CN1657653A - High-temp. alloy surface heat barrier coating and its preparation method - Google Patents
High-temp. alloy surface heat barrier coating and its preparation method Download PDFInfo
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- CN1657653A CN1657653A CN 200510059919 CN200510059919A CN1657653A CN 1657653 A CN1657653 A CN 1657653A CN 200510059919 CN200510059919 CN 200510059919 CN 200510059919 A CN200510059919 A CN 200510059919A CN 1657653 A CN1657653 A CN 1657653A
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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
- 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
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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
- 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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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- 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
- C23C28/3455—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 with a refractory ceramic layer, e.g. refractory metal oxide, ZrO2, rare earth oxides or a thermal barrier system comprising at least one refractory oxide layer
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Abstract
A coated heat barrier layer on the surface of refractory alloy is composed of an external ceramic layer, a metallic adhesive layer directly attached on the surface of refractory alloy, and a compact protecting layer between said ceramic layer and adhesive layer for preventing the chemical and physical corrosion to adhesive layer. Its preparing process is also disclosed.
Description
Technical field
The invention belongs to the hot-work technology, relate in the thermal barrier coating of high-temperature alloy surface preparation and the preparation method of this coating.
Background technology
The development trend of modern gas turbine engines is high thrust, high-level efficiency, low oil consumption and long lifetime.In order to realize these purposes, usually use thermal barrier coating (TBCs) technology in the engine thermal end pieces, utilize on the one hand zirconia ceramic layer is low in the thermal barrier coating thermal conductivity reduce hot-end component particularly turbine blade to the demand of cooling air, thereby improve the efficient of engine, improve motor performance; By using thermal barrier coating to significantly improve the work-ing life of turbine blade, reduce maintenance cost on the other hand, reduce cost.Product of the present invention can be as product such as the turbine blade under the hot conditions of gas turbine engine.
Traditional thermal barrier coating comprises the ceramic coating and the metal bonding coating on surface.The material of ceramic coating such as chemically stable zirconia material comprise stable zirconium white, the zirconium white of stable calcium oxide and the zirconium white of stabilized magnesium hydroxide of zirconium white, hafnia of stabilized with yttrium oxide.Metal bonding coating mainly comprises as MCrAlY series and Pt-Al series.
Common thermal barrier coating is a porous, and porosity is in 8～30% scopes.In use, oxygen in the environment directly arrives on the metal bonding coating by these holes, with bonding layer material generation chemical reaction, generated metal oxide layer (TGO), under the acting in conjunction of factors such as high temperature, burn into particle wash away, along with the growth of TGO,, cause the inefficacy of thermal barrier coating metal bonding coating and ceramic coating cracking at the interface.The method that generally adopts is the growth velocity that the antioxidant property that improves metal bonding coating reduces TGO for this reason, improves the antistripping ability of ceramic coating simultaneously.
Detonation flame spraying technology is one of technology most characteristic in the hot-spraying techniques, its ultimate principle is that the energy that utilizes detonation wave to produce heats, quickens powdered material, thereby acquisition coating, the coating of utilizing this technology to obtain has high density, high bonding strength etc., the coating that detonation flame spraying obtains is widely used in industrial circles such as oil, metallurgy, Aeronautics and Astronautics, by preparing coating, improve the use properties of body material at substrate material surface.
Summary of the invention
The objective of the invention is: propose a kind of thermal barrier coating of high-temperature alloy surface preparation, the protective layer of one deck densification is arranged in this thermal barrier coating, thereby improve the antistripping ability of thermal barrier coating under hot conditions; The preparation method that this has the thermal barrier coating of protective layer is proposed simultaneously.
Technical scheme of the present invention is: a kind of thermal barrier coating of high-temperature alloy surface, and superalloy 1 is meant the metallic substance that is used for engine structure spare, comprises element and these elementary composition alloys such as cobalt, nickel, aluminium, iron, chromium; Thermal barrier coating comprises outer field ceramic coating 3 and is attached directly to the metal bonding coating 2 on superalloy 1 surface, the material of ceramic coating 3 is chemically stable zirconia material, the zirconium white that comprises stabilized with yttrium oxide, the zirconium white that hafnia is stable, the zirconium white of stable calcium oxide and the zirconium white of stabilized magnesium hydroxide, the material of metal bonding coating 2 comprises MCrAlY series, MCrAlY series, cobalt, nickel, aluminium, iron, chromium, yttrium and these elementary composition alloys, it is characterized in that, between metal bonding coating 2 and ceramic coating 3 layer protective layer 4 is arranged, the material of protective layer 4 comprises aluminum oxide, titanium oxide, silicon oxide, zirconium white enhancing aluminum oxide (ZTA) and magnesium oxide and the mixture of forming by these oxide compounds; The thickness of protective layer 4 is 0.001mm～0.002mm; The porosity of protective layer is 2～8%, and the thickness of thermal barrier coating is 0.091mm～0.232mm.
The preparation method of high-temperature alloy surface thermal barrier coating is characterized in that as mentioned above,
(1) preparation metal bonding coating 2; Metal refining tack coat on the superalloy of selecting for use, adopt one of following processing method to be prepared:
A, thermospray comprise plasma spraying, HVOF (High Velocity Oxygen Fuel) and detonation flame spraying;
B, physical vapor deposition or chemical vapour deposition;
C, plating or Infiltration Technics;
The porosity of metal bonding coating 2 is that the thickness of 8～30% tack coats is the bonding strength of 0.030～0.080mm for assurance protective layer and metal bonding floor height, before the preparation metal bonding coating, need carry out blast to superalloy and handle; After adopting physical vapor deposition, chemical vapour deposition and vacuum plasma spray coating prepared metal bonding coating, carry out diffusion heat treatments according to common process;
(2) preparation protective layer 4; Utilize detonation flame spraying technology to prepare fine and close ceramic protective layer on metal bonding coating, the material of protective layer comprises: the mixture that aluminum oxide, titanium oxide, silicon oxide, zirconium white strengthen aluminum oxide and magnesium oxide etc. and be made up of these oxide compounds; The preparation technology of protective layer is a detonation flame spraying, and the detonation flame spraying processing step is as follows:
1) utilize the pressurized air of dry cleansing that product is carried out clean;
2) utilize detonation flame spraying equipment to prepare protective layer, wherein explosion gases is oxygen and acetylene, and the gas flow ratio of oxygen and acetylene is 1.2～1.4, and nitrogen is 1.12MPa as shielding gas pressure; The distance of detonation flame spraying is 50～120mm;
The thickness of protective layer is 0.001mm～0.002mm, and the porosity of protective layer is 2～10%; After detonation flame spraying technology is finished, when adopting gas-phase deposition to prepare ceramic layer, adopt mill processing or photetching method that protective layer is carried out bright and clean processing, improve the smooth finish of protective layer;
(3) preparation ceramic coating 3; Utilize electro beam physics vapour deposition or plasma spray coating process on protective layer, to prepare ceramic coating; the material of ceramic coating is chemically stable zirconia material; stable zirconium white, the zirconium white of stable calcium oxide and the zirconium white of stabilized magnesium hydroxide of zirconium white, hafnia that comprises stabilized with yttrium oxide; the porosity of ceramic coating 3 is 8～30%, and thickness of ceramic coating is 0.060～0.150mm.
Advantage of the present invention is: the present invention reduces the erosion of physics with the chemistry of metal bonding coating in the thermal barrier coating by fine and close protective layer, improves the antistripping ability of thermal barrier coating.At first sealer has been blocked impurity in the environment such as V205 etc. to the infiltration of thermal barrier coating with wash away; played the effect of physical barriers layer; secondly sealer has reduced in the environment as the diffusion of oxygen to matrix, has reduced the growth velocity of TGO, has played the effect of chemical barrier layer.
Description of drawings
Fig. 1 is the structural representation of thermal barrier coating of the present invention.Among the figure, the 1st, superalloy refers to be used for the metallic substance of engine structure spare, comprises for example element and these elementary composition alloys such as cobalt, nickel, aluminium, iron, chromium.The 2nd, metal bonding coating comprises for example element and these elementary composition alloys such as cobalt, nickel, aluminium, iron, chromium, yttrium.The 3rd, ceramic coating, material such as chemically stable zirconia material comprise stable zirconium white, the zirconium white of stable calcium oxide and the zirconium white of stabilized magnesium hydroxide of zirconium white, hafnia of stabilized with yttrium oxide.The 4th, protective layer, material comprises: the mixture that aluminum oxide, titanium oxide, silicon oxide, zirconium white strengthen aluminum oxide (ZTA) and magnesium oxide etc. and be made up of these oxide compounds.
Embodiment
Below the present invention is described in further details.The present invention relates to by utilizing detonation flame spraying technology on heat barrier coating bonding layer, to prepare fine and close protective layer, thereby improve the antistripping ability of thermal barrier coating under hot conditions.Referring to Fig. 1, the thermal barrier coating of high-temperature alloy surface of the present invention, superalloy 1 is meant the metallic substance that is used for engine structure spare, comprises element and these elementary composition alloys such as cobalt, nickel, aluminium, iron, chromium; Thermal barrier coating comprises outer field ceramic coating 3 and is attached directly to the metal bonding coating 2 on superalloy 1 surface, the material of ceramic coating 3 is chemically stable zirconia material, the zirconium white that comprises stabilized with yttrium oxide, the zirconium white that hafnia is stable, the zirconium white of stable calcium oxide and the zirconium white of stabilized magnesium hydroxide, the material of metal bonding coating 2 comprises MCrAlY series, MCrAlY series, cobalt, nickel, aluminium, iron, chromium, yttrium and these elementary composition alloys, it is characterized in that, between metal bonding coating 2 and ceramic coating 3 layer protective layer 4 is arranged, the material of protective layer 4 comprises aluminum oxide, titanium oxide, silicon oxide, zirconium white enhancing aluminum oxide (ZTA) and magnesium oxide and the mixture of forming by these oxide compounds; The thickness of protective layer 4 is 0.001mm～0.002mm; The porosity of protective layer is 2～8%, and the thickness of thermal barrier coating is 0.091mm～0.232mm.
The preparation method of high-temperature alloy surface thermal barrier coating is characterized in that as mentioned above,
(1) preparation metal bonding coating 2; Metal refining tack coat on the superalloy of selecting for use, adopt one of following processing method to be prepared:
A, thermospray comprise plasma spraying, HVOF (High Velocity Oxygen Fuel) and detonation flame spraying;
B, physical vapor deposition or chemical vapour deposition;
C, plating or Infiltration Technics;
The porosity of metal bonding coating 2 is 8～30%, and the thickness of tack coat is 0.030～0.080mm, for guaranteeing the bonding strength of protective layer and metal bonding floor height, before the preparation metal bonding coating, need carry out blast to superalloy and handle; After adopting physical vapor deposition, chemical vapour deposition and vacuum plasma spray coating prepared metal bonding coating, carry out diffusion heat treatments according to common process;
(2) preparation protective layer 4; Utilize detonation flame spraying technology to prepare fine and close ceramic protective layer on metal bonding coating, the material of protective layer comprises: the mixture that aluminum oxide, titanium oxide, silicon oxide, zirconium white strengthen aluminum oxide and magnesium oxide etc. and be made up of these oxide compounds; The preparation technology of protective layer is a detonation flame spraying, the detonation flame spraying processing step is as follows: 1) utilize the pressurized air of dry cleansing that product is carried out clean, 2) utilize detonation flame spraying equipment to prepare protective layer, wherein explosion gases is oxygen and acetylene, the gas flow ratio of oxygen and acetylene is 1.2～1.4, and nitrogen is 1.12MPa as shielding gas pressure; The distance of detonation flame spraying is 50～120mm; The thickness of protective layer is 0) .001mm～0.002mm, the porosity of protective layer is 2～10%; After detonation flame spraying technology is finished, when adopting gas-phase deposition to prepare ceramic layer, adopt mill processing or photetching method that protective layer is carried out bright and clean processing as required, improve the smooth finish of protective layer;
(3) preparation ceramic coating 3; Utilize electro beam physics vapour deposition or plasma spray coating process on protective layer, to prepare ceramic coating; the material of ceramic coating is chemically stable zirconia material; stable zirconium white, the zirconium white of stable calcium oxide and the zirconium white of stabilized magnesium hydroxide of zirconium white, hafnia that comprises stabilized with yttrium oxide; the porosity of ceramic coating 3 is 8～30%, and thickness of ceramic coating is 0.060～0.150mm.
Embodiment
Embodiment 1; selecting DZ125 for use is the matrix high temperature alloy; utilize multi-arc ion plating process to prepare the NiCrAlY metal bonding coating; adhesive layer thickness is 0.05mm～0.07mm; tack coat carries out diffusion heat treatments under 950 ℃ of vacuum conditions; soaking time is 3～5 hours; utilize detonation flame spraying prepared aluminum oxide supercoat on this basis; the thickness of aluminum oxide coating layer is 0.0015mm～0.002mm; the density of aluminum oxide coating layer is 2%～4%; utilize glossing that protective layer of alumina is polished, improve smooth finish.Detonation flame spraying technology is as follows: explosion gases is oxygen and acetylene, and the gas flow ratio of oxygen and acetylene is 1.2～1.4, and nitrogen is as shielding gas, and the purity of spray aluminum oxide powder is 99%.Utilize EB-PVD (electro beam physics vapour deposition) technology to prepare the YSZ (zirconium white of stabilized with yttrium oxide; ZrO2-8wt%Y2O3) ceramic coating; coat-thickness is 0.08mm～0.10mm; carry out cyclic oxidation at 1100 ℃; technology is insulation 30min; air cooling 5min; comparative test result is found; the sample that does not utilize detonation flame spraying prepared protective layer begins to occur weightlessness behind cyclic oxidation 200 times; and the sample that has sprayed protective layer begins to occur weightlessness behind cyclic oxidation 350 times; increased the coating protection sheath as can be seen, the antistripping ability of thermal barrier coating is improved.
Embodiment 2; selecting GH169 for use is the matrix high temperature alloy; utilize atmospheric plasma prepared NiCrAlY metal bonding coating; adhesive layer thickness is 0.075～0.120mm; utilize detonation flame spraying prepared aluminium oxide-titanium oxide protective layer on this basis; concrete technology is identical with embodiment 1; the stoicheiometry of aluminium oxide-titanium oxide is the aluminum oxide of 70wt%; the titanium oxide of 30wt%; the thickness of aluminium oxide-titanium oxide protective layer is 0.002mm～0.004mm; the density of aluminium oxide-titanium oxide protective layer is 3%～4%, utilize atmospheric plasma spraying YSZ (zirconium white of stabilized with yttrium oxide, ZrO2-8wt%Y2O3).1050 ℃ of insulations 5 minutes, carry out thermal shock test under the condition that air cooling is 25 ℃, there is not the sample of protective layer to occur peeling off at the 7th time, there is the sample of aluminium oxide-titanium oxide protective layer still intact at the 10th time.
Embodiment 3; selecting GH169 for use is the matrix high temperature alloy; utilize atmospheric plasma prepared NiCrAlY metal bonding coating; adhesive layer thickness is 0.075～0.120mm; utilize detonation flame spraying prepared aluminium oxide-titanium oxide protective layer on this basis; concrete technology is identical with embodiment 1; the chemistry of aluminium oxide-titanium oxide is joined the aluminum oxide for 60wt%; the titanium oxide of 40wt%; the thickness of aluminium oxide-titanium oxide protective layer is 0.002mm～0.004mm; the density of aluminium oxide-titanium oxide protective layer is 3%～4%, utilizes the zirconium white of atmospheric plasma spraying stabilized with yttrium oxide, ZrO2-20wt%Y2O3).950 ℃ of insulations 5 minutes, carry out thermal shock test under the condition that air cooling is 25 ℃, there is not the sample of protective layer to occur peeling off at the 10th time, there have aluminium oxide-titanium oxide to protect the sample that expands layer to be still intact at the 15th time.
Claims (3)
1, a kind of high-temperature alloy surface thermal barrier coating, superalloy [1] is meant the metallic substance that is used for engine structure spare, comprises element and these elementary composition alloys such as cobalt, nickel, aluminium, iron, chromium; Thermal barrier coating comprises outer field ceramic coating [3] and is attached directly to the metal bonding coating [2] on superalloy [1] surface, the material of ceramic coating [3] is chemically stable zirconia material, the zirconium white that comprises stabilized with yttrium oxide, the zirconium white that hafnia is stable, the zirconium white of stable calcium oxide and the zirconium white of stabilized magnesium hydroxide, the material of metal bonding coating [2] comprises MCrAlY series, MCrAlY series, cobalt, nickel, aluminium, iron, chromium, yttrium and these elementary composition alloys, it is characterized in that, between metal bonding coating [2] and ceramic coating [3] layer protective layer [4] is arranged, the material of protective layer [4] comprises aluminum oxide, titanium oxide, silicon oxide, zirconium white enhancing aluminum oxide (ZTA) and magnesium oxide and the mixture of forming by these oxide compounds; The thickness of protective layer [4] is 0.001～0.002mm; The porosity of protective layer is 2～8%, and the thickness of thermal barrier coating is 0.091mm～0.232mm.
2, a kind of preparation method of high-temperature alloy surface thermal barrier coating is characterized in that,
(1) preparation metal bonding coating [2]; Metal refining tack coat on the superalloy of selecting for use, adopt one of following processing method to be prepared:
A, thermospray comprise plasma spraying, HVOF (High Velocity Oxygen Fuel) and detonation flame spraying;
B, physical vapor deposition or chemical vapour deposition;
C, plating or Infiltration Technics;
The porosity of metal bonding coating [2] is 8～30%, and the thickness of tack coat is 0.030～0.080mm, for guaranteeing the bonding strength of protective layer and metal bonding floor height, before the preparation metal bonding coating, need carry out blast to superalloy and handle; After adopting physical vapor deposition, chemical vapour deposition and vacuum plasma spray coating prepared metal bonding coating, carry out diffusion heat treatments according to common process;
(2) preparation protective layer [4]; Utilize detonation flame spraying technology to prepare fine and close ceramic protective layer on metal bonding coating, the material of protective layer comprises: the mixture that aluminum oxide, titanium oxide, silicon oxide, zirconium white strengthen aluminum oxide and magnesium oxide etc. and be made up of these oxide compounds; The preparation technology of protective layer is a detonation flame spraying, and the detonation flame spraying processing step is as follows:
1) utilize the pressurized air of dry cleansing that product is carried out clean;
2) utilize detonation flame spraying equipment to prepare protective layer, wherein explosion gases is oxygen and acetylene, and the gas flow ratio of oxygen and acetylene is 1.2～1.4, and nitrogen is 1.12MPa as shielding gas pressure; The distance of detonation flame spraying is 50～120mm;
The thickness of protective layer is 0.001～0.002mm, and the porosity of protective layer is 2～10%; After detonation flame spraying technology is finished, as required, when adopting gas-phase deposition to prepare ceramic layer, adopt mill processing or photetching method that protective layer is carried out bright and clean processing, improve the smooth finish of protective layer;
(3) preparation ceramic coating [3]; Utilize electro beam physics vapour deposition or plasma spray coating process on protective layer, to prepare ceramic coating; the material of ceramic coating is chemically stable zirconia material; stable zirconium white, the zirconium white of stable calcium oxide and the zirconium white of stabilized magnesium hydroxide of zirconium white, hafnia that comprises stabilized with yttrium oxide; the porosity of ceramic coating [3] is 8～30%, and thickness of ceramic coating is 0.060～0.150mm.
3, the preparation method of high-temperature alloy surface thermal barrier coating according to claim 2 is characterized in that, when preparation protective layer [4], if the use temperature of superalloy [1] surpasses 1000 ℃, preferentially adopts the alumina material preparation.
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