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
  • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
  • C23C16/06—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of metallic material
  • C23C16/18—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of metallic material from metallo-organic compounds
• • 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
  • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
  • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
  • C23C16/448—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for generating reactive gas streams, e.g. by evaporation or sublimation of precursor materials
  • C23C16/4486—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for generating reactive gas streams, e.g. by evaporation or sublimation of precursor materials by producing an aerosol and subsequent evaporation of the droplets or particles

Definitions

• the present invention relates to the field of surface treatments by application of hard metal coatings for decorative purpose and / or protective against wear, corrosion or oxidation.
• It relates to a method of dry deposition of metal coatings, in particular based on chromium, for obtaining under atmospheric pressure monolayer coatings or nanostructured layer stacks. It also relates to a solution comprising a precursor of the metal to be deposited.
• Chrome coatings are widely used for decorative applications or for the protection of parts against wear and corrosion.
• Hard chromium appears irreplaceable as a metallurgical coating in the field of surface treatments, given its physicochemical characteristics: good resistance to wear due to a low coefficient of friction, high chemical resistance, hardness, aesthetic appearance interesting.
• the coatings for the two mentioned applications differ only in their thickness (low for decorative aspects, strong for protection). Chromium is therefore a treatment of choice in many industrial sectors (automotive, furniture, medical instruments, optics).
• Metallic coatings based on chromium or other metals are essentially obtained by the electro-plating method in bath which allows the treatment of the parade of small parts as flat products of larger dimensions.
• Chromium plating is a simple and easy to implement process, having low running costs and allowing the treatment of parts at very low temperature (less than 100 0 C).
• the chromium coatings thus obtained are often amorphous, having low hardnesses.
• An annealing at 500 ° C. is then necessary to arrive at hardnesses of the order of 1000 HV, this value tending to fall at a higher temperature (300 HV at 700 ° C.).
• the films are stressed in tension, which can lead to poor adhesion with the need for an intermediate layer (Ni).
• the films obtained are micro-cracked, which makes them vulnerable to corrosion, particularly if the coating protects a localized corrosion-sensitive part, made of stainless steel, for example.
• this wet surface treatment requires the use of chromium solutions baths most often hexavalent, or sometimes trivalent although the quality of the films obtained is generally less good. Since hexavalent chromium is known for its carcinogenic effects, industrialists using these bath chromium plating processes are in the binding goal of "zero discharge”. Moreover, European environmental standards will prohibit its use by 2007.
• chromium coatings with properties similar to those of electrolytic hard chromium, among which are the chemical deposition techniques.
• CVD chemical vapor deposition
• a metal powder is confined in the presence of a halide (NH 4 F or HF) and heated to high temperature (950-1050 ° C.).
• a halide NH 4 F or HF
• high temperature 950-1050 ° C.
• This process can operate at atmospheric pressure but the deposits are obtained only at high temperature because of the metal source of the halide type used.
• the so-called conventional CVD processes which directly use the vapors of the corresponding halide as their chromium source, operate under dynamic vacuum and at high temperature.
• organometallic molecular precursors were used in the laboratory (MOCVD process, for Metal Organic CVD). Given the low volatility and thermal instability of these organometallic precursors often in the form of powder, it is necessary to operate under reduced pressure. In addition, the prolonged heating of the precursor in the sublimation zone, even at a low temperature, can degrade the reagent before it arrives in the form of steam on the deposition zone, thus causing problems of reproducibility in terms of flow, gas composition initial reactive and therefore deposit quality.
• the precursors employed are preferably selected from sandwich compounds in which the zero oxidation state metal atom is bonded to two aromatic rings optionally substituted with alkyl groups.
• Obtaining a metal deposit then runs up against the fact that, during the decomposition of the precursor which proceeds from the dissociation of the metal-ligand bonds, the hydrocarbon ligands also undergo decomposition and bring their carbons, which causes the formation of ceramics of the type of chromium carbide and not of metallic chromium.
• a chlorinated or sulfurized additive is introduced into the reactor: the additive in powder form is introduced in the vapor state by a clean peripheral line, by entrainment in a gaseous flow, like the precursor.
• PVD Physical vapor deposition
• the present invention aims to meet this need. It relates to a process combining the technique of chemical vapor deposition and direct liquid injection, called DLI-CVD, wherein a solution comprising an organometallic precursor of the metal compound to be deposited and a chlorinated additive is introduced into a reactor. .
• the principle of the DLI-CVD technique is to introduce into a chemical vapor deposition chamber a solution of a precursor of the element to be deposited by periodic injection of droplets of said solution which are entrained by a carrier gas towards the deposit enclosure.
• a DLI-CVD device has been developed for the deposition of thin layers of oxides on microelectronic plates, but has never been used for deposition of non-noble metals at atmospheric pressure. This is because working at atmospheric pressure, which has a great advantage for low cost industrial production of large parts, imposes special conditions that have not been defined so far. Furthermore, the operating conditions are not easily transferable to the deposition of metal layers.
• the present invention overcomes these disadvantages by a process which can be carried out at temperatures below 550 ° C. and at atmospheric pressure, for depositing layers of hard chromium metal or of various other related metals, on steel supports or alloy, from a single solution.
• the method according to the invention thus makes it possible to envisage the deposition in industrial conditions of decorative and / or protective metal layers on large metal parts.
• the subject of the present invention is a process for depositing a hard coating of metallic chromium or of another metal whose chemical properties are close to those of chromium, by chemical vapor deposition on a metal substrate, which method essentially comprises the steps of: a) providing a solution containing, in a solvent free of oxygen atoms, i) a molecular compound of the family of bis (arenes) precursor of the metal to be deposited, the temperature of which of decomposition is between 300 0 C and 550 0 C and ii) a chlorinated additive, b) introducing said solution in aerosol form in an evaporator heated to a temperature between the boiling point of the solvent and the decomposition temperature precursor, c) aerosol vaporized by a flow of neutral gas from the evaporator to a CVD reactor comprising a susceptor supporting the substrate to reco irrigate, heated to a temperature above the decomposition temperature of the precursor and at most 550 0 C, the evaporator and
• the aerosol is formed according to the direct liquid injection technique by pulsed introduction of the solution of molecular precursor and chlorinated additive, fractionated into micro droplets.
• the aerosol is vaporized in an evaporator heated to at least the boiling point of the chosen solvent and well below the decomposition temperature of the precursor, the chlorinated additive and the solvent used.
• a gas stream arriving at the nose of the injector causes the precursor and solvent vapors of the evaporator to the deposition zone consisting of a susceptor heated by induction and supporting the substrate to be coated.
• the evaporator is heated to a temperature at least 50 ° C., and preferably at least 100 ° C., below the decomposition temperature of the precursor compound and at least 50 ° C. chlorinated additive.
• the aerosol is vaporized flash and avoids premature deposition on the walls of the evaporator.
• the injection parameters of the precursor solution are preferably set using a computer program. They are adjusted so as to obtain a mist of fine and numerous droplets, an essential condition for flash evaporation at atmospheric pressure, thanks to a short opening time of the injector and a high injection frequency.
• the micro-droplet fractionation of the solution can be carried out for example by means of a modified diesel automobile injector, set with a short opening time and a high injection frequency.
• the aerosol is obtained by pulsed injection with an opening time of less than 1 ms and a frequency greater than 4 Hz. The liquid injection thus constitutes a high-speed source of precursor solution, allowing a good coating deposition efficiency.
• the good conduct of the process according to the invention requires high gas flow rates.
• the flow rate of the neutral gas is advantageously between 4 cm / s and 10 cm / s.
• the gas flow rate is adjusted to more than 5000 cmVmn.
• the flow benefits in addition to the gravitational force.
• the neutral gas employed as the carrier gas should preferably be preheated, at least at the temperature of the evaporator, to obtain an effective vaporization which is difficult to achieve at atmospheric pressure, which explains that DLI-CVD techniques hitherto operated all under reduced pressure.
• the neutral gas is heated to a temperature at least equal to that of the evaporator before entering.
• the gas used is neutral in that it is not likely to oxidize the reactants in the presence.
• Nitrogen will preferably be chosen as carrier gas for its low cost, but helium or argon, benefiting from a better thermal conductivity, can also be used although more expensive.
• the stream of neutral gas arriving on the nose of the injector then drives the precursor and solvent vapors from the evaporator to the deposition zone.
• the metal element to be deposited is typically chromium, but it can also be any other metal whose chemistry and metallurgy are related to those of chromium.
• the metallic element can be chosen from Cr, Nb, V, W, Mo. The present description, mentioning most often chromium for the sake of simplicity, applies by generalization. other metals mentioned above.
• the precursor of the metallic element to be deposited is a compound containing no oxygen atom, chosen from the family of metal bis (arenes) of general formula (Ar) (Ar ') M where M is the zero oxidation state metal element, and Ar, Ar' each represents a benzene or benzene hydrocarbon aromatic ring substituted by alkyl groups.
• the precursor may be chosen from the family of bis (arene) chromium, preferably from bis (benzene) chromium or BBC, of formula Cr (C 6 H 6 ) 2 , bis (cumene) chromium of formula Cr (C 6 H 5 iPr) 2 , bis (methylbenzene) chromium of formula Cr (C 6 H 5 Me) 2 , and bis (ethylbenzene) chromium of formula Cr (C 6 H 5 Et) 2 .
• Only the BBC is in the form of a powder.
• the other precursors mentioned are liquid and could be directly injected without solvent.
• the BBC will preferably be chosen for its commercial availability, the knowledge of its reactivity in conventional vacuum MOCVD and its relatively low decomposition temperature (350 ° C.).
• an additive whose function is to prevent the heterogeneous decomposition of the aromatic ligands of the precursor, which would lead to formation of metal carbide and not metal.
• a chlorinated additive which is selected from the family of halogenated cyclic hydrocarbons of formula C n H m . p Cl p in which m> p.
• Hexachlorobenzene is preferably used as the chlorinated additive.
• the solvent of the precursor compound plays an important role in the successful completion of the process according to the invention. His choice must meet a set of chemical and physical criteria. Firstly, the boiling point of the solvent must be lower than the temperature of the evaporator to allow flash evaporation in the evaporator, typically heated to at least 150 ° C. The solvent chosen must also have a low viscosity. to facilitate the entrainment of the injectable solution by liquid way to the evaporator. It must not contain oxygen to avoid the risk of oxidation of the deposits by cracking the solvent used in the deposition zone. It must of course be chemically inert with respect to the precursor and the additive in solution and liquid under normal conditions.
• the vapor pressure will be sufficiently low at atmospheric pressure to allow storage of the injectable solution without evaporation of the solvent under normal conditions, in order to avoid the risk of reprecipitation of the precursor if the initial concentration reached saturation, resulting in the clogging of the injectors.
• the light hydrocarbon solvents are therefore discarded.
• the solvent is preferably chosen from hydrocarbons of general formula C x H y having a boiling point below 150 ° C.
• the solvent is advantageously a cyclic compound corresponding to the characteristics defined above, preferably chosen from toluene and cyclohexane.
• the precursor compound and the solvent are chosen so that the saturation concentration of the precursor compound in the solvent is greater than or equal to 0.01 mol / l in order to obtain a flow rate. acceptable precursor and much higher than conventional sublimation saturator method.
• the precursor compound and the chlorinated additive are in a molar ratio of at most 10%.
• the chromium deposits obtained are solid solutions supersaturated with carbon. Very interesting properties of hardness and friction behavior are associated with this particular structure.
• the carbon supersaturation on the order of 12 atomic% (compared to a few percent in conventional MOCVD) is the signature of the DLI-MOCVD process.
• Another object of the present invention is a process for obtaining multilayer coatings consisting of a stack of layers as described above successively deposited, the individual thickness of which may be from a few nanometers to a hundred nanometers.
• the nanostructuring of these multilayer metallurgical coatings gives them remarkable properties (protection, resistance to wear, hardness, etc.), which can be adjusted by controlling the period and modifying the nature of the constituent layers.
• the deposition steps a) to c) are repeated several times to obtain a nanostructured multilayer coating.
• the multilayer stack may consist of layers as previously described, with a different metal element for each, thanks to the alternating injection of two precursor solutions based on different metallic elements.
• the duration of deposition can also be modulated.
• each layer it is possible for each layer to repeat the steps of filing a) to c) by varying at least one of the following parameters:
• the deposition of metal layers as just described, alternately with the deposition of layers of other materials such as non-oxide ceramics, so as to form ceramic / metal architectures coatings.
• These ceramics are carbides, nitrides and carbonitrides of metal, which can be deposited with the same equipment by DLI-MOCVD, according to a process developed in the applicants' laboratories and described in detail in a patent application in their name, including the teachings are incorporated herein.
• the stack consists of layers of individual thickness ranging from a few nano meters to a hundred nano meters. The nanostructuration of these multilayer metallurgical coatings gives them remarkable adjustable properties by controlling the period and by varying the nature of the constituent layers (protection, wear resistance, hardness).
• a process for obtaining a hard coating of metallic chromium or of another metal of similar chemical properties, by chemical vapor deposition on a metal substrate, in which the deposition steps a) to c) are repeated several times alternately with the deposition of a non-oxide ceramic material, to obtain a nanostructured composite multilayer coating.
• Another object of the present invention is an injectable solution that is particularly suitable for carrying out the method as just described. More specifically, an injectable solution is claimed in a chemical vapor deposition device for obtaining a hard coating of chromium or of another metal whose chemical properties are close to those of chromium, which solution contains, in a solvent chosen from liquid hydrocarbons of general formula C x H y having a boiling point of less than 150 ° C. i) a molecular precursor compound of the metal to be deposited, the decomposition temperature of which is between 300 ° C.
• a chlorinated additive chosen from the family of halogenated cyclic hydrocarbons of formula C n H m . p Cl p in which m> p.
• the precursor is chosen according to the nature of the layer that is to be deposited.
• the metal is chosen from Cr, Nb, V, W, Mo.
• a chromium precursor associated with aromatic ligands is chosen.
• the injectable solution according to the invention comprises a precursor chosen from the family of bis (arene) chromium, preferably from the following compounds: bis (benzene) chromium, bis (cumene) chromium, bis (methylbenzene) chromium and bis (ethylbenzene) chromium.
• the chlorinated additive is hexachlorobenzene.
• the solvent is a cyclic hydrocarbon preferably chosen from toluene or cyclohexane.
• the precursor compound and the solvent are chosen so that the saturation concentration of the precursor compound in the solvent is greater than or equal to 0.01M.
• the precursor compound and the chlorinated additive are in a molar ratio of at most 10%.
• the method according to the invention as just described makes it possible to deposit, by a DLI-assisted MOCVD technique at low temperature and under atmospheric pressure, chromium-based protective and / or decorative metal coatings. of another transition metal, in the form of monolayer or multilayer.
• the method according to the invention is capable of being implemented, with the appropriate adaptations, for the treatment of large plates in the parade. It is thus the final step in the manufacture of metal parts including large parts, intended for use in the mechanical industry, which must be protected and / or decorated with a hard and colored layer. , resistant to wear, corrosion and oxidation. There may be mentioned the manufacture of parts requiring a surface treatment to improve their tribological characteristics such as gears or engine parts, or cutting tools.
• a method of manufacturing a metal part comprising a chemical vapor deposition operation of at least one layer of a hard chromium metal coating or a metal having chemical properties similar to those of chromium, said chemical vapor deposition being carried out by a deposition process as described above and advantageously with the aid of an injectable solution as described above.
• the DLI-MOCVD device used for the deposition of the metal layers which will be described in detail below, consists mainly of a vertical CVD reactor with cold walls coupled to a commercial pulsed injection system. It makes it possible to obtain monolayer metal coatings as well as nanostructured multilayer stacks of these same coatings.
• FIG. 1 In the configuration in which it is represented in FIG. 1, it comprises, centrally, an evaporator 3 opening into a deposition chamber 10 consisting of a vertical CVD reactor with cold walls.
• a pressurized storage tank 1 of the precursor solution at ambient temperature feeds an injector 2 whose opening towards the evaporator 3 is controlled by computer.
• a modified diesel automobile injector is conveniently used.
• a carrier gas supply line 4 arrives on the nose of the injector 2.
• a spool valve 5 makes it possible to isolate the evaporator 3 from the deposition chamber 10.
• the tapping 6 above the slide valve 5, allows the arrival of a reactive gas to obtain a ceramic / metal architecture coating.
• Stitching 7 above the slide valve 5 allows the evaporation of the evaporator 3 during purge or cleaning cycles of the latter.
• the flange 14 on which the connections 6 and 7 are made, as well as the inlet slide valve 5 of the reactor 10, are heated to a temperature close to that of the evaporator 3, that is to say at least 150 ° C.
• the gas flow arriving on the nose of the injector 2 drives the precursor and solvent vapors from the evaporator 3 to the deposition chamber 10 which comprises the susceptor 13 on which is placed the support to be covered.
• a baffle 8 makes it possible to stop any non-vaporized droplets at the outlet of the evaporator 3 and a grid 9 pierced with holes uniformly distributes the gas flow, the assembly being connected to the deposition chamber 10.
• This grid 9 allows a good distribution of the gas flow at the inlet of the deposition chamber 10, which contributes to obtaining a good surface finish of the coatings and uniformity of thickness.
• the evaporator 3 is located co-axially above the CVD reactor 10. The whole is provided with a primary pumping unit 11 for purging the system before any implementation. A system for recycling solvent vapors and by-products of the CVD reaction can be added.
• This device makes it possible to obtain hard chromium metal coatings as well as multilayer stacks of these same coatings at atmospheric pressure and at a low deposition temperature.
• the organometallic chromium precursor of bisarene: Cr (C 6 H 6 ) 2 or BBC type dissolved in degassed toluene and dehydrated on silica gel is used.
• the decomposition temperature of the BBC is 35 ° C.
• the saturation concentration of the BBC in toluene determined by UV-Vis spectrophotometry is 5.1 ⁇ 10 2 M, a solution is prepared at a lower concentration (here equal to 3.10 2 mol / 1), to avoid reprecipitation of the precursor which might clog the DLL system injector
• the chlorinated additive is C 6 Cl 6 .
• Purification by recrystallization may be considered to avoid oxygen contamination.
• Four solutions are prepared with a different C 6 Cl 6 ZBBC molar ratio (see table on the next page).
• the pressurized solution at 2.5 bars (relative) is injected at a rate of 1.4 ml / min at a frequency of 10 Hz and an opening time of 0.5 ms in the evaporator heated to 200 ° C., previously purged with nitrogen and at atmospheric pressure.
• [C6 C16] in mol / l C 6 C1 6 / BBC
• the substrates are 1 cm diameter SS304L steel pellets and Si (100) wafers. They are placed on a passive graphite susceptor made of SiC or stainless steel. After a purge phase, they are heated by induction at 500 ° C. under a flow of carrier gas (in this case nitrogen) of 4.2 cm / s (ie 5000 cm 2 / min for a reactor of 50 mm diameter), itself even preheated to the temperature of the evaporator, ie 200 ° C.
• carrier gas in this case nitrogen
• the deposition temperature is controlled by a thermocouple housed inside the susceptor.
• the CVD reactor is at atmospheric pressure.
• Deposition is carried out as indicated above until a thickness layer of about ten nanometers to a few microns is obtained according to the duration of the deposition.
• the growth rate is between 0.3 .mu.m / h and 0.5 .mu.m / h.
• the growth rate can be multiplied by increasing the frequency of the injector and therefore the precursor flow, without modifying the other parameters (opening time of the injector and gas flow).
• a metallic gray deposit of mirror appearance is obtained on the two substrates, with the four solutions.
• Electron probe microanalysis (EPMA) analyzes show a content of about fifteen atomic percent carbon, well above the solubility in the metal, the typical composition being Cr 0185 Co 1 I 5 .
• the layers consist of a solid solution of chromium that is unusually supersaturated with carbon (this solubility colossal C in Cr is not predicted by thermodynamics).
• this solubility colossal C in Cr is not predicted by thermodynamics.
• the surface of the coating is contaminated with chlorine and the deposit tends to a more amorphous and less well-defined crystallographic structure by X-ray diffraction.
• the chrome coatings obtained on mirror-polished 304L stainless steel are homogeneous and particularly dense. They have remarkable hardness.
• the hardness obtained by nanoindentation is 17 ⁇ 2.5 GPa (about 2 times more than the hard chromium produced by annealed electrodeposition which has the same cubic beak structure) on a 500 nm coating.
• the composition of the injectable solution is as follows.
• the chromium deposit is metallic gray mirror. This is due to a nodular surface morphology, responsible for a high surface roughness.
• the layer consists first of a dense surface structure, then nodular from a few hundred nanometers.
• Figure 3 shows the diagram obtained for a deposit on Si, compared to the stable carbide diagrams listed in the JCPDS database already mentioned. They show a crystallized structure of cubic mesh centered beak corresponding to the chromium whose peaks are marked by the black dots.
• Castaing microprobe (EPMA) analyzes reveal a Cr 01 S 5 Co 1 I 5 chemical composition. These coatings are adherent on mirror polished 304L stainless steel and on Si.

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