CN117684225A - Nickel-based superalloy Ru/Zr co-modified beta-NiAl coating capable of improving oxide film adhesion and preparation method thereof - Google Patents
Nickel-based superalloy Ru/Zr co-modified beta-NiAl coating capable of improving oxide film adhesion and preparation method thereof Download PDFInfo
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- 238000000576 coating method Methods 0.000 title claims abstract description 129
- 239000011248 coating agent Substances 0.000 title claims abstract description 121
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 75
- 229910000943 NiAl Inorganic materials 0.000 title claims abstract description 60
- 229910000601 superalloy Inorganic materials 0.000 title claims abstract description 32
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 238000009713 electroplating Methods 0.000 claims abstract description 57
- 239000000843 powder Substances 0.000 claims abstract description 40
- 238000000034 method Methods 0.000 claims abstract description 33
- 238000009792 diffusion process Methods 0.000 claims abstract description 30
- 239000011159 matrix material Substances 0.000 claims abstract description 24
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 22
- 239000000956 alloy Substances 0.000 claims abstract description 22
- 238000000137 annealing Methods 0.000 claims abstract description 19
- 239000007787 solid Substances 0.000 claims abstract description 16
- 230000008569 process Effects 0.000 claims abstract description 11
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims description 30
- 239000003795 chemical substances by application Substances 0.000 claims description 29
- 230000000149 penetrating effect Effects 0.000 claims description 29
- 239000008367 deionised water Substances 0.000 claims description 22
- 229910021641 deionized water Inorganic materials 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 239000007788 liquid Substances 0.000 claims description 21
- 238000005406 washing Methods 0.000 claims description 21
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 238000000227 grinding Methods 0.000 claims description 14
- 238000000498 ball milling Methods 0.000 claims description 12
- 238000005498 polishing Methods 0.000 claims description 12
- 238000005554 pickling Methods 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 11
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 11
- 230000004913 activation Effects 0.000 claims description 10
- 238000005520 cutting process Methods 0.000 claims description 10
- 238000007789 sealing Methods 0.000 claims description 9
- 238000004140 cleaning Methods 0.000 claims description 8
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 7
- 230000003213 activating effect Effects 0.000 claims description 7
- 238000005269 aluminizing Methods 0.000 claims description 7
- 239000010453 quartz Substances 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 7
- 238000009461 vacuum packaging Methods 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- HJPBEXZMTWFZHY-UHFFFAOYSA-N [Ti].[Ru].[Ir] Chemical compound [Ti].[Ru].[Ir] HJPBEXZMTWFZHY-UHFFFAOYSA-N 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 3
- 238000004321 preservation Methods 0.000 claims description 2
- 239000000758 substrate Substances 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims 3
- 239000013078 crystal Substances 0.000 claims 1
- 238000004881 precipitation hardening Methods 0.000 claims 1
- 238000007711 solidification Methods 0.000 claims 1
- 230000008023 solidification Effects 0.000 claims 1
- 238000007254 oxidation reaction Methods 0.000 abstract description 51
- 230000003647 oxidation Effects 0.000 abstract description 50
- 230000004584 weight gain Effects 0.000 abstract description 10
- 235000019786 weight gain Nutrition 0.000 abstract description 10
- 230000015556 catabolic process Effects 0.000 abstract description 5
- 230000007547 defect Effects 0.000 abstract description 5
- 238000006731 degradation reaction Methods 0.000 abstract description 5
- 239000011253 protective coating Substances 0.000 abstract description 4
- 230000008901 benefit Effects 0.000 abstract description 3
- 238000000151 deposition Methods 0.000 abstract 1
- 239000000203 mixture Substances 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 18
- 238000002441 X-ray diffraction Methods 0.000 description 17
- 229910000951 Aluminide Inorganic materials 0.000 description 15
- 238000010438 heat treatment Methods 0.000 description 13
- 239000010410 layer Substances 0.000 description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 239000007789 gas Substances 0.000 description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- 239000002585 base Substances 0.000 description 6
- 239000005995 Aluminium silicate Substances 0.000 description 5
- 235000012211 aluminium silicate Nutrition 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000004927 clay Substances 0.000 description 5
- 239000010431 corundum Substances 0.000 description 5
- 229910052593 corundum Inorganic materials 0.000 description 5
- 238000011049 filling Methods 0.000 description 5
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 5
- 235000019353 potassium silicate Nutrition 0.000 description 5
- 230000001681 protective effect Effects 0.000 description 5
- 238000005086 pumping Methods 0.000 description 5
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 5
- 239000012720 thermal barrier coating Substances 0.000 description 5
- 229910002515 CoAl Inorganic materials 0.000 description 4
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 4
- 239000003245 coal Substances 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 3
- 239000011247 coating layer Substances 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 238000005553 drilling Methods 0.000 description 3
- 238000004299 exfoliation Methods 0.000 description 3
- 238000011010 flushing procedure Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000004901 spalling Methods 0.000 description 3
- 239000011029 spinel Substances 0.000 description 3
- 229910052596 spinel Inorganic materials 0.000 description 3
- 230000037303 wrinkles Effects 0.000 description 3
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 238000005328 electron beam physical vapour deposition Methods 0.000 description 2
- 238000001764 infiltration Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000002028 premature Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/50—Electroplating: Baths therefor from solutions of platinum group metals
-
- 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
- C23C10/00—Solid state diffusion of only metal elements or silicon into metallic material surfaces
- C23C10/28—Solid state diffusion of only metal elements or silicon into metallic material surfaces using solids, e.g. powders, pastes
- C23C10/34—Embedding in a powder mixture, i.e. pack cementation
- C23C10/52—Embedding in a powder mixture, i.e. pack cementation more than one element being diffused in one step
-
- 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
- C23C10/00—Solid state diffusion of only metal elements or silicon into metallic material surfaces
- C23C10/60—After-treatment
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/34—Pretreatment of metallic surfaces to be electroplated
- C25D5/38—Pretreatment of metallic surfaces to be electroplated of refractory metals or nickel
- C25D5/40—Nickel; Chromium
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/48—After-treatment of electroplated surfaces
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electrochemistry (AREA)
- Mechanical Engineering (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
Abstract
The invention provides a nickel-based superalloy Ru/Zr co-modified beta-NiAl coating capable of improving oxide film adhesion and a preparation method thereof, belonging to the field of high-temperature protective coatings. And preparing the Ru/Zr co-modified beta-NiAl coating on the surface of the nickel-based superalloy by adopting a process combining electroplating and a solid powder embedding method. The process flow of the invention is as follows: pretreating a matrix; electroplating and depositing a Ru layer; embedding Al and Zr into the solid powder for co-permeation; finally, the Ru/Zr co-modified beta-NiAl coating is obtained on the surface of the matrix alloy after vacuum diffusion annealing treatment. The advantages of the inventionThe point: the preparation process is simple and the cost is low; no RuAl phase with poor oxidation resistance is generated in the preparation process; the composition controllability is high; the obtained coating is smooth and compact, and has no defects such as hole cracks and the like; after the coating is oxidized for 300 hours at the constant temperature of 1100 ℃, the oxide film on the surface of the coating is compact and complete, has no wrinkling and obvious flaking, and shows excellent oxide film adhesion; in addition, the coating does not generate beta-NiAl to gamma' -Ni 3 Degradation of Al, stable and slow oxidation weight gain, and excellent high-temperature oxidation resistance.
Description
Technical Field
The invention relates to the technical field of preparing high-temperature protective coatings on high-temperature alloy matrixes, in particular to a nickel-based superalloy Ru/Zr co-modified beta-NiAl coating capable of improving the adhesiveness of oxide films and a preparation method thereof.
Background
The nickel-based superalloy has higher strength and certain oxidation corrosion resistance at the high temperature of 650-1000 ℃, and is an indispensable material in the fields of aerospace, energy engineering, machinery manufacturing, petrochemical industry and the like. In particular in the aerospace field, nickel-based superalloys as high pressure turbine blade materials cannot be replaced by other materials for the current advanced aeroengines. However, with the continuous development of the fields of aerospace and the like, the service environment of the turbine blade of the advanced gas turbine engine is more severe, and the turbine blade is often damaged by high-temperature oxidation and hot corrosion environments. In order to protect these critical hot-end components and extend their service life, it is generally necessary to apply a high temperature protective coating to the hot-end component surface to improve the high temperature oxidation and hot corrosion resistance of the base alloy.
High temperature protective coatings have been developed up to now mainly through four generations, namely simple aluminide coatings (Simple aluminide coating), modified aluminide coatings (Modified aluminide coating), cladding coatings (MCrAlY coatings) and thermal barrier coatings (Thermal barrier coatings, TBCs). The simple aluminide coating has simple preparation process and low cost, and is widely applied to industrial production. However, simple aluminide coatings cannot be serviced at high temperatures for long periods of time, and the resulting oxide films are extremely prone to premature cracking and spalling, and have poor high temperature oxidation resistance. In order to improve the protection effect of the simple aluminide coating, researchers add Cr, co, si, pt, ru, zr and other elements into the modified aluminide coating or add various modified elements into the modified aluminide coating to prepare the multielement co-modified aluminide coating, so that the service life of the coating is effectively prolonged.
It has been found that the addition of Ru to the bond coat of a thermal barrier coating can effectively improve the creep properties of the coating, thereby inhibiting wrinkling, cracking and spalling of the coating during prolonged high temperature oxidation, whereas the oxidation rate of the coating is faster, and improvements in its preparation process are needed to avoid the formation of RuAl phases with poor oxidation resistance, or to add modifying elements to improve its high temperature oxidation resistance. It has been found that adding Zr to an aluminide coating forms a stripe-like Zr-rich oxide under the oxide film, which can act as a "pinning" to improve the adhesion of the oxide film; on the other hand, the addition of Zr can promote the formation of a denser oxide film, thereby reducing the oxidation rate. Therefore, ru and Zr are taken as modification elements together to prepare the composite modified aluminide coating with excellent crease resistance and high-temperature oxidation resistance and economic advantage.
The commonly used methods for preparing Ru modified aluminide coating or thermal barrier coating bond coat are magnetron sputtering, electron beam physical vapor deposition (EB-PVD), chemical Vapor Deposition (CVD), and the like. However, the equipment used in the methods has high cost, long preparation period and low efficiency, and RuAl phase with poor oxidation resistance can be formed. Therefore, the preparation method of the coating, which has simple preparation process and low cost and can avoid RuAl phase formation, has important significance.
Disclosure of Invention
The invention aims to provide a Ru/Zr co-modified beta-NiAl coating which is applied to nickel-based superalloy and can improve the adhesiveness of an oxide film and a preparation method thereof.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
the preparation method of the nickel-based superalloy Ru/Zr co-modified beta-NiAl coating capable of improving the adhesiveness of an oxide film comprises the following steps:
(1) The matrix pretreatment comprises the steps of sequentially carrying out rough grinding, fine grinding, polishing, alkali washing, acid washing and activation on the matrix alloy obtained by wire cutting;
(2) Electroplating the Ru layer, immersing the matrix alloy treated in the step (1) into electroplating solution, and electroplating to deposit the pure Ru layer;
(3) Preparing penetrant, mixing 20-30wt.% Al powder and 1-2wt.% NH 4 Cl、1-2wt.％ZrO 2 Powder and the balance Al 2 O 3 Ball milling and mixing the powder in Ar gas atmosphere to obtain uniform penetrating agent;
(4) Embedding Al and Zr in solid powder, co-infiltrating, embedding Ru layer in infiltrant, sealing, drying, and vacuum-sealing at-1.0X10 -1 Heat preservation is carried out for 2 hours at 900 ℃ in a furnace under the pressure of MPa for aluminizing;
(5) Vacuum diffusion annealing, namely vacuum packaging the Al and Zr co-infiltrated sample in a quartz tube, diffusion annealing for 2 hours at 1100 ℃, and taking out the sample after the sample is cooled to room temperature along with a furnace, namely obtaining the Ru/Zr co-modified beta-NiAl coating on the surface of the nickel-based superalloy.
In the step (1), the specific steps of the substrate pretreatment are as follows: firstly, roughly grinding a sample of a rectangular matrix alloy obtained by cutting warp yarns by using 200# and 400# SiC abrasive paper in sequence, finely grinding the sample by using 600# and 800# SiC abrasive paper, polishing by using a polishing machine, ultrasonically cleaning the sample by using an absolute ethyl alcohol solution for 10-20min, and drying; then sequentially placing the sample into alkaline washing liquid and pickling liquid at 50-60 ℃ for ultrasonic cleaning for 3-6min, washing with deionized water after each cleaning, and drying; then immersing the matrix into the activating solution for activation for 2-3min, wherein the activation temperature is 60-70 ℃.
The alkaline washing liquid in the step (1) is prepared from 20-40g/L NaOH and 20-40g/L Na 2 CO 3 And deionized water; the pickling solution is an HCl solution with the concentration of 10-20 vol%; the activating solution is prepared from 10-20g/L NH 2 SO 3 H. 1-2vol.% HCl and deionized water.
In the step (2), the specific step of electroplating the Ru layer is as follows: firstly stirring and heating the electroplating solution to 60-70 ℃, then fixing the sample treated in the step (1) at the center of an anode net drum by using a titanium wire hook, completely immersing the sample in the electroplating solution for 10-20min for preheating, then switching on a power supply for electroplating, and after the electroplating is finished, slowly flushing the sample by using deionized water and drying for standby.
In the step (2), the electroplating solution comprises the following components: ruCl 3 ·3H 2 O、NH 2 SO 3 H. HCl and deionized water, wherein the concentration is: ruCl 3 ·3H 2 O：4-10g/L；NH 2 SO 3 H:40-100g/L; HCl:1-2vol.%; ru electroplating processThe parameters are as follows: the pH value of the electroplating solution is 1-2; the current density is 1-2A/dm 2 The method comprises the steps of carrying out a first treatment on the surface of the The temperature of the electroplating solution is 60-70 ℃; the electroplating time is 80-100min; the anode is a titanium iridium ruthenium electrode, and the cathode is a sample to be plated; in the electroplating process, a heat collection type stirrer is adopted to stir and heat the electroplating liquid, and the stirring speed is 1000-2000r/min.
In the step (2), the thickness of the electroplated pure Ru layer is 4-10 mu m.
In the step (3), the specific steps for preparing the penetrating agent are as follows: 20-30wt.% Al powder and 1-2wt.% NH with purity of 99.99% 4 Cl、1-2wt.％ZrO 2 Powder and the balance Al 2 O 3 Placing the powder into a ball milling tank, pumping air in the tank by using a vacuum pump, introducing argon as protective gas, and then ball milling for 2-4 hours by using a planetary ball mill at a rotating speed of 200-300r/min to obtain the uniformly mixed penetrating agent.
In the step (4), the specific steps of embedding aluminizing are as follows: firstly, filling a penetrating agent into a corundum crucible, burying a test piece in the penetrating agent, ensuring that the thickness of the penetrating agent at the upper part and the lower part of the test piece is equivalent, keeping the distance between 1 cm and 2cm between all the test pieces at the same level, sealing the crucible and a cover by using refractory clay (mixed by kaolin and water glass in a ratio of 1:1), and drying for 2-4 hours at 80-100 ℃ in a drying box; then the fully dried crucible is put into a tube furnace, and the tube furnace is vacuumized to-1.0X10 by a vacuum pump -1 Heating to 900 ℃ at a heating rate of 10 ℃/min under MPa, preserving heat for 2 hours for aluminizing, finally taking out the sample after the sample is cooled to room temperature along with a furnace, putting the sample into an absolute ethyl alcohol solution, ultrasonically cleaning the sample for 10-15min, and drying the sample for later use.
In the step (5), the specific steps of vacuum diffusion annealing are as follows: and (3) placing the aluminized coating sample obtained by the treatment in the step (4) into a crucible, vacuum packaging the crucible into a quartz test tube, performing diffusion annealing at 1100 ℃ for 2 hours in a box furnace, and taking out the sample after the sample is cooled to room temperature along with the furnace, thus obtaining the Ru/Zr co-modified beta-NiAl coating on the surface of the nickel-based superalloy.
The Ru/Zr co-modified beta-NiAl coating prepared by the method has the thickness of 90-110 mu m; the main phase in the coating is beta-NiAl phase; the Ru content of the coating surface is 0.5-2wt.%, the Zr content is 0.1-0.3wt.%, the Ni content is 40-50wt.%, and the Al content is 20-30wt.%.
The invention has the following advantages:
1. the method comprises the steps of firstly adopting electroplating to deposit a Ru layer on the surface of the nickel-based superalloy, then adopting a solid powder embedding method to carry out Al and Zr co-permeation on the surface of the plated Ru, and finally carrying out 1100 vacuum diffusion annealing treatment to obtain a Ru/Zr co-modified beta-NiAl coating on the surface of the nickel-based superalloy;
2. the Ru/Zr co-modified aluminide coating is prepared on the surface of the nickel-based superalloy by adopting a process combining electroplating and a solid powder embedding method, and the content of Ru, zr and Al elements in the coating can be regulated and controlled by adjusting process parameters;
3. the invention adopts a process combining electroplating and a solid powder embedding method to prepare a Ru/Zr co-modified beta-NiAl coating on the surface of the nickel-based superalloy, and RuAl phase with poor oxidation resistance is not formed in the preparation process of the coating;
4. the Ru addition in the invention can effectively improve the surface quality of the aluminized coating, and after diffusion annealing, the surface of the aluminized coating added with Ru is smoother and denser, and has no obvious defects such as holes, cracks and the like;
5. the Ru/Zr co-modified beta-NiAl coating prepared by the invention effectively overcomes the defect that the traditional aluminide coating is easy to wrinkle and peel off in a high-temperature oxidation environment, an oxide film on the surface of the coating is still smooth and compact after being oxidized for 300 hours at the constant temperature of 1100 ℃, no wrinkles and obvious peeling off occur, the surface of the coating is still provided with a beta-NiAl phase through XRD detection, and no gamma' -Ni is detected 3 Al phase and spinel (NiAl 2 O 3 、CoAl 2 O 3 ) The diffraction peak of the (C) is stable and slow in oxidation weight gain, and excellent high-temperature oxidation resistance is shown.
Drawings
FIG. 1 is a cross-sectional morphology and surface XRD pattern of the electroplated Ru layer of example 1: (a) cross-sectional morphology; (b) a surface XRD pattern.
FIG. 2 shows the surface morphology and XRD pattern of a coating sample after vacuum diffusion annealing: (a) a single β -NiAl coating prepared in comparative example 1; (b) the Zr-modified beta-NiAl coating prepared in comparative example 2; (c) the Ru-modified beta-NiAl coating prepared in comparative example 3; (d) Ru/Zr co-modified beta-NiAl coating prepared in example 1; (e) XRD patterns of the four coatings.
FIG. 3 is a macroscopic photograph of the surface of a coating and flaking off after a coating coupon is oxidized at a constant temperature of 1100℃for 300 hours: (a) a single β -NiAl coating prepared in comparative example 1; (b) the Zr-modified beta-NiAl coating prepared in comparative example 2; (c) the Ru-modified beta-NiAl coating prepared in comparative example 3; (d) Ru/Zr co-modified beta-NiAl coating prepared in example 1.
FIG. 4 shows the surface morphology and XRD patterns of a coating sample after being oxidized at a constant temperature of 1100 ℃ for 300 hours: (a) a single β -NiAl coating prepared in comparative example 1; (b) the Zr-modified beta-NiAl coating prepared in comparative example 2; (c) the Ru-modified beta-NiAl coating prepared in comparative example 3; (d) Ru/Zr co-modified beta-NiAl coating prepared in example 1; (e) XRD patterns of the four coatings.
FIG. 5 shows the cross-sectional morphology of a coating sample after constant temperature oxidation at 1100 ℃ for 300 h: (a) a single β -NiAl coating prepared in comparative example 1; (b) the Zr-modified beta-NiAl coating prepared in comparative example 2; (c) the Ru-modified beta-NiAl coating prepared in comparative example 3; (d) Ru/Zr co-modified beta-NiAl coating prepared in example 1.
Fig. 6 is a graph showing oxidation kinetics for four coatings after 300h of constant temperature oxidation at 1100 ℃): (a) an oxidation time-oxidation weight gain curve; (b) A first-order fit curve of oxidation time versus oxidation weight gain square.
Detailed Description
The invention is described in detail below with reference to the drawings and examples.
Example 1:
example 1 is to prepare a Ru/Zr co-modified beta-NiAl coating on the surface of a nickel-based superalloy by adopting a method combining electroplating and a solid powder embedding method.
The matrix alloy adopts nickel-based superalloy DZ22B, and comprises the following components in percentage by mass: co:9.5, al:4.9, ti:1.9, cr:9,W:12, hf:1, C;0.14, nb:0.9, ni balance;
first, wire cutting is adoptedThe base alloy was cut into 10X 8X 3mm rectangular specimens and drilled at the edges of the specimensHoles are convenient for hanging and fixing the sample;
(1) Pretreatment of a matrix: sequentially carrying out rough grinding on the sample by using 200# and 400# SiC abrasive paper, carrying out fine grinding on the sample by using 600# and 800# SiC abrasive paper, polishing by using a polishing machine, and finally carrying out ultrasonic cleaning on the polished sample in absolute ethanol solution for 15min and drying for later use; then sequentially placing the sample into alkaline washing liquid and pickling liquid at 50 ℃ for ultrasonic cleaning for 5min, and then washing with deionized water and drying for later use; then the matrix is immersed into the activating solution for activation for 2min, and the activation temperature is 60 ℃.
The alkaline washing liquid consists of 20g/L NaOH and 20g/L Na 2 CO 3 And the balance deionized water; the pickling solution is a 10vol.% HCl solution; the activating solution is prepared from 10g/L NH 2 SO 3 H. 1vol.% HCl and balance deionized water.
(2) Electroplating a Ru layer: firstly stirring and heating the electroplating solution to 60 ℃, then fixing the sample treated in the step (1) at the center of an anode screen cylinder by using a titanium wire hook, completely immersing the sample in the electroplating solution for 15min for preheating, then switching on a power supply for electroplating, and after the electroplating is finished, slowly flushing the sample by using deionized water and drying for standby.
The electroplating solution comprises the following components: ruCl 3 ·3H 2 O、NH 2 SO 3 H. HCl and deionized water, wherein the concentration is: ruCl 3 ·3H 2 O：6g/L；NH 2 SO 3 H:60g/L; HCl:1vol.%; the Ru electroplating process parameters are as follows: the pH value of the electroplating solution is 1-2; the current density was 1.5A/dm 2 The method comprises the steps of carrying out a first treatment on the surface of the The temperature of the electroplating solution is 65 ℃; the electroplating time is 90min; the anode is a titanium iridium ruthenium electrode, and the cathode is a sample to be plated; in the electroplating process, a heat collection type stirrer is adopted to stir and heat the electroplating liquid, and the stirring speed is 1500r/min.
The cross-sectional morphology and the surface XRD pattern of the electroplated Ru layer are shown in figure 1, the average thickness of the Ru layer is 5 mu m, and the XRD pattern shows that the surface is pure Ru.
(3) Manufacturing processPreparing a penetrating agent: 30wt.% Al powder and 2wt.% NH with a purity of 99.99% 4 Cl、1wt.％ZrO 2 Powder and the balance Al 2 O 3 Putting the powder into a ball milling tank, pumping air in the tank by using a vacuum pump, introducing Ar gas as protective gas, and then ball milling for 4 hours by using a planetary ball mill at a rotating speed of 200r/min to obtain the uniform penetrating agent.
(4) Embedding Al and Zr into solid powder for co-infiltration: firstly, filling a penetrating agent into a corundum crucible, burying a test piece in the penetrating agent, ensuring that the thickness of the penetrating agent at the upper part and the lower part of the test piece is equivalent, keeping the same level of all the test pieces at 1-2cm intervals, sealing the crucible and a cover by using refractory clay (mixed by kaolin and water glass in a ratio of 1:1), and drying for 4 hours at 80 ℃ in a drying box; then the fully dried crucible is put into a tube furnace, and the tube furnace is vacuumized to-1.0X10 by a vacuum pump -1 And heating to 900 ℃ at a heating rate of 10 ℃/min under MPa, preserving heat for 2 hours to perform Al and Zr co-permeation, finally taking out the sample after the sample is cooled to room temperature along with a furnace, putting the sample into an absolute ethanol solution, and performing ultrasonic cleaning for 15 minutes and drying for later use.
(5) Vacuum diffusion annealing: and (3) placing the aluminized coating sample obtained by the treatment in the step (4) into a crucible, vacuum packaging the crucible into a quartz test tube, performing diffusion annealing at 1100 ℃ for 2 hours in a box furnace, and taking out the sample after the sample is cooled to room temperature along with the furnace, thus obtaining the Ru/Zr co-modified beta-NiAl coating on the surface of the nickel-based superalloy.
The thickness of the diffusion coating obtained in the step (5) is 90-110 mu m, the surface morphology and XRD spectrograms of the diffusion coating are shown in figures 2 (d) and (e), and the surface of the diffusion coating is smooth and compact and has no obvious defects such as holes, cracks and the like; the surface XRD pattern shows that the coating is mainly beta-NiAl phase, and RuAl phase is not found.
The macroscopic photograph of the surface and the peeling of the sample of the coating layer of this example after the constant temperature oxidation at 1100 ℃ for 300 hours is shown in fig. 3 (d), the oxide film on the surface is only slightly peeled off in the initial stage of oxidation, and the oxide film is not peeled off after the oxidation for 300 hours, thus showing excellent adhesion.
The surface morphology back-scattering image and XRD pattern of the sample of the coating layer after being oxidized at 1100 ℃ for 300 hours are shown in FIGS. 4 (d) and (e), and the surface oxide film is not obviously peeled off, showing thatExcellent anti-peeling ability; the surface of the coating has obvious beta-NiAl phase diffraction peak, and no gamma' -Ni is detected 3 Al phase and spinel (NiAl 2 O 3 、CoAl 2 O 3 ) Diffraction peaks.
The cross-sectional morphology of the sample of the coating of this example after 300h of constant temperature oxidation at 1100 ℃ is shown in FIG. 5 (d), the oxide film does not wrinkle and peel, the thickness is 6-10 μm, and the coating does not have beta-NiAl facing gamma' -Ni 3 Degradation of the Al phase.
The oxidation kinetics curve of the coating sample of the example after being oxidized for 300 hours at the constant temperature of 1100 ℃ is shown in FIG. 6, and the unit area oxidation weight gain of the sample after 300 hours is 1.589mg/cm 2 Oxidation rate constant K p ＝4.820×10 -3 mg 2 /cm 4 H, the oxidation weight gain curve tends to be stable in 50-300h, and excellent high-temperature oxidation resistance is shown.
Comparative example 1:
comparative example 1 is to prepare a single β -NiAl coating on the surface of a nickel-base superalloy using a solid powder embedding method.
The matrix alloy adopts nickel-based superalloy DZ22B, and comprises the following components in percentage by mass: co:9.5, al:4.9, ti:1.9, cr:9,W:12, hf:1, C;0.14, nb:0.9, ni balance;
cutting the matrix alloy into rectangular samples of 10X 8X 3mm by wire cutting, and drilling at the edges of the samplesHoles are convenient for hanging and fixing the sample;
(1) Pretreatment of a matrix: sequentially carrying out rough grinding on the sample by using 200# and 400# SiC abrasive paper, carrying out fine grinding on the sample by using 600# and 800# SiC abrasive paper, polishing by using a polishing machine, and finally carrying out ultrasonic cleaning on the polished sample in absolute ethanol solution for 15min and drying for later use; then sequentially placing the sample into alkaline washing liquid and pickling liquid at 50 ℃ for ultrasonic cleaning for 5min, and then washing with deionized water and drying for later use.
The alkaline washing liquid consists of 20g/L NaOH and 20g/L Na 2 CO 3 And the balance deionized water; pickling solution is 10vol.% HCl solutionAnd (3) liquid.
(2) Preparing a penetrating agent: 30wt.% Al powder and 2wt.% NH with a purity of 99.99% 4 Cl and the balance Al 2 O 3 Putting the powder into a ball milling tank, pumping air in the tank by using a vacuum pump, introducing Ar gas as protective gas, and then ball milling for 4 hours by using a planetary ball mill at a rotating speed of 200r/min to obtain the uniform penetrating agent.
(3) Embedding and infiltrating Al into solid powder: firstly, filling a penetrating agent into a corundum crucible, burying a test piece in the penetrating agent, ensuring that the thickness of the penetrating agent at the upper part and the lower part of the test piece is equivalent, keeping the same level of all the test pieces at 1-2cm intervals, sealing the crucible and a cover by using refractory clay (mixed by kaolin and water glass in a ratio of 1:1), and drying for 4 hours at 80 ℃ in a drying box; then the fully dried crucible is put into a tube furnace, and the tube furnace is vacuumized to-1.0X10 by a vacuum pump -1 Heating to 900 ℃ at a heating rate of 10 ℃/min under MPa, preserving heat for 2 hours for aluminizing, finally taking out the sample after the sample is cooled to room temperature along with a furnace, putting the sample into an absolute ethyl alcohol solution, ultrasonically cleaning the sample for 15 minutes, and drying the sample for later use.
(4) Vacuum diffusion annealing: and (3) placing the aluminized coating sample obtained by the treatment in the step (3) into a crucible, vacuum packaging the crucible into a quartz test tube, performing diffusion annealing at 1100 ℃ for 2 hours in a box furnace, and taking out the sample after the sample is cooled to room temperature along with the furnace, namely obtaining a single beta-NiAl coating on the surface of the nickel-based superalloy.
The thickness of the diffusion coating obtained in the step (4) is 100-120 mu m, the surface morphology and XRD spectrograms of the diffusion coating are shown in figures 2 (a) and (e), and the surface of the diffusion coating has more defects such as bulges, holes, cracks and the like; the surface XRD pattern shows that the surface is mainly beta-NiAl phase.
The macroscopic photograph of the surface and spalling of the sample of the coating of this example after constant temperature oxidation at 1100 ℃ for 300 hours is shown in fig. 3 (a), the coating spalls over a large area, exposing the base alloy.
The surface back scattering image and XRD pattern of the coating sample of the example after the coating sample is oxidized for 300 hours at the constant temperature of 1100 ℃ are shown in fig. 4 (a) and (e), the oxide film is severely peeled off, a large number of cracks exist, the coating fails, and a large area of matrix alloy is exposed; the coating surface detects stronger gamma' -Ni 3 Al phaseSpinel (NiAl) 2 O 3 、CoAl 2 O 3 ) Is a diffraction peak of (2).
The cross-sectional morphology of the sample of the coating of this example after 300h of constant temperature oxidation at 1100 ℃ is shown in FIG. 5 (a), severe wrinkling and flaking of the oxide film occur, and the consumption of Al in the coating is severe, resulting in beta-NiAl facing gamma' -Ni 3 Degradation of the Al phase cannot support the formation of new oxide films, which are only 1-3 μm thick.
The oxidation kinetics curve of the coating sample of the example after being oxidized for 300 hours at the constant temperature of 1100 ℃ is shown in FIG. 6, and the unit area oxidation weight gain of the sample after 300 hours is 10.800mg/cm 2 Oxidation rate constant K p ＝4.259×10 -1 mg 2 /cm 4 ·h。
Comparative example 2:
comparative example 2 is a Zr-modified β -NiAl coating prepared on the surface of a nickel-based superalloy using a solid powder embedding method.
The matrix alloy adopts nickel-based superalloy DZ22B, and comprises the following components in percentage by mass: co:9.5, al:4.9, ti:1.9, cr:9,W:12, hf:1, C;0.14, nb:0.9, ni balance;
cutting the matrix alloy into rectangular samples of 10X 8X 3mm by wire cutting, and drilling at the edges of the samplesHoles are convenient for hanging and fixing the sample;
(1) Pretreatment of a matrix: sequentially carrying out rough grinding on the sample by using 200# and 400# SiC abrasive paper, carrying out fine grinding on the sample by using 600# and 800# SiC abrasive paper, polishing by using a polishing machine, and finally carrying out ultrasonic cleaning on the polished sample in absolute ethanol solution for 15min and drying for later use; then sequentially placing the sample into alkaline washing liquid and pickling liquid at 50 ℃ for ultrasonic cleaning for 5min, and then washing with deionized water and drying for later use.
The alkaline washing liquid consists of 20g/L NaOH and 20g/L Na 2 CO 3 And the balance deionized water; the pickling solution is a 10vol.% HCl solution.
(2) Preparing a penetrating agent: 30wt.% Al powder and 2wt.% NH with a purity of 99.99% 4 Cl、1wt.％ZrO 2 And the balance Al 2 O 3 Putting the powder into a ball milling tank, pumping air in the tank by using a vacuum pump, introducing argon as protective gas, and then ball milling for 4 hours by using a planetary ball mill at a rotating speed of 200r/min to obtain the uniformly mixed penetrating agent.
(3) Embedding Al and Zr into solid powder for co-infiltration: firstly, filling a penetrating agent into a corundum crucible, burying a test piece in the penetrating agent, ensuring that the thickness of the penetrating agent at the upper part and the lower part of the test piece is equivalent, keeping the same level of all the test pieces at 1-2cm intervals, sealing the crucible and a cover by using refractory clay (mixed by kaolin and water glass in a ratio of 1:1), and drying for 4 hours at 80 ℃ in a drying box; then the fully dried crucible is put into a tube furnace, and the tube furnace is vacuumized to-1.0X10 by a vacuum pump -1 Heating to 900 ℃ at a heating rate of 10 ℃/min under MPa, preserving heat for 2 hours for aluminizing, finally taking out the sample after the sample is cooled to room temperature along with a furnace, putting the sample into an absolute ethyl alcohol solution, ultrasonically cleaning the sample for 15 minutes, and drying the sample for later use.
(4) Vacuum diffusion annealing: and (3) placing the aluminized coating sample obtained by the treatment in the step (3) into a crucible, vacuum packaging the crucible into a quartz test tube, performing diffusion annealing at 1100 ℃ for 2 hours in a box furnace, and taking out the sample after the sample is cooled to room temperature along with the furnace, thus obtaining the Zr modified beta-NiAl coating on the surface of the nickel-based superalloy.
The thickness of the diffusion coating obtained in the step (4) is 100-120 mu m, the surface morphology and XRD patterns of the diffusion coating are shown as figures 2 (b) and (e), and more bulges exist on the surface of the coating; the XRD pattern shows that the surface is mainly beta-NiAl phase.
The macroscopic photograph of the surface and exfoliation of the sample coating after constant temperature oxidation at 1100 ℃ for 300 hours is shown in fig. 3 (b), and the oxidized film is significantly exfoliated.
The surface back scattering image and XRD pattern of the sample of the coating of this example after being oxidized at 1100 ℃ for 300 hours are shown in figures 4 (b) and (e), and the coating is partially peeled off, exposing part of the base alloy; gamma' -Ni is detected on the surface of the coating 3 Al phase and spinel (NiAl 2 O 3 、CoAl 2 O 3 ) Diffraction peaks.
The cross section morphology of the coating sample of the example is as follows after the constant temperature oxidation of 1100 ℃ for 300 hoursFIG. 5 (b) shows that severe wrinkling and flaking of the oxide film occurred, and that the consumption of Al in the coating was severe, resulting in beta-NiAl facing gamma' -Ni 3 Degradation of the Al phase cannot support the formation of a new oxide film, and severe internal oxidation occurs, with the thickest oxide film reaching 20-30 μm.
The oxidation kinetics curve of the coating sample of the example after being oxidized for 300 hours at the constant temperature of 1100 ℃ is shown in FIG. 6, and the unit area oxidation weight gain of the sample after 300 hours is 8.445mg/cm 2 Oxidation rate constant K p ＝2.709×10 -1 mg 2 /cm 4 ·h。
Comparative example 3:
comparative example 3 is a Ru modified β -NiAl coating prepared on the surface of a nickel-based superalloy by a method combining electroplating and solid powder embedding.
The matrix alloy adopts nickel-based superalloy DZ22B, and comprises the following components in percentage by mass: co:9.5, al:4.9, ti:1.9, cr:9,W:12, hf:1, C;0.14, nb:0.9, ni balance;
cutting the matrix alloy into rectangular samples of 10X 8X 3mm by wire cutting, and drilling at the edges of the samplesHoles are convenient for hanging and fixing the sample;
(1) Pretreatment of a matrix: sequentially carrying out rough grinding on the sample by using 200# and 400# SiC abrasive paper, carrying out fine grinding on the sample by using 600# and 800# SiC abrasive paper, polishing by using a polishing machine, and finally carrying out ultrasonic cleaning on the polished sample in absolute ethanol solution for 15min and drying for later use; then sequentially placing the sample into alkaline washing liquid and pickling liquid at 50 ℃ for ultrasonic cleaning for 5min, and then washing with deionized water and drying for later use; then the matrix is immersed into the activating solution for activation for 2min, and the activation temperature is 60 ℃.
The alkaline washing liquid consists of 20g/L NaOH and 20g/L Na 2 CO 3 And the balance deionized water; the pickling solution is a 10vol.% HCl solution; the activating solution is prepared from 10g/L NH 2 SO 3 H. 1vol.% HCl and balance deionized water.
(2) Electroplating a Ru layer: firstly stirring and heating the electroplating solution to 60 ℃, then fixing the sample treated in the step (1) at the center of an anode screen cylinder by using a titanium wire hook, completely immersing the sample in the electroplating solution for 15min for preheating, then switching on a power supply for electroplating, and after the electroplating is finished, slowly flushing the sample by using deionized water and drying for standby.
The electroplating solution comprises the following components: ruCl 3 ·3H 2 O、NH 2 SO 3 H. HCl and deionized water, wherein the concentration is: ruCl 3 ·3H 2 O：6g/L；NH 2 SO 3 H:60g/L; HCl:1vol.%; the Ru electroplating process parameters are as follows: the pH value of the electroplating solution is 1-2; the current density was 1.5A/dm 2 The method comprises the steps of carrying out a first treatment on the surface of the The temperature of the electroplating solution is 65 ℃; the electroplating time is 90min; the anode is a titanium iridium ruthenium electrode, and the cathode is a sample to be plated; in the electroplating process, a heat collection type stirrer is adopted to stir and heat the electroplating liquid, and the stirring speed is 1500r/min.
(3) Preparing a penetrating agent: 30wt.% Al powder and 2wt.% NH with a purity of 99.99% 4 Cl and the balance Al 2 O 3 Putting the powder into a ball milling tank, pumping air in the tank by using a vacuum pump, introducing argon as protective gas, and then ball milling for 4 hours by using a planetary ball mill at a rotating speed of 200r/min to obtain the uniformly mixed penetrating agent.
(4) Embedding and infiltrating Al into solid powder: firstly, filling a penetrating agent into a corundum crucible, burying a test piece in the penetrating agent, ensuring that the thickness of the penetrating agent at the upper part and the lower part of the test piece is equivalent, keeping the same level of all the test pieces at 1-2cm intervals, sealing the crucible and a cover by using refractory clay (mixed by kaolin and water glass in a ratio of 1:1), and drying for 4 hours at 80 ℃ in a drying box; then the fully dried crucible is put into a tube furnace, and the tube furnace is vacuumized to-1.0X10 by a vacuum pump -1 Heating to 900 ℃ at a heating rate of 10 ℃/min under MPa, preserving heat for 2 hours for aluminizing, finally taking out the sample after the sample is cooled to room temperature along with a furnace, putting the sample into an absolute ethyl alcohol solution, ultrasonically cleaning the sample for 15 minutes, and drying the sample for later use.
(5) Vacuum diffusion annealing: and (3) placing the aluminized coating sample obtained by the treatment in the step (4) into a crucible, vacuum packaging the crucible into a quartz test tube, performing diffusion annealing at 1100 ℃ for 2 hours in a box furnace, and taking out the sample after the sample is cooled to room temperature along with the furnace, thus obtaining the Ru co-modified beta-NiAl coating on the surface of the nickel-based superalloy.
The thickness of the diffusion coating obtained in the step (5) is 90-110 mu m, the surface morphology and XRD spectra of the diffusion coating are shown in figures 2 (c) and (e), and the surface of the diffusion coating is flat and compact; the surface XRD spectrum shows that the surface is mainly beta-NiAl phase.
The macroscopic photograph of the surface and exfoliation of the sample coated with this example after constant temperature oxidation at 1100 ℃ for 300 hours is shown in fig. 3 (c), and the oxide film on the surface shows significant exfoliation.
The surface back scattering image and XRD pattern of the sample of the coating layer of the example after being oxidized for 300h at the constant temperature of 1100 ℃ are shown in fig. 4 (c) and (e), the surface oxide film is peeled off, and a new oxide film is generated at the peeling position; gamma' -Ni is detected on the surface of the coating 3 Diffraction peaks of Al phase.
The cross-sectional morphology of the sample of the coating of this example after 300h of constant temperature oxidation at 1100 ℃ is shown in FIG. 5 (c), the thickness of the oxide film is 12-18 μm, and the beta-NiAl phase gamma' -Ni does not occur in the coating and the base alloy 3 Degradation of Al phase, substantial gamma' -Ni in beta-NiAl phase under oxide film 3 And an Al phase.
The oxidation kinetics curve of the coating sample of the example after being oxidized for 300 hours at the constant temperature of 1100 ℃ is shown in FIG. 6, and the unit area oxidation weight gain of the sample after 300 hours is 2.940mg/cm 2 Oxidation rate constant K p ＝2.438×10 -2 mg 2 /cm 4 And h, after 210h, obvious flaking occurs, and the oxidation weight gain curve gradually rises.
Claims (8)
1. A nickel-based superalloy Ru/Zr co-modified beta-NiAl coating capable of improving oxide film adhesion and a preparation method thereof are characterized in that: according to the method, a Ru layer is deposited on the surface of a high-temperature alloy of a substrate through an electroplating method, al and Zr co-permeation is carried out on the surface of the Ru layer through a solid powder embedding method, and finally a Ru/Zr co-modified beta-NiAl coating is obtained on the surface of the nickel-based high-temperature alloy through vacuum diffusion annealing treatment.
2. The method for preparing the nickel-based superalloy Ru/Zr co-modified beta-NiAl coating according to claim 1, wherein the method comprises the following steps: the method comprises the following steps:
(1) The matrix pretreatment comprises the steps of sequentially carrying out rough grinding, fine grinding, polishing, alkali washing, acid washing and activation on the matrix alloy obtained by wire cutting;
(2) Electroplating the Ru layer, immersing the matrix alloy treated in the step (1) into electroplating solution, and electroplating to deposit the pure Ru layer;
(3) Preparing penetrant, mixing 20-30wt.% Al powder and 1-2wt.% NH 4 Cl、1-2wt.％ZrO 2 Powder and the balance Al 2 O 3 Ball milling and mixing the powder in Ar gas atmosphere to obtain uniform penetrating agent;
(4) Embedding Al and Zr in solid powder, co-infiltrating, embedding Ru layer in infiltrant, sealing, drying, and vacuum-sealing at-1.0X10 -1 Heat preservation is carried out for 2 hours at 900 ℃ in a furnace under the pressure of MPa for aluminizing;
(5) Vacuum diffusion annealing, namely vacuum packaging the Al and Zr co-infiltrated sample in a quartz tube, diffusion annealing for 2 hours at 1100 ℃, and taking out the sample after the sample is cooled to room temperature along with a furnace, namely obtaining the Ru/Zr co-modified beta-NiAl coating on the surface of the nickel-based superalloy.
3. The preparation method according to claim 2, characterized in that: the nickel-based superalloy is a precipitation hardening directional solidification columnar crystal superalloy.
4. The preparation method according to claim 2, characterized in that: in the step (1), the alkali washing liquid consists of 20-40g/L NaOH and 20-40g/LNa 2 CO 3 And deionized water, wherein the pickling solution is 10-20vol.% HCl solution, and the activating solution is 10-20g/L NH 2 SO 3 H. 1-2vol.% HCl and deionized water; ultrasonic cleaning is adopted for alkaline cleaning and acid washing, the temperature is 50-60 ℃, and the cleaning is carried out for 3-6min; the activation temperature is 60-70 ℃ and the activation time is 2-3min.
5. The preparation method according to claim 2, characterized in that: in the step (2), the electroplating solution comprises the following components: 4-10g/L RuCl 3 ·3H 2 O、40-100g/L NH 2 SO 3 H. 1-2vol.% HCl and balance deionized water; the Ru electroplating toolThe technological parameters are as follows: the pH of the electroplating solution is 1-2, and the current density is 1-2A/dm 2 The temperature of the electroplating solution is 50-70 ℃, the electroplating time is 80-100min, the anode is a titanium iridium ruthenium net barrel, the cathode is a sample to be plated, and the sample to be plated is fixedly arranged in the center of the anode net barrel by a titanium wire hook; in the electroplating process, a heat-collecting magnetic stirrer is adopted to heat and stir the electroplating liquid, and the stirring speed is 1000-2000r/min.
6. The preparation method according to claim 2, characterized in that: the thickness of the electroplated pure Ru layer obtained by the step (2) is 4-10 mu m.
7. The preparation method according to claim 2, characterized in that: in the step (3), the purity of the penetrating agent powder is 99.99 percent; the size scale of the penetrating agent powder is as follows: the average size of Al powder is 70 mu m, NH 4 The average particle diameter of Cl powder is 20 mu m, zrO 2 The average particle diameter of the powder is 20nm, al 2 O 3 The average particle size of the powder was 10. Mu.m.
8. The preparation method according to claim 2, characterized in that: the Ru/Zr co-modified beta-NiAl coating obtained in the step (5) has a flat and compact surface, and the thickness of the coating is 90-110 mu m; the Ru content of the coating surface is 0.5-2wt.%, the Zr content is 0.1-0.3wt.%, the Ni content is 40-50wt.%, and the Al content is 20-30wt.%.
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