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EP0389959B1 - Method for applying corrosion and abrasion protective coatings - Google Patents

Method for applying corrosion and abrasion protective coatings Download PDF

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Publication number
EP0389959B1
EP0389959B1 EP19900105401 EP90105401A EP0389959B1 EP 0389959 B1 EP0389959 B1 EP 0389959B1 EP 19900105401 EP19900105401 EP 19900105401 EP 90105401 A EP90105401 A EP 90105401A EP 0389959 B1 EP0389959 B1 EP 0389959B1
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EP
European Patent Office
Prior art keywords
layer
layers
alloy
sprayed
hard
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.)
Expired - Lifetime
Application number
EP19900105401
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German (de)
French (fr)
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EP0389959A1 (en
Inventor
Hans-Theo Steine
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.)
ECG Immobilier SA
Original Assignee
Castolin SA
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Filing date
Publication date
Application filed by Castolin SA filed Critical Castolin SA
Publication of EP0389959A1 publication Critical patent/EP0389959A1/en
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Publication of EP0389959B1 publication Critical patent/EP0389959B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C4/00Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/18After-treatment

Definitions

  • the invention relates to a method for producing wear-resistant and corrosion-resistant protective layers by thermal spraying according to the preamble of claim 1.
  • a first coating of a thickness between 0.0125 and 0.125 mm is applied to these objects, which is made of an alloy based on Ni, Co or Fe with proportions of chromium, aluminum and an element from the group containing yttrium and rare earths and then a second layer, the thickness of which is between half and four times the layer thickness of the first coating.
  • This second layer is highly corrosion-resistant and consists of an alloy with chromium, aluminum, elements of the group comprising yttrium, scandium, cerium, hafnium, zirconium, titanium and tantalum, supplemented by cobalt, nickel and iron with aluminum and chromium.
  • said article is subjected to a temperature treatment under protective gas, the temperature being between 1020 ° C. and 1200 ° C. for up to ten hours. Both layers are applied by means of plasma spraying.
  • a process for producing wear-resistant and corrosion-resistant layers by plasma spraying in which a coating material made of refractory metal carbides and a nickel-containing base alloy with 3 to 18 percent by weight boron is applied.
  • the carbides can be mixed with iron, cobalt or nickel and applied separately or mixed with the nickel-boron alloy.
  • a metal carbide layer (with or without metal binder) is first applied by means of plasma coating and then a second layer of a reactive Ni-based alloy. Then the thus coated article is heat treated so that the second layer melts, penetrates into the first layer and reacts with it.
  • GB-A-2 021 641 also describes a one-layer process which consists in that a mixture of metal carbides (with or without metal binder) and reactive nickel-based metal is applied in the plasma spraying process, after which the coated article is subjected to a heat treatment is subjected so that the reactive metal melts and reacts with the metal carbide portion.
  • US-A-3,054,693 discloses a coating process without any heat treatment. The main focus is on an alloy material made of molybdenum, which should alternate with layers of aluminum oxide.
  • the inventor has set himself the task of producing wear-resistant and corrosion-resistant coatings in a wide range with regard to composition and stress, in which the position of the hard materials can be influenced in a certain range.
  • the composition of the layers is predetermined by the spray material, and there is no possibility of influencing the position of any hard materials to be provided in the layer.
  • a hard material layer is sprayed on between a base layer and a cover layer made of an alloy based on Ni, Co and / or Fe, the layer thicknesses being between 0.02 mm and 0.5 mm, at a temperature between 600 ° and 1200 ° during the diffusion treatment; the diffusion time is from 10 min to 30 min.
  • different hard materials should be able to be used for the hard material layers per layer.
  • the coating according to the invention is thus produced by spraying two or more layers of alloys in layers, e.g. on Ni, Co and / or Fe basis with hard material intermediate layers, which are subsequently diffused with a heat treatment in a solid or partially liquid state to form a coating with the desired composition.
  • the variation in the composition of the coating is controlled via the layer thickness of the individual sprayed-on layers.
  • carbides, borides and / or silicides are used for the hard material intermediate layers.
  • the hard material layers mentioned can be constructed in such a way that different hard materials are used per layer.
  • An alloy based on Ni or Co is preferably used for the sprayed-on base or cover layer.
  • the intermediate layers from metals such as chromium, molybdenum and / or tungsten.
  • the diffusion process can be carried out in a vacuum furnace or in a muffle furnace with or without protective gas in the temperature range from 600 to 1200 ° C depending on the layer structure and alloy.
  • a protective coating against fretting should be applied to a machine part.
  • the diffusion process was carried out in a vacuum oven at a negative pressure of 1.33 Pa (10 ⁇ 2 Torr) in the temperature range from 900 to 1100 ° C for about 30 minutes.
  • Example I The same preparations and coatings as in Example I were selected, with the difference that the spraying was carried out with a plasma flame spray gun and the diffusion process was carried out in a muffle furnace with protective gas for 10 minutes.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Plasma & Fusion (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Coating By Spraying Or Casting (AREA)

Description

Die Erfindung betrifft ein Verfahren zum Herstellen von verschleiß- und korrosionsbeständigen Schutzschichten durch thermisches Spritzen nach dem Oberbegriff des Patentanspruches 1.The invention relates to a method for producing wear-resistant and corrosion-resistant protective layers by thermal spraying according to the preamble of claim 1.

Ein derartiges Verfahren beschreibt die FR-A-2 407 272 zur Verbesserung der Abnutzungseigenschaften von Gegenständen bei erhöhten Temperaturen; auf diese Gegenstände wird zuerst eine erste Beschichtung einer Dicke zwischen 0,0125 und 0,125 mm aufgetragen, die aus einer Legierung auf der Basis von Ni, Co oder Fe mit Anteilen an Chrom, Aluminium und einem Element aus der Yttrium und Seltene Erden enthaltenden Gruppe hergestellt wird, und dann eine zweite Schicht, deren Dicke zwischen der halben und der vierfachen Schichtdicke der ersten Beschichtung liegt. Diese zweite Schicht ist in hohem Maße korrosionsbeständig und besteht aus einer Legierung, mit Chrom, Aluminium, Elementen der Yttrium, Scandium, Cerium, Hafnium, Zirkonium, Titan und Tantal erfassenden Gruppe unter Ergänzung durch Kobalt, Nickel und Eisen mit Aluminium und Chrom. Nach dem zweiten Beschichtungsvorgang wird besagter Gegenstand einer Temperaturbehandlung unter Schutzgas unterworfen, wobei die Temperatur zwischen 1020°C und 1200°C während einer bis zu zehn Stunden beträgt. Beide Schichten werden auf dem Wege des Plasmaspritzens aufgetragen.Such a method is described in FR-A-2 407 272 for improving the wear properties of objects at elevated temperatures; a first coating of a thickness between 0.0125 and 0.125 mm is applied to these objects, which is made of an alloy based on Ni, Co or Fe with proportions of chromium, aluminum and an element from the group containing yttrium and rare earths and then a second layer, the thickness of which is between half and four times the layer thickness of the first coating. This second layer is highly corrosion-resistant and consists of an alloy with chromium, aluminum, elements of the group comprising yttrium, scandium, cerium, hafnium, zirconium, titanium and tantalum, supplemented by cobalt, nickel and iron with aluminum and chromium. After the second coating process, said article is subjected to a temperature treatment under protective gas, the temperature being between 1020 ° C. and 1200 ° C. for up to ten hours. Both layers are applied by means of plasma spraying.

Es handelt sich also um ein Zweischichtverfahren, wobei einerseits nur auf ganz bestimmte Materialarten der zu verbessernden Gegenstände abgehoben wird und außerdem für die äußere -- die Korrosionsbeständigkeit erbringende -- Schicht enge Vorgaben bezüglich ihrer Zusammensetzung gegeben sind.It is therefore a two-layer process, whereby on the one hand only certain types of material of the objects to be improved are lifted off and, furthermore, there are strict specifications regarding their composition for the outer layer, which provides corrosion resistance.

Aus der GB-A-2 021 641 ist ein Verfahren zur Herstellung verschleiß- und korrosionsfester Schichten durch Plasmaspritzen bekannt, bei dem ein Beschichtungsmaterial aus feuerfesten Metallkarbiden und einer Nickel enthaltenden Basislegierung mit 3 bis 18 Gewichtsprozenten Bor aufgetragen wird. Die Karbide können vermischt sein mit Eisen, Kobalt oder Nickel und gesondert oder vermischt mit der Nickel-Bor-Legierung aufgetragen werden. Bei diesem Zweischichtverfahren, wird zunächst eine Metallkarbidschicht (mit oder ohne Metallbinder) mittels Plasmabeschichtung aufgetragen und darüber eine zweite Schicht einer reaktiven Ni-Basis-Legierung. Dann wird der so beschichtete Gegenstand wärmebehandelt, so daß die zweite Schicht schmilzt, in die erste Schicht eindringt und mit ihr reagiert. Der Autor der GB-A-2 021 641 beschreibt auch ein Ein-Schicht-Verfahren, das darin besteht, daß im Plasmaspritzverfahren eine Mischung aus Metallkarbiden (mit oder ohne Metallbinder) und reaktivem Metall auf Nickelbasis aufgetragen wird, worauf der beschichtete Artikel einer Wärmebehandlung unterzogen wird, so daß das reaktive Metall schmilzt und mit dem Metallkarbidanteil reagiert. Schließlich offenbart die US-A-3 054 693 ein Beschichtungsverfahren gänzlich ohne Wärmebehandlung. Es wird vor allem auf einen Legierungswerkstoff aus Molybdän abgehoben, der sich mit Schichten aus Aluminiumoxid abwechseln soll.From GB-A-2 021 641 a process for producing wear-resistant and corrosion-resistant layers by plasma spraying is known, in which a coating material made of refractory metal carbides and a nickel-containing base alloy with 3 to 18 percent by weight boron is applied. The carbides can be mixed with iron, cobalt or nickel and applied separately or mixed with the nickel-boron alloy. In this two-layer process, a metal carbide layer (with or without metal binder) is first applied by means of plasma coating and then a second layer of a reactive Ni-based alloy. Then the thus coated article is heat treated so that the second layer melts, penetrates into the first layer and reacts with it. The author of GB-A-2 021 641 also describes a one-layer process which consists in that a mixture of metal carbides (with or without metal binder) and reactive nickel-based metal is applied in the plasma spraying process, after which the coated article is subjected to a heat treatment is subjected so that the reactive metal melts and reacts with the metal carbide portion. Finally, US-A-3,054,693 discloses a coating process without any heat treatment. The main focus is on an alloy material made of molybdenum, which should alternate with layers of aluminum oxide.

In Kenntnis dieses Standes der Technik hat sich der Erfinder die Aufgabe gestellt, verschleiß- und korrosionsbeständige Beschichtungen in einem weiten Bereich in Hinsicht auf Zusammensetzung und Beanspruchung herzustellen, bei denen die Lage der Hartstoffe in einem bestimmten Bereich beeinflußt werden kann. Beim Stande der Technik ist die Zusammensetzung der Schichten durch den Spritzwerkstoff vorgegeben, und es besteht keine Möglichkeit, die Lage gegebenenfalls vorzusehender Hartstoffe in der Schicht zu beeinflussen.Knowing this state of the art, the inventor has set himself the task of producing wear-resistant and corrosion-resistant coatings in a wide range with regard to composition and stress, in which the position of the hard materials can be influenced in a certain range. In the prior art, the composition of the layers is predetermined by the spray material, and there is no possibility of influencing the position of any hard materials to be provided in the layer.

Zur Lösung dieser Aufgabe führt die Lehre nach dem Patentanspruch 1. Besondere Weiterbildungen sind in den abhängigen Ansprüchen 2 bis 7 wiedergegeben.The teaching according to claim 1 leads to the solution of this problem. Special further developments are given in the dependent claims 2 to 7.

Zwischen einer Grundschicht und einer Deckschicht aus einer Legierung auf Ni-, Co- und/oder Fe-Basis wird eine Hartstoffschicht aufgespritzt, wobei die Schichtdicken zwischen 0,02 mm und 0,5 mm liegen, bei einer Temperatur zwischen 600° und 1200° während der Diffusionsbehandlung; die Diffusionszeit beträgt von 10 min bis 30 min. Zudem sollen bei mehr als drei aufgespritzten Schichten für die Hartstoffschichten pro Schicht verschiedene Hartstoffe verwendet werden können.A hard material layer is sprayed on between a base layer and a cover layer made of an alloy based on Ni, Co and / or Fe, the layer thicknesses being between 0.02 mm and 0.5 mm, at a temperature between 600 ° and 1200 ° during the diffusion treatment; the diffusion time is from 10 min to 30 min. In addition, in the case of more than three sprayed-on layers, different hard materials should be able to be used for the hard material layers per layer.

Die Herstellung der erfindungsgemäßen Beschichtung erfolgt also durch schichtweises Aufspritzen von zwei oder mehreren Schichten aus Legierungen z.B. auf Ni-, Co- und/oder Fe-Basis mit Hartstoffzwischenschichten, die nachträglich mit einer Wärmebehandlung in festen oder teilweise flüssigem Zustand zu einer Beschichtung mit gewünschter Zusammensetzung diffundiert werden.The coating according to the invention is thus produced by spraying two or more layers of alloys in layers, e.g. on Ni, Co and / or Fe basis with hard material intermediate layers, which are subsequently diffused with a heat treatment in a solid or partially liquid state to form a coating with the desired composition.

Die Variation der Zusammensetzung der Beschichtung wird über die Schichtstärke der einzelnen aufgespritzten Schichten gesteuert.The variation in the composition of the coating is controlled via the layer thickness of the individual sprayed-on layers.

Um eine gute Verschleißbeständigkeit zu erreichen, werden für die Hartstoffzwischenschichten Karbide, Boride und/oder Silicide verwendet. Außerdem können erfindungsgemäß die erwähnten Hartstoffschichten so aufgebaut werden, daß pro Schicht verschiedene Hartstoffe eingesetzt werden. Für die aufgespritzte Grund- bzw. Deckschicht wird bevorzugt eine Legierung auf Ni- /oder Co-Basis herangezogen.In order to achieve good wear resistance, carbides, borides and / or silicides are used for the hard material intermediate layers. In addition, according to the invention, the hard material layers mentioned can be constructed in such a way that different hard materials are used per layer. An alloy based on Ni or Co is preferably used for the sprayed-on base or cover layer.

Auch ist es vorgesehen, für den Fall, daß beispielsweise fünf Schichten aufgetragen werden, die Zwischenschichten aus Metallen wie Chrom, Molybdän und/oder Wolfram zu fertigen. Der Diffusionsvorgang kann in einem Vakuumofen oder in einem Muffelofen mit oder ohne Schutzgas im Temperaturbereich von 600 bis 1200°C je nach Schichtaufbau und Legierung durchgeführt werden.It is also envisaged, in the event that, for example, five layers are applied, to manufacture the intermediate layers from metals such as chromium, molybdenum and / or tungsten. The diffusion process can be carried out in a vacuum furnace or in a muffle furnace with or without protective gas in the temperature range from 600 to 1200 ° C depending on the layer structure and alloy.

Weitere Vorteile und Einzelheiten der Erfindung ergeben ich aus der nachfolgenden Beschreibung bevorzugter Beispiele.Further advantages and details of the invention result from the following description of preferred examples.

Beispiel IExample I

Auf ein Maschinenteil soll eine Schutzbeschichtung gegen Reibverschleiß aufgebracht werden.A protective coating against fretting should be applied to a machine part.

Auf die durch Strahlen vorbereitete Oberfläche wurden mit einem Flammspritzgerät fünf Schichten einer Schichstärke für die Legierungsschichten von 0,1 mm und die Hartstoffschichten von 0,2 mm in der Reihenfolge Legierungsschicht - Hartsoffschicht - Legierungsschicht - Hartstoffschicht - Legierungsschicht aufgespritzt. Als Legierungsschicht wurde für die Grund- und Deckschicht eine NiCrBSi Legierung verwendet. Und für die Zwischenschicht eine NiCr Legierung. Die zwei Hartstoffschichten bestanden aus Wolframkarbid.Five layers of a layer thickness for the alloy layers of 0.1 mm and the hard material layers of 0.2 mm were sprayed onto the surface prepared by blasting using a flame spraying device in the order of alloy layer - hard material layer - alloy layer - hard material layer - alloy layer. A NiCrBSi alloy was used as the alloy layer for the base and top layers. And a NiCr alloy for the intermediate layer. The two hard material layers consisted of tungsten carbide.

Der Diffusionsvorgang wurde im Vakuumofen bei einem Unterdruck von 1.33 Pa (10⁻² Torr) im Temperaturbereich von 900 bis 1100° C während etwa 30 min durchgeführt.The diffusion process was carried out in a vacuum oven at a negative pressure of 1.33 Pa (10⁻² Torr) in the temperature range from 900 to 1100 ° C for about 30 minutes.

Beispiel IIExample II

Es wurden die gleichen Vorbereitungen und Beschichtungen wie im Beispiel I gewählt mit dem Unterschied, daß das Aufspritzen mit einer Plasmaflammspritzpistole erfolgte und der Diffusionsvorgang in einem Muffelofen mit Schutzgas während 10 min durchgeführt wurde.The same preparations and coatings as in Example I were selected, with the difference that the spraying was carried out with a plasma flame spray gun and the diffusion process was carried out in a muffle furnace with protective gas for 10 minutes.

Claims (7)

  1. Method for applying abrasion- and corrosion-resistant protective coatings by thermal spraying, in which several thin layers of alloying materials are sprayed on with a predetermined layer thickness and then diffusion treatment is carried out at temperatures of up to 1200°C in the solid and partially liquid state and as a function of time in order to form a layer having a specific composition, characterised in that a hard coating is sprayed on between a ground coat and a top coat consisting of an alloy based on Ni, Co and/or Fe, the layer thicknesses being between 0.02 mm and 0.5 mm, and that the temperature during the diffusion treatment is between 600° and 1200° and the diffusion time is between 10 mins and 30 mins.
  2. Method according to claim 1, characterised in that different hard materials are used for each layer of the hard coatings when more than three layers are sprayed on.
  3. Method according to claim 1 or claim 2, characterised by a spray-applied hard coating consisting of carbides, borides and/or silicides.
  4. Method according to one of claims 1 to 3, characterised in that at least one of the layers of alloying materials consists of metals such as chromium, molybdenum and/or tungsten.
  5. Method according to one of claims 1 to 4, characterised by layer thicknesses in the region of 0.05 to 0.3 mm.
  6. Method according to one of claims 1 to 5, characterised by tungsten carbide as a hard coating with a layer thickness of 0.2 mm, the alloy layers being 0.1 mm thick.
  7. Method according to claim 6, characterised in that the diffusion process is effected in a vacuum furnace at a negative pressure of 1.33 Pa (10⁻² torr) in the temperature range of 900°C to 1100°C for approximately 30 mins, the ground coat and the top coat being an Ni-Cr-B-Si alloy and the intermediate layer between two hard coatings being an Ni-Cr alloy.
EP19900105401 1989-03-28 1990-03-22 Method for applying corrosion and abrasion protective coatings Expired - Lifetime EP0389959B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CH108189A CH677498A5 (en) 1989-03-28 1989-03-28
CH1081/89 1989-03-28

Publications (2)

Publication Number Publication Date
EP0389959A1 EP0389959A1 (en) 1990-10-03
EP0389959B1 true EP0389959B1 (en) 1994-09-14

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Family Applications (1)

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EP19900105401 Expired - Lifetime EP0389959B1 (en) 1989-03-28 1990-03-22 Method for applying corrosion and abrasion protective coatings

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EP (1) EP0389959B1 (en)
CH (1) CH677498A5 (en)
DE (1) DE59007099D1 (en)
ES (1) ES2063848T3 (en)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3941853C1 (en) * 1989-12-19 1991-04-11 Mtu Muenchen Gmbh
DE4134133A1 (en) * 1991-10-15 1993-04-22 Castolin Sa Coating aluminium@ contg. copper@ alloys with wear-resistant layer - using intermediate pptd. nickel@-, cobalt@ and/or iron@ based alloy to improve adhesion without using toxic flux
AT398580B (en) * 1991-11-05 1994-12-27 Strauss Helmut COATING FOR METAL OR NON-METAL SUBSTRATES, METHOD AND DEVICE FOR THE PRODUCTION THEREOF
RU2109843C1 (en) * 1996-12-17 1998-04-27 Йелстаун Корпорейшн Н.В. Method for manufacturing parts with hardened working surface
US6294260B1 (en) 1999-09-10 2001-09-25 Siemens Westinghouse Power Corporation In-situ formation of multiphase air plasma sprayed barrier coatings for turbine components
US6677064B1 (en) 2002-05-29 2004-01-13 Siemens Westinghouse Power Corporation In-situ formation of multiphase deposited thermal barrier coatings

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB400752A (en) * 1932-08-31 1933-11-02 Metallisation Ltd A method of protecting articles of oxidisable metals or metal alloys from oxidation, deterioration or corrosion
FR1046251A (en) * 1951-12-08 1953-12-04 Snecma Sintered ceramic-metal composite material which can be used in particular for the manufacture of thermal machine parts and the process for obtaining it
GB803649A (en) * 1955-10-22 1958-10-29 Birmingham Small Arms Co Ltd Improvements in or relating to sprayed metal coatings
US3054694A (en) * 1959-10-23 1962-09-18 Jr William L Aves Metal-ceramic laminated coating and process for making the same
FR1434158A (en) * 1964-11-25 1966-04-08 Sfec Improvements to refractory protective coatings, and method of manufacturing these elements
US3837894A (en) * 1972-05-22 1974-09-24 Union Carbide Corp Process for producing a corrosion resistant duplex coating
US4198442A (en) * 1977-10-31 1980-04-15 Howmet Turbine Components Corporation Method for producing elevated temperature corrosion resistant articles
US4173685A (en) * 1978-05-23 1979-11-06 Union Carbide Corporation Coating material and method of applying same for producing wear and corrosion resistant coated articles

Also Published As

Publication number Publication date
CH677498A5 (en) 1991-05-31
ES2063848T3 (en) 1995-01-16
EP0389959A1 (en) 1990-10-03
DE59007099D1 (en) 1994-10-20

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