EP2576863A1 - Method for producing a layer by means of cold spraying and use of such a layer - Google Patents

Method for producing a layer by means of cold spraying and use of such a layer

Info

Publication number
EP2576863A1
EP2576863A1 EP11723054.0A EP11723054A EP2576863A1 EP 2576863 A1 EP2576863 A1 EP 2576863A1 EP 11723054 A EP11723054 A EP 11723054A EP 2576863 A1 EP2576863 A1 EP 2576863A1
Authority
EP
European Patent Office
Prior art keywords
layer
particles
substrate
cold gas
workpiece
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP11723054.0A
Other languages
German (de)
French (fr)
Other versions
EP2576863B1 (en
Inventor
Axel Arndt
Christian Doye
Oliver Stier
Raymond Ullrich
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Siemens AG
Original Assignee
Siemens AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Siemens AG filed Critical Siemens AG
Publication of EP2576863A1 publication Critical patent/EP2576863A1/en
Application granted granted Critical
Publication of EP2576863B1 publication Critical patent/EP2576863B1/en
Active legal-status Critical Current
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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/02—Processes for applying liquids or other fluent materials performed by spraying
    • B05D1/12—Applying particulate materials
    • 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 producing a resistant to abrasive wear, such as particle erosion, resistant layer on a workpiece by cold gas spraying. In this process, particles are accelerated towards the surface of the substrate to be coated and remain on the substrate
  • a cold gas spraying installation ver ⁇ turns having a gas heating means for heating a gas.
  • a stagnation chamber is connected to the gas heater, which is the output side connected to a convergent ⁇ divergent nozzle, preferably a Laval nozzle.
  • Convergent-divergent nozzles have a sixteenlau ⁇ fenden section and a widening section, which are connected by a nozzle neck.
  • the convergent-divergent nozzle produces an output side Pul ⁇ verstrahl in the form of a gas stream having therein Par tikeln at high speed, so that the kinetic
  • Enough energy of the particles is sufficient so that they adhere to the surface ⁇ to be coated.
  • the preparation of a layer resistant to abrasive wear is described, for example, by RS Lima et al. , "Micrural Structural Characteristics of Cold-Sprayed Nanostructured WC-Co-Coatings", Thin Solid Films 416 (2002), pp. 129- 135.
  • the layer described there has a fine structure, which is used as a nanostructured WC co-coating. Coating is drawn. This can be deposited by cold gas spraying on a substrate, which due to the microstructure portion WC a high hardness and thus a high resistance to abrasi ⁇ ven wear arises.
  • the wear of such a hard layer depends primarily on how hard the particles in the abrasive medium are. If the abrasive medium itself has a hardness similar to that of WC, a comparatively high level of abrasive wear is also observed when using WC containing wear protection layers.
  • the object of the invention is to provide a method for producing an abrasive wear-resistant layer, with the layers can be produced which have a comparatively high abrasive wear resistance aufwei ⁇ sen.
  • Layer is porous and corresponds to the grain size of the layer structure in ⁇ We sentlichen the particle size.
  • Po ⁇ ren which form in the structure of the layer, exactly between the particles, while the particles largely remain in their form by adjusting the process parameters in cold gas spraying.
  • the relatively high Poro ⁇ sity of coating result, so to speak, a lo ⁇ ckeres metal structure wherein the selected metals create a duk ⁇ tiles conduct of the results.
  • the particles have an average particle size of 1 to 10 ⁇ m, preferably 2 to 5 ⁇ m.
  • the mean diameter of the particles is to be understood, which can be determined statistically by known methods. Also, particles that are not round, have such a mean diameter, so that their particle size can be specified.
  • the choice of relatively fine particles advantageously leads to a microporosity of the layer, so that these after the as described above, by plastic deformation of the porous particle composite can particularly effectively withstand particle erosion.
  • a layer of Ni is applied to the substrate, which holds the layer by forming common ⁇ more slowly diffusion zones or intermetallic phases.
  • This measure also makes it possible, in particular, to apply the stable layer to substrates which in themselves form a poor substrate for the selected metals. On the adhesive layer, which itself adheres well to the substrate, then the resistant layer can be deposited with good adhesion.
  • ge solves ⁇ that a porous cold gas sprayed layer consisting of Zn and / or Sn and / or Cu and / or Al and / or Ti and / or at least one of these metals as a main component con- tained alloy is used as a protective layer on a workpiece to be protected against abrasive wear, with pores between the cold gas-sprayed particles.
  • a porous cold gas sprayed layer consisting of Zn and / or Sn and / or Cu and / or Al and / or Ti and / or at least one of these metals as a main component con- tained alloy is used as a protective layer on a workpiece to be protected against abrasive wear, with pores between the cold gas-sprayed particles.
  • Such use thus includes that the layer is produced on the relevant workpiece by cold gas spraying.
  • the above ⁇ called ge already be achieved benefits.
  • the path is as already mentioned, trod that as a resistant layer against abra ⁇ sive wear a comparatively soft, ductile layer is used and not a hard wear protection layer, wherein the surprising effect is exploited that a soft, ductile layer can avoid attack by the abrasive medium by plastic deformation, so a layer removal is advantageously reduced.
  • the workpiece consists of a metal or a metal alloy that is nobler than the material of the particles.
  • Figure 1 is a schematic section through a
  • Embodiment of the layer according to the invention and FIGS. 2 to 7 are plan views of the surface of an exemplary embodiment of the invention
  • FIG. 1 shows the method steps of an exemplary embodiment of the method according to the invention.
  • a primer layer 12 has been applied by means of cold gas spraying first, which consists of nickel. Alternatively, this layer could also be applied electrochemically.
  • a stable layer is introduced ⁇ 13, which consists of particles 14 by cold gas spraying.
  • FIG. 1 also shows schematically the mechanism of how the layer 13 reacts to a stress by an abrasive particle 16.
  • HZO-Farbzinkstaubs su ⁇ perfein the Fa. Norzinco GmbH with particle sizes between 2 and 5 ym was produced by cold gas spraying a stable layer. The surface produced can be seen in Figures 2 and 5, respectively.
  • the particles 14 can still be seen on the surface, whereby pores between the particles can also be recognized.
  • the surface layer produced was be ⁇ is by sand blasting, wherein corundum is used having an average particle size of 120 .mu.m.
  • corundum particles 16 which strike the surface cause scratches 18, which produce depressions 17, as shown schematically in FIG.

Abstract

The invention relates to a method for generating an abrasive wear-resistant layer (13) on a substrate (11). According to the invention, said layer (13) consists of particles (14) of a ductile material, in particular Zn, wherein the parameters of the cold spraying process are set such that a comparatively loose laminate having pores (15) is formed by the spray particles (14). Said laminate advantageously and surprisingly exhibits high resistance to abrasive wear (for example by a particle (16)) because the layer (13) can avoid the attack by the particle (16) by plastic deformation and closure of the pores (15), whereby abrasive removal of the layer is advantageously low. The invention further relates to a use of a cold gas-sprayed layer as a protective layer against abrasive wear.

Description

Beschreibung description
Verfahren zum Herstellen einer Schicht mittels Kaltgassprit¬ zen und Verwendung einer solchen Schicht A method of forming a layer by means of cold gas fuel ¬ zen and use of such a layer
Die Erfindung betrifft ein Verfahren zum Erzeugen einer gegen abrasiven Verschleiß, beispielsweise Partikelerosion, beständigen Schicht auf einem Werkstück durch Kaltgasspritzen. Bei diesem Verfahren werden Partikel zur zu beschichtenden Ober- fläche des Substrates hin beschleunigt und bleiben an derThe invention relates to a method for producing a resistant to abrasive wear, such as particle erosion, resistant layer on a workpiece by cold gas spraying. In this process, particles are accelerated towards the surface of the substrate to be coated and remain on the substrate
Auftreffstelle am Substrat haften. Auf diesem Wege entsteht eine kaltgasgespritzte Schicht, wobei die Erfindung weiterhin eine Verwendung einer solchen porösen Schicht betrifft. Vorzugsweise wird zum Kaltgasspritzen, welches auch als kineti- sches Spritzen bezeichnet wird, eine Kaltgasspritzanlage ver¬ wendet, die eine Gasheizeinrichtung zum Erhitzen eines Gases aufweist. An die Gasheizeinrichtung wird eine Stagnationskammer angeschlossen, die ausgangsseitig mit einer konvergent¬ divergenten Düse, vorzugsweise einer Lavaldüse verbunden wird. Konvergent-divergente Düsen weisen einen zusammenlau¬ fenden Teilabschnitt sowie einen sich aufweitenden Teilabschnitt auf, die durch einen Düsenhals verbunden sind. Die konvergent-divergente Düse erzeugt ausgangsseitig einen Pul¬ verstrahl in Form eines Gasstroms mit darin befindlichen Par- tikeln mit hoher Geschwindigkeit, so dass die kinetischeAdhere to the impact site on the substrate. In this way, a cold gas-sprayed layer is formed, wherein the invention further relates to a use of such a porous layer. Preferably, for cold gas spraying, which is also referred to as kinetic ULTRASONIC spraying, a cold gas spraying installation ver ¬ turns having a gas heating means for heating a gas. To the gas heater, a stagnation chamber is connected, which is the output side connected to a convergent ¬ divergent nozzle, preferably a Laval nozzle. Convergent-divergent nozzles have a zusammenlau ¬ fenden section and a widening section, which are connected by a nozzle neck. The convergent-divergent nozzle produces an output side Pul ¬ verstrahl in the form of a gas stream having therein Par tikeln at high speed, so that the kinetic
Energie der Partikel ausreicht, damit diese auf der zu be¬ schichtenden Oberfläche haften bleiben. Enough energy of the particles is sufficient so that they adhere to the surface ¬ to be coated.
Die Herstellung einer gegen abrasiven Verschleiß beständigen Schicht ist beispielsweise durch R. S. Lima et al . , „Mic- rostructural Characteristics of Cold-Sprayed Nanostructured WC-Co-Coatings", Thin Solid Films 416 (2002), S. 129 - 135 beschrieben. Die dort beschriebene Schicht weist ein feines Gefüge auf, welches als nanostrukturiertes WC-Co-Coating be- zeichnet wird. Dieses lässt sich durch Kaltgasspritzen auf einem Substrat abscheiden, wobei wegen des Gefügeanteils WC eine hohe Härte und damit ein hoher Widerstand gegen abrasi¬ ven Verschleiß entsteht. The preparation of a layer resistant to abrasive wear is described, for example, by RS Lima et al. , "Micrural Structural Characteristics of Cold-Sprayed Nanostructured WC-Co-Coatings", Thin Solid Films 416 (2002), pp. 129- 135. The layer described there has a fine structure, which is used as a nanostructured WC co-coating. Coating is drawn. This can be deposited by cold gas spraying on a substrate, which due to the microstructure portion WC a high hardness and thus a high resistance to abrasi ¬ ven wear arises.
Allerdings ist der Verschleiß einer solchen harten Schicht in erster Linie davon abhängig, wie hart die Teilchen in dem abrasiven Medium sind. Sofern das abrasive Medium selbst eine ähnliche Härte wie WC aufweist, ist bei Verwendung von WC enthaltenen Verschleißschutzschichten ebenfalls ein vergleichsweise hoher abrasiver Verschleiß festzustellen. However, the wear of such a hard layer depends primarily on how hard the particles in the abrasive medium are. If the abrasive medium itself has a hardness similar to that of WC, a comparatively high level of abrasive wear is also observed when using WC containing wear protection layers.
Die Aufgabe der Erfindung liegt darin, ein Verfahren zum Erzeugen einer gegen abrasiven Verschleiß beständigen Schicht anzugeben, mit dem sich Schichten erzeugen lassen, die einen vergleichsweise hohen abrasiven Verschleißwiderstand aufwei¬ sen . The object of the invention is to provide a method for producing an abrasive wear-resistant layer, with the layers can be produced which have a comparatively high abrasive wear resistance aufwei ¬ sen.
Diese Aufgabe wird mit dem eingangs genannten Verfahren er- findungsgemäß dadurch gelöst, dass die Partikel aus Zn und/oder Sn und/oder Cu und/oder AI und/oder Ti und/oder einer zumindest eines dieser Metalle als Hauptbestandteil ent¬ haltenen Legierung bestehen. Außerdem wird die Geschwindigkeit der auf das Substrat auftreffenden Partikel so einge- stellt, dass die sich aus diesen Partikeln ausbildende This object is achieved with the method mentioned inven- tion achieved according to a consist of at least one of these metals as a main component ent ¬ preserved alloy that the particles of Zn and / or Sn and / or Cu and / or Al and / or Ti and / or , In addition, the velocity of the particles impinging on the substrate is adjusted so that the particles that form from these particles
Schicht porös ist und die Korngröße des Schichtgefüges im We¬ sentlichen der Partikelgröße entspricht. Damit liegen die Po¬ ren, die sich im Gefüge der Schicht ausbilden, genau zwischen den Partikeln, während die Partikel durch Einstellung der Verfahrensparameter beim Kaltgasspritzen in ihrer Form weitgehend erhalten bleiben. Durch die vergleichsweise hohe Poro¬ sität des Beschichtungsergebnisses entsteht sozusagen ein lo¬ ckeres Metallgefüge, wobei die ausgewählten Metalle ein duk¬ tiles Verhalten an den Tag legen. Wird die beständige Schicht im Folgenden beispielsweise durch Partikelerosion beansprucht, so kommt es zunächst zu einer plastischen Verformung der Partikel in der Schicht, die zwar zu einer Verfestigung des Gefüges und zu einer Verringerung von dessen Porosität führt, jedoch gewährleistet, dass durch den Angriff der abra- siven Partikel nur ein geringer Materialabtrag der Schicht zu beobachten ist. Man kann die Beanspruchung der beständigen Schicht durch die Partikel also als eine Art Mikroschmieden bezeichnen, wobei die plastische Verformung der Partikel im Gefüge der beständigen Schicht dazu führt, dass ein Material¬ abtrag weitgehend vermieden wird. Layer is porous and corresponds to the grain size of the layer structure in ¬ We sentlichen the particle size. Thus, the Po ¬ ren, which form in the structure of the layer, exactly between the particles, while the particles largely remain in their form by adjusting the process parameters in cold gas spraying. The relatively high Poro ¬ sity of coating result, so to speak, a lo ¬ ckeres metal structure wherein the selected metals create a duk ¬ tiles conduct of the results. Will the stable layer In the following, for example, claimed by particle erosion, it comes first to a plastic deformation of the particles in the layer, which leads to a hardening of the structure and to a reduction of its porosity, but ensures that by the attack of the abrasive particles only a slight material removal of the layer is observed. Can be described as a kind of micro-forging, the strain of the resistant layer by the particles so, the plastic deformation of the particles resulting in the structure of the resistant layer, that a material ¬ removal is substantially avoided.
Hierin liegt ein überraschender Effekt, der der erfindungsgemäß hergestellten porösen Schicht mit einer hohen Duktilität zugrunde liegt. Anstatt, wie durch R.S. Lima et al . angege¬ ben, eine Verschleißschutzschicht mit einer möglichst hohen Härte zur Verfügung zu stellen, wird gemäß der vorliegenden Erfindung ein gegenteiliger Weg beschritten, nämlich die beständige Schicht so auszuführen, dass eine Beanspruchung durch ein abrasives Medium eine Verformung der Schicht erlaubt, um einen abrasiven Verschleiß dieser Schicht durch ein plastisches Ausweichen der betroffenen Schichtpartikel zu un¬ terbinden . Gemäß einer vorteilhaften Ausgestaltung der Erfindung ist vorgesehen, dass die Partikel eine mittlere Partikelgröße von 1 bis 10 ym, bevorzugt 2 bis 5 ym, aufweisen. Als Partikel¬ größe im Sinne der Erfindung soll der mittlere Durchmesser der Partikel verstanden werden, welcher sich nach bekannten Verfahren statistisch ermitteln lässt. Auch Partikel, die nicht rund sind, weisen einen solchen mittleren Durchmesser auf, so dass deren Partikelgröße angegeben werden kann. Die Wahl von verhältnismäßig feinen Partikeln führt vorteilhaft zu einer Mikroporosität der Schicht, so dass diese nach dem oben beschriebenen Mechanismus durch plastische Verformung des porösen Partikelverbundes besonders wirkungsvoll einer Partikelerosion widerstehen kann. Gemäß einer anderen Ausgestaltung der Erfindung ist vorgesehen, dass vor dem Aufbringen der Schicht eine Haftvermittlerschicht, insbesondere eine Schicht aus Ni, auf das Substrat aufgebracht wird, welche die Schicht durch Ausbildung gemein¬ samer Diffusionszonen oder intermetallischer Phasen festhält. Hiermit lässt sich vorteilhaft die Haftung der Schicht auf dem Substrat durch Ausbildung von Diffusionszonen oder intermetallischen Phasen verbessern, damit die Beanspruchung durch das abrasive Medium nicht zu einem Abplatzen der Schicht führt. Diese Maßnahme ermöglicht insbesondere auch die Auf- bringung der beständigen Schicht auf Substraten, welche an sich für die ausgewählten Metalle einen schlechten Untergrund bilden. Auf der Haftvermittlerschicht, welche selbst gut auf dem Substrat haftet, lässt sich dann die beständige Schicht mit einer guten Haftung abscheiden. Herein lies a surprising effect which underlies the porous layer having a high ductility produced according to the invention. Instead, as described by RS Lima et al. angege ¬ ben to provide a wear protection layer with the highest possible hardness, according to the present invention, an opposite approach is taken, namely to perform the resistant layer so that a stress by an abrasive medium allows deformation of the layer to abrasive wear this layer by a plastic evasion of the affected layer particles to un ¬ terbinden. According to an advantageous embodiment of the invention, it is provided that the particles have an average particle size of 1 to 10 μm, preferably 2 to 5 μm. As particle size ¬ the purposes of the invention, the mean diameter of the particles is to be understood, which can be determined statistically by known methods. Also, particles that are not round, have such a mean diameter, so that their particle size can be specified. The choice of relatively fine particles advantageously leads to a microporosity of the layer, so that these after the as described above, by plastic deformation of the porous particle composite can particularly effectively withstand particle erosion. According to another embodiment of the invention it is provided that prior to applying the layer of an adhesion promoter layer, in particular a layer of Ni is applied to the substrate, which holds the layer by forming common ¬ more slowly diffusion zones or intermetallic phases. This advantageously makes it possible to improve the adhesion of the layer to the substrate by forming diffusion zones or intermetallic phases, so that the stress caused by the abrasive medium does not lead to the layer spalling off. This measure also makes it possible, in particular, to apply the stable layer to substrates which in themselves form a poor substrate for the selected metals. On the adhesive layer, which itself adheres well to the substrate, then the resistant layer can be deposited with good adhesion.
Weiterhin wird die eingangs angegebene Aufgabe dadurch ge¬ löst, dass eine poröse kaltgasgespritzte Schicht, die aus Zn und/oder Sn und/oder Cu und/oder AI und/oder Ti und/oder einer zumindest eines dieser Metalle als Hauptbestandteil ent- haltenen Legierung besteht, als Schutzschicht auf einem gegen abrasiven Verschleiß zu schützenden Werkstück verwendet wird, wobei sich zwischen den kaltgasgespritzten Partikeln Poren befinden. Eine solche Verwendung beinhaltet also, dass die Schicht auf dem betreffenden Werkstück durch Kaltgasspritzen hergestellt wird. Mit der Verwendung der kaltgasgespritzten Schicht im Sinne der Erfindung werden die oben bereits ge¬ nannten Vorteile erreicht. Hierbei wird, wie bereits erwähnt, der Weg beschritten, dass als beständige Schicht gegen abra¬ siven Verschleiß eine vergleichsweise weiche, duktile Schicht verwendet wird und nicht eine harte Verschleißschutzschicht, wobei der überraschende Effekt ausgenutzt wird, dass eine weiche, duktile Schicht dem Angriff durch das abrasive Medium durch plastische Verformung ausweichen kann, weswegen ein Schichtabtrag vorteilhaft verringert wird. Furthermore, the above-mentioned object is characterized ge solves ¬ that a porous cold gas sprayed layer consisting of Zn and / or Sn and / or Cu and / or Al and / or Ti and / or at least one of these metals as a main component con- tained alloy is used as a protective layer on a workpiece to be protected against abrasive wear, with pores between the cold gas-sprayed particles. Such use thus includes that the layer is produced on the relevant workpiece by cold gas spraying. With the use of cold gas sprayed layer according to the invention the above ¬ called ge already be achieved benefits. In this case, the path is as already mentioned, trod that as a resistant layer against abra ¬ sive wear a comparatively soft, ductile layer is used and not a hard wear protection layer, wherein the surprising effect is exploited that a soft, ductile layer can avoid attack by the abrasive medium by plastic deformation, so a layer removal is advantageously reduced.
Gemäß einer Ausgestaltung der Erfindung ist vorgesehen, dass das Werkstück aus einem Metall oder einer Metalllegierung besteht, das/die edler ist als das Material der Partikel. Mit anderen Worten soll das Metall oder die Metalllegierung desAccording to one embodiment of the invention, it is provided that the workpiece consists of a metal or a metal alloy that is nobler than the material of the particles. In other words, the metal or metal alloy of the
Werkstücks in der elektrochemischen Spannungsreihe ein größe¬ res Standardwasserstoffelektrodenpotential aufweisen als das Material, aus dem die Partikel sind. Hierdurch wird vorteil¬ haft erreicht, dass die erfindungsgemäße Schicht gleichzeitig einen sog. kathodischen Korrosionsschutz für das Substrat darstellt. Auch wenn die Schicht durch den fortschreitenden abrasiven Verschleiß an einigen Stellen des Werkstücks voll¬ ständig abgetragen sein sollte, so gewährleistet die verletz¬ te Schicht weiterhin einen Korrosionsschutz, da diese dann als Opferanode wirkt. Mit anderen Worten wird ein elektroche¬ mischer Angriff des Werkstücks dadurch verhindert, dass sich das unedlere Metall der Schicht auflöst, wodurch das Material des Werkstücks geschützt wird. Weitere Einzelheiten der Erfindung werden nachfolgend anhand der Zeichnung beschrieben. Gleiche oder sich entsprechende Zeichnungselemente sind in den einzelnen Figuren mit jeweils den gleichen Bezugszeichen versehen und werden nur insoweit mehrfach erläutert, wie sich Unterschiede zwischen den ein- zelnen Figuren ergeben. Es zeigen: Workpiece in the electrochemical series have a greater ¬ than standard hydrogen electrode potential than the material from which the particles are. This will ¬ advantageous way achieved that the layer of the invention is a so-called. Cathodic corrosion protection for the substrate simultaneously. Even if the layer should be fully ¬ constantly abraded by the progressive abrasive wear in some parts of the workpiece, the Hurt ¬ th layer ensures further comprises a corrosion protection, since this then acts as a sacrificial anode. In other words, an electrochemical ¬ mixer attack of the workpiece is prevented by the less noble metal of the layer dissolves, whereby the material of the workpiece is protected. Further details of the invention are described below with reference to the drawing. Identical or corresponding drawing elements are each provided with the same reference numerals in the individual figures and will only be explained several times to the extent that differences arise between the individual figures. Show it:
Figur 1 einen schematischen Schnitt durch ein Figure 1 is a schematic section through a
Ausführungsbeispiel der erfindungsgemäßen Schicht und Figuren 2 bis 7 Aufsichten auf die Oberfläche eines Aus¬ führungsbeispiels der erfindungsgemäßenEmbodiment of the layer according to the invention and FIGS. 2 to 7 are plan views of the surface of an exemplary embodiment of the invention
Schicht, die verschiedene Verschleißsta- dien der Oberfläche Partikelerosion darstellen, jeweils schematisch und als Fotografie . Layer, which represent different wear patterns of the surface particle erosion, each schematically and as a photograph.
Anhand von Figur 1 lassen sich die Verfahrensschritte eines Ausführungsbeispiels des erfindungsgemäßen Verfahrens dar¬ stellen. Auf einem Werkstück 11 ist mittels Kaltgasspritzens zunächst eine Haftvermittlerschicht 12 aufgebracht worden, die aus Nickel besteht. Alternativ könnte diese Schicht auch elektrochemisch aufgebracht werden. In einem weiteren Schritt wird durch Kaltgasspritzen eine beständige Schicht 13 aufge¬ bracht, welche aus Partikeln 14 besteht. Diese lassen sich in ihrer Kontur im Schnitt gemäß Figur 1 noch deutlich erkennen, da die Parameter des Kaltgasspritzens so eingestellt werden, dass die Partikel 14 sich beim Aufprall auf das Werkstück 11 (Substrat) kaum verformen. Allerdings ist der kinetischeFIG. 1 shows the method steps of an exemplary embodiment of the method according to the invention. On a workpiece 11, a primer layer 12 has been applied by means of cold gas spraying first, which consists of nickel. Alternatively, this layer could also be applied electrochemically. In a further step, a stable layer is introduced ¬ 13, which consists of particles 14 by cold gas spraying. These can be clearly seen in their contour in section according to Figure 1, since the parameters of the cold gas spraying are set so that the particles 14 hardly deform upon impact with the workpiece 11 (substrate). However, the kinetic is
Energieeintrag in die Partikel genügend groß, damit diese auf der Haftvermittlerschicht 12 bzw. auf benachbarten PartikelEnergy input into the particles sufficiently large, so that they on the adhesion promoter layer 12 and on adjacent particles
14 haften bleiben. Zwischen den Partikeln bilden sich Poren14 adhere. Pores form between the particles
15 aus, welche zu einem lockeren Schichtgefüge führen. 15 off, which lead to a loose layer structure.
Der Figur 1 lässt sich weiterhin schematisch der Mechanismus entnehmen, wie die Schicht 13 auf eine Beanspruchung durch ein abrasives Teilchen 16 reagiert. Dieses verformt die bean¬ spruchten Partikel 14 plastisch, wobei gleichzeitig die Poren zwischen diesen Partikeln geschlossen werden. Es verbleibt eine Vertiefung 17 in Form eines Kraters oder Kratzers, wobei jedoch hierbei das Schichtmaterial nicht oder nur kaum abge¬ tragen wird, sondern der Beanspruchung durch das abrasive Teilchen 16 unter plastischer Verformung ausweicht. Unter Verwendung eines sogenannten HZO-Farbenzinkstaubs su¬ perfein der Fa. Norzinco GmbH mit Partikelgrößen zwischen 2 und 5 ym wurde durch Kaltgasspritzen eine beständige Schicht hergestellt. Die hergestellte Oberfläche lässt sich Figur 2 bzw. 5 entnehmen. Zu erkennen sind an der Oberfläche noch die Partikel 14, wobei auch Poren zwischen den Partikeln erkennbar sind. Die erzeugte Schichtoberfläche wurde durch Sandstrahlen be¬ handelt, wobei Korund mit einer mittleren Partikelgröße von 120 ym verwendet wurde. Wie Figur 3 bzw. 6 zu entnehmen ist, bewirken die ersten Korund-Partikel 16, die die Oberfläche streifen, Kratzer 18, welche Vertiefungen 17 erzeugen, wie sie in Figur 1 schematisch dargestellt sind. FIG. 1 also shows schematically the mechanism of how the layer 13 reacts to a stress by an abrasive particle 16. This deforms the bean ¬ sprayed particles 14 plastically, while the pores between these particles are closed. There remains a recess 17 in the form of a crater or scratches, but in this case the layer material is not or only hardly abge ¬ wear, but the stress escapes by the abrasive particles 16 under plastic deformation. Using a so-called HZO-Farbzinkstaubs su ¬ perfein the Fa. Norzinco GmbH with particle sizes between 2 and 5 ym was produced by cold gas spraying a stable layer. The surface produced can be seen in Figures 2 and 5, respectively. The particles 14 can still be seen on the surface, whereby pores between the particles can also be recognized. The surface layer produced was be ¬ is by sand blasting, wherein corundum is used having an average particle size of 120 .mu.m. As can be seen in FIGS. 3 and 6, the first corundum particles 16 which strike the surface cause scratches 18, which produce depressions 17, as shown schematically in FIG.
Wird die Oberfläche über einen längeren Zeitraum durch Sandstrahlen beansprucht, so entsteht ein Oberflächenbild gemäß Figur 4 bzw. 7. Es wird deutlich, dass die verschiedenen Kratzer 18, die durch die Korund-Partikel 16 erzeugt werden, sich überlagern und überschneiden. Hierdurch wird deutlich, dass auch eine mehrfache plastische Verformung des Schicht¬ werkstoffes möglich ist, auch wenn die ursprüngliche Oberflä¬ chenbeschaffenheit, bestehend aus Partikeln 14, nach einem längeren Angriff durch das abrasive Medium nicht mehr zu erkennen ist. Dennoch ist auch in diesem Stadium der Beanspruchung der abrasive Abtrag an Zink noch relativ gering. If the surface is subjected to sandblasting over a relatively long period of time, a surface image appears according to FIGS. 4 and 7. It becomes clear that the various scratches 18 which are produced by the corundum particles 16 overlap and overlap. This makes it clear that a multiple plastic deformation of the layer ¬ material is possible, even if the original Oberflä ¬ chenbeschaffenheit consisting of particles 14, after a prolonged attack by the abrasive medium is no longer visible. Nevertheless, even at this stage of the stress, the abrasive removal of zinc is still relatively low.

Claims

Patentansprüche claims
1. Verfahren zum Erzeugen einer gegen abrasiven Verschleiß widerstandsfähigen Schicht (13) auf einem als Substrat ver- wendeten Werkstück (11) durch Kaltgasspritzen, bei dem Partikel (14) zur zu beschichtenden Oberfläche des Substrates hin beschleunigt werden und an der Auftreffstelle am Substrat haften bleiben, 1. A method for producing a wear-resistant layer (13) on a workpiece used as a substrate (11) by cold gas spraying, in which particles (14) are accelerated towards the surface of the substrate to be coated and adhere to the impact on the substrate stay,
d a d u r c h g e k e n n z e i c h n e t , characterized ,
dass die Partikel (14) that the particles (14)
• aus Zn und/oder Sn und/oder Cu und/oder AI und/oder Ti und/oder einer zumindest eines dieser Metalle als Haupt¬ bestandteil enthaltenden Legierung bestehen, und • of Zn and / or Sn and / or Cu and / or Al and / or Ti and / or at least one of these metals containing as a main ingredient ¬ alloy, and
• mit einer Geschwindigkeit auf das Substrat auftreffen, dass die sich ausbildende Schicht porös ist und die • impinge on the substrate at a rate that the forming layer is porous and the
Korngröße des Schichtgefüges im wesentlichen der Parti¬ kelgröße entspricht. Grain size of the layer structure essentially corresponds to the Parti ¬ kelgröße.
2. Verfahren nach Anspruch 1, 2. The method according to claim 1,
d a d u r c h g e k e n n z e i c h n e t , characterized ,
dass die Partikel (14) eine mittlere Partikelgröße von 1 bis 10 ym, bevorzugt 2 bis 5 ym aufweisen. the particles (14) have an average particle size of 1 to 10 μm, preferably 2 to 5 μm.
3. Verfahren nach einem der vorangehenden Ansprüche, 3. The method according to any one of the preceding claims,
d a d u r c h g e k e n n z e i c h n e t , characterized ,
dass vor dem Aufbringen der Schicht (13) eine Haftvermittlerschicht (12), insbesondere eine Schicht aus Ni, auf das Sub¬ strat aufgebracht wird, welche die Schicht (13) durch Ausbil¬ dung gemeinsamer Diffusionszonen oder intermetallischer Pha- sen festhält. that prior to applying the layer (13) an adhesive layer (12), in particular a layer of Ni is applied to the sub ¬ strat, which holds the layer (13) by Ausbil ¬ dung common diffusion regions or intermetallic phases.
4. Verwendung einer porösen kaltgasgespritzten Schicht, die aus Zn und/oder Sn und/oder Cu und/oder AI und/oder Ti und/oder einer zumindest eines dieser Metalle als Hauptbe¬ standteil enthaltenden Legierung besteht und bei der sich zwischen den kaltgasgespritzten Partikeln (14) Poren (15) be finden, als Schutzschicht auf einem gegen abrasiven Verschleiß zu schützenden Werkstück (11) . 4. Use of a porous cold gas-sprayed layer consisting of Zn and / or Sn and / or Cu and / or Al and / or Ti and / or at least one of these metals containing as Hauptbe ¬ was partially alloy and in which between the cold gas sprayed particles (14) has pores (15) be found, as a protective layer on an abrasive wear to be protected workpiece (11).
5. Verwendung nach Anspruch 4, 5. Use according to claim 4,
d a d u r c h g e k e n n z e i c h n e t , characterized ,
dass die Partikel (14) eine mittlere Partikelgröße von 1 bis 10 ym, bevorzugt 2 bis 5 ym aufweisen. the particles (14) have an average particle size of 1 to 10 μm, preferably 2 to 5 μm.
6. Verwendung nach einem der Ansprüche 4 oder 5, 6. Use according to one of claims 4 or 5,
d a d u r c h g e k e n n z e i c h n e t , characterized ,
dass das Werkstück (11) aus einem Metall oder einer Metallle gierung besteht, dass die elektrochemisch edler ist als das Material der Partikel. in that the workpiece (11) consists of a metal or a metal alloy, that is electrochemically nobler than the material of the particles.
EP11723054.0A 2010-05-31 2011-05-31 Method for producing a layer by means of cold spraying and use of such a layer Active EP2576863B1 (en)

Applications Claiming Priority (2)

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DE102010022597A DE102010022597A1 (en) 2010-05-31 2010-05-31 Method for producing a layer by means of cold gas spraying and use of such a layer
PCT/EP2011/058919 WO2011151313A1 (en) 2010-05-31 2011-05-31 Method for producing a layer by means of cold spraying and use of such a layer

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Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102010022597A1 (en) 2010-05-31 2011-12-01 Siemens Aktiengesellschaft Method for producing a layer by means of cold gas spraying and use of such a layer
US10245615B2 (en) * 2010-07-15 2019-04-02 Commonwealth Scientific And Industrial Research Organisation Surface treatment
DE102012211440A1 (en) * 2011-10-21 2013-04-25 Mahle International Gmbh piston
EP2669399B1 (en) 2012-06-01 2016-10-12 Oerlikon Metco AG, Wohlen Bearing and thermal spray method
JP5535280B2 (en) * 2012-07-23 2014-07-02 株式会社不二機販 Method for strengthening welding tip and welding tip
DE102012023210A1 (en) * 2012-11-28 2014-05-28 Wieland-Werke Ag Copper strip for the production of printed circuit boards
DE102019205961B3 (en) * 2019-04-25 2020-10-15 Volkswagen Aktiengesellschaft Component for a wheel suspension of a vehicle

Family Cites Families (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19747386A1 (en) * 1997-10-27 1999-04-29 Linde Ag Process for the thermal coating of substrate materials
US6365222B1 (en) * 2000-10-27 2002-04-02 Siemens Westinghouse Power Corporation Abradable coating applied with cold spray technique
US6706319B2 (en) * 2001-12-05 2004-03-16 Siemens Westinghouse Power Corporation Mixed powder deposition of components for wear, erosion and abrasion resistant applications
CA2378993C (en) * 2002-03-26 2007-12-18 National Research Council Of Canada Acousto-immersion coating and process for magnesium and its alloys
WO2005079209A2 (en) * 2003-11-26 2005-09-01 The Regents Of The University Of California Nanocrystalline material layers using cold spray
KR20050081252A (en) 2004-02-13 2005-08-18 고경현 Porous metal coated member and manufacturing method thereof using cold spray
DE102004043914A1 (en) * 2004-09-10 2006-03-16 Linde Ag Bronze slip bearing is fabricated by cold gas spray application of a suitable alloy
US7479299B2 (en) * 2005-01-26 2009-01-20 Honeywell International Inc. Methods of forming high strength coatings
SG141297A1 (en) 2006-09-11 2008-04-28 United Technologies Corp Method for processing titanium alloy components
EP1903127A1 (en) * 2006-09-21 2008-03-26 Siemens Aktiengesellschaft Process of manufacturing of workpieces by cold gas spraying and turbine workpiece
US8192792B2 (en) 2006-10-27 2012-06-05 United Technologies Corporation Cold sprayed porous metal seals
US8147982B2 (en) 2007-12-19 2012-04-03 United Technologies Corporation Porous protective coating for turbine engine components
DE102009036407A1 (en) 2009-08-06 2011-02-10 Mtu Aero Engines Gmbh Abradable blade tip pad
KR101445624B1 (en) 2009-11-10 2014-09-29 덴끼 가가꾸 고교 가부시키가이샤 β-SIALON, METHOD FOR PRODUCING SAME AND LIGHT-EMITTING DEVICE USING SAME
DE102010022597A1 (en) 2010-05-31 2011-12-01 Siemens Aktiengesellschaft Method for producing a layer by means of cold gas spraying and use of such a layer

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2011151313A1 *

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Publication number Publication date
EP2576863B1 (en) 2020-03-18
US20130142950A1 (en) 2013-06-06
DE102010022597A1 (en) 2011-12-01
US8993048B2 (en) 2015-03-31
WO2011151313A1 (en) 2011-12-08

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