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EP1379708B1 - Coating powder based on chemically modified titanium suboxides - Google Patents

Coating powder based on chemically modified titanium suboxides Download PDF

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Publication number
EP1379708B1
EP1379708B1 EP02740417A EP02740417A EP1379708B1 EP 1379708 B1 EP1379708 B1 EP 1379708B1 EP 02740417 A EP02740417 A EP 02740417A EP 02740417 A EP02740417 A EP 02740417A EP 1379708 B1 EP1379708 B1 EP 1379708B1
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EP
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Prior art keywords
coating powder
coating
powder according
powder
sub
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German (de)
French (fr)
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EP1379708A2 (en
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Lutz-Michael Berger
Sven Thiele
Manfred Nebelung
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Fraunhofer Gesellschaft zur Foerderung der Angewandten Forschung eV
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Fraunhofer Gesellschaft zur Foerderung der Angewandten Forschung eV
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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
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
    • C23C4/10—Oxides, borides, carbides, nitrides or silicides; Mixtures thereof
    • C23C4/11—Oxides

Definitions

  • the invention relates to coating powders based on chemically modified suboxides of titanium having the general formula Ti n-2 Me 2 O 2n-1 , wherein Me is Cr or V, for use in various coating technologies (such as the different variants of thermal spraying such as plasma spraying, high velocity flame spraying (HVOF) and detonation spraying, and other processes such as laser coating).
  • thermal spraying such as plasma spraying, high velocity flame spraying (HVOF) and detonation spraying, and other processes such as laser coating.
  • the coating powder according to the invention can be applied to various components.
  • the layers are characterized by high electrical conductivity and solid lubricant properties.
  • application possibilities for the components coated with the powder according to the invention are derived as a functional layer for fuel cells, in electrochemical plants, in vehicle construction, in mechanical engineering, and in other economic sectors.
  • Coating powders based on titanium suboxides in addition to a detailed representation of the prior art in DE 100 00 979 (to avoid unnecessary repetition, reference is made to this representation only). These powders are characterized in that n in the formula Ti n O 2n-1 has a narrow range of n ⁇ 2 or narrower and the coating powder particles have a particle size in the range 10-90 microns. In coating experiments, however, it was found that the layers sprayed from this powder had an oxygen deficit compared to TiO 2 , but a disturbing partial oxidation during the coating process is unavoidable.
  • the coating powders according to the invention are modified by at least one metallic alloying element and can be described by the general formula Ti n-2 Me 2 O 2n-1 , where Me is Cr or V and the coating powder is a grain size in the range of 10-90 microns.
  • the coating powders contain one or more further alloying elements which stabilize or are inert to individual phases of the general formula Ti n-2 Me 2 O 2n-1 .
  • Titanium suboxides with planar defect structures can also be described as homologous series with the formula x TiO 2 * Ti 2 O 3 . They can be located next to the in DE 100 00 979 also easily synthesized by a solid state reaction of starting mixtures of different molar ratios of TiO 2 and Ti 2 O 3 . Ti 2 O 3 can be replaced by a variety of other trivalent metal oxides in this reaction. However, according to the current state of science and technology, there are only a few trivalent metal oxides in which the reaction products have the structure of Magnéli phases. These are in particular Cr 2 O 3 and V 2 O 3 .
  • modified titanium suboxides with the structure of Magnéli phases which are described by the general formula Ti n-2 Cr 2 O 2n-1 , with n ⁇ 4 can be produced easily .
  • Magnéli phases of the structure Ti n-2 Cr 2 O 2n-1 form with n ⁇ 4 in air.
  • Another way of making the phases is, as mentioned above, of P. Sujatha Devi, J. Solid State Chemistry, Vol. 110, 1994, p. 345-349 , described.
  • vanadium modified titanium suboxides with the structure of Magnéli phases described by the general formula Ti n-2 V 2 O 2n-1 with n ⁇ 3, for example according to the in US 5,049,537 simply produce these methods.
  • the toxicity of V 2 O 3 and other valence vanadium vanadium oxides requires increased precautions in the synthesis of the Magnéli phases, the preparation of the coating powders, and their processing by thermal spraying.
  • n in the formula Ti n-2 Me 2 O 2n-1 comprises a range of n ⁇ 2.
  • a narrower range of n ⁇ 1 can be achieved while adhering to narrower technological parameter limits during production.
  • n ⁇ 5 it is possible that only phases corresponding to a discrete value of n are present in the coating powder. This means that the coating powder is single-phase, if only one phase is known for n. If several phases are known for a discrete n, they may be present next to each other. Due to the ever smaller differences in the oxygen contents with increasing n, the coating powders with n ⁇ 5 can be prepared so that in addition to the desired phase n nor a second phase n + 1 or n-1 is present.
  • the coating powder for special requirements has a particle size in the range 10-45 microns.
  • the coating powders according to the invention can have different properties with respect to their porosity and their morphology, and the preparation can in principle be carried out in different ways.
  • the preferred variant consists in that the synthesis takes place via a solid-state reaction of homogeneous starting mixtures of finely dispersed titanium dioxide powder and trivalent metal oxide powder, in particular Cr 2 O 3 and V 2 O 3 of different molar ratios.
  • the homogeneous starting mixtures may contain the further alloying elements, for example in the form of oxides.
  • doping, metal powder or to Oxides decomposing compounds of the alloying metals can also be used.
  • an additional reduction can be carried out with a solid or gaseous reducing agent.
  • the suboxide Ti n-2 Me 2 O 2n-1 can optionally be processed by grinding processes and the grain size can be reduced.
  • the preparation of the coating powder from the synthesized powders of the composition Ti n-2 Me 2 O 2n-1 is preferably carried out by agglomeration, sintering and fractionation according to the in DE 100 00 979 described method steps, without changing the phase composition.
  • Spray drying is the preferred method for agglomeration.
  • the starting oxides TiO 2 and Cr 2 O 3 can be spray-dried together in the required ratio, and the corresponding Magnéli phases are obtained in the softened coating powder by reaction sintering.
  • Another possibility of production is to adjust the final phase composition during sintering of the coating powder from previously synthesized powders. This is done, for example, by changing the sintering temperature with respect to the synthesis temperature.
  • the grain size of the primary individual particles does not change or only slightly.
  • the grain size of the sintered individual particles in the coating powder particles is ⁇ 5 ⁇ m.
  • these coating powders are characterized inter alia by a spherical morphology and a porosity of greater than 3%, preferably greater than 10% ,
  • the porosity of the coating powders is determined by mercury porosimetry. When calculating the porosity, the intruded volume at a pressure corresponding to a pore diameter> 1 micron, is not taken into account, as this mercury in the Cavities between the individual coating powder particles is pressed. Due to the porosity and the fine individual particles, these coating powders are also characterized by specific surface areas> 1 m 2 / g.
  • coating powders according to the invention Another possibility for producing the coating powders according to the invention is that the synthesis of Ti n-2 Me 2 O 2n-1 is realized directly in the production of coating powders in other processes, for example melting and breaking or sintering and breaking. These coating powders can be easily further reduced with a gaseous reducing agent. The morphology, grain size and the particle size distribution of the starting powder are essentially retained. Thus, these coating powders may also have a different, for example, an angular morphology and have a porosity ⁇ 10%, preferably ⁇ 5%.
  • All coating powders according to the invention can be processed into layers with various surface technologies. They are particularly suitable for the process group of thermal spraying, such as, for example, plasma spraying, high-speed flame spraying (HVOF) and detonation spraying, and also laser and hybrid coating methods. No or only slight changes in the chemical phase composition are detectable in the layers relative to the coating powder. In particular, when using Ti n-2 Cr 2 O 2n-1 , there are no oxidation processes and thus changes in the chemical phase composition. The structure of the Magnéli phases can be transferred from the coating powder into the layer.
  • thermal spraying such as, for example, plasma spraying, high-speed flame spraying (HVOF) and detonation spraying, and also laser and hybrid coating methods.
  • HVOF high-speed flame spraying
  • detonation spraying laser and hybrid coating methods.
  • No or only slight changes in the chemical phase composition are detectable in the layers relative to the coating powder.
  • Ti n-2 Cr 2 O 2n-1 there are no oxidation processes and
  • the layers are preferably used as electrically conductive ceramic layers, which at the same time have high mechanical wear and corrosion resistance. In addition, they can also be used as solid-state lubricant and wear-resistant coatings. If the layers are made porous by the choice of suitable coating parameters, they are also suitable for use as electrode layers.
  • the suspension was treated simultaneously with 1.5% by weight of a matched binder of polyvinyl alcohol and polyethylene glycol and then prepared by spray-drying granules in a spherical form.
  • the debinding and sintering of the granules to the coating powder are carried out in a single-stage annealing in flat graphite crucibles under argon at a heating rate of 5 K / min to 600 ° C and 10 K / min to the sintering temperature of 1300 ° C with an isothermal holding time of 30 min ,
  • the sintered powders were subjected to gentle grinding.
  • the separation of the fraction> 45 .mu.m was carried out by sieving, the fraction ⁇ 10 .mu.m by air classification.
  • the fines content of the powder ⁇ 10 ⁇ m after fractionation was 4%.
  • the particle size distribution of the coating powder particles was measured by means of a laser diffraction meter by means of dry dispersion. The measurement revealed the granulometric characteristics d 10 of 15 ⁇ m, d 50 of 28 ⁇ m and d 90 of 43 ⁇ m.
  • the internal open porosity of the coating powder was determined to be 11% by means of mercury porosimetry. When calculating the porosity, the intruded volume was not taken into account at a pressure corresponding to a pore diameter> 1 ⁇ m, since this mercury is forced into the voids between the individual coating powder particles.
  • the specific surface area of the powder was 1.55 m 2 / g.
  • the coating powder was then subjected to atmospheric plasma spraying (APS) using an argon / hydrogen plasma with a power of 42 kW at gas flows of Ar 45 l / min; H 2 10 1 / min (each under standard conditions) applied to a steel substrate roughened by sandblasting immediately before spraying.
  • APS atmospheric plasma spraying
  • the spray distance was 110 mm and the powder delivery rate 35g / min. In this case, a layer thickness of 300 microns was achieved.
  • X-ray phase analysis were in the sprayed layer of Ti 2 Cr 2 O 7 detected.

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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)
  • Inorganic Compounds Of Heavy Metals (AREA)
  • Coating By Spraying Or Casting (AREA)
  • Pigments, Carbon Blacks, Or Wood Stains (AREA)

Abstract

A coating powder based on chemically modified titanium suboxides, for use in various coating techniques. Coatings produced from this powder are characterized by high electroconductivity, good solid lubricating properties and resistance to wear. For these reasons, there are numerous possibilities of use of components which were coated by suitable processes with this powder, especially as functional layers for fuel cells in electrochemical installations, in the new car industry, in mechanical engineering and in other economic activities. The coating powder based on titanium suboxides having a defined defect structure is characterized in that it is modified by at least one metallic alloying element and described by general formula: Ti<SUB>n-2</SUB>Me<SUB>2</SUB>O<SUB>2n-1</SUB>.

Description

Die Erfindung betrifft Beschichtungspulver auf der Basis von chemisch modifizierten Suboxiden des Titans mit der allgemeinen Formel Tin-2Me2O2n-1, wobei Me Cr oder V ist, für die Anwendung in verschiedenen Beschichtungstechnologien (wie beispielsweise den unterschiedlichen Varianten des thermischen Spritzens, wie zum Beispiel Plasmaspritzen, Hochgeschwindigkeitsflammspritzen (HVOF) und Detonationsspritzen, sowie weiteren Verfahren wie Beschichten mittels Laser). Mittels der genannten Beschichtungsverfahren kann das erfindungsgemäße Beschichtungspulver auf verschiedene Bauteile aufgetragen werden. Die Schichten zeichnen sich neben einer hohen Verschleiß-, Oxidations- und Korrosionsbeständigkeit durch hohe elektrische Leitfähigkeit und Festkörperschmierstoffeigenschaften aus. Aus diesen Gründen leiten sich für die mit dem erfindungsgemäßen Pulver beschichteten Bauteile Anwendungsmöglichkeiten als funktionelle Schicht für Brennstoffzellen, in elektrochemischen Anlagen, im Fahrzeugbau, Maschinenbau, und anderen Wirtschaftszweigen ab.The invention relates to coating powders based on chemically modified suboxides of titanium having the general formula Ti n-2 Me 2 O 2n-1 , wherein Me is Cr or V, for use in various coating technologies (such as the different variants of thermal spraying such as plasma spraying, high velocity flame spraying (HVOF) and detonation spraying, and other processes such as laser coating). By means of the coating methods mentioned, the coating powder according to the invention can be applied to various components. In addition to high resistance to wear, oxidation and corrosion, the layers are characterized by high electrical conductivity and solid lubricant properties. For these reasons, application possibilities for the components coated with the powder according to the invention are derived as a functional layer for fuel cells, in electrochemical plants, in vehicle construction, in mechanical engineering, and in other economic sectors.

Beschichtungspulver auf der Basis von Titansuboxiden werden neben einer ausführlichen Darstellung des Standes der Technik in DE 100 00 979 (um unnötige Wiederholungen zu vermeiden, wird an dieser Stelle lediglich auf diese Darstellung verwiesen) beschrieben. Diese Pulver sind dadurch gekennzeichnet, dass n in der Formel TinO2n-1 einen engen Bereich von n ± 2 oder enger aufweist und die Beschichtungspulverteilchen eine Korngrösse im Bereich 10-90 µm aufweisen. In Beschichtungsexperimenten wurde jedoch gefunden, dass die aus diesem Pulver gespritzten Schichten zwar ein Sauerstoffdefizit im Vergleich zu TiO2 aufwiesen, aber eine störende teilweise Oxidation während des Beschichtungsprozesses unvermeidlich ist. Darüber hinaus ließen sich die für die Titansuboxide der Formel TinO2n-1 typischen Planardefekte (Magnéli-Phasen) nicht auf die thermisch gespritzen Schichten übertragen ( Berger L.-M., Thiele S., Nebelung M., Storz O., Gasthuber H., Spray Powders and Coatings on the Basis of Titanium Suboxides; in Thermal Spray 2001: New Surfaces for a New Millenium; Proceedings of the International Thermal Spray Conference; 28-30 May 2001, Singapore, Ed.: C.C. Berndt, K.A. Khor, E.F. Lugschneider; Materials Park/Ohio: ASM International, 2001, p. 291-300 ).Coating powders based on titanium suboxides, in addition to a detailed representation of the prior art in DE 100 00 979 (to avoid unnecessary repetition, reference is made to this representation only). These powders are characterized in that n in the formula Ti n O 2n-1 has a narrow range of n ± 2 or narrower and the coating powder particles have a particle size in the range 10-90 microns. In coating experiments, however, it was found that the layers sprayed from this powder had an oxygen deficit compared to TiO 2 , but a disturbing partial oxidation during the coating process is unavoidable. In addition, the typical of the titanium suboxides of the formula Ti n O 2n-1 Planardefekte (Magnéli phases) could not on the transferring thermally sprayed layers ( Berger L.-M., Thiele S., Nebelung M., Storz O., Gasthuber H., Spray Powders and Coatings on the Base of Titanium Suboxides; in Thermal Spray 2001: New Surfaces for a New Millenium; Proceedings of the International Thermal Spray Conference; 28-30 May 2001, Singapore, Ed .: CC Berndt, KA Khor, EF Lugschneider; Materials Park / Ohio: ASM International, 2001, p. 291-300 ).

In der Publikation von P. Sujatha Devi "Preparation of Fine Particle Cr2Ti2O7 Powders by the Citrate Gel Process", Journal of Solid State Chemistry, Vol. 110, 1994, p. 345-349 , wird eine Möglichkeit der Synthese feindisperser Ti2Cr2O7 - Pulver beschrieben. Diese Pulver haben ein Maximum der Partikelgrößenverteilung bei rund 1-2 µm und sind somit auf Grund mangelnder Förderfähigkeit als Beschichtungspulver nicht geeignet.In the publication of P. Sujatha Devi "Preparation of Fine Particle Cr2Ti2O7 Powders by the Citrate Gel Process", Journal of Solid State Chemistry, Vol. 110, 1994, p. 345-349 , a possibility of the synthesis of finely dispersed Ti 2 Cr 2 O 7 powder is described. These powders have a maximum of the particle size distribution at about 1-2 microns and are therefore not suitable due to lack of eligibility as a coating powder.

In US-A-6,017,592 ( DE 196 51 094 , A1) werden Tin-2Cr2O2n-1-Beschichtungen und thermisches Spritzen als ein mögliches Beschichtungsverfahren genannt. Auf die Herstellung dieser Schichten und verwendete Beschichtungspulver wird nicht eingegangen. Daraus, dass es beim thermischen Spritzen in Abhängigkeit von den Beschichtungspulvereigenschaften und den verwendeten Beschichtungsparametern zu chemischen und Phasenveränderungen kommen kann, ergibt sich die Notwendigkeit geeignete Pulver zur Verfügung zu stellen.In US-A-6,017,592 ( DE 196 51 094 , A1) Ti n-2 Cr 2 O 2n-1 coatings and thermal spraying are mentioned as a possible coating method. The preparation of these layers and coating powder used is not discussed. From the fact that chemical spraying may result in chemical and phase changes depending on the coating powder properties and coating parameters used, there is a need to provide suitable powders.

In EP 1 061 153 A1 werden Schichten mit einer anderen Defektstruktur (Kationendefekte) beschrieben.In EP 1 061 153 A1 Layers with a different defect structure (cation defects) are described.

Es ist Aufgabe der vorliegenden Erfindung, Beschichtungspulver auf der Basis von Suboxiden des Titans mit der Struktur von Magnéli-Phasen zu beschreiben, die sich durch Oxidationsbeständigkeit auszeichnen, und bei denen die Planardefektstruktur der Magnéli-Phasen unabhängig von der Beschichtungstechnologie, in die Schichten übertragen werden kann.It is an object of the present invention to describe coating powders based on suboxides of titanium having the structure of Magnéli phases, which are distinguished by oxidation resistance, and in which the Planardefektstruktur the Magnéli phases, regardless of the coating technology, are transferred to the layers can.

Es ist somit Aufgabe der Erfindung ein Beschichtungspulver der genannten Art anzugeben, das sich für die Anwendung unterschiedlicher Beschichtungstechnologien eignet und aus dem Schichten herstellbar sind, die sich durch überlegene elektrische Festkörperschmierstoff- und Verschleißschutzeigenschaften auszeichnen.It is therefore an object of the invention to provide a coating powder of the type mentioned, which is suitable for the application of different coating technologies and can be produced from the layers, which are characterized by superior electrical Festkörperschmierstoff- and anti-wear properties.

Erfindungsgemäß werden diese Aufgaben mit dem Beschichtungspulver gemäß einem oder mehreren der Ansprüche von 1 bis 13 gelöst.According to the invention, these objects are achieved with the coating powder according to one or more of claims 1 to 13.

Unabhängig von ihrer Herstellung ist es allen erfindungsgemäßen Beschichtungspulvern gemeinsam, dass diese durch wenigstens ein metallisches Legierungselement modifiziert sind und mit der allgemeinen Formel Tin-2Me2O2n-1 beschrieben werden können, wobei Me Cr oder V ist und das Beschichtungspulver eine Korngröße im Bereich von 10-90 µm aufweist. Vorteilhafterweise enthalten die Beschichtungspulver ein oder mehrere weitere Legierungselemente, die einzelne Phasen der allgemeinen Formel Tin-2Me2O2n-1 stabilisieren oder inert sind.Regardless of their preparation, it is common to all the coating powders according to the invention that they are modified by at least one metallic alloying element and can be described by the general formula Ti n-2 Me 2 O 2n-1 , where Me is Cr or V and the coating powder is a grain size in the range of 10-90 microns. Advantageously, the coating powders contain one or more further alloying elements which stabilize or are inert to individual phases of the general formula Ti n-2 Me 2 O 2n-1 .

Titansuboxide mit planaren Defektstrukturen (Magnéli-Phasen mit der allgemeinen Formel TinO2n-1) können auch als homologe Serie mit der Formel x TiO2*Ti2O3 beschrieben werden. Sie lassen sich neben den in DE 100 00 979 genannten Verfahren auch durch eine Festkörperreaktion aus Ausgangsmischungen unterschiedlicher Molverhältnisse von TiO2 und Ti2O3 leicht synthetisieren. Ti2O3 kann in dieser Reaktion durch eine Vielzahl von anderen dreiwertigen Metalloxiden ersetzt werden. Nach dem gegenwärtigen Stand von Wissenschaft und Technik existieren jedoch nur wenige dreiwertige Metalloxide bei denen die Reaktionsprodukte die Struktur von Magnéli-Phasen aufweisen. Hierbei handelt es sich insbesondere um Cr2O3 und V2O3.Titanium suboxides with planar defect structures (Magnéli phases with the general formula Ti n O 2n-1 ) can also be described as homologous series with the formula x TiO 2 * Ti 2 O 3 . They can be located next to the in DE 100 00 979 also easily synthesized by a solid state reaction of starting mixtures of different molar ratios of TiO 2 and Ti 2 O 3 . Ti 2 O 3 can be replaced by a variety of other trivalent metal oxides in this reaction. However, according to the current state of science and technology, there are only a few trivalent metal oxides in which the reaction products have the structure of Magnéli phases. These are in particular Cr 2 O 3 and V 2 O 3 .

Durch Festkörperreaktion von Ausgangsmischungen unterschiedlicher Molverhältnisse von TiO2 und Cr2O3 lassen sich modifizierte Titansuboxide mit der Struktur von Magnéli-Phasen, die durch die allgemeine Formel Tin-2Cr2O2n-1 beschrieben werden, mit n≥4 einfach herstellen. Reine Titansuboxide mit der Struktur von Magnéli-Phasen, die durch Reaktion von TiO2 und Ti2O3 entstehen, bilden sich nur, wenn die Reaktion in inerter Atmosphäre, zum Beispiel in Argon, durchgeführt wird. Im Gegensatz dazu bilden sich Magnéli-Phasen der Struktur Tin-2Cr2O2n-1 mit n≥4 an Luft. Dies bedeutet, dass diese Phasen oxidationsbeständig sind und somit einen gravierenden Nachteil der reinen Titansuboxide mit der Struktur von Magnéli-Phasen nicht aufweisen. Die Phase Tin-2Cr2O2n-1 mit n=3 (TiCr2O5) bildet sich nur, wenn sie durch weitere Legierungselemente, wie z. B. Aljuminium, stabilisiert wird. Weitere Legierungselemente können auf alle Phasen Tin-2Cr2O2n-1 stabilisierend wirken. Eine weitere Möglichkeit der Herstellung der Phasen wird, wie oben genannt, von P. Sujatha Devi, J. Solid State Chemistry, Vol. 110, 1994, p. 345-349 , beschrieben.By solid-state reaction of starting mixtures of different molar ratios of TiO 2 and Cr 2 O 3 , modified titanium suboxides with the structure of Magnéli phases, which are described by the general formula Ti n-2 Cr 2 O 2n-1 , with n≥4 can be produced easily , Pure titanium suboxides with the structure of Magnéli phases, which are formed by the reaction of TiO 2 and Ti 2 O 3 , form only when the reaction is carried out in an inert atmosphere, for example in argon. In contrast, Magnéli phases of the structure Ti n-2 Cr 2 O 2n-1 form with n≥4 in air. This means that these phases are resistant to oxidation and thus do not have a serious disadvantage of the pure titanium suboxides with the structure of Magnéli phases. The phase Ti n-2 Cr 2 O 2n-1 with n = 3 (TiCr 2 O 5 ) is formed only if they are supported by other alloying elements, such as. As aluminum, is stabilized. Further alloying elements can stabilize Ti n-2 Cr 2 O 2n-1 on all phases. Another way of making the phases is, as mentioned above, of P. Sujatha Devi, J. Solid State Chemistry, Vol. 110, 1994, p. 345-349 , described.

Auch durch die Verwendung von Vanadium lassen sich modifizierte Titansuboxide mit der Struktur von Magnéli-Phasen, die durch die allgemeine Formel Tin-2V2O2n-1 mit n≥3 beschrieben werden, zum Beispiel nach den in US 5,049,537 genannten Verfahren einfach herstellen. Jedoch erfordert die Toxizität von V2O3 und Vanadiumoxiden anderer Wertigkeit des Vanadiums erhöhte Vorsichtsmaßnahmen bei der Synthese der Magnéli-Phasen, der Herstellung der Beschichtungspulver und deren Verarbeitung durch thermisches Spritzen.Also by the use of vanadium, modified titanium suboxides with the structure of Magnéli phases described by the general formula Ti n-2 V 2 O 2n-1 with n≥3, for example according to the in US 5,049,537 simply produce these methods. However, the toxicity of V 2 O 3 and other valence vanadium vanadium oxides requires increased precautions in the synthesis of the Magnéli phases, the preparation of the coating powders, and their processing by thermal spraying.

Es ist weiterhin von Vorteil, wenn n in der Formel Tin-2Me2O2n-1 einen Bereich von n ± 2 umfasst. Bei erhöhten Anforderungen an das Material kann unter Einhaltung engerer technologischer Parametergrenzen bei der Herstellung ein engerer Bereich von n ± 1 realisiert werden. Bei n < 5 ist es möglich, dass im Beschichtungspulver nur Phasen vorliegen, die einem diskreten Wert für n entsprechen. Dies bedeutet, dass das Beschichtungspulver einphasig vorliegt, wenn für n nur eine Phase bekannt ist. Wenn für ein diskretes n mehrere Phasen bekannt sind, können diese nebeneinander vorliegen. Durch die immer kleineren Unterschiede in den Sauerstoffgehalten mit steigendem n können die Beschichtungspulver mit n ≥ 5 so hergestellt werden, dass neben der angestrebten Phase n noch eine zweite Phase n+1 oder n-1 vorliegt.It is also advantageous if n in the formula Ti n-2 Me 2 O 2n-1 comprises a range of n ± 2. In the case of increased demands on the material, a narrower range of n ± 1 can be achieved while adhering to narrower technological parameter limits during production. At n <5, it is possible that only phases corresponding to a discrete value of n are present in the coating powder. This means that the coating powder is single-phase, if only one phase is known for n. If several phases are known for a discrete n, they may be present next to each other. Due to the ever smaller differences in the oxygen contents with increasing n, the coating powders with n ≥ 5 can be prepared so that in addition to the desired phase n nor a second phase n + 1 or n-1 is present.

Es ist von Vorteil wenn das Beschichtungspulver bei speziellen Anforderungen eine Korngröße im Bereich 10-45 µm aufweist.It is advantageous if the coating powder for special requirements has a particle size in the range 10-45 microns.

Die erfindungsgemäßen Beschichtungspulver können bezüglich ihrer Porosität und ihrer Morphologie unterschiedliche Eigenschaften aufweisen und die Herstellung kann prinzipiell auf unterschiedlichen Wegen erfolgen. Die bevorzugte Variante besteht darin, dass die Synthese über eine Festkörperreaktion von homogenen Ausgangsmischungen feindisperser Titandioxidpulver und dreiwertiger Metalloxidpulver, insbesondere Cr2O3 und V2O3 unterschiedlicher Molverhältnisse erfolgt. Die homogenen Ausgangsmischungen können die weiteren Legierungselemente, z.B. in der Form von Oxiden, enthalten. Es gibt jedoch eine Vielzahl weiterer Möglichkeiten der Dotierung, Metallpulver oder sich zu Oxiden zersetzende Verbindungen der Legierungsmetalle können ebenfalls eingesetzt werden. Nach der Festkörperreaktion kann eine zusätzliche Reduktion mit einem festen oder gasförmigen Reduktionsmittel erfolgen. Auf diesen unterschiedlichen Synthesewegen lassen sich feindisperse Pulver entsprechend der Formel Tin-2Me2O2n-1 mit Me = Cr oder V, herstellen, die vorteilhafterweise eine Korngröße <5 µm besitzen. Nach der Synthese kann das Suboxid Tin-2Me2O2n-1 gegebenenfalls durch Mahlprozesse aufbereitet und die Korngröße verringert werden.The coating powders according to the invention can have different properties with respect to their porosity and their morphology, and the preparation can in principle be carried out in different ways. The preferred variant consists in that the synthesis takes place via a solid-state reaction of homogeneous starting mixtures of finely dispersed titanium dioxide powder and trivalent metal oxide powder, in particular Cr 2 O 3 and V 2 O 3 of different molar ratios. The homogeneous starting mixtures may contain the further alloying elements, for example in the form of oxides. However, there are a variety of other possibilities of doping, metal powder or to Oxides decomposing compounds of the alloying metals can also be used. After the solid-state reaction, an additional reduction can be carried out with a solid or gaseous reducing agent. On these different synthesis paths can be finely dispersed powder according to the formula Ti n-2 Me 2 O 2n-1 with Me = Cr or V, produce, which advantageously have a particle size <5 microns. After the synthesis, the suboxide Ti n-2 Me 2 O 2n-1 can optionally be processed by grinding processes and the grain size can be reduced.

Die Herstellung des Beschichtungspulvers aus den synthetisierten Pulvern der Zusammensetzung Tin-2Me2O2n-1 erfolgt vorzugsweise durch Agglomerieren, Sintern und Fraktionieren nach den in DE 100 00 979 beschriebenen Verfahrensschritten, ohne dabei die Phasenzusammensetzung zu verändern. Sprühtrocknung ist das bevorzugte Verfahren für das Agglomerieren. In einer Verfahrensvariante können die Ausgangsoxide TiO2 und Cr2O3 im benötigten Verhältnis zusammen sprühgetrocknet werden und durch Reaktionssintern werden die entsprechenden Magnéli-Phasen in dem gesinderten Beschichtungspulver erhalten. Eine weitere Möglichkeit der Herstellung besteht darin, aus vorher synthetisierten Pulvern die endgültige Phasenzusammensetzung während der Sinterung des Beschichtungspulvers einzustellen. Das erfolgt beispielsweise durch Veränderung der Sintertemperatur gegenüber der Synthesetemperatur. Beim Sintern verändert sich die Korngröße der primären Einzelpartikel nicht oder nur wenig. Die Korngröße der zusammengesinterten Einzelpartikel in den Beschichtungspulverteilchen beträgt <5 µm. Üblicherweise liegen nicht mehr als 15% der gesinterten Beschichtungspulverteilchen unterhalb des angestrebten Korngrößenbereiches, dieser Wert kann bei Notwendigkeit durch wiederholtes Fraktionieren stark herabgesetzt werden. Vorteilhafterweise zeichnen sich diese Beschichtungspulver neben der Existenz nur einer Phase oder eines engen Bereiches von n in Tin-2Me2O2n-1 in der Phasenzusammensetzung unter anderem durch eine kugelige Morphologie und eine Porosität größer 3%, vorzugsweise größer 10%, aus.The preparation of the coating powder from the synthesized powders of the composition Ti n-2 Me 2 O 2n-1 is preferably carried out by agglomeration, sintering and fractionation according to the in DE 100 00 979 described method steps, without changing the phase composition. Spray drying is the preferred method for agglomeration. In a process variant, the starting oxides TiO 2 and Cr 2 O 3 can be spray-dried together in the required ratio, and the corresponding Magnéli phases are obtained in the softened coating powder by reaction sintering. Another possibility of production is to adjust the final phase composition during sintering of the coating powder from previously synthesized powders. This is done, for example, by changing the sintering temperature with respect to the synthesis temperature. During sintering, the grain size of the primary individual particles does not change or only slightly. The grain size of the sintered individual particles in the coating powder particles is <5 μm. Usually not more than 15% of the sintered coating powder particles are below the desired particle size range, this value can be greatly reduced if necessary by repeated fractionation. Advantageously, in addition to the existence of only one phase or a narrow range of n in Ti n-2 Me 2 O 2n-1 in the phase composition, these coating powders are characterized inter alia by a spherical morphology and a porosity of greater than 3%, preferably greater than 10% ,

Die Porosität der Beschichtungspulver wird durch Quecksilberporosimetrie bestimmt. Bei der Berechnung der Porosität wird das intrudierte Volumen bei einem Druck, der einem Porendurchmesser > 1 µm entspricht, nicht berücksichtigt, da dieses Quecksilber in die Hohlräume zwischen die einzelnen Beschichtungspulverteilchen gedrückt wird. Durch die Porosität und die feinen Einzelpartikel sind diese Beschichtungspulver auch durch spezifische Oberflächen > 1 m2/g gekennzeichnet.The porosity of the coating powders is determined by mercury porosimetry. When calculating the porosity, the intruded volume at a pressure corresponding to a pore diameter> 1 micron, is not taken into account, as this mercury in the Cavities between the individual coating powder particles is pressed. Due to the porosity and the fine individual particles, these coating powders are also characterized by specific surface areas> 1 m 2 / g.

Eine weitere Möglichkeit der Herstellung der erfindungsgemäßen Beschichtungspulver besteht darin, dass die Synthese von Tin-2Me2O2n-1 direkt bei der Beschichtungspulverherstellung bei anderen Verfahren, z.B. Schmelzen und Brechen oder Sintern und Brechen realisiert wird. Diese Beschichtungspulver können leicht mit einem gasförmigen Reduktionsmittel weiter reduziert werden. Dabei bleibt die Morphologie, Korngröße und die Korngrößenverteilung des Ausgangspulvers im Wesentlichen erhalten. So können diese Beschichtungspulver auch eine andere, z.B. eine kantige Morphologie besitzen und eine Porosität <10%, vorzugsweise < 5%, aufweisen.Another possibility for producing the coating powders according to the invention is that the synthesis of Ti n-2 Me 2 O 2n-1 is realized directly in the production of coating powders in other processes, for example melting and breaking or sintering and breaking. These coating powders can be easily further reduced with a gaseous reducing agent. The morphology, grain size and the particle size distribution of the starting powder are essentially retained. Thus, these coating powders may also have a different, for example, an angular morphology and have a porosity <10%, preferably <5%.

Alle erfindungsgemäßen Beschichtungspulver können mit verschiedenen Oberflächentechnologien zu Schichten verarbeitet werde. Besonders geeignet sind sie für die Verfahrensgruppe des thermischen Spritzens, wie zum Beispiel Plasmaspritzen, Hochgeschwindigkeitsflammspritzen (HVOF) und Detonationsspritzen, sowie Beschichtungsverfahren mittels Laser und Hybridverfahren. In den Schichten sind gegenüber dem Beschichtungspulver keine oder nur geringe Veränderungen in der chemischen Phasenzusammensetzung nachweisbar. Insbesondere bei der Verwendung von Tin-2Cr2O2n-1 kommt es zu keinen Oxidationsprozessen und damit zu Veränderungen der chemischen Phasenzusammensetzung. Die Struktur der Magnéli-Phasen kann aus dem Beschichtungspulver in die Schicht übertragen werden.All coating powders according to the invention can be processed into layers with various surface technologies. They are particularly suitable for the process group of thermal spraying, such as, for example, plasma spraying, high-speed flame spraying (HVOF) and detonation spraying, and also laser and hybrid coating methods. No or only slight changes in the chemical phase composition are detectable in the layers relative to the coating powder. In particular, when using Ti n-2 Cr 2 O 2n-1 , there are no oxidation processes and thus changes in the chemical phase composition. The structure of the Magnéli phases can be transferred from the coating powder into the layer.

Die Schichten werden vorzugsweise als elektrisch leitfähige keramische Schichten eingesetzt, die gleichzeitig eine hohe mechanische Verschleiß- und Korrosionsbeständigkeit aufweisen. Daneben können sie auch als Festkörperschmierstoff- und Verschleißschutzschichten eingesetzt werden. Wenn die Schichten durch die Wahl geeigneter Beschichtungsparameter porös hergestellt werden, eignen sie sich auch für den Einsatz als Elektrodenschichten.The layers are preferably used as electrically conductive ceramic layers, which at the same time have high mechanical wear and corrosion resistance. In addition, they can also be used as solid-state lubricant and wear-resistant coatings. If the layers are made porous by the choice of suitable coating parameters, they are also suitable for use as electrode layers.

Das erfindungsgemäße Beschichtungspulver soll im nachfolgenden Ausführungsbeispiel näher beschrieben werden.The coating powder according to the invention will be described in more detail in the following embodiment.

Ausführungsbeispielembodiment

2 mol eines feindispersen Titandioxidpulvers und 1 mol eines feindispersen Chromoxidpulvers Cr2O3 werden durch Mischmahlung in einer Kugelmühle innig miteinander vermischt, durch Pressen verdichtet und in einem Ofen unter Luft bei 1380°C (Haltezeit 4h) zur vollständigen Umsetzung gebracht. Dabei entsteht ein einphasiges Ti2Cr2O7, oder anders ausgedrückt 2TiO2*Cr2O3. Das Pulver wird durch Aufmahlen in einer Planetenkugelmühle in einen feindispersen Zustand mit einer mittleren Korngröße von 3,9 µm versetzt. Anschließend wird dieses Pulver in Wasser dispergiert und in einer Kugelmühle 16h gemahlen. Dabei wurde die Suspension gleichzeitig mit 1,5 Mass.-% eines angepaßten Binders aus Polyvinylalkohol und Polyethylenglykol versetzt und anschließend durch Sprühtrocknung Granalien in einer kugeligen Form hergestellt. Das Entbindern und die Sinterung der Granalien zum Beschichtungspulver erfolgen in einer einstufigen Temperung in flachen Graphittiegeln unter Argon mit einer Aufheizgeschwindigkeit von 5 K/min bis 600°C und 10 K/min bis zur Sintertemperatur von 1300°C mit einer isothermen Haltezeit von 30 min. Die gesinterten Pulver wurden einer schonenden Mahlung unterzogen. Die Abtrennung der Fraktion > 45 µm erfolgte durch Sieben, die der Fraktion < 10 µm durch Windsichten. Der Feinanteil des Pulver <10 µm nach der Fraktionierung betrug 4%.2 mol of a finely dispersed titanium dioxide powder and 1 mol of a finely dispersed chromium oxide powder Cr 2 O 3 are intimately mixed by mixing in a ball mill, compacted by pressing and brought to completion in a furnace under air at 1380 ° C (holding time 4h). This results in a single-phase Ti 2 Cr 2 O 7 , or in other words 2Ti O 2 * Cr 2 O 3 . The powder is made by milling in a planetary ball mill in a finely dispersed state with a mean grain size of 3.9 microns. Subsequently, this powder is dispersed in water and ground in a ball mill for 16 h. In this case, the suspension was treated simultaneously with 1.5% by weight of a matched binder of polyvinyl alcohol and polyethylene glycol and then prepared by spray-drying granules in a spherical form. The debinding and sintering of the granules to the coating powder are carried out in a single-stage annealing in flat graphite crucibles under argon at a heating rate of 5 K / min to 600 ° C and 10 K / min to the sintering temperature of 1300 ° C with an isothermal holding time of 30 min , The sintered powders were subjected to gentle grinding. The separation of the fraction> 45 .mu.m was carried out by sieving, the fraction <10 .mu.m by air classification. The fines content of the powder <10 μm after fractionation was 4%.

Durch Röntgenphasenanalyse wurde nachgewiesen, dass sich die Phasenzusammensetzung des Beschichtungspulvers gegenüber dem feindispersen Ausgangspulver nicht verändert hat. Die Korngrößenverteilung der Beschichtungspulverpartikel wurde mit Hilfe eines Laserbeugungsmeßgerätes mittels Trockendispergierung gemessen. Die Messung ergab die granulometrischen Kennwerte d10 von 15 µm, d50 von 28 µm und d90 von 43 µm. Die innere offene Porosität des Beschichtungspulvers wurde°mit Hilfe der Quecksilberporosimetrie mit 11 % bestimmt. Bei der Berechnung der Porosität wurde das intrudierte Volumen bei einem Druck, der einem Porendurchmesser > 1 µm entspricht, nicht berücksichtigt, da dieses Quecksilber in die Hohlräume zwischen die einzelnen Beschichtungspulverteilchen gedrückt wird. Die spezifische Oberfläche des Pulvers betrug 1,55 m2/g.X-ray phase analysis showed that the phase composition of the coating powder did not change with respect to the finely dispersed starting powder. The particle size distribution of the coating powder particles was measured by means of a laser diffraction meter by means of dry dispersion. The measurement revealed the granulometric characteristics d 10 of 15 μm, d 50 of 28 μm and d 90 of 43 μm. The internal open porosity of the coating powder was determined to be 11% by means of mercury porosimetry. When calculating the porosity, the intruded volume was not taken into account at a pressure corresponding to a pore diameter> 1 μm, since this mercury is forced into the voids between the individual coating powder particles. The specific surface area of the powder was 1.55 m 2 / g.

Das Beschichtungspulver wurde anschließend durch atmosphärisches Plasmaspritzen (APS) unter Verwendung eines Argon/Wasserstoff-Plasmas mit einer Leistung von 42 kW bei Gasflüssen von Ar 45 l/min; H2 10 1/min (jeweils unter Standardbedingungen) auf ein unmittelbar vor dem Spritzen durch Sandstrahlen aufgerauhtes Stahlsubstrat aufgebracht. Der Spritzabstand betrug 110 mm und die Pulverförderrate 35g/min. Dabei wurde eine Schichtdicke von 300 µm erzielt. Durch eine Röntgenphasenanalyse wurden in der gespritzten Schicht des Ti2Cr2O7 nachgewiesen.The coating powder was then subjected to atmospheric plasma spraying (APS) using an argon / hydrogen plasma with a power of 42 kW at gas flows of Ar 45 l / min; H 2 10 1 / min (each under standard conditions) applied to a steel substrate roughened by sandblasting immediately before spraying. The spray distance was 110 mm and the powder delivery rate 35g / min. In this case, a layer thickness of 300 microns was achieved. By X-ray phase analysis were in the sprayed layer of Ti 2 Cr 2 O 7 detected.

Claims (13)

  1. A coating powder based on chemically modified titanium suboxides with planar defect structures of the Magnéli phases, characterised in that the powder is modified by at least one metallic alloying element and is described by the general formula Tin-2Me2O2n-1, wherein Me is Cr or V and the coating powder has a particle size in the range of 10 - 90 µm.
  2. The coating powder according to Claim 1, characterised in that one or a plurality of further alloy elements are included.
  3. The coating powder according to Claim 1 or 2, characterised in that if the first metal alloy element is chromium, the composition of the powder is described by the general formula Tin-2Cr2O2n-1 with n ≥ 4.
  4. The coating powder according to Claim 3, characterised in that if the first metal alloy element is chromium, the composition of the powder is described by the general formula Tin-2Cr2O2n-1 with n ≥ 3, wherein the composition is stabilised by a further metallic alloying element.
  5. The coating powder according to Claim 1 or 2, characterised in that if the first metallic alloying element is vanadium, the composition of the powder is described by the general formula Tin-2V2O2n-1 with n ≥ 3.
  6. The coating powder according to one or more of Claims 1 to 5, characterised in that n comprises a range n ± 2.
  7. The coating powder according to one or more of Claims 1 to 5, characterised in that n comprises a range n ± 1.
  8. The coating powder according to one or more of Claims 1 to 5, characterised in that only one phase is present, which phase corresponds to a discrete value for n when n < 5.
  9. The coating powder according to one or more of Claims 1 to 5, characterised in that two phases are present when n ≥ 5.
  10. The coating powder according to one or more of Claims 1 to 9, characterised in that this powder has a particle size in the range 10-45 µm.
  11. The coating powder according to one or more of Claims 1 to 10, characterised in that the coating powder has a spherical morphology and an open porosity greater than 3%, and consists of individual particles of the grain size range < 5 µm sintered together.
  12. The coating powder according to Claim 11, characterised in that the open porosity of the coating powder consisting of individual particles sintered together is greater than 10%.
  13. The coating powder according to one or more of Claims 1 to 10, characterised in that the coating powder has an angular morphology and an open porosity of less than 10%.
EP02740417A 2001-03-05 2002-03-04 Coating powder based on chemically modified titanium suboxides Expired - Lifetime EP1379708B1 (en)

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DE10110448 2001-03-05
DE10110448A DE10110448A1 (en) 2001-03-05 2001-03-05 Coating powder based on titanium sub-oxides with defined defect structure used in coating technology is modified by alloy elements stabilizing defect structure during processing of coating powder
PCT/EP2002/002323 WO2002079535A2 (en) 2001-03-05 2002-03-04 Coating powder based on chemically modified titanium suboxides

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DE102004046320A1 (en) * 2004-09-17 2006-05-11 Bundesanstalt für Materialforschung und -Prüfung (BAM) Friction materials / tribological materials for radial and axial foil bearings
US20080112879A1 (en) * 2006-11-15 2008-05-15 Mccracken Colin G Production of high-purity titanium monoxide and capacitor production therefrom
US20080253958A1 (en) * 2006-11-15 2008-10-16 Mccracken Colin G Production of high-purity titanium monoxide and capacitor production therefrom
WO2008083894A2 (en) * 2007-01-11 2008-07-17 Ciba Holding Inc. Pigment mixtures
DE102012107499A1 (en) * 2012-08-16 2014-05-22 Dr. Ing. H.C. F. Porsche Aktiengesellschaft Method for coating surface of e.g. cylinder portion of combustion engine, involves feeding coating material of thermal spraying device as solid and subjecting solid to pretreatment prior to melting for setting defined structure
US9672953B2 (en) * 2014-03-27 2017-06-06 EboNEXT Technologies (BVI) Devices and methods for advanced phase-locked materials
US9994785B2 (en) 2014-04-02 2018-06-12 Rolls-Royce Corporation Thermally stable self-lubricating coatings
CN112479702A (en) * 2020-11-27 2021-03-12 安徽盈锐优材科技有限公司 Preparation method of chromium oxide and titanium oxide composite powder for plasma spraying

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US3816348A (en) * 1972-04-24 1974-06-11 Du Pont Compositions for stable low resistivity resistors
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DE10000979C1 (en) 1999-10-01 2001-05-10 Daimler Chrysler Ag Coating powder used in plasma spraying, high speed flame spraying and detonation spraying of components of engines is based on a titanium sub-oxide
US6524750B1 (en) * 2000-06-17 2003-02-25 Eveready Battery Company, Inc. Doped titanium oxide additives

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WO2002079535A2 (en) 2002-10-10
JP2004524445A (en) 2004-08-12
JP4421820B2 (en) 2010-02-24
DE10110448A1 (en) 2002-09-19
ATE364733T1 (en) 2007-07-15
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EP1379708A2 (en) 2004-01-14

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