• With the advent of World War I, the Society was asked for its opinion on such weighty
matters as the optimum size for the navy and how to defend against submarine attacks on U.S.
shipping.
1918
• The purpose of the
Appalachian South
Meeting was to tour
electrochemical centers in
that region for the
education of northern and
western members. It was
necessary to get the
permission of the Director-General of Railroads (the war was still on) to use a special train.
Everywhere the party went it was received with “distinguished consideration”. At some places
the railway stations were decorated with bunting and banners of welcome stretched across the
streets. At others, school children waving flags lined up on the pavement and greeted the party
with cheers. The trip included the interesting experiment of “ducking in flour for coins” (pictured
at left).
The Colin Fink Era...

1921
• Shortly after the fall meeting,
Joseph W. Richards died suddenly.
The Society held an extraordinary
meeting in his memory in New York
City. The Society now needed a
secretary as dedicated to its needs as
was Richards. Fortunately, Colin C.
Fink, who had also served as
president, was such a man. Fink was a Fink
hands-on, take-charge kind of person.
The Society was equally fortunate that during Fink’s 26-year tenure, Columbia University not
only allowed Fink to pursue his duties as secretary but provided sufficient office space to house
the Society’s operations.
• The Society’s bylaws were changed to provide for the formation of the Divisions, with
representation on the Board. Members were allowed to register for membership in any Division
of interest.
• The roots of the High Temperature Materials Division (HTM) trace back to 1921, when
it was founded as the Electrothermics Division, the first formalized division of the Society.
1922
• The Electrodeposition Division was officially formed at the spring meeting, but the first
important symposium on the science of electroplating was recorded in the 1913 volume of the
Transactions.
• The fall meeting was held in Montreal. Prohibition was the law of the land in the U.S., and
the Canadian venue was perhaps an attractive one for those who enjoyed a little wine with
dinner. An old-fashioned smoker was on the program, and given the venue and the convivial
atmosphere, there was doubtless a session of Section Q. Smoking was quite in fashion in those
days and smoke-filled rooms were by no means restricted to political conventions.
1925
• Irving Fellner and E. M.
Honan were asked to draw up a
design for a Society Emblem in
1924. That drawing (pictured at
left) was rejected; but in 1925, a
new design was accepted by the
Board. The Society seal made its
first appearance on the masthead of
the December 1925 issue of the Bulletin. The center field of the design incorporates a Weston
Standard Cell and an arc playing between horizontal electrodes, symbolizing electrolytic and
electrothermic reactions. With the addition of the incorporation notice, the final version of the
Society’s corporate seal was approved in 1930.
• The Transactions
often make reference to
programs for the “ladies.”
In the early days, any
women in attendance
were almost certainly the
spouses of the male
members or guests. A
notable visit for all at the
spring meeting was a visit
to the Niagara Falls Power Company. The visitors witnessed a demonstration of the power
company’s Large Scale Model of the Falls (pictured at left). The model was 1/100th of the size
of the Falls and used 28,000 liters of water per minute. As the number of women participating as
technical registrants increased, the term “nontechnical registrant” was used, but the interesting
programs continued to be offered.
1926
• Colin G. Fink patented the chromium plating process. (Columbia University’s chemistry
department is still the repository of Fink’s famous doorknobs, the first objects to be plated with
chromium by this process.)
1927
• Werner
Heisenberg
proposed the
Uncertainty
Principle.
• Thirteen
Charter
Members Charter members photographed at the Silver Jubilee
attended the Meeting in 1927 in Philadelphia. From left to right
Society’s Silver are: Carl Hambuechen, J. H. Clamer, Louis
Jubilee Meeting in Kahlenberg, Wilder D. Bancroft, Herbert H. Dow,
Philadelphia. Frederick M. Becket, Lawrence Addicks, Samuel S.
Papers were Sadtler, Alfred H. Cowles.
presented by
Peter Debye and Victor LaMer on Debye
the electrochemistry of concentrated
solutions; these papers were important in developing the theoretical aspects of this subject.
Debye would go on to win the Nobel Prize in Chemistry in 1936.
• The Northwest
Train Trip was unlike
any Society meeting
before, or since. The trip
consisted of technical
sessions and a great deal
of sightseeing. The
meeting “began” in
Chicago, Illinois on
September 5 and made its
way to Vancouver, British
Columbia. There were
many stops along the
way, including one to the famous Leonard copper mine in Montana, where members had the
opportunity to don authentic mining apparel (pictured at left). The meeting “ended” on
September 21 back in Chicago.
1928
• A major development was the
receipt of $25,000 from Edward
Goodrich Acheson to establish a
fund that would support a gold medal
and prize award. The Acheson Award
became a major award of the Society.
The spirit of giving was rampant in
1928, for later that year, a fellowship
Acheson
fund was established, following
another gift of $25,000, this time
from Edward Weston.
1930
• The international nature of
the Society was officially
recognized by dropping
“American” from the name. The
Electrochemical Society was
incorporated in the State of New
York, and the basic design of the
Society Seal with the addition of
the notice of incorporation was
modified to its current form (as pictured at left).
1931
• Max Knoll and Ernst Ruska invented the electron microscope and Ernest Lawrence
invented the cyclotron.
• A significant event of the Salt Lake City meeting was the establishment of the Electronics
Division. This Division was to remain quiescent for two decades or so before becoming a major
force in the Society.
1935
• At the fall meeting in
Washington, DC, the Acheson Medal
was awarded to F. J. Tone, president
of the Carborundum Company and a
former Society president. However,
headlines in the Washington Post on
the following morning read,
“Franchot Tone’s Father Receives a
Tone
Medal.” Franchot Tone was a leading
Hollywood actor, who had portrayed
characters such Roger Byam in the original 1935 “Mutiny on the Bounty.” In his final
presidential address back in 1904, Joseph Richards had referred to Tone’s “electrometallurgical
triumph” of producing silicon: “I had a somewhat uncanny feeling when Mr. Tone introduced
me to his half a ton of silicon… What will be made of it? Can it become as useful as iron?
Probably not. Can application be found for it, which will bring it among the ordinary metals of
everyday life? Possibly.” The answers to his questions would have astounded Richards and Tone
alike!
1936
• The Niagara Falls meeting
presented exhibits of products of the
electrochemical industries. A former
president, the eminent Willis R.
Whitney, presented an entertaining
and informative address entitled,
“More Research.” The talk was wide
ranging, covering subjects as diverse
Whitney
as turtles, blushing shrimp, winking
of the eye and the optic nerve,
battleship communications, and luminaries such as Volta and Bacon. Whitney, founder of the
General Electric Research Laboratories and a Society president, was the object of Section Q’s
attention at an earlier Niagara Falls meeting (1909). Whitney was known to be an avid hunter of
Indian relics. At a picnic down in the gorge, Whitney found a nice arrowhead. He then found
some other arrowheads and naturally became quite enthusiastic. Then he found a really good one
– made of carborundum! Section Q had struck again.
• The Physical Electrochemistry Division was originally established as the General and
Theoretical Electrochemistry Division at the spring meeting. Chairmanship and responsibility for
organization of the new Division were delegated to Duncan A. MacInnes, who in 1936 also
took office as president of the Society. MacInnes went on to receive the Acheson Medal in 1948.
1938
• The Great Depression and the low level of membership in the 1930s raised doubts as to the
financial solvency and stability of the Society, in spite of the dedicated work of Secretary Fink.
President R. L. Baldwin convened an informal meeting to consider whether the Society should
dissolve or possibly affiliate with ACS. (At one Board of Directors meeting, a member reported
that he had offered the Society to the AIME and that the offer was rejected!) The alternative was
to continue, with efforts to raise more funds, attract new members, and improve meeting quality.
Needless to say, this latter course was chosen.
1940
• The founding of the Electro-Organic Division (now called the Organic and Biological
Electrochemistry Division) was spearheaded by Society president H. J. Creighton during the
years 1939-1940. He had the assistance of Sherlock Swann, Jr., who would go on to publish
(with Richard C. Alkire) the 1,000-page Bibliography of Electro-Organic Synthesis in 1979.
1941
• A category of Sustaining Membership was established as a means whereby industrial
companies could support the Society. This “Contributing Membership” program, as it is now
called, was initiated by Colin G. Fink in 1940, and he was largely responsible for obtaining the
first members. The recipient of Fink’s first letter of solicitation was the Mathieson Alkali Works.
They have since become a part of the Olin Corporation, which remained an active Contributing
Member. The other charter members were the Dow Chemical Corporation and Canadian
Industries, Ltd. (now ICI Canada, Inc.).
1942
• The Corrosion Division had its origin in the Corrosion Technical Committee, formed in
1922 under the chairmanship of Colin Fink. In 1942, the Corrosion Division was formally
established as the sixth Division of the Society.
1943
• One of the first Technical Committees established by the Board in 1915 was the Chlorine
and Caustic Committee, which reported annually on the technical developments and statistical
data of the chlorine-alkali industry. This committee was replaced in 1943 by the newly formed
Industrial Electrolysis Division, which later would become the Industrial Electrolysis and
Electrochemical Engineering Division (IEEE).
1945
• Vannevar Bush proposed “hypertext,” a PC prototype that would display text and pictures
from microfilm. The former MIT professor was President Roosevelt’s science counsel during
WWII. The year also saw the first test explosion of a nuclear device near Los Alamos, New
Mexico.
1946
• The Dielectric Science and Technology Division was founded in 1945 as the Electric
Insulation Division. Thomas D. Callinan, a later chairman of the Division, would note in 1952
that already there was a shift of interest from “power transmission to intelligence transmission”
and suggested that the recently discovered transistor would have a major impact on the field of
dielectrics.
• The University of Pennsylvania developed the ENIAC computer, containing 18,000
vacuum tubes.
• A Committee on Future Activities, under the chairmanship of former president H. S.
Lukens, made some far-reaching recommendations, including that a monthly journal be
established and that steps be taken to advance the professional status of members.
1947
• Considering that batteries are as “electrochemical” as anything can be, it might come as a
shock to learn that the Battery Division was not formed until 1947. During World War II, work
on batteries became extensive, and it was clear that a home had to be found where battery
information could be freely exchanged and reviewed for publication; the Society was the obvious
choice.
• In the spring, Colin G. Fink announced his resignation as Secretary, to take effect on July 1
of that year. He had served for 26 years and, by sheer personal effort and devotion, had
maintained the Society headquarters and minimized costs during a period of meager finances.
• Robert M. Burns accepted the

post of secretary with the proviso that
an assistant secretary and a managing
editor be hired. Robert J. Hollian
became the first assistant secretary.
Burns was to serve just two years as
secretary but, before, during, and after
his term, his influence on the future of
the Society was profound. No one
else has served the Society as Burns
president, vice-president, secretary,
and treasurer. His additional contributions as editor of the Journal and chairman of the
Publication Committee would influence greatly the early development of the Journal into a
quality scientific and technical publication.
• Late in the year, an event would occur that would result not only in an expanded ECS but
also in technological marvels that would change the way of life for many of the world’s
inhabitants. The event was, of course, the invention of the transistor on Christmas Eve, at Bell
Laboratories in Murray Hill, New Jersey.
Transition and Revival...
Read
1948
• The Journal of The
Electrochemical Society debuted in
January 1948; and publication of
Transactions was discontinued after
the 1949 issues. This publication of
technical papers on a monthly basis
provided much earlier distribution of
the content than had been possible
through the Transactions. Robert Uhlig
Burns, who was also serving as
secretary at the time, was the first editor. Harold J. Read served as Technical Editor, with the
responsibility for reviewing all papers assigned to Divisional representatives for their
appropriateness and technical content. He served until 1950 and would be named an Honorary
Member in 1986.
• One of the Society’s prime objectives was to fill an obvious need for a Corrosion
Handbook. ECS sponsored the publication and appointed Herbert H. Uhlig editor. When it was
published in 1948, it became the second of the Society’s monographs, and would go on to sell
over 24,000 copies. In the following year, Uhlig would become editor of the Journal and would
serve until 1951.
1949
• Henry B. Linford became secretary and served from 1949 to 1959. Linford, a professor at
Columbia University, completed the transformation of the Society office and operations. The
post of secretary had been an elective one throughout the history of the Society until Linford’s
appointment by the Board. The post then reverted to being an elective one upon Linford’s
election as vice-president in 1958. Henry Linford would become president in 1961 and Honorary
Member in 1974. Linford’s 35-year career at Columbia was marked by his distinguished
teaching, and an ECS award for teaching would be named for him.
1951
• Carl Djerassi (ECS plenary lecturer, fall 2000) synthesized the first steroid oral
contraceptive, the key to the development of “the Pill.”
• The Corrosion Handbook had been so successful, that the Board established the Palladium
Medal Award, employing royalties from the book and palladium metal generously donated by
the International Nickel Company. The first recipient of the Palladium Medal Award was Carl
Wagner, who was presented with the award at the 1951 fall meeting. Wagner was honored for
his outstanding contributions to the theory of oxidation and tarnishing of metals. Wagner was
also widely known for his seminal contributions in the field of defect chemistry of solid-state
materials.
1952
• The spring
meeting in Philadelphia
celebrated the 50th
Anniversary of the
Society. A highlight of
the meeting was a talk
by Lawrence Addicks.
He recalled some of his
Addicks
founding colleagues.
Richards “liked to
appear in remarkable A group of past presidents attended the 50th
gray frock coats… and anniversary meeting in Philadelphia.
kept a herd of St. Pictured here are (seated, left to right): H. S.
Bernard dogs at his Lukens, C. G. Fink, L. Addicks, F. C.
house on the Lehigh Mathers, and W. G. Harvey; (standing, left
campus making it look to right): R. M. Burns, A. T. Hinkley, H. J.
like a Swiss hospice.” Creighton, W. C. Moore, G. W. Heise, and J.
Wilder Bancroft was A. Lee.
remembered as often
“saying plaintively,
‘You can never convince anybody with facts,’ a remark of much wisdom.” Leo Baekeland
wasn’t happy when “we started to substitute a lantern (projector in today’s terms) for the
blackboard.” Baekeland’s experience with the lantern when lecturing at Columbia was that
“when he turned the lights back on he found that half his audience had sneaked out and the other
half was asleep.” Recognition of the anniversary year was emphasized in the Journal, which
published an anniversary feature in every issue that year.
• The presentation of 137 papers at the fall meeting in Montreal was the first to require
simultaneous sessions.
1953
• James Watson and Francis Crick proposed the double helix structure for DNA.
• The Society’s first monograph began life as a 1941 symposium on plating, sponsored by
the Electrodeposition Division. A volume was published in 1942 and was entitled Modern
Electroplating. A revised volume with some new material appeared in 1953, also as Modern
Electroplating, sponsored by the Society and published by John Wiley & Sons (New York). This
“first” edition would be followed by three others.
1955
• Cecil V. King became editor of
the Journal and served in that
capacity until 1969. King would write
a number of memorable editorials for
the Journal. King would become
president of the Society (1971-1972)
and would receive the Acheson
Award in 1974.
• Robert Shannon began to King
manage the Society office in 1955 as
assistant secretary. In 1958, he was named executive secretary, the title he had when he died
suddenly in 1964.
1957
• The Washington, DC meeting featured a symposium on “The Structure of Electrolytic
Solutions,” which was held in honor of the 70th anniversaries of Arrhenius’ postulation of the
theory of electrolytic dissociation. The National Science Foundation gave a $10,000 grant to the
Society for the publication of a proceedings volume, the beginning of a succession of grants for
similar symposia held by the Society.
1958
• Jack Kilby of Texas Instruments invented the integrated circuit. Kilby received the 2000
Nobel Prize in Physics for his work, and was the keynote speaker at the Society’s first meeting in
China in 2001.
• Wilson Greatbatch invented the implantable cardiac pacemaker. In The New York Times
Magazine article (December 9, 2001), the 82-year-old Greatbatch said, “I’m going to build a
rocket that has a propulsion that will give an acceleration of one G… One day we will be able to
get halfway to Mars in 25 hours. We don’t have the rocket or spaceship yet. But it will happen.”
Greatbatch has been a member of ECS since 1985.
1960
• Theodore Maiman invented the laser (light amplification by stimulated emission of
radiation).
1961
• Soviet cosmonaut Yuri Gagarin became the first human in space.
1963
• Electrochemical Technology began in 1963 in order to publish informative technical
articles that merited publication but did not report original research, as was required by the
Journal. The first editor, Al Loonam, did an outstanding job in launching and sustaining the new
publication. (When Loonam died suddenly in 1965, Norman Hackerman agreed to take over the
reins of Electrochemical Technology in addition to his duties as editor of the Journal.) The
publication had a relatively short life. A later committee recommended that the Society publish
only the Journal, and that it include three technical sections: Electrochemical Science, Solid-
State Science, and Electrochemical Technology. These recommendations were adopted and put
in effect in 1969. The changes resulted in more economical publication and more editorial
efficiency.
1964
• At one of these programming
sessions in 1964, the Society suffered
a great loss when Bob Shannon,
Executive Secretary of the Society,
was stricken with a heart attack and
died. Ernest G. Enck stepped in to
fill the vacancy. Enck was a dedicated
active member of the Society and
would go on to serve the Society until Enck
the end of January 1976.
1965
• One of the members of the
Electronics Division and co-founder
of Intel, Gordon Moore, proposed in
1965 that the number of transistors on
a silicon chip would double every
year (later revised to every 18
months). Moore joined the Society in
1957 and would give two plenary
Moore
talks, in 1981 and 1997.
1967
• Although many changes had taken place in publications, there was no assured record of
papers presented at meetings, for Divisions had the option of publishing booklets of abstracts
from their symposia, or not. To bridge the gap, the Society began to publish softcover volumes
containing Meeting Abstracts (then called Extended Abstracts) of all the papers to be presented at
the meetings.
• In the mid-1960s, the question was raised as to whether the name of the Society reflected
its broad interests. There were strong feelings on this matter, but the response to a 1967 letter
poll was overwhelmingly in favor of retaining the current name, rather than changing it to
another, such as the J. Willard Gibbs Society. Back in 1863, Yale University had granted its
first PhD in science to Gibbs. In 1876 and 1878, Gibbs established the field of chemical
thermodynamics with the publication of his treatises on thermodynamics, which were to be of
great significance to electrochemistry.
1968
• Richard Bechtold, on a lengthy
European assignment, resigned as
secretary. The Board appointed
Dennis Turner, secretary-elect, to fill
the remaining four months of
Bechtold’s term. When Turner took
over as secretary he found that,
surprisingly, the secretary was in
charge of finances, while the treasurer Turner
was in charge of meetings! Turner
quickly reversed this assignment of duties to its more logical condition with the treasurer being
in charge of finances. Turner was responsible for a number of beneficial changes to the Society’s
staffing and governance, and would give over three decades of service to the Society. He was
president from 1978 to 1979, received the prestigious Acheson Award in 1992, and received the
Vittorio de Nora Award in 2000. Turner would also serve as the Society historian for a number
of years, write a number of “ECS Classics” articles for Interface, and prepare material for the
100th anniversary history book.
1969
• The U.S. Defense Department developed the “Arpanet,” the precursor to the Internet. Intel
designed the first microprocessor. People walked on the moon for the first time – Neil Armstrong
and the U.S. Apollo 11 mission.
• The Society introduced softbound volumes containing the full-length papers of symposia.
These Symposium Volumes (renamed Proceedings Volumes in 1976), available either at the
meeting or shortly thereafter, were to be available as up-to-date treatments of the particular fields
of the symposia.
• The post of Technical Editor of

the Journal was eliminated and
Norman Hackerman was appointed
Editor for a period that would run
until 1990. Hackerman joined the
Society in 1943. In addition to his
editorial responsibilities, he served as
chairman of the Corrosion Division
(1951) and was elected president in
1957. He received the Olin Palladium Hackerman
Medal Award in 1965, was made an
Honorary Member in 1973, and received the Acheson Award in 1984. Hackerman would have an
illustrious career outside of ECS as well. He joined The University of Texas chemistry
department in 1945, and eventually became Vice-President, Provost, Vice-Chancellor for
Academic Affairs, and finally the University’s President in 1967. In 1970, Hackerman would
become President of Rice University until his retirement in 1985.
1970
• After the Richards Lectures
were discontinued in 1958, the
practice of having plenary lectures
didn’t begin until 1970. The new
series began with Leo Brewer, who
spoke on “Electrons – The Universal
Glue.” The list of notables, in both
series, includes a number of Nobel
Laureates: William Shockley (Physics Brewer
1955), Arthur L. Schawlow (Physics
1981), Jean-Marie Lehn (Chemistry 1987), Rudolph A. Marcus (Chemistry 1992), Richard E.
Smalley (Chemistry 1996), and William D. Phillips (Physics 1997).
• The list of Nobel Laureates involved with ECS goes on, including those who have joined
the Society or have spoken at its meetings, including: Fritz Haber (Chemistry 1918), Peter Debye
(Chemistry 1936), Linus Pauling (Chemistry 1954 and Peace 1962), Walter Brattain (Physics
1955), Jaroslav Heyrovsky (Chemistry 1959), and Jack Kilby (Physics 2000).
1971
• The Society Headquarters moved to U.S. Route 1, in the Princeton, New Jersey area. The
building had been constructed using steel that came from the India Pavilion at the last New York
World’s Fair. The period on U.S. Route 1 was not without incident. One day, a U.S. Mail truck
dropped a bag of Society mail containing meeting registrations and checks on the busy highway.
Unfortunately, the mail was scattered and largely destroyed by passing cars and trucks. The
building itself was not of the highest quality construction. The roof leaked and water would
sometimes emerge from electrical outlets. Wind would blow through the building even when the
windows were closed. On the occasion of the Society hosting an open house for the Metropolitan
New York Section, a water main burst, resulting in several inches of ice covering the parking lot.
1972
• The Society Headquarters office was assigned responsibility for the nontechnical
arrangements of Society meetings. This action benefited the meetings by relieving the Sections
of the problems associated with organizing them and by making accessible other venues that
could handle multisession meetings with over 1,000 attendees.
New Horizons...
1973
• The solid-state revolution was in full swing. The Society presented its first Solid State
Science and Technology Award to William G. Pfann at the spring meeting in Chicago. Pfann
was honored for his invention of zone refining, which yielded semiconductor materials of
unprecedented purity. Not your typical Bell Labs researcher, Pfann joined the Bell Labs
Chemical Research Department as a technician with no college degree in 1935 and was to
become one of Bell Labs’ most productive scientists.
1974
• Because of what happened with one of its major awards, the Society could be said to have
been involved in the Cold War! Professor V. G. Levich was named the 1973 recipient of the
Palladium Medal Award. However, the Soviet Union would not allow him to come to the
meeting to receive the award. After some controversy and a number of failed attempts, the prize
was finally delivered to Levich by Bruce Hannay at Bell Labs in 1980.
• In 1974, the Society first presented its fourth major award, the Electrochemical Science and
Technology Award, to Abner Brenner. Brenner, who died in 1999 at the age of 91, was best
known for his invention of the electroless nickel-plating process, upon which a whole industry is
based, as well as his many other seminal contributions to the field of electrodeposition. Prolific
to the end, he received his last of over 30 patents at the age of 90!
• In 1977, this award would begin to undergo a number of changes. Vittorio De Nora and
the Diamond-Shamrock Company, agreed to fund an endowment with a gift of $70,000. In 1990,
de Nora most generously added $70,000 to the endowment. In 1991, after the company had been
re-structured, the award was renamed the Vittorio de Nora Award. The award’s namesake is
most known for his contributions to industry in the manufacture of chlorine and in the
development of dimensionally stable anodes, which have revolutionized the electrochemical
(chlor-alkali) and electrometallurgical industries. He was named an Honorary Member in 1982.
1975
• Ernest G. Enck had served the Pfann
Society as a member, officer, and
staff member for many years and after Levich
announcing his retirement, was
named Executive Secretary Emeritus Brenner
and Honorary Member. V. H. “Bud”
Branneky became the executive De Nora
secretary of the Society. Branneky
was slated to serve the Society until 1991, and also would become an Honorary Member. His
tenure as executive secretary would be characterized by a dedication to maintaining a high sense
of fiscal responsibility in the Society.
1976
• The Board of Directors approved the formation of the Energy Technology Group, with
Jerry Woodall (dry) and Supramaniam Srinivasan (wet) as the co-founders. (It would become the
Energy Technology Division in 1987.) The Society’s first Group was formed to act as a bridge
between the “wet” and “dry” sides of the house in energy-related matters and to cover those
areas of energy-related topics not being adequately covered in the existing Divisions. (“Dry”
here refers to the solid-state, high temperature materials, dielectrics, etc. areas; while “wet”
encompasses the more conventional electrochemistry including batteries, corrosion,
electroplating and electrodeposition, and biological electrochemistry.)
• The Council of Sections Excellence Award was established under the guidance of
Gwendolyn B. Wood and was first presented to the New York Metropolitan Section for the
1975-1976 period. Wood had been an active member of the Society from 1952 until her death in
1975, actively supporting the National Capital Section and serving on the Council of Sections.
1977
• Society Secretary Paul Milner and Executive Secretary Branneky introduced computer
technology for handling Society business. Paul Milner would give many years of service to the
Society, providing his services and expertise behind the scenes as well as in more prominent
Society roles. He became a member in 1958, secretary from 1974 to 1980, and would become
president in 1984. He continued to assist the Society staff in solving computer and software
problems, and wrote several programs to help in many phases of Society business. A state-of-
the-art Milner computer program to help reduce lag time in the Journal was introduced in 1991
and lag times indeed improved remarkably.
1979
• Joan Berkowitz became the first woman president of the Society. Berkowitz joined the
Society in 1961. She was active in what is now the HTM Division and served as vice-chairman
and chairman. She became a Divisional editor of the Journal in 1966 and served on many
Society committees. Berkowitz designed, for the lunar space program, experiments in metals
melting and eutectic solidification in space; and coauthored a monograph on industrial utilization
of NASA developments in electroplating.
Branneky
Wood
Milner
Berkowitz
1980
• Society
Headquarters
moved from
rented space on
U.S. Route 1 to
its own building
at 10 South
Main Street in
Pennington, New
Jersey (pictured
at left). The
property In 1980, the peripatetic Society finally owned its own
originally was building, in Pennington, NJ, which it would occupy until
purchased in 1999.
1849 by one D.
C. Titus, a cabinetmaker according to an 1860 map. In 1902, Titus’ daughter, Rosalie Blackwell,
inherited the property, tore the old building down, and rebuilt it in 1903. Rosalie was reportedly
the first female lawyer in the United States.
1981
• Gerd Karl Binnig and Heinrich Rohrer invented the scanning tunneling microscope.
1982
• Under the leadership of George Gillooly, F. M. Ryan, and Martin Royce, luminescence
activity was resurrected. Their efforts culminated in 1982 with the formation of the Group that
would become, in 1993, the Luminescence and Display Materials Division (LDM) of the
Society. The LDM Division had its roots in the Electronics Division and the first luminescence
symposium was held in 1945 at a regional meeting of the Metropolitan New York Section.
1985
• Sir Harold Kroto, J. R. Heath,
S. C. O’Brien, R. F. Curl, and
Richard Smalley discovered the
unusual stability of the carbon-60
Buckminsterfullerene molecule
and deduce its structure. Smalley
later would give a talk at an early
ECS fullerenes symposium. A new class of
1986 materials came on
the scene in the 1980s
• K. Alex Mueller and J. Georg —the interesting
Bednorz discovered high- carbon-60 molecule
temperature superconductivity in — that would lead to
ceramic materials. the field known as
1987 fullerenes.
• The Society held its first joint international meeting with the Electrochemical Society of
Japan and the Japan Society of Applied Physics, in Hawaii, and it was the largest meeting in the
Society’s history to this point. Over 1,700 papers were presented, which resulted in a huge
“souvenir” – the meeting abstracts volume was almost 3" thick!
1988
• President Ron Enstrom appointed an ad hoc Long Range Planning Committee consisting of
Richard Alkire, Ralph Brodd, Larry Faulkner, Florian Mansfeld, Barry Miller, Arnold Reisman,
Laura Rothman, Forrest Trumbore, Bruce Wagner, and Dennis Turner as Chairman. Their report,
submitted to the Executive Committee in 1988, treated 14 different issues, a couple of which
were thought to deserve immediate attention. A major revision of the Journal and its editorial
staff structure was recommended to improve the quality of the Journal and the efficiency of
reviewing manuscripts; and a new publication was recommended to communicate better with the
membership, making the Journal a strictly technical journal. It was felt that the Society needed
to recognize active members who had made significant contributions to science and technology,
through the establishment of the category of Fellow. These recommendations were all adopted.
• The rapid growth of electrochemical sensor science and technology spawned many
symposia on sensors in the early 1980s. Dennis Turner decided that the Society needed a Sensor
Group and, to that end, organized a symposium on Chemical Sensors for the 1987 fall meeting in
Honolulu. The Sensor Group (now the Sensor Division) was approved by the Board of Directors
at the spring meeting in Atlanta.
1989
• When Martin Fleischmann and Stanley Pons announced “Cold Fusion” on March 23,
1989, a special evening session was quickly scheduled to the upcoming spring meeting in Los
Angeles. By the evening of May 8, the session featured talks by the principals, supporters, and
critics. The criticisms were devastating and cold fusion was to fade from the scene until 2002,
when new announcements would emerge.
1990
• Tim Berners-Lee, of CERN,
coined the name World Wide Web for
the global hypertext system.
• Following the recommendation
of the last Long Range Planning
committee, a new Editorial Board
structure for the Journal was
introduced. Reduction of lag time for Miller
manuscripts became a principal goal.
Norman Hackerman retired from the Journal after 40 years service as Technical Editor and
Editor.
• Barry Miller became Editor of the Journal in 1990, after his serving as a Divisional Editor
(1974-1989) under Hackerman. He was chairman of the Physical Electrochemistry Division
(1987-1989) and a coorganizer of the first symposia within the Society on fullerenes and on high
temperature superconductors. Miller would be made an ECS Fellow in 1992 and become
president in 1997. He was instrumental in the planning of the Society’s first joint international
meeting in Europe – the fall 1997 meeting in Paris.
1991
• Roque J. Calvo was named
Executive Secretary upon Bud
Branneky’s retirement. During
Calvo’s administration, the needs of
the Society would change in ways,
and at a pace, undreamed of by his
many predecessors. Technological
advances would greatly affect the way
Calvo
Headquarters did business. It would
begin with modems, faxes, and LANs
and rapidly progress to advanced databases and online publishing. Calvo’s title changed from
Executive Secretary to Executive Director in 1994.
1992
• During the fall meeting in
Toronto, it was announced that
Rudolph Marcus had won the
Nobel Prize in Chemistry. Marcus
was attending the meeting and the
Society staff quickly arranged a
full-scale reception in his honor.
The publications staff made some
quick changes to the new members
magazine, which had been some
time in the planning. After obtaining a good photograph of Marcus, and quick conferences with
the designer, the inaugural cover of Interface featured a Nobel Laureate.
• That new magazine was the implementation of a 1988 recommendation. It was intended to
serve all the functions of the “C” pages of the Journal, to broaden communication with the
members, and encourage new members to join the Society. The first issue of Interface, with Paul
Kohl as editor, appeared in the winter of 1992.
1993
• A major new class of materials had burst upon the scene in the 1980s – a form of carbon
containing 60 atoms in a structure resembling a soccer ball (called Buckyballs, after the architect
Buckminster Fuller) – and spurred a worldwide effort that became known as fullerenes. The New
Technology Subcommittee responded by sponsoring symposia on the topic. The response was
outstanding and a Fullerenes Group was formed at the fall meeting. (At the time of this writing,
the Group is applying for Divisional status.)
1995
• Early in the year, the Society launched the ECS Website and in June, began accepting
electronic meeting abstracts via e-mail.
• Paul A. Kohl became Editor of the Journal. Kohl had served as the first editor of Interface,
the Society’s members’ magazine, until his appointment to the Journal. Kohl received the
Society’s Carl Wagner Award in 2001.
• Jan Talbot became editor of Interface when Kohl was named editor of the Journal. Talbot
was a member of a number of Society committees, co-chaired many symposia, organized the
first few general Society student poster sessions, and co-edited a proceedings volume. In 2001,
Talbot would become Society president.
1996
• Two outstanding past presidents died just a few months apart: Charles W. Tobias and N.
Bruce Hannay. Both had distinguished careers in science and technology and contributed greatly
to the growth and stature of the Society.
• Charles Tobias is credited with founding the modern science of electrochemical
engineering through his teaching and research at the University of California, Berkeley. Tobias
contributed to the Society in many ways: through presentations of his work at meetings and in
publications, and his service as a leader of the Physical Electrochemistry Division and as Society
president (1970-1971). The Society honored him with numerous awards: Edward G. Acheson
Award and Prize in 1972, Honorary Member in 1977, Henry Linford Award for Distinguished
Teaching in 1982, and the Vittorio de Nora Medal and Prize in 1990.
• N. Bruce Hannay had a distinguished career at Bell Laboratories, rising to be vice-
president of research and patents from 1973 until he retired in 1982. He was a leader in the
research and development work that produced practical transistors and other solid-state devices.
He became involved in the Electronics Division of the Society soon after the transistor was
invented and was influential in improving the stature of the Division and in attracting to the
Society many new members involved in the new science and technology of semiconductors.
Hannay received many honors and awards, including the Society’s Edward G. Acheson Award
and Prize in 1976, the Perkin Medal in 1983, and the Gold Medal of the American Institute of
Chemists.
1997
• The year saw the first meeting Kohl
of the Society outside the U.S. or
Canada, and it was the first joint Talbot
venture with the International Society
of Electrochemistry (ISE). The fall Tobias
meeting, the largest in the Society’s
history, was held in Paris, France. Hannay
The meeting was a rousing success,
with 2,900 registrants and 2,463
papers, though the tragic death of Britain’s Princess Diana in Paris added a sobering note.
• Although the charter members of the Society had long since passed away, a very nice
remembrance of one of them came in 1997. The Society received a large bequest from the estate
of Carl Hering, a founding member and the Society’s first Secretary. The Society placed the
money in a separate fund, the interest to be used to help support the Centennial activities planned
for the 2002 spring meeting in Philadelphia.
1998
• In July, the rapid-publication
online journal, Electrochemical
and Solid-State Letters, was
launched. It was the first journal in
the field to use a system of
publishing papers online first – one
article at a time, as soon as they
have been accepted and prepared
for publication – with paper
publication to follow. Letters was
the natural outgrowth of the former
Accelerated Brief Communications and the subsequent Letters section of the Journal. To further
ensure its success, ECS developed a copublication agreement with the Electron Devices Society
of the IEEE. The online publication also benefits from an arrangement with the American
Institute of Physics (AIP) to produce the journal in a special format, enabling wide
interconnection among all online technical journals.
1999
• With so much
growth, the Society
Headquarters staff needed
more space, and was
finally able to move in
December to a new
building at 65 South
Main Street, just down
the street from the The central building on the ECS
existing Headquarters "campus" at 65 South Main Street in
Office. Pennington, NJ.
• Krishnan Rajeshwar was

named Editor of Interface, after Jan
Talbot resigned to take up her new
role as a vice-president of the Society.
Rajeshwar brought a number of
innovations to the magazine,
including alternating issues featuring
Divisions, with ones focused on
special topics. “Raj,” as he is known, Rajeshwar
has been a member since 1978 and has been active on many committees. He was chairman of the
Energy Technology Division and the New Technology Subcommittee. He has been an organizer
for many ECS symposia as well as an editor for proceedings volumes.
2000
• The Board of Directors unanimously voted to adopt an Official Acronym and Tagline to
identify Society (displayed below). The adoption of "ECS" formalized the shorthand that had
been used informally for decades by the members. The tagline would also help to give more
prominence to the “dry” side of the house, a need recognized by many planning committees
since the 1950s.
2001
• The 10th
International Meeting
on Lithium Batteries
(IMLB X) was held in
Como, Italy. The
conference was organized
by Bruno Scrosati, who
became an ECS vice- The Society’s first meeting in Europe,
Scrosati
president, and who is and its largest to date, was sponsored
scheduled to become jointly with the International Society of
(2003-2004) the Society’s Electrochemistry (ISE). Pictured here at
first president from the meeting are (left to right): Katsumi
outside North America. Niki, president of ISE; Jean-Marie
The tenth IMLB was the Lehn, guest plenary lecturer and 1987
first organized by ECS, Nobel Laureate (Chemistry); Laurence
and the program included M. Peter, ISE Pergamon Medal
the presentation of the lecturer; and Barry Miller, president of
first special award of the ECS.
European Section, the
Volta Medal. It was given to Michel Armand for excellence in electrochemical and solid-state
science in Europe.
• The International Semiconductor Technology Conference (ISTC), organized by Ming
Yang of Texas Instruments, was held in Shanghai in May and was a first in many respects. It was
the first ISTC meeting and it was the Society’s first major meeting in China. The highlight of the
conference was the plenary address given by Jack Kilby, the winner of the Nobel Prize in
Physics (2000) for his invention of the integrated circuit.
• The spring meeting
had what must have been
one of the liveliest and
most spirited plenary
lectures in the history of
ECS. With copious use of
buckets of liquid nitrogen,
flipping of flattened
frozen exploding balloons
into the audience,
levitation of spinning Phillips
magnets, Nobel Laureate
William Phillips made sure that no one dozed off during his early morning lecture on laser
cooling.
Today and Tomorrow...

At the beginning of 2002, the membership stands at a little over 8,000. Every continent on
the globe is represented in the ranks, with approximately 40% of the membership coming from
outside the U.S. Just as the country that gave birth to ECS has become even more of a melting
pot, so has ECS continued to embrace a broad spectrum of people, research, and ideas. With the
assimilation of so much new communications technology, and the scheduling of meetings all
over the world, members from outside North America are able to take a more active role in
Society affairs.
The Journal has become the top-ranked technical journal for publication in the various
disciplines covered by the Society. Electrochemical and Solid-State Letters has become a
medium for rapid dissemination of important work. Interface not only keeps its members
informed, but also delivers informative articles and comments about technical interests and
achievements in the field.
The Society maintains its alertness in recognizing and encouraging the incorporation of new
areas into the Division/Group structure, and the resulting meetings grow larger, proceedings
volumes more prolific, both offering a broader range of technical content.
All together, ECS continues to be that “forum” for electrochemical and solid-state science
and technology that C. J. Reed envisioned over one hundred years ago.
The Society officially adopted

the use of the acronym - ECS -
and an official Tagline:. “the
society for solid-state and
electrochemical science and
technology”.
Acknowledgements
2002) with permission of The Electrochemical Society, Inc. and the author.
The article was prepared by Mary Yess, Interface’s Managing Editor, based on the ECS
centennial history book:
The Electrochemical Society 1902-2002: A Centennial History, F.A. Trumbore and D.R. Turner,
The Electrochemical Society, Pennington, NJ, 2002.
All photographs, unless otherwise noted, are from the ECS archives at ECS Headquarters and at
the Chemical Heritage Foundation in Philadelphia.
Photos of Paul Heroult, Charles M. Hall, and Herbert Dow are provided courtesy of the Williams
Haynes Portrait Collection, Chemical Heritage Foundation Image Archives, Othmer Library of
Chemical History, Philadelphia, PA.
The image of the Manufacturers' Club came from the 1914 “Yearbook of the Twentieth Annual
Architectural Exhibition,” which was held by the Philadelphia Chapter of the American Institute
of Architects, and the T-Square Club. Image courtesy of The Athenaeum of Philadelphia.
Photo of Willis Whitney courtesy of the Williams Haynes Portrait Collection, Chemical Heritage
Foundation Image Archives, Othmer Library of Chemical History, Philadelphia, PA.
Photo of Gordon Moore © 1996 Louis F. Bachrach.
Bibliography
• The Electrochemical Society 1902-2002: A Centennial History, F.A. Trumbore and D.R.
Turner, The Electrochemical Society, Pennington, NJ, 2002.
• A history of The Electrochemical Society, R.M. Burns and E.G. Enck (editors), The
Electrochemical Society, Princeton, NJ 1977.
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The purpose of this paper is to deal with the solution of the inverse kinematics problem in

ELECTROCHEMICAL MACHINING (ECM)

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Today and Tomorrow...

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