EP1464716B1 - Alliage quasi-cristalline de Ti-Cr-Al-Si-O et son utilisation comme revêtement - Google Patents

Alliage quasi-cristalline de Ti-Cr-Al-Si-O et son utilisation comme revêtement Download PDF

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Publication number
EP1464716B1
EP1464716B1 EP04101277A EP04101277A EP1464716B1 EP 1464716 B1 EP1464716 B1 EP 1464716B1 EP 04101277 A EP04101277 A EP 04101277A EP 04101277 A EP04101277 A EP 04101277A EP 1464716 B1 EP1464716 B1 EP 1464716B1
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sio
compound
range
coating
sample
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German (de)
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EP1464716A1 (fr
EP1464716A8 (fr
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Valery Dr. Shklover
Maxim Dr. Konter
Anton Dr. Kaiser
Kenneth Franklin Prof. Dr. Kelton
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General Electric Technology GmbH
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Alstom Technology AG
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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
    • C23C4/06—Metallic material
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/16—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of other metals or alloys based thereon
    • C22F1/18—High-melting or refractory metals or alloys based thereon
    • C22F1/183—High-melting or refractory metals or alloys based thereon of titanium or alloys based thereon
    • 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
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • 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
    • C23C30/00—Coating with metallic material characterised only by the composition of the metallic material, i.e. not characterised by the coating process

Definitions

  • the present invention relates to quasi-crystalline or approximant Compounds, a process for their preparation and uses of such Compounds in particular in connection with the coating of heat exposed components.
  • An approximant is a chemical structure of similar composition to that of the associated quasicrystal, wherein the approximant periodic structures with very large unit cells and very similar local order as those of the corresponding one Quasicristalls has.
  • the approximant is referred to in this context as ⁇ (TiCrSiO) or 1/1 phase, this is the most important phase in these examined alloys.
  • Neutron studies show that the oxygen atoms at which octahedral positions are arranged, probably a bond to the titanium atoms present. Thus, based on energy bills, the existence suspected of a network of octahedrons.
  • the titanium-based quasicrystalline materials can be classified as metallic Alloys with internal ceramic layers are considered.
  • the thermal conductivity of quasicrystalline alloys and their Approximants in which only long-wave phonons can propagate are lower than those of typical metal alloys. This was for example in the following Publications: P. Archambault, P. Plaindoux, E. Belin-Ferre and J.M. Dubois: Thermal and Electronic Properties of AlCoFrCr Approximant of the Decagonal Phases, Quasicrystals, MRS, 535, 409 (1999); J.M. Dubois: New Prospects From Potential Applications of Quasicrystal Materials, Mat. Sc. and Engineering, 294-296, 4 (2000).
  • the thermal conductivity of exclusively aluminum-based Quasicrystal alloys (or their approximants) are also studied Service.
  • Icosahedral, quasi-crystalline alloys of the Ti 68-x Cr 32 Si x type with 6 ⁇ x ⁇ 18 are disclosed by Zhang, X.; Kelton, KF, "Icosahedral phase formation in Ti 68-x Cr 32 Si x alloys" Philosophical Magazine Letters, 1990, Vol. 62, No.4, 265-271, 1990.
  • connection should have advantageous properties, as in particular in connection with the use as a coating of components flowed around by hot gases, which are used for example in gas turbines, are required. So shall the Connection respectively the class of connections a corresponding strength respectively strength and density, is said to have a low thermal conductivity as far as possible also constitute a diffusion barrier for oxygen, a have high stability with respect to oxidation, and possibly the Observation of diffusion reactions between the compound and the material, on which the compound is applied allow.
  • the atomic percentage of oxygen is in the range of 8-20%, preferably 8 to 15%. Below this content, the desired structure is not formed, and above forms an oxide phase.
  • the atomic percentage of aluminum is advantageously adjusted to a range of 2 to 5%. Of course, corresponding combinations of such materials are conceivable.
  • the core of the invention thus consists of the usual strength for titanium alloys and density, as well as the low thermal conductivity of quasicrystalline alloys.
  • the ceramic allow Interlayers prevent diffusion through the layer (Diffusion barrier).
  • the proposed compounds also have improved stability with respect to oxidation compared to normal titanium alloys, and they allow observation of the diffusion reaction between the titanium-based coatings and the base material (for example aluminum or steel). Coatings of such material can accordingly a Allow reduction of manufacturing costs and improve the protection of allow coated gas turbine components. In other words, pointing Such coatings have high resistance to those typically found in Gas turbines (especially with blades or vanes) occurring Conditions on (high temperature, corrosive environment, strong mechanical Loads, etc.).
  • the atomic percentage of Oxygen can be adjusted in the range of 8 to 12%, and that of aluminum in the range of 1.5 to 3%.
  • compositions can be used very advantageously: Ti 60 Cr 32 Si 4 (SiO 2 ) 4 ; Ti 60 Cr 25 Si 5 (SiO 2 ) 10 ; Ti 65 Cr 25 Si 2.5 (SiO 2 ) 7.5 ; Ti 60 Cr 30 (SiO 2 ) 10 ; Ti 60 Cr 30 Al 2 Si 3 (SiO 2 ) 5 ; Ti 60 Cr 30 Al 3 Si 2 (SiO 2 ) 5 ; Ti 60 Cr 30 Al 2 Si 3 (SiO 2 ) 5 ; Ti 60 Cr 30 Si 5 (SiO 2 ) 5 .
  • the present invention relates to a method for producing a Connection as just described.
  • the individual components respectively Components are advantageously under protective gas or vacuum melted together. This can be done for example in an arc become. But there are also other methods conceivable such as sintering, PVD (Physical Vapor Deposition), plasma spray method etc.
  • the material is tempered.
  • the compound is after their fusion under protective gas particularly preferably in an oven annealed, wherein the material is preferably at a temperature in the range of 1000 to 1300 degrees Celsius is maintained for a period of 80 to 200 hours, and then cooled in the oven.
  • the annealing can be done by different methods, such as gradually, with a scheme of incremental or incremental decreasing temperature or a combination of such schemes used can be.
  • the advantageous properties of the material occur especially when used as a coating. Describes accordingly a further embodiments of the inventive method, the application the compound as a coating on a material, in particular method such as plasma spray or vapor deposition may be used, optionally followed by annealing.
  • the present invention relates to the use of a compound, such as it has been characterized above, respectively produced according to a procedure as above has been described. It is the use of such Material as a material for a component which is exposed to high temperatures, d. H. which is exposed to hot gases in particular, or of hot gases is flowed around. In particular, it is for example a component of a Gas turbine, particularly preferably a blade or vane one Gas turbine.
  • a further preferred use according to the invention is characterized in that that the compound is particularly preferred as the coating directly the hot Gas exposed surface is present. It may optionally below the Coating of said material, a further functional layer in particular for adhesion or for further barrier effect.
  • such a coating has a thickness in the range of 10-400 ⁇ m, particularly preferably in the range of 100 to 300 ⁇ m
  • thermal stress as well as the oxidation of rotor blades or vanes in gas turbines under the influence of the high temperature in combination with the oxidative respectively corrosive conditions reduces the possible lifetime respectively the maximum possible design of the temperature of the combustion process, which on the one hand reduces the efficiency of the combustion Turbine reduced and on the other hand the maintenance costs increased.
  • materials such as yttria-stabilized zirconia (yttrium stabilized ZrO 2 , abbreviated YSZ) are known in connection with the coating of such loaded components. Such coatings are referred to as ceramic thermal barrier layers.
  • the proposed oxygen-containing quasicrystalline alloys based on Titanium have internal ceramic interlayers. Correspondingly protect the materials of the underlying component (metal, eg alloys) oxidation, since the diffusion of oxygen through the layer is prevented. In addition, they lead to a reduction in their low thermal conductivity the surface temperature of the underlying metal of the blades of the Compressor or the gas turbine (especially in the case of internal cooling). In other words, the proposed materials assume the function of a Diffusion barrier (DB) as well as those of a thermal thermal barrier coating (thermal barrier coating, abbreviated TBC).
  • DB Diffusion barrier
  • TBC thermal thermal barrier coating
  • the reduced weight (compared with Blades made of nickel-based superalloys) as well as the possibility of Observation of the diffusion reaction between the coating and the base material allows to ensure a better adhesion to the base material.
  • the observation the diffusion reaction can be carried out, for example, by polishing samples and be brought into contact with a coating according to the invention. Subsequently cuts can be made and TEM or SEM shots of these cuts, in which case the extent of the diffusion is easily recognizable.
  • Embodiments Ti-1, Ti-2 and Ti-3 were after fused together annealed in a resistance oven, keeping at 1225 degrees for 144 hours Celsius (constant temperature) was maintained, and the samples in aluminum crucibles were kept under argon atmosphere. Then they were in the oven cooled.
  • the Ti-4 sample was annealed at 1080 degrees Celsius for 80 Hours in a zirconium crucible.
  • the samples Ti-11 and Ti-12 were also melted down analogously and at more than 1000 degrees during more than 50h tempered.
  • Table 1 also indicates the density, which was determined by measuring the Mass and a measurement of the volume determined according to the Archimedes principle. For the Volume measurement was made as a displacement medium of water at a temperature of 20 Used degrees Celsius. So that the liquid is not immersed in the Pores of the body could penetrate, the body was determined after the determination of Dry weight saturated with this liquid. For fine-capillary substances is suitable especially a potion after cooking. For this purpose, the specimens before the Dried impregnation at 110 ° C to constant weight and then in water of Ambient temperature set. The water is brought to a boil and at least Kept at boiling temperature for 30 minutes. The comparatively low density makes that proposed compounds due to the associated small moving Masses suitable for coatings of moving parts.
  • the Heat capacity measured at 100 degrees Celsius.
  • the Heat capacity was measured continuously by differential thermal analysis (DTA) certainly.
  • DTA differential thermal analysis
  • the measurement was carried out in argon atmosphere. It shows the advantageous for such compounds relatively low Heat capacity.
  • the thermal conductivity ⁇ measured at 100 degrees Celsius.
  • the measurement of density and heat capacity are listed above.
  • the temperature conductivity (TLF) was measured by the laser flash method at certain temperature levels (room temperature, 100, 200, 400, 600, 800, 1000 and 1200 ° C). At each temperature, 5-10 individual measurements were made. From this an average value of the TLF at the also averaged temperature was calculated.
  • a Laserflash system from Netzsch was used (Germany, measurements up to 2000 ° C are possible).
  • the solid-state laser has a wavelength of 1064 nm and a maximum energy output of about 20 joules per shot.
  • the pulse duration can be varied from 0.2 to 1.2 ms.
  • the thermal diffusivity ⁇ indicated in FIG. 6 was measured using the laser flash method in the ACCESS device (E. Pfaff. Report 72-00 (20.09.2000) of Rheinisch-West methodische Technische Hochhoff Aachen).
  • FIGS. 1 to 4 show powder X-ray diffraction patterns of the samples according to FIG. Table 1.
  • the intensity (I) is shown as a function of the diffraction angle (2 theta).
  • the Measurements were taken in a PADX Powder Diffractometer (Scintag, USA), ⁇ of Cu radiation, Ge detector, instead.
  • Fig. 1 shows different powder X-ray diffraction patterns for sample Ti-4.
  • the diffraction pattern for a specimen Ti-4 annealed in a zirconium dioxide crucible is shown in FIG. 1a).
  • FIGS. 1a) -c) with quadrilaterals and arrows the peaks of the structure ⁇ (TiCrSi), ie of the 1/1 approximant of the cubic structure Ti 75-x Cr 25 Si x , where 10 ⁇ x ⁇ 20, are indicated Exclusively with squares, the peaks belonging to the structure Ti 5 Si 3 are given. It can thus be seen how different structures exist side by side.
  • Fig. 1b shows a corresponding sample, which is annealed in a graphite crucible has been.
  • Fig. 1c shows a sample which has not been tempered.
  • FIG. 2 shows corresponding diffraction patterns of the samples Ti-1 (FIG. 2a, not annealed, FIG. VACUMET), Ti-2 ( Figure 2b, not annealed, VACUMET) and Ti-3 ( Figure 2c, not annealed, VACUMET).
  • VACUMET is the melting of Ti alloys in the induction furnace in vacuum with low argon partial pressure (15 Torr) designated in specially prepared graphite crucibles. Again, the individual phases are assigned next to each other.
  • Fig. 3 shows the diffraction patterns of the sample Ti-2, wherein a) a tempered sample b) a non-annealed sample; and c) a non-annealed sample in the VACUMET method.
  • Fig. 4 shows the corresponding diffraction patterns for different ones Method of preparation of sample Ti-3 (a: annealed, b: unannealed, VACUMET). Again, it can be seen how similar these two ways of production Structures arise at least in relation to the diffraction pattern.
  • Fig. 5 the samples were further examined in a Hitachi S-900 "in-lens" field emission scanning electron microscope with an acceleration voltage of 30kV using a standard Everhard-Thornley SE detector and a YAG type BSE detector were used. From the backscattering patterns of Fig. 5a) and b) the different structures and the size of the domains are visible. The light-colored areas denote the alpha phase, the dark areas the phase of Ti 5 Si 3 . It can be seen that larger domains are formed in sample Ti-2 (FIG. 5a) than in sample Ti-4. Both images are images of the surface and refer to measurements of annealed samples.
  • Fig. 5c shows a normal SEM image of the sample Ti-2 after being oxidized at 800 degrees Celsius under air for 500 hours.
  • the uppermost, light layer is a layer of TiO 2
  • the underlying intermediate layer consists of CrO 2 , where u. U. between an adhesion layer is arranged.
  • the lower part of the picture shows the alloy itself.
  • Fig. 5d) shows a backscattering image of the identical sample.
  • Figures 5c) and d) are images of sections perpendicular to the surface of the samples.
  • FIG. 6 shows the thermal diffusivity of the samples Ti-1 (reference numeral 11), Ti-2 (Reference 12), Ti-3 (Reference 13).
  • the thermal diffusivity is one Material property which depicts the speed with which heat passes through a body diffuses. It is a function of the thermal conductivity of the Body as well as its heat capacity. A high thermal conductivity increases the thermal diffusivity of the body, as it allows a rapid migration of heat allowed by the body. On the other hand, a large heat capacity is the reduce thermal diffusivity of the body, as transported heat preferably in Body is stored and not forwarded by this. From Figure 6 is can be seen, in particular the sample Ti-2 just at high temperatures has low thermal diffusivity, which is for the proposed uses is advantageous. Basically, as usual, increasing thermal diffusivity noted for increasing temperature.
  • Fig. 7 shows the thermal conductivity of the samples Ti-1 (reference numeral 11), Ti-2 (Reference 12), Ti-3 (Reference 13), and Ti-4 (Reference 14).
  • the low thermal conductivity is especially low for Sample Ti-2 observe. It must be noted, however, that the thermal conductivity a corresponding layer of YSZ would be even lower, such a layer is but much more brittle and mechanically much less stable than all of the proposed alloys which have typical ductile properties for metals. Basically, there is a not very strongly varying thermal conductivity over the observed and relevant temperature range.
  • FIG. 8 shows the thermal conductivity of a plurality of samples, as summarized in the list of reference numerals. It can be seen that the thermal conductivity of the comparative sample Ti-2 (reference numeral 10) is located in the middle region. Typical samples of YSZ (yttrium stabilized ZnO 2 ) have lower values as well as corresponding AlCo alloys (reference numerals 5-7). As already mentioned in connection with FIG. 7, however, these samples have worse mechanical properties than the proposed compounds.
  • Fig. 9 shows powder diffraction pattern of the sample Ti-2, wherein measurements after different times of oxidation were made. It is about a sample prepared prior to its oxidation in a tempering process had been. The oxidation took place under air at 950 degrees Celsius. It can be recognized how successive oxides are formed on the surface, but how the Condition substantially stabilized after about 50 hours.
  • Fig. 10 shows the corresponding pattern of the same sample, in which case the oxidation at 1100 Degrees Celsius has been performed. One finds a similar behavior as in FIG. 9. Oxidation kinetics were also investigated and shown in FIG. 11. There a slow oxidation is preferred, turns out according to FIG. 11a) at 800 degrees Celsius tempered sample as outstanding. The tempering found during a Time of place. As a comparison material TiAl was given. In particular from FIG 11b), the superiority of samples which have been annealed can be recognized, wherein low temperature annealing usually provides greater stability in terms of oxidation seems to be.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Physics & Mathematics (AREA)
  • Plasma & Fusion (AREA)
  • Thermal Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Turbine Rotor Nozzle Sealing (AREA)

Claims (13)

  1. Composé en forme d'icosaèdre, quasi-cristallin ou présent en tant qu'approximation de la composition nominale : TivCrwAlxSiyOz où
    v = 60-65
    w = 25-30
    x = 0-6
    y = 8-15
    z = 8-20
    et où
    la teneur en pour cent atomique d'oxygène se situe dans le domaine de 8 à 15 %, et celle de l'aluminium dans le domaine de 2 à 5 %.
  2. Composé selon la revendication 1, caractérisé en ce que
    v = 60
    w = 30
    x = 0-3
    y = 8-15, en particulier de préférence 8-10
    z = 8-20, en particulier de préférence 8-10
    où la teneur en pour cent atomique d'oxygène se situe dans le domaine de 8 à 12%, et celle de l'aluminium dans le domaine de 1,5 à 3%.
  3. Composé selon l'une quelconque des revendications précédentes, caractérisé en ce que
    v = 60
    w = 30
    x = 0-2
    y = 8-10
    où la teneur en pour cent atomique de l'oxygène se situe dans le domaine de 10% et celle de l'aluminium dans le domaine de 1,5 à 2,5%.
  4. Composé selon l'une quelconque des revendications précédentes, caractérisé en ce qu'il s'agit d'au moins une des compositions suivantes: Ti60Cr32Si4 (SiO2)4 ; Ti60Cr25Si5(SiO2)10; Ti65Cr25Si2,5(SiO2)7,5; Ti60Cr30(SiO2)10 ; Ti60Cr30Al2Si3(SiO2)5 ; Ti60Cr30Al3Si2(SiO2)5 ; Ti60Cr30Al2Si3(SiO2)5 ; Ti60Cr30Si5(SiO2)5.
  5. Procédé pour la fabrication d'un composé selon l'une quelconque des revendications 1 à 4, caractérisé en ce que les composants sont fondus ensemble sous gaz de protection ou sous vide.
  6. Procédé selon la revendication 5, caractérisé en ce que la fusion est effectuée dans un arc électrique.
  7. Procédé selon l'une quelconque des revendications 5 ou 6, caractérisé en ce que le composé, après sa fusion, est soumis à une trempe, en particulier de préférence dans un four, de préférence à une température dans le domaine de 1000 à 1300 degrés Celsius pendant une période de 80 à 200 heures, la trempe se faisant de préférence pendant 7 jours à la température de 1100 degrés Celsius, et cette opération étant suivie d'un refroidissement dans le four.
  8. Procédé selon la revendication 7, caractérisé en ce que la trempe se produit par étapes, un schéma avec une température augmentant ou diminuant par étapes ou une combinaison de schémas de ce genre pouvant être utilisé(e).
  9. Procédé selon l'une quelconque des revendications 5 à 8, caractérisé en ce que le composé est appliqué en tant que revêtement sur un matériau, des procédés comme le procédé de pulvérisation à plasma ou le dépôt à partir de la phase vapeur pouvant être utilisés, avec à la suite, le cas échéant, une trempe.
  10. Utilisation d'un composé selon l'une quelconque des revendications 1 à 4, fabriqué de préférence selon l'une quelconque des revendications 5 à 9 en tant que matériau pour une pièce qui est exposée à des températures élevées et qui est exposée en particulier à des gaz chauds, respectivement qui est balayée par ces derniers.
  11. Utilisation d'un composé selon la revendication 10, caractérisée en ce qu'il s'agit d'une pièce d'une turbine à gaz ou d'un compresseur, en particulier de préférence d'une aube mobile ou d'une aube directrice d'une turbine à gaz ou d'un compresseur.
  12. Utilisation selon l'une quelconque des revendications 10 ou 11, caractérisée en ce que le composé est présent en tant que revêtement, en particulier de préférence de la surface exposée directement aux gaz chauds, une couche de fonction supplémentaire étant présente, le cas échéant, sous le revêtement, en particulier en vue de promouvoir l'adhésion ou en vue de conférer une action barrière.
  13. Utilisation selon la revendication 12, caractérisée en ce que le revêtement présente une épaisseur dans le domaine de 10 - 400 µm, en particulier de préférence dans le domaine de 100 à 200 µm.
EP04101277A 2003-03-31 2004-03-29 Alliage quasi-cristalline de Ti-Cr-Al-Si-O et son utilisation comme revêtement Expired - Fee Related EP1464716B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US401696 2003-03-31
US10/401,696 US7060239B2 (en) 2003-03-31 2003-03-31 Quasicrystalline alloys and their use as coatings

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EP1464716A1 EP1464716A1 (fr) 2004-10-06
EP1464716A8 EP1464716A8 (fr) 2004-12-29
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102012219856A1 (de) * 2012-10-30 2014-04-30 Siemens Aktiengesellschaft Turbinenschaufel und Verfahren zur Herstellung einer Turbinenschaufel mit hoher Oberflächenhärte

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CN210227766U (zh) * 2018-07-27 2020-04-03 佛山市顺德区美的电热电器制造有限公司 炒锅
CN113956689B (zh) * 2018-11-02 2023-07-21 佛山市顺德区美的电热电器制造有限公司 形成准晶涂层的方法和系统以及锅具

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US5256369A (en) * 1989-07-10 1993-10-26 Nkk Corporation Titanium base alloy for excellent formability and method of making thereof and method of superplastic forming thereof
ATE127860T1 (de) 1990-05-04 1995-09-15 Asea Brown Boveri Hochtemperaturlegierung für maschinenbauteile auf der basis von dotiertem titanaluminid.

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102012219856A1 (de) * 2012-10-30 2014-04-30 Siemens Aktiengesellschaft Turbinenschaufel und Verfahren zur Herstellung einer Turbinenschaufel mit hoher Oberflächenhärte

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US7060239B2 (en) 2006-06-13
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EP1464716A8 (fr) 2004-12-29
DE502004000215D1 (de) 2006-02-02

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