Spectrochimica Acta Part B 61 (2006) 2 – 30

www.elsevier.com/locate/sab

Review

Atmospheric pressure plasmas: A review

Claire Tendero a,*, Christelle Tixier a, Pascal Tristant a, Jean Desmaison a, Philippe Leprince b
a 1
Laboratoire Sciences des Procédés Céramiques et Traitements de Surfaces, UMR CNRS 6638, Université de Limoges, France
b
Laboratoire de Physique des Gaz et des Plasmas, UMR CNRS 8578, Université Paris XI, Orsay, France 2

Received 17 July 2005; accepted 5 October 2005

Available online 18 November 2005

Abstract

This article attempts to give an overview of atmospheric plasma sources and their applications. The aim is to introduce, in a first
part, the main scientific background concerning plasmas as well as the different atmospheric plasma sources (description, working
principle). The second part focuses on the various applications of the atmospheric plasma technologies, mainly in the field of surface
treatments.
Thus this paper is meant for a broad audience: non-plasma-specialized readers will find basic information for an introduction to plasmas
whereas plasma spectroscopists who are familiar with analytical plasmas may be interested in the synthesis of the different applications of the
atmospheric pressure plasma sources.
D 2005 Elsevier B.V. All rights reserved.

Keywords: Plasma; Atmospheric; Review; Surface treatment; DBD; Corona; Torch

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
2. Part A. Basic and fundamentals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
2.1. Definitions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
2.1.1. Plasma generation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
2.1.2. Plasmas classification. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
2.2. Atmospheric pressure plasmas: LTE or non-LTE? . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
2.2.1. LTE plasmas . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
2.2.2. Non-LTE plasmas. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
2.2.3. Atmospheric pressure plasmas . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
2.3. Overview of various atmospheric plasma sources . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
2.3.1. DC and low frequency discharges . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
2.3.2. RF discharges. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
2.3.3. Microwave induced plasmas (MIPs) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
2.3.4. Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
3. Part B. Applications of the various atmospheric plasma sources . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
3.1. Spectroscopic analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18
3.2. Gas treatments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18
3.2.1. Gas cleaning . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18
3.2.2. Gas synthesis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19

* Corresponding author. Tel.: +33 6 16 77 73 47; fax: +33 5 55 42 36 80.

E-mail address: tendero_claire@yahoo.fr (C. Tendero).
1
ENSIL, 16 rue d’Atlantis, Parc d’ESTER Technopole, BP 6804, 87068 Limoges, France.
2
LPGP, Université Paris Sud, Bat 210, ave G. Clemenceau, 91405 Orsay Cedex, France.

0584-8547/$ - see front matter D 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.sab.2005.10.003
 C. Tendero et al. / Spectrochimica Acta Part B 61 (2006) 2 – 30 3

3.3. Material processing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20

3.3.1. Surfaces treatments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20
3.3.2. Surface coating . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21
3.3.3. Bulk material treatments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24
3.4. Lamps . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25
4. Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25
Acknowledgments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 27
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 27

1. Introduction The atmospheric plasmas described in this paper are

Plasmas are chemically active media. Depending on the way
they are activated and their working power, they can generate
low or very high ‘‘temperatures’’ and are referred correspond-
ingly as cold or thermal plasmas. This wide temperature range
enables various applications for plasma technologies: surface
coatings, waste destruction, gas treatments, chemical synthesis,
machining. . . Nevertheless, many of these techniques have not
been industrialized, albeit environmental norms are strictly
followed.
Thermal plasmas (especially arc plasma) were extensively
industrialized, principally by aeronautic sector. Cold plasma
technologies have been developed in the microelectronics but
their vacuum equipment limits their implantation.
To avoid drawback associated with vacuum, several labora-
tories have tried to transpose to atmospheric pressure processes
that work under vacuum for the moment. Their researches have
led to various original sources that are described here.
This paper is a review about atmospheric plasmas. It is
mainly about the technologies that are still under development
in laboratories whereas arc and inductive plasmas are briefly
discussed.
After a summary about the different kinds of plasmas, the
various sources are described in term of design, working
conditions and plasma properties. Then the study focuses on
their applications (spectroscopic analysis, gas treatments and
materials proceedings) and concludes with a comparative
synthesis of each system (applications, advantages, limits).
generated from electrical energy. The electric field transmits
energy to the gas electrons (which are the most mobile charged
species). This electronic energy is then transmitted to the
neutral species by collisions. These collisions [2] follow
probabilistic laws and can be divided in:
& Elastic collisions: they do not change the internal energy of
the neutral species but slightly rise their kinetic energy
& Inelastic collisions: when electronic energy is high enough,
the collisions modify the electronic structure of the neutral
species. It results in the creation of excited species or ions if
the collisions are energetic enough.
Most of the excited species have a very short lifetime and
they get to ground state by emitting a photon. The ‘‘metastable
species’’ are also excited states but with a long lifetime because
their decay by emission of radiation is hampered as there are no
allowed transitions departing from the respective state: decay
can only take place by energy transfers through collisions.
2.1.2. Plasmas classification
Depending on the type of energy supply and the amounts of
energy transferred to the plasma, the properties of the plasma
change, in terms of electronic density or temperature. These
two parameters distinguish plasmas into different categories,
presented in see Fig. 1. The atmospheric plasma sources
described in this paper are supposed to be positioned near the
glow discharges and the arcs.

2. Part A. Basic and fundamentals

2.1. Definitions

Plasma is a more or less ionized gas. It is the fourth state of

matter and constitutes more than 99% of the universe. It
consists of electrons, ions and neutrals which are in funda-
mental and excited states. From a macroscopic point of view,
plasma is electrically neutral. However, it contains free charge
carriers and is electrically conductive.

2.1.1. Plasma generation

A plasma is created by applying energy to a gas [1] in order
to reorganize the electronic structure of the species (atoms,
molecules) and to produce excited species and ions. This
energy can be thermal, or carried by either an electric current or Fig. 1. 2D classification of plasmas (electrons temperature versus electrons
electromagnetic radiations. density) [5].
4 C. Tendero et al. / Spectrochimica Acta Part B 61 (2006) 2 – 30

Table 1 ˝ E H+ = 13.58 eV is the ionization energy of the hydrogen

Main characteristics of LTE and non-LTE plasma atom
LTE plasmas Non-LTE plasmas ˝ T is the plasma temperature.
Current Thermal plasmas Cold plasmas
name This criterion shows the strong link that exists between the
required electron density for LTE and the energy of the first
Properties Te = T h Te H T h
High electron density: Lower electron density: excited state.
1021 – 1026 m 3 <1019 m 3 Those rules for LTE are very strict. Thus most of the
Inelastic collisions between Inelastic collisions between plasmas deviate from LTE, especially all types of low density
electrons and heavy particles electrons and heavy particles plasma in laboratories.
create the plasma reactive induce the plasma chemistry.
species whereas elastic Heavy particles are slightly
collisions heat the heavy heated by a few elastic 2.2.2. Non-LTE plasmas
particles (the electrons collisions (that is why the Departure from Boltzmann distribution for the density of
energy is thus consumed) electrons energy remains excited atoms can explain the deviation from LTE. Indeed, for
very high) low-lying levels, the electron-induced deexcitation rate of the
atom is generally lower than the corresponding electron-
Examples Arc plasma (core) Glow discharges
[117] Te = T h å 10,000 K Te å 10,000 – 100,000 K induced excitation rate because of a significant radiative
T h å 300 – 1000 K deexcitation rate [4].
Another deviation from LTE is induced by the mass
In this classification, a distinction can be made between: difference between electrons and heavy particles. Electrons
move very fast whereas heavy particles can be considered static:
& Local thermodynamic (or thermal) equilibrium plasmas electrons are thus likely to govern collisions and transitions
(LTE) phenomena. Deviations from LTE are also due to strong
& Non-local thermodynamic equilibrium plasmas (non-LTE). gradients in the plasma and the associated diffusion effects.
It has been shown that the LTE distribution can be partial.
2.2. Atmospheric pressure plasmas: LTE or non-LTE? For example, LTE can be verified for the levels close to
ionization threshold [7] (e.g., 5p levels and higher, in argon
The Local Thermodynamic Equilibrium notion [3] is really plasma): such plasmas are pLTE (partial LTE).
important, especially for a spectroscopic study of the plasma, The non-LTE plasmas can be described by a two-
since the determination of the plasma parameters (particles temperature model: an electron temperature (Te) and a heavy
distribution functions; electron, excitation, vibration particle temperature (T h). Regarding the huge mass differ-
temperatures. . .) is based on relationships which differ for ence between electrons and heavy particles, the plasma
plasmas in LTE or not. temperature (or gas temperature) is fixed by T h. The higher
the departure from LTE, the higher the difference between Te
2.2.1. LTE plasmas and T h is.
LTE plasma requires that transitions and chemical reactions Table 1 sums up the main characteristics of LTE and non-
are governed by collisions and not by radiative processes. LTE plasmas. More details on LTE and deviations from LTE
Moreover, collision phenomena have to be micro-reversible. It are developed in the books by Huddlestone and Leonard [8],
means that each kind of collision must be balanced by its Griem [9], Lochte-Holtgreven [10] and Mitchner and Kruger
inverse (excitation/deexcitation; ionization/recombination; ki- [11].
netic balance) [4].
Moreover LTE requires that local gradients of plasma
properties (temperature, density, thermal conductivity) are
low enough to let a particle in the plasma reach the equilibrium:
diffusion time must be similar or higher than the time the
particle need to reach the equilibrium [5]. For LTE plasma, the
heavy particles temperature is closed to the electrons temper-
ature (ex: fusion plasmas).
According to the Griem criterion [6], an optically thin
homogeneous plasma is LTE if the electron density fulfills:
 3  
23 E21 kT

ne ¼ 9:10 m3
EHþ EHþ
where

˝ E 21 represents the energy gap between the ground state and Fig. 2. Evolution of the plasma temperature (electrons and heavy particles) with
the first excited level, the pressure in a mercury plasma arc [5].
 C. Tendero et al. / Spectrochimica Acta Part B 61 (2006) 2 – 30
2.2.3. Atmospheric pressure plasmas
Fig. 2 shows the influence of the pressure on the transition
from a glow discharge (Te > T h) to an arc discharge.
Low pressure plasmas (10 4 to 10 2 kPa) are non-LTE.
Heavy particles temperature is lower than the electronic one.
The inelastic collisions between electrons and heavy particles
are excitative or ionizing. These collisions do not rise the heavy
particles temperature.
When the pressure becomes higher, collisions intensify.
They induce both plasma chemistry (by inelastic collisions)
and heavy particles heating (by elastic collisions). The
difference between Te and T h is reduced: plasma state becomes
closer to LTE but does not reach it. The significant gradient of
properties in plasma restricts a particle, moving in the
discharge, achieving equilibrium.
The density of the feeding power influences a lot the
plasma state (LTE or not). On the whole, a high power
density induces LTE plasmas (e.g. arc plasmas) whereas
non-LTE plasmas are favored by either a low density of
feeding power or a pulsed power supply. In this latter case,
the short pulse duration prevents the equilibrium state from
establishing.
Finally, it is important to note that an atmospheric plasma jet
can be divided in two zones:
& a central zone or plasma core which is LTE
& a peripheral zone which is non-LTE. In this plume, heavy
particles temperature is much lower than electrons one.
Indeed, for a free-burning argon arc [6], operating
conditions (a pressure of 300 kPa, currents of 300 to 400
A) are necessary to reach a LTE state in the central portion.
These conditions lead to an electron density of 1024 m 3 in
the center. Departures from LTE occur in the outer regions
of such arcs where the electron density decreases below
1024 m 3.
Thus, the local thermodynamic equilibrium is a primor-
dial notion since it induces the temperature of the plasma.
It strongly depends on the kind of plasma source and is
Fig. 3. Electrons and ions frequencies in cold plasmas [99].
5
determining for its applications. In the next part, the various
atmospheric plasma sources are described in terms of
design, operating conditions (power supply, plasma
excitation. . .).
2.3. Overview of various atmospheric plasma sources
The excitation frequency is important since it influences the
behavior of the electrons and the ions. Fig. 3 shows an example
of the variation range for f pe (frequency of the electrons in the
plasma) and f pi (ions frequency) in cold plasmas (e.g. glow
discharges).
The atmospheric plasma sources can be classified regarding
their excitation mode. Three groups are then highlighted:
& the DC (direct current) and low frequency discharges;
& the plasmas which are ignited by radio frequency waves;
and
& the microwave discharges.
Table 4 reports the main characteristics of these various
plasma sources.
Among them, the emerging of original microplasmas [12]
is quite interesting. The trend of miniaturization of plasma
systems is important in order to create low-powered directive
portable systems and to reduce instrument and operation
costs.
2.3.1. DC and low frequency discharges
Depending on their design, the DC and low frequency
discharges can work either with a continuous or a pulsed mode.
A pulsed working mode enables the injection of large energy
amounts in the discharge while the system warming up is
limited. On the other hand, a pulsed power supply is
technically more complex than a DC source and compromises
the reproducibility of the process.
2.3.1.1. Continuous working mode: the arc plasma torches. The
arc plasma torches [13] are fed by a DC power supply. They can be
6 C. Tendero et al. / Spectrochimica Acta Part B 61 (2006) 2 – 30
Fig. 4. Principle of arc plasma torches (left: current-carrying arc, right: transferred arc).
divided into two categories: current-carrying arc and transferred
arc (see Fig. 4). They both consist of:
& a cathode where electrons are emitted;
& a plasma gas injection system; and
& a nozzle which confines the plasma.
In a current-carrying arc torch, the nozzle which is
positively polarized is the anode. In the case of a transferred
arc torch, the treated material is the anode whereas the nozzle is
at a floating potential.
The arc is ignited between the cathode and the anode and
ionizes the plasma gas. The plasma temperature varies from
8 000 K (plasma envelop) to 15 000 K (plasma core) which
enables high temperature applications (use of the thermal effect
of the plasma). An arc plasma is a very conductive media
(I = 50– 600 A). The gas is highly ionized and the electronic
density is about 3.1023 m 3.
Through the years, the arc plasma torches have been
improved and are strongly implanted in industries:
& a high-energy, high velocity torch: Plazjet [14] (see Fig. 5);
& a structure with three cathodes and a segmented anode:
TRIPLEX (Fig. 6);
Fig. 5. High velocity Plazjet [100] (Tafa, Praxair).
& a torch working with a long plasma column stabilized by
vortices [15]; and
& A miniature seal-less plasma torch designed by CEA [15]
(licensed by Europlasma).
2.3.1.1.1. Pencil-like torches. Those last 5 years, low-
powered flexible and innovative arc plasma torches have been
commercialized:
& Plasmapen and Plasmapen Xtension to increase the size of
the treated surface (PVA-TEPLA [16]): see Fig. 7;
& Plasma-JetR from Corotec Corporation [17];
& Openair technology (patterned by PlasmatreatR [18] ) is
well implanted in production lines (automobile, textile,
packaging. . .).
They all use a homogeneous, low-powered, current-
carrying arc plasma jet to prepare a surface prior to joining
it with adhesives, coating it, or printing upon it.
On the opposite of the classical arc plasma torches, the
discharge generates very little heat, which allows surface
treatment of various materials including low temperature
degradable materials (polymers).
The classical arc torches can be classified as LTE discharges.
They are characterized by rather high temperatures and are used
Fig. 6. Sultzer Metco Triplex II Plasma Spray Gun [101].
 C. Tendero et al. / Spectrochimica Acta Part B 61 (2006) 2 – 30 7

Fig. 9. Hollow needle to plate discharge [102] (left: positive needle, right:
negative needle).
Fig. 7. Plasmapen (left) and Plasmapen Xtension (right), PVA-TEPLA [16].

As the plasma volume is very small, the main corona

for applications where heat is required (welding, cutting,
drawback regarding surfaces treatments is the thin size of
spraying. . .), whereas the low-powered pencil-like torches
the treated surface. To increase the size of the surface
involve a non-LTE discharge: they create a ‘‘chemically rich
treatment, the cathode wire can be replaced by a planer
environment’’ which is used for low temperature applications.
electrode which is parallel to the treated surface: this system
generates micro-arcs (streamers) that are perpendicular to
2.3.1.2. Pulsed working mode
the gap between the electrodes. The streamers always
2.3.1.2.1. Corona discharge. Corona [19] discharge is a
initiate at the same place (default on the surface) causing
non-LTE discharge with low current density. The device
a non-homogeneous treatment on the material surface. To
(Fig. 8) consists of a cathode-wire and an anode (the treated
avoid this problem, a dielectric barrier discharge was
material), the DC power supply is pulsed. The plasma creates a
developed.
lighting crown around the wire: that is why this discharge is
2.3.1.2.2. Dielectric barrier discharge. The DBD device
called ‘‘Corona’’.
(see Fig. 10) consists of two plane-parallel metal electrodes: at
When a negative high voltage is applied to the wire, the
least one of these electrodes is covered by a dielectric layer. To
discharge is a negative corona. The positive ions are
ensure stable plasma operation, the gap which separates the
accelerated towards the wire where secondary electrons are
electrodes is limited to a few millimeters wide. Plasma gas
emitted and accelerated into the plasma: this moving front of
flows in the gap. The discharge is ignited by means of a
high-energy (about 10 eV) electrons followed by a tail of lower
sinusoidal [21] or pulsed [22] power source. Depending on the
energy electrons (about 1 eV) is called a streamer [96].
working gas composition, the voltage and frequency excitation,
Inelastic collisions occur between these high-energy electrons
the discharge can be either filamentary or glow [23,24]. A
and heavy particles and induce the formation of chemically
filamentary discharge is formed by micro-discharges or
reactive species.
streamers [25] that develop statistically on the dielectric layer
The pulses duration is shorter than the time necessary
surface. The use of helium as plasma gas seems to favor a glow
for the arc creation: when each pulse ends, the discharge
discharge (high energetic He metastable species [24], Penning
extinguishes before it becomes too conductive. The transi-
effect [23,26]).
tion into spark [20] is then avoided. The current discharge
The dielectric layer plays an important part by:
is very low: 10 10 to 10 5 A. A positive corona also
exists: the positive polarized wire acts as the anode (see
& limiting the discharge current and avoiding the arc
Fig. 9).
transition that enables to work with a continuous or pulsed
mode.
& distributing randomly streamers on the electrode surface
and ensuring a homogeneous treatment. The streamer
creation is due to the electrons accumulation on the
dielectric layer.

The described DBD device is the most common one and

other systems have been developed:

& a DBD with a brush-style cathode [27] that consists of 25

fine stainless wires. This process is convenient for non-
conductive sample treatment,
& a system with a special designed cathode [28] which can be
Fig. 8. Principle of a corona discharge. a applied to metallic and dielectric surface treatment,
8 C. Tendero et al. / Spectrochimica Acta Part B 61 (2006) 2 – 30
Fig. 10. Principle of dielectric barrier discharge (picture: a non-equilibrium diffuse plasma at atmospheric pressure [103]).
& a DBD with spiral electrodes [29] that are used for coating
in the tube interior,
& a device where the dielectric layer consists of capillary
dielectrics [30] or a disc of glass beads [31].
2.3.1.2.3. The derived-from-Corona processes. A lot of
industries have developed processes which are similar to
corona treating systems, even if they use an alternative power
supply rather than a pulsed one:
& ALDYNEi (created by Air Liquide and Softal [32]) is
mainly adapted to on-line surfaces treatments of polymers
(Fig. 11).
& Corona treatment systems are manufactured by 3DT [33]:
BottleDynei, FlexyDynei, PlasmaDynei which make it
possible to Corona treat any three-dimensional polymeric
surface delicately, quickly and efficiently.
& The ‘‘AcXys Technologies’’ system [34] was developed
by T. Sindzingre et al. (Société AcXys Technologies
[35], France). It consists of two cylindrical concentric
electrodes. The plasma gas is introduced in the gap
between the electrodes through an inlet in the outer
electrode (see Fig. 12). The inner electrode is connected
with a high voltage and low frequency source. The
discharge is initiated in the gap. The afterglow, where
long lifetime species are accessible, exits by an outlet in
Fig. 11. Principle of Aldynei process.
the outer electrode situated on the opposite side of the
gas inlet. Physical and chemical treatments occur in this
afterglow.
2.3.1.2.4. Microplasma. DC-operating microplasma on
glass chips (see Fig. 13) were developed by J.K. Evju et al.
[36] for the chemical modification of microchannel walls.
The microchannels are formed by hot imprinting PS
between glass microscope slides. Microelectrodes for plasma
generation are fashioned from platinum wires that are
sharpened by etching with alternating current in 6 M
NaOH.
A similar micro-source was designed by Bessoth and
coworkers [37] for gas detection: the plasma is generated in
a 70-Am deep and 500-Am wide channel between two tungsten
electrodes.
2.3.2. RF discharges
Regarding their structure, the RF sources can work with a
high or low power supply. It influences the properties of the
plasma and thus its potential applications.
The impedance matching can be either inductive (high
powered discharges) or capacitive.
2.3.2.1. High powered discharges
2.3.2.1.1. The ICP torches. The inductive discharges have
been known for a long while. The RF torch is simply designed
(see Fig. 14). The plasma is initiated and maintained by an RF
fed helical coil.
Fig. 12. Principle of AcXys process.
 C. Tendero et al. / Spectrochimica Acta Part B 61 (2006) 2 – 30
Fig. 13. DC microdischarge design.
The current that flows in the RF coil induces a time-
varying magnetic field nearby the plasma zone. The resulting
electric ring field (see Faraday law) accelerates the electrons
and thus maintains the discharge. The frequency of the
generated plasma is higher than 1 MHz. This frequency level
implies that electrons follow the electric field oscillations and
neither ions nor electrons can reach the torch wall. This lack
of contact between the plasma and the wall reduces the
pollution of plasma and torch walls which enables to work
with different gases: inert, reductive, oxidant, nitriding gas
[38].
The plasma is enclosed in a ceramic tube (quartz, silicon
nitride) that is cooled by air or water, depending on the
working power. The inductive torches work in a wide
power range: 20 kW– 1000 kW, with a gas flow rate of
10 –200 slm. A higher working power is accompanied with
lower torch diameter and lower plasma frequency (see
Table 2).
These sort of inductive torches are presently very well
developed (in particular by EFD induction SA [39], Tekna
Plasma System Inc [40]. . .). They can be applied to spectro-
scopic analysis, toxic waste treatment. . .
2.3.2.1.2. The IST system. An intelligent electrodes design
makes it possible to treat very complex surfaces in a fast and
efficient way. The IST society has developed an RF pulsed
discharge to decontaminate the interior of plastic bottles [41].
This process is the DBD adaptation to the complex surfaces
treatment.
Without introducing an electrode inside the bottle, the plasma
is however generated inside the bottle with the help of
surrounding and top central electrodes (see Fig. 15) and is
stabilized by the dielectric walls. To make the discharge
initiation easier, argon can flow nearby the central electrode.
Fig. 14. RF plasma torch (Teckna Plasma System Inc [40]).
9
Table 2
RF torches characteristics with a 6000 K argon plasma [118]
Working power (kW) Torch diameter(mm) Working frequency (kHz)
50 42 1020
80 54 630
300 104 166
700 159 72
This system needs high power source (20 kW) but the use of
impulsions makes it possible to treat low temperature degradable
materials.
2.3.2.2. Low-powered discharges. To initiate the discharge in
the gas, a voltage must be applied between the electrodes. This
breakdown voltage depends on the value of P  d where P is the
pressure and d the gap between the electrodes. Paschen laws
[19] show that working at atmospheric pressure implies a thin
gap (several millimeters) in order to have a realistic voltage.
In these discharges, the impedance matching is capacitive.
2.3.2.2.1. The atmospheric pressure plasma jet (APPJ). The
APPJ [19] is a small (L < 20 cm) RF plasma torch that works at low
power. It was developed by J.Y. Jeong et al. (University of
California, Los Angeles) in collaboration with J. Park et al. (Los
Alamos National Laboratory [42]).
This system (see Fig. 16) consists of two concentric
electrodes through which the working gas flows. By applying
RF power to the inner electrode at a voltage between 100 and
150 V, the gas discharge is ignited. The ionized gas exits
through a nozzle since the gas velocity is about 12 m s 1. The
low injected power enables the torch to produce a stable
discharge and avoids the arc transition.
The same research team (Park and coworkers [43], UCLA)
designed a rectangular version of the APPJ. This source
produces a volumetric and homogeneous discharge in a 1.6 mm
wide gap between two planar aluminum electrodes. Both
electrodes are perforated to let the plasma gas flow through
them. The upper electrode is connected to the RF power supply
while the lower electrode is grounded. It has been recently
applied to the deposition of hydrogenated amorphous silicon
[44] with silane added downstream of the hydrogen– helium
plasma.
10 C. Tendero et al. / Spectrochimica Acta Part B 61 (2006) 2 – 30

Fig. 15. Principle of IST process.

Both sources are commercialized by Surfx Technologies
[45] (Atomfloi: see Fig. 17).
2.3.2.2.2. The cold plasma torch. The cold plasma torch
[46] developed by H. Koinuma et al. (Institute of Technology,
Tokyo) lies between the DBD and APPJ structures.
The device is shown in Fig. 18 and its properties are
reported in Table 4. The RF electrode is a stainless-steel
needle. A quartz tubing is inserted between the cathode and
anode to ensure both plasma stability and homogeneity. The
plasma gas flows into the gap between the cathode and the
dielectric tube.
2.3.2.2.3. The hollow cathode systems. Designed by Janèa
et al. (Masaryk University, Brno, Republic Czech), the RF
pencil (see Fig. 19) is very close [47] to the cold plasma torch.
This coaxial device is very small (L < 10cm). The RF electrode
is a hollow needle; the plasma gas flows inside it. This cathode
is inserted into a quartz tube. The plasma is generated inside
the hollow electrode. The gas speed is high enough to make the
plasma jet flow outside the sharp top of the needle.
A barrier torch [48] which is similar to the RF pencil was
also developed in Czech Republic by Hubièka et al. (Academy
of Sciences, Prague): see Fig. 20. A quartz tube is inserted into
the RF hollow electrode. The working gas is injected inside the
dielectric tube. The dielectric layer stabilizes the discharge and
limits the electrode heating. The discharge remains stable in the
case of a multi-nozzle torch-barrier device. A larger surface
zone can be treated.
In the same category, the HEIOS and HELIOS systems [49]
were introduced by Bardos and Barankova. They create stable
and uniform RF plasma over large area. HEIOS is a cylindrical
hollow cathode whose open structure is made with 900
channels where the working gas flows: it is a 900 hollow
simultaneously working cathodes assembling that generates a
stable discharge over 7 cm2. HELIOS [50] design is based on
the same idea: it is a rectangular hollow cathode that generates
stable and uniform RF plasma over 20 cm2. The design of these
sources allows their direct scaling up for large area plasma
applications.
2.3.2.2.4. Microplasma. Recently, small-scale and low
power plasmas have been investigated by several authors.
Those microplasmas can be applied in various fields, as
summarized in Table 3 (Fig. 21).

Fig. 16. APPJ design.

 C. Tendero et al. / Spectrochimica Acta Part B 61 (2006) 2 – 30
Fig. 17. Atmofloi plasma can clean and activate surface prior to bonding [45].
2.3.3. Microwave induced plasmas (MIPs)
The electrode-less microwave systems all work according
the same principle. Microwaves are guided along the system
and transmitted energy to the plasma gas electrons. Elastic
collisions between electrons and heavy particles occur. Due to
the large mass of heavy particles, the collided electrons
rebound whereas the heavy particles remain static. The
electrons are thus accelerated (they get kinetic energy) and
the heavy particles are slightly heated. After several elastic
collisions (which follow probabilistic laws), the electrons get
enough energy to produce inelastic exciting or even ionizing
collisions. The gas is partially ionized and becomes plasma
which supports microwave propagation [51].
The next described microwave plasma sources are all
designed according to the same idea. They consist of:
˝ a microwave power source (power supply, magnetron and
circulator to protect the magnetron from the reflected power);
˝ microwave equipment (wave guides, tuning system);
˝ an ignition system; and
˝ gas injections.
Fig. 18. Cold plasma torch design.
11
Fig. 19. RF pencil design.
The discharge ignition is the key to microwave sources.
Indeed, a self-ignition of the discharge ensures flexible
operating conditions and enables the industrialization of the
process. The energy, transmitted to the gas electrons, has to be
high enough to initiate the plasma. In the literature, several
methods are suggested to concentrate the microwave energy:
˝ The indirect ignition with a conductive rod [52] which plays
the part of an antenna. The microwave are then caught and
concentrated at the tip of the rod.
˝ A resonator cavity [53] that makes the electric field
maximum where the plasma gas flows.
˝ A helical coil [54] that induces a circularly polarized wave.
The energy which is transferred to electrons is then enhanced.
˝ A material with electrically conductive and heat-resistive
properties [55]. This material can generate easily stable
plasma when irradiated by microwaves in an argon flow.
Fig. 20. Barrier torch design.
12 C. Tendero et al. / Spectrochimica Acta Part B 61 (2006) 2 – 30

Table 3
Examples of RF microplasma sources
Source Source characteristics Applications
Micro-structured electrode (MSE) [119,120] Capacitively coupled discharge Fluorinated waste gas treatment
Micro-reactor volume: 60.5 mm3 Diamond-like carbon deposition
Multi-reactor (MSE array) volume: 16  60.5 mm3 Sterilization

Capacitively coupled microplasma Microchannel: 10 mm long, 200 – 500 Am deep Detector for gas chromatography
CCAP [121] See Fig. 21

Miniaturized plasma jet source [122] Inductively coupled discharge Optical emission spectroscopic
Discharge tube: 1 1  30 mm3 analysis of liquid sample
Plasma source chip: 15  30 mm2

These atmospheric MIPs can be classified in three categories:
˝ resonant cavity plasmas;
˝ free expanding torches; and
˝ microplasmas.
2.3.3.1. Resonant structures. The Beenakker [56] cavity is
the most-well known resonant cavity to generate microwave
plasmas.
A resonator cavity uses resonance phenomena to amplify a
wave. Its interior surfaces reflect one type of wave. When a
wave that is resonant with the cavity enters, it bounces back
and forth within the cavity, with low-energy loss: a standing
wave is thus generated. As more waves enter the cavity, they
combine with the standing wave and reinforce it, increasing its
energy. This energy is used to initiate the discharge.
The resonance frequency of the cavity strongly depends on
its geometry parameters, especially on its radius (see Fig. 22).
Thus, it is necessary to fit the geometry of the cavity with the
frequency delivered by the microwave generator (2.45 GHz), in
order to ensure the ignition of the plasma.
2.3.3.2. Free expanding plasma torches. These sources
create a plasma that flows in open air. Regarding the structure
of the torches, a distinction can be made between the metallic
and the semi-metallic torches.
2.3.3.2.1. Metallic torches. The TIA (torche à injection
axiale) microwave plasma torch was developed by Moisan et al.
[57]. It works with a conventional wave guide-to-coaxial line
transition. The plasma gas flows in the inner coaxial line
conductor and exits through a nozzle (see Fig. 23). The
microwaves are generated by the magnetron and reach the
working gas using rectangular and coaxial guides. The discharge
is ignited on top of the nozzle. The plasma consists of a needle-
like converging filamentary cone with a tail flame on top of it
(see Fig. 24).
The guide selects the propagating modes: TE10 in the
rectangular guide (E z = 0 with z the wave propagation direction)
and TEM in the coaxial line (E z = Hz = 0), which limits the
energy loss that could come from parasite modes excitation.
Impedance matching functions are achieved using two intrinsic
tuning elements (movable plungers: short circuit and initiator):
the transition between TE10 and TEM modes is then optimized
and the reflected power is minimized.
This metallic microwave torch was patented by P. Leprince
et al. [58] (Laboratoire de Physique des Gaz et des Plasmas,
Orsay, France).
Other laboratories have studied other microwave torches
using the same wave guide-to-coaxial line transition. The design
changes slightly depending on the torch application field.
In order to limit the interactions with surrounding atmo-
sphere, Jasinski et al. [59] confined the plasma by putting a
quartz tube around the nozzle.
Okamoto et al. [54] have put a quartz tube (longer than the
coaxial line) inside the inner conductor to inject aerosol
samples and confine the plasma (torch for spectroscopic

Fig. 21. Design of a capacitively coupled microplasma (CCMP). Fig. 22. Resonance modes and frequencies of a cylindrical cavity [104].
 C. Tendero et al. / Spectrochimica Acta Part B 61 (2006) 2 – 30
Fig. 23. TIA design.
analysis). The discharge ignition is induced by a helical coil.
This torch produces annular-shaped plasma.
Suzuki et al. [60] have designed a torch that uses the guide-
coaxial line transition without movable plunger initiator. Water
flows inside the inner conductor whose top is made of
molybdenum to prevent thermal damage. A copper nozzle is
fitted at the end of the torch. The plasma gas is injected in the
coaxial line gap. The discharge is generated in the space
between the molybdenum top and the nozzle where the
electrical field concentrates.
As the TIA design is quite sophisticated, its construction
requires advanced and expensive workmanship. Thus, this
coaxial torch has been simplified. Moisan et al. have designed
the TIAGO (TIA sur guide d’onde). It is a simple and compact
one-nozzle unit [61] but electromagnetic radiation can be
emitted from the gap between the nozzle and the wave guide.
Fig. 24. The three different zones that can be distinguished in typical plasmas
produced by the TIA [105].
13
To protect the personnel and instrumentation from those
radiations, Jasinski et al. [62] have placed a cylindrical metal
grid inside the reactor, coaxially around the nozzle. This grid
influences the plasma flame, improving its stability. This
system is called the Microwave Torch Discharge (MTD).
In United Kingdoms, a very simple structure was developed
by S.R. Wylie et al. [63]: the Microwave Plasma Jet (MPJ).
The plasma cavity consists of a rectangular wave guide section
that ends at a copper plate acting as a short circuit. The gas
nozzle is situated inside the cavity directly above an aperture in
the wave guide, one-quarter wavelength from the short circuit,
where the maximum electric field is produced. This system can
work either at 2.45 GHz or at 896 MHz [64] (this latter
wavelength limits the electromagnetic radiation, in spite of the
wave guide aperture).
2.3.3.2.2. Semi-metallic torches. The design of this
torches is very similar the one of the metallic torches. The
main difference is the propagation mode of the electromagnetic
waves, as there is no guide-to-coaxial line transition. In the
semi-metallic torches, the plasma gas flows through a quartz
tube (which is transparent to microwave radiations). Instead of
burning out on top of the nozzle, the discharge is initiated in the
zone where the quartz tube intersects the rectangular wave
guide [65] (see Fig. 25).
This system (also called ‘‘guide-surfatron [66]’’) involves
surface waves: the propagation mode is converted from the
TE01 mode (in the rectangular wave guide) into the TM01 mode
(in the quartz capillary). The microwaves propagate along the
interface between the quartz tube and the plasma: then, the
plasma can be extended over long distances.
In the literature, this simplest semi-metallic torch is called
Microwave Plasma Torch (MPT). It was first developed by Jin
and coworkers [67] for atomic emission spectroscopy, as a
possible alternative to the ICPs in analytical chemistry. The
MPT creates a flame-like discharge: in general the flame is
luminous and white-colored with a fainter central channel [68].
14 C. Tendero et al. / Spectrochimica Acta Part B 61 (2006) 2 – 30

Fig. 25. MPT design.

Fig. 26. Pulsed microwave torch design (Baeva et al.).

The key remains the way to initiate the discharge: it has to irradiation on the perovskite type powders. These powders
be self-ignited in order to ensure flexible operating conditions are electrically conductive and thermally resistant.
and to make the industrialization of the process possible. All those microwave plasma torches are still in development
Thus Y.C. Hong et al. [69] have designed an original system in laboratories. CyrannusRI (cylindrical resonator with annular
made of a three microwave plasma torches line. Each torch is slots) is an example of industrialized microwave atmospheric
turned on by tungsten igniters (similar to spark plugs) positioned plasma source. It generates a homogeneous plasma in a quartz
slightly away from the center of the wave guide. This kind of tube (Fig. 27) and was developed in Germany by Iplas [72].
ignition enables the use of a very low cost microwave power
supply (magnetrons used in typical home microwave ovens).
Still in order to achieve flexible operating conditions, Pott et
al. [70] have developed a torch with a resonant cavity (see Fig.
26). Moreover the working gas flows with a superimposed
vortex. This kind of injection avoids wall burning and
stabilizes the discharge. This torch works with a pulsed power
supply, which limits the system heating while working with
high-energy amounts (and thus very energetic plasma species).
Another way of igniting the discharge is the one developed
by Sugiyama et al. [71]. They found that an atmospheric argon
cold plasma discharge could be generated by microwave Fig. 27. The CyrannusRI source (Iplas, Germany) [72].
 C. Tendero et al. / Spectrochimica Acta Part B 61 (2006) 2 – 30 15

Table 4
Characteristics of atmospheric plasma sources
Excitation Source Plasma properties Operating conditions
Industrialized sources
DC/Low frequency Arc torch [5,123] Te = T h å 8000 – 14,000 Ks Gas: Ar /He
n e = 1021 – 1026 m 3 Gas flow: 10 – 150 slm
Power: 10 – 100 kW
PlasmatreatR [124] T h < 700 K Gas: air
Gas flow: 117 slm

Pulsed DC/Low frequency Corona [19] Te = 40,000 – 60,000 K Gas: air

T h < 400 K
n e = 1015 – 1019 m 3
DBD [43] Te = 10,000 – 100,000 Km Some 100 W
T h < 700 K Plasma gas: 5 – 40 slm
n e å 1018 – 1021 m 3

Radio frequency ICP [5,123] Te = T h = 6000 – 11,000 Ks Gas: Ar/He

n e = 1021 – 1026 m 3 Gas flow: 10 – 200 slm
Power: 50 – 700 kW

Pulsed radio frequency IST [41] T h < 400 K Gas: surrounding air
No gas flow
Power: 20 kW

Microwave Cyrannus [72] T h < 700K Gas: Ar/O2

Power: 6 kW

Still in laboratory development sources

DC Microplasma – Power: 500 V; 250 AA

Radio frequency APPJ [19] Te = 10,000 – 20,000 Ks, m, l

Gas: O2 /He
T h < 600 K Gas flow: 50 – 90 slm
n e = 1017 – 1018 m 3 Power: some 100 W
Cold plasma torch [19] Te = 10,000 – 20,000 Ks, l
Gas: Ar
T h < 700 K Gas flow <1 slm
n e = 1017 – 1018 m 3 Power: 100 W
Hollow cathode [48,49] Te = 3000 – 11,000 Ks Gas: Ar, He
T h < 800 K Gas flow <2 slm
n e å 1017 – 1018 m 3 Power: some 100 W
Microplasma CCAP [12] Te = 1850 – 2300 K Gas: Ar
Gas flow: <0.2 slm Power: 5 – 25 W

Microwave TIA [125] Te = 13,000 – 14,000 K s Gas: He

T h = 2400 – 2900 Ks Gas flow: 2 – 6 slm
n e å 1021 m 3 Power: 100 W – 2 kW
MTD [62] Te = 17,000 – 20,000 Ks Gas: N2
T h = 1500 – 4000 Ks Gas flow: 1 – 3 slm
n e = 1020 – 1021 m 3 Power: 100 W – 400 W
MPJ [63] Te = 12,000 – 17,000 Ks Gas: Ar
T h = 5000 – 10,000 Ks Gas flow: 2 – 7 slm
n e å 1022 m 3 Power: 2 – 5 kW
MPT [126,127] Te = 16,000 – 18,000 Ks Gas: Ar
T h = 3000 – 3500 Ks Gas flow <1 slm
n e å 1020 – 1021 m 3 Power: some 100 W
Baeva et al. [70] Te å 7000 Ks Resonant cavity
T h å 7000 Ks Pulsed MW power supply
n e å 1019 m 3 Gas: N2
Gas flow: 30 slm
Power: 800 W
Sugiyama et al. [128] Te å 90,000 Ks Ignition by perovskite powder
T h å 1000 Kt Gas: Ar/H2
n e å 1017 m 3 Gas flow: 0.3 – 1.2 slm
Power: some 100 W
s
: temperatures calculated from spectrometric measurements.
m
: temperatures calculated from models.
l
: temperatures calculated from Langmuir probe measurements.
t
: temperatures measured by thermocouple.
16 C. Tendero et al. / Spectrochimica Acta Part B 61 (2006) 2 – 30

Table 6
Ozone density in atmospheric plasma discharges [19]
Excitation Source Ozone density (cm 3)
DC Arc plasma torch <1010
Pulsed DC Corona 1018
Low frequency DBD 1018
RF APPJ 1016

energy is much higher (24 eV), resulting in a 4000 or 5000 K

Fig. 28. Classification of atmospheric pressure plasma sources.
This system is well adapted to surface preparation (polymer
activation) but its closed design avoids direct integration to
production lines.
2.3.3.3. The microstrip plasma. Bilgic et al. [73] have
developed a low-powered, compact microwave induced plasma
source. It basically consists of a planar microstrip line on fused
silica as dielectric substrate and a massive copper ground plate. It
involves surface waves that propagate in a gas channel along the
interface between the dielectric substrate and the plasma. The
tiny size of the system limits the energy loss in the dielectric.
This microstrip plasma technology has been mainly applied
to atomic emission spectroscopy [74].
2.3.4. Summary
Table 4 shows the characteristics of the various atmospheric
plasma sources in terms of plasma properties (electron
temperature and density, gas temperature) and working condi-
tions (power supply, gas flow). The nature of the plasma gas is
important since it influences the plasma temperature. The
temperature [75] does not change if the working gas is argon,
argon/hydrogen, nitrogen, air, oxygen, argon/helium because
the ionization energies are very closed (between 13.5 and 16
eV). On the other hand, in a helium plasma, the ionization
gap temperature.
The plasma temperatures evaluation must be carefully
considered. Plume temperatures evaluated from thermocouple
measurements are likely to correspond to heavy particles
temperature (that fixes the gas temperature). The plasma core
temperature is recorded by spectroscopic measurements. Spa-
tially resolved measurements have to be carefully done with the
appropriate techniques depending on whether LTE applies or not.
It is now interesting to place the various discussed sources
on Fig. 1, in order to know more about the properties of the
different plasmas which condition their applications.
Indeed, glow discharges involve high chemical reactivity
and low plasma temperatures whereas arc and ICP
discharges provide much higher gas temperatures. Thus
glow-discharge-like plasmas suit for applications that need
both chemical reactivity and low temperature of the plasma
(surface activation, coatings. . .). Arc-discharge-like plasmas
are required for high temperature applications (welding,
melting. . .).
Fig. 28 classifies the various plasma sources regarding their
electronic density and temperature. It puts the light on general
trends:
˝ Corona, APPJ, Sugiyama et al. microwave torch and DBD
involve the same temperature and density as a glow
discharge. They can be applied to low temperature processes
[23,43]. The DBD characteristics are between those of glow
discharge and those of arc discharge. This can be correlated
to two working modes that have been observed experimen-
tally: a glow and a filamentary discharge.

Table 5
Gas cleaning by atmospheric plasma
Excitation Source Working Plasma Pollutant Destruction Observations
conditions efficiency
Semi-metallic Kiyokawa and al. 0.6 slm 90 W Ar NO 2000 ppm 98% Reaction products: N2 and O2
microwave torch torch [129] Ar/12% O2/2% H2O 18%
Baeva and al. 20 slm A few N2/NO NO 500 ppm 50% –
torch [130,131] pulsed kW N2/NO/10%O2 – Reaction products: NO and NO2
10 slm 1 MW N2/NO/2%O2 50% Complex design
pulsed

Metallic microwave TIA [132] 1 slm 220 W Air/CHCl3 CHCl3 (3%) 100% Reaction products: CO2, CO, NOx ,
torch HCl, COCl2, H2O
MTD [62] 2 slm 400 W air CFC 50% 100% Destruction is more efficient in air
than in N2 No production of NOx
torch is more efficient than low
pressure plasma
MPJ [133] 5 slm 400 W N2/NO NO 100 ppm 90% No production of NOx
 C. Tendero et al. / Spectrochimica Acta Part B 61 (2006) 2 – 30 17

Fig. 30. Professor Hicks’ group (UCLA: Chemical Engineering Department,

Semiconductors Manufacturing) has developed the APPJ for cleaning, etching
and deposition of materials. The ‘‘cold flame’’ (T ¨75 -C) is impinging on the
hand of a student. [107].

intermediary between a homogeneous and an arc discharge.

Fig. 29. A cold atmospheric plasma is sterilizing a dental needle at
Loughborough University (plasma and pulsed power research group) [106].
˝ The properties (e.g. n e, Te) of the microwave metallic
torches (TIA, MPJ) are similar to those of the arc plasmas.
These sources suit for high temperature processes [168].
˝ Microwave torches (Baeva et al., MTD, MPT) produce
plasmas with characteristics (n e, Te) that are just between
those of arc plasmas and those of glow discharge. The plasma
generated by those microwave torches is thus likely to be an
This behavior enables a wide range of applications for those
plasma sources. Depending on the plasma zone that is
involved for the treatment, it is possible to use either rather
high temperatures or chemical reactivity of the plasma [70].
3. Part B. Applications of the various atmospheric plasma
sources
The described atmospheric plasma sources are very
different (structure, power supply, plasma temperature, work-
ing conditions) and therefore they have various applications.

Table 7
Surface cleaning by atmospheric plasma
Excitation Source Contaminant Plasma Treatment Observations
(substrate) duration
Low frequency DBD Ag2S (Ag) Ar 180 s Ag2S layer is removed
[26]
Oil (Al, Si) Air, O2 A few sec Lubricant is totally removed if the plasma gas flow rate is low (1 – 5
[134,135] slm). With a high flow rate, polymerization of the oil occurs
Plasma cleaning is more efficient in air than in O2: importance of the
metastable N2 species
Fe2O3 (Fe) Ar/N2 60 s Surface is cleaned
[136] Complete cleaning mechanism is not yet established: it is different from
a simple etching mechanism by nitrogen active species)

Pulsed low Glow DBD Oil (Fe) O2 10 min Oil is removed

frequency [137] DBD is as efficient for oil removal as ultrasonic cleaning in acetone

Radio Plasma Corrosion Ar 30 s Reduction of the corrosion products on antique metallic artifacts
frequency pencil [47] (archeological The object is immersed in a chemically reactive liquid in order to
metal artifacts) combine the efficiency of the plasma treatment and the selectivity of the
chemical processes
APPJ [138] Biological, He/O2 30 s Neutralization of chemical and biological agents (e.g. mustards, anthrax)
chemical agents APPJ operates at low temperature and does not generate harmful or toxic
(glass) products: thus it is suitable for rapid decontamination of material and
safe for personnel
Pulsed radio IST system Micro-organism Air 15 ms Sterilization and deodorization inside PET bottles
frequency [41] (PET bottle) No damage (mechanical, thermal) on the surface
Industrial process: 36,000 bottles per hour

Semi-metallic MPT Fe2O3 (Fe) He, Ne, Ar 120 s Surface is cleaned: FeOOH groups are completely removed. Importance
microwave [136,139] effect of metastable species for breaking bounds
torch Negligible influence of the temperature and the UV photons on cleaning
Sugiyama and Iron oxide (Fe) Ar/H2 15 s Oxide layer is removed but the surface is slightly damaged
al torch [128]
18 C. Tendero et al. / Spectrochimica Acta Part B 61 (2006) 2 – 30

Table 8
Surface etching by atmospheric plasma
Excitation Source Plasma Substrate Etching rate Observations
1
Low frequency DBD [31] He/O2 Organic materials 0.2 Am min Not uniform etching

Radio frequency APPJ [140] He/O2 Kapton 8 Am min 1 Chemical process: influence of the oxygen
He/O2/CF4 SiO2 1.2 Am min 1 metastable species and atoms
W 1 Am min 1
Ta 2 Am min 1
Cold plasma He/CF4 Si 0.3 Am min 1 Emission intensity (OES) of F* is related
torch [47] to the etching rate of Si

The following part mainly focuses on the applications of the
plasma sources that are still under development in laboratories.
The well-developed and industrialized processes are only
mentioned.
3.1. Spectroscopic analysis
As the RF inductively coupled plasmas (ICPs), atmospheric
plasma sources that have been described can be used as
excitation sources for spectroscopic analysis [76]. The micro-
plasmas are particularly interesting as this technology has the
potential of further integration with complementary devices
onto a single ‘‘chip’’, resulting in miniaturized total analytical
systems [73].
Since this article is aimed at making analytical spectro-
chemists more familiar with atmospheric plasmas in a wider
range of applications, the analytical applications will not be
detailed. Standard works on this field have been reported in
various reference books [77 – 79].
3.2. Gas treatments
3.2.1. Gas cleaning
Gas cleaning is a huge economical and ecological issue.
Pollutants are various:
& volatile organic compounds (VOCs): carbon monoxide,
chlorofluorocarbons (CFCs), hydrofluorocarbons (HFCs),
hydrochlorofluorocarbons (HCFCs). . .
& inorganic compounds: nitrogen oxides (NOx ), sulfur dioxide
(SO2). . .
Those toxic pollutants come from engines exhaust gases,
electric plants, chemical industry (solvents, paints,
varnishes), petrochemical industry. . . Those compounds are
emitted to the atmosphere and cause environmental pro-
blems [80] such as the depletion of the ozone layer, the
greenhouse effect, the smog (which is a mixture of solid
particles and ozone that comes from the reaction between

Table 9
Surface activation by atmospheric plasma
Excitation Source Plasma Substrate Observations
Pulsed DC Corona [141] Air PP (E: 26 mJ m 2) Increase in PP surface energy: 43 mJ m 2
Surface energy value remains stable during 100 days

Low frequency DBD [23] He PP (E: 26 mJ m 2) Activation efficiency depends on the discharge mode
Filamentary discharge increases the PP surface energy value to 45 mJ m 2
Values as high as 62 mJ m 2 are obtained with a glow discharge
Improvement of wettability is due to O implantation and N atoms density at the
PP surface
O comes from impurities in the plasma gas (N2, H2O) that are excited, ionized
by highly energetic He metastable species
Aldynei [142] Gas mixture PP (E: 26 mJ m 2) Increase in PP surface energy: 60 mJ m 2
based on N2 Surface energy value remains stable during 100 days
AcXys [143] Air PP (h: 95-) Decrease in water contact angle: 25-
Contact angle value remains stable over 3 weeks
Plasmatreat Air PP (E: 26 mJ m 2) Increase in PP surface energy: 56 mJ m 2
[124] Improvement of wettability due to the increase of oxygen concentration and
the changes of the topology substrate surface induced by the thermal
component of the plasma
Radio frequency HELIOS Air/Ne PE (E: 33 mJ m 2) Increase in PE surface energy: 57 mJ m 2
[50,144] Dehydrogenation + C=C bonds formation (FTIR)
Uniformity of the activation over 20 cm2

Semi-metallic Sugiyama and Ar/O2 PP (h: 100-) Decrease in water contact angle: 80-
microwave al. torch [145] CO, O – CO – O bounds formation (XPS)
torch Ar/CF4 Increase in water contact angle: 125-
CF, CF2, C-CFn, CF-CFn bounds formation (XPS)
 C. Tendero et al. / Spectrochimica Acta Part B 61 (2006) 2 – 30
NOx and VOCs under UV irradiation). . . Therefore,
effective processes are developed to limit and remove these
pollutants. Among them, atmospheric pressure plasma
techniques are becoming important because of their high
reactivity.
The plasma treatment principle can be described as
following: toxic molecules are decomposed by collisions with
energetic plasma species. This decomposition leads to free
radicals that combine to form inoffensive molecules.
The performances of a few atmospheric plasma sources,
used for NOx or VOCs destruction in various atmospheres, are
illustrated in Table 5.
The removal efficiency is estimated by the analysis of
outgoing treated gas by FTIR spectroscopy [130,62], optical
emission spectroscopy and TCD gas chromatography [129].
Those results reveal that atmospheric plasma sources are
suitable for gas cleaning even if the process still needs to be
improved: the efficiency has to be increased and no toxic
products must be generated by the reactions.
The gas injection seems to be a key point. It must be
designed in order to increase the pollutants stay-time in the
plasma and then the removal [131]. Moreover, an optimal flow
rate must be adapted: lower flow rate increase pollutants dwell
time in the discharge, enhancing the process efficiency but may
result in poor stability of the plasma.
The admixture of oxygen lowers the reductive potential of
plasma reactors for NOx destruction. The O2 molecule ionization
consumes plasma energy: the energy amount which is available
for NOx decomposition is then reduced. Moreover, collisions
between N2 and O2 can form NOx and then compete with
destruction reactions [130]. As this NO creation is enhanced by
high temperature, the system must not warm up. That is why
Baeva and al. [131] have chosen a pulsed power source.
3.2.2. Gas synthesis
As the plasma is a high chemically reactive media, various
products can be synthesized: hydrocarbons, ozone, etc. . .
Downstream of the reactor, the products are identified by gas
chromatograph (GC) coupled with mass spectroscopy (MS).
Their amounts can be determined by GC detectors [81]: FID
(flame ionization detector) for hydrocarbons and TCD (thermal
conductivity detector) for H2, O2.
Fig. 31. Plasma-JetR corona [17] (left) and BottleDynei [33] treating systems for 3D products (right). The plasma increases the surface tension of the material to
strengthen its wettability. This creates a powerful bond between the printing ink, adhesive or coating and the material surface.
19
Fig. 32. Ink spreading on a sample before (left side of the sample) and after
(right side of the sample) treatment by the Plasma pen (Tepla-PVA) [16].
3.2.2.1. Hydrocarbons. Acetylene production by arc plasma
(C1 – C4 hydrocarbons cracking in H2 presence) has been
industrialized for years (Hüls [38]: Marl, Germany). This
process is very flexible: production can be adjusted to
acetylene needs (no storage).
In Japan, methane conversion [81] using a pulsed discharge
(corona) has been investigated in laboratory in order to produce
higher hydrocarbon fuels such as alcohol and formaldehyde.
As those chemical compounds are liquid under normal
conditions, it is more economical and safer to transport them
over large distances than gaseous methane or hydrogen. In
China, a diesel engine fuel additive has been synthesized from
DME conversion [82] by DBD in order to suppress the
emissions of soot and smoke.
3.2.2.2. Ozone. Ozone has various applications in chemical
and pharmaceutical industries [83] and treatment of water, of
paper dough, of food.
Ozone can be generated in oxygen, air or N2/O2 plasma.
First a diatomic oxygen molecule has to be split. The resulting
free radical oxygen is thereby free to react with diatomic
oxygen to form the triatomic ozone molecule [84].
Plasma ozone laboratory generators work following the
corona discharge principle (wire-to-cylinder reactor [85])
whereas industrialized generators are bases on the DBD
principle (cylinder – cylinder reactor). Table 6 gives an idea of
the ozone density in various plasma discharges and confirms that
DBD and corona discharges suit for ozone generation.
20 C. Tendero et al. / Spectrochimica Acta Part B 61 (2006) 2 – 30

Fig. 33. In-line PlasmatreatR treatment of EPDM/TPE extrusion before flocking, ice-coating, or taping [18].

Basically there are two ozone generation technologies [86]:
& Ultraviolet
& Plasma (corona or DBD).
The plasma generators are preferable for large quantities of
ozone. UV ozone generators produce concentrations between
0.1% and 0.001% by weight, while corona discharge systems
generate between 1% and 6% by weight.
3.3. Material processing
In this part a distinction is made between:
& surfaces treatments: cleaning, activation, etching, coatings. . .
& bulk material treatment: powder treatment, machining
(cutting, welding. . .), toxic waste treatment. . .
3.3.1. Surfaces treatments
There are many ways to treat surfaces: cleaning (decon-
tamination, grease removal), activation (adherence or anti-
adherence properties), etching, functionalization (electrical
conductivity, protection against corrosion, chemical
barrier. . .). Note that the cleaning and activation steps often
precede the deposition phase, and the surface quality is
determinant for the coating quality.
3.3.1.1. Surface cleaning. Surface cleaning consists of
removing contaminants (oil, dust, oxides, biological and
chemical agents: see Fig. 29. . .) from the substrate surface.
Surfaces have been degreased by halogenated solvents for a
long time. However, because of the strict environmental norms
(Montreal protocol [87], CE 2037/2000 regulation [88]) and
the hazardous effect of the solvents on the environment [89]
(ozone layer depletion, greenhouse effect, smog), solvent
alternative have been developed. Among those alternatives,
plasma seems to be suitable for surfaces cleaning, as shown in
Table 7. The cleaned samples are analyzed by XPS in order to
estimate the contaminant removal.
Those plasma treatments operate at low temperature (see
Fig. 30) which enables the cleaning of low temperature
degradable materials (e.g. PET).
Even if the cleaning mechanisms are not yet identified, they
seem to depend on the kind of plasma source [136]. Metastable
energetic species [134,136] (e.g. N2, He) seem to play a
determining part in contaminant destruction process. The
temperature influence is clearly less important, even negligible.
3.3.1.2. Surface etching. Surface etching consists in remov-
ing material from the treated sample surface in order to create a
relief (e.g. a hole in a dielectric material which will be
metallized after the etching step). Table 8 presents some results
for surface etching by atmospheric plasma.

Fig. 34. Plasma spray principle [108].

 C. Tendero et al. / Spectrochimica Acta Part B 61 (2006) 2 – 30 21

Table 10
Examples of APS coatings [146 – 149]
APS coating Functions Examples of applications
Zn, Al Resistance to wet corrosion Water or gas pipes
(petrochemistry), bridge
metallic structures. . .
Electromagnetic protection Computers
for electronic equipment
Al2O3 Electrical insulation Ozonors, oven inductors
CoCrAlY Resistance to dry corrosion Aeronautic: gas turbine
Nuclear
Zn, Sn, Cu Electrical conductivity Connecting welding
Al2O3 Biocompatibility Biomedical: artificial
hydroxyapatite limb (hip, knee. . .),
Fig. 35. SEM observation of an alumina APS coating section [109]. implants (tooth. . .)
ZrO2 – Y2O3 Thermal barrier Turbine combustor, rocket
nozzle
Cr2O3 Wear resistance Mechanic, army, aeronautic,
The etching rate depends on several parameters: plasma
ZrO2 – NiCrAlY metallurgy, paper industry,
composition (influence of F* [46], oxygen species [140]), petrochemistry
substrate nature, working conditions (power, gas flow, sub-
strate position). Helium is used as plasma gas in order to
stabilize the discharge. The metastable energetic species
enhance the etching efficiency and they play an essential part surface whereas h < 90- is measured with a hydrophobic
in excitation, ionization and dissociation phenomena. surface.
& the surface energy evaluation by calibrated inks (as shown
3.3.1.3. Surface activation. Surface activation consists in by Fig. 32).
grafting chemical functions (plasma active species) on the
material surface in order to give it specific properties by Spectroscopic analysis of the treated surfaces (FTIR, XPS)
varying its surface energy. The plasma composition influences can link the surface energy evolution to the surface composi-
the treated material superficial properties (see Table 9). tion and the chemical bounds.
For example, an argon – oxygen plasma leads to the Atmospheric plasma can treat various materials even those
grafting of polar and hydrophilic functions (oxygen groups), which are low temperature degradable (as polymers are). The
which increase the material surface energy. This kind of surface activation remains stable over a quite long period:
activation is useful to prepare the surface before other treated substrates can thus be stored. Nevertheless, handling a
treatments: metallization, painting, printing, coating, sticking, sample between two treatment steps can damage the surface.
bonding (see Fig. 31). On the other hand, Ar-CF4 plasma Then, it is interesting to integrate the plasma system into the
leads to the surface fluorination and induces anti-adherence production line (see Fig. 33).
properties.
The treatment efficiency can be characterized by two 3.3.2. Surface coating
methods: Deposits functionalize the material surface (chemical
barrier, resistance to corrosion, electrical conductivity. . .) while
& the measurement of the contact angle h between the treated the intrinsic bulk properties (mechanical especially) remain
surface and a drop of water: h < 90- means a hydrophilic unchanged.

Fig. 36. Coating of a wide range of materials, including ceramics, is performed with (fully automated) atmospheric plasma spray (left: Plasma and Thermal Coatings
Ltd. [110], right: Plasma Giken co [111]).
22 C. Tendero et al. / Spectrochimica Acta Part B 61 (2006) 2 – 30

Two kinds of atmospheric plasma coatings are where the powder particles are accelerated and heated [5]. Then
developed: the high velocity molten (or semi molten) particles strike the
substrate surface where they are flattened (splat) and
& air plasma spray (APS), dramatically frozen: during this rapid solidification, metasta-
& plasma enhanced chemical vapor deposition (PECVD). ble (or even glassy) phases can be created (see Fig. 34).
The coating is formed when millions of particles are
3.3.2.1. APS coatings. The coating material, fine powder deposited on top of each other: it consists of layered splats
suspended in the carrier gas, is injected into the plasma jet, [90]. Its structure is lamellar with an interconnected porosity

Table 11
Examples for oxide coatings by atmospheric plasma
Excitation Source Plasma Coating (substrate) Observations Applications
[deposition rate]
Low frequency DBD (glow) N2/SiH4/N2O SiOx [150] (Si) Nano and micro-particles formation –
[2.2 Am h 1] Morphology (dense or powder) and thickness of the
film depend on the substrate position in the discharge
Substrate is not heated
He/HMDSO SiO2 [151] (Al) Si – O bonds and low C impurities (XPS, FTIR Food wrapping
[7.2 Am h 1) analysis) (chemical barrier)
The mass transport by precursor ions plays an
important part in the film formation
Protection of Al surface against NaOH (0.1 N)

Radio frequency Barrier torch He/aerosol of CeOx (Al) Stoichiometry: excess of oxygen (in comparison with Optic
[152,153] water solution [0.5 Am h 1] CeO2), carbon contamination (XPS, electron
of Ce salts microprobe analysis)
Pollution by the surrounding atmosphere and
incomplete precursor decomposition
He/vapors of InOx , SnOx High adhesion and transparency of the film, electrical TCO films
solid or liquid (polymer) conductivity r InO: 104 S cm 1 (transparent
precursor [2.1 Am h 1] Stoichiometry ¨In2O3 and carbon contamination conductive oxides)
containing In, Sn <10% (electron microprobe analysis)
Treatment temperature ¨300 K
APPJ [154] He/O2/TEOS SiO2 (Si) Si – O bonds, no carbon impurities (FTIR), good Microelectronic
[18 Am h 1] electric properties (dielectric layer)
Good surface morphology (peak-to-valley surface
roughness: 20 ÅV by AFM)
Sample heating: 350 -C Food wrapping
Cold plasma Ar/TMOS/H2 SiO2 (Si) FTIR spectrum similar to the one of thermal CVD Microelectronic
torch [36 Am h 1] SiO2 film; homogeneous coating
[155,156] Stoichiometry SiO2, carbon impurities <1% (XPS
analysis)
Sample heating: 500 -C
Influence of H2 as plasma gas
He/O2/TEOT TiO2 (Si) Amorphous TiO2 film (XPS, X-ray analysis), good Microelectronic
[54 Am h 1] electric properties
Influence of H2 as plasma gas on the film structure: it
changes from anatase to rutile by admixing H2
Sample heating: 500 -C
ICP torch [157] Liquid precursor YBa2Cu3O7 Films are black, dense smooth, highly textured Superconductor
carried by O2 (CaO – ZrO2) (X-ray diffraction analysis)
[6 Am h 1] Sample heating: 450 -C

Microwave Cavity [158] N2/HMDS SiO2 (C fibers) Coating is dense, homogeneous, amorphous (TEM Metal-matrix
analysis), good adhesion composites
SiO2 stoichiometry (EDX analysis), SiC particles
formation (precursor decomposition)
Plasma process (remote mode) doesn_t degrade the
mechanical properties of the fibers but has no
significant effect on improving the C fiber/Al matrix
interface
CyrannusR-I Ar/O2/HMDSO SiO2 (Si) E – H tuning at low pressure (5 mbar) before reaching Chemical barrier,
[159] [9 Am h 1] the atmospheric pressure to ensure a stable discharge protection against
Si – O bonds (FTIR analysis) corrosion
Problem: NOx generation with an air plasma
 C. Tendero et al. / Spectrochimica Acta Part B 61 (2006) 2 – 30 23

Table 12
Examples for polymer coatings by atmospheric plasma
Excitation Source Plasma Coating (Substrate) Observations Applications
[deposition rate]
Low frequency DBD He/C2H4 PE (Si) No difference in the chemical structures between a Protective layer
(glow) [28] [1 Am h 1] low and an atmospheric pressure plasma-polymerized
film (FTIR analysis)
Distribution of the film thickness depends on the Adhesion layer
high-voltage electrode design
High power induces powder formation
He/C2F4 (CF2)n Hydrophobic layer (h: 98-) Non adhesive layer
[29] (PVC tube) Chemical structure: CF2 monomers (FTIR, ATR, Biomedical
[3 Am h 1] XPS analysis) (blood circulating
Fluoro-polymer coating onto the inner surface of tube)
PVC tube

Radio frequency Plasma Ar/He/HMDS Si based polymer Plasma polymers are stable, cross-linked but the film Protective layer
pencil [47] [6 Am h 1] is not uniform
Deposition on a substrate immersed in liquid

Table 13
Examples for carbon coatings by atmospheric plasma
Excitation Source Plasma Coating (Substrate) Observations Applications
[deposition rate]
Low frequency DBD (glow) He/H2/CH4 Carbon nanotubes Multi-wall carbon nanotubes deposition with outer diameter Nanotechnology
[160] (Ni) and number density of 40 – 50 nm and 109 – 1010 cm 2
respectively (SEM, TEM analysis)
Wall defects associated with Ni particles aggregation H2 storage
Substrate heating: 600 -C Material reinforcement
Carbon [27] (quartz) Uniform, black coating Mechanic
[1.4 Am h 1] Substrate heating: 400 -C

Microwave MPT [161] Ar/C2H4/iron Carbon nanotubes Single wall carbon nanotubes both in bundles and insolated Nanotechnology
semi-metallic vapor (metal) with diameters ranging from 0.9 to 1.5 nm
torch Results comparable to laser ablation and arc discharge H2 storage
techniques
Problem of carbon deposition in the plasma tube: discharge Material
destabilization reinforcement

DC Arc plasma CH4/H2 Diamond (Mo) Surface morphology and crystal structure of the synthetic Mechanic
torch [162] *precursor [150 Am h 1] diamond is strongly dependant on process conditions (CH4
can also be amount, substrate temperature
liquid [163] Best quality film with 4% CH4, at 950 -C Electronic

rate that can reach 30% (see Fig. 35). Its thickness goes from DC torches [90] are widely used for this spray process but
50 Am to a few millimeters. ICP torches [91] can also suit.
As the plasma jet temperature reaches 15 000 K, lots of APS coatings have been implanted in industry for years.
materials (metals, ceramics, cermets) can be sprayed (Fig. 36) The development of this process is strongly due to the
provided they melt: the difference between their melting and aeronautic sector [92].
decomposition or evaporation temperature must be greater than
300 K.
Table 15
Waste treatment by atmospheric plasma
Table 14 Excitation Source Applications
Powder treatments by atmospheric plasma
DC Arc plasma REFIOMS vitrification: EDF process [38],
Excitation Source Applications
torch EUROPLASMA process [166]
DC Arc plasma Ultra fin powder synthesis (metallic: silver, Medical waste pyrolysis [5]
torch copper; ceramic: nitrides, carbides, Hazardous waste decomposition [167]:
composites; carbon) [164,165] PLASMION process [38]
RF ICP torch Densification: sintering, spheroidization [5] Microwave Metallic torch Vitrification of chloride waste [60],
Microwave Semi-metallic Oxide ceramic melting, spheroidization radioactive products [168]
torch [127] Decontamination of nuclear waste [60]
24 C. Tendero et al. / Spectrochimica Acta Part B 61 (2006) 2 – 30
Table 16
Material machining by atmospheric plasma
Excitation Source Applications
DC Arc plasma Welding (see Fig. 37): MIG, TIG
torch PTA recharging
Cutting of ceramics [169], metals (see Fig. 37)
Microwave Metallic Ceramic processing [168]: production of
torch alumina beads, quartz glass fibers
Cutting by a hybrid plasma-laser system [166]
Table 10 gives examples of APS coatings and the properties
they confer to the treated materials.
Although plasma spraying has been widely developed, the
fundamentals of this process are not completely identified yet
(e.g. plasma jet behavior, coating formation, interaction
between the plasma and the injected particles) [5].
3.3.2.2. PECVD coatings. PECVD deposits precursors are
gas (or liquid carried by gas). The plasma (thermal or cold) is
used as a chemically reactive media to activate the coating
reactions. The reactive species are carried to the surface
substrate where they adsorb, they react and the reaction by-
products desorb. The coating grows by a germination-growth
phenomenon.
Two PECVD configurations can exist: direct or remote. In
the direct mode, the gas plasma and the precursor are injected
in the discharge. This mode ensures the complete precursor
decomposition.
In the remote mode, only the gas plasma is excited in the
discharge. The precursor is introduced in the afterglow where the
long lifetime species are the only ones to exist. This configu-
ration enables a better reaction control as there are fewer reactive
species. The precursor is partially broken: it enables the
adsorption of larger molecule fragments at the substrate surface.
The working mode (glow or afterglow) strongly influences
the nature and thus the properties of the coating. Moreover, in a
remote mode, the substrate is positioned far from the glow, in a
low temperature zone: it is then possible to make a deposit on
polymers.
Various substrates can be coated, even fine particles
provided the reactor design includes a fluidized bed [93] or a
system to vehicle particles to the discharge (ultrasonic horn
[94], cyclone [95]) and to store them.
Fig. 37. Material machining by atmospheric plasma (welding [112,113] on the left, cutting [114] on the right).
All materials can be deposited assuming that a gas (or
liquid) precursor exists: then oxide, polymer, carbon coatings
can be realized: see Tables 11 –13.
Plasma is a very complex and reactive media. Thus,
deposition mechanisms are far from being elucidated even if
studies and models are developed [21,154,163,151].
Working parameters influence the film quality: substrate
heating and H2 used as plasma gas seem to favor the
impurities desorption and to improve the surface morphology
[155].
3.3.3. Bulk material treatments
The following applications use the high temperature that
can be generated by atmospheric thermal plasmas (the flame
core in particular). The plasma sources are thus arc or
microwave plasma essentially. Arc plasmas have been
implanted in industries for years: their applications as heat
source are then numerous and various. Microwave plasma
sources are still developed in laboratories.
Four kinds of applications are presented:
& Fine particles treatment,
& Toxic waste treatment,
& Material machining, and
& Metallurgy.
3.3.3.1. Powder treatment. Particles synthesis and treatment
require both the high temperature (> 1 500 K) and the chemical
reactivity of the plasma. Table 14 gives examples of powder
treatments by atmospheric plasma.
The main problem is the collection and handling of those fin
explosive particles (use of PTFE filtering films, on line
treatment in glove-boxes to avoid any reaction with the
surrounding atmosphere) [90].
3.3.3.2. Toxic wastes treatment. Plasma treatment of toxic
wastes (asbestos products, hazardous industrial waste, radioac-
tive residues) is an essential issue: it takes part in the waste
recycling.
The plasma high temperatures induce fast and complete
pyrolysis of organic hazardous wastes. Inorganic wastes are
melted and vitrified, resulting in the waste passivation and in
its volume reduction, as shown in Table 15.
 C. Tendero et al. / Spectrochimica Acta Part B 61 (2006) 2 – 30
Fig. 38. High intensity plasma arc lamp (Courtesy of OSRAM Sylvania
[115]).
3.3.3.3. Material machining. As this kind of application
requires high temperatures, plasma sources such as arc plasma
torch or microwave torch are used for material machining, as
shown in Table 16.
For welding or cutting by arc plasma, an inert gas (Ar, He)
sheath is used to avoid contamination from the surrounding
media (Fig. 37).
3.3.3.4. Metallurgy. The use of plasmas in metallurgy is
based on the very high temperature that can be generated. Thus
only the high power arc plasmas suit for this kind of
application. The working power can reach several megawatts.
Such high-energy levels are necessary for:
& extractive metallurgy: metallurgic ores are reduced into
various metallic alloys at high temperature [5],
& melting –purification: the metal melts under inert atmo-
sphere and slowly solidifies in a cooled copper mould. The
solidification can be well controlled with an inductive
heating system (e.g. Leybold Heraeus process for large scale
titanium remelting, Germany [39]),
& heating: cements industry (EDF, Lafarge Coppée [13]),
& ...
3.4. Lamps
High pressure plasmas are very radiative media. If they emit
in the visible domain, they can be used as light sources. Two
kinds of lamps have to be considered:
&Electroded lamps [96]
Fig. 39. Principle of the sulfur lamp [116].
25
They work following an arc mode (see Fig. 38). Among the
most developed lamps, the high pressure mercury (HMP) emits
mainly green lines. Other colors can be obtained by adding
other materials into the discharge.
&Electrode-less lamps
There is an increasing interest in electrode-less lamps since
they avoid reactions between the electrode and the plasma.
These discharges are fed with microwave [97]. In 1994 Fusion
Lighting Systems produced the Solar 1000, a microwave-
driven high pressure lamp with sulfur as the radiating medium
[98]. This sulfur lamp (see Fig. 39) displays lots of advantages:
excellent coloring, very high radiative efficiency, no electrode
(then a long bulb lifetime is likely to be expected) and less
environmentally damaging than mercury. The main problem is
the magnetron power supply (low lifetime and efficiency).
4. Conclusion
The potential applications of the atmospheric plasma
sources are conditioned by the plasma properties (especially
the gas temperature), and therefore by the plasma excitation.
For example, polymer surface treatment requires low tempera-
tures (below 500 K) whereas plasma cutting and welding of
metals necessitate high temperatures (higher than 1500 K).
Table 4 shows that low temperatures can be obtained either
with low working power (some hundreds of watts) or in the
plasma plume with higher power (especially for the microwave
plasmas). Nevertheless, the distance from the plasma core
should be limited to have sufficient density of active species.
Thus it is not possible for arc or inductive plasmas to combine
low temperature and active zone.
High gas temperatures can only be obtained with high
working power and inductive or microwave plasmas are the
most suitable.
This study shows that the microwave plasmas have the
widest range of applications (both low and high temperatures),
even if their role in the surface coating has not been explored
yet (see Table 17). Arc and inductive plasma are required
where high working power is necessary, whereas low and radio
frequency plasmas suit for applications that need active species
and low temperature.
Regarding the development of these sources, the arc
and inductive plasmas are the most implanted in the
industry, in various domains (see Table 18). DBD and
26 C. Tendero et al. / Spectrochimica Acta Part B 61 (2006) 2 – 30

Table 17
Synthesis of laboratory atmospheric plasma sources
Excitation Source Applications Advantages Limits
Radio frequency Hollow cathode Surface treatments: cleaning, Complex surface treatments Only low temperatures applications
sources, APPJ, decontamination, activation, Easy handling Small treated surface
cold plasma torch etching, coating Simple design

Microwave Metallic torches Spectroscopic analysis Complex surface treatments Microwave device (expensive power supply,
very accurate machining, safety rules)
Gas cleaning Suitable for both low and Discharge ignition
Toxic waste treatment high temperature applications Small treated surface
Machinings
Semi-metallic Spectroscopic analysis Complex surface treatments Difficult to industrialize
torches (stability problems, lifetime)
Gas cleaning Large range of applications Microwave device
Surface treatments: (rather low temperatures) Discharge ignition
cleaning, activation,
coating
Powder treatment Small treated surface
Lamps

corona sources have also been known for a long time and It is also interesting to note the emerging of various simple
now they can be adapted to the treatment of three- and easy handling torches (plasmatreatR, plasmajetR). They
dimensional pieces (line of 3DT products: BottleDynei, are very well adapted to surface activation (even polymer) and
FlexyDynei. . .). can treat very complex pieces (inside of holes, etc. . .).

Table 18
Synthesis of industrial atmospheric plasma sources
Excitation Source Applications Advantages Limits
DC Arc plasma Coatings (APS) Can be adapted to a robot Noise, powder emission, radiations
torch Machining Complex surfaces treatment Cathode erosion
Toxic waste treatment High deposition rate, thick coatings, Various parameters make the process
wide range of deposited materials control difficult
Powder treatment
Lamps

RF ICP torch Spectroscopic analysis Can work with very high power Noise, powder emission, radiations
Coatings (TPCVD) No electrode Not easy maneuverable: the substrate
has to move
Toxic waste treatment Complex surfaces treatment
Powder treatment

Pulsed DC Corona Ozone production Complex surfaces treatment Inhomogeneous treatment

Surface activation Easy handling Surface can be damaged

Low frequency DBD Ozone production Treatment of large plane surfaces Problems of stability (deposition on the
electrode)
Surface activation, cleaning Easy to handle Gap size limits the thickness of the
treated piece
Plasma Surface cleaning, activation Multi-nozzle system High flow rate
treatR Complex surfaces treatment Not enough energy to remove oil
Can be adapted to a robot
AcXys Surface activation, cleaning Treatment of large surfaces, complex pieces High flow rate
Can be adapted to a robot Not enough energy to remove oil

Pulsed radio IST Sterilization, deodorization Fast treatment of complex surfaces –

frequency 36,000 bottles per hour
Reduced cost comparing to other
sterilization methods

Microwave CyrannusR Cleaning and activation of Stable and homogeneous discharge The quartz tube diameter limits the
polymer surfaces size of the treated surface
Complex surfaces treatment The closed design avoids direct
integration to production lines
 C. Tendero et al. / Spectrochimica Acta Part B 61 (2006) 2 – 30 27

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APS Air plasma spray 20
[19] A. Schütze, J.Y. Jeong, S.E. Babayan, J. Park, G.S. Selwyn, R.F. Hicks,
DBD Dielectric barrier discharge 6
The atmospheric-pressure plasma jet: a review and comparison to other
DC Direct current 5
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HEIOS Hollow electrode with integrated open structure 9
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[21] C. Jimenez, S. Martin, N. Gherardi, J. Durand, D. Cot, F. Massines,
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MPJ Microwave Plasma Jet 12
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MPT Microwave plasma torch 12
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pLTE Partial local thermodynamic equilibrium 3
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PTA Plasma transferred arc 23
[23] F. Massines, G. Gouda, A comparison of polypropylene-surface
RF Radio frequency 7
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TIA Torche à injection axiale 11
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