IEEE TRANSACTIONS ON PLASMA SCIENCE, VOL. 19, NO.
6, DECEMBER 1991
Nonequilibrium Volume Plasma Chemical Processing
Baldur Eliasson, Senior Member, IEEE, and Ulrich Kogelschatz
(Invited Review Paper)
Abstract-A review is presented of plasma chemical processes
occurring in the volume part of electrical nonequilibrium dis-
charges. The role of energetic electrons as initiators of chemical
reactions in a cold background gas is discussed. Different dis-
charge types (glow, corona, silent, RF, and microwave discharges)
are investigated with respect to their suitability for plasma chem-
ical processing. Emphasis is placed on the requirements of ini-
tiating and maintaining the discharge and, at the same time,
optimizing plasma parameters for the desired chemical process.
Using large-scale industrial ozone production as an example, the
detailed process of discharge optimization is described. Other
applications of volume plasma processing include other plasma
chemical syntheses as well as decompositionprocesses such as flue
gas treatment and hazardous waste disposal. If large gas volumes
have to be handled, mainly the silent discharge and possibly also
corona discharges have a chance of industrial acceptance as far
as nonequilibrium plasma processing is concerned.
I. INTRODUC~ION
I N the following review paper, a synopsis is presented of the
plasma processing which can take place in the volume part
of an electrical discharge. Plasma chemistry can be divided
into two parts:
volume chemistry; e.g., ozone production in a silent
discharge, and
surface chemistry; e.g., etching, deposition, or surface
modification.
This treatment is restricted to volume chemistry. In its
simplest form a discharge apparatus consists of the electrodes,
possibly other surfaces, and the discharge volume itself where
the actual discharge occurs (Fig. 1). In the discharge volume
the interaction between accelerated charged particles (i.e.,
electrons and ions) and other chemical species (i.e., atoms,
molecules and radicals) takes place. This interaction can lead
to the destruction of a chemical species. For example, a mol-
ecule can become excited to such an extent that it falls apart;
i.e., dissociates. It can also lead to the synthesis or creation
of a new chemical species. Excited atoms and molecules have
a much greater reactivity than atoms and molecules in the
ground state. The same applies to ions. In a typical discharge
situation many processes run concurrently. It is therefore
always the aim to influence the plasma parameters in such
a way that certain desired reactions are favored and other
undesired reactions are suppressed. During this optimization
Manuscript received May 19, 1989; revised July 29, 1991.
The authors are with k e a Brown Boveri Corporate Research, Baden,
Switzerland.
IEEE Log Number 9104413.
0093-3813/91$01.00 0 1991 IEEE
1063
Electrode Eleclrode
w
I1 il Dischargevolume
Electric field
Gas density
Gas Temperature
Electron Temperature
Power Supply
(DC, AC, Pulsed)
Fig. 1. The elements of a volume discharge
process one has to pay attention to two fundamental aspects
of plasma chemistry:
the requirements for initiating and sustaining the dis-
charge plasma, and
the requirements of the chemical processes induced in
that plasma.
The text will be organized accordingly, with a first part
describing the physics of the plasma-generating discharge and
a following part describing the chemical processes carried out
in such plasmas. The emphasis will be on processes that have
gained industrial acceptance, and on recent developments with
a potential for future applications.
Besides concentrating on volume plasma chemistry, another
important restriction of this paper is that it will only deal
with plasmas which are not in equilibrium. This means that
the electrons in the plasma have a much higher energy or
temperature than the neutral gas particles. A prime example
of the plasmas and chemistry under consideration is the
generation of ozone in a silent discharge. Plasmas in thermal
equilibrium, where all particles have approximately the same
temperature or kinetic energy, are not the subject of this paper.
Also, plasmas under extreme conditions like fusion plasmas
which contain particles at an extremely high temperature lie
outside the scope of this paper.
The first investigations into nonequilibrium plasma chem-
istry of any importance can be traced back to Siemens’s
experiments with the silent discharge for generating ozone in
the 1850’s. Ozone synthesis in silent discharges remains to this
day the most important application of nonequilibrium plasma
chemistry. The first industrial plasmachemical process was the
synthesis of nitric oxide in an ac arc at the end of the 19th
century.
Another kind of discharge which was used already at the
beginning of the century for gas-phase plasma chemistry is
the high-voltage glow discharge which is essentially a low-
1064
pressure discharge. Except for the electrode regions, it is
a fairly homogeneous discharge and very well suited for
studying plasmachemical processes. In the early 1920’s such
discharges were used to generate excited species in hydrogen,
nitrogen, and oxygen. Early examples of plasmachemical
synthesis were the generation of hydrazine and hydrogen
peroxide. Standard texts treating plasma chemistry, including
the early history, are listed in [1]-[6].
PLASMA
11. THENONEQUILIBRIUM
A . Definition of a Nonequilibrium Plasma
A plasma is a collection of positively and negatively charged
particles in an otherwise neutral gas. The charged particles
are electrons and ions which again are charged atomic or
molecular fragments. In this review we are dealing with
plasmas of a low degree of ionization. This means that the
total number density of charged particles is much less than
the total number density of the neutral particles. The plasmas
in question are also quasi-neutral, which means that the total
density of positive charge carriers is practically equal to the
total density of negative charge carriers. If we supply energy
to such a plasma by applying a potential difference across
it, the electric field will act upon the charged particles and
impart energy to them. The neutral particles-i.e., the bulk of
the gas-are not directly affected by the field. The electrons
due to their light mass are immediately accelerated to higher
velocities than the heavier ions in the time available between
collisions. The energy they lose through the collisions is taken
up by the collision partners. If the pressure is small enough
or the field is high enough, the electrons and partly the ions
will, on the average, have a kinetic energy which is higher
than the energy corresponding to the random motion of the
molecules. In this case we speak of a nonequilibrium plasma.
If, on the other hand, the pressure is so high that the charged
particles do not move very far before the next collision or the
field is very low, the kinetic energy of the charged particles
may tend toward the kinetic energy of the neutrals-i.e., to
the state of equipartition of energy. In this case we speak of
a plasma in equilibrium. Very often a plasma in equilibrium
is a plasma at high temperature. At high temperature, the
number of collisions between all particles increases to such
an extent that energy is equally distributed among all particles
and degrees of freedom. Equilibrium plasmas are therefore
often referred to as hot plasmas, and nonequilibrium plasmas
as cold plasmas.
Fig. 2 shows schematically how the high electron tempera-
ture in a mercury-vapor discharge tends toward the increasing
gas temperature as the mercury pressure increases. From
this figure one is tempted to conclude that nonequilibrium
discharges are restricted to the low-pressure regime and equi-
librium discharges to the high-pressure regime. This is true
only for stationary discharges. Since it takes a certain time or
a certain number of collisions to establish equilibrium between
the electrons and heavy particles, it is possible to have transient
nonequilibrium discharges also at higher pressures.
IEEE TRANSACTIONS ON PLASMA SCIENCE, VOL. 19, NO. 6, DECEMBER 1991
t ’
10 I
Fig. 2. Schematic diagram of electron temperature and gas temperature as a
function of pressure in a mercury-vapor discharge [7, p. 1301.
A very important parameter for all nonequilibrium plasmas
is the reduced field E l n ; i.e., the electric field divided by the
neutral gas density n. In discharge physics, this parameter has
its own unit, viz. Townsend (Td). 1 Td equals 10-17Vcm2.
The reduced field determines the electron energy in a plasma.
It is also a measure of the breakdown strength of a plasma. A
typical gas ( 0 2 , Nz, air) breaks down around 100 Td.
The reduced field also determines whether a plasma is in
equilibrium or not. Only at very low E / n values (< 1 Td)
does the electron energy come close to the kinetic energy of
the heavy particles and equilibrium conditions can be expected.
The inherent advantage of nonequilibrium discharges over
equilibrium discharges is the following: if one wants to excite
only a small fraction of the gas atoms or molecules, only,a
nonequilibrium discharge can provide electrons or ions at the
right energy. The bulk of the gas is more or less left untouched
and the losses are thus kept at a minimum.
B. Generation of Nonequilibrium Plasmas
It is customary to divide nonequilibrium plasmas into dis-
tinctive groups depending on the mechanism used for their
generation, their pressure range, or the electrode geometry. In
this section we will briefly list the most notable characteristics
of the following five nonequilibrium discharges:
1) glow discharge
2) corona discharge
3 ) silent discharge
4) RF discharge
5 ) microwave discharge.
In Fig. 3 the discharges are grouped according to their
temporal behavior, pressure range, and appearance.
1) The Glow Discharge: The stationary glow discharge is
a low-pressure discharge, usually between flat electrodes en-
capsulated in a tube (Fig. 4). Since the pressure is typically
smaller than 10 mbar, the reduced field can therefore be quite
high. Due to the high energy of the electrons, they excite the
neutral atoms and molecules, easily producing for each gas
a typical glow (therefore the name). This is the discharge of
the fluorescent tube. Typical parameters of glow discharges
are summarized in Table I (the numbers should be taken as a
rough indication of the order of magnitude).
One reason for the popularity of glow discharges is the
comparatively low voltage and current needed to run them. It
ELIASSON AND KOGELSCHATZ: NONEQUILIBRIUM VOLUME PLASMA CHEMICAL PROCESSING 1065

temporal
behaviour
t homogeneous
-
inhomogeneous
homogeneity

silent
discharge

Fig. 5. The corona discharge-inhomogeneous discharge at atmospheric

corona pressure.
discharge

localized filamentary glow (corona) is observed if the point is

low
- high
pressure
negative, or a more homogeneous glow in the case of a positive
point. In both cases, the volume exposed to the action of the
corona is very much smaller than the total discharge volume.
Fig. 3. Various discharge types arranged according to temporal behavior,
pressure, and appearance.
The behavior of positive and negative coronas is somewhat
different [8]-[ 101:
a) Positive corona: There is a corona inception voltage
which depends on the radius of the point and the gap spacing.
If the voltage is increased, streamers are produced which
lead to the typical corona phenomenon. A still higher voltage
transforms the streamer corona into a homogeneous glow
around the point. By increasing the voltage further, breakdown
occurs and a spark bridges the gap.
Fig. 4. The glow discharge-homogeneous discharge at low pressure. 6) Negative corona: Once the corona inception voltage is
exceeded, so-called Trichel pulses are generated. Short current
TABLE I
pulses are observed with a frequency which is proportional to
CHARACTERISTICPARAMETERS OF GLOWDISCHARGES the applied voltage, and also depends on the radius of the
pressure < 10 mbar point. As the voltage is increased further, a glow develops
before complete breakdown occurs.
electric field 10 Vlcm Due to space-charge phenomena in the neighborhood of
reduced field 50 Td the point, the negative corona is less sensitive to the radius
of curvature of the point than the positive corona. It is the
electron energy 0.5-2 eV or 5000-20000 K small radius of curvature of the point that leads to the high
electron density fields necessary for ionizing the neutral molecules. The field
l o x - 10” (‘111- %
drops rapidly as one moves away from the point toward the
degree of ionization 10-6 - lo-’ other electrode. It is very important that the applied voltage
is not too high, since otherwise the corona might bridge
the gap and produce a spark and breakdown. In this sense
has become an important laboratory tool for plasma chemical the corona discharge can be considered a partial breakdown.
investigations. Because of the low pressure and the resulting The main characteristics of corona discharges are listed in
low mass flow, the glow discharge has not been used for Table 11. Due to the small active volume around the point,
industrial production of chemicals. In the lighting industry, the corona discharge is not very well suited for industrial
however, the neon tubes used for outdoor advertising and production of large quantities of chemical species. There are,
however, applications where only very small concentrations of
the fluorescent tubes are examples of practical applications of
excited or charged species are needed. Typical examples are
glow discharges. Miniature glow discharges can also be found
electrostatic precipitators or copying machines where corona
in the new energy-efficient light bulbs.
discharges are used to produce charged particles. Another
2) The Corona Discharge: The main disadvantage of the
possible large-scale application is the treatment of flue gases.
glow discharge when it comes to industrial applications is Corona discharges are also used in high-speed printout devices,
its extremely low pressure. If one increases the pressure, one in dry-ore separation systems, and in radiation detectors [8].
has to increase the field accordingly. At higher pressures and Other important applications include the surface treatment of
fields, one normally finds that the discharge becomes highly polymers.
unstable and turns into a high-current arc discharge if the 3) The Silent Discharge: The silent discharge is predes-
power supply provides enough current. One way of stabilizing tined for applications in volume plasma chemistry. It has
the discharge at high pressure is the use of inhomogeneous inherent advantages over the discharges which have been
electrode geometries; e.g., a pointed electrode and a plane treated until now. It combines the large volume excitation
such as in Fig. 5 or a thin wire. of the glow discharge with the high pressure of the corona
At atmospheric pressure we do not necessarily need an discharge. Typical parameters of silent discharges are listed in
enclosure. The discharge has become very inhomogeneous. A Table 111.
1066 IEEE TRANSACTIONS ON PLASMA SCIENCE, VOL. 19, NO. 6, DECEMBER 1991

TABLE I1
CHARACTERISTIC PARAMETERS OF CORONA DISCHARGES
pressure 1 bar

electric field 0.5-50 kV/cm, variable

reduced field 2-200 Td, variable

electron energy 5 eV, variable

electron density 1 0 1 ’ 3 r n - 3 ,variable Fig. 6. The silent discharge. One electrode is covered by a dielectric.
Microdischarges in the discharge gap.
degree of ionization small, variable

TABLE I11
CHARACTERISTIC
PARAMETERSOF SILENT
DISCHARGES
pressure 1 bar

electric field 0.1-100 kVicm

reduced field 1-500 Td

electron energy 1-10 eV

electron density 101 c111-3

degree of ionization 10-4

The main elements of a silent discharge configuration are

shown in Fig. 6. A characteristic of the silent discharge is that a
dielectric layer covers at least one of the electrodes, sometimes
both. For this reason the silent discharge is also referred
to as the “dielectric-barrier discharge,” or simply, “barrier
discharge.” The dielectric is the key for the proper functioning
of the discharge. Once ionization occurs at a location in the
Fig. 7. Photograph of microdischarges in air (original size: 6 x 6 cm;
discharge gap the transported charge accumulates on the di- exposure time: 20 ms).
electric. The field due to this charge reduces the field in the gap
and interrupts the current flow after a few nanoseconds. The t
duration of the current pulse depends on the pressure and the
effective ionization characteristics of the gas as well as on the
dielectric properties [ l l ] . By applying a sinusoidal voltage of
sufficient amplitude a large number of such microdischarges is
induced. They are randomly distributed in space and time. Fig.
7 shows a photograph of the microdischarges taken through a
transparent electrode. At the maximum and minimum of the
applied voltage the displacement current is zero ( d U / d t = 0)
and the microdischarge activity stops, only to start again when
the breakdown field is reached in the gap during the next half-
wave (Fig. 8). The dielectric serves two functions: it limits the
amount of charge transported by a single microdischarge, and
distributes the microdischarges over the entire electrode area.
The silent discharge is an excellent source of filaments
containing energetic electrons. In most gases the reduced field
at breakdown corresponds to electron energies of about 1-10
eV. This is the ideal energy range for the excitation of atomic Fig. 8. Schematic diagram of bursts of microdischarges during application
and molecular species and the breaking of chemical bonds. of a sinusoidal voltage.
4) The RF Discharge: Radio frequency (RF) discharges are
used extensively in the laboratory to produce plasmas for between 2-60 MHz is especially a widespread laboratory
optical emission spectroscopy and for plasmachemical inves- tool for spectroscopic analysis. Very common is the industrial
tigations. The inductively coupled plasma (ICP) operating frequency of 13.56 MHz. One advantage of RF discharges
ELIASSON AND KOGELSCHATZ: NONEQUILIBRIUM VOLUME PLASMA CHEMICAL PROCESSING
(b) (c)
Fig 9 Typical arrangements for RF discharges [4, p 611
is that the electrodes can be kept outside of the discharge
volume, thus avoiding electrode erosion and contamination
of the plasma with metal vapor. Since the wavelength of
the electric field is much larger than the vessel dimensions,
reasonably homogeneous plasmas can be generated. RF dis-
charges work well at low pressure, but are used also at
atmospheric pressure. Low-pressure RF discharges for etching
purposes have found widespread applications in semiconductor
manufacturing [ 121-[ 141. As long as the collision frequency
is higher than the frequency of the applied field, the discharge
behaves very much like a dc discharge. This implies that
nonequilibrium conditions can be expected at low pressures,
whereas thermal plasmas are generated at about atmospheric
pressure. Fig. 9 shows three typical electrode configurations
for RF discharges. While Fig. 9(a) and (b) use capacitive
coupling and are mainly used at low pressure, the configuration
shown in Fig. 9(c) uses inductive coupling by placing the
discharge in the magnetic field of an induction coil. This
arrangement is typical for RF torches and is used at pressures
of up to 1 bar.
5) The Microwave Discharge: In the microwave region
(0.3-10 GHz) the wavelength of the electromagnetic field
becomes comparable to the dimensions of the discharge
vessel, which necessitates other coupling mechanisms. Most
microwave-induced plasmas are produced in a waveguide
structure or resonant cavity. As the dimensions of the
cavities diminish when the frequency increases, the maximum
microwave frequencies used for discharge applications are
usually below 3 GHz. A very common frequency is 2.45 GHz,
which is also used in microwave ovens.
Since at these frequencies only the light electrons can follow
the oscillations of the electric field, microwave plasmas are
normally far from local thermodynamic equilibrium. They can
be operated in a wide pressure range, starting from below 1
mbar to about atmospheric pressure.
An interesting development is the use of microwaves to in-
duce surface-wave-sustained discharges [ 151. They can operate
over a large frequency and pressure range and can produce
large-volume nonequilibrium plasmas of reasonable homo-
geneity. The plasma is contained in a dielectric tube of a few
centimeters diameter and is sustained by an electromagnetic
wave which uses only the plasma column and the tube as its
propagating media. Plasma columns of up to 4-m length have
1067
been thus produced. Due to the large pressure range under
which these discharges can be operated, electron densities
between los and 1015c~1-3have been reported. These surface
wave plasmas have many similarities with the positive column
of a glow discharge. Applications so far have been limited to
elemental analysis and lasing media. The ease of operation
and the possibility of imposing a gas flow and to influence
plasma parameters makes these discharges attractive also for
plasmachemical investigations.
111. PHYSICS AND CHEMISTRY OF NONEQUILIBRIUM PLASMAS
Plasmachemical processing always deals with two distinc-
tive aspects: namely, the physics of the discharge, and the
chemical reactions in the plasma. In order to discuss the most
important features, it is helpful to treat these two related, albeit
different, aspects separately. In this section we will briefly
describe the physical part of plasma chemistry; i.e., the physics
of the discharge itself. In the following section we will take a
closer look at the chemical aspects of plasma processing.
A . Breakdown and Average Electron Energy
In plasma chemistry it is the electrical discharge which
furnishes the energy which initiates the chemical reactions. In
the case of nonequilibrium plasmas, this energy is very often
transferred solely by the electrons.
In a glow discharge the electrons are constantly gaining
energy from the applied field. Due to the low pressure, they
cannot collide often enough with the neutrals to come into
equilibrium with the heavy particles. The stationary state is
primarily governed by the energy losses the electrons and
ions incur by recombining on the walls of the enclosure of
the discharge. The situation is similar in RF or microwave
discharges.
In a corona or a silent discharge the situation is entirely
different. Here, due to the high pressure, the fast electrons
do transfer their total energy to the surrounding atoms and
molecules. Spark or arc formation is prevented by the special
electrode configurations used. In the case of the corona, it is
the rapidly dropping electric field which stops the electrons on
their way to the anode. And in the case of the silent discharge,
it is the dielectric barrier which limits the current that can flow.
In general, one distinguishes between two kinds of break-
down in a discharge gap. If the product of gas density n and
gap width ct is small, a Townsend breakdown occurs [16],
[17]. It is started by a succession of avalanches which interact
with the electrodes through charged particles and photons. If
the product nd is large, a streamer breakdown is initiated.
Due to a high concentration of space charge at the head of
the electron avalanche and the resulting high eigenfield, the
streamer becomes self-propagating and causes breakdown in
a single transit. The effective reduced field at breakdown is
considerably higher than in the case of the classical Townsend
breakdown. The streamer leaves behind a fairly homogeneous
conducting channel of low electric field filled with charged
and excited particles. Because of the fairly high energies of
the electrons (-5 eV) and their limited lifetime, they lose very
little of their energy through elastic collisions with neutrals.
1068
The energy of the electrons is determined by two param-
eters:
the total field they are subjected to-in this case it consists
of the applied field and the (possibly much higher)
eigenfield
interaction with other particles.
The equation that describes the above is the Boltzmann
equation. In its simplest schematic form it can be written as
The Boltzmann equation describes the change in the electron
energy distribution function (EEDF) f (z,71, t ) as a function of
space (z), velocity ('U), and time ( t ) due to binary collisions
with particles. The acceleration a is proportional to the force
acting upon the electron. In the case of an electric field,
a = e E / m , where m is the mass of the electron with charge e.
The collision term
describes the change of the EEDF due to collisions of the
electrons with other particles. This term is the connecting link
between the physics of the electrons and the chemistry of the
species present.
Each process has an optimum set of parameters at which
the yield of the process is at a maximum; e.g., the average
energy of the electrons which collide with the molecules
is a very important parameter. If we want to dissociate a
molecule, the energy delivered to that molecule must exceed
the dissociation or bond energy of the bond we want to break.
In case of a silent discharge, one can easily influence the
electron energy by changing the product n d . According to
Paschen, in a homogeneous electric field the condition for
discharge initiation is solely a function of n d . In Fig. 10, it
was assumed that the effective reduced field at breakdown is
50% higher than the Paschen field. Alternatively, one can also
influence the electron energy by applying a very fast rising
voltage pulse to the discharge gap.
In the case of glow discharges, one has less control over
the average energy of the electrons. In the positive column
of a glow discharge in a tube, the state of the discharge is
determined primarily by energy losses caused by particles
recombining on the walls of the discharge tube. Only by
changing the wall geometry-i.e., by changing the diameter of
the tube-can one affect the electron temperature. The margin
for variation is here, however, inherently much less than in
the case of the silent discharge. In a corona discharge, one can
slightly influence the electron energy by changing the radius
of curvature of the point or its polarity.
The silent discharge is not only instationary, but also a
very inhomogeneous supply of electrons. This is in contrast
to both glow discharges and high-frequency discharges, which
tend to be both stationary as well as homogeneous discharges.
The corona discharge has something in common with both
IEEE TRANSACTIONS ON PLASMA SCIENCE, VOL. 19, NO. 6, DECEMBER 1991
"-
Average electron energy
: 8-
I 10-
L
Fig. 10. The dependence of the reduced field El11 and the average electron
energy ( E ) on the product 7 ~ d .
discharge types. It can be stationary or instationary, but it is
always inhomogeneous.
The spatial inhomogeneity of the silent discharge is due to
the fact that the microdischarges are single transit discharges.
They start where the conditions are favorable (i.e., rough
surface, high local field, initial electrons). In the end, they are
self-propagating-i.e., they propagate under the influence of
their own eigenfield-and become more or less independent of
what is going on around them. Such a propagation is inhomo-
geneous by its very nature. A homogeneous discharge-i.e., a
one-dimensional discharge-does not produce high eigenfields
as easily.
Over long time periods the microdischarges, which are
randomly distributed by the way they are initiated, fill the
available volume evenly. Thus the inhomogeneity of the silent
discharge does not lead to a disadvantage. To the contrary, this
way the excited species in the microdischarge filaments can
diffuse into the regions between the filaments which are free of
charged particles, and initiate the chemical reactions before the
next discharge strikes at the same location. This separation of
electron-producing regions and chemically active regions can,
no doubt, be very beneficial in certain cases; e.g., when the
desired products are destroyed by energetic electrons.
B. The Initiation of Chemical Reactions in a Plasma
In nonequilibrium discharges, the fast electrons created by
the discharge mechanism mainly initiate the chemical reactions
in the plasma. The fast electrons collide with gas molecules
and excite them to higher energy levels, thereby losing part
of their energy which is replenished by the electric field. The
excited molecule can now, due to its high internal energy,
either dissociate or initiate other reactions.
In plasma chemistry it is very important that the transfer
of energy via electrons to the species which take part in the
reactions is very efficient. This is accomplished most easily by
a short electron pulse. This is what occurs in a microdischarge.
Fig. 11 shows the evolution of the different particle species
initiated by a single microdischarge in "air" (80% N2, plus
20% 0 2 ) . The short current pulse of roughly 10-ns duration
ELIASSON AND KOGELSCHATZ: NONEQUILIBRIUM VOLUME PLASMA CHEMICAL PROCESSING 1069

20%02+80%N,

10-’O lo-* IO6 IO2 1 10‘t (sec)

Fig 11 The chemical reactions initiated by a microdischarge in ‘dir” [18]

deposits energy in various excited levels of NI and 0 2 , some t m

of which lead to dissociation and finally to the formation of
ozone and different nitrogen oxides. After about 50 ns, most
charge carriers have disappeared and the chemical reactions
proceed without major interference from charge carriers and
without major electric losses. For this example, a reaction
scheme treating 143 reactions among 30 reacting species was
used [18]. In order to be able to perform such calculations, the
following data and techniques must be available. Fig. 12. The reaction A+B + C+D. If one of the reactants is brought to an
excited state+.g., B = M’, it can surmount the activation energy En and
C. The Chemistry of Nonequilibrium Discharges thus initiate the reaction [19, p. 4191.

As we have seen in the preceding section, it is mainly

the fast electrons created by the discharge that initiate the Once the cross section is known as a function of energy or
chemistry which takes place in the plasma. The electrons ( e ) velocity and the electron distribution function has been calcu-
collide with gas molecules (B, M) and excite them to higher lated by solving the Boltzmann equation, the rate coefficient
energy levels, thereby losing the corresponding amount of their can be calculated by solving the integral:
own energy. The excited molecule can now, due to its high
internal energy, initiate some reaction (Fig. 12). For example,
(4)
the reaction scheme might look like this:
0
e+ M + M* + e (2) where the electron energy distribution function has been
A + M* -+ C + D. (3) normalized as
+ +
As the reaction A M i C D might only take place at very
high temperatures, it is actually reaction (2) which initiates the
production of the species C and D (Fig. 12).
I
0
f ( € ) d € = 1. (5)

Every reaction is characterized by a few main characteristics

In the case of a reaction between two atoms or molecules,
such as the reactants (e.g., A, M* above), the products (e.g., C,
the procedure is basically the same. Only here, one has to take
D above), the pressure, the temperature, the heat of the reaction
the movements of both partners, A and B into account; i.e.,
( H at constant pressure, U at constant volume), and the rate
one has to average over two distribution functions, f A and f B .
coefficient p. The rate coefficient for electronic reactions, viz.
The main types of reactions occurring in a volume plasma
+
e B -+ products, can be calculated once two relations are
are listed in Table IV. The symbols A, B stand for atoms,
known:
A*, B2 for molecules, and e stands for an electron. M is a
the distribution of electron energies
the cross section 0 for the process in question.
temporary collision partner, and species marked by or - +
are ions. The excited species are marked by an asterisk (*).
1070 IEEE TRANSACTIONS ON PLASMA SCIENCE, VOL. 19, NO. 6, DECEMBER 1991

TABLE IV whereas the electron can be pictured as a bullet traveling at

THE MAIN PLASMA REACTIONS a certain speed determined by its kinetic energy. The photon
carries an energy which is determined by its frequency v or
Electron/Molecular Reactions
wavelength A. Photochemistry is a specific branch of chemistry
Excitation: e + .Az 3 -1;+ e dealing with photon-initiated processes. Photochemistry does
Dissociation e+ .42 - 2.4 + e not fall within the scope of this paper otherwise than in that one

Attachment e + .A2 - -42

cannot help but create a lot of photons during the electronic
processes which occur in a discharge.
Dissociative attachment e + .A2 - .4- + .A To a first approximation one could say that there is not a

Ionization e + .42 - .A$ + 2c

major difference between exciting a molecule with an electron
or a photon, except for the fact that the photon energy can
Dissociative ionization e +e\. - .%++.A+r
be more sharply defined and that photon cross sections tend

Recombination e + A; - A.2
to be considerably smaller than electronic ones. In principle,
it is possible to create a monochromatic; i.e., monoenergetic
Detachment e + .A; - + 2r light beam that will stay monoenergetic while passing through
the plasma. This is different for an electron beam. Even if
AtomiciMolecular Reactions we enter the plasma with a monoenergetic electron beam,
collisions with the particles will soon establish an electron-
Pennning Dissociation AI* + A.1 + 2.4+ 11
energy distribution that depends on the electric field and gas
Pennning Ionization 11* + .A2 - -4; +'\I+<> properties. Thus plasma chemistry will always be less selective
Charge Transfer ;\*+I3 - B*+.A
than photochemistry. The great advantage of plasma chemistry
is that electrons can be generated at much higher efficiencies
Ion Recombination .4-+B+ - .AB than photons.
Neutral Recombination ;\+B+1I - .AB+\I
IV. OZONESYNTHESIS
Decomposition
Electronic ?+AB - .A+B+c'
A. Ozone Applications and Ozone Properties

Atomic =\*+Be - AB+B

The generation of ozone in silent discharges is the most
important application of nonequilibrium discharges for plasma
chemical synthesis.' Historically, the silent discharge dates

-
Synthesis back to 1857, when Werner von Siemens showed that ozone
Electronic e + .A .A* + e can be produced in an oxygen flow passing through an
X*+B - AB
annular discharge space between two coaxial glass cylinders.

Atomic A +B - .AB
To describe the electron household of a nonequilibrium
volume discharge, mainly four reactions are of importance.
In a stationary situation, electron losses by attachment and re-
combination have to be balanced by ionization and detachment
processes. For the treatment of the whole system, powerful
computer codes are needed to solve the Boltzmann equation
and to handle systems of stiff differential equations describing
the many reactions.
D. Radiative Effects in Plasmas
In a plasma created by a discharge, in general we shall
not only find electrons, ions, atoms, and molecules, but also
photons. Many excited states drop back to a lower state by
emitting a photon. If the photons are energetic enough, they
can also initiate chemical reactions.
AS stated earlier. the electrons are merelv the carriers of
energy for the process we want to initiate. a similar way,
the photon is an energy carrier, but with ''Inewhat different
characteristics. It has no mass and moves at the speed of light,
The electrical discharge was sustained by an alternating high
voltage applied through the glass walls. Siemens referred to
this process as "the electrolysis of the gas phase."
Shortly after 1900 the first larger industrial ozone-generating
systems for the treatment of drinking water were installed in
Nice, France (1907) and St. Petersburg, Russia (1910). Today,
more than 1500 drinking water plants throughout the world
use ozone generators utilizing silent discharges to convert
the diatomic oxygen molecule ( 0 2 ) to the chemically much
more active triatomic ozone molecule ( 0 3 ) . Larger installations
can have a considerable power consumption, on the average
more than 1 MW for the 25 major installations. This clearly
demonstrates that ozone synthesis has become one of the most
important plasmachemical processes [20]. As far as power
consumption is concerned, it is rivaled only by the synthesis
of acetylene, for which a thermal plasma process is used.
Historically, the main application of ozone has been linked
to the development of water purification processes. Ozone is
a strong oxidizing agent, stronger than all other industrial
chemicals with the exception of fluorine. It is a practically
..
An economically even more important application of nonequilibrium
discharges is thin film deposition and etching in the microelectronics industry.
Here the aim is surface modification. This plasmachemical application lies
outside the scope of our article, and is covered in a separate article of this
volume.
ELIASSON AND KOGELSCHATZ NONEQUILIBRIUM VOLUME PLASMA CHEMICAL PROCESSING
colorless gas with a characteristic odor. Due to its oxidizing
power, it finds applications as a potent germicide and viricide
as well as a strong bleaching agent.
In water purification the main purpose for installing ozona-
tion stages is the reduction of turbidity, the removal of
taste, color, odor, dissolved manganese and iron, as well as
disinfection. Modern drinking-water treatment plants can have
up to three ozonation stages. Due to its unique properties ozone
has found many additional applications. In the chemical and
pharmaceutical industry ozone has been used for the oxidation
of oleic acid, the synthesis of certain hormones and vitamins,
of camphor and perfumes as well as for the production of
hydrochinone. Applications in waste-water treatment include,
besides disinfection, the removal of color and odor and the
degradation of oil, phenolic compounds, and cyanides.
Among the main bleaching processes, the treatment of
kaolin, textiles, wax, and increasingly also pulp should be
mentioned. Ozone is also used to prevent fouling in closed
cooling water circuits. New applications of ozone for deNO,
and deSO, processes (removal of nitrogen and sulfur oxides
from the flue gas of large-scale burning processes) are already
being investigated on a pilot plant scale, and their performance
and economics look promising [21].
In many of the above-mentioned applications, ozone is
increasingly used to replace other oxidants that present more
environmental problems. Since strong oxidizing agents are
chemically active species, the storage, handling, and trans-
portation of such chemicals may represent substantial hazards.
Another problem is the question of residues and side reactions.
In both respects, ozone represents a superior choice. Due to
its inherent instability, ozone is neither stored nor shipped.
It is always generated on the site at a rate controlled by
the process. Since only oxygen is added to the system, no
objectionable by-products and residues are to be expected.
The natural decay products of ozone are oxygen and also,
in the presence of organic substances, CO2. Due to its better
environmental compatibility it is to be expected that ozone
will to some extent replace other chemical oxidants. More
stringent legislation with respect to the trihalomethane content
of potable water and the chlorine content of waste water from
pulp factories will accelerate the substitution of chlorine and
chlorine dioxide in these applications.
B. Technical Ozone Generators
In principle, ozone can also be prepared by chemical or
photolytic methods. However, these procedures have been
confined to laboratory applications. Small amounts of ozone
can be generated by electrolysis in electrochemical cells. They
are mainly used for the preparation of ultrapure water for
manufacturing processes in the microelectric and pharmaceuti-
cal industries [22]. Large-scale ozone generation for industrial
purposes has been exclusively based on special nonequilibrium
discharges-the silent discharge. A schematic drawing of the
discharge configuration was given in Fig. 6. The feed gas,
dehumidified air or oxygen, passes through a narrow discharge
gap of about 1-mm width. Through the action of the discharge
part of the oxygen is converted to ozone. In most technical
1071
d5charge g a p ( 1-3") cooled steel tube
l(t1 f--
I I
I- L I 1OOOmm
A
Fig. 13. Schematic diagram of an ozone discharge tube.
be
An 0
or *I
Oxygen cootant Ozone
Fig 14 Technical ozone generator with frequency converter and HV
transformer
ozone generators glass is used as the dielectric. The use of
other dielectric materials like ceramics and enamel coatings
has also been reported. Since the current can pass through
the dielectric only in the form of a displacement current, the
discharge has to be driven by an alternating voltage. The
required voltage is in the range of 5-20 kV. Most technical
ozone generators use glass tubes of about 1.5-2-mm wall
thickness acting as a dielectric barrier. These tubes have an
internal metal coating serving as the high voltage electrode.
The glass tubes are mounted in stainless-steel tubes of slightly
larger diameter to form an annular discharge gap of 1-3-mm
width and 1-2-m length (Fig. 13).
Since large electrode areas are required for mass ozone pro-
duction, several hundred of these discharge tubes are mounted
in a steel tank in a configuration similar to that of a cross-
flow heat-exchanger (Fig. 14). An important property of the
silent discharge is that many elements can be electrically
linked in parallel and can be fed from a common power
supply. Unlike other gas discharges, the silent discharge does
not need external elements to distribute the current evenly to
the individual discharge tubes. The cooling water is passing
between the steel tubes which are welded to the two end
flanges to form a hermetically sealed compartment. Efficient
heat removal is essential for good ozonizer performance.
Traditionally, technical ozone generators were fed from the
mains using just a step-up transformer. Recent developments
for high-power ozonizers make use of thyristor-controlled
frequency converters operating between 500 Hz and a few
kilohertz that impress a square-wave current. This change of
technology brought several advantages. In addition to raising
the efficiency, the power density of these ozone generators
1072 IEEE TRANSACTIONS ON PLASMA SCIENCE, VOL. 19, NO. 6, DECEMBER 1991

Fig. 15. Four out of five ozone generators at the Los Angeles Aqueduct Filtration Plant. With a rated capacity of
187.5 kg ozone per hour, this is the world’s largest ozone installation operating on oxygen.

could be increased by an order of magnitude resulting in much dissociation are available: one via excitation of the i13C,
more compact ozone installations. The peak voltage was re- level with a threshold energy of 6 eV, and another via
duced to such an extent that problems with dielectric failure of excitation of the B 3Y; level with a threshold of 8.4 eV:
the glass tubes could be practically eliminated. In addition, the
implementation of modern power electronics resulted in less e +0 2 -+ e + C ) 2 ( A 3 C T )+ e + O ( 3 P )+ O ( 3 P ) (6)
bulky high voltage transformers and compensation networks P +0 2 4 e + 0+33c;) + e + o ( 9 )+ q 3 P ) . (7)
and provided a convenient way to link the ozone generators to
superimposed process control [20]. The photographs of Figs.
15 and 16 show modern ozone generators in a major water Thus, in principle, electrons of an average energy of about
treatment facility and a view of the discharge tubes inside the 6-9 eV would be ideal. In oxygen this corresponds to reduced
ozone generator, respectively. fields of about 150-350 Td. Detailed calculations about the
fraction of the energy going into different electronic reaction
paths in oxygen show that about 80% of the electron energy
C. Optimization of Microdischarge Properties
can be utilized for the dissociation process in the specified
As was pointed out already in Section 11-B,the silent E / n range [ l l ] . Since, according to Paschen, the E / n at
discharge operating at about atmospheric pressure consists of breakdown is only a function of the product gap spacing times
a large number of statically distributed microdischarges. Each particle density ( 7 1 4 , we can clearly influence this parameter
microdischarge lasts only for a few nanoseconds and reaches by changing the gap spacing and the pressure in the gap.
current densities of 100 - 1000A/cm2 in nearly cylindrical The next step after the dissociation is a three-body reaction
filaments of roughly 100-pm radius [ll]. At the dielectric, of 0 and 0 2 , leading to the 0 3 molecule:
these microdischarges spread into surface discharges that can
cover a much wider area. These microdischarges represent the 0 + O2 + M + O3 + M (8)
same physical phenomenon as the partial discharges occurring
in voids of solid insulation under ac stress. The main difference in which M is a third collision partner: 0 2 , 0 3 , 0, or in the
is that in the silent discharge configuration due to the larger case of air also, N2. The time scale for this reaction to occur
gap widths, the microdischarges tend to be “stronger” and that at atmospheric pressure is a few microseconds. Unfortunately,
we try to cultivate and optimize certain properties such as the even during this short time, other competing side reactions
electron energy and electron density. Using ozone formation come into play:
in oxygen discharges as an example, this optimization process
will be described.
0+0 +hl+ 0 2 +M (9)
The first step toward ozone formation in gas discharges is
the dissociation of 0 2 molecules by electron impact. Starting
from ground-state 0 2 molecules, two reaction paths toward 0 + O3 -+ 202

- -
ELIASSON AND KOGELSCHATZ: NONEQUILIBRIUM VOLUME PLASMA CHEMICAL PROCESSING 1073

Fig. 16. End on view of discharge tubes inside an ozone generator

OXYGEN
10-2
The undesired side reactions (9) and (11) pose an upper
0, 1 limit on the desirable atom concentration, is (Le., the degree
of dissociation) in the microdischarges, and finally also on
the maximum attainable ozone concentration. Their influence
becomes increasingly important at relative atom concentrations
larger than lop4. From this point of few it would be ideal to
work with rather “weak” microdischarges resulting in a relative
atom concentration of 5 because only at such low atom
concentrations does every oxygen atom result in the formation
TIME 1
5 )
of an ozone molecule.
Fig. 17. Evolution of different particle species following a microdischarge Unfortunately, there are other considerations that have an
in pure oxygen [ll].
influence on this choice. The plasma in the discharge filaments
consists of other charge carriers in addition to electrons-in
oxygen, mainly the ions O+, 0:, 0-, O,, and 0,. Since
ionic reactions do not appreciably contribute to ozone for-
+0 0; + 20.2 (11) mation, energy losses due to ions must be minimized. Cal-
where 0; is a transient excited state in which the ozone culations and experiments show that a considerable fraction
molecule is initially formed after the recombination of an 0 of the discharge energy can be dissipated by ionic species in
atom with an 0 2 molecule according to reaction (8). In ozone weak microdischarges. The situation improves when at higher
research, complex reaction schemes treating about 70 reactions electron and ion densities recombination becomes faster than
among 16 different particle species in pure oxygen are used to the time an ion requires to drift through the gap. In the limiting
describe and optimize ozone generation in a microdischarge case of high electron densities, the ions are more or less
(Fig. 17). stationary and the energy is mainly dissipated by electrons.
1074
OXYGEN
0.11 ' ' ' l l , l ' l 1 ' 1'1,1,1 ' I
0.01 0.1
SPECIFIC ENERGY ( e V / O p )
Fig. 18. Development of the ozone concentration as a function of the specific
energy for different temperatures.
Thus optimizing the microdischarges for the ozone-
formation process is essentially finding a compromise
between having excessive energy losses due to ions in
weak microdischarges and avoiding undesired chemical side
reactions if the microdischarges become too strong. In
oxygen, a reasonable compromise can be found at a relative
atom concentration of about 2 The "strength" of a
microdischarge can be characterized by the amount of charge
transported by a microdischarge or by the energy density
deposited in the discharge channel after termination of the
current flow. Since the interruption of the current in an
individual microdischarge is caused by a local reduction of
the electric field due to space-charge accumulation on the
dielectric, we can influence the microdischarges by changing
the thickness or the dielectric constant of the dielectric barrier.
After the termination of a microdischarge, the generated ozone
diffuses out of the volume of the current filament. Since the
electric field is reduced at this particular location, further
microdischarges will occur at other positions in the gap.
Technical ozone concentrations are built up through the ac-
tion of a large number of microdischarges. A volume element
traveling through the discharge gap will typically be exposed
to the action of several hundred microdischarges before it
reaches the end of the discharge tube. The ozone concentration
rises with the amount of energy deposited in the gas, or, in
other words, with the number of microdischarges. It is interest-
ing to note that after a certain number of microdischarges, an
equilibrium is reached at a certain saturation concentration x3s.
From now on each microdischarge will destroy as much ozone
as it creates. As Fig. 18 shows, the saturation concentration
depends strongly on the gas temperature in the discharge
gap. This is the main reason why ozonizers need an efficient
cooling system and narrow discharge gaps to remove the heat
generated by the discharge.
v. SYNTHESIS OF OTHER COMPOUNDS
A. The Simple N2lH2, H2I02, and N2I02 Compounds
Although ozone and acetylene are the only compounds that
are produced in gas discharges on an industrial scale, many
attempts have been made to synthesize other compounds in a
plasma. The general scheme is to excite or dissociate the pri-
mary constituents and influence the parameters in such a way
IEEE TRANSACTIONS ON PLASMA SCIENCE, VOL. 19, NO. 6, DECEMBER 1991
H2
N i , H i , NHX,N2H,N,H
N2
Fig. 19. Transient species and products in a H z / N ~plasma.
' 8 1 L l J -i
10
H: H;.o+,o; ,O~.HO+,HO
Fig. 20. Transient species and products in a H2/02 plasma.
that the intermediate species react to form new compounds.
Thus from nitrogen and hydrogen, in principle NH3 and N2H4
can be formed (Fig. 19).
While ammonia formation in plasmas is studied mainly
for academic reasons, there has been considerable interest in
finding a cheaper way to produce the expensive hydrazine.
Hydrazine is an important reducing agent which has also been
used as a propellant for rockets and which may find applica-
tions as a clean burning fuel. N2H4 has been synthesized in
glow discharges as well as in silent discharges. In most cases
the feed gas was NH3 rather N2 plus H2 [l].
Also, the simple H2I02 compounds can be formed in a
plasma (Fig. 20). Again, glow discharges and silent discharges
have been used. Hydrogen peroxide, H202, is an important
industrial product and is used as a bleaching agent and disin-
fectant. Although considerable progress has been reported on
the plasmachemical hydrogen peroxide synthesis in ozonizer-
like discharge configurations, for the time being there seems to
be no chance to beat the classical electrolytic H202 generation
as far as power consumption is concerned.
In principle, all known nitrogen oxides NO, NO;?, NO3,
N205, and N20 have been detected in the output of air-fed
ozonizers [23].Under normal operating conditions, traces of
N 2 0 and N205 can be detected in addition to ozone. It has
long been known that the parameters can be changed in such
a way that no ozone is produced (discharge poisoning). Under
these conditions, the lower oxides NO and NO2 can be found
in addition to "laughing gas" N20. While these compounds are
undesired side-products of ozone generation from air, research
efforts have been oriented toward NO production in thermal
plasmas (241.
B. Organic Compounds
Some hydrocarbons have also been synthesized in gas dis-
charges. The most important process is the acetylene synthesis
at the Hiils AG in Germany. Up to 19 10-MW arc discharges
are used to produce C2H2 in the range of more than 100000
t/yr. In this process, methane is decomposed in a hydrogen
plasma. At about 3000 K, C2H2 and C2H are the predominant
ELIASSON AND KOGELSCHATZ: NONEQUILIBRIUM VOLUME PLASMA CHEMICAL PROCESSING
hydrocarbon species. In a rapid quench most of the C2H2 can
be recovered, and part of the C2H can also be converted to
C2H2. This process has been in operation since 1939 and,
despite rising electricity costs, apparently is still competitive.
Research activities are oriented toward turning this one-stage
process into a two-stage process by injecting the methane
behind the arc discharge and toward using other feed stocks
like crude oil and coal [25].
Much more complicated organic compounds have also been
synthesized in a plasma. For this process, mainly low-pressure
glow discharges at low power densities would be the choice.
According to Suhr [26], several hundred organic substances
have been subjected to glow discharges in order to synthesize
other organic compounds. Organometallic compounds espe-
cially have recently gained much attention, because they can
be used as starting materials for metal deposition techniques
~71.
C. Excimers
An interesting new application of silent discharges is its
use for the generation of excimers to produce UV radiation
[28], [29]. Excimers (excited dimers, trimers) such as Xe;,
KrF*, and ArZF* are excited molecular complexes that do not
possess a stable ground state. Thus they are not known from
classical chemistry, but can be formed under special discharge
conditions. Most excimers are inherently unstable and decay
within nanoseconds. During their decay the excitation energy
is given off in the form of UV or VUV radiation. Some of the
excimer systems are known to be quite efficient fluorescers,
which means that they can be used to transform discharge
energy into UV radiation in a very efficient way. This is
also the principle of excimer UV lasers, which are pumped
by high-pressure transient glow discharges. Silent discharges
can be used for the efficient generation of incoherent excimer
radiation. In xenon, for example, the weakly bound excited
dimer state lies about 7-eV above the repulsive ground state.
Thus we expect UV radiation at 170 nm if this excimer can
be generated. The excimer is formed in a three-body reaction
between excited- and ground-state xenon atoms:
e t Xe i Xe* +e (12)
Xe* + X e t Xe -+ Xe; + X e (13)
+
Xe; -+ Xe t Xe VUV radiation. (14)
The obtained spectrum of Fig. 21 shows narrow-band radi-
ation peaking at 172 nm and having a half-width of about 12
nm, which is, no doubt, due to the Xe; excimer. With other
gas mixtures, other excimers could be obtained that radiate
in different spectral ranges: Ar; at 127 nm, Kr; at 147 nm,
ArC1* at 175 nm, KrC1* at 222 nm, and XeC1* at 308 nm
[30]. The large number of known excimers suggests that it
should be possible to build such an excimer UV source for
any desired wavelength region. The experience with silent
discharges suggests that different geometries and high power
levels are conceivable. These new intense UV sources are
likely to find interesting applications in photochemistry, UV
curing, photo deposition, photo etching, and photo degradation
[311.
1075
100 150 200 250 300
WAVELENGTH ( nm )
Fig. 21. Emission spectrum of the S e ; excimer radiation from a silent
discharge in xenon.
D. Liquid and Solid Products
So far, only gas phase reactions have been mentioned. In
principle, plasmachemical synthesis is not necessarily confined
to the gas phase. The final product may also appear in the
liquid or even solid phase. For example, 0 3 or H202 can
easily be removed from the gas phase by using cold traps.
This helps to keep the concentration in the gas phase low
and to reduce back reactions. Also, hydrazine can be removed
from the gas phase by solving it in liquid ethyleneglycol. As a
matter of fact, a liquid film can replace the dielectric layer in
a silent discharge configuration (Fig. 6). Also, solid products
can be the result of a plasma reaction. Examples for solid final
products are ultrafine ceramic or metal particles which can be
obtained by quenching thermal plasmas. Recent investigations
focus on the generation of fine powders of nitrides, carbides,
and oxides [32]. Applications for such submicron-size particles
include their use as catalysts or pigments and as components
for high-tech ceramics. Since these particles are mostly formed
by nucleation in the quenching zones of thermal plasmas, this
subject lies outside the scope of this paper.
The preceding sections dealt with the synthesis of stable end
products. In many applications also the generation of transient
species such as ions, excited atoms, molecules, and radicals
which then interact with surfaces is of interest.
VI. REMOVALAND DESTRUCTION
OF UNDESIRED SPECIES
A. Flue Gas Treatment
Plasma chemistry is not only used for the synthesis of new
compounds, but also for the aimed destruction or removal
of certain undesired species. For example, laboratory and
,
pilot plant studies are under way to find alternative ways
for flue gas cleaning [33]-[37]. In fossil-fuel-fired power
plants, the main aim is the reduction of NO, and S02,
both of which cause considerable air pollution and contribute
to acid rain formation. In other flue gases-i.e., from the
incineration of municipal waste-heavy metals may cause
additional problems. Since large amounts of gas have to be
treated, the process must operate at about atmospheric pressure
and at moderate temperatures. Studies are under way using
corona discharges or even electron beam injection. Through
the generation of excited species and reactive radicals and
the addition of NH3, the ammonium salts (NH4)2S04 and
1076
H.V.
U H,SO,
A HNO,
BOILER
A A
I
+SQ
--+
+ X +
A n
0
CORONA
Fig. 22. Schematic diagram of a corona process for flue gas treatment involving a combined reduction of nitrogen oxide and
sulphur oxide concentrations 1371.
NH4N03 are formed that can be removed by electrostatic
precipitators and may be used as fertilizers. Fig. 22 shows
a sketch of a combined deN0,-deSO, pilot installation using
a corona discharge for the flue gas treatment of 1000 m3/h
in Italy [37].As far as removal of heavy metals is concerned,
encouraging results have been reported regarding the reduction
of mercury vapor in corona discharges [33].
B. Treatment of Hazardous Wastes
Nonequilibrium discharges may also be used for detoxi-
fication processes. Evidently, all organic compounds can be
decomposed in a thermal plasma at high temperatures. In gen-
eral, this requires a large amount of energy to raise the total gas
temperature to several thousand degrees. In many cases it may
be more economical to split the toxic substances (conceivably
PCB’s, dioxines, solvent vapors, nerve gases, pesticides) by
the attack of charged particles or reactive intermediates in
a nonequilibrium discharge. The silent discharge in glass or
quartz vessels is ideally suited for this process and can handle
large amounts of gas if required. Laboratory experiments in
this direction treating certain model substances have been
reported by Sheinson [38].
VII. FUTURE
TRENDS
No doubt, low-pressure nonequilibrium discharges will re-
main an important research tool in volume plasma processing.
Due to their mass flow limitations, they are not likely to be
used for large-scale plasma synthesis. Their main technical im-
portance will remain in surface plasma chemistry for etching,
deposition, and surface modification applications, especially
in the semiconductor industry.
The use of corona discharges for surface treatment and as
a source of charged particles will continue. We also expect to
see ever increasing pilot facilities to investigate the potential of
pulsed coronas for flue gas cleaning. An interesting proposal
is to combine the deNO,/deSO, process with the dust removal
requirements by using the same corona for the charging
process of an electrostatic precipitator. This way, the energetic
IEEE TRANSACTIONS ON PLASMA SCIENCE, VOL. 19, NO. 6, DECEMBER 1991
A n
0
ELECTROSTATIC
PRECIPITATOR
I\
A
.A
0 I
A U .
.
e
A
A
a 0
0
A An
0
electrons are used to initiate the chemical reactions while, at
the same time, the ions are taken advantage of for charging
the fly-ash particles [36].
The silent discharge is the most likely candidate to reach
economic breakeven in other large-scale nonequilibrium pro-
cesses, in addition to ozone synthesis (391. The individual
microdischarges provide an ideal controllable medium for
nonequilibrium plasma processes. The control over electron
energy and electron density, as well as gas temperature and
pressure and its large gas-handling capacity suggest new
applications also for removal and destruction of undesired
compounds. Among the most exciting recent developments
of the silent discharge are novel sources of ultraviolet and
vacuum ultraviolet excimer radiation. They can be assembled
in large installations for industrial UV processing.
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(SUPPI.).
Baldur Eliasson (S’62-SM74) was born in Reyk-
javik, Iceland, in 1937. He received the M.Sc.
degree in electrical engineering from the Federal
Institute of Technology in Zurich, Switzerland, in
1962, and the Ph.D. degree in microwave theory
from the same institution in 1966.
After having spent 3 years at the radio astronomy
department at the California Institute of Technology,
Pasadena, studying the OH emissions from the
galaxy, he joinedthe Brown Boveri Research Center
in Daettwil, Switzerland, in 1969. He has been
involved in research in coherent optics, gas discharge physics, environmental
technologies, and plasma chemistry. Currently, he is in charge of a project
investigating new applications of carbon dioxide.
Dr. Eliasson is a member of the American Physical Society and the
European Physical Society.
Ulrich Kogelschatz was born in Arnsberg, Ger-
many, in 1937. He received the Vordiplom (B.S.)
in 1960, Diplom (M.S.) in 1963, and the Dr.rer.nat.
(Ph.D.) in 1968 in physics from Kiel University
(Germany).
During 1958-1959 he studied at Wesleyan Uni-
versity, Middletown, CT, as a Grantee on the Ful-
bright Program, and in 1968-1969 he held an NRC
Research Associateship at NASAnangley Research
Center, Hampton, VA. In 1969 he joined the Brown
Boveri Research Center, Baden, Switzerland, and
worked on electric arcs in supersonic flows, plasma diagnostics, and on
optimizing ozone generation in nonequilibrium plasmas. Currently, at Asea
Brown Boveri Corporate Research, he is in charge of a project investigating
new methods of UV generation and UV applications.
Dr. Kogelschatz is a member of the Optical Society of America, the
International Ozone Association, and the German and European Physical
Societies. He is also a member of the editorial board of Plasma Chemistry and
Plasma Processing and of the IUPAC Subcommittee on Plasma Chemistry.