WO2006108395A1 - Vorrichtung und verfahren zur plasmabeschichtung - Google Patents
Vorrichtung und verfahren zur plasmabeschichtung Download PDFInfo
- Publication number
- WO2006108395A1 WO2006108395A1 PCT/DE2006/000638 DE2006000638W WO2006108395A1 WO 2006108395 A1 WO2006108395 A1 WO 2006108395A1 DE 2006000638 W DE2006000638 W DE 2006000638W WO 2006108395 A1 WO2006108395 A1 WO 2006108395A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- component
- plasma
- vacuum chamber
- resonant circuit
- inductance
- Prior art date
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05B—SPRAYING APPARATUS; ATOMISING APPARATUS; NOZZLES
- B05B7/00—Spraying apparatus for discharge of liquids or other fluent materials from two or more sources, e.g. of liquid and air, of powder and gas
- B05B7/16—Spraying apparatus for discharge of liquids or other fluent materials from two or more sources, e.g. of liquid and air, of powder and gas incorporating means for heating or cooling the material to be sprayed
- B05B7/22—Spraying apparatus for discharge of liquids or other fluent materials from two or more sources, e.g. of liquid and air, of powder and gas incorporating means for heating or cooling the material to be sprayed electrically, magnetically or electromagnetically, e.g. by arc
- B05B7/222—Spraying apparatus for discharge of liquids or other fluent materials from two or more sources, e.g. of liquid and air, of powder and gas incorporating means for heating or cooling the material to be sprayed electrically, magnetically or electromagnetically, e.g. by arc using an arc
- B05B7/226—Spraying apparatus for discharge of liquids or other fluent materials from two or more sources, e.g. of liquid and air, of powder and gas incorporating means for heating or cooling the material to be sprayed electrically, magnetically or electromagnetically, e.g. by arc using an arc the material being originally a particulate material
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05H—PLASMA TECHNIQUE; PRODUCTION OF ACCELERATED ELECTRICALLY-CHARGED PARTICLES OR OF NEUTRONS; PRODUCTION OR ACCELERATION OF NEUTRAL MOLECULAR OR ATOMIC BEAMS
- H05H1/00—Generating plasma; Handling plasma
- H05H1/24—Generating plasma
- H05H1/26—Plasma torches
- H05H1/32—Plasma torches using an arc
- H05H1/42—Plasma torches using an arc with provisions for introducing materials into the plasma, e.g. powder, liquid
Definitions
- the invention is based on a device and a method for plasma coating large-volume components by means of a high-frequency electromagnetic field.
- the functionality and the properties of the. can be selected by appropriate choice of the plasma parameters such as pressure, temperature and plasma composition
- Surface can be specifically influenced and changed.
- Methods are known in the art for treating, modifying or coating a surface of any material that uses particle or energy streams from a plasma. These include, among others, plasma spraying, arc plasma melting,
- Plasma heat treatment process plasma CVD process and
- Plasma cleaning The modification of the functionality of workpiece surfaces takes place by targeted attack of plasma particles. This can be done by interaction with particles having certain chemical properties or by the action of radiation emitted by the plasma.
- the coating material is added by supplying energy in the vapor or gaseous state and deposited from the vapor or gas phase on the component.
- a plasma torch is used to generate a plasma.
- a flowing gas is passed through an arc ionized and heated to temperatures of 10,000 to 20,000 K.
- the flowing gas is ionized by applying a high frequency electromagnetic field to a cylindrical coil.
- a cylindrical discharge vessel which is made of a dielectric material, a relatively dense plasma with a high energy density is formed.
- plasma temperatures of up to 20,000 K can be achieved.
- thermal plasmas described above are suitable for the machining of components that are characterized by a certain temperature capability. For components made of plastic or already painted components, which may be exposed to a maximum temperature of only 100-200 0 C, such methods can not be used.
- high frequency generators are also used. Their frequency range is between a few hundred kilohertz and several ten gigahertz.
- the plasma is made swell on the surfaces of electrodes or antennas and spreads out into the room.
- the coating material is removed by sputtering from a so-called sputtering target or vaporized in the physical vapor deposition process, PVD for short, and then deposits on the component.
- PVD physical vapor deposition process
- a disadvantage is that the composition and the temperature of the plasma changes with increasing distance from the plasma torch. This makes it difficult to deposit a uniform layer over the entire surface of the component.
- only coatings of a limited number of brush materials can be produced by these methods.
- a disadvantage of the plasma treatment of the entire surface of a large component with the PVD method is that the mean free path length must be large and the pressure in the vacuum chamber must be very small. This is associated with a high technical and financial expense due to the size of the component associated size of the vacuum chamber.
- the known methods are not suitable for the treatment of gaps, joints, cavities and undercuts, which occur in the bodies of vehicles.
- the surfaces facing away from the plasma source are not exposed to a uniform plasma. On the surfaces facing the plasma source, uniform processing can not be guaranteed due to the high gradients. This is especially true for machining operations that are dominated by radiation processes.
- the device according to the invention with the features of claim 1 and the method according to the invention with the features of claim 15 have the advantage that large components can be subjected over the entire surface of a uniformly acting plasma treatment and provided with a uniform coating.
- the treatment and coating includes both the outer and the inner surfaces. Columns, joints, cavities and undercuts are also processed. Such areas occur in particular on components which are composed of several elements.
- the device according to the invention and the method according to the invention can be used with any components of different sizes.
- the component is introduced into a vacuum chamber of the plasma coating apparatus. Subsequently, the component is connected to a resonant circuit with high-frequency generator. For this purpose, either one pole or two poles of the resonant circuit are connected to the component. In the first case, the second pole is earthed. The component thus forms part of the resonant circuit.
- the high-frequency alternating current flows through the component.
- the inductance and the capacitance of the component thereby influence the inductance and the capacitance of the resonant circuit.
- the resonant circuit which consists of the component to be machined and its own capacitances and inductances, must be adapted accordingly.
- the adjustment of the capacitances and inductances of the resonant circuit can be done either manually or automatically.
- an automatic setting first the capacitance and the inductance of the component are determined.
- the variation of the capacitances and inductances of the resonant circuit causes a change of the frequency.
- an additional plasma torch which is connected to the vacuum chamber is ignited and the coating material (s) is introduced into the plasma jet.
- the one with the Coating plasma jet then expands into the vacuum chamber and interacts with the plasma in the vicinity of the device. In this case, a homogeneous and uniform coating of the coating materials is deposited on the entire surface of the component.
- one or more plasma torches can be arranged on the vacuum chamber.
- a plurality of openings for connecting the plasma torches may be provided on the vacuum chamber. If the openings can be closed by flanges in the event of non-use.
- a chemical treatment of the surface of the component can be carried out before the plasma coating.
- the plasma radiation can influence the physical properties of the surface. These include, for example, the crosslinking of UV varnishes. Due to the formation of surface discharges electrical effects occur on the surface, which can be used for their processing.
- the distance between the electrodes and the component does not have to be set.
- the plasma is generated by the formation of eddy currents on the surface of the component.
- the alternating current flowing through the component causes oscillating magnetic fields, which propagate depending on the geometry of the component in its environment.
- the temporal change of the magnetic field leads to electric fields, which are responsible for the generation and maintenance of the plasma in the environment of the component.
- the plasma which is generated by means of the resonant circuit on the surface of the component, has a relatively low energy density.
- the associated temperature is usually not sufficient alone to vaporize a coating material.
- the additional plasma torch ensures that any coating materials in the vapor or gas phase can be made available. Whether a material can be used as a coating material does not depend on the boiling temperature but on the energy density in the additional plasma torch. Examples of coating materials are titanium dioxide, titanium-H-butoxide, ceramics, zirconium chloride or oxychlorides.
- the coating materials can be introduced in the solid, liquid or gaseous state via the feed devices into the plasma of the plasma torch.
- the coating materials may be present in pure form or as a chemical compound in combination with other substances. Solid coating materials can also be present in solution. This provides an additional extension of the spectrum of possible coating materials.
- the additional plasma torch is preferably an arc plasma torch having a cathode and an anode.
- Arc plasma torch the working gas is initially at a very high
- the temperature and pressure prevailing in the plasma torch are adjusted according to the chemical requirements resulting from the particular coating. This is done, for example, by the choice of the gas flow, the power of the direct current and a suitable one
- the transport device for introducing the component into the vacuum chamber on one or more rails and a drive.
- the rails can be adapted to the component.
- an electrical insulation is provided to isolate the component against the vacuum chamber.
- the resonant circuit has high-frequency lines.
- the vacuum chamber bushings are provided with electrical insulation for the high-frequency lines.
- metal sheets, tubes and / or grids are provided in the vacuum chamber.
- the component represents an antenna, from which electromagnetic waves are radiated into the space of the vacuum chamber. This effect can be supported by other antenna-like elements in the vicinity of the component. These include metal sheets or grids. Spirally arranged pipes, for example made of copper, can also bring about this effect.
- the electromagnetic waves are coupled into these parts and provide additional plasma generation at a certain distance from the component. In this way, the radiation flux of the plasma can be controlled in the direction of the component.
- the arc plasma torch on several expansion stages for the mixing of different coating materials.
- Each expansion stage has a supply device for introducing a gas, a liquid and / or a powder into the plasma.
- the different expansion stages are arranged in the beam direction of the plasma jet in succession.
- the cross sections of the different expansion stages can be different.
- the cross section increases from expansion stage to expansion stage in beam direction.
- the choice of a suitable expansion ratio also ensures that the plasma provided with the coating materials flows into the vacuum chamber and not in the direction of the cathode of the plasma torch.
- the plasma jet cools before interacting with the plasma on the device.
- a mixing chamber adjoins the expansion stages in the flow direction.
- a mixing of different coating materials is achieved by turbulence of the plasma jet.
- the plasma torch together with the mixing chamber form a double Laval nozzle.
- the cross-section of the mixing chamber narrows in the flow direction to then expand again and narrow again.
- the mixing chamber is connected as an anode or placed on the same potential as the anode. This keeps the temperature in the plasma torch high.
- the chemical reactions in the plasma torch can be controlled in this way.
- a working gas is added to the vacuum chamber.
- the pressure in the vacuum chamber can be increased. For example, pressures of up to 1,000 Pa are possible.
- the working gas interacts chemically with the surface of the component. Depending on the requirements, different gases can be used as working gases.
- an additional liquid is evaporated and added via a valve in the vacuum chamber.
- the liquid vapor fulfills the same task as the working gases.
- an alternating voltage of 0.1 to 10 MHz is fed into the resonant circuit via the high-frequency generator. Particularly preferably, the alternating voltage is between 1 and 4 MHz.
- the vacuum chamber is evacuated to a pressure between 0.05 and 1000 Pa.
- the working pressure can be increased to a few 10 mbar depending on the application.
- FIGS. 1 and 2 show a circuit diagram of the device according to FIGS. 1 and 2,
- FIG. 4 shows a device for plasma treatment in a view from the side, Figure 5 arc plasma torch in longitudinal section,
- FIG. 6 Schematic diagram of the arc plasma torch according to FIG. 5.
- Figures 1 and 2 show a device for plasma coating in a view from the front and from above.
- a component 1 to be machined is retracted into a vacuum chamber 3 via rails 2 and rollers not visible in the drawing.
- an insulation 4 is provided, which isolates the component 1 against the vacuum chamber 3.
- the contact between a high-frequency resonant circuit and the component is closed. This is done via a sliding contact, which is not recognizable in the drawing, and which adheres to the component 1 by positive locking.
- the component is now part of the resonant circuit.
- the resonant circuit is apart from the component 1 from a high-frequency generator 5 with a feedback coil 11 shown in Figure 3, a coaxial cable 6, an outer resonant circuit 7 and a high-frequency supply line 8, at the ends of the sliding contact is provided.
- a high-frequency feedthrough 9 is provided for the high-frequency supply line 8.
- a reflector 10 is provided for the plasma.
- FIG 3 shows schematically the circuit diagram of the device according to Figures 1 and 2.
- the circuit allows the optimization of the plasma treatment.
- the high frequency generator 5 supplies the resonant circuit via a coaxial cable 6 with alternating current.
- the high-frequency generator 5 has a feedback coil 11 whose inductance is automatically adjustable.
- three capacitors 12 are provided in the outer resonant circuit 7 . They can all or only partially be integrated into the resonant circuit to change the total capacity.
- the inductance of the resonant circuit is in essentially determined by the component 1.
- the component 1 is connected via the high-frequency supply line 8 to the outer resonant circuit 7.
- a coil 13 is provided on the outer resonant circuit.
- a further coil 14 is provided with a tap on the high-frequency supply line 8 directly to the coil 13. This is integrated only when necessary to adapt the total inductance in the resonant circuit.
- the high-frequency supply line 8a is used instead of the high-frequency supply line 8.
- the component 1 can optionally be earthed via the ground line 15.
- the contact between component 1 and resonant circuit is checked. If the contact meets the requirements, the vacuum chamber 3 is evacuated. After the pressure in the vacuum chamber 3 has reached a certain value dependent on the type of treatment, high-frequency alternating current is fed into the resonant circuit. On the surface of the component 1, the plasma is created, which is needed for the treatment of the component.
- the control of the plasma influence on the surface of the component takes place by controlling the anode voltage of a transmitter tube 16, which feeds the alternating current into the resonant circuit.
- the transmitter tube is not shown in the drawing.
- the efficiency of the coupling of the electrical power into the plasma is controlled.
- the fine tuning of the resonant circuit during the plasma treatment is carried out by varying the inductance of the feedback coil of the resonant circuit.
- there is also the option of making the coarse tuning of the system by inserting additional inductors 14 or capacitors 12 in the resonant circuit to the component to be machined.
- FIG. 4 shows the device for plasma coating according to FIGS. 1 and 2 in a view from the side.
- FIGS. 1 and 2 there are several in the representation according to FIG arranged one above the other components 17 in the vacuum chamber 3.
- the arc plasma torch 19 can be seen, which generates the plasma jet 20.
- the plasma jet 20 extends above the components 17 in the vacuum chamber 3.
- the beam profile of the plasma jet 20 widens with increasing distance from the arc plasma torch 19.
- the expansion of the plasma jet 20 depends on the pressure ratio between the pressure in the plasma torch and the pressure in the vacuum chamber. In the case of strong pressure differences, the plasma jet is widened so much that the components are wholly or partly in the plasma jet of the plasma torch. If this is not possible due to the boundary conditions, a second or third plasma torch can be connected to the vacuum chamber if required.
- FIG. 5 shows the plasma torch 19 with a cathode 21, an anode 22 and two expansion stages 23 and 24.
- the cathode has the shape of a cylinder with a cone at its front end.
- the anode 22 is tubular and encloses the cathode 21.
- Cathode 21 and anode 22 are coaxial with each other.
- the gas to be ionized is supplied via the slit-shaped nozzle 25 between the anode and the cathode.
- a first coating material is introduced into the plasma ignited by an arc between the anode 22 and the cathode 21 via a feed device 26.
- a second coating material is introduced into the plasma ignited by an arc between the anode 22 and the cathode 21 via a feed device 27.
- the feeders 26 and 27 are also referred to as precursor feeds. They consist of a perpendicular to the axis of the anode and the cathode extending recess 29 and a funnel-shaped portion 30. Depending on the application, the recess and the funnel-shaped portion may extend at an angle deviating from 90 ° to the axis of the anode and cathode.
- the introduction of the coating materials can also be tangential to the axis of the anode and To the funnel-shaped section 30, a tube or hose with a powder conveyor, a metering pump or a metering valve can be connected. These are not shown in the drawing.
- the two expansion stages differ in their opening cross-section.
- the inner diameter of the second expansion stage 24 is greater than the inner diameter of the first expansion stage 23. This prevents the coating materials introduced by the feeders 26 and 27 from flowing back to the cathode 21.
- the plasma jet 20 provided with the coating materials emerges from the arc plasma burner 19 at the opening 28 and enters the vacuum chamber 3.
- the arc plasma torch 19 with its fastening part 3 is fastened directly to the vacuum chamber 2.
- the first and second expansion stages 23 and 24 are at the same potential as the anode 22. This is shown in FIG.
- the anode 22 the first expansion stage 23 and the second expansion stage 24 are manufactured in one piece. However, it is also possible to provide separate components for this, which can be interconnected. This achieves a modular design.
- the individual expansion stages can in this case be put together depending on the application and coating material.
- the arc plasma torch 19 is ignited as soon as the plasma generated by the resonant circuit and the high-frequency generator 5 has spread to the components 17 in the vacuum chamber 3.
- the plasma jet 20 of the arc plasma torch 19 provided with the coating materials expands through the opening 28 into the vacuum chamber. It interacts with the plasma at the components 17. This results in a uniform deposition of the coating materials on the surfaces of the components 17.
- the arc plasma torch 19 and the high-frequency generator 5 are turned off.
- the arc plasma burner 19 is first switched off and then the high-frequency generator 5 with a certain time delay. Only when both plasma torches are switched off, the vacuum chamber 3 is vented. The contact with the resonant circuit is released and the component 1 or the components 17 are transported out of the vacuum chamber 3.
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- Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Plasma & Fusion (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Electromagnetism (AREA)
- Plasma Technology (AREA)
- Coating By Spraying Or Casting (AREA)
- Nozzles (AREA)
Abstract
Description
Claims
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2008505728A JP5305900B2 (ja) | 2005-04-11 | 2006-04-11 | プラズマコーティングを施す装置および方法 |
EP06722775.1A EP1872637B1 (de) | 2005-04-11 | 2006-04-11 | Vorrichtung und verfahren zur plasmabeschichtung |
DE112006001571T DE112006001571A5 (de) | 2005-04-11 | 2006-04-11 | Vorrichtung und Verfahren zur Plasmabeschichtung |
CN2006800117659A CN101156504B (zh) | 2005-04-11 | 2006-04-11 | 等离子喷涂设备及方法 |
US11/918,187 US20090123662A1 (en) | 2005-04-11 | 2006-04-11 | Plasma Coating Device and Method |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE102005016582 | 2005-04-11 | ||
DE102005016582.6 | 2005-04-11 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2006108395A1 true WO2006108395A1 (de) | 2006-10-19 |
Family
ID=36778061
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/DE2006/000638 WO2006108395A1 (de) | 2005-04-11 | 2006-04-11 | Vorrichtung und verfahren zur plasmabeschichtung |
Country Status (6)
Country | Link |
---|---|
US (1) | US20090123662A1 (de) |
EP (1) | EP1872637B1 (de) |
JP (1) | JP5305900B2 (de) |
CN (1) | CN101156504B (de) |
DE (1) | DE112006001571A5 (de) |
WO (1) | WO2006108395A1 (de) |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2008110151A2 (de) * | 2007-03-09 | 2008-09-18 | Dr. Laure Plasmatechnologie Gmbh | VERFAHREN UND VORRICHTUNG ZUR PLASMAGESTÜTZTEN OBERFLÄCHENBEHANDLUNG GROßVOLUMIGER BAUTEILE |
WO2008104160A3 (de) * | 2007-02-26 | 2008-11-13 | Laure Plasmatechnologie Gmbh D | Vorrichtung und ein verfahren zur plasmagestützten beschichtung und oberflächenbehandlung grossvolumiger bauteile |
EP2711441A1 (de) | 2012-09-21 | 2014-03-26 | Reinhausen Plasma GmbH | Vorrichtung und Verfahren zur Erzeugung eines Schichtsystems |
CN106507574A (zh) * | 2016-09-29 | 2017-03-15 | 成都真火科技有限公司 | 一种用于航空材料的喷涂方法 |
CN115608580A (zh) * | 2022-11-03 | 2023-01-17 | 天津双微电子科技有限公司 | 一种等离子涂敷结构 |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE102009010497A1 (de) * | 2008-12-19 | 2010-08-05 | J-Fiber Gmbh | Mehrdüsiger rohrförmiger Plasma-Abscheidebrenner zur Herstellung von Vorformen als Halbzeuge für optische Fasern |
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-
2006
- 2006-04-11 JP JP2008505728A patent/JP5305900B2/ja not_active Expired - Fee Related
- 2006-04-11 CN CN2006800117659A patent/CN101156504B/zh not_active Expired - Fee Related
- 2006-04-11 US US11/918,187 patent/US20090123662A1/en not_active Abandoned
- 2006-04-11 WO PCT/DE2006/000638 patent/WO2006108395A1/de active Application Filing
- 2006-04-11 DE DE112006001571T patent/DE112006001571A5/de not_active Withdrawn
- 2006-04-11 EP EP06722775.1A patent/EP1872637B1/de not_active Not-in-force
Patent Citations (6)
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DE4135326C1 (en) | 1991-10-25 | 1993-06-09 | Siemens Ag, 8000 Muenchen, De | Coating components by thermal spraying - using preheating kiln to heat workpiece before plasma spraying in vacuum chamber |
US5810963A (en) * | 1995-09-28 | 1998-09-22 | Kabushiki Kaisha Toshiba | Plasma processing apparatus and method |
US5902563A (en) * | 1997-10-30 | 1999-05-11 | Pl-Limited | RF/VHF plasma diamond growth method and apparatus and materials produced therein |
EP1113711A2 (de) * | 1999-12-31 | 2001-07-04 | GTV-Gesellschaft für thermischen Verschleiss-Schutz mbH | Plasmabrenner und Verfahren zur Erzeugung eines Plasmastrahls |
WO2002085532A1 (en) | 2001-04-24 | 2002-10-31 | Innovative Technology, Inc. | A apparatus and process for solid-state deposition and consolidation of high velocity powder particles using thermal plastic deformation |
WO2005069703A2 (de) * | 2004-01-15 | 2005-07-28 | Dr. Laure Plasmatechnologie Gmbh | Plasmabehandlung grossvolumiger bauteile |
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WO2008104160A3 (de) * | 2007-02-26 | 2008-11-13 | Laure Plasmatechnologie Gmbh D | Vorrichtung und ein verfahren zur plasmagestützten beschichtung und oberflächenbehandlung grossvolumiger bauteile |
JP2010519693A (ja) * | 2007-02-26 | 2010-06-03 | ドクトル・ラウレ・プラスマテヒノロギー・ゲゼルシャフト・ミト・ベシュレンクテル・ハフツング | 体積の大きな構成部品にプラズマ支援によるコーティングおよび表面処理を施す装置および方法 |
WO2008110151A2 (de) * | 2007-03-09 | 2008-09-18 | Dr. Laure Plasmatechnologie Gmbh | VERFAHREN UND VORRICHTUNG ZUR PLASMAGESTÜTZTEN OBERFLÄCHENBEHANDLUNG GROßVOLUMIGER BAUTEILE |
WO2008110151A3 (de) * | 2007-03-09 | 2009-11-19 | Dr. Laure Plasmatechnologie Gmbh | VERFAHREN UND VORRICHTUNG ZUR PLASMAGESTÜTZTEN OBERFLÄCHENBEHANDLUNG GROßVOLUMIGER BAUTEILE |
EP2711441A1 (de) | 2012-09-21 | 2014-03-26 | Reinhausen Plasma GmbH | Vorrichtung und Verfahren zur Erzeugung eines Schichtsystems |
DE102012108919A1 (de) * | 2012-09-21 | 2014-05-15 | Reinhausen Plasma Gmbh | Vorrichtung und Verfahren zur Erzeugung eines Schichtsystems |
CN106507574A (zh) * | 2016-09-29 | 2017-03-15 | 成都真火科技有限公司 | 一种用于航空材料的喷涂方法 |
CN115608580A (zh) * | 2022-11-03 | 2023-01-17 | 天津双微电子科技有限公司 | 一种等离子涂敷结构 |
Also Published As
Publication number | Publication date |
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JP2008538797A (ja) | 2008-11-06 |
US20090123662A1 (en) | 2009-05-14 |
EP1872637A1 (de) | 2008-01-02 |
CN101156504A (zh) | 2008-04-02 |
EP1872637B1 (de) | 2014-05-07 |
CN101156504B (zh) | 2012-07-18 |
JP5305900B2 (ja) | 2013-10-02 |
DE112006001571A5 (de) | 2008-03-27 |
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