Title of Invention

PLASMA TREATMENT PROCESS AND DEVICE

Abstract The invention relates to a plasma surface treatment method for the surface of an object or particles to be treated consisting in creating a plasma and applying said plasma against the surface to be treated. The inventive method is characterized in that the surface to be treated is excited or the plasma is made to vibrate acoustically in order to create a relative wave motion between the plasma and the surface to be treated.
Full Text Process for plasma surface treatment and device for realizing the process
The present invention concerns a process for plasma surface treatment and a device for
realization of the process. The treatment can be deposition of a barrier film or plurality
of thin films, sterilization, cleaning, etching, or creation of a surface alloy. The present
invention also concerns a process for treatment or production of powders with plasma.
In the current state of the art, plasma depositions are offered in vacuum and at
atmospheric pressure. The vacuum technologies provide for a uniform treatment of
complex surfaces such as the inner surface of a PET bottle, but they are slow and
relatively expensive, since it is necessary to create, and work in, a vacuum chamber. The
corresponding equipment is complex, extremely costly, and difficult to adapt to different
types of container. The requirement that the equipment be perfectly tight is very difficult
to satisfy and has repercussions on the reliability of the process and uniformity of the
results.
Processes working with plasmas at atmospheric pressure have been discussed in several
publications, for instance the patent GB 1,098,693, the patent application WO 97/22369,
and the patent application WO 99/46964.
In the patent GB 1,098,693, a device for treatment of the inner surface of a plastic bottle
designed to sterilize this surface is described. The device comprises a central electrode
introduced into the bottle and an external electrode surrounding the bottle, the two
electrodes forming a coaxial system connected to a high-frequency current source.
Argon (Ar) is introduced into the bottle through a hole in the central electrode in order
to reduce the electric potential needed to create the plasma. The device described in this
patent is characterized by a high electric field, of the order of 450 V/cm, and a very
weak current, of the order of a few milliamperes. The treatment time is too long and the
power too low for this process to find industrial application and to be able to compete
with the vacuum plasma techniques.
In the patent application WO 97/22369 concerning the sterilization of plastic containers
it is proposed to form a plasma with a source of RF current providing a high-amplitude
current. It is proposed, moreover, to take the central electrode out of the bottle, which
permits a rhythm of PET bottle sterilization in line with industrial needs. It is a
disadvantage of the process and of the device described in this application that they will
not permit a uniform treatment of the surface to be treated. It is to be expected that the
plasma covers only part of this surface. This results in poor sterilization of surface parts
that have not been in contact with the plasma. For the same reasons such a process
would not be able to provide a uniform barrier all over the inside walls of a container.
In the patent application WO 99/46964, a surface treatment process is described where a
pulsed plasma string is formed at atmospheric pressure which sweeps the surface to be
treated by relative motion of this surface and the device producing and defining the
plasma string. One might expect that such a process would be able to yield a layer that is
impermeabilizing, for instance, or could uniformly sterilize the surface to be treated,
since the plasma string sweeps all of the surface to be treated. In reality it is found to be
difficult to obtain a surface treatment, and more particularly the deposition of a film or a
sterilization of satisfactory quality.
For reasons of local heating the plasma column must be moved relative to the surface to
be treated. The velocity dictated by the need not to overheat the material of the surface
to be treated is higher than the optimum speed of treatment in many applications. One of
the consequences is that a boundary layer of cold gas drawn along by the object blows
into the discharge and moves it away from the surface to be treated. This removal lowers
the diffusive flux of active plasma particles toward the surface to be treated. This
problem can be resolved in part by renewing the discharge by pulses. However, the
pulse frequency is also dictated by the need not to overheat the material of the surface to
be treated, and hence cannot he optimized for different applications.
The volume of plasma created by known processes for atmospheric plasma treatment is
large and leads to poor yields, since large part of the energy input is lost for heating the
surrounding gas and the object to be treated. For applications involving the deposition of
barrier films, on the other hand, powder forms in the bulk of the plasma string (SiO2
powder, for instance) and deposits on the surface to be treated. This powder, which
adheres but weakly to the surface, represents an obstacle to the creation of high-quality
films.
The disadvantages and limitations of known plasma treatment processes are not limited
to the points described above. For example, in the case of plasmas close to a
thermodynamic equilibrium state, such as would arise from the process described in
WO 99/46964, it is difficult to perform an electron bombardment of the surface to be
treated, since in general the mean path of the electrons (= 10-4 cm) relative to the elastic
interactions of the surface to be treated is shorter than the thickness of the plasma
boundary layer (= 10-2 cm). It follows that it is difficult for such a process to adapt the
substrate/film interface to a desired quality of treatment, for instance by activating the
surface to be treated prior to film deposition so as to ensure good adhesion. It follows
that it would be equally difficult to produce films consisting of several layers differing
in their composition, with each layer being activated prior to deposition of the following
layer.
Experience shows that despite the relative motion of the plasma and object to be treated
in known processes, local overheating is inevitable and provokes electrical discharge
breakdowns that give rise to defects and local destruction of the surface to be treated.
This disadvantage is particularly important in certain applications, as will be explained
by way of example hereinafter.
Polymerizable materials such as PET (polylethyleneterephthalate), PE (polyethylene),
PP (polypropylene) and others are used in various industries for products such as con-
tainers for beverages and food, the pharmaceutical and perfume bottles and tubes,
gasoline tanks, containers for chemical products, as well as the neon tubes for night-
time advertizing, particularly for reasons of low cost and weight of these materials. Yet
one of the disadvantages of polymeric materials is thsir gas permeability. The
permeability of the PET bottles used in the food industry, for instance, lets oxygen
diffuse through the bottle wall and oxidize the food or beverages, which for this reason
progressively lose their properties such as their taste, odor or color. Carbonated
beverages to the contrary lose their carbon dioxide.. Excessive plastic container per-
meability shortens the time of conservation of the foods. Gas diffusion across the plastic
walls can have ill effects on large number of other products such as pharmaceuticals,
cosmetics, hygiene and housekeeping products. In the case of gasoline tanks or other
containers holding chemicals, the permeability of the plastic materials allows these
chemicals to penetrate into the plastic material so that this can no longer be recycled
easily and may present a fire hazard. The permeability of plastics implies that neon tubes
in plastic have a lifetime too short to be marketable.
Another problem of plastic materials arises from aromatic molecules such as acet-
aldehyde forming in the bulk material and then diffusing toward the surface where they
enter the liquid held by the container. Such molecules alter the taste and odor of the
beverage or food item.
One solution consists in coating the inside of the container by an impermeable film
called "barrier". Different compositions such as carbon, aluminum oxide, and silicon
oxide (S1O2) can form barriers on polymers. The deposition of a barrier film can be
carried out by plasma in contact with the surface, and in the presence of a gas furnishing
the molecules that will form the layer. However, the plastic materials mentioned above
do not withstand temperatures above around 60 to 70 ºC, so that it is difficult with the
known plasma treatment processes to avoid local overheating or obtain a sufficiently
high quality of the treatment. For instance, the barrier films deposited on PET bottles by
traditional industrial plasma treatment processes yield a factor (RIF) of impermeability
enhancement relative to the untreated material that is of the order of 20 to 30 for oxygen
or 5 to 6 for CO2. Typical defects of such barrier layers are lack of adhesion and
flexibility and the appearance of cracks leading to a loss of impermeability. These
defects may also represent a hazard for the consumer.
Many other materials do not withstand the temperature rise that would be required for
optimizing the plasma surface treatment process. This is the case, for instance, with the
silicon wafers used in semiconductor industry. The semiconducting structures at the
surface of the circuits can in fact be altered or damaged by high treatment temperatures
because of an accelerated particle diffusion across the interfaces of the different layers
deposited on the silicon wafer.
As concerns powders, in particular powders formed of composite grains, physical,
chemical methods of powder production are known for producing grains comprising a
core and a peripheral layer or zone. The composition of the peripheral zone or outer
layers may be different to that of the core. Known methods of the disadvantage of being
relatively slow and costly, and moreover do not enable the formation of very thin
uniform outer layers.
It is known to produce non-composite powders from a gas by means of a plasma
treatment. Known powder producing methods consume a lot of energy and are relatively
slow and costly.
In view of the drawbacks cited above, it is an objective of the present invention to
provide a plasma surface treatment process that is performant and reliable in an
industrial environment, as well as a device for performing a plasma surface treatment
process that is performant and reliable in an industrial environment.
It is advantageous to provide a plasma surface treatment process as well as a device for
realizing the process that can be used to treat the surfaces of materials that are sensitive
to high temperatures.
It is advantageous to be able to deposit a barrier on containers (particularly plastic
containers such as PET bottles in the food industry, polyethylene tubes in perfumery,
and gasoline tanks in the automobile) that is strong, flexible and has a good imper-
meability. It would be advantageous to be able to simultaneously treat the inner and
outer surfaces of hollow objects (bottles, tubes, tanks). It is advantageous to be able to
treat the surface of a complex object.
It is advantageous to provide a plasma surface treatment process as well as a device for
realizing the process that can be used to deposit several layers of different materials on a
surface to be treated.
It is advantageous to provide a plasma surface treatment process as well as a device for
realizing the process that can be used to deposit one or several layers of different
materials on the surface of a sub-micronic or nanometric core or nucleus, thereby
producing powders with composite grains.
It is advantageous to provide a process for producing powder grains with outer or
superficial layers surrounding the core or nucleus of the grain having a good uniformity
and a specified thickness.
It is advantageous to provide a method for producing composite powder grains of sub-
micronic or nanometric size, that is efficient and low-cost.
It is advantageous to provide a method for producing composite powder grains formed
of a nucleus and one or more outer layers surrounding the nucleus, the powder having
different physical, chemical properties than the properties of the nucleus alone.
Another object of the invention is to provide a method of producing powders from a gas,
by means of plasma treatment, that is efficient, low-cost and that enables the production
of powders of high quality.
It is advantageous to provide a method of producing powders formed of mono-
crystalline grains of nanometric size.
It is also advantageous to be able to perform other surface treatments such as cleaning,
etching, surface activation, sterilization or the formation of surface alloys.
It is also be advantageous in many applications, moreover, to realize a process of plasma
surface treatment at atmospheric pressure as well as a device for realizing the process.
Accordingly the present invention provides plasma treatment process of an
object's surface to be treated, comprising the creation of a plasma, the
application of the plasma to the surface to be treated, characterized in that the
surface to be treated is excited or the plasma is acoustically vibrated so that a
relative undulating movement between the surface to be treated and plasma is
created, energy for the excitation of the surface to be treated supplied by the
plasma creation process.
The present invention also provides method of producing powder comprising the
generation of a pulsed plasma in a chamber comprising plasma chemical gases,
and the simultaneous generation of acoustic vibrations in the chamber, the
gases being decomposed by the plasma to form clusters whose degree of
structuration is determined by the simultaneous action of the plasma and
acoustic vibrations.

Ill the present invention, a process for plasma treatment of an object's surface to be
treated comprises the creation of a plasma, the application of the plasma to the surface
to be treated, and the excitation of the surface to be treated, such that it vibrates and
undulates. The energy for excitation of the surface may come from the process creating
the plasma, from an external source, or from a combination of these two sources. The
vibration preferably takes place while the plasma is being applied to the surface to be
treated, but depending on the treatment to carry out, it may also take place just prior to
and/or just after the application phase.
The energy for excitation of the surface that comes from the process creating the plasma
can advantageously come from a shock wave developing at the plasma front during its
creation. The shock wave is created by arranging that the front of plasma development
will create within the plasma a pressure such that its ratio to the ambient pressure be
above the critical value for formation of a shock wave in the given gaseous medium.
This is obtained by selection and control of the plasma generation parameters,
particularly the energy density and the lifetime of the plasma development front.
The energy for surface excitation coming from an external source can come from a
vibration generator brought in contact with the object to be treated, or not in direct
contact with the object to be treated, which emits acoustic waves, for instance ultrasonic
waves. For many applications and many objects to be treated, the vibration frequency
will advantageously be within the range of ultrasonic frequencies. The external
generator can also furnish enery in the form of shock waves.
The vibration of the surface to be treated can be the result of excitation of one or several
cigenfrequencies and their harmonics associated with the body of the object to be
treated, by an abrupt leap of energy (shock) and/or by the action of an external generator
emitting one of several frequencies close to or identical with eigenfrequencies or their
harmonics associated with the object to be treated. The vibration of the surface to be
treated can also result from forced frequencies when an external generator emits
frequencies that are not harmonics of the eigenfrequencies of the object to be treated.
For most applications the plasma is preferably created with an electrical or electro-
magnetic energy source operated continuously, by unipolar or alternating pulses, or at
high frequency. This may for instance be a discharge of the capacitive or inductive type,
or high-frequency waves. However, the plasma can also be created by adiabatic
compression or by shock waves, furnished for instance by an adiabatic-compression or
shock-wave generator.
The plasma created by a surface treatment process according to advantageous
embodiments of the invention may be in thermodynamic disequilibrium for large part of
the plasma's lifetime,
The process according to the invention is very advantageous, since it permits utilization
of a cold plasma while intensifying the interaction of the plasma with the surface to be
treated, and hence to optimize the plasma surface treatments for a large range of
applications, including treatments of objects consisting of materials withstanding only a
very slight temperature increase, such as PET and semiconductors. The wave motion of
the atoms and molecules of the surface to be treated actually intensifies the effect of the
activated plasma particles on the surface to be treated. Because of the intensified effect,
one has a larger choice of plasma generation modes (adiabatic compression, shock
waves, electrical discharge) and can optimize the process depending on the features
(material, shape, dimensions) of the object to be treated and treatment to be performed.
It is possible in particular to use a "cold" atmospheric plasma (as defined by R. F.
Baddour and R. S. Timmins in "The Applications of Plasmas to Chemical Process",
MIT Press, page 17), that is, out of thermodynamic equilibrium, so that the insulating
surface to be treated remains cold while electrons can bombard the surface to activate it.
This plasma can for instance consist of a network of filaments that appear, move along
the surface, and disappear within times sufficiently short to not heat up the surface to be
treated. As concerns the surface treatment of powder grains, the plasma may for
example be formed within the volume of a recipient containing the powder grains.
The process according to the invention also permits, on one hand an acceleration of the
surface treatment, in that the ionization and activation of the plasma particles is
produced with the aid of shock waves issuing from discharge filament branches while
these are reflected by the surface to be treated, and on the other hand an intensification
of the surface treatment without any important increase in temperature of the object to
be treated, since the vibrations of the surface to be treated act upon the interaction with
the plasma, essentially like the atomic agitation produced by an increase in temperature
of the object.
The surface treatment can be further intensified by adding the vibrations of an external
acoustic frequency or ultrasound generator, preferably adjusted so as to amplify the
eigenfrequencies of the object to be treated. The improved interaction of the plasma
with the surface to be treated at low temperature has many other advantageous
consequences. For instance, composite films of good quality can be obtained by the
successive deposition of layers that adhere well to the substrate and have different
physical, physicochemical, and mechanical properties.
It is another advantage of the process according to the invention that it permits treatment
of the inner walls of a complex object lacking axes of symmetry, such as a gasoline
tank.
In a process according to the present invention, it is also possible to produce powders
formed of grains comprising a core or nucleus and a peripheral zone or outer layers of
one or more different layers resulting from the deposit of a substantially uniform and
homogeneous film of atoms and/or molecules that may provide the powder with
properties that are different from the properties of the powder comprising only the
nucleus material, for example optical properties.
In the present invention, the composite powders may be made by depositing films on
grain nuclei by means of a plasma at atmospheric pressure. The plasma serves on the
one hand to heat and activate the surface of the grain nuclei for their entry into contact
with the atoms and/or molecules of gas used to form the outer layers.
The same plasma, or plasma generated downstream of the plasma activating the grain
nuclei with an independent plasma generator, activates the atoms and molecules of a
gaseous mixture comprising gases and/or vapors that are superheated. When the nuclei
are brought into contact with the gaseous atoms and molecules, the plasma deposits a
substantially homogenous molecular or atomic film on the surface of the nuclei which
give the resulting powder physical chemical properties different from a powder
comprised only of the nuclei, for example the optical properties may be changed.
In particular, the parameters controlling the plasma are chosen such that the film deposit
is particularly homogeneous and very thin.
The components of the plasma generating the film are chosen such that the forces of
attraction between the particles of the film have a centripetal component that assists in
solidifying the structure of the peripheral layer or film. The smaller the size of the
nuclei, the larger this centripetal component is. It is therefore particularly important in
the case of sub-micronic or nanometric nuclei. In such cases, in order to separate
effectively the grain nuclei floating in the supplied gas (for example argon) and to apply
a vibration movement that catalyzes the process of surface deposition, the nuclei may be
subjected to acoustic vibrations, in particular ultrasonic vibrations that may be generated
by an external generator or thai may generated by the plasma itself, in a mode of
generation of plasma by impulsions, as described herein below.
According to another aspect of the invention, a process of producing powders comprises
the generation of a plasma in pulses in a container comprising gases, and by the
simultaneous generation of acoustic vibrations in this container, the gases being
decomposed by the plasma in order to form clusters and powder grains in which the
degree of structuration is determined by the simultaneous action of the plasma and the
acoustic vibrations. The acoustic vibrations may be produced by an external generator
and/or by the process of creation of the plasma itself, as described herebelow.
A device of plasma surface treatment according to the invention can advantageously
comprise an external acoustic vibration generator.
A device of plasma surface treatment according to the invention can advantageously
comprise a vibration sensor. The vibration sensor allows one to check and/or analyze the
eigenfrequencies of the object to be treated, in order to adjust the device, for instance the
parameters of the electrical circuit for generation of the electric discharge for creation of
the plasma, for the production of shock waves which will produce vibration of the
surface to be treated of a specific object to be treated, or for verifying the perfect
functioning of the process and particularly the quality of the vibrations of the surface to
be treated in an industrial process. In the presence of variations in the expected
frequency and amplitude spectra, one might thus be informed about a possible failure or
quality reduction of the surface treatment being carried out.
A device of plasma surface treatment according to the invention can advantageously
comprise one or several live electrodes provided with one or several process gas supply
ducts for generation of one or several plasma jets by electrical discharge. The live
electrode can advantageously be rotating, so that it will be able to move the plasma or
plasmas by electrostatic and hydrodynamic effects along the surface to be treated.
The device may comprise a live electrode that is in the form of a liquid jet that can
execute a motion relative to the object to be treated, in order to project a conducting
liquid jet against a wall of the object to be treated so that a plasma is created on the
other side of the wall.
According to an embodiment of the invention, the electrodes for plasma generation by
electrical discharge can be connected to the opposite poles of an electrical circuit. These
electrodes can be utilized to generate a plasma on both sides of a wall of an object to be
treated, the fluxes of the plasma being antiparallel on the two sides.
One can also furnish a device with at least two live electrodes in order to treat respective
sides of one wall of an object to be treated, the plasma fluxes on the two sides being
parallel and directed toward a grounding electrode,
A plasma surface treatment device according to the invention can advantageously
comprise a liquid bath into which the objects to be treated, particularly containers, are
immersed while plasma is applied to the inner surface to be treated. This can for
instance be bottles or other containers partly immersed into the liquid bath, with their
neck remaining above the surface of the liquid. The liquid thus is in contact with the
outside of the container, which offers the advantage that the container wall can be
cooled very efficiently and the plasma applied for a longer time. When an external
source of vibrations is used, then the liquid will on the other hand serve to make the
vibrations more uniform across the container wall, and thus on the container's inner
surface to be treated.
A plasma surface treatment device according to the invention can advantageously
comprise a system of surface quality control after or during the treatment with a laser
beam recording, either the number of photons emitted by non-linear effects during
passage of the laser beam across the surface treated, or the decrease of the flux of
primary protons due to their recombination resulting from non-linear effects, the laser
beam system being provided with a device for the detection and analysis of the beam
reflected from the surface to be treated or traversing the surface to the treated.
A plasma surface treatment device according to the invention may comprise an
enclosure in which the objects to be treated are arranged, and a piston for compressing
the process gas in the section of the enclosure where the objects to be treated are
arranged, so as to create a plasma by adiabatic compression The piston can be driven by
a device with compressed air or other gases located in the section of the enclosure above
the piston.
A plasma surface treatment device according to the invention may advantageously
comprise an enclosure with one section where the objects to be treated are arranged, and
with another section where a process gas is kept under pressure and which is separated
from the other section by a wall that can be removed or destroyed in order to permit
instant decompression of the compressed gas for the purposes of creating a shock wave
that moves in the direction of the objects to be treated.
Other advantageous aspects of the invention will becom e apparent from the claims,
from the following description and from the attached drawings in which:
Figures la and lb are simplified schematic illustrations of devices for the treatment of
surfaces of objects to be treated, according to the invention;
Figures 2a and 2b are electron-microscopic (SEM) surface photographs of the treated
surface of a PET bottle with a silicon-oxide-based barrier;
Figure 2c is a SEM photograph of the treated surface of a PET bottle with a silicon-
oxide-based barrier obtained by an atmospheric plasma deposition process according to
the invention;
Figures 3a to 3c are simplified perspective views of devices for plasma surface
treatment according to embodiments of the invention, in these particular cases for the
treatment of inner walls of bottles;
Figures 4a and 4b are high-speed photographs of PET bottles obtained during their
plasma surface treatment according to the invention using a process gas prepared from a
mixture of hexamethyldisiloxane, oxygen, and argon, the treatment in Figure 4a being
different to the treatment in Figure 4b by the electrical power supplied;
Figure 5 illustrates plots of voltage U and current I as functions of time for a plasma
generated by electrical pulse discharges according to the invention, either in a unipolar
mode (plots A1 and A2) or in a high-frequency mode (plot B);
Figure 6 is a sectional view across part of the wall of an object to be treated during a
plasma treatment according to the invention;
Figure 7 is a view of an oscilloscope screen connected to a vibration sensor measuring
the vibrations of an object to be treated during a plasma treatment according to the
invention, here of an 0.5-liter PET bottle during treatment by an electrical pulse
discharge with the aid of a high-frequency generator producing a branched network of
plasma filaments according to the invention;
Figure 8 is a simplified sectional view of a plasma surface treatment device for a
container of complex shape according to the invention;
Figure 9 is a simplified sectional view of another embodiment of a device for plasma
treatment of a container of complex shape where the grounded electrode is in the form
of a conducting liquid jet;
Figure 10 is a simplified sectional view with an electric circuit diagram of a device for
plasma surface treatment of the two sides of a container wall according to the invention;
Figure 11 is a view similar to that of Fig. 10 of another variant according to the
invention;
Figures 12 and 13 are simplified sectional views with an electric circuit diagram of a
device for the plasma treatment of inner surfaces of a plurality of containers such as
bottles, the plasma being generated by electrical pulse discharges;
Figure 14 is a simplified sectional view of a plasma treatment device according to the
invention where the plasma is produced by adiabatic (isentropic) compression;
Figure 15a is a simplified sectional view of a plasma treatment device according to the
invention where the plasma is produced by expansion of compressed gas generating a
shock wave;
Figures 15b and 15c are simplified views of the device of Figure 15a illustrating the
movement of the shock waves and the creation of the plasma; and
Figure 16 is a simplified sectional view of a device for the plasma treatment of powders
according to this invention.
Referring to Figures la and lb, a device 1 for the treatment of a surface 2 of an object to
be treated 3 generally comprises a device for plasma generation 4 including a gas supply
system and an electrode 5, and a holding device 6 for holding the object to be treated.
The treatment device 1 may also comprise an external vibration generator 7 that can
induce the surface 2 of the object to be treated to vibrate, by means of an oscillator in
direct contact with the object or via sonic (acoustic) waves without direct contact.
A plasma 8 is created on the surface 2 of object 3 by the plasma generator 4 in a gas that
can be activated plasma-chemically and is directed toward the surface 2 by a duct 9 of
the gas supply system, where the duct can be formed within the electrode 5,
The surface to be treated is excited so as to vibrate, that is, it performs a wave motion.
The energy needed to generate the wave motion of the surface to be treated can be
derived from a shock wave arising in the process of plasma creation, from a shock wave
created by an external generator, of from an external vibration generator 7. A shock
wave causes a body to vibrate in a transitory mode at its eigenfrequencies. The vibration
amplitude can be boosted by an external vibration generator adjusted so as to generate
vibrations at one or several eigenfrequencies of the object to be treated. As the vibration
modes of bodies are extremely complex, the optimum choice of frequencies may be
determined by tests, that is by adjusting the frequency differently for each of a certain
number of samples and determining the features of surface treatment quality.
An analysis of the surface treatment process according to the invention shows that by
realizing wave motion of the particles of the surface to be treated one can intensify the
physicochemical interaction between the plasma particles and the surface particles. By
its nature and effects, this intensification resembles that accompanying an increase in
temperature of the surface to be treated when in contact with the plasma, be it a vacuum
plasma, an atmospheric plasma or a high-pressure plasma.
Thus, a very important aspect of the invention is to intensify the process of plasma-
chemical interaction, be it for deposition of a film, for etching, the creation of a surface
alloy, or other kinds of treatment, without raising in any significant manner the
temperature of the object to be treated. This technical solution is very important and
opens up wide perspectives, particularly for the plasma treatment of bodies made of
material not withstanding heating. On the other hand it allows the effects of a cold
plasma on a surface to be valorized in a novel way, that is, the effects of a plasma out of
thermodynamic and chemical equilibrium (see the definition on page 27 of the book of
Baddour and Timmins cited earlier). The possibility of exciting the surface to be treated
by a mechanical vibration while leaving it cold allows one in fact to decisively remedy
the disadvantage inherent in the use of a cold plasma on a cold surface, since the
interaction between the plasma and the surface to be treated is strongly intensified.
Figures 2a and 2b present SEM (Surface Electron Microscope) photographs of the
surface of an 0.5-liter-capacity PET bottle after a plasma treatment without excitation of
the surface to be treated. In this case a silicon oxide film was deposited. The plasma
employed in this example is a HF (high-frequency) pulse discharge plasma generated in
a mixture of hexamethyldisiloxane vapors and argon. After the treatment the bottle was
mechanically folded, and in these photographs one notices chips 10 and scales 11
formed on the surface. These chips and scales can fall off and become incorporated into
the liquid, thus representing a hazard to the consumer This also increases the
permeability of the surface. By tests involving these bottles it could be established that
the impermeability RIF (Relative Impermeability Factor) of the barrier film was about
10 for oxygen, relative to an untreated surface. In the case of Fig. 2c the same surface
treatment was carried out while adding vibrations having a frequency of about 21 kHz,
that is, in the ultrasonic region, with the aid of an external ultrasound generator. The
temperature of the PET walls of the bottle was measured during the treatment with a
thermocouple, which showed that the temperature did not rise above 45 °C. This
temperature is well below the maximum temperature of PET treatment, which is about
60 to 70 °C. The bottle was then folded mechanically in the same way as the samples of
Figures 2a and 2b, and one can notice in the SEM photograph that the barrier film
obtained is sound and flexible, since neither chips nor scales are formed. The level of
impermeability of the barrier film is very high. According to sample measurements, the
RTF is about 30 for oxygen, relative to an untreated surface.
It should be noted that the process according to the invention allows one to employ a
plasma in vacuum, under atmospheric pressure, or under high pressure, since the action
exerted by the vibrations of the surface to be treated on the interaction of this surface
with the plasma does not significantly change with the pressure at which the plasma is
generated. The treatment efficacy, on the other hand, again does not sigmeantly change
with the manner in which the plasma is generated, be it in a continuous manner, with
supply from dc sources, ac sources, high-frequency, microwaves, or pulses. In the latter
case, the pulse period is preferably longer than the period of the vibration to which the
object to be treated is subjected, in order to make sure that the contact between the
plasma and the surface to be treated comes about.
The shock wave originating with plasma creation can be generated by isochoric heating
of a fraction of the volume of gas that can be activated plasma-chemically, by emitting
an electrical pulse discharge obeying certain parameters, directly into the process gas.
The volume fraction in question heats up, its pressure rises rapidly above the critical
pressure above which a shock wave forms which propagates throughout the volume of
the gas mixture and is followed by a plasma formed by particles of the process gas that
are heated, excited, and ionized. This procedure is above all efficient when the electric
current pulses are accomplished along the surface of the body to be treated, which
consists of insulating materials. It can be used to good advantage to treat a complicated
surface such as the inner walls of bottles, tubes, gasoline tanks and other containers.
In Fig. 3a, a device 1 for the treatment of an inner surface 2 of an object to be treated 3,
here a bottle, comprises a device for plasma generation 4 by electrical pulse discharges
that is provided with a gas supply system comprising a duct 9 which can also function as
live electrode 5, a holding device 6 with an insulating element 12 for holding the object
to be treated, and a grounding electrode 15. The treatment device 1 can also include an
external vibration generator 7, here an ultrasound generator, that can cause the inner
surface 2 of the bottle to vibrate, a vibration sensor 13 that can be connected to a
command module of the vibration generator 7, and a temperature sensor 14, for instance
a thermocouple, to check the temperature of the container wall.
A plasma 8 is created inside the container 2 by current pulses flowing from the central
electrode 5 that is working in the electric or autoelectromc field emission mode (as
defined in the monograph of S. Krapivma, Plasmachemical processes in engineering,
Chemistry Publ., Leningrad (1981), p. 27) to the grounding electrode 15. The grounding
electrode 15 is arranged and shaped so that it can sustain the amplitude of the applied
electric field and admit the creation of branched plasma discharges consisting of a
superficial network of plasma filaments 16. The amplitude of the applied electric field
must be large enough to ensure discharge initiation by breakdown.
Electrode 5 which also functions as a duct 9 through which the process gas is introduced
into the container can be inclined forming an angle or to the container's axis of
symmetry, so as to favor plasma formation along its inner surface 2. A gas having a
weak ionization energy is used, such as argon, in order to optimize discharge
localization along the container's inner surface.
Referring to Figs 5 and 6, the branched plasma discharge is developed by a current pulse
(I) having a rising flank of duration. so that the plasma inside the filaments of the
branched discharge starts to form and heat up isochorically. The time band designated as
t1 in Fig. 5 corresponds to the phase of isochoric heating of the plasma filaments. For t1
one has the relation: t1 created, and a is the speed of sound in the non-ionized medium surrounding the
filament. Typically d~ 1 mm and a ~ 3.102 m/s so that t1 At the end of time t\ the pressure rise inside the filament, which depends on the features
of discharge development, and particularly on the heating of the plasma supplied with
energy by the current, generates a shock wave exciting and ionizing the gas around the
filament. The activation is intense above all in zone 19 between plasma filament 16 and
the surface to be treated 2, on account of the incident wave 17 intersecting with the
wave 18 reflected from the surface to be treated. The current that is initially localized in
this filament, after development of the aforementioned shock waves passes mainly to the
zone 19 that is restricted to the reflected wave 18 within which a cold plasma out of
thermodynamic equilibrium develops which has a very good contact with the surface to
be treated.
The amplitude of the energy developed by the electric current pulse is such that part of
the energy of the incident shock wave is transmitted to the material of the object to be
treated, via a penetrating shock wave 20 which is dissipated in the form of vibrations at
eigenfrequencies of the object to be treated, which can be in the range of audible
frequencies or of ultrasonic frequencies. The presence of vibrations can be controlled
advantageously with the aid of an acoustic sensor 13 in the treatment device. These
acoustic vibrations will subject the atoms of the object to be treated to oscillations
which make them depart from and return to their positions of static equilibrium, and
during their departure create a situation that favors their chemical union with the
particles of the medium that is ionized and activated by the plasma, for instance with
silicon and oxygen atoms during deposition of a SiOx film.
Figure 7 shows records of the vibration frequencies of a PET bottle (0.5 liters) obtained
during the treatment by a HF pulse discharge producing a branched jet of plasma
filaments according to the invention. One sees that the trains of acoustic vibrations
having a relatively large amplitude have frequencies which more particularly are about
6080 Hz and 10,000 Hz.
Particularly in the ultrasonic region, acoustic vibrations applied during the surface
treatment exert a catalyzing role that is similar to an increase in temperature of the
object to be treated. Ultrasonic vibrations have the advantage that the object to be
treated remains relatively cold as compared to traditional plasma treatment processes,
since the energy of the ultrasonic vibrations is dissipated in the volume bordering the
shock wave, rather than locally. Thus, the heating of the object to be treated that results
from dissipation of the waves will be relatively slight.
The current pulses should anyhow be limited in time. The energy set free during current
flow in the plasma, which at first is out of thermodynamic equilibrium, is expended on
one hand for activating the carrier gas particles (for example, O2, O, Si, maybe C, II), on
the other hand for heating the object to be treated, as well as the plasma itself, which
increases in volume. These last-mentioned effects constitute a certain disadvantage for
the surface treatment and should be eliminated. In fact, when films are deposited on the
surface to be treated, the bulk plasma heating favors the formation of powder which will
deposit on the surface to be treated, and contaminate it, resulting for instance in poor
adhesion of the film to the surface to be treated and in poor barrier quality.
Returning to Fig. 5, the time band designated by t2 in Fig. 5 corresponds to a phase of
expansion of the plasma filaments. The current pulse duration 6 is selected such that the
plasma remains cold and develops along the surface to be treated, and that the
temperature of the object to be treated will not rise above its temperature of destruction.
This can be controlled by temperature measurements of the object during or
immediately after its treatment with a temperature sensor, for instance a thermocouple
14 positioned close to or on the object to be treated, as shown in Fig. 3, and connected
to the plasma generation device 4. In an industrial process, the sensor can be employed
in the phase of startup to adjust and calibrate the plasma generation parameters, and
particularly the pulse duration t2 and pulse interval duration t2.
On the other hand, the current pulse duration t2 must be sufficient to activate and
precipitate a maximum number of particles from the plasma-chemically activated
medium onto the surface to be treated, which is verified by evaluating the actual results
of the treatment on a certain number of samples.
As the plasma filaments that trigger the mechanism described above are spaced
relatively far apart, the pulses must be repeated in order to uniformly coat the entire
surface to be treated. The time interval t2 between two pulses should be longer than the
"post-discharge" plasma lifetime t4 (as defined, for instance, in the monograph of A.
Ricard, Plasmas Reactifs, SFV, 1995), and long enough so that the particles that have
precipitated on the surface to be treated and have been brought in contact with the
particles of the surface itself, can attain their final stable (or metastable) state that will
be determinant for the required properties of the surface to be treated, in order tor the
filaments not to return onto the sites of prior filaments when a new pulse is applied.
For instance, during deposition of a polymer film based on the plasma precipitation of a
mixture of activated C, H, and CHy particles, the time interval t3 between the plasma
pulses should be such that between the plasma pulses the polymerization process can be
completed on the surface to be treated. This completion is advantageously accelerated
by the presence of acoustic vibrations.
For plasmas containing compounds such as O2, N2, H2, Si, and C, the time interval
between pulses will preferably be t3 = 1 to 10 ms.
Advantageously, an acoustic vibration, preferably in the region of ultrasonic fre-
quencies, that is being applied to the object to be treated, prior to the plasma treatment,
offers the advantage of promoting the expulsion of foreign gases absorbed in the surface
layers of the surface to be treated. Through the expulsion of these absorbed gases, it can
be avoided that during local heating of the material by the plasma, a flux of these gases
would be created that opposes the flux of activated plasma particles and would prevent
them from reaching the surface to be treated.
Advantageously, by applying an acoustic vibration after the plasma treatment to the
object to be treated one will be able to expel the residual gases and the powder particles
that might have become adsorbed during treatment on the treated surface.
The acoustic vibrations of the object to be treated which airise from the creation of a
branched network of plasma filaments according to the invention can be supplemented
by acoustic, and particularly ultrasonic, vibrations from an external source such as an
ultrasonic vibration generator. The frequency can be selected so as to be equal to one of
the eigenfrequencies of the object to be treated, which can be measured with a vibration
sensor. In this case the resonance effect will substantially improve the quality of the
applied treatment. Other advantageous frequencies exist at which the ultrasonic
vibration of the object to be treated can be amplified, particularly the frequency a/D,
where D is the diameter of the container and a is the speed of sound.
Figures 4a and 4b show photographs taken with a high-speed camera of a branched
plasma discharge generated with a device such as described in relation to Figs. 3, 5, and
6. In the case illustrated, the bottle rests on a plate that is grounded and in contact with
an acoustic vibration generator. The parameters for plasma creation used in these
examples are:
in Figs. 4a and 4b,

photographic exposure time: 0.5 ms,
vibration frequency of the external vibration generator: ƒ= 120 kHz;
in Fig. 4a,
electric threshold potential U= 15 kV,
process gas: argon;
in Fig. 4b,
electric threshold potential U=10 kV,
process gas: a mixture of hexamethyldisiloxane, oxygen, and argon.
The branched plasma filaments being created move rapidly along the surface to be
treated, and vanish. Each discharge is preceded by a superficial breakdown such as
represented by the voltage peak 53 in Fig. 5, which gives rise to a precursor channel.
The lifetime of these branched filaments corresponds to the pulse frequency of the
current source that creates them. The filament network covers large part of the surface to
be treated, according to the photographs, and the filaments follow the exact shape of the
surface irregularities of this surface, including the bottom.
The inventors of the present invention have realized that in traditional processes the
plasma tends to become detached from the surface of the object to be treated, since the
motion of the object or electrode gives rise to gas motions that perturb the plasma and
particularly the air inflows brought about by the boundary layer of the container wall
which tend to repel the plasma from the surface to be treated. When the plasma moves
away from the surface to be treated, this diminishes or cancels the concentration
gradient of the active particles on the surface to be treated, and thus prevents the surface
treatment, such as deposition of a film. In the present invention, the problem is avoided
by the fact that the duration of the current pulses creating the plasma in the shape of a
branched filament network is selected to be short enough to ensure that the motion of
the surface to be treated is so small relative to the spot occupied by the network that the
pulse duration t2 is smaller than the ratio (div) between the width (d) of a filament and
the speed (v) of motion of the surface to be treated in relation to the plasma. Assuming
that this speed be 1 m/s (a speed that is often realized in practice), and that the width of
a filament is 1 mm, a maximum value of 10-3 s is obtained for t2. The pulse duration t2 is
actually subject to an even stricter condition, viz., the limitation imposed on the
temperature of heating of the surface to be treated. The tests performed while
developing this invention have shown that this requirement limits the pulse duration t2
to a value not in excess of about 3-10-4 s. The high-frequency photographs such as those
of Figs. 4a and 4b show that during this time period, the filaments remain attached to the
surface to be treated, and that no hydrodynamic effect is observed.
For an optimum scanning of the surface to be treated by the branched plasma network,
such as that shown in Figs. 3a and 3b, one can move the plasma filaments further apart
or closer together, in other words, vary the density of the bundle of plasma filaments, by
selecting the shape and position of the grounding electrode 15. In Fig. 3a, for instance,
one sees a branched bundle of low density, while in Fig. 3b one sees a bundle of plasma
filaments highly concentrated on account of having placed an electrode 15' of small
surface area outside, and radially disposed relative to the axis of symmetry of the bottle
underneath the insulating holder 12.
For the plasma to sweep all of the container surface, one can carry out a relative motion
between the grounding electrode and the object to be treated, for instance by rotating the
holder 12 on which the container sits, or by rotating the live or grounding electrode
while keeping the holder at rest, or also by moving a magnetic or electromagnetic field
or generating a hydrodynamic effect in the process gases.
So as to simplify the device, one can advantageously achieve the plasma sweep along
the surface to be treated, by moving the process gas supply nozzle, for instance by
performing a rotation about the axis of axial symmetry of the bottle as shown in Figs. 3a
to 3c. One can also improve the scanning by a treatment device such as shown in Fig.
3c, which has a gas supply device 5' provided with a feeding head 24 having a plurality
of inclined ducts 9a, 9b, 9c forming an angle a with the axis of symmetry of the bottle,
and distributed around this axis of symmetry. The ducts 25 can at the same time serve as
electrodes coupled to the plasma generation device 4. The feeding head 24 can be
mounted so as to be rotating relative to the holder 12 of container 3. The device allows a
plurality of branched plasma jets 8a, 8b, 8c to be generated which are distributed around
the inner surface of this container. Rotating the process gas supply ducts causes the
plasma to be rotated through hydrodynamic and electrostatic effects. The hydrodynamic
effect also improves the evacuation of residual gases after the treatment.
The entire surface of the container can therefore be treated, either by one or several
sweeps of the plasma when the grounded electrode or the live electrode which serves at
once as the process gas supply duct is moved, or by repeated pulses on the entire surface
to be treated, but without motion of the latter.
An important moment in the realization of the process is the feeding of the gas mixture
to the surface to be treated. The gases that bring the molecules for deposition of a film,
an impermeable film for instance, can be mixed with the gas used for plasma formation,
and supplied through the ducts 9, 9a, 9b, 9c in the live electrode, they can be present in
the container 3 prior to the start of surface treatment, or they can be supplied into the
container by a separate source. The nozzle of the live electrode may direct the gases for
film coating downstream of the forming plasma. It is important that the breakdown
voltage in the gas mixture be lower than that of ambient air. For this reason the gas
mixture preferably contains argon. The supply system is designed for the consecutive
utilization of several gas mixtures having different compositions which will allow a
barrier film to be created, for instance, in the form of several layers having different
chemical compositions. The deposition of a barrier film on the inside of a bottle can
advantageously be terminated with the deposition of an organic layer of the type of CxHy
that will prevent foaming of a carbonated liquid subsequently filled into the bottle.
A critical region of the object to be treated, particularly in the case of objects having a
narrow neck such as bottles or the part of the inner surface close to the open end of the
container (for instance of a cylindrical plastic tube), is the inclined or receding pan of
the inner surface close to the neck. It is advantageous in order to ensure an efficient
surface treatment of this part to have ducts 9a, 9b, 9c inclined by an angle a relative to
the axis of axial symmetry of the container or at least the part close to the part of the
neck 26.
In the particular case where the object to be treated is a plastic tube, it turns out to be
important, for instance during a treatment by which a barrier is deposited, not to treat the
end of the tube that is to be closed, since the deposited film may prevent the welding of
this end after filling of the tube by a consumer good. In this case angle a will be so
selected that the gas mixture fed through ducts 9, 9a, 9b, 9c will contact the wall to be
treated, only below the annular surface that should not be treated. In the particular case
where a bottle is treated, it is possible at the end of the operations to only coat the lower
part of the bottle with a polymer layer preventing foaming of the beverage during filling,
while the neck lacks this layer and hence favors foaming. This would cause the beverage
to foam when poured, an effect desired in the case of beer.
By adequate selection of the angle a one can also minimize the accumulation of residual
treatment products, by admitting a circulation of the gases toward the open side of the
container, here the neck. One also can inject the feed gases as a coaxial cone to an
axisymmetric object to be treated, so that the feed gases are uniformly distributed over
all of the surface to be treated. In this case the residual gases are evacuated by a central
evacuating duct along the axis of this cone.
By virtue of the contact between the plasma and the surface to be treated by a process
according to the invention, one can deposit barrier layers, for instance layers containing
SiOx which is cheap and well suited for containers intended for food, by the following
effects. First the gases absorbed in the walls of the object to be treated are desorbed by
the acoustic effect of a shock wave arising with the creation of the plasma and/or
coming from an external source of ultrasonic vibrations, and are thus eliminated from
the wall's surface layer. The plasma might also produce a superficial etching of some
atomic layers liberating chemical bonds which will react with the excited particles in the
plasma, particularly certain particles such as silicon and oxygen fed with the surface
treatment gas. The mechanism is not fully known, but it may be that the SiOx molecules
occupy chemical bonds at the polymer surface and function as crystallization sites for
formation of a barrier layer of SiOx on the surface to be treated.
For the creation of flexible, nonbreaking barrier films having good adhesion to the
walls, it is possible through the present invention to successively deposit layers having
different chemical compositions, and in particular to superimpose layers of SiOx and
CHy nicely adhering to the substrate and to each other.
In the embodiment of Fig. 8 for treatment of the inner surface 2 of a container 3 of
complex shape, the pulse discharge of plasma in the shape of a plasma filament network
is formed between a live electrode 5 serving at once as a process gas duct and a
grounding electrode 15 that can be moved in three dimensions by a mechanism (not
shown) allowing electrode 15 to run across all of the outer surface of the container so as
to pull a branched plasma filament network across all of the inner surface 2 of the
container.
In the embodiment of Fig. 9, the surface treatment of a container 3 of complex shape
(for instance a gasoline tank) is carried out as follows. A live electrode 5 supplied by a
current source 4 is situated on the outside of an enclosure 27 of the device. The
container 3 is placed inside the enclosure 27, which is made of insulating material and
ventilated by a flow of air or other gas 28. Two ducts 29, 30 are used to bring the gas
mixture into the tank 3 and to evacuate the residual gases from the tank, respectively.
The tank can be moved and rotated through a mechanism holding the tank (not shown).
The grounded electrode can have the form of an electrically conducting liquid jet 31
coming from an injector 32 supplied by a pump 33. The electrically conducting liquid
34 collecting on the bottom 35 of the enclosure is continuously recirculated into the
system of the grounded electrode. The discharge between said electrodes develops in the
form of a branched plasma filament network 8.
In the embodiments of Figs. 10 and 11, two solutions for the simultaneous treatment of
internal and external sides 2a, 2b of the wall of a container 3 made of insulating material
are shown.
In the embodiment of Fig. 10, discharges are produced so that the branched plasma
filament networks 8a and 8b are formed in an alternating way to both sides of the wall
while the two electrodes 5a, 5b are connected to opposite poles of the electrical circuit
54 of the plasma generation device 4. The container is placed on a holder 6 made of
insulating material that can be rotated.
In the embodiment of Fig. 11, the electrical arrangement proposed allows the discharges
to be carried out in the form of branched plasma filament networks 8a, 8b supplied in
parallel. The tank 3 is in this case placed on a holder 12, and the two discharges make
use of one grounded electrode 15.
In these two embodiments, live electrodes 5a, 5b serve as gas ducts. The gas mixtures
sustaining the discharges may differ between the two sides of the container wall so that
deposits having different compositions and properties might be formed.
In the embodiment of Fig. 12, the discharges are generated such that the branched
network of plasma filaments 8a, 8b are formed on the inner surfaces of the recipients 3a,
3b placed one next to the other. The two electrodes 5a, respectively 5b, arc connected to
opposite poles of the electric circuit 54 of the plasma generation device 4, such that the
plasma filaments 8a, 8b are attracted together by electrostatic forces which help in
applying them against the inner surface of the recipients 3a, respectively 3b.
As in the other embodiments, the recipients 3a, 3b may be placed on rotatable dielectric
supports 12 that also comprise a grounded electrode 15.
A plurality of pairs of containers 3a, 3b supplied by electrodes pairs 5a, 5b connected to
opposite poles of an electrical circuit 54, as shown in Fig. 13, may be treated
successively by means of an electronic or electrical switch 56.
In the embodiments of Figures 12 and 13, it may be noted that the formation of
branched network of plasma filaments 8a, 8b against the internal surfaces of the
containers placed one next to the other, is advantageous in view of the good application
of the plasmas against the surface to be treated due to their mutual attraction. The
plasmas thus espouse the interior shape of the containers, thus ensuring a uniform and
effective treatment over the all innersurface of the container.
The process claimed can be put to practice with equipment consisting essentially of two
conveyors feeding and withdrawing the objects to be treated, and a rotating circular tray
at the periphery from where the objects to be treated are moved, each provided with a
system of distribution of the gas mixtures, a current source, appropriate devices for
measurements and checks, and one or more sources of acoustic vibrations, particularly
ultrasonic vibrations, ensuring realization of the process. The sources of acoustic
vibrations may be mounted onto the container bottom holders, so as to enhance the
efficiency of the treatment on the container bottom surface. The current sources can be
arranged to serve groups of objects to be treated.
During its treatment, each of the objects to be treated could be subjected to air cooling
by forced convection to the object's untreated wall, for instance to the side not treated,
when dealing with a container being treated.
In one mode of realization of the invention the objects to be treated could be immersed
into a liquid through which they would be subjected to the uniform action of acoustic
vibrations, and particularly of ultrasonic vibrations, over their entire surface. This could
for instance be bottles or other containers partially immersed into the liquid bath, with
the necks remaining outside, so that the liquid would be in contact with the container's
outer surface, which has the advantage that the container walls can be cooled very
efficiently and the plasma applied for a longer time. On the other hand, when an external
source of vibrations is employed, the liquid allows these vibrations to be more
uniformly distributed over the container walls, and thus to produce more uniform
vibrations on the container's inner surface to be treated.
In order to simplify the electrical connections to the treatment device, the device can be
provided with a system of capacitors through which the high-frequency (HF> electrical
energy is transmitted to the live electrodes without the need for a direct contact.
In the case of deposition of films on containers consisting of transparent, amorphous
material, the treatment device may advantageously include a system of laser beams for
quality control of the film deposited. Such a system will record, either the number of
photons emitted by non-linear effects while the laser beam passes through said film or
the decrease of the flux of primary photons caused by their recombination as a result of
non-linear effects.
In the case of an etching treatment carried out by plasma at an object such as a single-
crystal silicon wafer onto which a microelectronic structure partly protected by masks
consisting of photoresist material is deposited, one can advantageously apply a wave
motion to the object to be treated, in a particular direction such as perpendicularly to the
wafer surface, so as to produce an anisotropic etching. The degree of amsotropy will
depend on the amplitude and frequency of the wave motion imposed upon the surface to
be treated.
When the object to be treated is a metal sheet, a plastic foil, or a textile sheet, then this
object can be subjected to the simultaneous action of a plasma flux scanning the surface
of this object and of a vibrating motion of the object which will intensify the cleaning,
degreasing, etching treatment or film deposition caused by the plasma flux.
A similar and equally efficient realization is feasible when the object to be treated is a
metallic wire, textile fiber, or polymer filament.
Another embodiment of the present invention consists in generating the plasma
simultaneously in two spots on the surface of an asymmetrically shaped object to be
treated, for instance a container of large volume and complicated configuration, where
two high-frequency discharges in the form of branched plasma filament networks are
produced between two capacitive electrodes provided with a scanning motion along the
outer surface of the object to be treated.
A mode of plasma generation constituting great practical interest consists in generating
plasma by adiabatic (isentropic) compression. A device for treatment by generation of
such a plasma is shown in Fig. 14.
The treatment device 1 includes an enclosure 36 comrpising a section that is the
chamber of piston 37 and a section containing the seats for the objects to be treated 38, a
solid piston 39, a gas compression device 40 provided with means for rapid expansion,
an acoustic vibration generator 7, an entry duct for the process gas with valve 41, and a
duct for gas evacuation with valve 42. The section with the seats for the objects 38
comprises a portion of side wall 43, a portion of bottom wall 44 fixed to the portion of
side wall via a vacuum seal and vibration damping device 45. Piston 39 is mounted so
as to slide inside the piston chamber 37 of enclosure 36, while the section of the
chamber above the piston can rapidly be filled by high-pressure gas generated by the gas
compression device 40 that is connected to this section of the chamber by a duct 46. An
exit duct 47 with valve 48 allows the gases to be evacuated from the section of the
enclosure above the piston when the piston 39 is lifted back up. The entry and exit duct
41, 42 allows the section with the seats of the objects to be filled with process gas, to
evacuate the gas after treatment, and to fill it again with process gas.
When the piston is at the upper dead center, then the interior of the enclosure is first
evacuated by a vacuum pump (not shown) connected to exit 42, then filled with a
process gas supplied by the entry duct 41. The compression device 40 includes a
compressed-air reservoir connected via an actuating valve with the section of the
enclosure above the piston. The piston 39 is pushed downward by the compressed air
and only stops when at the lower dead center 50.
The dimensions (diameter and height) of the enclosure, the initial process gas pressure,
and the pressure exerted on the piston are so calculated that during its motion from the
upper dead center 49 to the lower dead center 50, the piston compresses the process gas
along the adiabatic curve of Hugogniot.
The plasma is generated by adiabatic compression It pushes the piston back, the piston
returning to its upper dead center 49 while the gas above the piston is evacuated during
its up-stroke via the duct 47. This embodiment has the advantage that the plasma is
generated unformly throughout the treatment space, so that the treatment will be carried
out in a uniform way on all sides of the objects to be treated which are present in the
enclosure.
The dynamics of the compression process is calculated so that a plasma having given
parameters is formed in the treatment zone of the enclosure, and that vibrations are
generated by the external source of vibrations 7 operating preferably at one of the
eigenfrequencies of the objects to be treated, or at a multiple of one of the
eigenfrequencies.
Another mode of plasma generation that may also be of practical interest is the
generation of plasma by a shock wave. A device allowing such a plasma to be generated
is schematically illustrated in Figs. 15a to 15c.
The treatment device 1 according to Fig. 15a comprises an enclosure 36 with a first
section 37 holding compressed gas that is connected via a duct 46 with a valve to a gas
compression device 40, and a section housing the objects to be treated 38, with a
process gas entry duct 41 provided with a valve and a process gas evacuation duct 42
provided with a valve. The section housing the objects tc be treated comprises a portion
of side wall 43 and a bottom portion 44 which are joined via a vacuum seal acting as
vibration absorber 45. The device further comprises an external ultrasonic vibration
generator 7 arranged underneath the bottom portion 44. A removable separating wall 51
can be arranged so as to hermetically separate the section holding the compressed gas 37
from the section housing the objects to be treated 38.
At the start of the treatment process a vacuum pump connected to the evacuating duct
42 empties the section 38 of the enclosure which subsequently is tilled with a process
gas supplied by the entry duct 41. The compression device 40 compresses a process gas
in the section holding the compressed gas 37. Finally the removable wall 51 is abruptly
lifted in order to connect the two enclosure sections 37, 38.
The dimensions (diameter and height) of the enclosure, the initial pressure of the
process gas, the position of the separating wall, the pressure of the compression gas, and
other parameters are so calculated that the process gas compression behind the shock
wave occurs according to the adiabatic curve of Poisson, The dynamics of the
compression process produced by the incident and reflected shock wave is calculated in
such a way that a plasma of given parameters is formed in the zone of the object to be
treated. The object 3 is subjected to the plasma-chemical action of the plasma created
behind the reflected shock wave 52', the plasma resulting from the twofold compression
by the incident wave 52 and the reflected wave 52'. Part of the energy of the incident
shock wave 52 is absorbed by the object to be treated 3, in the form of a shock wave 52"
propagating inside the object at the speed of sound, which is rather higher that the speed
of sound in the plasma. The wave inside the object is reflected at the opposite wall 26,
and thus performs a forth-and-back motion becoming dissipated in the form of acoustic
vibrations.
These vibrations of the surface of the object to be treated provoke an intensification of
the plasma-chemical reactions between the plasma and the particles of the surface to be
treated 2a. One can boost the amplitude of the vibrations by an external source of
vibrations 7 emitting for instance a frequency close to or identical with one of the
eigenfrequencies of the object or a multiple of this frequency.
However, the frequency of this external vibration can be selected so as to correspond,
neither to the vibration frequency of the shock wave in the object to be treated nor to an
eigenfrequency of the object to be treated.
Referring to Fig. 16, another embodiment is shown for forming a plasma in a reactor 36
in which gas and vapors Q1 and Q2 are introduced by the entry ports 41 The
decomposition of the gas in the plasma forms clusters and powders, in particular nano-
powders, whereby the degree of structuration, the form, and the quantity is determined
by the simultaneous action of the plasma and ultrasonic vibrations. The vibrations are
for example transmitted to the reactor by an ultrasonic generator 7, or generated in the
chamber 36 by current pulses in the plasma as described previously, such that the front
of development of the plasma has the characteristics described in relation to Fig. 5.
In this manner, for example, nano-powders of SiO2 in the form of monocrystals having
an average dimension of around 20 nm with a dispersion of ±20%, have been produced
from the decomposition of hexamethyldisiloxane in a process gas comprising
argon+oxygen. The productivity of the method was increased 35-fold, all other
parameters being equal, by including an acoustic vibration of 45 kHz frequency (2 kW
power) in the high frequency electrical discharge (HF) plasma (power 45kW, diameter
of the plasma flux: 35 mm).
In the device according to Fig. 16. the ultrasonic generator 7 comprises an ultrasound
transmitter 58 mounted coaxially within the chamber 36, which in this example has a
cylindrical shape, such that the powder particles are produced and treated in the annular
space between the ultrasonic transmitter 58 and the wall of the chamber 36. The device
may further comprise a cooling circuit 60 around a portion of the chamber 36 and
having entry and exit ports 62, 64 for the circulation of a cooling liquid. The plasma 8 is
created in a portion 66 of the chamber around which the electrodes 5 connected to a
current source 4 are placed, for example a high frequency current source, for the
generation of plasma in the portion 66 of the chamber, either by capacitive or inductive
effect. If the external acoustic generator is supplied, the plasma may be created in the
chamber by conventional means. However, in the absence of an external vibration
generator, the acoustic vibrations may be generated by the process of generation of the
plasma in pulses respecting the conditions described in relation to Fig. 5.
The device of Fig. 16 may also be used for the treatment of powder nuclei or grains,
which for example may be introduced with the gas mixture Q1, Q2 in order to form
composite powder grains. The plasma activates the atoms and molecules of the gas
mixture that are in contact with the powder nuclei in order to form homogeneous atomic
or molecular films or layers around the nuclei. The acoustic vibrations undulate the
plasma ions or the grain nuclei, or both, such that the relative undulating movement
between the nuclei surface and the plasma ions catalyzes the deposition process. The
powder 70 thus produced or treated is collected in a collector 68 arranged under the
outlet tube 36.
Another variant of the present invention comprises imposing an acoustic vibration for
surface etching by plasma. The object to be treated is for example a semi-conductor
plaque such as a mono-crystalline silicium plaque covered with a structure comprising
masks, as commonly found in semi-conductor technology. The plasma is preferably an
atmospheric plasma. The silicium plaque is wounded on a support and arranged to be
subjected to an atmospheric plasma jet, in which etching gases, such as CF4 are injected.
The support is subjected to an ultrasound vibration perpendicular to the plaque, for
example at a frequency of 15 kHz.
Experiments have shown that on application of the ultrasonic vibration, cleaning may be
effected in an anisotropic manner in the sense that the etching speed VII in the direction
parallel to the vibrational movement (i.e. perpendicular to the surface of the silicium
plaque) is superior to the etching speed in the perpendicular direction v. By varying the
power P of the vibration between 0.1 and 2 kW, it was possible to obtain a ratio vII/v
varying between 1.2 and 30. This ratio increases by a factor of 1.5 with an increase in
the frequency of 15 to 45 kHz.
The plasma treatment process of the present invention may advantageously be used for
cleaning, or etching, or scaling metallic sheets or wires. For example, an aluminum
sheet passing through a plasma curtain may be cleaned of its oil or grease layer
remaining after rolling. The application of an acoustic vibration intensifies the
aforementioned treatment in a significant manner For example, in a practical
experiment, a virtual complete cleaning was obtained for a linear power density of
1kW/cm of plasma for a sheet velocity through the plasma of 3 m/sec. By applying an
ultrasonic vibration to the aluminum foil through the support or roller in contact with
the foil (v = 45 kHz, P = 0.1 kW/cm), it was possible to reduce the electric power by
half (that is 0.5 kW/cm) to achieve the same cleanliness results.
In the case of treatment of an internal or external surface of a hollow body of
asymmetric shape, having for example the shape of a large volume container with
complex configuration, it is possible to generate the plasma in the form of a branched
network at two regions on the surface of the body to be treated, for example by two high
frequency discharges in the form of a branched network of plasma filaments between
two capacitive electrodes that sweep along the outer surface of the body.
By way of example, in a practical experiment, the internal surface of an automobile fuel
reservoir made of a single layer polyethylene, was covered with a barrier film with the
aid of high frequency plasma discharges at 13.56 MHz. The plasma discharges in the
form of a branched network of filaments, were created in a gas mixture of argon, oxygen
and HMDS. The average power of the discharge was 5 kW. In 60 seconds, the interior
surface of the container was covered with a film of SiO2 of 0.1 µm thickness,
representing a barrier improvement factor for hydrocarbon molecules of around 1000.
Nonlimiting examples of realization of the process according to the invention are given
hereafter.
Example 1
Deposition of a silicon oxide film on the inner surface of a single-layer PET bottle (0.5
liters) by the HF method
Base products used consecutively and repetitively: Ar, O2, Hexamethyldisiloxane
(HDMS), CH4
Maximum voltage of the current source: 21 kV
Discharge current amplitude: 10 A

Duration of treatment: 30 s
Major barrier material: SiOx (x = 1.96)
Barrier thickness: 180 - 190 A
Magnitude of barrier for oxygen (volume of oxygen diffusing across the bottle wall per
day):
prior to treatment: 0.06 cm3/bottle-day
after treatment: 0.0001 cm3/bottle-day
Relative barrier coefficient for oxygen: BIF* ~ 60
Barrier coefficient for CO2: BIF* ~ 1 5
*) BIF = Barrier Improvement Factor
Example 2
Deposition of a silicon oxide film on a single-layer polyethylene tube (200 ml)
Base products used consecutively: Ar, O2, HDMS, TEOS, CH4
Maximum voltage of the current source: 10 kV
Discharge current amplitude: 8 A
t1 = 2 us
t2 = 200 us
t3 = 10 ms
Duration of treatment: 30 s
Major barrier material: SiOx (x = 1.95)
Barrier thickness: 250 Å
Magnitude of barrier for oxygen:
prior to inside treatment: 0.7 cm3/tube-day
after inside treatment: 0.005 cm3/tube-day
after outside treatment: 0.1 cm3/tube-day
after treatment on both sides: 0.002 cm3/tube-day
Barrier coefficient for oxygen:
after inside treatment: BIF ~ 140
after outside treatment: BIF ~ 7
after treatment on both sides: BTF ~350.
Example 3.
Deposition of a silicon oxide film (SiO2) by decomposition of HDMS in an
atmospheric plasma in the interior of the container (PET bottles) under the following
conditions:
Frequency (v) of the undulations (exterior source of ultrasound with different
energy densities) applied to the container during the plasma treatment :
v = 3.101 kHz.
- Amplitude (1) of the undulations (measured by a high speed camera: 10
frames/sec) :
1= 1/v. V(E/p)
where p is the density of the treated material.
Increase of the temperature (AT) of the container wall following an atmospheric-
plasma treatment (measured with an infrared pyrometer) :
?T= 10K.
In these conditions, the energy density (E) of the undulating movement is :
E und = ½ p2V2
The thermal energy density (Et) communicated to the object hy the plasma and
corresponding to a temperature of ?T de 10K is
ET= pc?T
where c is the thermal capacitance of the material.
The ratio (R) of the above values is : R= E und / E1 = ½l2v2/ c?T.
Following the undulating regimes (1) imposed on the process, we have :
Table N°l :
The result obtained by this experiment allows us to conclude that in the case of a film
deposition by atmospheric plasma, the energy density of the undulating movement is
superior to around one hundredth of the thermal energy density communicated to the
body to be treated by the plasma. In a general manner, this implies that the application
of an undulating movement only becomes effective when its intensity is such that the
energy density of this movement is significant in relation to the increase in thermal
energy of the body to be treated, the latter being proportional to the increase of the
temperature of the body before and/or during treatment. The thermal energy may be
communicated to the body to be treated by a heat source, in particular the heat source
provided by the plasma itself.
In this example, 1e minimum ratio R of the energy densities, for which an undulating
movement becomes effective, has been found to be around one over a hundred.
Considering the complex nature of the interaction between the surface that is on the one
hand undulating, and on the other hand heated, with the plasma, it is possible that the
aforementioned ratio is around one hundredth for the particular process of depositing a
silicium oxide film, but different for other processes, for example for etching, activation
or sterilization of surfaces. In a general manner, it should thus be retained that the word
"significant" means that the energy density of the undulating movement should be a
significant fraction of the thermal energy density, probably above one thousandth. The
example shows that the actual value of the ratio exists but needs to be determined for
each particular situation.
Example 4
During the film deposition treatment mentioned in Example 3, the thickness of
the boundary layer concerning the diffusion of particles (Si) towards the wall
surface to be treated, was estimated on the basis of estimations of the average
temperature of the plasma based on spectroscopic data mentioned in the article:
A. Kakliougin, P. Koulik, et al., "HF Atmospheric Plasma Sterilization of
Dielectric Containers Inside Surface" CIP 2001, published by SVF; 1st Edition
May 2001, p. 28. According to these estimations, the thermal speed (VY ) of
diffusing particles was estimated at vT~ 103 m/s. The concentration nT / npl of the
diffusing particles of Si was measured by flow-meters and was equal to 10-5
(ratio of the particle density of Si to the total density of plasma particles), and the
effective section of the diffusing particles was evaluated at 10-18 m2 according to
Braun (S. Braun, Basic Processes in Gas Discharges. Cambridge, MTI, 12,
1959).
The duration of treatment by plasma was ?t = 30sec.
In these conditions, the thickness 5 of the boundary layer for the regimes
described in the preceding article is calculated according to the formula : d == vT .

where nsol is the density of particles of the deposited layer (~ 1028m-3), where the
thickness is A, and Q is the effective section of the diffusing particles.
According to the undulating regimes imposed in the process, we have :
These results show that when the amplitude of the undulating movement is
superior to the thickness of the boundary layer between the plasma and the object
to be treated, we obtain, in these experimental conditions, a layer of silicium
oxide of measurable thickness (in other words, the process is effective).
This result implies that the undulating movement applied to the surface to be
treated is effective, once it provokes a turbulent plasma, the latter substantially
intensifying the molecular exchange between the plasma and the surface to be
treated, accompanied, for example, by film deposition as mentioned in this
example.
Example 5
Surface treatment of particles (nuclei) to form composite grains
WE CLAIM :
1. Plasma treatment process of an object's surface to be treated, comprising
the creation of a plasma , the application of the plasma to the surface to be
treated, characterized in that the surface to be treated is excited or the plasma is
acoustically vibrated so that a relative undulating movement between the surface
to be treated and plasma is created, energy for the excitation of the surface to be
treated supplied by the plasma creation process.
2. Process as claimed in claim 1, wherein the surface to be treated is
excited, or the plasma is acoustically vibrated by means of an external vibration
generator, in combination with the energy source supplied by the plasma
creation process.
3. Process as claimed in claim 1 or 2 wherein ultrasound is generated.
4. Process as claimed in claim 2 or 3, wherein the vibration frequency of the
generator is adjusted to a frequency close to or identical with one of the
eigenfrequencies of the object to be treated.
5. Process as claimed in any of the preceding claim, wherein the frequency
and amplitude of the vibrations of the object to be treated are measured by
means of a vibration sensor in order to identify the eigenfrequencies of the object
to be treated and/or to control the excitation of the surface to be treated.
6. Process as claimed in any of the preceding claim , wherein the surface to
be treated is excited by a shock wave produced during creation of the plasma.
7. Process as claimed in any of the preceding claim, wherein the excitation
of the surface to be treated is brought about just prior to and/ or during and/or
just after application of the plasma to the surface to be treated.
8. Process as claimed in any of the preceding claim, wherein the plasma is
created in a gaseous medium comprising a process gas that can be activated
plasma-chemically, the process gas being in contact with the surface to be
treated.
9. Process as claimed in any of the preceding claim, wherein the plasma is
generated by pulses, the lifetime of the plasma generated being longer than the
period of wave motion of the surface to be treated.
10. Process as claimed in claim 9, wherein the plasma pulse is generated by
i
an essentially adiabatic and isentropic compression of a gaseous medium
comprising a process gas that can be activated plasma-chemically.
11. Process as claimed in claim 9, wherein the pulses are generated by
incident shock waves and shock waves reflected from the surface to be treated.
12. Process as claimed in claim 9, wherein the pulses are generated by
unipolar or high-frequency electrical current pulses.
13. Process as claimed in any of the preceding claim, wherein the rise time
(t1) of the electric current amplitude of a pulse is shorter than the ratio d/v of
diameter d of the plasma channel created, to the speed of sound v in the
gaseous medium surrounding the plasma channel.
14. Process as claimed in claim 12 or 13, wherein the sonic shock waves are
created by an electric breakdown during the creation of a plasma channel or
filament.
15. Process as claimed in claims 12 to 14, wherein the length (t2) of an
electric pulse is adjusted so as to avoid superficial heating of the surface to be
treated, above the critical temperature of instability of the material.
16. Process as claimed in any of the claims 12 to 15, wherein the interval
between pulses (t3) is longer than the post-discharge time (t4) in order to allow a
majority of the particles" of the surface to be treated, to attain a stable or
metastable state.
17. Process as claimed in any of the claims 12 to 16, wherein a plasma is
created in the form of a branched plasma filament network generating shock
waves.
18. Process as claimed in any of the claims 12 to 17, wherein the plasma is
moved over the surface to be treated, by a relative motion between an electrode
and the object to be treated and/ or by a magnetic field in motion and/or by a
hydrodynamic effect of a process gas in which the plasma is created.
19. Process as claimed in any of the preceding claim, wherein the pulse
length (t2) is inferior to the ratio between the width of a plasma filament applied to
the surface to be treated , and the velocity of motion of the surface to be treated
relative to the plasma.
20. Process as claimed in any of the claims 12 to 19, wherein the plurality of
ramified plasma branches distributed over the surface to be treated are
simultaneously created and applied.
21. Process as claimed in any of the preceding claims, wherein the plasma is
fed successively with process gases having different compositions, for different
successive treatments of the surface to be treated.
22. Process as claimed in any of the preceding claims, wherein the process
gases include argon, organometallic vapors such as those of silicon and oxygen,
and hydrocarbons.
23. Process as claimed in any of the claims 2 to 4 in cases of treatment of
bottles or other deep containers, wherein vibrations are generated underneath a
container bottom opposite to a neck so as to enhance the treatment efficiency on
the bottom.
24. Process as claimed in any of the claims 2 to 5, wherein an anisotropic
etching of the surface to be treated is executed by the generation of vibrations in
a particular direction relative to the surface to be treated.
25. Process as claimed in any of the preceding claim in the case of etching
treatment of a semiconductor surface, wherein vibrations are executed moving in
a direction essentially perpendicular to said surface.
26. Process as claimed in any of the claims 1 to 16, wherein the plasma
treatment is an etching treatment, and the undulating movement of the surface
to be treated, such as a surface of a monocrystalline silicon wafer on which a
microelectronic structure is deposited and partially protected by masks in
photoresist material, is effected in a specific direction, such as perpendicularly to
the surface of the wafer, which enables an isotropic etching treatment to be
performed, the degree of anisotropy depending on the amplitude and the
frequency of the undulating movement applied on the surface to be treated.
27. Process as claimed in any of the claims 1 to 16, wherein the body to be
treated is a sheet of metal or piastic or textile subject to the simultaneous action
of a plasma flux and a vibration movement of the support that fixes the position
of the sheet in relation to the plasma flux.
28. Process as claimed in any of the claims 1 to 16, wherein the plasma is
generated simultaneously on two positions of the interior surface of a body to be
treated of large volume and complex configuration, by two high frequency
discharges in the form of networks of ramified filaments of plasma between to
capacitive electrodes provided with a sweeping movement along the external
surface of the body to be treated.
29. Process as claimed in any of the preceding claims, wherein the energy
density communicates to the object to be treated by undulating movement is
superior to one per thousand of the increase of thermal energy density
communicated to the object before or after treatment.
30. Process as claimed in any of the preceding claims, wherein the energy
density communicated to the object to be treated by undulating movement is
superior to one per cent of the increase of thermal energy density
communicated to the object before or after treatment.
31. Process as claimed in any of the preceding claims, wherein the amplitude
of the undulating movement is substantially superior to the thickness of the
boundary layer that is formed between the plasma and the surface of the object
during plasma treatment, this effect being accompanied by a turbulent plasma.
32. Device for the realization of a surface treatment process as claimed in one
of claim 1 to 31, wherein it comprises a device for plasma generation and a
vibration pickup arranged so as to measure the vibrations emitted by the object
to be treated, during the plasma surface treatment process.
33. Device for the realization of a Surface treatment process as claimed in one
of claim 1 to 31, wherein it comprises a device for plasma generation and a laser
system that can emit a laser beam across a wall of the object to be treated, and
a sensor for the reflected laser beams or laser beams crossing the wall in order
to detect the number of photons emitted by non-linear effects during passage of
the laser beam across the surface treated, or the decrease in the flux of primary
photons caused by their recombination due to non-linear effects.
34. Device for the realization of a surface treatment process as claimed in one
of claims 1 to 31, wherein it comprises a device for plasma generation and a
liquid bath for immersion of the objects to be treated during the plasma surface
treatment.
35. Device for the realization of a surface treatment process as claimed in
claim 10, wherein it comprises an enclosure with a section intended to house the
objects to be treated, and a section of piston chamber, the sections being
separated by a piston, the piston being able to be rapidly moved within the
enclosure toward the objects to be treated in order to compress the process gas
surrounding the objects to be treated to a pressure above the critical pressure of
plasma creation in the given process gas.
36. Device for the realization of a surface treatment process as claimed in
claim 11, wherein it comprises an enclosure with a section housing the objects to
be treated, and a section of a chamber in compression comprising a compressed
process gas, where the sections of the enclosure are separated by a wall that
can be removed or destroyed.
37. Device as claimed in any one of claims 33 to 36, wherein a vibration
pickup is arranged so as to measure the vibrations emitted by the object to be
treated, during the plasma surface treatment process.
38. Device as claimed in any one of claims 32, 33, 35 to 37, wherein a laser
system that can emit a laser beam across a wall of the object to be treated and
includes a sensor for the reflected laser beams or laser beams crossing the wall
in order to detect the number of photons emitted by non-linear effects during
passage of the laser beam across the surface treated, or the decrease in the flux
of primary photons caused by their recombination due to non-linear effects.
39. Device as claimed in any one of claims 32 or 33, wherein it comprises a
device for cooling the object to be treated, by a flow or projection of a liquid over
the object to be treated.
40. Device as claimed in any one of the preceding claim, wherein the
cooling device blows air or another gas over the object to be treated, during or
just after plasma application to the surface to be treated.
41. Device as claimed in any one of claims 37 to 40, wherein the device for
plasma generation comprises an electrode that can be moved relative to the
object to be treated.
42. Device as claimed in any one of claims 32 to 34, 39 to 41, wherein the
device for plasma generation comprises an electrode comprising a duct for gas
feed.
43. Device as claimed in any one of the preceding claim, wherein the
electrode comprises a plurality of gas feed ducts.
44. Device as claimed in any one of the preceding claims, wherein the
electrode comprises a rotating feeding head onto which the duct or ducts of
process gas supply for the treatment of essentially axisymmetric containers are
mounted.
45. Device as claimed in any one of claims 41 to 44, wherein the angle of
inclination of the process gas supply ducts is adjustable so that the angle of
incidence of the process gas can be adjusted relative to the surface to be
treated.
46. Device as claimed in any one of claims 41 to 44, wherein the process gas
supply ducts for the treatment of essentially axisymmetric containers are
essentially arranged in the form of a cone for distributing the process gas in an
essentially axisymmetric manner.
47. Device for the realization of a surface treatment process as claimed in any
one of the above claims 1 to 31, wherein that a device for plasma generation by
electric discharge with an electrode in the form of a conducting liquid jet that can
be directed against one wall of the object to be treated, on the side opposite to
the surface to be treated.
48. Device as claimed in any one of the preceding claims, wherein it
comprises the supplementary features of one or more of claims 32 to 34.
49. Device as claimed in claim 32 to 48, wherein it comprises means for
recording and checking the plasma parameters during the treatment.
50. Device as claimed in any of the preceding claim, wherein the means for
recording and checking the parameters are able to record and/or check the rising
flank of the electric voltage and/or electric current pulse.
51. Device as claimed in claim 49 or 50, wherein the means for recording and
checking the parameters are able to record and/ or check the amplitude and
length of the pulses as well as of the pause between pulses.
52. Device as claimed in claim 49, 50 or 51, wherein the means for recording
and checking the parameters are able to record and/ or check the amplitude and
frequency of the acoustic vibrations emitted by the object to be treated.+
53. Device as claimed in claim 49, 50, 51 or 52, wherein the means for
recording and checking the parameters are able to record and/or check the
temperature of the object to be treated.
54. Method of producing powder comprising the generation of a pulsed
plasma in a chamber comprising plasma chemical gases, and the simultaneous
generation of acoustic vibrations in the chamber, the gases being decomposed
by the plasma to form clusters whose degree of structuration is determined by
the simultaneous action of the plasma and acoustic vibrations.
55. Method as claimed in any of the preceding claim, wherein the plasma is
vibrated acoustically by an external vibration generator.
56. Method as claimed in claim 54 or 57, wherein ultrasound is generated.
57. Method as claimed in claim 54, 55, or 56, wherein the frequency and
amplitude of vibrations are measured by means of a vibration sensor.
58. Method as claimed in claim 54 to 57, wherein the plasma is vibrated by
shock waves produced during the plasma creation process.
59. Method as claimed in any of claims 54 to 58, wherein the duration of each
plasma pulse is superior to the period of a vibration cycle.
60. Method as claimed in claim 54 to 59, wherein the pulses are generated by
electrical current pulses that are uni-polar or at high frequency.
61. Plasma treatment process of an object's surface to be treated,
substantially as herein described, particularly with reference to the
accompanying drawings.
62. Device for the realization of a surface treatment process, substantially as
herein described, particularly with reference to and as illustrated in the
accompanying drawings.
The invention relates to a plasma surface treatment method for the surface of an
object or particles to be treated consisting in creating a plasma and applying said
plasma against the surface to be treated. The inventive method is characterized
in that the surface to be treated is excited or the plasma is made to vibrate
acoustically in order to create a relative wave motion between the plasma and
the surface to be treated.

Documents:

1223-kolnp-2003-granted-abstract.pdf

1223-kolnp-2003-granted-assignment.pdf

1223-kolnp-2003-granted-claims.pdf

1223-kolnp-2003-granted-description (complete).pdf

1223-kolnp-2003-granted-drawings.pdf

1223-kolnp-2003-granted-examination report.pdf

1223-kolnp-2003-granted-form 1.pdf

1223-kolnp-2003-granted-form 18.pdf

1223-kolnp-2003-granted-form 2.pdf

1223-kolnp-2003-granted-form 3.pdf

1223-kolnp-2003-granted-form 5.pdf

1223-kolnp-2003-granted-gpa.pdf

1223-kolnp-2003-granted-reply to examination report.pdf

1223-kolnp-2003-granted-specification.pdf


Patent Number 226715
Indian Patent Application Number 1223/KOLNP/2003
PG Journal Number 52/2008
Publication Date 26-Dec-2008
Grant Date 24-Dec-2008
Date of Filing 24-Sep-2003
Name of Patentee APIT CORP. S.A.
Applicant Address 10 AVENUE DE FRANCE, CH-1950 SION
Inventors:
# Inventor's Name Inventor's Address
1 SAMSONOV MICKHAIL 10 RUE DE LICHTENBERG, F-67400 ILLKIRCH-GRAFFEN STADEN
2 KOULIK PAVEL 29 RUE DU, GLOECKELSBERG, F-67113 BLAESHEIM
3 CHEREPANOV ALEXANDER 16B DOMAINE DE L'ILE, F-67400 ILLKIRCH-GRAFFEN STADEN
4 PETROV EVGUENII 14 DOMAINE DE L'ILE, F-67400 ILLKIRCH-GRAFFEN STADEN
PCT International Classification Number A61L
PCT International Application Number PCT/IB02/01001
PCT International Filing date 2002-03-26
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 01810318.4 2001-03-27 EUROPEAN UNION
2 01120974.9 2001-08-31 EUROPEAN UNION
3 01810915.7 2001-09-20 EUROPEAN UNION