Classifications

• • 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
  • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
  • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
  • C23C14/34—Sputtering
  • C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
  • C23C14/352—Sputtering by application of a magnetic field, e.g. magnetron sputtering using more than one target
• • C—CHEMISTRY; METALLURGY
  • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
  • C22C—ALLOYS
  • C22C16/00—Alloys based on zirconium
• • 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
  • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
  • C23C14/02—Pretreatment of the material to be coated
  • C23C14/027—Graded interfaces
• • 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
  • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
  • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
  • C23C14/14—Metallic material, boron or silicon
• • 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
  • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
  • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
  • C23C14/54—Controlling or regulating the coating process
  • C23C14/548—Controlling the composition
• • C—CHEMISTRY; METALLURGY
  • C30—CRYSTAL GROWTH
  • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
  • C30B23/00—Single-crystal growth by condensing evaporated or sublimed materials
  • C30B23/02—Epitaxial-layer growth
  • C30B23/06—Heating of the deposition chamber, the substrate or the materials to be evaporated
  • C30B23/066—Heating of the material to be evaporated
• • C—CHEMISTRY; METALLURGY
  • C30—CRYSTAL GROWTH
  • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
  • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
  • C30B29/10—Inorganic compounds or compositions
  • C30B29/52—Alloys

Definitions

• the invention relates to a method for depositing on a substrate a thin layer of metal alloy and new metal alloys that can be deposited on a substrate by implementing the method.
• amorphous metals (A. Inoue, Buik Amorphous Alloys, Materials Science Foundations, Vol.6, 1999) must be prepared by fast solidification, which limits the thickness of the pieces (less than 0.2 mm for ribbons).
• new alloys were discovered which have a greater ability to vitrify (Zr-Ti-Cu-Ni-Be, Ti-Zr-Cu-Ni-Be, Zr-Ti-Al-Cu -Ni) and which provide access to massive amorphous metal parts whose smallest dimension can reach 20 or even 30 mm.
• high-entropy alloys Other alloys recently discovered and composed of a number of elements between 5 and 13 and whose atomic percentage of the main elements does not exceed 35% (known as high-entropy alloys) are also of strong interest from the point of view of their properties. Composed of solid solutions and having a nanostructured phase (nanocrystalline precipitate in a matrix amorphous or crystalline), some compositions show very high hardness and a temperature withstand greater than 1000 ° C. (Multi-principal-element alloys with improved oxidation and wear resistance for thermal spray coating, Ping-Kang HUANG, Jien-Wien YEH, Tao-Tsung SHUN and Swe-Kai CHEN, Advanced Engineering Materials 2004, 6, No. 1 -2 p.74).
• high-entropy alloys have better thermal stability than zirconium-based (Zr) amorphous metal alloys, higher toughness (130 to 1100 Hv - Vickers hardness index) than conventional alloys, and better corrosion resistance. .
• These high entropy alloys have physical characteristics that make them potential candidates in all technical applications where high hardness, resistance to wear and oxidation, good chemical inertness are required at high temperature.
• these alloys can be used for the coating and manufacture of metal parts, parts used in the chemical industry, or functional coatings (non-stick surfaces, surfaces with tribo logical properties).
• these high entropy alloys have good wear resistance (similar to ferrous alloys of the same hardness).
• most of these alloys show good corrosion resistance (as good as stainless steels, especially when they contain elements such as Cu, Ti, Cr, Ni or Co), excellent resistance to oxidation (up to 1100 ° C., especially when they contain elements such as Cr or Al) (nanostructured High-Entropy Alloys with multiple principal elements: novel alloy design concepts and outcomes, Jien-Wei Yeh et al., advanced engineering materials 2004, 6, No. 5).
• the designed target is a disk composed of several alternative sectors of Pb, Ti, Zr forming a circular target. They showed that the composition of films for i elements can be predicted using the following equation (1)
• Xi [(Yi * Ai * 100 / ⁇ Yi * Ai)] (1) where Yi: is the atomization rate of the element i. Ai: is the area of element i.
• the composition of the deposited alloy is fixed. To modify the composition of this alloy (during the process or later), it is necessary to modify the geometry (number and size of portions) of the target. To do this, a new target must be developed.
• the target alloy comprises a strong majority element
• a target designed using equation (1) will be unbalanced (the surface of the other elements involved in the composition of the final deposit will be low or even unrealizable particularly in the case of where the proportion in the deposit is low and the rate of spraying is high) and it will not be possible to achieve the target composition.
• the composition of the deposited alloy is determined by the configuration of the targets, which must be modified ex situ.
• the alloys targeted are special alloys, rich in aluminum.
• the object of the invention is to be able to make deposits of particular alloys (amorphous alloys rich in Zr and Ti and high entropy alloys) of variable compositions (in a wide range) by only playing on the experimental conditions of deposition, in particular on the power applied on the targets.
• the composition of the alloy can be modified without the need to develop a new target.
• the object of the invention is also to be able to obtain metal alloys comprising at least four elements while controlling the composition of the alloys obtained in a wide range.
• the inventors have discovered, surprisingly, that these problems could be solved by the use of at least two targets composed of several sectors comprising pure crystalline elements and / or alloyed elements and by the realization of magnetron sputtering deposits.
• One of the targets may contain one or more sectors consisting of allied elements, the other sectors being mono-elementary.
• the use of allied elements makes it possible not to multiply the number of targets and sectors composing these targets, in the case of alloys containing the largest number of elements.
• Allied elements are alloys of 2 to many elements.
• the subject of the invention is therefore a method for depositing on a substrate a thin layer of metal alloy comprising at least four elements, said alloy being
• an amorphous alloy containing, in atomic percentage, at least 50% of the elements Ti and Zr, the proportion of Ti possibly being zero;
• a high entropy alloy consisting of solid solutions whose microstructure contains nanocrystallites inserted into a matrix and whose elements are chosen from the group consisting of Al, Co, Cr, Cu, Fe, Ni, Si, Mn, Mo, V , Zr and Ti (these elements constitute the matrix and the nanocrystallites inserted into this matrix, the matrix plays the role of a continuous phase in which the nanocrystallites are dispersed); by simultaneous magnetron sputtering of at least two targets which are placed in an enclosure containing a plasma-containing gaseous medium and at least one of which contains at least two of said elements of the alloy to be deposited, each of the targets being fed independently one from the other by an electric power generator.
• amorphous alloy is meant an alloy containing only an amorphous phase or an alloy in which some crystallites may be present in the middle of a majority amorphous phase.
• the alloy is an alloy of
• This alloy is an amorphous alloy containing in atomic percentage at least 50% of elements Ti and Zr; Zr being the majority element and being obligatorily present while the proportion in Ti can be zero.
• the elements constituting the remaining part are advantageously chosen from the group consisting of Al, Co, Cr, Cu, Fe, Ni, Si, Mn, Mo and V.
• the alloy compositions particularly targeted are Zr 4815 Ti 515 Al 1 !
• the alloy is a high entropy alloy.
• a high entropy alloy is an alloy that does not contain a major element but consists of 5 to 13 elements present in equimolar amount ranging from 5% to 35%. The interest is that in such an alloy the formation of random solid solutions is favored over the synthesis of fragile crystalline intermetallic phases. In addition, it consists of nanocrystallites dispersed in an amorphous or crystalline matrix.
• a high entropy alloy contains at least 5 elements selected from the group consisting of Al, Co, Cr, Cu, Fe, Ni, Si, Mn, Mo, V, Zr and Ti.
• Particularly targeted alloy compositions are of high entropy alloys 5 to 13 main components in equimolar ratios, each having a lower atomic percentage 35% as FeCoNiCrCuAlMn, FeCoNiCrCuAl 0, 5, CuCoNiCrAlFeMoTiVZr, CuTiFeNiZr, AlTiVFeNiZr, MoTiVFeNiZr, CuTiVFeNiZrCo, AlTiVFeNiZrCo,
• MoTiVFeNiZrCo CuTiVFeNiZrCoCr, AlTiVFeNiZrCoCr, MoTiVFeNiZrCoCr,
• the principle of sputtering is based on the establishment of an electric discharge between two conductive electrodes placed in an enclosure where there is a reduced pressure of inert gas, resulting in the appearance at the anode of a thin layer of the compound constituting the counter electrode.
• the sputtering process used is magnetron sputtering.
• the magnetron sputtering technique involves confining electrons using a magnetic field near the target surface. By superimposing a perpendicular magnetic field on the electric field, the trajectories of the electrons wrap around magnetic field lines (cycloidal movement of electrons around the field lines), increasing the chances of ionizing the gas near the cathode .
• the magnetic field increases the density of the plasma which results in an increase in the current density on the cathode. High spray rates and a decrease in the temperature of the substrate can thus be obtained.
• the plasmagenic gaseous medium ensures a correct spraying yield without inducing pollution.
• the plasmagenic gaseous medium is advantageously constituted by helium, neon, argon, crypton or xenon, preferably by argon.
• each target is powered by an independent electric power generator, able to provide a power density of between 0.1 and 100 W / cm 2 of the target surface, in particular between 1 and 10 W / cm 2 . It has been found that by varying the power of each of the magnetrons, it is possible to control the composition of the metal alloy films obtained and to vary it over a wide range. It is also possible to vary the crystalline structure of the layers.
• Targets can be powered at the same or different constant levels of electrical power.
• at least two of said targets are supplied with substantially different levels of electrical power.
• at least two of said targets are fed at constant levels of equal electrical power.
• the process may be suitable for the deposition of alloys having a compositional gradient. A concentration gradient of one or more elements makes it possible to ensure good anchoring of the alloy on the substrate and / or good properties (especially anti-adhesive properties, wear resistance, corrosion resistance) on the surface.
• the power supply power of at least one of the targets is variable, preferably continuously, for at least a portion of the duration of the realization of the deposit.
• the process may also be suitable for deposition on the same substrate of layers of alloys of different compositions.
• it allows the manufacture of deposits consisting alternately of an alloy composition and then another.
• the substrate is mounted on a rotating support placed opposite the targets.
• Said rotary support is driven with a rotational speed sufficient to ensure good homogeneity of the alloy during deposition.
• it is not necessary that said rotary support is driven by a translation movement.
• At least one of said targets contains only one element of the alloy to be deposited (called mono-elementary target).
• the mono-elementary target may consist of the element mainly present in the desired amorphous alloy.
• at least one of the targets has on the surface a mosaic structure containing several elements, in a pure form and / or alloy, of the alloy to be deposited. All targets can be mosaic targets.
• each of the elements is assembled in one or more zones of variable geometric shape and these zones are grouped together to form the target.
• Each element can be grouped in the same zone.
• the zones can optionally be superimposed.
• the target may consist of a disc of only one of the elements in which openings are drilled which are superimposed (at the openings) other discs formed other elements.
• the zones could also be organized as camembert (alternating triangular zones of each of the elements forming a circular zone).
• the subject of the invention is also a metallic alloy in the form of a thin layer comprising at least four elements, capable of being deposited on a substrate by implementing the method according to the invention, said alloy being: an amorphous alloy containing at least 50% by atomic percentage of the elements Ti and Zr, the proportion of Ti possibly being zero; or
• a high entropy alloy consisting of solid solutions whose microstructure contains nanocrystallites inserted into a matrix and whose elements are chosen from the group consisting of Al, Co, Cr, Cu, Fe, Ni, Si, Mn, Mo, V , Zr and Ti (these elements constitute the matrix and the nanocrystallites inserted into this matrix, the matrix plays the role of a continuous phase in which the nanocrystallites are dispersed).
• These metal alloys are in the amorphous state or comprise at least one nano-crystalline phase.
• amorphous alloy an alloy containing only an amorphous phase or an alloy in which some crystallites may be present in the middle of a majority amorphous phase.
• the alloy is an "Inoue” type alloy.
• This alloy is an amorphous alloy containing in atomic percentage at least 50% of the elements Ti and Zr; Zr being the majority element and being obligatorily present while the proportion in Ti can be zero.
• the elements constituting the remaining part are advantageously chosen from the group consisting of Al, Co, Cr, Cu, Fe, Ni, Si, Mn, Mo and V, more advantageously in the group consisting of Al, Cu and Ni.
• the alloy is a high entropy alloy, that is to say in which there is no main or majority element. It consists of 5 to 13 elements present in equimolar amount ranging from 5% to 35%, which favors the formation of random solid solutions and a microstructure containing nanocrystallites inserted into a matrix.
• the high entropy alloy contains at least 5 elements selected from the group consisting of Al, Co, Cr, Cu, Fe, Ni, Si, Mn, Mo, V, Zr and Ti. The chosen elements have the capacity to form stable solid solutions between them.
• a metal alloy can be obtained which has a concentration gradient over at least a part of its thickness, by varying the power applied to at least one of the targets during the process.
• the metal alloy may be in the form of successive layers of alloys of different compositions.
• the metal alloy may be in the form of a layer formed alternately of an alloy composition and then another.
• the method according to the invention makes it possible to obtain metal alloys whose atomic percentages do not vary with the duration of the deposition (thus the composition is independent of the deposition time) and whose thickness depends on the deposition time.
• metal alloys which are in the form of a thin layer, in particular of a thin layer with a thickness of between 10 nm and 10 ⁇ m, advantageously between 0.1 and 1 ⁇ m. This range of layer thickness is most often sufficient to modify the surface properties.
• the power applied can also be modified during the process, which makes it possible to obtain metal alloys having a concentration gradient of at least one element or layers of alloys of different compositions.
• the metal alloy is in the form of a layer having a concentration gradient of at least one element increasing in the vicinity of the interface with the substrate, to reinforce the bonding of the alloy. deposited on the substrate.
• the metal alloy is in the form of a layer having a concentration gradient of at least one element between the interface and the free surface of the alloy, in order to modify the surface properties of the alloy. adhesion, hardness.
• the metal alloy can be deposited on any type of substrate. In particular, it is deposited on a metal or polymeric substrate.
• the particularly targeted alloy compositions are amorphous metal alloys such as
• the amorphous metal alloys generally have a Young's modulus lower than those of metals or stainless steels.
• the elastic zone is therefore very extensive in the field of constraints. In a range of temperatures close to the glass transition, these alloys have the interesting property of recovering their shape after deformation, where all the other metals would be deformed and entered in the plastic domain.
• the amorphous metal alloys are insensitive to corrosion, in particular because they do not have crystallized grains and grain boundaries through which corrosion develops in the crystallized alloys.
• the amorphous metal alloys have a very low coefficient of friction.
• the particularly targeted alloy compositions are nanocrystalline high-entropy alloys of 5 to 13 main elements in equimolar ratios, each having an atomic percentage of less than 35% such as FeCoNiCrCuAlMn, FeCoNiCrCuAl 0 , 5 ,
• High entropy alloys characterized by staying at higher temperatures than glasses, can be used in technical applications, wear, corrosion and oxidation resistance are required at high temperature.
• the amorphous metal alloys and high entropy alloys therefore have beneficial applications in many fields, particularly in the field of food coatings (release coatings) or in the automobile.
• the piston compresses the fresh gases, the pressure due to the combustion of the mixture and the reciprocating displacement.
• the piston is composed of segments located in grooves formed around the periphery of the piston, said segments provide sealing (fire-break segment, sealing segment, scraper segment).
• segments consist of soft cast iron coated with a layer of chromium or molybdenum.
• the amorphous or high entropy metal alloys have properties very close to the coatings already used. They have a very good strength below the crystallization temperature, a very good hardness, and are resistant to corrosion.
• An amorphous or high entropy metal alloy has a very low coefficient of friction, so the wear generated by friction is less, therefore there is less heating of the material, frictional loss, and the amorphous metallic alloy present. very good resistance to fatigue.
• Deposits made by sparking have a roughness too great to allow tribological tests, deposits made by dipping as for chromium are difficult to achieve because it is necessary to ensure a sufficient cooling rate, plus a significant thickness of coating would result in a cost price higher.
• it is possible deposit thin layers of amorphous or high entropy metal alloy. It is also possible to control the thickness of the deposit and thus limit the cost. It is therefore possible to replace the chromium or molybdenum layer with a metal alloy layer, which improves the friction resistance and fatigue resistance of the coated part (segment).
• Amorphous or high entropy metal alloys can also be used for coating bearings in the engine.
• the role of the bearing is to allow a good rotation of the crankshaft.
• a pad must have good mechanical strength, good conformability, good incrustability, good resistance to galling, good corrosion resistance, good temperature resistance, good adhesion to the support and good thermal conductivity.
• Amorphous or high entropy metal alloys can also find other applications in the automobile: camshaft, diesel injection pump, turbocharger.
• FIG. 1 exploded view of the mosaic target consisting of Cu, Zr, Al and Ni;
• FIG. 2 linear representation of the proportion of measured element (by X-ray fluorescence) as a function of the ratio (Pzr + 0.3Pmixt) / (Pzr + Pmixte)
• Pzr is the power applied to the zirconium target
• Pmixte is the power applied to the mosaic target
• Figure 4 diffractograms obtained by X-ray diffraction deposits 1, 3, 5, 9 and 7 of Example 1;
• Figure 5 Atomic% of the six elements according to the deposit number of Example 2.
• Figure 7 X-ray diffractograms of deposits 1 to 8 of Example 2;
• Example 1 Metallic alloy films of complex composition obtained by magnetron sputtering
• Metal alloy films of the Zr-Cu-Al-Ni family were made by plasma spraying of mosaic targets.
• the target composition was Zr55Cu3oAlioNi5.
• silicon wafers (100) (coated with the native oxide) were chosen as substrates. They are cut (1.5 * 1.5 cm 2 ), cleaned and glued on the sample holder in the reactor via an airlock.
• Argon is introduced at a pressure of 0.21 Pa (2.times.10.sup.- 3 mb), before each deposition the targets are prepulverized for 4 min to eliminate the residual oxidation possible during deposition the substrate is rotated ( about 1 turn in 20 s) to ensure a good homogeneity of the composition in the plane Deposits of (2 to 20) min are made
• the powers imposed on each magnetron are independent, they were varied from (110) to 520) W which corresponds to voltages on the targets of (110 to 390) V and currents of (0.4 to 1.7) A. On this type of magnetron when setting the power, voltage and current are then automatically adjusted to meet the power requirement.
• composition was made by X-ray analysis (Energy Dispersive Spectroscopy) during scanning electron microscopy (SEM) observations on the thickest deposits (20 min).
• the target composition is not obtained.
• Table 3 EDS analysis carried out on deposits 2 and 3 It can be seen that the atomic percentages do not vary with the duration of the deposit, therefore the composition is independent of the duration of the deposit.
• Table 4 EDS analysis performed on deposits 3, 5, 7 and 9 The results on four deposits of 20 min show that the composition of the alloy varies according to the power applied to the targets. By playing on the powers applied, it is thus possible to obtain a metal alloy very close to the intended composition (deposit No. 7).
• the deposit thickness of 20 min was measured by SEM on sectional views. It depends directly on the total sum of the powers applied to the targets as shown in the graph in FIG. 3.
• the deposition rates obtained are relatively high from 70 nm / min to 120 nm / min, which makes it possible to produce thick films in a time. reasonable.
• the crystalline structure of the deposits was studied by grazing incidence X-ray diffraction in order to exalt the signal coming from the film with respect to the substrate.
• the diffractograms obtained have one or two broad peaks characteristic of an amorphous or nanocrystalline phase (FIG. 4).
• Example 2 High-entropy metal alloy films obtained by magnetron sputtering
• Metal alloy films of the Al-Co-Cr-Cu-Fe-Ni family were made by plasma spraying of mosaic targets.
• the target composition was AlCoCrCuFeNi.
• targets are used: one consisting entirely of Al (target 1), another mosaic containing the elements Cu and Cr in the following surface proportions: Cu: 39%, Cr: 61% (target 2) and a third consisting of magnetic elements: Co, Fe and Ni in the following surface proportions: Co: 29.5%, Fe: 39% and Ni: 31.5% (target 3).
• the geometry of the targets is that used in Example 1: Pieces of Co and Ni plates are placed under a hole-pierced Fe disk for the target 3. Cu and Cr half-disks are stacked to allow an adjustment of easier stoichiometry (target X).
• the targets are discs 10 cm in diameter and a few mm thick.
• the targets are cleaned with acetone and then with alcohol after machining on the magnetrons placed at 30 ° relative to the normal of the substrate.
• the powers imposed on each magnetron vary from (12 to 558) W which corresponds to tensions on the targets of (298 to 465) V and currents of (0.04 to 1.2) A.
• the deposition protocol remains unchanged compared to Example 1, only change the rotational speed of the substrate (1 turn in 5 s) and the deposition time (25 min).
• composition was made by X-ray analysis (Energy Dispersive Spectroscopy) during observations by scanning electron microscopy (SEM).
• Table 7 EDS Analysis Performed on the Deposits Nos. 1 to 8
• Figure 5 shows the atomic% of the six elements according to the deposit number.
• the atomic zone between 5 and 35% corresponds to the definition domain of high entropy alloys.
• the deposit thickness of 25 min was measured by SEM on sectional views. It depends directly on the total sum of the powers applied to the targets as shown in FIG. 6 graph.
• the deposition rates obtained are relatively high from 36 nm / min to 90 nm / min, which makes it possible to produce thick films in a time. reasonable.
• the crystalline structure of the deposits has been studied by X-ray diffraction.
• the diffractograms obtained have one or two broad peaks characteristic of an amorphous or nanocrystalline phase (FIG. 7).
• a CFC structure faces centered cubic
• a BCC structure centered cubic
• Layer 1 has both structures
• Layer 4 has a BCC structure
• Layer 5 has a CFC structure
• Example 3 high entropy metal alloy film having a concentration gradient obtained by magnetron sputtering.
• Metal alloy films of the Al-Co-Cr-Cu-Fe-Ni family were made by plasma spraying of mosaic targets.
• the intended composition was
• the concentration of the element Al was varied in the thickness of the layer while keeping constant the atomic concentrations of the other elements.
• the configuration of the targets of Example 2 was repeated identically and the power is varied on the aluminum target. Since the aluminum target (target 1) is mono-elemental, a variation in the power applied makes it possible to vary the stoichiometry in the film.
• the targets are cleaned with acetone and alcohol after machining and then fixed on the magnetrons placed at 30 ° to the normal of the substrate.
• the deposition protocol remains unchanged with respect to example 1 only change the rotational speed of the substrate (1 turn in 5 s) and the deposition time set at 25 min.
• the powers imposed on the magnetrons 2 and 3 are set at 558 W and 210 W respectively. This corresponds to voltages on the 465 and 467 V targets and currents of 1.2 and 0.35 A.
• the power on the aluminum target varies from 0 to 580 W from the interface to the surface, which which corresponds to a voltage between 0 and 736 V and a current between 0 and 0.79 A.
• composition was made by X-ray analysis (Energy Dispersive Spectroscopy) during observations by scanning electron microscopy (SEM). The results are given in FIG. 9, where the atomic percentage ratio of aluminum to copper and the atomic percentage ratio of iron to copper are reported.

Landscapes

• Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• Metallurgy (AREA)
• Organic Chemistry (AREA)
• Mechanical Engineering (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Crystallography & Structural Chemistry (AREA)
• Inorganic Chemistry (AREA)
• Physical Vapour Deposition (AREA)

Applications Claiming Priority (2)

Publications (1)

Family

ID=37907982

Family Applications (1)

Country Status (5)

Cited By (1)

Families Citing this family (64)

Family Cites Families (11)

• 2006
  • 2006-09-08 FR FR0607876A patent/FR2905707B1/fr not_active Expired - Fee Related
• 2007
  • 2007-09-10 US US12/440,259 patent/US20090301610A1/en not_active Abandoned
  • 2007-09-10 WO PCT/EP2007/059487 patent/WO2008028981A2/fr active Application Filing
  • 2007-09-10 CA CA2662734A patent/CA2662734C/fr active Active
  • 2007-09-10 EP EP07820102A patent/EP2082074A2/de not_active Withdrawn

Non-Patent Citations (1)

Also Published As

Similar Documents

Legal Events