CN114147169B - Method for improving interface stability of metal core coating - Google Patents
Method for improving interface stability of metal core coating Download PDFInfo
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- CN114147169B CN114147169B CN202010932055.1A CN202010932055A CN114147169B CN 114147169 B CN114147169 B CN 114147169B CN 202010932055 A CN202010932055 A CN 202010932055A CN 114147169 B CN114147169 B CN 114147169B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22C—FOUNDRY MOULDING
- B22C3/00—Selection of compositions for coating the surfaces of moulds, cores, or patterns
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22C—FOUNDRY MOULDING
- B22C9/00—Moulds or cores; Moulding processes
- B22C9/02—Sand moulds or like moulds for shaped castings
- B22C9/04—Use of lost patterns
- B22C9/043—Removing the consumable pattern
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22C—FOUNDRY MOULDING
- B22C9/00—Moulds or cores; Moulding processes
- B22C9/22—Moulds for peculiarly-shaped castings
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- 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
- C23C14/16—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
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- 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
- C23C14/24—Vacuum evaporation
- C23C14/32—Vacuum evaporation by explosion; by evaporation and subsequent ionisation of the vapours, e.g. ion-plating
- C23C14/325—Electric arc evaporation
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- 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
- C23C14/3435—Applying energy to the substrate during sputtering
- C23C14/3442—Applying energy to the substrate during sputtering using an ion beam
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- 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
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- 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
- C23C16/22—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 inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/40—Oxides
- C23C16/401—Oxides containing silicon
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- 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
- C23C16/22—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 inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/40—Oxides
- C23C16/403—Oxides of aluminium, magnesium or beryllium
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- 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
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- 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
- C23C16/52—Controlling or regulating the coating process
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- 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
- C23C16/56—After-treatment
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- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
- C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
- C23C28/322—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer only coatings of metal elements only
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- 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
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- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
- C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
- C23C28/345—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one oxide layer
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C19/00—Alloys based on nickel or cobalt
- C22C19/03—Alloys based on nickel or cobalt based on nickel
- C22C19/05—Alloys based on nickel or cobalt based on nickel with chromium
- C22C19/051—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W
- C22C19/056—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W with the maximum Cr content being at least 10% but less than 20%
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Abstract
The invention discloses a method for improving interface stability of a metal core coating, belongs to the technical field of metal protective coatings, mainly aims at solving the interface problem of silicon oxide and high-temperature alloy, and specifically comprises the following steps: optimizing a coating and a pre-oxidation technology, reducing the generation of silicon oxide and maximizing the content of aluminum oxide in an inert oxidation film; and the second step is to utilize a high-melting-point metal coating, wherein the high-melting-point metal coating is deposited on the surface of the core inert oxide film, and silicon oxide and deposited metal elements are subjected to chemical reaction and diffusion in a vacuum and high-temperature environment to form a more stable interface type, so that the stability of the interface is greatly improved, and the coating structure is an intermetallic compound layer/an inert oxide layer/a metal coating. The invention can be used in the field of precision casting and is used for producing hollow blades.
Description
Technical Field
The invention relates to the technical field of metal protective coatings, in particular to a method for improving interface stability of a metal core coating.
Background
The turbine blade is one of hot end key parts of an aircraft engine and a gas turbine, and the higher the temperature bearing capacity of the blade is, the higher the working efficiency is. In order to improve the working efficiency, the blade is improved in terms of materials and structures, the higher the melting point of the blade material is, the higher the working efficiency is, however, the working temperature of the blade exceeds the melting point of the high-temperature alloy, and the temperature bearing capacity of the material is very close to the limit; on the other hand, then design the structure of blade, the hollow structure of blade can not form through machining, can only place the precision casting core in advance before pouring the blade, then gets rid of the core through chemical corrosion means, and then reaches hollow structure, lets in cooling air and takes away the heat, has realized air cooling, and air cooling can the effectual service temperature who improves the blade, therefore cooling efficiency is especially important to turbine blade.
With the development of cooling technology and casting technology, the service performance requirement of the casting core is higher and higher, the ceramic core is required to have high cooling efficiency at present, the cooling channel is designed to be finer and more complex, and the corresponding size is finer and finer. However, the fine part of the ceramic core has reduced performance, especially strength and thermal shock resistance, so that the ceramic material is limited by its own property and size. In order to solve the problem of the part of the ceramic material, a molybdenum-based metal core is adopted to replace the part of a fine ceramic core, so that a ceramic-metal composite core with a more advanced cooling structure is prepared, however, the key point of the application of the molybdenum-based metal core is the reasonable design of a protective coating of the molybdenum alloy.
The preparation and service process of the molybdenum-based metal core comprises the steps of pre-depositing an intermetallic compound layer on a molybdenum-based metal core, pre-oxidizing to form an inert oxide coating, performing a series of precision casting processes including core assembly, wax mold preparation, shell molding, dewaxing and the like, putting a ceramic module into a directional furnace, vacuumizing, heating to 1000-1300 ℃, preserving heat, heating to 1500-1650 ℃, preserving heat for a period of time, pouring high-temperature alloy, keeping a certain speed for extraction, taking out after cooling, removing the shell and removing the core.
As shown in fig. 1 (a), after pouring DSM11 superalloy at 1550 ℃, the coating resists the alloy erosion and protects the molybdenum-based metal core substrate, but the DSM11 alloy surface can undergo severe interfacial reactions (as shown in fig. 1 (b)), which may be due to silicon oxide chemical reactions with the reactive elements Al, cr, ti, etc. in the superalloy above 1550 ℃ causing silicon oxide to adhere to the cast surface and cause surface defects (as shown in fig. 2). To avoid the effects of silica, it is necessary to improve the stability of the metal core coating interface and the surface quality of the cast part.
Disclosure of Invention
In order to solve the problem of unstable interface between silicon oxide and high-temperature alloy in an inert oxide layer of a metal molybdenum core, the invention provides a method for improving the interface stability of a metal core coating.
In order to realize the purpose, the technical scheme adopted by the invention is as follows:
a method for improving interface stability of metal core coating, said method comprises in molybdenum-base metal core surface preparation coating course, through optimizing the coating composition and pre-oxidation technology to improve the stability of interface between coating and the core; the method specifically comprises the following steps:
(1) Pure molybdenum or molybdenum alloy is taken as a metal core matrix, and the codeposition of silicon and aluminum elements is carried out on the core matrix by adopting a chemical vapor deposition or in-situ chemical vapor deposition process (carried out in a heating furnace or a chemical vapor deposition furnace), wherein the deposition temperature is 900-1300 ℃, and the deposition time is 2-30 h; after deposition, the temperature is reduced to 800 ℃ at the cooling rate of 1-15 ℃/min, then the heating system is closed, and the temperature is cooled to room temperature along with the furnace, thus forming the composite coating containing aluminum silicon on the matrix.
(2) Pre-oxidation treatment: pre-oxidizing the core substrate with the coating deposited in the step (1), wherein the treatment process comprises the following steps: firstly introducing air or oxygen, controlling the flow at 1-100 sscm, then heating to 1000-1100 ℃, and preserving the heat for 1-5 h; then heating to 1200-1400 ℃ at the heating rate of 1-15 ℃/min, and preserving the heat for 1-8 h; and after the heat preservation is finished, opening a vacuum system for vacuumizing or introducing inert gas to reduce the concentration of oxygen in the furnace, closing a heating system, and cooling along with the furnace.
(3) Depositing a high-melting-point metal coating on the surface of the sample subjected to the pre-oxidation treatment in the step (2), wherein the deposition mode is arc ion plating, electroplating, magnetron sputtering, vacuum evaporation, chemical vapor deposition and the like; the melting point of the high-melting-point metal coating is higher than 1600 ℃.
In the step (1), the metal core substrate is pretreated before use, and the process is as follows: firstly, grinding with 240# -800# sandpaper, then sequentially cleaning in deionized water and absolute alcohol, and drying for later use.
In the step (1), when co-deposition of silicon and aluminum elements is performed, due to the difference of aluminum and silicon elements, the coating first forms a low-melting-point aluminide coating, and then is converted (wholly or partially) into a high-melting-point silicide coating.
In the step (1), when codeposition of silicon and aluminum elements is carried out, an aluminum-containing intermetallic compound layer is formed on the substrate, and then an inert oxide layer (aluminum oxide and silicon oxide) is formed on the intermetallic compound layer; the total thickness of the composite coating is more than 30 mu m, and the low-melting-point phase can disappear in the later pre-oxidation process.
In the step (3), the refractory metal coating is a chromium, hafnium, iridium or platinum coating.
In the step (1), when the codeposition of silicon and aluminum elements is carried out on the core substrate, one or more of chromium, zirconium, titanium and magnesium elements can be simultaneously deposited.
In the step (2), after pre-oxidation, the mixture is cooled to below 500 ℃ along with the furnace in the cooling process and taken out.
In the step (3), the thickness of the deposited metal coating is 0.1-20 μm.
The design mechanism of the invention is as follows:
firstly, co-depositing aluminum and silicon elements on a molybdenum-based metal core substrate to prepare a composite coating, wherein the composite coating is in a structure of a substrate/intermetallic compound layer/inert oxide layer/metal coating; during codeposition, different differences are presented in the deposition process due to the self characteristics of Al and Si elements, the melting point of Al is 660 ℃, the melting point of Si is 1414 ℃, the activity of Al is higher than that of Si under the condition of 1000 ℃, al is deposited on the coating firstly, al8Mo3 phase appears, the activity of Si is increased along with the temperature increase, and the diffusion coefficient of Si in the matrix is increased (Dsi is more than D) Al ) With increased Si content instead of Al 8 Mo 3 Presence of Mo (Si, al) 2 To Al 8 Mo 3 Partly or wholly converted to Mo (Si, al) 2 Even the innermost layer is MoSi 2 . The coating thus first forms low melting Al below 1600 deg.C 8 Mo 3 Phase, then modified silicide phase (Mo (Si, al) above 1600 ℃ occurs 2 And MoSi 2 ). And then adopting a pre-oxidation technology, wherein the growth process of the oxide film in the pre-oxidation technology is multi-stage step temperature rise oxidation, and the oxide film is cooled to below 500 ℃ along with the furnace in the temperature reduction process and then taken out. The temperature of the pre-oxidation technology must be higher than 1000 ℃ to ensure that low melting point Al possibly remains in the coating 8 Mo 3 The phases decompose at high temperatures and are guaranteed to disappear during the pre-oxidation, with a total coating thickness above 30 μm. In the pre-oxidation technology, after the content of aluminum oxide in an oxidation film reaches the maximum, vacuumizing or introducing argon to reduce the oxygen concentration and protect a sample;
and finally, depositing a high-melting-point metal coating on the surface of the metal core, and forming a more stable interface type by utilizing element chemical reaction and diffusion in a vacuum and high-temperature environment, so that the influence of silicon oxide is reduced, and the stability of the interface is improved. The melting point of the high-melting-point coating metal is over 1600 ℃, so that the high-melting-point coating metal is not melted before the high-temperature alloy is poured, and after the high-temperature alloy is poured, the metal enters the alloy melt and does not influence or improve the performance of the alloy.
The beneficial results of the present invention are as follows:
1. active elements are added into the coating to adjust the structure of the coating, so that the effect of the coating on resisting the corrosion of the high-temperature alloy is ensured, the toughness of the coating is obviously enhanced, and the bonding force with a substrate interface is increased.
2. The content of alumina in the coating is maximized by optimally controlling pre-oxidation parameters (time, temperature, oxygen concentration).
3. The metal coating is deposited in advance, the matrix protective coating of the core is coated, the deposited metal elements react with silicon oxide under high-temperature vacuum, the interface of an external oxide layer is more stable, and meanwhile, the deposited metal elements are melted into the high-temperature alloy to avoid influencing the performance of the high-temperature alloy.
4. By stabilizing the interface, the interfacial clearance of the core and superalloy is reduced to a maximum of 23um, which facilitates precise control of the cavity dimensions of the blade.
Drawings
FIG. 1 shows low melting point Al 8 MO 3 A picture of the failure section of the sample when the phase exists; wherein: (a) A core substrate after pouring DSM11 superalloy at 1550 ℃, (b) a DSM11 superalloy surface after pouring at 1550 ℃.
FIG. 2 is a core prior to modification by the present invention; wherein: (a) an interface of the core with the alloy, (b) a surface of the DSM11 alloy, (c) a surface of the core.
FIG. 3 is a core resulting from a modification of the process of the present invention; wherein: (a) an interface of the core with the alloy, (b) a surface of the DSM11 alloy, (c) a surface of the core.
Detailed Description
For a further understanding of the present invention, the following description is given in conjunction with the examples which are set forth to illustrate, but are not to be construed to limit the present invention, features and advantages.
The invention improves the stability of the coating interface of the metal core by optimizing the coating and pre-oxidation technology and utilizing the high-melting-point metal coating, and adopts the following specific scheme:
the optimized coating adopts aluminum and silicon elements for codeposition, and beneficial elements such as chromium, zirconium, titanium, magnesium and the like can be further added into the coating. Due to the difference of the properties of the elements, al is firstly formed in the aluminum-silicon codeposition process 8 Mo 3 Coating, then forming silicide coating, coating low-melting point Al 8 Mo 3 The phases are completely eliminated after the pre-oxidation technology, the high-melting-point coating structure is maintained, and the condition that the cast sample does not lose efficacy is ensured. The method comprises the following steps: firstly, grinding with 240# -800# abrasive paper in advance, sequentially cleaning in deionized water and absolute alcohol, drying for later use, secondly, adopting chemical vapor deposition-codeposition elements at the temperature of 900-1300 ℃ for 2-30 h, thirdly, cooling to 800 ℃ at the speed of 1-15 ℃/min according to a program, closing a heating system, and cooling to room temperature along with a furnace.
The pre-oxidation technology is carried out according to the sequence of placing a sample in advance, opening a pre-heating program and cooling under the vacuum low-oxygen condition, and comprises the following steps: step one, putting a deposited coating sample which is cooled to room temperature into an alumina crucible, wherein a certain gap is formed between the samples, and 5-120 meshes of alumina can be filled into the samples in order to keep uniform heating and no deformation of the samples; step two, opening a heating device, heating to 1000-1100 ℃, preheating and preserving heat for 1-5 h, wherein the heat preservation time can be determined according to the size of the sample; step three, heating the preheated coating sample to 1200-1400 ℃ at the speed of 1-15 ℃/min, and keeping the temperature for 1-8 h; opening a vacuum system or introducing inert gas to reduce the concentration of oxygen in the furnace; and simultaneously, closing the heating system and cooling along with the furnace.
The high melting point metal coating is deposited, and the metal coating can be deposited by different methods, such as vacuum evaporation, arc ion plating, electroplating and the like, and can be set according to the deposition method of the deposited metal element.
The service environment of the high-melting-point coating is put into a directional furnace: the die set is put into a vacuum directional furnace for a certain time before the high-temperature alloy is poured.
The melting point of the high-melting-point metal coating is higher than 1600 ℃, and the high-temperature alloy is not melted in the vacuum orientation furnace without pouring. Meanwhile, after the high-temperature alloy is poured, the metal does not influence or improve the performance of the alloy after entering the alloy melt.
The high-melting-point metal can perform interface chemical reaction with silicon oxide in a vacuum and high-temperature environment to form more stable oxide, reduce the influence of the silicon oxide on the surface of the coating and further improve the interface.
Comparative example 1
Using a cold-rolled molybdenum plate (with the purity of 99.99%) as a core substrate, cutting the core substrate into 24mm, 2mm, 0.4mm by spark lines, polishing the surface by 240# to 800# abrasive paper, cleaning by deionized water, drying, ultrasonically cleaning by absolute ethyl alcohol and drying. Silicon-aluminum codeposition is carried out by adopting an in-situ chemical vapor deposition method, wherein the raw materials are as follows: silicon powder (300-500 meshes, analytical purity 99.95%), aluminium powder (300-500 meshes, analytical purity 99.95%), activating agent (NH) 4 Cl, analytical grade 99.5%), inert filler (Al) 2 O 3 100-300 meshes), according to the proportion of silicon powder: aluminum powder: activating agent: the method comprises the following steps of (1) mixing inert filler =15 by a ratio of 80 (wt%), mixing the powder for 10 hours by a powder ball mill after mixing, placing a mold core substrate and the mixed powder into a deposition tank, placing the deposition tank into a central area of a heating furnace, closing a furnace door of the heating furnace, keeping good air tightness, opening a gas outlet valve of the heating furnace, opening argon, introducing argon for 15-20 minutes or longer, heating to 200 ℃ at 5 ℃/min, keeping the temperature for 30 minutes, simultaneously introducing argon again for 30 minutes, closing the gas inlet valve, then opening a vacuum pump, adjusting the vacuum pressure to-0.06 MPa-0.02 MPa, closing the gas outlet valve, heating to 1000 ℃ at 5 min/DEG C, heating to 1100 ℃ at 2 ℃/min, keeping the pressure at +0 MPa-0.04 MPa, keeping the temperature for 5-20 hours, and naturally cooling to room temperature at a speed of 2 ℃/min. The co-deposited coating is detected to find that the low melting point Al exists in the core coating 8 Mo 3 Phase, such as direct casting of DSM11 alloy, can cause failure of the coating, as shown in fig. 1, the low melting phase melts at the high temperature of the casting and the coating is quickly destroyed.
Cleaning the surface of the metal core subjected to in-situ chemical vapor deposition by using deionized water, drying, cleaning the surface of a sample by using absolute ethyl alcohol, drying, putting the sample into an alumina crucible, and then putting the alumina crucible into a muffle furnace; introducing air into the furnace, controlling the air flow at 5sscm, carrying out isothermal oxidation at 1300 ℃ for 1-10 h, taking out and cooling. Assembling the core into wax film, making shell (dipping slurry, sand spraying repeatedly until required thickness, drying), steam dewaxing at 100-260 deg.C, heating to 900 deg.C, and holding temperature for 1h to fire the shell. Putting the shell group into a vacuum directional furnace, vacuumizing to below 1Pa, heating to 1550 ℃, pouring DSM11 high-temperature alloy, extracting at 6mm/min, cooling to room temperature, and taking out and removing the shell.
In this example, the core after co-deposition of Si and Al is subjected to isothermal oxidation, and although the low-melting-point phase is completely converted into the high-melting-point phase (alumina and silica), the silica content generated on the coating surface is high, and the alloy quality is affected after the DSM11 superalloy is poured.
Comparative example 2
In this example, the difference from comparative example 1 is: the coating is prepared by chemical vapor deposition, and the process is as follows: punching a substrate to be placed on a sample rack conveniently, placing the substrate in a reaction chamber, closing a CVD furnace door, pumping the reaction chamber to a vacuum of less than 200pa, heating to 900-1200 ℃, opening a flow controller, and controlling the volume flow ratio H 2 ：AlCl 3 ：SiCl 4 =1:1.2:2, preserving the heat for 2 to 20 hours, then cooling to 800 ℃ at a speed of 10 ℃/min according to the program, closing the heating system, and cooling along with the furnace. Taking out the sample, cleaning the surface of the sample by using deionized water, drying, cleaning the surface of the sample by using absolute ethyl alcohol, drying, putting the sample into an alumina crucible, and then putting the sample into a muffle furnace; introducing air into the furnace, controlling the air flow at 5sscm, carrying out isothermal oxidation at 1300 ℃ for 1-10 h, taking out and cooling. Assembling the core into wax film, making shell (dipping and sanding are repeated until the required thickness is reached, drying is carried out), steam dewaxing is carried out at 100-260 ℃, and the shell is fired by heating to 900 ℃ and keeping the temperature for 1 h. Putting the shell group into a vacuum directional furnace, vacuumizingAnd (3) emptying to below 1Pa, heating to 1550 ℃, pouring DSM11 high-temperature alloy, drawing out at the speed of 6mm/min, cooling to room temperature, taking out and removing shells.
In this example, the core after co-deposition of Si and Al is subjected to isothermal oxidation, and although the low-melting-point phase is completely converted into the high-melting-point phase (alumina and silica), the silica content generated on the coating surface is high, and the alloy quality is affected after the DSM11 superalloy is poured.
Comparative example 3
In this example, the difference from comparative examples 1 to 2 is that: the surface of the core substrate is subjected to different pre-oxidation processes after a coating containing Al and Si is prepared by adopting chemical vapor deposition or in-situ chemical vapor deposition; the pre-oxidation process in this example is: putting the samples into a heating furnace, putting the deposited coating samples cooled to room temperature into an alumina crucible, and filling 36-mesh alumina into the samples to keep uniform heating and prevent the samples from deforming; introducing air into the furnace, controlling the air flow at 5sscm, opening a heating device, heating to 1100 ℃, preheating and preserving heat for 2 hours, wherein the heat preservation time can be determined according to the size of a sample; heating the preheated coating sample to 1300 ℃ at the speed of 5 ℃/min, and keeping the temperature for 2h; opening a vacuum system or introducing inert gas to reduce the concentration of oxygen in the furnace; and simultaneously, closing the heating system and cooling along with the furnace. And after the deposition is finished, closing the substrate, stopping, opening the chamber after the substrate is cooled to room temperature, and taking out the workpiece. Assembling the core into wax film, making shell (dipping and sanding are repeated until the required thickness is reached, drying is carried out), steam dewaxing is carried out at 100-260 ℃, and the shell is fired by heating to 900 ℃ and keeping the temperature for 1 h. Putting the shell group into a vacuum directional furnace, vacuumizing to below 1pa, heating to 1550 ℃, pouring DSM11 high-temperature alloy, extracting at 6mm/min, cooling to room temperature, and taking out and removing the shell.
In this example, the core after the co-deposition of Si and Al was subjected to a step oxidation to form a low-melting-point phase Al 8 Mo 3 The phase decomposition is converted into a high melting point phase, and the content of the generated silicon oxide on the surface of the coating is lower due to the step oxidation, but a small amount of silicon oxide still damages the alloy surface after DSM11 high-temperature alloy pouring due to the existence of the silicon oxideThe surface influences the quality of the alloy.
Example 1
In the present example, the difference from comparative examples 1-3 is that after the pre-oxidation treatment of comparative example 3, the metal coating is deposited by arc ion plating, the sample is installed in the coating chamber, and the vacuum system is opened to vacuumize to 1X 10 -3 And pa, heating the sample in the chamber to 300-600 ℃, introducing argon working gas, applying a negative bias of 1000-300V to the sample, sequentially increasing the negative pressure at intervals of a certain time to carry out ion bombardment, then applying a negative bias of 200V to the sample, carrying out chromium plating for 25min, adjusting the negative bias to 100V and the chromium plating time to 35min, adjusting the negative bias to 70V, carrying out chromium plating for 300min, and repeating the steps until the thickness of the chromium layer is 4 mu m and the chromium plating is finished. After deposition, stopping heating, cooling the substrate to room temperature, opening the chamber, taking out the workpiece, assembling the core into a wax film, making a shell (dipping slurry and sanding are repeated until the required thickness is reached, and drying), performing steam dewaxing at 100-260 ℃, heating to 900 ℃, and keeping the temperature for 1h to fire the shell. Putting the shell group into a vacuum directional furnace, vacuumizing to below 1pa, heating to 1550 ℃, pouring DSM11 high-temperature alloy, extracting at 6mm/min, cooling to room temperature, and taking out and removing the shell.
The modified core is shown in fig. 3: the interface of the core and the alloy, (b) the surface of the DSM11 alloy, and (c) the surface of the core show that after the high-temperature alloy is poured, the coating prepared by the invention can resist the corrosion of the high-temperature alloy, the obdurability of the coating is obviously enhanced, and the bonding force with the interface of a matrix is increased. The influence of silicon oxide on the alloy can be blocked due to the existence of the metal coating.
Example 2
In the present example, the difference from comparative examples 1 to 3 is that: the sample subjected to the pre-oxidation treatment in comparative example 3 was plated with a platinum metal layer using an ion sputtering apparatus. The target material is pure platinum, the pre-oxidized sample is placed in a reaction chamber of an ion sputtering instrument, the vacuum pump is started to adjust the pressure to 10Pa, the time is set to 400s, after the deposition is finished, the power supply is turned off, and the sample is taken out. Filling the core into wax film, making shell (dipping and sanding are repeated until the required thickness is reached, drying is carried out), steam dewaxing is carried out at 100-260 ℃, and the shell is fired by heating to 900 ℃ and keeping the temperature for 1 h. Putting the shell group into a vacuum directional furnace, vacuumizing to below 1pa, heating to 1550 ℃, pouring DSM11 high-temperature alloy, pumping out at the speed of 6mm/min, cooling to room temperature, taking out and removing shells.
The coating prepared by the invention can resist the corrosion of high-temperature alloy, the toughness of the coating is obviously enhanced, and the bonding force with the substrate interface is increased. The influence of silicon oxide on the alloy can be blocked due to the existence of the metal coating.
The above embodiments are not limited to the present invention, and any modification and variation within the spirit and scope of the present invention will be apparent to those skilled in the art from the following claims.
Claims (7)
1. A method of improving interfacial stability of a metal core coating, comprising: in the method, in the process of preparing the coating on the surface of the molybdenum-based metal core, the stability of an interface between the core and the coating is improved by optimizing the components of the coating and a pre-oxidation technology; the method specifically comprises the following steps:
(1) Pure molybdenum or molybdenum alloy is taken as a metal core matrix, and codeposition of silicon and aluminum elements is carried out on the core matrix by adopting a chemical vapor deposition or in-situ chemical vapor deposition process, wherein the deposition temperature is 900-1300 ℃, and the deposition time is 2-30 h; after deposition, cooling to 800 ℃ at a cooling rate of 1-15 ℃/min, then closing a heating system, and cooling to room temperature along with the furnace, thus forming the composite coating containing aluminum silicon on the matrix; when codeposition of silicon and aluminum elements is carried out, firstly, an aluminum-silicon-containing intermetallic compound layer is formed on a substrate, and then an inert oxide layer is formed on the intermetallic compound layer; the total thickness of the composite coating is more than 30 mu m, and the low-melting-point phase in the composite coating can disappear in the later pre-oxidation process;
(2) Pre-oxidation treatment: pre-oxidizing the core substrate with the coating deposited in the step (1), wherein the treatment process comprises the following steps: firstly, introducing air or oxygen, controlling the flow at 5 to 100sscm, then heating to 1000-1100 ℃, and preserving heat for 1-5 h; then heating to 1200-1400 ℃ at the heating rate of 1-15 ℃/min, and preserving the heat for 1-8 h; after the heat preservation is finished, opening a vacuum system for vacuumizing or introducing inert gas to reduce the concentration of oxygen in the furnace, closing a heating system, and cooling along with the furnace;
(3) Depositing a high-melting-point metal coating on the surface of the sample subjected to the pre-oxidation treatment in the step (2), wherein the deposition mode is arc ion plating, electroplating, magnetron sputtering, vacuum evaporation or chemical vapor deposition; the melting point of the high melting point metal coating is higher than 1600 ℃.
2. The method of increasing the interfacial stability of a metallic core coating according to claim 1, wherein: in the step (1), the metal core substrate is pretreated before use, and the process comprises the following steps: firstly, grinding with 240# -800# sandpaper, then sequentially cleaning in deionized water and absolute alcohol, and drying for later use.
3. The method of increasing the interfacial stability of a metallic core coating of claim 1, wherein: in the step (1), when the codeposition of silicon and aluminum elements is carried out, the coating firstly forms low-melting-point Al due to the difference of the aluminum and silicon elements 8 MO 3 Coating and then converting all or part of the coating into a high melting point silicide coating.
4. The method of increasing the interfacial stability of a metallic core coating of claim 1, wherein: in the step (3), the high-melting-point metal coating is a chromium coating, a hafnium coating, an iridium coating or a platinum coating.
5. The method of increasing the interfacial stability of a metallic core coating of claim 1, wherein: in the step (1), when the codeposition of silicon and aluminum elements is carried out on the core substrate, one or more of chromium, zirconium, titanium and magnesium elements are simultaneously deposited.
6. The method of increasing the interfacial stability of a metallic core coating of claim 1, wherein: in the step (2), after pre-oxidation, the mixture is cooled to below 500 ℃ along with the furnace in the cooling process and taken out.
7. The method of increasing the interfacial stability of a metallic core coating according to claim 1, wherein: in the step (3), the thickness of the deposited metal coating is 1-20 μm.
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