CN112011812A - Preparation method of low-diffusivity platinum modified metal bonding layer for nickel-based fourth-generation single-crystal high-temperature alloy - Google Patents
Preparation method of low-diffusivity platinum modified metal bonding layer for nickel-based fourth-generation single-crystal high-temperature alloy Download PDFInfo
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Abstract
The invention relates to the field of single crystal high temperature alloys, in particular to a preparation method of a low-diffusivity platinum modified metal bonding layer for a nickel-based fourth-generation single crystal high temperature alloy. The method comprises the following process flows: carrying out surface treatment on the nickel-based fourth-generation single crystal superalloy; obtaining a Ni-Re coating by using an electroplating process; obtaining a Pt coating by using an electroplating process; after the composite coating is obtained, diffusion annealing is carried out in vacuum; and aluminizing by using an embedding or CVD chemical vapor deposition method to obtain the single-phase Pt modified metal bonding layer. On the basis of the Pt modified aluminide coating taking the nickel-based fourth-generation monocrystal as the base body, the Re-containing diffusion barrier for slowing down mutual diffusion between the Pt modified aluminide coating and the base body is added, and the downhill diffusion of elements between the base body and the Pt modified aluminide coating in the high-temperature oxidation process, particularly the diffusion of Al to the base body, is effectively inhibited. The method has the advantages of simple preparation process, low cost, uniform distribution and controllable content of the Re element, and can be used for realizing large-scale production.
Description
Technical Field
The invention relates to the field of single crystal high temperature alloys, in particular to a preparation method of a low-diffusivity platinum modified metal bonding layer for a nickel-based fourth-generation single crystal high temperature alloy.
Background
In order to subject aircraft gas turbine engine hot end components, such as turbine blades, to higher temperatures during development, high temperature resistant thermal barrier coatings are often applied to the surfaces thereof. The Thermal Barrier Coatings (TBCs) are integrated thermal protection technologies which are characterized in that high-temperature-resistant, low-thermal-conductivity and corrosion-resistant ceramic materials are compounded with a base alloy in a coating form so as to reduce the surface temperature of a metal hot-end component and improve the high-temperature oxidation corrosion resistance of the base alloy. In order to solve the problem that the linear expansion coefficients of the high-temperature alloy substrate and the ceramic layer are greatly different, a metal bonding layer is necessary to be applied between the high-temperature alloy substrate and the ceramic layer. The metal bonding layer has good oxidation resistance and corrosion resistance, and the currently used mature bonding layer is an MCrAlY (M is Co, Ni or Co + Ni and the like) coating and a platinum-aluminum coating, and the latter has better high-temperature oxidation resistance and thermal corrosion resistance in a service environment of more than 1000 ℃. When the high-temperature alloy is in service in a high-temperature environment, the Al element in the bonding layer can be combined with O in the air to form an oxide film (TGO), so that further diffusion of O is prevented, and the oxidation effect on the high-temperature alloy is slowed down. However, since the difference between the composition of most bonding layers and the base alloy is large, an oxidation resistant element such as Al in the coating layer diffuses into the base alloy, and a base element such as Ni in the alloy diffuses into the coating layer. On one hand, the mutual diffusion consumes Al element in the coating, so that the coating is poor in Al, and the degradation of the coating is accelerated; on the other hand, the insoluble elements in the matrix alloy are separated out in a needle-tip-shaped TCP brittle phase, so that the mechanical property of the single crystal alloy is reduced. The application of a ceramic diffusion barrier layer in the coating is effective to slow the formation of the TCP phase and Secondary Reaction Zone (SRZ) in the base alloy and to retard coating degradation during high temperature oxidation. However, the inherent brittleness of the ceramic diffusion barrier increases the stress at the interface during service of the coating, which increases the cracking tendency of the coating. In addition, the ceramic diffusion barrier and the interface have low bonding strength, so that the protection effect is easily lost in the long-term service process. Therefore, a metal-based diffusion barrier with better bonding property with a substrate and a coating and closer mechanical property is urgently needed.
Disclosure of Invention
The invention aims to provide a preparation method of a low-diffusivity platinum modified metal bonding layer for a nickel-based fourth-generation single-crystal high-temperature alloy.
The technical scheme of the invention is as follows:
a preparation method of a low-diffusivity platinum modified metal bonding layer for a nickel-based fourth-generation single-crystal superalloy, which comprises the following steps:
(1) conventional surface treatment: pre-grinding a substrate on No. 120, No. 200, No. 400, No. 600 and No. 800 sandpaper in sequence, performing sand blasting on the pre-ground substrate, and then performing ultrasonic treatment to remove oil in a mixed solution of boiling NaOH aqueous solution and acetone and ethanol in sequence, wherein the concentration of the NaOH aqueous solution is 5-15 g/L;
(2) Ni-Re composite electroplating: the electroplating solution is prepared from potassium perrhenate, nickel sulfate, sodium chloride, boric acid, sodium sulfate and sodium dodecyl sulfate as raw materials, is prepared into an aqueous solution, the pH value is maintained between 4 and 5.5, the temperature of the solution is kept between 40 and 65 ℃ in the electroplating process, and the current density is 1 to 5A/dm2Taking a pure nickel plate as an anode and a matrix as a cathode, wherein the thickness of the Ni-Re plating layer is 3-10 mu m;
(3) annealing the plated layer electroplated with Ni-Re in a vacuum environment: a vacuum annealing furnace is used, and the vacuum degree in the annealing process is ensured to be 6 multiplied by 10-3Pa or less, rate of temperature rise during annealingKeeping the temperature at 800-1000 ℃ for 1-4 h at the temperature below 10 ℃/min, and cooling to room temperature along with the furnace to remove residual stress in the coating and ensure that the coating and the matrix alloy are combined more firmly;
(4) and (3) electroplating Pt on the prepared Ni-Re plating layer: an alkaline platinizing process is adopted, the pH value is maintained between 7 and 11 during platinizing, and the temperature is controlled between 60 and 90 ℃ during electroplating; the current density is 1-5A/dm2Electroplating by taking pure platinum or platinum-plated titanium mesh as an anode, wherein the thickness of the plated Pt layer is 2-8 mu m;
(5) and (3) performing diffusion annealing on the plated layer plated with Pt in a vacuum environment: a vacuum annealing furnace is used, and the vacuum degree in the annealing process is ensured to be 6 multiplied by 10-3Pa below, and the heating rate is below 10 ℃/min during annealing; in the annealing process, firstly, heat preservation is carried out for 2-4 hours at 400-700 ℃ so as to remove residual hydrogen in the coating; after dehydrogenation, continuously heating to 1000-1100 ℃, preserving heat for 1-4 h, and cooling to room temperature;
(6) and after diffusion annealing, aluminizing by adopting an embedding or chemical vapor deposition method to obtain the NiRePtAl bonding layer with low diffusivity.
The preparation method of the low-diffusivity platinum modified metal bonding layer for the nickel-based fourth-generation single-crystal superalloy comprises the step (1) of preparing a substrate of the low-diffusivity platinum modified metal bonding layer for the nickel-based fourth-generation single-crystal superalloy, wherein the substrate is the nickel-based fourth-generation single-crystal superalloy DD 91.
The preparation method of the low-diffusivity platinum modified metal bonding layer for the nickel-based fourth-generation single crystal superalloy comprises the following steps of (2): 0.15-1 mol/L of nickel sulfate, 0.2-0.5 mol/L of sodium chloride, 0.3-0.6 mol/L of boric acid, 0.2-0.7 mol/L of sodium sulfate, 0.005-0.05 mol/L of potassium perrhenate, 0.0002-0.0007 mol/L of sodium dodecyl sulfate and the balance of water.
The preparation method of the low-diffusivity platinum modified metal bonding layer for the nickel-based quaternary single-crystal superalloy comprises the following steps of (4): 0.01-0.05 mol/L dinitroso diammine platinum, 0.1-0.5 mol/L sodium nitrite, 0.02-0.06 mol/L sodium citrate, 0.02-0.06 mol/L sodium acetate and the balance of water.
The preparation method of the low-diffusivity platinum modified metal bonding layer for the nickel-based quaternary single-crystal superalloy is indispensable for the step of annealing the Ni-Re plating layer in a vacuum environment, and the Pt electroplating operation is carried out in time after the annealing.
The preparation method of the low-diffusivity platinum modified metal bonding layer for the nickel-based fourth-generation single-crystal superalloy is used for obtaining the low-diffusivity NiRePtAl, and the low-diffusivity NiRePtAl is mainly divided into three layers, wherein the outer layer is a single-phase beta- (Ni, Pt) Al coating, the inner layer is an inter-diffusion zone (IDZ), and a Re-containing Diffusion Barrier (DB) is arranged between the beta- (Ni, Pt) Al layer and the IDZ.
According to the preparation method of the low-diffusivity platinum modified metal bonding layer for the nickel-based quaternary single-crystal superalloy, the thickness range of a single-phase beta- (Ni, Pt) Al coating is 20-30 mu m, the thickness range of a Re-containing diffusion barrier is 3-10 mu m, and the thickness range of a mutual diffusion region is 10-30 mu m.
According to the preparation method of the low-diffusivity platinum modified metal bonding layer for the nickel-based quaternary single-crystal superalloy, the total thickness of the low-diffusivity platinum modified metal bonding layer ranges from 30 to 80 micrometers, and the aluminum content of the low-diffusivity platinum modified metal bonding layer ranges from 30 to 60 wt.%.
The design idea of the invention is as follows:
the invention discloses a low-diffusivity platinum modified metal bonding layer capable of reducing mutual diffusion between the bonding layer and a substrate, and simultaneously has good stability at high temperature, and the diffusion barrier has good matching property with the substrate and a single-phase beta- (Ni, Pt) Al coating. The thermal expansion coefficients of the Re-containing diffusion barrier and the matrix alloy and the single-phase beta- (Ni, Pt) Al coating are relatively close, and Re is very stable at high temperature; the solubility of Al in the Re-containing diffusion barrier is low, so that the diffusion of Al in the bonding layer to a substrate can be effectively inhibited. Re-containing diffusion barriers are introduced between the single-phase beta- (Ni, Pt) Al coating and the substrate to reduce the diffusivity of elements between the bonding layer and the substrate.
The invention has the advantages and beneficial effects that:
1. the invention introduces the Re-containing diffusion barrier by using an electroplating method, and the Re element is uniformly distributed. The Re content in the NiRePtAl bonding layer can be flexibly controlled by adjusting the components of the rhenium-nickel electroplating solution.
2. The Re-containing diffusion barrier obtained by the invention still has good stability at a high temperature of 1200 ℃, can effectively prevent mutual diffusion between the coating and the substrate, and has good matching performance with the coating and the substrate.
3. The invention mainly uses electroplating process and chemical vapor deposition process, is not limited by the shape of the part, and can be used for producing parts with complex shapes.
4. The preparation method is simple in preparation process and low in cost. The process flow is simple and easy to operate, large-scale vacuum equipment such as EB-PVD equipment is not needed, and the manufacturing cost is greatly reduced.
Drawings
FIG. 1 shows the cross-sectional shapes of the Ni-Re plating layer (a) and the Ni-Re + Pt plating layer (b).
Figure 2 is the NiRePtAl bond line XRD results after aluminizing. In the figure, the abscissa 2Theta represents the diffraction angle (deg.), and the ordinate Intensity represents the relative Intensity (a.u.).
Fig. 3 shows the surface (a, secondary electrons) and cross-sectional (b, backscattered electrons) morphology of the NiRePtAl bondline. In the figure, DB represents the Re-containing diffusion barrier, and IDZ represents the interdiffusion region.
FIG. 4 is a cross-sectional profile of a NiRePtAl bond layer (a, c) and a PtAl bond layer (b, d) after oxidation at 1200 ℃ for 40h (a, b) and 100h (c, d). In the figure, crack represents the occurrence of cracks in the oxide film, IDZ represents the interdiffusion zone, SRZ represents the secondary reaction zone, and bridging represents the exfoliation of the oxide film.
FIG. 5 is a graph of the high temperature oxidation kinetics of a NiRePtAl bond coat versus a PtAl bond coat at 1200 ℃. In the figure, the abscissa represents Time (h), and the ordinate represents Mass gain (mg/cm) for oxidative weight gain2)。
FIG. 6 shows the surface (a, B) and cross-sectional (c, d) shapes of Ni-Re plating layers after electroplating and annealing by the electroplating solutions A (a, c) and B (B, d).
FIG. 7 is a cross-sectional profile of a NiRePtAl bonding layer electroplated with electroplating baths A (a) and B (b).
Detailed Description
In the specific implementation process, the technology for preparing the low-diffusivity Pt modified metal bonding layer on the fourth-generation nickel-based single crystal superalloy comprises the following process flows of: carrying out surface treatment on the fourth-generation nickel-based single crystal superalloy; obtaining a Ni-Re plating layer by using an electroplating process, and annealing the plating layer electroplated with Ni-Re in a vacuum environment; and (3) obtaining a Pt coating by using an electroplating process, performing diffusion annealing on the composite coating after the Pt coating is electroplated in a vacuum environment, and aluminizing by using an embedding or CVD chemical vapor deposition method to obtain the single-phase Pt modified metal bonding layer.
The present invention will be described in further detail below with reference to examples.
Example 1
(1) Performing conventional surface treatment on the nickel-based fourth-generation single crystal superalloy DD 91:
the matrix alloy is processed into small 10 multiplied by 20 multiplied by 2mm samples by a linear cutting method, and the samples are subjected to water grinding and fillet rounding on SiC sand paper of 120#, 200#, 400#, 600# and 800# in sequence on a pre-grinding machine. In the embodiment, the chemical components of the fourth generation nickel-based single crystal superalloy DD91 are (mass fraction, wt.%) 12-Co,19.4-Cr + Mo + W + Ta,5.4-Re,3-Ru, and the balance Ni;
the pre-ground sample is subjected to dry sand blasting by corundum (220 meshes), then the substrate is boiled in NaOH aqueous solution with the concentration of 10g/L for 10min to remove surface oil stains, and then the substrate is soaked in mixed solution of absolute ethyl alcohol and acetone (the volume ratio is 1: 1) for ultrasonic cleaning for 10min and then dried for later use.
(2) Electroplating Ni-Re on the treated substrate according to the following steps:
the plating solution was prepared in advance, and the formulation of the Ni-Re plating solution is shown in Table 1. A pure nickel plate (purity: 99 wt%) is used as an anode, a substrate immersed in the electroplating solution is used as a cathode, a constant current is introduced by using a double-pulse power supply, and a Ni-Re plating layer is deposited on the cathode. The whole electroplating process is carried out at a constant temperature of 60 ℃, the pH value of the Ni-Re electroplating solution is maintained between 4 and 5.5, and the current density is maintained at 5A/dm2. As shown in FIG. 1(a), the cross-sectional morphology of the sample after Ni-Re electroplating was determined by Scanning Electron Microscopy (SEM), and it can be seen that the Ni-Re plating thickness was about 6 μm.
TABLE 1 formulation of Ni-Re electroplating bath
| Electroplating bath composition | Content (mol/L) |
| Nickel sulfate (Ni)2SO4·6H2O) | 0.6 |
| Sodium chloride (NaCl) | 0.35 |
| Boric acid (H)3BO3) | 0.5 |
| Sodium sulfate (Na)2SO4) | 0.4 |
| Potassium perrhenate (K)2ReO4) | 0.005 |
| Sodium dodecyl sulfate (C)12H25SO4Na) | 0.00035 |
| Balance of | Water (W) |
(3) Vacuum annealing of the Ni-Re plating layer: placing the sample in a vacuum annealing furnace, and controlling the vacuum degree in a vacuum chamber to be 5 multiplied by 10- 3Heating is started after Pa, and the heating rate is 10 ℃/min. Keeping the temperature at 1000 ℃ for 2h, and cooling to room temperature along with the furnace.
(4) And (3) platinum plating is carried out on the Ni-Re plating layer: the formulation of the Pt plating solution is shown in Table 2, using a platinum mesh (purity: 99 wt.%) as the anode, a substrate immersed in the plating solution as the cathode, and applying a double pulse power supplyConstant current, pure Pt was deposited on the cathode. The whole electroplating process is carried out at a constant temperature of 90 ℃, the pH value of the Pt electroplating solution is maintained between 7 and 11 (adjusted by ammonia water), and the current density is maintained at 5A/dm2. As shown in FIG. 1(b), the cross-sectional morphology of the sample after Pt electroplating was determined by Scanning Electron Microscopy (SEM), and the thickness of the Pt coating was about 5 μm.
TABLE 2 formulation of Pt electroplating baths
| Electroplating bath composition | Content (mol/L) |
| Dinitroso diammine platinum (Pt (NH)3)2(NO2)2) | 0.03 |
| Sodium nitrite (NaNO)2) | 0.15 |
| Sodium citrate (Na)3C6H5O7·2H2O) | 0.04 |
| Sodium acetate (CH)3COONa·3H2O) | 0.04 |
| Balance of | Water (W) |
(5) And (3) diffusion annealing of the composite coating: placing the sample in a vacuum annealing furnace, and controlling the vacuum degree in a vacuum chamber to be 3 multiplied by 10-3Heating is started after Pa, and the heating rate is 8 ℃/min.In the annealing process, the temperature is kept at 500 ℃ for 2 hours to remove residual hydrogen on the coating, so that the bulging phenomenon is prevented; after dehydrogenation, continuously heating to 1030 ℃ and preserving heat for 2h, and cooling to room temperature along with the furnace;
after diffusion annealing, a gas-phase aluminizing method is adopted for high-temperature low-activity gas-phase aluminizing treatment. The aluminizing agent is Fe-Al powder and an activator NH4Mixed powder of Cl, wherein: NH (NH)4Cl accounts for 1-4 wt.%, and the Al content in the Fe-A1 powder is about 51 wt.%. And uniformly suspending the sample above the aluminizing agent by 5-10 cm, vacuumizing, and filling argon as a protective gas to heat. The heating rate is about 10 ℃/min, the temperature can be kept after the heating is carried out to 1000-1080 ℃, and the heat preservation time is 2-6 h. And after the heat preservation is finished, cooling to room temperature along with the furnace. Finally, the NiRePtAl bonding layer is obtained, and the aluminum content in the NiRePtAl bonding layer is 50 wt.%.
As shown in fig. 2, from the XRD results after aluminizing, it is clear that the NiRePtAl bonding layer contains a single-phase β - (Ni, Pt) Al coating layer in the depth range detected by the X-ray. As shown in fig. 3(a), the surface morphology of the nireptadal bonding layer after aluminizing is shown in the figure, and it can be seen that the surface of the nireptadal bonding layer is composed of undulations formed by grain boundaries and pits formed in the grains, which is consistent with the common single-phase PtAl bonding layer. As shown in fig. 3(b), the cross-sectional shape of the nierptal bonding layer after aluminizing is shown in the figure, the nierptal bonding layer is mainly divided into three layers, the outer layer is a single-phase β - (Ni, Pt) Al coating, the inner layer is an interdiffusion zone (IDZ), and a Diffusion Barrier (DB) containing Re is arranged between the β - (Ni, Pt) Al layer and the IDZ. Wherein the thickness of the single-phase beta- (Ni, Pt) Al coating is about 25 μm, the thickness of the interdiffusion region is about 15 μm, the thickness of the Re-containing diffusion barrier is about 3 μm, and the total thickness of the NiRePtAl bonding layer is 46 μm.
The low diffusivity NiRePtAl bonding layer and the PtAl bonding layer obtained in the embodiment are subjected to constant temperature oxidation at 1200 ℃, and as shown in FIG. 4, the NiRePtAl bonding layers (a, c) and the PtAl bonding layers (b, d) have cross-sectional shapes after being oxidized for 40 hours and 100 hours at 1200 ℃. As can be seen from fig. (a) and (b), the oxide film of the nireptadal bonding layer was intact after 40h of oxidation, no Secondary Reaction Zone (SRZ) appeared below the interdiffusion zone (IDZ), the low diffusivity was determined by the thickness of the SRZ, which is thinner than the PtAl bonding layer, i.e., indicating a lower diffusivity; the oxide film of the PtAl bonding layer is cracked, and a secondary reaction zone having a conical distribution is formed below the interdiffusion zone. As can be seen from fig. (c) and (d), the oxide films of both the nireptadal bonding layer and the PtAl bonding layer exhibited cracks and peeling after 100 hours of oxidation, but the oxide film state of the former was significantly better than that of the latter; the conical secondary reaction zone below the PtAl bonding layer interdiffusion zone expands laterally and longitudinally, whereas the NiRePtAl bonding layer only shows a very small amount of needle-tip TCP phases. As shown in fig. 5, the nireptadal bonding layer and the PtAl bonding layer have smaller oxidation weight gain as seen from the high temperature oxidation kinetics curves at 1200 ℃.
Example 2
Considering that the Re content of the diffusion barrier needs to be properly adjusted within a certain range according to the service environment of the coating and the difference of the matrix in the actual process of the coating. This example will provide coatings of two different Ni-Re contents, 90Ni-10Re (wt.%) and 80Ni-20Re (wt.%), by changing the formulation of the Ni-Re plating bath.
(1) Processing the matrix alloy into small samples of 10 multiplied by 20 multiplied by 2mm by a linear cutting method, sequentially processing the samples on SiC sand paper of 120#, 200#, 400#, 600# and 800# on a pre-grinding machine and rounding off;
(2) the pre-ground sample is subjected to dry sand blasting by corundum (220 meshes), then the substrate is boiled in NaOH aqueous solution with the concentration of 8g/L for 10min to remove surface oil stains, and then the substrate is soaked in mixed solution of absolute ethyl alcohol and acetone (the volume ratio is 1: 1) for ultrasonic cleaning for 10min and then dried for later use.
(3) Electroplating Ni-Re on the treated substrate according to the following steps:
the plating solutions were prepared in advance, and the formulation of the Ni-Re plating solution A is shown in Table 3, and the formulation of the Ni-Re plating solution B is shown in Table 4. A pure nickel plate (purity: 99 wt.%) is used as anode, the matrix immersed in the electroplating solution is used as cathode, and a double-pulse power supply is used to apply constant current to deposit Ni-Re on the cathode. The whole electroplating process is carried out at a constant temperature of 60 ℃, and the current density is kept at 5A/dm2。
Table 3 shows the formulation of Ni-Re electroplating bath A
| Electroplating bath composition | Content (mol/L) |
| Nickel sulfate (Ni)2SO4·6H2O) | 0.6 |
| Sodium chloride (NaCl) | 0.35 |
| Boric acid (H)3BO3) | 0.5 |
| Sodium sulfate (Na)2SO4) | 0.4 |
| Potassium perrhenate (K)2ReO4) | 0.005 |
| Sodium dodecyl sulfate (C)12H25SO4Na) | 0.00035 |
| Balance of | Water (W) |
Table 4 shows the formulation of Ni-Re plating bath B
| Electroplating bath composition | Content (mol/L) |
| Nickel sulfate (Ni)2SO4·6H2O) | 0.15 |
| Sodium chloride (NaCl) | 0.35 |
| Boric acid (H)3BO3) | 0.5 |
| Sodium sulfate (Na)2SO4) | 0.55 |
| Potassium perrhenate (K)2ReO4) | 0.02 |
| Sodium dodecyl sulfate (C)12H25SO4Na) | 0.00035 |
| Balance of | Water (W) |
And after the electroplating is finished, carrying out vacuum annealing on the Ni-Re plating layer. Placing the sample in a vacuum annealing furnace, and controlling the vacuum degree in a vacuum chamber to be 5 multiplied by 10-3Heating is started after Pa, and the heating rate is 10 ℃/min. Keeping the temperature at 1000 ℃ for 2h, and cooling to room temperature along with the furnace.
As shown in FIG. 6, the Ni-Re plating layer after electroplating and annealing by the electroplating solutions A (a, c) and B (B, d) had surface and cross-sectional shapes. As can be seen from fig. 6, the surface and cross-sectional profiles of the two coatings are consistent. FIG. A) And (b) illustrates that no cracks are generated on the surface of the plating layer; it can be seen from FIGS. (c) and (d) that the distribution of Re element in the plated layer after annealing is uniform. The composition of the coating was further analyzed by an energy spectrometer (EDS), and the results are shown in table 5. It can be seen that ReO in Ni-Re plating solutions was changed4 -And Ni2+The concentration can control the Ni-Re ratio in the plating layer, thereby obtaining diffusion barriers with different Re contents.
Table 5 shows the Ni-Re contents (by EDS) of the different regions shown in FIG. 6
In this example, when the Ni-Re plating solutions A and B were used, the Ni-Re plating layers were 6 μm thick.
(4) And (3) platinum plating is carried out on the Ni-Re plating layer: the Pt plating bath formulations are shown in Table 6. A platinum wire mesh (purity: 99 wt.%) is used as an anode, a substrate immersed in the electroplating solution is used as a cathode, and a double-pulse power supply is used for introducing a constant current to deposit pure Pt on the cathode. The whole electroplating process is carried out at a constant temperature of 90 ℃, the pH value of the Pt electroplating solution is maintained between 7 and 11 (adjusted by ammonia water), and the current density is maintained at 5A/dm2The Pt coating thickness was about 5 μm.
TABLE 6 formulation of Pt electroplating bath
| Electroplating bath composition | Content (mol/L) |
| Dinitroso diammine platinum (Pt (NH)3)2(NO2)2) | 0.02 |
| Sodium nitrite (NaNO)2) | 0.1 |
| Sodium citrate (Na)3C6H5O7·2H2O) | 0.03 |
| Sodium acetate (CH)3COONa·3H2O) | 0.05 |
| Balance of | Water (W) |
(5) And (3) diffusion annealing: placing the sample in a vacuum annealing furnace, and controlling the vacuum degree in a vacuum chamber to be 3 multiplied by 10-3Heating is started after Pa, and the heating rate is 8 ℃/min. In the annealing process, the temperature is kept at 500 ℃ for 2 hours to remove residual hydrogen on the coating, so that the bulging phenomenon is prevented; after dehydrogenation, continuously heating to 1030 ℃ and preserving heat for 2h, and cooling to room temperature along with the furnace;
(6) after diffusion annealing, a gas-phase aluminizing method is adopted for high-temperature low-activity gas-phase aluminizing treatment. The aluminizing agent is Fe-Al powder and an activator NH4Mixed powder of Cl, wherein: NH (NH)4Cl accounts for 1-4 wt.%, and the Al content in the Fe-A1 powder is about 51 wt.%. And uniformly suspending the sample above the aluminizing agent by 5-10 cm, vacuumizing, and filling argon as a protective gas to heat. The heating rate is about 10 ℃/min, the temperature can be kept after the heating is carried out to 1000-1080 ℃, and the heat preservation time is 2-6 h. And after the heat preservation is finished, cooling to room temperature along with the furnace. The NiRePtAl bonding layer was finally obtained, with an aluminum content of 52 wt.% in the NiRePtAl bonding layer.
As shown in fig. 7(a) - (b), in this example, when Ni — Re plating solution a was used, the resulting nireptadal bonding layer was mainly divided into three layers, the outer layer was a single-phase β - (Ni, Pt) Al coating layer, the inner layer was an interdiffusion zone (IDZ), and a Re-containing Diffusion Barrier (DB) was located between the β - (Ni, Pt) Al layer and the IDZ. Wherein the thickness of the single-phase beta- (Ni, Pt) Al coating is about 25 μm, the thickness of the interdiffusion region is about 15 μm, the thickness of the Re-containing diffusion barrier is about 3 μm, and the total thickness of the NiRePtAl bonding layer is 46 μm. When the Ni-Re electroplating solution B is used, the finally obtained NiRePtAl bonding layer SEM sectional morphology is basically consistent with that when the Ni-Re electroplating solution A is used. Wherein the thickness of the single-phase beta- (Ni, Pt) Al coating is about 25 μm, the thickness of the interdiffusion region is about 27 μm, the thickness of the Re-containing diffusion barrier is about 4 μm, and the total thickness of the NiRePtAl bonding layer is 48 μm.
The example results show that on the basis of a platinum modified aluminide coating taking a fourth generation nickel-based single crystal superalloy as a substrate, the invention adds a Re-containing diffusion barrier for slowing down mutual diffusion between the coating and the substrate, and effectively inhibits the downhill diffusion of elements between the substrate and the coating in the high-temperature oxidation process, particularly the diffusion of Al to the substrate. The method has the advantages of simple preparation process, low cost, uniform distribution and controllable content of the Re element, no limitation of the shape of the part, and realization of large-scale production of complex parts.
Claims (8)
1. A preparation method of a low-diffusivity platinum modified metal bonding layer for a nickel-based fourth-generation single crystal superalloy is characterized by comprising the following specific steps of:
(1) conventional surface treatment: pre-grinding a substrate on No. 120, No. 200, No. 400, No. 600 and No. 800 sandpaper in sequence, performing sand blasting on the pre-ground substrate, and then performing ultrasonic treatment to remove oil in a mixed solution of boiling NaOH aqueous solution and acetone and ethanol in sequence, wherein the concentration of the NaOH aqueous solution is 5-15 g/L;
(2) Ni-Re composite electroplating: the electroplating solution is prepared from potassium perrhenate, nickel sulfate, sodium chloride, boric acid, sodium sulfate and sodium dodecyl sulfate as raw materials, is prepared into an aqueous solution, the pH value is maintained between 4 and 5.5, the temperature of the solution is kept between 40 and 65 ℃ in the electroplating process, and the current density is 1 to 5A/dm2Taking a pure nickel plate as an anode and a matrix as a cathode, wherein the thickness of the Ni-Re plating layer is 3-10 mu m;
(3) annealing the plated layer electroplated with Ni-Re in a vacuum environment: a vacuum annealing furnace is used, and the vacuum degree in the annealing process is ensured to be 6 multiplied by 10-3Pa below, the heating rate is below 10 ℃/min during annealing, the temperature is kept at 800-1000 ℃ for 1-4 h, and the temperature is cooled to room temperature along with the furnace to remove residual stress in the coating and ensure thatThe combination between the plating layer and the base alloy is firmer;
(4) and (3) electroplating Pt on the prepared Ni-Re plating layer: an alkaline platinizing process is adopted, the pH value is maintained between 7 and 11 during platinizing, and the temperature is controlled between 60 and 90 ℃ during electroplating; the current density is 1-5A/dm2Electroplating by taking pure platinum or platinum-plated titanium mesh as an anode, wherein the thickness of the plated Pt layer is 2-8 mu m;
(5) and (3) performing diffusion annealing on the plated layer plated with Pt in a vacuum environment: a vacuum annealing furnace is used, and the vacuum degree in the annealing process is ensured to be 6 multiplied by 10-3Pa below, and the heating rate is below 10 ℃/min during annealing; in the annealing process, firstly, heat preservation is carried out for 2-4 hours at 400-700 ℃ so as to remove residual hydrogen in the coating; after dehydrogenation, continuously heating to 1000-1100 ℃, preserving heat for 1-4 h, and cooling to room temperature;
(6) and after diffusion annealing, aluminizing by adopting an embedding or chemical vapor deposition method to obtain the NiRePtAl bonding layer with low diffusivity.
2. The method for preparing the platinum modified metal bonding layer with low diffusivity for the nickel-based quaternary single crystal superalloy according to claim 1, wherein in the step (1), the substrate is the nickel-based quaternary single crystal superalloy DD 91.
3. The method for preparing the low-diffusivity platinum modified metal bonding layer for the nickel-based quaternary single-crystal superalloy according to claim 1, wherein in the step (2), the components of the electroplating solution are in the following ranges: 0.15-1 mol/L of nickel sulfate, 0.2-0.5 mol/L of sodium chloride, 0.3-0.6 mol/L of boric acid, 0.2-0.7 mol/L of sodium sulfate, 0.005-0.05 mol/L of potassium perrhenate, 0.0002-0.0007 mol/L of sodium dodecyl sulfate and the balance of water.
4. The method for preparing the low-diffusivity platinum modified metal bonding layer for the nickel-based quaternary single-crystal superalloy according to claim 1, wherein in the step (4), the Pt electroplating solution comprises the following components: 0.01-0.05 mol/L dinitroso diammine platinum, 0.1-0.5 mol/L sodium nitrite, 0.02-0.06 mol/L sodium citrate, 0.02-0.06 mol/L sodium acetate and the balance of water.
5. The method for preparing the low-diffusivity platinum modified metal bonding layer for the nickel-based quaternary single-crystal superalloy according to claim 1, wherein a step of annealing the Ni-Re plating layer in a vacuum environment is indispensable, and the Pt electroplating operation is performed in time after the annealing.
6. The method of claim 1, wherein the low diffusivity NiRePtAl is obtained by the method and is mainly divided into three layers, the outer layer is a single-phase beta- (Ni, Pt) Al coating, the inner layer is an inter-diffusion zone (IDZ), and a Re-containing Diffusion Barrier (DB) is arranged between the beta- (Ni, Pt) Al layer and the IDZ.
7. The preparation method of the low-diffusivity platinum modified metal bonding layer for the nickel-based quaternary single-crystal superalloy according to claim 6, wherein the thickness range of the single-phase beta- (Ni, Pt) Al coating is 20-30 μm, the thickness range of the Re-containing diffusion barrier is 3-10 μm, and the thickness range of the mutual diffusion region is 10-30 μm.
8. The preparation method of the low-diffusivity platinum modified metal bonding layer for the nickel-based quaternary single-crystal superalloy according to claim 6, wherein the total thickness of the low-diffusivity platinum modified metal bonding layer is 30-80 μm, and the aluminum content of the low-diffusivity platinum modified metal bonding layer is 30-60 wt.%.
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