The invention relates to a method for continuous atmospheric-pressure plasma treatment of workpieces, in particular boards or sheets of material according to the preamble of claim 1 and/or the preamble of claim 6.
In the finishing industry or in the production of plastic films, the film is activated at the surface by a plasma treatment at atmospheric pressure, also known as a corona treatment. An industrial corona system usually comprises a high-voltage electrode and a counter-electrode designed as a roll which is guided over the plastic film in close proximity thereto. The electrode is arranged parallel to the roll, the electrode being connected to a high voltage of approx. 10 kilovolts at approx. 20-40 kilohertz and the roll being connected to ground potential. Due to the potential difference in the air gap between the high-voltage electrode and the roll with the plastic film, amounting to a few millimeters, a corona discharge develops with a conventional practical power output of 1 to 5 kilowatts per meter. The plastic film is activated by the corona discharge, i.e., oxidized at the surface.
Due to this activation, the surface tension is increased to thereby ensure adequate adhesion of printing inks and adhesives.
With the device described above, thin plastic films can be treated, but materials greater than 6 mm in thickness such as foam, plastic sheeting, plastic sections several centimeters thick or even wooden boards of similar thicknesses cannot be treated in this way. The reason for the restriction is the unequal development of the discharge channels with an increase in the electrode gap which thus results in an irregular activation of the surface of the material.
DE 102 28 506 A1 discloses a method for continuous atmospheric pressure plasma treatment of electrically insulated workpieces that operates by a different principle, but this method includes all of the features of the preamble of claim 1. Thus two barrier electrodes arranged with a distance between them are used here, a plasma discharge is ignited in the gap formed between the barrier electrodes and is then expelled by a gas stream in the direction of the surface to be treated.
In the method disclosed in the aforementioned publication, the plasma acts only along a narrow strip, the width of which corresponds essentially to the width of the gap left between the barrier electrodes on the surface of the workpiece to be treated.
Against this background, the present invention describes a method with which a workpiece can be subjected to an atmospheric pressure plasma treatment continuously along a larger working width.
A first possibility for such a method is defined in claim 1, this method being based on the method disclosed in DE 102 28 506 A1.
An alternative possibility for such a method is described in claim 6.
Advantageous refinements of the method according to claim 2 are specified in greater detail in the dependent claims 2 through 5.
The electrode consists of at least two barrier electrodes but more than two barrier electrodes may also be aligned in rows one after the other, leaving a gap after each.
The surfaces of the barrier electrodes facing the surface of the workpiece to be treated is acted upon by the high voltage. Therefore, due to the effect described above, a plasma discharge is ignited over the entire width of the surface of the workpiece to be treated, this plasma discharge being made possible by the ignition voltage which is reduced, due to the plasma species present in the space between the electrode and the workpiece because of the plasma gas expelled from the gap, thus allowing treatment of the surface of the workpiece over its entire width. This phenomenon is referred to here as “capacitive coupling discharge.”
According to a simple variant, the electrode is composed of two single channel barrier electrodes. According to this invention, as the workpiece approaches the electrode, capacitive coupling occurs due to the dielectric mass of the workpiece as the workpiece is brought to an adjusted distance in proximity to the electrode with a suitable choice of the other parameters (high voltage, atmosphere). Due to the presence of the plasma species formed in the gap between the barrier electrodes and driven out of the gap in the direction of the workpiece surface, a uniform discharge therefore develops between the barrier electrodes and the workpiece resembling a glow discharge in a vacuum plasma. The electrode is operated mainly with air as the process gas, but it may also be operated in foreign gas atmosphere, e.g., in nitrogen or mixtures of nitrogen with other gases such as oxygen, carbon dioxide, hydrogen or noble gases. Due to the discharge, the workpiece surface is oxidized, depending on the type of gas, and/or other chemical groups, e.g., amines, amides or imides are incorporated. Therefore, the surface energy of the workpiece is increased and thus the adhesion of paints, enamels, adhesives or other coatings is improved or made possible. An advantage of this inventive method is in particular the fact that due to the capacitive coupling, the discharge is adapted to the dimensions of the workpiece, i.e., the discharge is ignited primarily on the workpiece surface but not beside it. This results in a location-specific discharge and also leads to savings of the energy required for igniting and maintaining the discharge.
The gap between the barrier electrodes is preferably between 0.5 millimeter and 5 millimeters wide. Gaps of these widths are especially suitable for ignition of the desired plasma with the voltage ranges preferred for performing this method.
The barrier electrodes are preferably made of aluminum oxide ceramic. This material is especially resistant.
The barrier electrodes are made of rectangular tubes each having one or more channels.
The barrier electrodes are preferably arranged on a holding body. However, the barrier electrodes may also be attached to a holding plate by means of electrode carriers via insulators. By sealing off the design space between the barrier electrodes and the holding plate, in this case a chamber is formed into which air or another gas can be fed, to then flow through the gap as a result of the excess pressure which then builds up and to drive the discharge out of the gap in the direction of the workpiece.
With a process management according to claim 2, an additional coating of the workpiece surface with chemical compounds formed from the precursors in the plasma can be achieved.
According to a refinement of the present invention, a counter-electrode is arranged as described in claim 3. The counter-electrode may be formed preferably as a supporting surface designed as an electrode. In the case of thick insulating materials such as sheets, sections, hollow chamber sections, web plates, etc., the counter-electrode may be omitted. Materials having a low dielectric mass such as plastic films, foams, air cushion film, paper, plastic fibers or natural fibers, granules or powders should be treated with a counter-electrode. The counter-electrode may serve as a dielectric mass (roller, conveyor belt) and/or as a ground metal roll or plate with a dielectric (silicone or ceramic) or may be designed without a dielectric. In the case of a dielectric roll, treatment of the back side is prevented or greatly suppressed in treatment of plastic films when there are indentations in the roll in the case of a dielectric roll with a capacitive coupling discharge. A counter-electrode can also be an electrode designed in mirror image to the electrode producing the discharge. Then the workpiece is passed between two electrodes. This also allows two-sided treatment of the substrate.
To create a high voltage as is necessary for ignition of the plasma discharge, preferably a symmetrical transformer with a primary coil connected to a generator and with two secondary coils each connected to one of the barrier electrodes is used (claim 4). Instead of operation with one shared transformer, operation with two separate transformers is also possible. They may be operated in synchronized operation or in push-pull operation.
In the case of electrically conductive materials such as metallized plastic films, the high voltage is reduced to one-half by a symmetrical transformer. This prevents damage to the thin metal layer by the plasma discharge.
To be able to reliably divert the ozone and other byproducts formed in the plasma discharge from the processing site, the electrode is preferably arranged in a tunnel-like housing that is open on the side facing the top side of the workpiece and the housing is connected to a suction exhaust (see claim 5).
An alternative method which solves the same problem as described above does not rely on a refinement of the state of the art according to DE 102 28 506 A1, but instead uses an alternative approach. This method is characterized in claim 6.
The essential invention of the method here consists of controlling the ignition of plasma in a certain range through the type of atmosphere in this area and adjusting a suitable high-voltage accordingly. In this variant, a plasma should be ignited only on the side of the sheet or board of material that is opposite the electrode. To do so, in the area between the electrode and the first side of the workpiece, a first atmosphere is established in which a plasma does not yet ignite at a selected high voltage. On the opposite side of the sheet of material, a second atmosphere differing from the first atmosphere is established in which a plasma ignition can already take place, induced by the high voltage applied by the electrode. Thus in a targeted manner, a plasma is ignited only on the “back side” of the sheet or board of material so that a large area plasma treatment is performed there. Here again, this is a “capacitively coupling discharge” in the sense of the present invention, with the discharge also over the entire width and length of the electrodes in this example, but limited to the dimensions of the respective material to be treated.
Additional advantages and features of the invention are derived from the following description of the invention on the basis of exemplary embodiments depicted in the figures, in which
a and 4b show two possible wiring variants of an alternative embodiment of an electrode with two double-channel barrier electrodes;
In the figures, the same or similar elements are labeled with the same reference numerals.
In this example, a sinusoidal voltage between 10 and 60 kilovolts with a frequency of 1 to 100 kilohertz, preferably 5 to 30 kilohertz is used. The voltage may also be pulsed. Due to the symmetrical transformer, the voltage is applied uniformly to the two barrier electrodes 1a, 1b so that a plasma can be ignited in the gap 12. The gap 12 has a gap width of 0.5 to 5 millimeters, preferably 1 millimeter. Due to the flow of the gas 11 into the gap 12 and/or through the gap in the direction of the surface of the workpiece 13, the ignited plasma 4 is conveyed in the direction of the surface of the workpiece 13 that is to be treated. In the plasma gas, the ignition voltage is reduced. Therefore, in approach of the workpiece 13 to a distance of 1 millimeter to 20 millimeters from the electrodes, there is a capacitive coupling due to the dielectric mass of the workpiece 13 and thus a uniform discharge 4 developments between the surface of the workpiece 13 that is to be treated and the facing surfaces of the barrier electrodes 1a, 1b. This discharge is like a glow discharge in a vacuum plasma. Due to the capacitive coupling, the discharge 4 is adapted in its dimensions to the dimensions of the workpiece, i.e., the discharge 4 ignites primarily on the workpiece surface and not beside it. This is indicated schematically in
During operation of the device, the workpiece 13 has been moved beneath the electrodes formed by the two barrier electrodes 1a, 1b so that a continuous plasma treatment of the surface of the workpiece 13 facing the electrode can be achieved along its entire width.
Due to the gas 11 (e.g., air) which is supplied via the holding body 2, not only is the discharge deflected out of the gap 12 in the direction of the surface of the workpiece 13 that is to be treated, but at the same barrier electrodes 1a, 1b are also cooled.
The thermal stress on the workpiece to be treated is low. After a treatment with the device depicted in
In addition to an electric wiring for a so-called capacitively coupling discharge, like that shown in
With a modified device that has a double-channel tube instead of each of two simple rectangular tubes as barrier electrodes 1a, 1b, capacitively coupling discharges can be achieved (see
In these cases, the barrier electrodes 1 are implemented by two double-channel tubes, each being equipped with conductors 3. The barrier electrodes are either connected to the symmetrical transformer in parallel, as illustrated in
It is important for the precursors 14 not to be fed between the electrodes, which are connected to the high voltage, in order to prevent the latter from being coated.
Finally,
This shows how an electrode, which in this case is made up of a double-channel barrier electrode 1a, 1b, is arranged on one side of a workpiece 13 (a sheet or panel of material) and a housing 9 is arranged on the opposite of the workpiece 13 with respect to the electrodes 1a, 1b. An atmosphere fed into the housing 9 is such that, when an ac high voltage is applied to the electrodes 1a, 1b, this atmosphere allows ignition of a plasma discharge 4 on this side of the workpiece 13, with a different accordingly prevailing in the area between the electrodes 1a, 1b and the workpiece 13 to suppress a plasma discharge. In this way the workpiece 13 is coated over a large area of the “back side” which is opposite the electrodes 1a, 1b. The atmosphere in the housing 9 is also removed by suction in this method to prevent unwanted plasma products, especially ozone, from entering the environment. This figure additionally shows how precursors 14 are introduced into the area of the plasma discharge 4. This is possible but not necessary for the inventive method. This method functions equally well without the introduction of precursors.
The electrodes 1a, 1b may also be, for example, an electrode formed by two individual barrier electrodes separated from one another by a gap (an electrode pair). As long as the gap is not too great, a continuous plasma discharge will still develop on the side of the workpiece 13 facing the housing 9, producing a desired surface change on this side of the workpiece.
Other possible applications are conceivable, for example, for internal treatment and/or internal coating of planar three-dimensional components, where electrically insulated workpieces having multiple channels are treated and coated in the interior. This is done by passing a noble gas such as argon through the channels, thereby lowering the ignition voltage according to Paschen's law so that the discharge is ignited in the interior. As already described above, the capacitively coupling discharge is ignited mainly on the workpiece and not in the gas space beside it and therefore is ignited mainly in the channels of the workpiece. If the carrier gas stream is provided with the vapor and/or aerosol of a precursor, then layers are deposited in the channels. In the treatment, the workpiece lies on a counter-electrode. Instead of the pure noble gas, mixtures with air, nitrogen, oxygen and the like may also be used.
Furthermore, a capacitive coupling may be performed in a large volume reaction chamber. The plasma discharge is ignited throughout the entire chamber in the case of a large volume chamber through which a noble gas flows, by attaching the barrier electrodes through the capacitive coupling described above. Depending on the size of the chamber, several electrodes may be necessary. Instead of a pure noble gas, mixtures with air and nitrogen, oxygen and the like may again be used here. Here again, precursors may be added to the carrier gas in the case when coating is desired.
In this reaction, it is also conceivable to treat melts on an extruder. Polymer melts can also be treated with a capacitively coupling discharge shortly after discharge from an extruder nozzle to thereby ensure adhesion to a web to be coated.
It is also possible with the inventive device and/or with the inventive method to activate liquids in the mode of the capacitively coupling plasma discharge. Then chemical reactions may be induced at the plasma-liquid interface, their products then being able to diffuse into the liquid. It is also possible to crosslink thin liquid films by using a plasma discharge according to this invention.
Description of Treatment Example:
1. Treatment not Including the Back Side by Capacitively Coupling Discharge
An LDPE film with a surface energy (before the plasma treatment) of 30 mN/m on both sides was plasma treated on the side facing the barrier electrodes. The LDPE film was freely clamped, i.e., no counter-electrode was used. The plasma treatment was performed with a pair of electrodes according to
An electric energy of 500 watts was applied to the double barrier electrode at a frequency of the ac high voltage of 8 kilohertz. Blowing air was fed into the gap between the two double-channel tubes of the double barrier electrodes at essentially atmospheric pressure. Under the aforementioned boundary conditions, the plasma between the barrier electrodes ignited and was expelled by the blowing air onto the LDPE film. The ignition voltage in this range was reduced due to the plasma species blown out into the interspace between the double barrier electrode and LDPE film to such an extent that a “secondary ignition” of a large area plasma was ignited in the entire area between the surfaces of the barrier electrodes facing the surface of the LDPE film and the surfaces facing the film (remote discharge). Ten treatments were performed in this way.
The surface energy was measured with test inks according to the DIN ISO 8296.
On the basis of the plasma treatment described above, on the barrier electrode side of the LDPE film, an increase in the surface energy to 42 mN/m could be achieved through a capacitively coupling discharge; this is a typical value for a print pretreatment. The surface energy on the side of the LDPE film facing away from the barrier electrodes (back side of the film) still amounted to 30 mN/m. Thus, no treatment has taken place here.
2. Treatment of Web Plates
A 7.5 mm thick polypropylene web plate with a surface energy (before the plasma treatment) of 30 mN/m on both sides was plasma treated on the side facing the barrier electrodes. This was done by freely clamping the polypropylene web plate, i.e., no counter-electrode was used.
The plasma treatment was performed with a pair of double-channel tubes according to
The web plate was moved beneath the electrode system using a linear table at the rate of 10 m/min.
The electric energy applied to the double barrier electrode was 500 watts at a frequency of the ac high voltage of 8 kilohertz. The distance between the barrier electrodes and the web plate was 1.0 mm. Blowing air was fed into the gap between the two double-channel tubes of the double barrier electrodes.
Under the boundary conditions defined above, the plasma ignited between the barrier electrodes and was expelled onto the web plate by the blowing air. The ignition voltage was reduced in this area due to the plasma species blown out into the interspace between the double barrier electrodes and the web plate until a “secondary ignition” of a large area plasma was ignited in the entire area between the surfaces of the barrier electrodes facing the plate and the surface of the web plate (remote discharge). Two treatments were performed.
The surface energy is measured with test inks according to DIN ISO 8296.
This plasma treatment resulted in an increase in the surface energy to 50 mN/m owing to the capacitively coupling discharge on the barrier electrode side of the polypropylene web plate; this is a typical value for adhesive bondability. The back side of the web plate did not receive any treatment and the value of the surface energy remained at the original level of 30 mN/m.
1
a, b Barrier electrode
2 Holding body
3 Electric conductor
4 Plasma discharge
5 Transformer
6 Secondary coil
7 Generator
8 Primary coil
9 Housing
10 Suction
11 Gas
12 Gap
13 Workpiece
14 Precursor
15 Electric mass
P Arrow
Number | Date | Country | Kind |
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10 2005 029 360.3 | Jun 2005 | DE | national |
Filing Document | Filing Date | Country | Kind | 371c Date |
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PCT/EP2006/005839 | 6/19/2006 | WO | 00 | 12/20/2007 |