EP1785508A2 - Method of manufacturing a photocatalyst active layer - Google Patents

Method of manufacturing a photocatalyst active layer Download PDF

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Publication number
EP1785508A2
EP1785508A2 EP06022877A EP06022877A EP1785508A2 EP 1785508 A2 EP1785508 A2 EP 1785508A2 EP 06022877 A EP06022877 A EP 06022877A EP 06022877 A EP06022877 A EP 06022877A EP 1785508 A2 EP1785508 A2 EP 1785508A2
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Prior art keywords
metal
cold gas
photocatalytically active
particles
powder
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German (de)
French (fr)
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EP1785508A3 (en
EP1785508B1 (en
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Peter Heinrich
Heinrich Prof. Dr. Kreye
Tobias Schmidt
Frank Dr. Gärtner
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Linde GmbH
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Linde GmbH
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C24/00—Coating starting from inorganic powder
    • C23C24/02—Coating starting from inorganic powder by application of pressure only
    • C23C24/04—Impact or kinetic deposition of particles

Definitions

  • the invention relates to a method for the production of metallic objects, such as films, sheets or moldings, with photocatalytically active surface according to the preamble of claim 1.
  • the peculiarity of the photocatalytically active components mainly titanium dioxide is to break the bonds in the molecules of pollutants and to decompose the substances in question into harmless, simply structured reaction products.
  • the object of the invention is to improve a corresponding process for the production of photocatalytically active layers on metals in such a way that more adhesive, long-term stable layers are produced.
  • This object is achieved in that instead of the pure oxide ceramic, a mixture of oxide ceramic and metallic powder is injected.
  • the injection of hard ceramic with a metal mixture has the advantage that there are always components that can deform when hitting. Especially the metal parts deform on impact, forming a new matter that penetrates into the existing layer, thus increasing the adhesion and the resistance.
  • the metal particles penetrate into the gaps, but also penetrates a metal impinging ceramic particles into the metal and is thereby enclosed by the metal and firmly connected to the metal.
  • metals and metal alloys in question are virtually all metals and metal alloys in question, which can be injected without ceramic additive.
  • Tuned to the application of the photocatalytic layer are e.g. Metals such as aluminum and copper or their alloys are interesting, which can be easily deformed (flexible tapes). Aluminum and copper are also interesting if the photocatalytically active layer should have good electrical conductivity and good thermal conductivity. In particularly aggressive environments, corrosion resistant nickel alloys or tantalum can be used.
  • the size of the particles can be in the range from 3 to 100 ⁇ m, both in the case of the metallic component and in the case of the ceramic component, and preferably in the range of 10 to 50 ⁇ m in the case of the metallic component.
  • spraying with a high-pressure system is usually carried out at pressures of 20 to 40 bar and gas temperatures of 100 to 600 ° C.
  • spraying with so-called portable devices is operated with pressures up to 10 bar and gas temperature of 300 to 600 ° C.
  • Titanium dioxide has proved to be particularly preferred as the ceramic material.
  • This powder occurs in different crystal structures, with the photocatalytically active phase anatase (anatase) being metastable. When heated to temperatures in the range 600 to 800 ° C, this phase converts to the thermodynamically more stable phase rutile, which, however, has a significantly lower efficiency than photocatalyst. Such a conversion and impairment of the photocatalytic properties can not be avoided in plasma spraying and HVOF spraying. In the case of the cold gas spraying according to the invention, by contrast, the photocatalytically active phase anatase remains fully preserved since the temperatures of the gas used for spraying are below 600 ° C.
  • anatase it is desirable to shift the photocatalytic effectiveness of the material from the UV range into the range of visible light by modifying or doping the titanium dioxide. This would significantly improve the effectiveness as a photocatalyst in daylight.
  • the photocatalytic effectiveness of anatase is greater when this material is in the nanocrystalline state, i. a powder or a layer of crystals whose dimensions are well below one micron or below 100 nm. Both developments are contrary to cold gas spraying, since the heating in this process is so low that the modified or doped state is retained and the extremely small crystals do not grow in the injection process.
  • an agglomerated (agglomerated) powder may also be used in which each particle consists of many small ceramic oxide and metal particles.
  • Small particles in the size of, for example, 0.5 to 2 ⁇ m are agglomerated by the spray-drying method known and practiced in the art into larger particles of 3 to 100 ⁇ m in diameter so that each individual particle then consists of smaller particles of both components. This happens, for example, in that the small particles are provided with an organic binder and the suspension is then dried in a stream of hot air or gas. The binder evaporates and the smaller particles are "glued together" or connected to one another by diffusion processes.
  • a powder in which the oxide-ceramic particles are each coated with a metal or a metal alloy. This coated powder is then applied to the metallic or ceramic substrates by cold gas spraying. In this case, the layer is abraded or ground in a second step by mechanical or chemical post-processing in order to expose the titanium dioxide, which is still encased in the shell after spraying, on the layer surface.
  • the metal content should be between 10% and 90%. Preferably between 30% and 60%.
  • the catalytic effect of the metallic surface is already present when the surface is occupied in a monolayer of titanium dioxide particles. This even if the monolayer is not nationwide. Surface coverage ranges from 5%, with 5-100% exhibiting a photocatalytic effect, wherein preferably a surface coverage of between 30 and 80% is set.
  • the inventive methods can be used to apply thicker layers, which are then much more loadable, since the metal components used serve as adhesives.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Catalysts (AREA)

Abstract

In a process to manufacture metallic objects e.g. foil, sheet metal components or formed components bearing a photo-catalytic active surface, the active material is applied as a cold gas spray incorporating a ceramic oxide and a metallic powder. The cold gas incorporates titanium dioxide powder e.g. Atanas. The individual ceramic oxide particles are encased within a metal or metal alloy representing 30-60% Vol. The metal surface has a photo-catalytic particle coating represents 30-80% of the surface area. The outer layer is subject to further mechanical or chemical treatment.

Description

Die Erfindung betrifft ein Verfahren zur Herstellung von metallischen Gegenständen, wie Folien, Blechen oder Formteilen, mit photokatalytisch aktiver Oberfläche nach dem Oberbegriff des Anspruchs 1. Die Besonderheit der photokatalytisch aktiven Komponenten (hauptsächlich Titandioxid) besteht darin, die Bindungen in den Molekülen von Schadstoffen aufzubrechen und die betreffenden Substanzen dadurch in ungefährliche, einfach aufgebaute Reaktionsprodukte zu zerlegen.The invention relates to a method for the production of metallic objects, such as films, sheets or moldings, with photocatalytically active surface according to the preamble of claim 1. The peculiarity of the photocatalytically active components (mainly titanium dioxide) is to break the bonds in the molecules of pollutants and to decompose the substances in question into harmless, simply structured reaction products.

Das Auftragen unterschiedlicher Komponenten auf zahlreichen Untergründen durch thermisches Spritzen hat sich aufgrund der hohen Variabilität von verschiedenen Grund- und Schichtwerkstoffen und seiner hohen Flexibilität bewährt.The application of different components on numerous substrates by thermal spraying has proven itself due to the high variability of different base and layer materials and its high flexibility.

Es wurde bereits vorgeschlagen ( DE 10 2004 038 795 ) photokatalytisch aktive Oberflächen in Kunststoffen durch Kaltgasspritzen herzustellen. Dabei werden Partikel aus dem photokatalytisch aktiven oxidischen Material durch ein Trägergas beschleunigt, dringen beim Aufprall auf die Polymeroberfläche ganz oder teilweise ein und bilden aufgrund ihrer hohen kinetischen Energie einen mechanisch fest anhaftenden Verbund Polymer/Oxid. Diese Anmeldung bezieht sich nur auf Polymerschichten. Dabei ist zu bedenken, dass die katalytische Wirkung des TiO2 auch zur Zersetzung des Kunststoffs führen kann.It has already been proposed ( DE 10 2004 038 795 ) to produce photocatalytically active surfaces in plastics by cold gas spraying. In this case, particles from the photocatalytically active oxidic material are accelerated by a carrier gas, penetrate completely or partially upon impact with the polymer surface and, due to their high kinetic energy, form a mechanically adhering composite polymer / oxide. This application relates only to polymer layers. It should be remembered that the catalytic effect of TiO 2 can also lead to the decomposition of the plastic.

Aus der Literaturstelle: Formation of TiO2 photocatalyst through cold spraying von Chang-Jiu Li, Guan-Jun Yang, Xin-Chun Huang, Wen-Ya Li, Xián / PRC , and Akira Ohmori Osaka / J, Proceedings ITSC, May 10-12,2004, Osaka, Japan , ist es bekannt, photokatalytisch aktives Pulver (TiO2) auf eine Metalloberfläche mit Kaltgas zu spritzen. Dabei werden Anataspulver mit 10-45 µm durch Agglomeration ultrafeiner Partikel hergestellt. Die Primärpartikelgröße der ultrafeinen Partikel sind 200 und 7 Nanometer. Diese Pulver werden auf Edelstahlplatten gespritzt. Problematisch beim Kaltgasspritzen von Titandioxid ist, dass dieses Material sich nicht plastisch verformen kann. Die Haftung der Partikel auf dem metallischen Substrat erfolgt nur dadurch, dass sich das Metall verformt. Ein auf ein bereits haftendes Partikel auftreffendes zweites Partikel dürfte deswegen kaum haften. Dieses Problem wird in dieser Literaturstelle nicht angesprochen, geschweige denn gelöst. Es werden Aufnahmen (rasterelektronenmikroskopische Aufnahmen von der Oberfläche) von porösen TiO2-Schichten gezeigt, bei denen die zweite und weiter folgenden Partikellagen vermutlich nicht kratzfest mit der ersten Partikellage verbunden sein dürften.From the literature: Formation of TiO 2 photocatalyst through cold spraying of Chang-Jiu Li, Guan-Jun Yang, Xin-Chun Huang, Wen-Ya Li, Xián / PRC , and Akira Ohmori Osaka / J, Proceedings ITSC, May 10-12,2004, Osaka, Japan , It is known to inject photocatalytically active powder (TiO 2 ) on a metal surface with cold gas. Anatase powders of 10-45 μm are produced by agglomeration of ultrafine particles. The primary particle size of the ultrafine particles are 200 and 7 nanometers. These powders are sprayed on stainless steel plates. The problem with cold gas spraying of titanium dioxide is that this material can not plastically deform. The adhesion of the particles on the metallic substrate takes place only in that the metal deforms. Therefore, a second particle impinging on an already adhering particle is unlikely to adhere. This problem is discussed in this reference not addressed, let alone solved. Shoots (scanning electron micrographs of the surface) of porous TiO 2 layers are shown in which the second and subsequent particle layers probably should not be connected to the first particle layer in a scratch-resistant manner.

Aufgabe der Erfindung ist es, ein entsprechendes Verfahren für die Herstellung photokatalytisch aktiver Schichten auf Metallen dahingehend zu verbessern, dass besser haftende, langzeitbeständige Schichten erzeugt werden.The object of the invention is to improve a corresponding process for the production of photocatalytically active layers on metals in such a way that more adhesive, long-term stable layers are produced.

Diese Aufgabe wird dadurch gelöst, dass anstelle der reinen Oxidkeramik ein Gemisch aus Oxidkeramik und metallischem Pulver gespritzt wird. Das Spritzen von harter Keramik mit einem Metallgemisch hat den Vorteil, dass hier immer Komponenten vorhanden sind, die sich beim Auftreffen verformen können. Gerade die Metallanteile verformen sich beim Auftreffen, bilden damit eine in die vorhandene Schicht eindringende neue Materie und erhöhen so die Haftung und die Beständigkeit.This object is achieved in that instead of the pure oxide ceramic, a mixture of oxide ceramic and metallic powder is injected. The injection of hard ceramic with a metal mixture has the advantage that there are always components that can deform when hitting. Especially the metal parts deform on impact, forming a new matter that penetrates into the existing layer, thus increasing the adhesion and the resistance.

Die Metallpartikel dringen in die Lücken ein, aber ebenso dringt auch ein auf Metall auftreffendes Keramikpartikel in das Metall ein und wird dabei von dem Metall umschlossen und mit dem Metall fest verbunden.The metal particles penetrate into the gaps, but also penetrates a metal impinging ceramic particles into the metal and is thereby enclosed by the metal and firmly connected to the metal.

Als Metall bzw. metallische Komponente kommen praktisch alle Metalle und Metalllegierungen in Frage, die sich auch ohne Keramikzusatz spritzen lassen. Abgestimmt auf die Anwendung der photokatalytischen Schicht sind z.B. Metalle wie Aluminium und Kupfer bzw. deren Legierungen interessant, die sich gut verformen lassen (flexible Bänder). Aluminium und Kupfer sind auch interessant, wenn die photokatalytisch aktive Schicht eine gute elektrische Leitfähigkeit und gute Wärmeleitfähigkeit aufweisen soll. In besonders aggressiver Umgebung können korrosionsbeständige Nickellegierungen oder Tantal eingesetzt werden.As a metal or metallic component are virtually all metals and metal alloys in question, which can be injected without ceramic additive. Tuned to the application of the photocatalytic layer are e.g. Metals such as aluminum and copper or their alloys are interesting, which can be easily deformed (flexible tapes). Aluminum and copper are also interesting if the photocatalytically active layer should have good electrical conductivity and good thermal conductivity. In particularly aggressive environments, corrosion resistant nickel alloys or tantalum can be used.

Die Größe der Partikel kann sowohl bei der metallischen als auch bei der keramischen Komponente im Bereich von 3 bis 100 µm liegen, bei der metallischen Komponente vorzugsweise im Bereich 10 bis 50 µm. Beim Spritzen mit einem Hochdrucksystem arbeitet man üblicherweise bei Drücken von 20 bis 40 bar und Gastemperaturen von 100 bis 600 °C. Beim Spritzen mit sog. tragbaren Geräten wird mit Drücken bis 10 bar und Gastemperatur von 300 bis 600 °C gearbeitet.The size of the particles can be in the range from 3 to 100 μm, both in the case of the metallic component and in the case of the ceramic component, and preferably in the range of 10 to 50 μm in the case of the metallic component. When spraying with a high-pressure system is usually carried out at pressures of 20 to 40 bar and gas temperatures of 100 to 600 ° C. When spraying with so-called portable devices is operated with pressures up to 10 bar and gas temperature of 300 to 600 ° C.

Als besonders bevorzugt hat sich als Keramikwerkstoff Titandioxid erwiesen. Dieses Pulver kommt in verschiedenen Kristallstrukturen vor, wobei die photokatalytisch besonders aktive Phase Anatas (Anatase) metastabil ist. Bei Erwärmung auf Temperaturen im Bereich 600 bis 800 °C wandelt diese Phase sich in die thermodynamisch stabilere Phase Rutil um, die jedoch eine deutlich geringere Wirksamkeit als Photokatalysator besitzt. Eine solche Umwandlung und Beeinträchtigung der photokatalytischen Eigenschaften lässt sich beim Plasmaspritzen und beim HVOF-Spritzen nicht vermeiden. Beim erfindungsgemäßen Kaltgasspritzen bleibt dagegen die photokatalytisch aktive Phase Anatas voll erhalten, da die Temperaturen des zum Spritzen verwendeten Gases unter 600 °C liegen.Titanium dioxide has proved to be particularly preferred as the ceramic material. This powder occurs in different crystal structures, with the photocatalytically active phase anatase (anatase) being metastable. When heated to temperatures in the range 600 to 800 ° C, this phase converts to the thermodynamically more stable phase rutile, which, however, has a significantly lower efficiency than photocatalyst. Such a conversion and impairment of the photocatalytic properties can not be avoided in plasma spraying and HVOF spraying. In the case of the cold gas spraying according to the invention, by contrast, the photocatalytically active phase anatase remains fully preserved since the temperatures of the gas used for spraying are below 600 ° C.

Möglich ist auch, die photokatalytischen Eigenschaften von Anatas zu verbessern. Man ist derzeit bestrebt, durch eine Modifikation bzw. Dotierung des Titandioxids die photokatalytische Wirksamkeit des Materials vom UV-Bereich in den Bereich des sichtbaren Lichts zu verschieben. Das würde die Wirksamkeit als Photokatalysator bei Tageslicht bedeutend verbessern. Zum Anderen hat man bereits festgestellt, dass die photokatalytische Wirksamkeit von Anatas größer ist, wenn dieses Material im nanokristallinen Zustand vorliegt, d.h. ein Pulver oder eine Schicht aus Kristallen besteht, deren Abmessungen deutlich unter einem Mikrometer bzw. unter 100 nm liegt. Beide Entwicklungen kommen dem Kaltgasspritzen entgegen, da die Erwärmung bei diesem Verfahren so gering ist, dass auch der modifizierte oder dotierte Zustand erhalten bleibt und die extrem kleinen Kristalle im Spritzprozess nicht wachsen.It is also possible to improve the photocatalytic properties of anatase. At present, it is desirable to shift the photocatalytic effectiveness of the material from the UV range into the range of visible light by modifying or doping the titanium dioxide. This would significantly improve the effectiveness as a photocatalyst in daylight. On the other hand, it has already been found that the photocatalytic effectiveness of anatase is greater when this material is in the nanocrystalline state, i. a powder or a layer of crystals whose dimensions are well below one micron or below 100 nm. Both developments are contrary to cold gas spraying, since the heating in this process is so low that the modified or doped state is retained and the extremely small crystals do not grow in the injection process.

Statt eines Gemisches von zwei Pulvern kann auch ein agglomeriertes (zusammengeballtes) Pulver verwendet werden, bei dem jedes Partikel aus vielen kleinen Keramikoxid- und Metallpartikeln besteht. Kleine Partikel in der Größe von z.B. 0,5 bis 2 µm werden durch das in der Technik bekannte und praktizierte Verfahren des Sprühtrocknens zu größeren Partikeln mit 3 bis 100 µm Durchmesser agglomeriert, so dass dann jedes einzelne Partikel aus kleineren Partikeln beider Komponenten besteht. Dies geschieht z.B. dadurch, dass die kleinen Partikel mit einem organischen Binder versehen werden und die Suspension dann in einem heißen Luft- bzw. Gasstrom getrocknet wird. Dabei verdampft der Binder und die kleineren Partikel werden miteinander "verklebt" bzw. durch Diffusionsprozesse miteinander verbunden.Instead of a mixture of two powders, an agglomerated (agglomerated) powder may also be used in which each particle consists of many small ceramic oxide and metal particles. Small particles in the size of, for example, 0.5 to 2 μm are agglomerated by the spray-drying method known and practiced in the art into larger particles of 3 to 100 μm in diameter so that each individual particle then consists of smaller particles of both components. This happens, for example, in that the small particles are provided with an organic binder and the suspension is then dried in a stream of hot air or gas. The binder evaporates and the smaller particles are "glued together" or connected to one another by diffusion processes.

In einer Ausführung der Erfindung kann statt des Gemisches Metall und Oxidkeramik ein Pulver verwendet werden, bei dem die Oxidkeramik-Partikel je mit einem Metall oder einer Metalllegierung ummantelt sind. Dieses ummantelte Pulver wird dann durch Kaltgasspritzen auf die metallische oder keramische Trägermaterialien aufgetragen. In diesem Fall wird die Schicht in einem zweiten Arbeitsschritt durch mechanische oder chemische Nachbearbeitung auf- oder angeschliffen, um das nach dem Spritzen noch in Ummantelung eingeschlossene Titandioxid an der Schichtoberfläche freizulegen.In one embodiment of the invention, instead of the mixture of metal and oxide ceramics, a powder can be used in which the oxide-ceramic particles are each coated with a metal or a metal alloy. This coated powder is then applied to the metallic or ceramic substrates by cold gas spraying. In this case, the layer is abraded or ground in a second step by mechanical or chemical post-processing in order to expose the titanium dioxide, which is still encased in the shell after spraying, on the layer surface.

Versuche haben ergeben, dass der Metallanteil zwischen 10 % und 90 % liegen sollte. Bevorzugt zwischen 30 % und 60 %.Tests have shown that the metal content should be between 10% and 90%. Preferably between 30% and 60%.

Die katalytische Wirkung der metallischen Oberfläche ist schon dann gegeben, wenn die Oberfläche in einer Monolage von Titandioxidpartikeln belegt ist. Dies auch dann, wenn die Monolage nicht flächendeckend ist. Es reichen Flächenbelegungen ab 5 %, wobei 5-100 % eine photokatalytische Wirkung zeigen, wobei vorzugsweise eine Flächenbelegung zwischen 30 und 80 % eingestellt wird. Mit den erfindungsgemäßen Verfahren können neben Monolagen auch dickere Schichten aufgetragen werden, die dann wesentlich belastbarer sind, da die verwendeten Metallanteile als Haftmittel dienen.The catalytic effect of the metallic surface is already present when the surface is occupied in a monolayer of titanium dioxide particles. This even if the monolayer is not nationwide. Surface coverage ranges from 5%, with 5-100% exhibiting a photocatalytic effect, wherein preferably a surface coverage of between 30 and 80% is set. In addition to monolayers, the inventive methods can be used to apply thicker layers, which are then much more loadable, since the metal components used serve as adhesives.

Claims (6)

Verfahren zur Herstellung von metallischen Gegenständen, wie Folien, Blechen oder Formteilen, mit photokatalytisch aktiver Oberfläche durch das Auf- oder Einbringen von photokatalytisch aktivem Material mittels Kaltgasspritztechnik, dadurch gekennzeichnet, dass der Spritzwerkstoff Oxidkeramik und ein metallisches Pulver enthält.A process for the production of metallic objects, such as films, sheets or moldings, with photocatalytically active surface by the application or incorporation of photocatalytically active material by means of cold gas spraying, characterized in that the spray material contains oxide ceramics and a metallic powder. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass für das Kaltgasspritzen ein Titandioxidpulver, bevorzugt Anatas, verwendet wird.A method according to claim 1, characterized in that a titanium dioxide powder, preferably anatase, is used for the cold gas spraying. Verfahren nach dem Oberbegriff des Anspruchs 1, dadurch gekennzeichnet, dass die einzelnen Oxidkeramikpartikel mit einem Metall oder einer Metalllegierung ummantelt sind.Method according to the preamble of claim 1, characterized in that the individual oxide ceramic particles are coated with a metal or a metal alloy. Verfahren nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass der volumetrische Metallanteil zwischen 10 und 90 %, bevorzug zwischen 30 und 60 %, beträgt.Method according to one of the preceding claims, characterized in that the volumetric metal content is between 10 and 90%, preferably between 30 and 60%. Verfahren nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass die Metalloberfläche mit einem Flächenanteil von 5 bis 100 %, vorzugsweise von 30 bis 80 %, mit photokatalytisch aktiven Partikeln bedeckt ist.Method according to one of the preceding claims, characterized in that the metal surface is covered with a surface portion of 5 to 100%, preferably from 30 to 80%, with photocatalytically active particles. Verfahren nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass die aufgebrachte Schicht mechanisch oder chemisch nachbearbeitet wird.Method according to one of the preceding claims, characterized in that the applied layer is mechanically or chemically post-processed.
EP06022877A 2005-11-08 2006-11-02 Method of manufacturing a photocatalytic active layer Not-in-force EP1785508B1 (en)

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DE102012001361A1 (en) 2012-01-24 2013-07-25 Linde Aktiengesellschaft Method for cold gas spraying

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WO2009118335A1 (en) 2008-03-28 2009-10-01 Siemens Aktiengesellschaft Method for producing a coating through cold gas spraying
US8241702B2 (en) 2008-03-28 2012-08-14 Siemens Aktiengesellschsft Method for producing a coating through cold gas spraying
CN101978098B (en) * 2008-03-28 2013-02-13 西门子公司 Method for producing a coating through cold gas spraying
DE102012001361A1 (en) 2012-01-24 2013-07-25 Linde Aktiengesellschaft Method for cold gas spraying
EP2620525A1 (en) 2012-01-24 2013-07-31 Linde Aktiengesellschaft Method for cold gas spraying
WO2013110441A1 (en) 2012-01-24 2013-08-01 Linde Aktiengesellschaft Method for cold gas spraying

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EP1785508A3 (en) 2007-08-22
EP1785508B1 (en) 2009-04-08
DE502006003370D1 (en) 2009-05-20
DE102005053263A1 (en) 2007-05-10
US20070148363A1 (en) 2007-06-28
ATE428007T1 (en) 2009-04-15

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