EP0521138B1 - Alliages d'aluminium, les substrats revetus de ces alliages et leurs applications - Google Patents

Alliages d'aluminium, les substrats revetus de ces alliages et leurs applications Download PDF

Info

Publication number
EP0521138B1
EP0521138B1 EP92904842A EP92904842A EP0521138B1 EP 0521138 B1 EP0521138 B1 EP 0521138B1 EP 92904842 A EP92904842 A EP 92904842A EP 92904842 A EP92904842 A EP 92904842A EP 0521138 B1 EP0521138 B1 EP 0521138B1
Authority
EP
European Patent Office
Prior art keywords
alloys
thermal
alloy
application
quasicrystalline
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
EP92904842A
Other languages
German (de)
English (en)
French (fr)
Other versions
EP0521138A1 (fr
Inventor
Jean-Marie Dubois
Antoine Pianelli
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.)
Centre National de la Recherche Scientifique CNRS
Original Assignee
Centre National de la Recherche Scientifique CNRS
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Centre National de la Recherche Scientifique CNRS filed Critical Centre National de la Recherche Scientifique CNRS
Publication of EP0521138A1 publication Critical patent/EP0521138A1/fr
Application granted granted Critical
Publication of EP0521138B1 publication Critical patent/EP0521138B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C45/00—Amorphous alloys
    • C22C45/08—Amorphous alloys with aluminium as the major constituent
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C21/00—Alloys based on aluminium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C21/00—Alloys based on aluminium
    • C22C21/06—Alloys based on aluminium with magnesium as the next major constituent
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C21/00—Alloys based on aluminium
    • C22C21/12—Alloys based on aluminium with copper as the next major constituent

Definitions

  • the present invention relates to alloys, the essential constituent of which is aluminum, the substrates coated with these alloys and the applications of these alloys, for example for the constitution of thermal protection elements.
  • European patent 100287 describes a family of amorphous or microcrystalline alloys having improved hardness, usable as reinforcing elements of other materials or for obtaining surface coatings improving the resistance to corrosion or wear.
  • a large number of the alloys described in this patent are not stable at temperatures above 200 ° C., and during a heat treatment, in particular the treatment to which they are subjected when deposited on a substrate, they change their structure: return to the microcrystalline state in the case of essentially amorphous alloys, grain enlargement for the essentially microcrystalline alloys which initially have a grain size less than one micron.
  • This change in crystalline or morphological structure induces a change in the physical characteristics of the material which essentially affects its density. This results in the appearance of micro-cracks, hence a brittleness, which adversely affects the mechanical stability of the materials.
  • Thermal stability is an essential property for an alloy to be used as a thermal barrier.
  • Thermal barriers are assemblies of one or more materials intended to limit the heat transfer to or from parts and components of equipment in many domestic or industrial devices. Mention may be made, for example, of the use of thermal barriers in heating or cooking devices, irons at the level of the fixing of the hot part to the carcass and of the thermal insulation; in cars, at several points such as the turbocharger, the exhaust pipe, the insulation of the passenger compartment, etc .; in aeronautics, for example on the rear part of compressors and reactors.
  • Thermal barriers are sometimes used in isolation in the form of a screen, but very often they are directly associated with the heat source or the part to be protected for reasons of mechanical strength.
  • mica sheets, ceramic plates, etc. are used in household utensils, adapting them by screwing or gluing, or sheets of agglomerated glass wool supported by a metal sheet.
  • a particularly advantageous method for adding a thermal barrier to a part, in particular to a metallic part consists in depositing on a substrate the material constituting the barrier in the form of a layer of thickness determined by a thermal spraying technique such as plasma spraying. for example.
  • thermal barrier with other materials also deposited in layers by thermal spraying.
  • these other materials can be intended to ensure the protection of the barrier vis-à-vis external aggressions such as for example mechanical shocks, a corrosive medium, etc ... or can serve as a bonding sub-layer to the substrate.
  • zirconia The most frequently used material in aeronautics to form thermal barriers is yttria zirconia which withstands very high temperatures.
  • the deposition of zirconia is carried out by plasma spraying according to a conventional technique from powder of the material.
  • d specific mass
  • some of its mechanical properties, such as hardness, resistance to wear and abrasion are low.
  • thermal barrier Other materials are used as a thermal barrier.
  • alumina which has a specific mass lower than that of zirconia, a diffusivity and a specific heat higher than those of zirconia, but whose mechanical properties are not satisfactory.
  • the object of the present invention is to provide a family of alloys having high hardness and thermal stability, improved ductility and resistance to corrosion.
  • the present invention thus relates to a new family of alloys, the essential constituent of which is aluminum.
  • the invention also relates to the metallic coatings obtained from these alloys.
  • Another object of the invention consists of the substrates coated with said alloys.
  • This orthorhombic phase O 1 is said to be approximate to the decagonal phase. It is so close to it that it is not possible to distinguish its X-ray diffraction pattern from that of the decagonal phase.
  • This phase is an approximate phase of the icosahedral phase.
  • phase C of cubic structure, very often observed in coexistence with the approximate phases or true quasicrystallines.
  • a diffraction diagram of this cubic phase has been published (C. Dong, JM Dubois, M. de Boissieu, C. Janot; Neutron diffraction study of the peritectic growth of the Al 65 Cu 20 Fe 15 icosahedral quasicrystal; J. Phys. Condensed Matter, 2 (1990), 6339-6360) for a sample of pure cubic phase and of composition Al 65 Cu 20 Fe 15 in number of atoms.
  • This phase is isotype of a hexagonal phase, noted ⁇ AlMn, discovered in Al-Mn alloys containing 40% by weight of Mn [MA, Taylor, Intermetallic phases in the Aluminum-Manganese Binary System, Acta Metallurgica 8 (1960) 256] .
  • the cubic phase, its substructures and the phases derived therefrom, constitute a class of approximate phases of the quasicrystalline phases of neighboring compositions.
  • alloys of the present invention there may be mentioned those, designated below by (II), which have the above atomic composition (I) in which 0 ⁇ b ⁇ 5, 0 ⁇ b ' ⁇ 22 and / or 0 ⁇ c ⁇ 5, and M represents Mn + Fe + Cr or Fe + Cr.
  • These alloys (II) are more particularly intended for the coating of cooking utensils.
  • Another particularly interesting family designated hereinafter by (III), presents the aforementioned atomic composition (I) in which 15 ⁇ d ⁇ 30 and M represents at least Fe + Cr, with an atomic ratio Fe / Cr ⁇ 2.
  • These alloys (III) have a particularly high resistance to oxidation.
  • Another family of alloys (V) which are interesting in that they offer improved resistance to grain growth up to 700 ° C. presents the composition of the alloys (I) with 0 ⁇ e ⁇ 1, N being chosen from W, Ti, Zr, Rh, Nb, Hf and Ta.
  • alloys (VII) having composition (I) and which exhibit improved ductility are those for which c> 0, preferably 0 ⁇ c ⁇ 1, and / or 7 ⁇ b ' ⁇ 14.
  • the alloys of the present invention are distinguished from the alloys of the prior art, and in particular those of EP 356 287 by their copper content which is lower, or even zero. Alloys are therefore less sensitive to corrosion in an acid medium. In addition, the low copper content is more favorable for obtaining improved ductility by adding other elements such as B or C. In the alloys of the present invention, the copper can be replaced in whole or in part by cobalt. These alloys are therefore particularly advantageous with regard to hardness, ductility and resistance to corrosion both in an alkaline medium and in an acidic medium in the range of intermediate pHs (5 ⁇ pH ⁇ 7). The combination of these different properties offers the alloys of the present invention a wide range of applications.
  • the alloys of the present invention can for example be used as an anti-wear or reference surface coating or for the production of metal-metal or metal-ceramic joints. They are also suitable for all uses involving food contact.
  • the alloys of the invention preferably those of group (VII), can also be used for anti-shock surfaces.
  • the alloys according to the invention of groups (III) and (V) are preferably used.
  • the alloys of group (III) will preferably be used, whereas those of groups (III) and (IV) are particularly suitable for surfaces resistant to corrosion.
  • the alloys of groups (III), (IV) and (VII) are particularly suitable for producing anti-cavitation or anti-erosion surfaces.
  • thermal protection elements for a substrate, in the form of a thermal barrier or in the form of a bonding underlayer for barriers.
  • thermal consist of conventional materials. They have good thermal insulation properties, good mechanical properties, a low specific mass, good resistance to corrosion, especially to oxidation, and great ease of use.
  • the quasicrystalline alloys of the present invention are therefore suitable substitutes for the replacement of many thermal barrier materials, and in particular of zirconia, with respect to which they have advantages of low specific mass, excellent mechanical properties with regard to hardness, improved resistance to wear, abrasion, scratch, as well as corrosion.
  • the diffusivity of the materials constituting the thermal protection elements of the present invention is reduced when the porosity of the materials increases.
  • the porosity of a quasi-crystalline alloy can be increased by an appropriate heat treatment.
  • the materials constituting the thermal protection elements of the present invention may contain a small proportion of heat conducting particles, for example crystals of metallic aluminum.
  • the thermal conduction of the material will be dominated by the conduction properties of the matrix as long as the particles do not coalesce, that is to say as long as their volume proportion remains below the percolation threshold. For approximately spherical particles with a weakly distributed radius, this threshold is around 20%.
  • This condition implies that the material constituting the thermal protection element contains at least 80% by volume of quasi-crystalline phases as defined above. Preferably, therefore, materials containing at least 80% of quasi-crystalline phase are used, for their application as thermal barrier.
  • the thermal protection elements can be used as thermal barriers. Such temperature conditions correspond to most domestic or automotive applications. In addition, they have a great ability to withstand the stresses due to the expansion of the support and their coefficient of expansion is intermediate between that of metal alloys and that of insulating oxides.
  • the quasicrystalline alloys constituting the thermal barriers can contain stabilizing elements chosen from W, Zr, Ti, Rh, Nb, Hf and Ta. The content of stabilizing element is less than or equal to 2% by number of atoms.
  • the thermal barriers of the present invention can be multi-layer barriers having an alternation of layers of materials which are good conductors of heat and layers of materials which are poor conductors which are alloys. almost crystalline.
  • Such structures constitute, for example, abradable thermal barriers.
  • the thermal protection elements of the present invention can be used as a bonding undercoat for a layer serving as a thermal barrier and consisting of a material of the prior art such as zirconia.
  • the materials constituting the thermal protection elements of the present invention become superplastic. They therefore correspond well to the conditions of use required for the production of a bonding sub-layer while being capable of participating themselves in the insulation of the substrate.
  • the thermal protection elements of the present invention can be used up to a few tens of degrees from the melting point of the material from which they are made. This limit is around 950 ° C to 1200 ° C depending on the composition.
  • the alloys according to the invention can be obtained by conventional metallurgical production processes, that is to say which comprise a slow cooling phase (ie ⁇ T / t less than a few hundred degrees).
  • ingots can be obtained by melting separate metallic elements or pre-alloys in a graphite crucible brazed under a covering of protective gas (argon, nitrogen), of covering flux used in conventional metallurgy, or in a crucible kept under vacuum. It is also possible to use refractory ceramic or copper crucibles cooled by high frequency current heating.
  • the preparation of the powders necessary for the metallization process can be carried out for example by mechanical grinding or by atomization of the liquid alloy in a jet of argon according to a conventional technique.
  • the alloying and atomization operations can be carried out in sequence without requiring the casting of intermediate ingots.
  • the alloys thus produced can be deposited in thin form, generally up to a few tens of micrometers, but also in thick form, up to several millimeters, by any metallization technique, including those which have already been mentioned.
  • the alloys of the present invention can be used in the form of a surface coating by deposition from a pre-prepared ingot, or of ingots of the separate elements, taken as targets in a sputtering reactor, or also by vapor phase deposition. produced by vacuum melting of the massive material. Other methods, for example those which use sintering of agglomerated powder, can also be used.
  • the coatings can also be obtained by thermal spraying, for example using an oxy-gas torch, a supersonic torch or a plasma torch. The thermal spraying technique is particularly interesting for the development of thermal protection elements.
  • Some alloys have been subjected to temperature maintenance under secondary vacuum or in air in order to assess their thermal stability and their ability to resist oxidation.
  • the morphology of the phases and the grain size obtained in the raw state of preparation were analyzed by optical micrography using an Olympus microscope.
  • the hardness of the alloys was determined using the WOLPERT V-Testor 2 durometer under loads of 30 and 400 grams.
  • An estimate of the ductility of certain alloys was obtained by measuring the length of the cracks formed from the angles of the cavity under load of 400 grams. An average value of this length, as well as the hardness, was evaluated from at least 10 different fingerprints distributed on the sample. Another estimate of the ductility is based on the amplitude of the deformation produced before rupture during a compression test applied to a cylindrical specimen of 4.8 mm in diameter and 10 mm in height machined with perfectly parallel faces perpendicular to the cylinder axis. An INSTROM brand traction / compression machine was used.
  • the electrical resistivity of the samples was measured at room temperature on cylindrical specimens 20 mm long and 4.8 mm in diameter.
  • the classic 4-point method was used, with a constant measurement current of 10 mA.
  • the voltage across the interior electrodes was measured with a high-precision nanovoltmeter. A measurement was made as a function of the temperature using a specifically adapted oven.
  • the melting temperatures of some alloys were determined on heating with a speed of 5 ° C / min by Differential Thermal Analysis on a SETARAM 2000C device.
  • the crystallographic structure of the alloys was defined by analysis of their X-ray diffraction diagram and their electron diffraction diagrams.
  • a series of alloys has been developed by melting pure elements in a high frequency field under an argon atmosphere in a cooled copper crucible.
  • the total mass thus produced was between 50 g and 100 g of alloy.
  • the melting temperature which depends on the composition of the alloy, has always been found in the temperature range between 950 and 1200 ° C.
  • a solid cylindrical test tube 10 mm + 0.5 mm in diameter and a few centimeters in height was formed by aspiration of the liquid metal in a quartz tube. The the cooling rate of this sample was close to 250 ° C per second. This sample was then cut with a diamond saw to shape the metallography and hardness specimens used in the examples below.
  • test piece Part of the test piece was fragmented for thermal stability tests and a crushed powder fraction for X-ray diffraction analysis of each alloy. A similar assembly was used to obtain the 4.8 mm diameter cylindrical samples intended for electrical resistivity. The cooling rate of the test piece was then close to 1000 ° C per second.
  • Table 1 below gives the content of the quasi-crystalline phase of the alloys according to the invention obtained, as well as the melting temperature of some of them.
  • alloys 2, 5, 7, 8, 9, 19, 22 predominantly have pnase O 1 and alloy 1 predominantly phase C.
  • Alloy 3 mainly contains phase H.
  • Alloy 6 consists essentially of phase H, as well as a small fraction of phase C.
  • the other alloys contain variable proportions of phases C, O 1 , O 3 , O 4 (and H for 23 ).
  • a bath of one hundred (100) kilograms of an alloy producing a mass fraction of more than 95% of quasicrystalline phase has been developed.
  • the nominal composition of the alloy was Al 67 Cu 9.5 Fe 12 Cr 11.5 in number of atoms (alloy 39).
  • This composition was made from industrial metallic components, namely aluminum A5, a Cu-Al-Fe alloy containing 19.5% Al by weight, 58.5% Cu by weight and 21.5% Fe by weight. These elements and alloys were introduced cold into a graphite crucible brazed with alumina. Their merger was carried out under a hedging flow which was maintained until the end of the operation. A 125 kW high frequency current generator was used.
  • the specific heat of the alloy was determined in the temperature range 20-80 ° C with a SETARAM scanning calorimeter.
  • the thermal diffusivity of a pellet of this alloy 15 mm thick and 32 mm in diameter was deduced from the temperature / time curve measured on one face of the pellet knowing that the opposite face, previously blackened, was irradiated with a laser lightning of calibrated power and shape.
  • the thermal conductivity is deduced from the two previous measurements, knowing the specific mass of the alloy which was measured by the Archimedes method by immersion in butyl phthalate maintained at 30 ° C ( ⁇ 0.1 ° C) and found equal to 4.02 g / cm 3 .
  • the thermal stability of some alloys of the present invention has been evaluated.
  • the selected alloys were subjected to maintenance at different temperatures for periods ranging from a few hours to several tens of hours.
  • Fragments extracted by breaking the ingots prepared according to Example 1 were placed in quartz ampoules sealed under secondary vacuum. The volume of these fragments was of the order of 0.25 cm 3 .
  • the ampoules were placed in an oven previously heated to the treatment temperature. At the end of the treatment, they were cooled under vacuum to ambient temperature by natural convection in air or at a controlled speed. The fragments were then ground for X-ray diffraction examination. Electron diffraction examinations were also carried out.
  • the experimental conditions of the heat treatments are summarized in table 3 below.
  • the alloys of the present invention are thermally stable in the sense that their structure, as it is characterized by the appropriate diffraction figures, does not change essentially during isothermal heat treatments at temperatures which can reach the temperature of alloying of alloys. In other words, the mass fraction of quasicrystalline phase present in the raw state of production does not decrease during temperature maintenance.
  • the alloys of the present invention are polycrystalline materials whose morphology has been studied by optical microscopy according to a conventional metallography technique.
  • the 10 mm diameter pellets prepared according to the method of Example 1 were finely polished and then attacked with an appropriate metallographic reagent.
  • the metallographic images were photographed with an Olympus optical microscope, working in white light. The grain size observed is between a few micrometers and a few tens of micrometers.
  • the Vickers hardnesses of the alloys of the present invention and of certain alloys of the prior art were measured at ambient temperature on fragments of alloys produced according to the method of Example 1, coated in a resin for metallographic use, then finely polished. Two loads of the microdurometer, respectively 30g and 400g, were used. The results are given in Table 5 below.
  • the Vickers hardnesses observed for the alloys of the present invention are particularly high in comparison with the Vickers hardnesses under load of 400 grams noted for the alloys of the prior art prepared as in Example 3 (sample 41 to 46).
  • the ductility of alloys with high hardness is relatively low.
  • the alloys of the present invention containing cobalt have a higher ductility.
  • additions for example of boron or carbon.
  • compositions 41 to 46 and 40 are alloys of the prior art, the others are alloys according to the invention.
  • compositions of the prior art have an electrical resistivity at room temperature which is between a few ⁇ cm and a few tens of ⁇ cm.
  • alloy 42 of composition Al 85 Cr 15 in number of atoms which has a resistivity of 300 ⁇ cm.
  • This value is to be compared with the presence of a rate of quasicrystalline phase fairly close, although lower, of 30% by mass. This state is however metastable and has only been achieved thanks to the high cooling rate which characterizes the method of preparation of the present test pieces.
  • the characteristic values of the electrical resistivity of the alloys of the present invention are between 300 and 600 ⁇ cm.
  • Such high values mean the quasicrystalline alloys of the present invention for any application where this property must be taken advantage of, such as for example Joule heating, resistors with high heat dissipation, electromagnetic coupling, possibly high frequency.
  • an alloy representative of the family (III) has a low temperature coefficient of the electrical resistivity (1 / ⁇ d ⁇ / dT).
  • the relative variation of the electrical resistivity was measured with the temperature of a test piece of alloy 2.
  • This test piece was prepared from a strip 0.1 mm thick and 1.2 mm wide. produced by quenching the liquid alloy on a copper drum, the surface of which scrolled at a speed of 12 m / s (technique, known as melt spinning).
  • the ingot brought to the liquid state had been prepared according to the method of Example 1.
  • the test piece was heated at a constant speed of 5 ° C./minute and kept in contact with four platinum wires according to the so-called measurement method. in four points.
  • the difference between potential electrodes was 20 mm and the potential measurement carried out with a precision nanovoltmeter.
  • a constant current of 10 mA flowed through the test tube through the other two electrodes.
  • the measuring device was kept under a protective argon flow in a suitable oven. It was found that the variation in resistance is linear, which demonstrates that no transformation of the sample takes place during the measurement or during the following heating cycle, in confirmation of the great thermal stability of the alloys (example 4).
  • the temperature coefficient deduced from the curve (1 / ⁇ (20 ° C)) ( ⁇ (T) - ⁇ (20 ° C)) / ⁇ T is -3.10 -4 . This low value distinguishes the alloy for applications where it is preferable to keep the characteristics of the material within a narrow range depending on the temperature, such as, for example, electromagnetic induction heating.
  • test tube 10 mm in diameter and 3 mm thick prepared according to the procedure of Example 1, was immersed for 30 h in a corrosive solution, at different temperatures. The solution was stirred for the duration of the immersion and kept at temperature by a thermostatically controlled bath. After 30 hours, the weight loss of each test piece was determined.
  • the present invention provides alloys which have excellent corrosion resistance in an acid medium (No. 2, having a Cu content greater than 5 atomic%), or in a strongly alkaline medium (No. 3 and 6, having a cobalt content greater than 5 atomic%).
  • the quasicrystalline alloys of the present invention combine several properties which designate them very particularly for many applications in the form of surface coatings: high hardness, low but not negligible ductility, thermal stability, high corrosion resistance.
  • high hardness low but not negligible ductility
  • thermal stability high corrosion resistance
  • An ingot of two kilograms of the alloy produced according to Example 2 was reduced to powder by grinding using a mill with carbide steel concentric rollers.
  • the powder thus obtained was sieved so as to retain only the fraction of grains whose size was between 25 ⁇ m minimum and 80 ⁇ m maximum.
  • a deposit of 0.5 mm thick was then produced by spraying this powder onto a mild steel plate previously sandblasted. This projection was carried out by means of a Metco flame torch supplied with a mixture proportioned with 63% hydrogen and 27% oxygen. The operation was carried out under a protective atmosphere of 30% hydrogenated nitrogen so as to prevent any oxidation of the sample.
  • the thermal diffusivity ⁇ , the specific mass d and the specific heat Cp were determined near ambient temperature for several samples prepared according to example 1 and a sample prepared according to example 2.
  • the samples prepared according to the method of l Example 1 are pellets 10 mm in diameter and 3 mm thick.
  • the sample of Example 2 is a pellet 32 mm in diameter and 15 mm thick.
  • test pieces The opposite faces of each pellet have been mechanically polished under water, taking great care to guarantee their parallelism.
  • the structural state of the test pieces was determined by X-ray diffraction and by electron microscopy. All the selected samples contained at least 90% by volume of quasicrystalline phase as defined above.
  • the thermal diffusivity has been determined using a laboratory device combining the laser flash method with an Hg-Cd-Te semiconductor detector.
  • the laser was used to supply pulses of power between 20 J and 30 J with a duration of 5.10 -4 s, to heat the front face of the specimen and the semiconductor thermometer was used to detect the thermal response on the opposite side of the test piece.
  • Thermal diffusivity was deduced from the experiments according to the method described in "A. Degiovanni, High Temp. - High Pressure, 17 (1985) 683".
  • the specific heat of the alloy was determined in the temperature range 20-80 ° C with a SETARAM scanning calorimeter.
  • the thermal conductivity ⁇ is deduced from the two previous measurements, knowing the specific mass of the alloy which was measured by the Archimedes method by immersion in butyl phthalate maintained at 30 ° C ( ⁇ 0.1 ° C).
  • Table 9 contains, for comparison, the values relating to some materials of the prior art (samples 50 , 60, 70, 80, 90, 100, 110, 120 and 130 ), some of which are known as thermal barrier (samples 50, 60, 70, 80 ).
  • the thermal conductivity of the quasicrystalline alloys constituting the protective elements of the present invention is considerably lower than that of metallic materials (aluminum metal or Al 2 Cu quadratic), given by way of comparison. It is two orders of magnitude less than that of aluminum and an order of magnitude to that of stainless steel usually considered as a good thermal insulator. In addition, it is lower than that of alumina and quite comparable to that of zirconia doped with Y 2 O 3 , considered as the archetype of thermal insulators in industry.
  • the thermal diffusivity of the alloys 90, 100, 110, 120 and 130 was determined. These alloys, which form defined aluminum compounds, have compositions close to those of the quasi-crystalline alloys which can be used for the protective elements of the present invention. However, they do not have the quasi-crystalline structure defined above. In all cases, their thermal diffusivity is greater than 5.10 -6 m 2 / s, that is to say much greater than that of the alloys used for the present invention.
  • the measurement of the thermal diffusivity was carried out according to the method of Example 11. Each test tube was placed under a stream of purified argon in the center of an oven heated by the Joule effect; the temperature rise rate, programmed by computer, varied linearly at the rate of 5 ° C / min. All the samples in accordance with the present invention show an approximately linear increase in ⁇ with temperature. The value of ⁇ determined at 700 ° C is close to twice that measured at room temperature. Likewise, the specific heat increases with temperature and reaches from 800 to 900 J / kgK at 700 ° C. The specific mass decreases on the order of 1 to 2% as indicated by thermal expansion or neutron diffraction measurements. Consequently, the thermal conductivity remains below 12 W / mK, that is to say the thermal conductivity of stainless steels which are used for certain thermal insulation applications.
  • Figures 1, 2 and 3 respectively represent the evolution of ⁇ as a function of the temperature for alloys 28, 31 and 33.
  • the measurements recorded during heating are represented by black squares, those recorded during cooling by white squares .
  • the variation in the thermal expansion of alloy 2 was measured.
  • the thermal expansion curve shows that the expansion coefficient depends very little on the temperature and is worth 9.10 -6 / ° C, a value close to that of stainless steels.
  • a first series of test pieces has been produced.
  • the substrate was a massive copper cylinder having a diameter of 30 mm and a height of 80 mm and the coating was applied with a plasma torch according to a conventional technique.
  • the C0 test piece is the uncoated copper cylinder.
  • the test piece C1 was coated on its entire surface with a layer of 1 mm thick of the alloy 2 and the test piece C2 was coated with a layer of 2 mm thick of the alloy 2.
  • the C5 test piece comprises a layer of alloy 2 constituting the thermal protection element of the present invention serving as a bonding layer and a layer of yttria zirconia.
  • the C3 and C4 test pieces used for comparison respectively comprise a layer of yttria-containing zirconia and a layer of alumina.
  • test pieces A0 to A2 Another series of test pieces was produced with, as support, a stainless steel tube having a length of 50 cm, a diameter of 40 mm, a wall thickness of 1 mm (test pieces A0 to A2).
  • the support tube is coated at one of its ends over a length of 30 cm.
  • the deposits were made with an oxy-gas torch. Table 10 below gives the nature and thickness of the layers for the different test pieces. The precision on the final thicknesses of the deposits was ⁇ 0.3 mm. All the test pieces were fitted with very low inertia Chromel - Alumel thermocouples.
  • FIG. 4 represents a test piece of the copper cylinder type 1 comprising a coating 2 and provided with a central thermocouple 3 and a lateral thermocouple 4, the two being inserted up to half the length of the cylinder.
  • FIG. 5 represents a hollow tube 5 in which a flow of hot air 6 is passed and which is provided with three thermocouples designated respectively by T1, T2 and T3, the first two being inside the tube and placed respectively at the beginning of the coated area and at the end of the coated area, and the third being on the outer surface of the coating.
  • test pieces C0, C1, C2, C3, C4 and C5 were placed on their base on a refractory brick. Successive heat pulses lasting 10 s were applied to each specimen at 60 s intervals and the response of the thermocouples was recorded. These pulses were produced by the flame of a torch, placed at a constant distance from the test tube and oriented opposite the thermocouple close to the surface. The flow of combustion gases was carefully controlled and kept constant throughout the experiment. Two series of experiments were carried out: one with test tubes initially at 20 ° C and the other with test tubes initially at 650 ° C.
  • test pieces C0 to C5 make it possible to define three parameters which summarize the results of the experiment, namely the maximum difference P in temperature between the two thermocouples, ⁇ T / ⁇ t the rate of temperature rise of the lateral thermocouple 4 during the pulse and the temperature increment ⁇ T produced in the center of the test piece (thermocouple 3). These data are shown in Table 10. It was found that the zirconia layer of the specimen C3 did not resist more than three pulses and was cracked from the first pulse. The C2 sample did not start to crack until the sixth pulse and the C1 sample withstood more than 50 pulses. These results show that the protective elements of the present invention, used as a thermal barrier, have performances at least equivalent to those of zirconia.
  • the thermal protection element of the present invention constitutes an undercoat. It was found that the zirconia layer of the C3 specimen did not resist more than three heat pulses and was cracked from the first pulse. For the C5 test tube, also subjected to a series of thermal pulses, the surface temperature of the zirconia deposit, measured by a third thermocouple placed in contact with the deposit at the end of the tests, stabilized at 1200 ° C. . The experiment focused on 50 pulses and the C5 specimen resisted without apparent damage, although the coefficient of expansion of copper is close to double that of the quasi-crystalline alloy, which would imply significant shear stresses. at the substrate / deposition interface, if the underlay material did not become plastic.
  • the thermal protection elements of the present invention are therefore well suited to the production of bonding sub-layers, in particular for thermal barriers.
  • TABLE 10 20 - 100 ° C 650 - 550 ° C coating material ⁇ T ⁇ 0.5 ° C ° C ⁇ T / ⁇ t ° C / s P ⁇ 0.5 ° C ° C ⁇ T ⁇ 0.5 ° C ° C ⁇ T / ⁇ t ° C / s P ⁇ 0.5 ° C ° C C0 nil 27 2.85 5.4 22 2.3 ⁇ 1 C1 Al 70 Cu 9 Fe 10.5 Cr 10.5 1 mm 24 2.8 3.8 11 1.1 6 C2 Al 70 Cu 9 Fe 10.5 Cr 10.5 2mm 18 1.3 0 25 0.3 4.7 C5 Al 70 Cu 9 Fe 10.5 Cr 10.5mm ZrO 2 -Y 2 O 3 8% 1 mm 23 2.6 4.2 13 1.2 2.5 C3 1 mm yttria zirconia 24 2.75 4.7 14
  • thermal protection element of the present invention to the insulation of a reactor.
  • Test specimens A0, A1 and A2 were used to assess the ability of the alloys of the invention to thermally insulate a device.
  • the test pieces were each provided with 3 thermocouples T1, T2 and T3 as shown in FIG. 5.
  • a current of hot air at constant flow rate was sent through the stainless steel tube constituting the substrate of each test piece.
  • the inlet air temperature, measured using the T1 thermocouple was 300 ⁇ 2 ° C.
  • the surface temperature, measured using the T3 thermocouple was recorded as a function of time from the start of the hot air generator.
  • the T2 thermocouple made it possible to verify that the transient conditions for establishing the hot air flow were identical for all the measurements.
  • Figures 6 and 7 show the evolution of the surface temperature of each of the test pieces A0, A1 and A2 as a function of time.
  • the surface temperature of the test piece A0 (without coating) exceeds at equilibrium that of the test piece A2 by 35 ° C approximately and that of the A1 test tube of 27 ° C.
  • the thermal protection elements of the present invention give interesting results with regard to thermal insulation.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Powder Metallurgy (AREA)
  • Physical Vapour Deposition (AREA)
EP92904842A 1991-01-18 1992-01-15 Alliages d'aluminium, les substrats revetus de ces alliages et leurs applications Expired - Lifetime EP0521138B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FR9100549A FR2671808B1 (fr) 1991-01-18 1991-01-18 Alliages d'aluminium a proprietes specifiques.
FR9100549 1991-01-18
PCT/FR1992/000030 WO1992013111A1 (fr) 1991-01-18 1992-01-15 Alliages d'aluminium, les substrats revetus de ces alliages et leurs applications

Publications (2)

Publication Number Publication Date
EP0521138A1 EP0521138A1 (fr) 1993-01-07
EP0521138B1 true EP0521138B1 (fr) 1997-11-19

Family

ID=9408814

Family Applications (1)

Application Number Title Priority Date Filing Date
EP92904842A Expired - Lifetime EP0521138B1 (fr) 1991-01-18 1992-01-15 Alliages d'aluminium, les substrats revetus de ces alliages et leurs applications

Country Status (7)

Country Link
EP (1) EP0521138B1 (ja)
JP (1) JP3244178B2 (ja)
AU (1) AU648876B2 (ja)
DE (1) DE69223180T2 (ja)
ES (1) ES2110492T3 (ja)
FR (1) FR2671808B1 (ja)
WO (1) WO1992013111A1 (ja)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10332420A1 (de) * 2003-07-16 2005-02-10 Alstom Technology Ltd Aluminiumbasierte multinäre Legierungen und deren Verwendung als wärme- und korrosionsschützende Beschichtungen
FR2939125A1 (fr) * 2008-12-01 2010-06-04 Saint Gobain Coating Solution Revetement de dispositif de mise en forme de produits en verre
WO2010063930A1 (fr) * 2008-12-01 2010-06-10 Saint-Gobain Coating Solution Revetement de dispositif de mise en forme de produits en verre

Families Citing this family (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2699554B1 (fr) * 1992-12-23 1995-02-24 Metallisation Ind Ste Nle Barrières thermiques, matériau et procédé pour leur élaboration.
DE4425140C1 (de) * 1994-07-15 1995-07-13 Thomas Dipl Phys Eisenhammer Strahlungswandler zur Umsetzung von elektromagnetischer Strahlung in Wärme und von Wärme in elektromagnetische Strahlung
FR2744839B1 (fr) 1995-04-04 1999-04-30 Centre Nat Rech Scient Dispositifs pour l'absorption du rayonnement infrarouge comprenant un element en alliage quasi-cristallin
FR2737505B1 (fr) * 1995-07-31 1997-10-24 Gaz De France Revetement en materiau quasi-cristallin et son procede de depot
FR2745304B1 (fr) * 1996-02-23 1998-05-22 Centre Nat Rech Scient Procede de preparation d'alliages quasicristallins al cu fe mb, les alliages obtenus et leurs applications
FR2745300B1 (fr) * 1996-02-23 1998-04-30 Peugeot Revetements anti-usure et/ou de protection thermique pour des pieces telles que des pieces de moteur de vehicule automobile
ES2131451B1 (es) * 1996-10-04 2000-02-16 Inst Nacional De Tecnica Aeroe Recubrimientos cuasicristalinos tipo barrera termica para la proteccion de componentes de las zonas calientes de turbinas.
DE19859477B4 (de) * 1998-12-22 2005-06-23 Mtu Aero Engines Gmbh Verschleißschutzschicht
FR2833020B1 (fr) * 2001-11-30 2004-10-22 Inst Francais Du Petrole Utilisation d'alliages d'aluminium quasi-cristallins dans des applications du raffinage et de la petrochimie
US20040022662A1 (en) * 2002-07-31 2004-02-05 General Electric Company Method for protecting articles, and related compositions
DE10358813A1 (de) * 2003-12-16 2005-07-21 Alstom Technology Ltd Quasikristalline Legierungen und deren Verwendung als Beschichtung
FR2866350B1 (fr) * 2004-02-16 2007-06-22 Centre Nat Rech Scient Revetement en alliage d'aluminium, pour ustensile de cuisson
JP2016156055A (ja) * 2015-02-24 2016-09-01 トヨタ自動車株式会社 断熱材料
CN105821261B (zh) * 2016-05-30 2017-10-27 广州晶品智能压塑科技股份有限公司 一种高耐腐蚀性的制盖机模具材料
CN106498247A (zh) * 2016-12-05 2017-03-15 郑州丽福爱生物技术有限公司 一种耐冲击耐磨复合合金材料及其制备方法
EP3428628A1 (en) 2017-07-11 2019-01-16 Centre National De La Recherche Scientifique Method of authenticating an object with x-ray diffraction

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2635117B1 (fr) * 1988-08-04 1993-04-23 Centre Nat Rech Scient Materiaux de revetement pour alliages d'aluminium
EP0489427A1 (en) * 1990-12-05 1992-06-10 Sumitomo Metal Industries, Ltd. Surface-coated aluminum material
FR2673871B1 (fr) * 1991-03-13 1995-03-10 Centre Nat Rech Scient Cordon pour revetement par projection au chalumeau et son utilisation pour deposer sur un substrat une phase quasi cristalline.

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
US pages 6525 - 6528; C. BERGER ET AL: 'EXPERIMENTAL EVIDENCE FOR THE EXISTENCE OF ENHANCED DENSITY OF STATES AND CANONICAL SPIN-GLASS BEHAVIOR IN AL-MN(-SI) QUASICRYSTALS' *

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10332420A1 (de) * 2003-07-16 2005-02-10 Alstom Technology Ltd Aluminiumbasierte multinäre Legierungen und deren Verwendung als wärme- und korrosionsschützende Beschichtungen
US7169478B2 (en) 2003-07-16 2007-01-30 Alstom Technology Ltd. Aluminum-based multinary alloys and their use as heat- and corrosion-resistant coatings
FR2939125A1 (fr) * 2008-12-01 2010-06-04 Saint Gobain Coating Solution Revetement de dispositif de mise en forme de produits en verre
FR2939126A1 (fr) * 2008-12-01 2010-06-04 Saint Gobain Coating Solution Revetement de dispositif de mise en forme de produits en verre
WO2010063930A1 (fr) * 2008-12-01 2010-06-10 Saint-Gobain Coating Solution Revetement de dispositif de mise en forme de produits en verre
EA022538B1 (ru) * 2008-12-01 2016-01-29 Сэн-Гобэн Коутинг Солюшн Покрытие для устройства, предназначенного для формования стеклянных изделий

Also Published As

Publication number Publication date
DE69223180T2 (de) 1998-04-23
FR2671808A1 (fr) 1992-07-24
WO1992013111A1 (fr) 1992-08-06
DE69223180D1 (de) 1998-01-02
AU648876B2 (en) 1994-05-05
FR2671808B1 (fr) 1994-06-17
ES2110492T3 (es) 1998-02-16
JPH05505649A (ja) 1993-08-19
AU1271792A (en) 1992-08-27
EP0521138A1 (fr) 1993-01-07
JP3244178B2 (ja) 2002-01-07

Similar Documents

Publication Publication Date Title
EP0521138B1 (fr) Alliages d'aluminium, les substrats revetus de ces alliages et leurs applications
EP0572646B1 (fr) Utilisation d'un alliage d'aluminium quasi-cristallin pour l'élaboration d'un élément de protection thermique
US5652877A (en) Aluminum alloys, substrates coated with these alloys and their applications
EP0605273B1 (fr) Barrières thermiques, materiau et procédé pour leur élaboration
Hidouci et al. Microstructural and mechanical characteristics of laser coatings
Sabard et al. Microstructural evolution in solution heat treatment of gas-atomized Al alloy (7075) powder for cold spray
US5204191A (en) Coating materials for metal alloys and metals and method
Yeh et al. Formation of simple crystal structures in Cu-Co-Ni-Cr-Al-Fe-Ti-V alloys with multiprincipal metallic elements
Koike et al. In situ observation of partial melting in superplastic aluminum alloy composites at high temperatures
Anandkumar et al. Wear behavior of Al–12Si/TiB2 coatings produced by laser cladding
Stella et al. Cavitation erosion of plasma-sprayed NiTi coatings
Ji et al. Spray forming thick nanostructured and microstructured FeAl deposits
Wolf et al. Recent developments on fabrication of Al‐matrix composites reinforced with quasicrystals: from metastable to conventional processing
Sichani et al. The effect of APS parameter on the microstructural, mechanical and corrosion properties of plasma sprayed Ni-Ti-Al intermetallic coatings
CN101144159A (zh) 一种纳米/亚微米TiB-TiC增强钛基复合材料(TiB+TiC)/Ti的制备方法
Tseng et al. Mechanical properties of Pt-Ir and Ni-Ir binary alloys for glass-molding dies coating
EP0356287B1 (fr) Matériaux de revêtement pour alliages métalliques et métaux
FR3096989A1 (fr) Procédé de fabrication additive d’une pièce en un alliage CCA nitruré
EP0504048A1 (fr) Cordon pour revêtement par projection au chalumeau et son utilisation pour déposer sur un substrat une phase quasi cristalline
Lin et al. Orderly nucleation and competitive growth behaviors of Ti-Al intermetallic compounds in Ti/TiAl3 diffusion couple under high temperature
CN111663070B (zh) 一种耐高温氧化的AlCoCrFeNiSiY高熵合金及其制备方法
Matsuda et al. Rapid solidification processing of a Mg-Li-Si-Ag alloy
Montealegre et al. Influence of the yttria content on the oxidation behaviour of the intermetallic Fe40Al Alloy
Relue et al. Corrosion performance of different aluminum alloy deposits fabricated by lateral friction surfacing
Zhang et al. Microstructure and elevated temperature flexure testing of tungsten produced by electron beam additive manufacturing

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): CH DE ES FR GB IT LI

17P Request for examination filed

Effective date: 19930122

17Q First examination report despatched

Effective date: 19941129

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): CH DE ES FR GB IT LI

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REF Corresponds to:

Ref document number: 69223180

Country of ref document: DE

Date of ref document: 19980102

ITF It: translation for a ep patent filed

Owner name: NOTARBARTOLO & GERVASI S.P.A.

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2110492

Country of ref document: ES

Kind code of ref document: T3

GBT Gb: translation of ep patent filed (gb section 77(6)(a)/1977)

Effective date: 19980130

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed
REG Reference to a national code

Ref country code: GB

Ref legal event code: IF02

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20090115

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20110202

Year of fee payment: 20

Ref country code: CH

Payment date: 20110124

Year of fee payment: 20

Ref country code: DE

Payment date: 20110121

Year of fee payment: 20

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: ES

Payment date: 20110125

Year of fee payment: 20

Ref country code: GB

Payment date: 20110120

Year of fee payment: 20

Ref country code: IT

Payment date: 20110125

Year of fee payment: 20

PGRI Patent reinstated in contracting state [announced from national office to epo]

Ref country code: IT

Effective date: 20110616

REG Reference to a national code

Ref country code: DE

Ref legal event code: R071

Ref document number: 69223180

Country of ref document: DE

REG Reference to a national code

Ref country code: DE

Ref legal event code: R071

Ref document number: 69223180

Country of ref document: DE

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

REG Reference to a national code

Ref country code: GB

Ref legal event code: PE20

Expiry date: 20120114

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20120411

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION

Effective date: 20120116

Ref country code: DE

Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION

Effective date: 20120116

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION

Effective date: 20120114