阅读说明：本技术 一种镍基合金镍铼-三氧化二铝扩散障的制备方法及其应用 (Preparation method and application of nickel-based alloy nickel-rhenium-aluminum oxide diffusion barrier ) 是由 田礼熙 刘文韬 彭晓 于 2020-07-15 设计创作，主要内容包括：本发明提供了一种镍基合金镍铼-三氧化二铝扩散障的制备方法及其应用,包含以下步骤：在溶剂中加入Al<Sub>2</Sub>O<Sub>3</Sub>微粒和添加剂,得到电泳悬浮液；将镍基合金浸入电泳悬浮液,通过电泳工艺在镍基合金表面沉积Al<Sub>2</Sub>O<Sub>3</Sub>镀层；再在蒸馏水中加入铼酸铵、柠檬酸、糖精、十二烷基硫酸钠,待溶解后加入氨基磺酸镍,常温下加入氨水调节pH值,得到电镀溶液；将表面沉积Al<Sub>2</Sub>O<Sub>3</Sub>镀层的镍基合金浸入电镀溶液,以镍基合金为阴极进行电镀,电镀后经清洗、干燥后得到表面沉积NiRe-Al<Sub>2</Sub>O<Sub>3</Sub>扩散障的镍基合金。本发明提供的方法,制备工艺简便、效率高、成本低且容易产业化。(The invention provides a preparation method and application of a nickel-based alloy nickel-rhenium-aluminum oxide diffusion barrier, which comprises the following steps: adding Al to the solvent 2 O 3 Microparticles and additives to obtain an electrophoretic suspension; immersing the nickel-based alloy into an electrophoresis suspension, and depositing Al on the surface of the nickel-based alloy by an electrophoresis process 2 O 3 Plating; adding ammonium rhenate, citric acid, saccharin and sodium dodecyl sulfate into distilled water, adding nickel sulfamate after dissolving, and adding ammonia water at normal temperature to adjust the pH value to obtain an electroplating solution; depositing Al on the surface 2 O 3 Immersing the nickel-based alloy of the plating layer into an electroplating solution, electroplating by taking the nickel-based alloy as a cathode, cleaning and drying after electroplating to obtain NiRe-Al deposited on the surface 2 O 3 Nickel-based alloys of diffusion barriers. The method provided by the invention has the advantages of simple and convenient preparation process, high efficiency, low cost and easy industrialization.)

1. A preparation method of a nickel-based alloy nickel-rhenium-aluminum oxide diffusion barrier is characterized by comprising the following steps:

s1 adding Al into the organic solvent₂O₃Uniformly mixing the particles and the additive by ultrasonic waves to obtain an electrophoresis suspension;

s2: immersing the nickel-base alloy in the electrophoretic suspension, and performing Al by using the electrophoretic process and the nickel-base alloy as a cathode₂O₃Depositing and drying to obtain surface deposited Al₂O₃A plated nickel-based alloy;

s3: sequentially adding ammonium rhenate, citric acid, saccharin and sodium dodecyl sulfate into a certain amount of distilled water, adding nickel sulfamate after the ammonium rhenate, the citric acid, the saccharin and the sodium dodecyl sulfate are completely dissolved, stirring, uniformly mixing, adding ammonia water at normal temperature to adjust the pH value of the solution to be 8-8.5, and obtaining an alkaline NiRe electroplating solution;

s4: depositing Al on the surface obtained in the step S2₂O₃Immersing the nickel-based alloy of the coating into alkaline NiRe electroplating solution, electroplating by taking an electrolytic nickel plate as an anode and the nickel-based alloy as a cathode, ultrasonically cleaning for 5 minutes by using absolute ethyl alcohol after electroplating, and drying to prepare the NiRe-Al deposited on the surface₂O₃Nickel-based alloys of diffusion barriers.

2. The method as claimed in claim 1, wherein the organic solvent in step S1 is one of ethanol, acetone, and acetylacetone, or a mixture thereof.

3. The method as claimed in claim 1, wherein Al in step S1 is selected from the group consisting of Al, Ni, Re, and Al, and wherein the diffusion barrier is formed by a chemical vapor deposition method₂O₃Single particle size of 20nm to 1 μm or arbitrary mixture of different particle sizes, Al₂O₃The mass concentration of the particles in the suspension is 4-16 g/L.

4. The method for preparing the Ni-Re-Al oxide diffusion barrier of Ni-based alloy according to claim 1, wherein the additive in the step S1 is MgCl₂·6H₂O or I₂The mass concentration of the additive in the suspension is 0.6-1.6 g/L.

5. The method for preparing a ni-re-alumina diffusion barrier of ni-ni alloy according to claim 1, wherein the electrophoresis process parameters in the step S2 are as follows: the temperature is room temperature, the voltage is 60-100V, and the single electrophoretic deposition time is 15-20 seconds.

6. The method for preparing the nickel-based alloy nickel-rhenium-aluminum oxide diffusion barrier according to claim 1, wherein the electrophoresis process in the step S2 comprises multiple electrophoresis, the high-temperature alloy is taken out after single electrophoresis is completed, the electrophoresis is repeated after the high-temperature alloy is naturally dried in air, and the total electrophoresis time is 2-4 times.

7. The method for preparing the nickel-based alloy nickel-rhenium-aluminum oxide diffusion barrier according to claim 1, wherein the alkaline NiRe electroplating solution in the step S3 comprises the following components in percentage by mass: 5-20 g/L ammonium rhenate, 50-100 g/L citric acid, 1-2 g/L saccharin, 0.1-0.5 g/L sodium dodecyl sulfate and 150-250 g/L nickel sulfamate.

8. The method for preparing the nickel-based alloy nickel-rhenium-aluminum oxide diffusion barrier according to claim 1, wherein the electroplating process parameters in the step S4 are as follows: the working current density is 1-5A/dm²The temperature is 30-60 ℃, and the electroplating time is 10-30 min.

9. The method for preparing the Ni-Re-Al diffusion barrier of the Ni-Re-Al alloy as claimed in any one of claims 1 to 8, wherein the NiRe-Al diffusion barrier is formed by mixing Ni, Re and Al₂O₃The thickness of the diffusion barrier is 1 to 5 μm.

10. The application of nickel-base alloy Ni-Re-Al oxide diffusion barrier is characterized by that it uses NiRe-Al₂O₃Depositing diffusion barrier on the surface of the nickel-based alloy, and then depositing the diffusion barrier on the surface of the nickel-based alloy₂O₃And depositing a protective coating on the surface of the diffusion barrier.

Technical Field

The invention relates to a method for preparing a thermal diffusion barrier on a metal surface, in particular to a preparation method and application of a nickel-based alloy nickel-rhenium-aluminum oxide diffusion barrier.

Background

High temperature alloys generally require two performance requirements, namely excellent high temperature mechanical properties and high temperature corrosion resistance. In practice, however, for the same alloy, the properties of these two aspects are sometimes contradictory and cannot be optimized simultaneously. In order to solve the contradiction between the two, the process improvement only depending on the high-temperature alloy matrix material cannot meet the performance requirement of the development of the modern aerospace plane, and the problems are solved by depositing an alloy coating on the alloy surface through a high-temperature protective coating and applying an oxide ceramic coating on the alloy coating surface. The coatings are generally thin and serve primarily to protect the base metal from high temperature corrosion. While the high temperature strength requirements are largely borne by the matrix alloy itself. Because the base alloy and the protective coating can be designed separately, the alloy part with the protective coating can maintain enough high-temperature strength of the alloy and have excellent high-temperature corrosion resistance.

The composite materials such as NiAl, PtAl, McrAlY and the like are high-temperature protective coating base materials commonly used for high-temperature alloys, but the mutual diffusion of the coating and a matrix can be generated due to element concentration difference in the long-time high-temperature oxidation process, so that the surface structure of the alloy is degraded, the creep property is reduced, and the problem becomes an important factor for limiting the application of the protective coating. In order to effectively reduce the adverse effect of interdiffusion on the high temperature oxidation resistant protective outer layer system, applying a diffusion barrier between the high temperature oxidation resistant protective outer layer and the base alloy is an effective way. At present, the diffusion barrier mainly comprises two systems of metal and oxygen ceramic, wherein the former has good interface obdurability but insufficient diffusion resistance, and the latter has strong diffusion resistance but insufficient interface obdurability. The metal and ceramic composite system is expected to solve the problems, but a simple and convenient method is not available at present, so that high ceramic particle composite quantity can be obtained, metal components, grain size and the particle size and volume fraction of a ceramic phase can be easily regulated, and an ideal diffusion barrier cannot be obtained.

Disclosure of Invention

In order to solve the technical problem, the first aspect of the present invention provides a method for preparing a nickel-based alloy nickel-rhenium-aluminum oxide diffusion barrier, comprising the following steps:

s1 adding Al into the organic solvent₂O₃Microparticles and additives, ultraUniformly mixing the mixture by sound to obtain an electrophoresis suspension;

s2: immersing the nickel-base alloy in the electrophoretic suspension, and performing Al by using the electrophoretic process and the nickel-base alloy as a cathode₂O₃Depositing and drying to obtain surface deposited Al₂O₃A plated nickel-based alloy;

s3: sequentially adding ammonium rhenate, citric acid, saccharin and sodium dodecyl sulfate into a certain amount of distilled water, adding nickel sulfamate after the ammonium rhenate, the citric acid, the saccharin and the sodium dodecyl sulfate are completely dissolved, stirring, uniformly mixing, adding ammonia water at normal temperature to adjust the pH value of the solution to be 8-8.5, and obtaining an alkaline NiRe electroplating solution;

s4: depositing Al on the surface obtained in the step S2₂O₃Immersing the nickel-based alloy of the coating into alkaline NiRe electroplating solution, electroplating by taking an electrolytic nickel plate as an anode and the nickel-based alloy as a cathode, ultrasonically cleaning for 5 minutes by using absolute ethyl alcohol after electroplating, and drying to prepare the NiRe-Al deposited on the surface₂O₃Nickel-based alloys of diffusion barriers.

Further, the organic solvent in the step S1 is one of ethanol, acetone, and acetylacetone, or a mixture thereof at any ratio.

Further, Al in the step S1₂O₃Single particle size of 20nm to 1 μm or arbitrary mixture of different particle sizes, Al₂O₃The mass concentration of the particles in the suspension is 4-16 g/L.

Further, the additive in the step S1 is MgCl₂·6H₂O or I₂The mass concentration of the additive in the suspension is 0.6-1.6 g/L.

Further, the electrophoresis process parameters in the step S2 are as follows: the temperature is room temperature, the voltage is 60-100V, and the single electrophoretic deposition time is 15-20 seconds.

Further, the electrophoresis process in the step S2 includes multiple electrophoresis, the superalloy is taken out after single electrophoresis is completed, the electrophoresis is repeated after the single electrophoresis is naturally dried in the air, and the total electrophoresis time is 2-4 times.

Further, the alkaline NiRe electroplating solution in the step S3 comprises the following components by mass: 5-20 g/L ammonium rhenate, 50-100 g/L citric acid, 1-2 g/L saccharin, 0.1-0.5 g/L sodium dodecyl sulfate and 150-250 g/L nickel sulfamate.

Further, the electroplating process parameters of the step S4 are as follows: the working current density is 1-5A/dm²The temperature is 30-60 ℃, and the electroplating time is 10-30 min.

Further, the NiRe-Al₂O₃The thickness of the diffusion barrier is 1 to 5 μm.

The second aspect of the invention provides an application of nickel-based alloy nickel-rhenium-aluminum oxide diffusion barrier, namely, NiRe-Al₂O₃Depositing diffusion barrier on the surface of the nickel-based alloy, and then depositing the diffusion barrier on the surface of the nickel-based alloy₂O₃And depositing a protective coating on the surface of the diffusion barrier.

The invention has the beneficial effects that: the two-step method of electrophoresis and electrodeposition not only breaks through the technical bottleneck that the traditional composite electrodeposition particles have low composite quantity and are difficult to accurately control, but also has the characteristics of simple equipment, small investment, simple and convenient operation, high deposition efficiency and the like, has low preparation cost, and is easy to realize industrial production. Furthermore, Al in the electrophoretic fluid can be controlled as required₂O₃The particle size of the particles is obtained to obtain the electrophoresis layers with different void ratios, so as to reach Al in the diffusion barrier₂O₃Regulation of the volume fraction of (a); through the change of electroplating solution components and current density, the regulation and control of NiRe metal components and grain size are realized, and NiRe-Al with good interface toughness and strong diffusion resistance is obtained₂O₃A diffusion barrier. NiRe-Al₂O₃The diffusion barrier layer can be used for inhibiting the mutual diffusion of elements between the high-temperature structural material and the surface protective coating, and provides guarantee for the long-term stability of the high-temperature mechanical property of the nickel-based alloy material.

Drawings

In order to more clearly illustrate the technical solution of the present invention, the drawings used in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it should be obvious for those skilled in the art that other drawings can be obtained according to these drawings without creative efforts.

FIG. 1 shows the surface deposition of Al in example 1₂O₃The appearance of the nickel base alloy of the plating layer;

FIG. 2 shows the deposition of NiRe-Al on the surface of a nickel-based alloy in example 1₂O₃A diffusion barrier microstructure diagram;

FIG. 3 shows the results of example 1 in the case of NiRe-Al₂O₃Depositing a NiCrAlY coating on the surface of the diffusion barrier to obtain a nickel-based superalloy microstructure;

FIG. 4 shows the results of example 1 in the case of NiRe-Al₂O₃Depositing a NiCrAlY coating on the surface of the diffusion barrier to obtain a microstructure diagram of the nickel-based superalloy after high-temperature treatment;

FIG. 5 is a microstructure diagram of a nickel-based superalloy obtained by depositing a NiCrAlY coating directly on the surface of a nickel-based alloy in comparative example 1 after high temperature treatment.

Detailed Description

The following is a preferred embodiment of the present invention, and it should be noted that it is obvious to those skilled in the art that various modifications and improvements can be made without departing from the principle of the present invention, and these modifications and improvements are also considered to be within the scope of the present invention.