CN113699415B - Corrosion-resistant and high-temperature oxidation-resistant Co-based high-temperature alloy coating and preparation method thereof - Google Patents
Corrosion-resistant and high-temperature oxidation-resistant Co-based high-temperature alloy coating and preparation method thereof Download PDFInfo
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- CN113699415B CN113699415B CN202110866781.2A CN202110866781A CN113699415B CN 113699415 B CN113699415 B CN 113699415B CN 202110866781 A CN202110866781 A CN 202110866781A CN 113699415 B CN113699415 B CN 113699415B
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C19/00—Alloys based on nickel or cobalt
- C22C19/07—Alloys based on nickel or cobalt based on cobalt
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C24/00—Coating starting from inorganic powder
- C23C24/08—Coating starting from inorganic powder by application of heat or pressure and heat
- C23C24/10—Coating starting from inorganic powder by application of heat or pressure and heat with intermediate formation of a liquid phase in the layer
- C23C24/103—Coating with metallic material, i.e. metals or metal alloys, optionally comprising hard particles, e.g. oxides, carbides or nitrides
Abstract
The invention discloses a novel Co-based high-temperature alloy coating with corrosion resistance and high-temperature oxidation resistance and a preparation method thereof. Co-based and the novel Co-based coating of the invention are prepared on Q235 by adopting a plasma cladding technology, and the performance of the coating is compared by calculating the dilution ratio, an electrochemical experiment and an oxidation experiment. The results show the addition of 0.5wt% Y 2 O 3 The corrosion resistance of the novel Co-based high-temperature alloy coating is far higher than that of the coating without adding Y 2 O 3 The Co-based superalloy coating. Cyclic oxidation was carried out at 1000 ℃ with the addition of 0.5wt% Y 2 O 3 The oxide layer of the Co-based high-temperature alloy coating is compact and has excellent protectiveness, so that the novel Co-based high-temperature alloy coating prepared by the invention has good high-temperature oxidation resistance and corrosion resistance.
Description
Technical Field
The invention belongs to the technical field of metal materials, and particularly relates to a corrosion-resistant and high-temperature oxidation-resistant Co-based high-temperature alloy coating and a preparation method thereof.
Background
The high-temperature alloy is widely applied to fields of aeroengines, automobile engines, gas turbines, nuclear power, petrochemical industry and the like by virtue of excellent oxidation resistance and thermal corrosion resistance. In many fields of application, aerospace still occupies the most important position, accounting for 55% of the total demand, and the power industry follows, accounting for 20%. However, due to the limitation of the melting point of the conventional Ni-based superalloy, the improvement of the temperature-bearing capacity is very limited, and therefore, the development of a high-temperature structural material with higher temperature-bearing capacity is a key research direction in aerospace. Compared with Ni-based alloy, Co-based alloy has higher initial melting temperature (about 1495 ℃), better hot corrosion resistance and wear resistance. In general, Co-based alloy powders have superior high temperature performance over Fe-based, Ni-based superalloys. Therefore, in order to protect the parts of the aircraft engine from high temperature corrosion and high temperature oxidation and to improve the stability of the alloy, it is necessary to develop a novel Co-based superalloy.
Disclosure of Invention
The invention provides a corrosion-resistant and high-temperature oxidation-resistant Co-based high-temperature alloy coating and a preparation method thereof, and aims to prepare a low-cost Co-based alloy coating which has a large area and is well combined with a Q235 matrix, meets the high-temperature oxidation-resistant requirement on the surface of Q235 with low cost.
The invention is realized by the following technical scheme:
a corrosion-resistant and high-temperature oxidation-resistant Co-based high-temperature alloy coating comprises the following components in percentage by mass: 1.16 wt% C, 30.19 wt% Cr, 1.09 wt% Si, 2.50 wt% Ni, 2.54 wt% Fe, 0.15 wt% Mo, 4.47 wt% W, 0-1 wt% Y 2 O 3 And the balance being Co.
Further, the coating element components comprise the following components in percentage by mass: 1.16 wt% C, 30.19 wt% Cr, 1.09 wt% Si, 2.50 wt% Ni, 2.54 wt% Fe, 0.15 wt% Mo, 4.47 wt% W, 0.5wt% Y 2 O 3 And the balance being Co.
Further, the raw material powder of the coating element is 100-150 meshes.
Si and Mo are added mainly to increase the fluidity of the alloy, improve the casting performance, enhance the deoxidation effect of the melt and facilitate the control of the content of S. The influence of the addition of Si on the oxidation behavior of the superalloy is positive, and the addition of Si inhibits the out-diffusion of metal ionsAnd oxygen ions are diffused inward, the presence of Si promotes Cr 2 O 3 So that continuous Cr can be rapidly formed 2 O 3 And a protective layer. W is dissolved in the matrix in a solid solution mode to play a solid solution strengthening role, so that the alloy has higher high-temperature strength. The addition of Cr may increase the oxidation properties of the alloy.
The rare earth or rare earth oxide can enhance the adhesiveness and compactness of an alloy oxide film, refine crystal grains and is a strengthening element between a crystal boundary and a dendrite, thereby obviously improving the comprehensive performance of the alloy. Due to Y 2 O 3 Contains rare earth element Y, so that it not only can strengthen alloy, but also can greatly improve oxidation resistance of alloy. Thus, Y is added to the Co-based superalloy 2 O 3 The corrosion resistance and the high-temperature oxidation resistance of the coating can be improved.
The inventor obtains in the experimental process that Y is reasonably added 2 O 3 Is favorable for the corrosion resistance and high-temperature oxidation resistance of the Co-based high-temperature alloy coating, and proper amount of Y 2 O 3 The method is favorable for promoting the grain refinement and improving the adhesion and the anti-stripping performance of the oxide skin, thereby improving the high-temperature oxidation resistance of the coating. But too high Y 2 O 3 But rather coarsens the grains and excess Y during high temperature oxidation 2 O 3 Will react with Cr 2 O 3 Formation of YCrO 3 The anti-peeling property of the oxide layer is deteriorated, thereby lowering the high temperature oxidation resistance of the coating layer. Y added in consideration of comprehensive properties of the novel Co superalloy coating 2 O 3 Should not be too high, so that Y is added 2 O 3 The content of (b) was determined to be 0.5 wt.%.
Further, the preparation method of the coating is a plasma cladding technology.
Further, the plasma cladding technology has the following process parameters: the working current is 90-95A, the plasma gas flow is 1.5-2L/min, the powder feeding speed is 8-9 r/s, the protective gas flow is 4-10L/min, the welding speed is 3-4 mm/s, the progressive distance is 2.5-3 mm, and the powder feeding gas flow is 2-2.5L/min.
Compared with other technologies, the plasma cladding technology has the following advantages: the cladding layer has uniform structure, low porosity and low dilution rate; no specific requirements are made on the size, the shape and the field of the workpiece; the material is wide in application, and can be used for micro-atomizing nickel, cobalt, iron or copper-based powder; the device is simple, easy to automate, convenient to operate, high in production efficiency, energy-concentrated and efficient.
Further, the plasma cladding equipment is a plasma arc powder surfacing machine with the model of DML-03 AD.
Compared with the prior art, the invention has the beneficial effects that:
according to the invention, a large-area cobalt-based high-temperature alloy coating is prepared on the surface of Q235 by a plasma cladding technology, and the optimal technological parameters are subjected to surfacing cladding on the surface of a matrix after a test. Is added with Y 2 O 3 Y in the coating layer 2 O 3 The particles can be used as oxides, especially Cr 2 O 3 Thereby promoting Cr 2 O 3 Is performed. At Y 2 O 3 In an alloy with a content of 0.5wt.%, more spinel oxide, i.e. NiCr, is formed during the oxidation cycle 2 O 4 And CoCr 2 O 4 While the presence of spinel oxides reduces the rate of oxidation. Furthermore, Y 2 O 3 The addition of (2) improves the adhesion and spalling resistance of the oxide skin, and reduces the Cr-poor area. The novel Co-based high-temperature alloy coating prepared by the invention has excellent high-temperature oxidation resistance and corrosion resistance.
Drawings
FIG. 1 is a schematic diagram of a plasma cladding process.
FIG. 2 is a rectangular novel Co-based superalloy coating deposited on Q235 by plasma cladding.
FIG. 3 is a graph showing the addition of 0.5wt% of Y 2 O 3 Cross-sectional SEM images of Co-based superalloy coatings.
FIG. 4 shows no addition of Y 2 O 3 Adding 0.5wt% of Y 2 O 3 And adding 1wt% of Y 2 O 3 SEM image of the near surface of the Co-based superalloy coating.
FIG. 5 shows no addition of Y 2 O 3 Adding 0.5wt% of Y 2 O 3 And add1wt% of Y 2 O 3 Polarization curve of the Co-based superalloy coating.
FIG. 6 shows no addition of Y 2 O 3 Adding 0.5wt% of Y 2 O 3 And adding 1wt% of Y 2 O 3 The weight gain curve of the Co-based superalloy at 1000 ℃ cyclic oxidation and (G) + ) 2 And oxidation time.
FIG. 7 shows no addition of Y 2 O 3 Adding 0.5wt% of Y 2 O 3 And adding 1wt% of Y 2 O 3 Cross-sectional SEM images of Co-based superalloys at 1000 deg.c cyclic oxidation.
FIG. 8 shows no addition of Y 2 O 3 Adding 0.5wt% of Y 2 O 3 And 1wt% of Y is added 2 O 3 The XRD pattern of the Co-based high-temperature alloy under the cyclic oxidation at the temperature of 1000 ℃.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be further described with reference to the following embodiments. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
Examples
A corrosion and high temperature oxidation resistant Co-based superalloy coating, having the composition shown in table 1:
table 1: co-based alloy coating composition
| Chemical elements | C | Cr | Si | Ni | Fe | Mo | W | Co | Y2O3 |
| wt% | 1.16 | 30.19 | 1.09 | 2.50 | 2.54 | 0.15 | 4.47 | Bal | 0-1 |
And (3) avoiding the influence of water possibly contained in the powder on the coating quality, so that the uniformly mixed powder is put into a vacuum drying oven to be dried at the temperature of 110 ℃ for 120 min for later use.
A plasma arc powder surfacing machine is adopted, and the model is DML-03 AD. In the plasma cladding process, the powder feeding mode is synchronous powder feeding. The method mainly comprises the following steps: firstly, proportioning Co-based powder raw materials and doped Y 2 O 3 Homogenizing the powder, and drying in a drying oven for later use; secondly, optimizing the technological parameters of the novel Co-based coating by plasma cladding; thirdly, based on the optimized process, proper adjustment of experimental parameters is carried out to prepare novel CAn o-based coating; fourthly, characterizing the obtained cladding coating tissues; and fifthly, feeding back an experimental result and adjusting proper cladding process parameters. The obtained better cladding process parameters are shown in table 2:
table 2: cladding parameters
| Parameter name | Parameter(s) |
| Working current (A) | 90-95 |
| Plasma gas flow (L/min) | 1.5-2 |
| Powder feeding speed (r/s) | 8-9 |
| Protective gas flow (L/min) | 4-10 |
| Welding speed (mm/s) | 3-4 |
| Progressive distance (mm) | 2.5-3 |
| Powder feeding gas flow (L/min) | 2-2.5 |
The schematic diagram of the plasma cladding used is shown in fig. 1.
After plasma coating, the coating was stripped from the substrate by wire cutting, samples were cut to 5X 3mm and 10X 3mm sizes, and 6 surfaces of each component were sanded with No. 240, No. 800, No. 1200, No. 2000 sandpaper to make a smooth finish. Then, XRD, SEM and EDS detection analysis is carried out. FIG. 3 is a graph showing the addition of 0.5wt% of Y 2 O 3 The cross-section SEM image of the Co-based high-temperature alloy coating shows that the coating is tightly combined with the matrix without holes and gaps, and the preparation process and parameters of the coating are feasible. The dilution rate of the coating is 9% -20%, the dilution rate is moderate, the bonding performance of the cladding layer and the substrate is good, the cladding layer can be metallurgically bonded with a Q235 substrate, the cladding layer cannot be excessively diluted by the substrate, and the coating performance is good.
In the present invention, 0.5wt% of Y is added 2 O 3 The structure in the middle of the back coating is refined, the mechanical property of the coating can be improved by refining grains, the added rare earth Y has large ionic radius and low solubility in oxides, and segregation is easy to occur in a grain boundary or an interface. The rare earth Y partially condensed on the interface can reduce the concentration of S, P, C and other impurities on the interface, thereby purifying the interface and improving the bonding strength of the interface, so 0.5wt% of Y is added 2 O 3 The coating surface is denser.
Cutting the sample into 10X 3mm blocks according to the electrochemical test standard, welding 20 cm copper wires on the block surface, sealing by epoxy resin, covering the exposed copper wires by the epoxy resin, and grinding and polishing to obtain the electrochemical corrosion pattern. A CS150 electrochemical workstation is adopted to test the corrosion performance of the sample, a calomel electrode (SCE) is taken as a reference electrode, Pt is taken as a counter electrode, a sample is taken as a working electrode, and a normal-temperature 3.5% NaCl solution is taken as an electrolyte to carry out an electrochemical corrosion experiment on the coating. Before the polarization curve starts to be measured, the sample is soaked in an etching solution until the open circuit self-etching potential is stable, the scanning speed in the experimental process is 0.5 mV/s, and the scanning range is-2V to + 2V.
Y is added in the invention 2 O 3 The corrosion resistance of the post-coating is improved, wherein the post-coating is used as a novel Co-based high-temperature alloy coating in the inventionIn the electrochemical etching, 0.5wt% of Y is added 2 O 3 The polarization resistance of the novel Co-based high-temperature alloy coating is 4.4 times that of the Co-based high-temperature alloy coating which is not added. The corrosion parameters are as follows:
table 3: corrosion parameters
| Test specimen | Co radical | Co group + (0.5wt%) Y2O3 | Co radical + (1wt%) Y2O3 |
| Self-etching potential Ecorr (V vs. SCE) | -1.01312 | 0.91702 | -0.99802 |
| Self-corrosion current density Icorr (A/cm2) | 1.82E-05 | 2.85E-06 | 1.29E-05 |
| βa (1/V) | 0.25943 | 0.1488 | 0.30323 |
| βb (1/V) | 0.11946 | 0.09262 | 0.10531 |
| Polarization resistance Rp (omega cm2) | 1955.898 | 8694.137 | 2625.418 |
The cyclic oxidation test of the invention is completed according to HB5258-2000 method for testing oxidation resistance of steel and high-temperature alloy. In the experimental process, the coating and the crucible are respectively placed in a high-temperature furnace to carry out a 1000 ℃ high-temperature cyclic oxidation experiment, the coating and the crucible are taken out every 10 hours and weighed, then the coating and the crucible are placed in the high-temperature furnace to carry out next oxidation, and the oxidation weight gain result is processed according to HB5258-2000 standard. According to the results of the cyclic oxidation experiment, the cyclic oxidation weight gain of the prepared coating is shown in FIG. 6, and it can be seen that the weight gain of the coating follows the parabolic law, and the (G) of the coating + ) 2 Graph with time t. It can be seen that 0.5wt% Y is added 2 O 3 The oxidation performance of the novel Co-based coating of (a) is the best.
FIG. 7 is an oxidized cross-sectional view of the coating with the addition of 0.5wt% Y 2 O 3 Y in the coating 2 O 3 The particles can be used as oxides, especially Cr 2 O 3 Thereby promoting Cr 2 O 3 Is performed. As can be seen in the figure, at Y 2 O 3 In an alloy with a content of 0.5wt.%, more spinel oxide, i.e. NiCr, is formed during the oxidation cycle 2 O 4 And CoCr 2 O 4 . The results show that the presence of spinel oxide reduces the oxidation rate. Furthermore, Y 2 O 3 The addition of (2) improves the adhesion and the anti-stripping performance of the oxide skin, and reduces the poor Cr area. While adding 1wt% of Y 2 O 3 In the coating, the oxidation resistance is rather lowered because a sufficient amount of Y is added to the coating 2 O 3 High-temperature oxidation at later stage can generate YCrO 3 ，YCrO 3 Compressive stress was generated on the matrix phase grains (YCrO was not found in XRD analysis) 3 Peak, causeWhen the solubility of this phase in the heterogeneous mixture is lower than the limit of XRD detection, there is no peak on XRD), the scale tends to crack and peel with the accumulation of stress, thus resulting in deterioration of the oxidation resistance of the coating layer. Thus, 0.5wt% of Y is optionally added 2 O 3 The new Co-based coatings of (a) perform best.
The above-described embodiments are only preferred embodiments of the present invention and are not intended to limit the present invention. Various changes and modifications can be made by those skilled in the art, and any modification, equivalent replacement, and improvement made within the principle of the present invention should be included in the scope of the present invention.
Claims (3)
1. The corrosion-resistant and high-temperature oxidation-resistant Co-based high-temperature alloy coating is characterized in that the preparation method of the coating is a plasma cladding technology, and the coating is prepared on the surface of Q235;
the coating comprises the following components in percentage by mass: 1.16 wt% C, 30.19 wt% Cr, 1.09 wt% Si, 2.50 wt% Ni, 2.54 wt% Fe, 0.15 wt% Mo, 4.47 wt% W, 0.5wt% Y 2 O 3 The balance being Co;
the plasma cladding technology comprises the following technological parameters: the working current is 90-95A, the plasma gas flow is 1.5-2L/min, the powder feeding speed is 8-9 r/s, the protective gas flow is 4-10L/min, the welding speed is 3-4 mm/s, the progressive distance is 2.5-3 mm, and the powder feeding gas flow is 2-2.5L/min.
2. The Co-based superalloy coating with corrosion resistance and high temperature oxidation resistance as claimed in claim 1, wherein the raw material powder of the coating element is 100-150 mesh.
3. The Co-based superalloy coating of claim 1, wherein the plasma overlay device is a plasma arc powder surfacing machine, model DML-03 AD.
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| CN104195548A (en) * | 2014-09-11 | 2014-12-10 | 王晓飚 | Zinc-corrosion-resistant coating cobalt-based alloy powder for laser cladding |
| CN108823564A (en) * | 2018-07-04 | 2018-11-16 | 湖南工业大学 | A method of corrosion-inhibiting coating is prepared using laser melting and coating technique |
| CN112760640A (en) * | 2020-12-25 | 2021-05-07 | 重庆机电增材制造有限公司 | Valve core of regulating valve and laser strengthening manufacturing method thereof |
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- 2021-07-29 CN CN202110866781.2A patent/CN113699415B/en active Active
Patent Citations (6)
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| CN101187022A (en) * | 2007-12-11 | 2008-05-28 | 沈阳大陆激光技术有限公司 | Laser cladding Co-based alloy powder for conductor roll |
| CN101444981A (en) * | 2008-12-30 | 2009-06-03 | 东北大学 | In-situ preparation of cobalt-base alloy gradient coating on aldary surface through laser induction, and method thereof |
| CN102990058A (en) * | 2012-12-18 | 2013-03-27 | 江苏新亚特钢锻造有限公司 | Oxide particle reinforced laser-clad high abrasion resistance cobalt-base alloy powder and preparation method thereof |
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| CN108823564A (en) * | 2018-07-04 | 2018-11-16 | 湖南工业大学 | A method of corrosion-inhibiting coating is prepared using laser melting and coating technique |
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