CN113699415A - Novel Co-based high-temperature alloy coating resistant to corrosion and high-temperature oxidation and preparation method thereof - Google Patents
Novel Co-based high-temperature alloy coating resistant to corrosion and high-temperature oxidation and preparation method thereof Download PDFInfo
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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
-
- 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
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Abstract
本发明公开了一种抗腐蚀、抗高温氧化的新型Co基高温合金涂层及其制备方法。采用等离子熔覆技术在Q235上制备Co基和本发明新型Co基涂层，通过计算稀释率、电化学实验和氧化实验来对比涂层的性能。结果表明添加0.5wt％Y2O3的新型Co基高温合金涂层的耐蚀性远高于未添加Y2O3的Co基高温合金涂层。在1000℃条件下进行循环氧化，添加了0.5wt％Y2O3的Co基高温合金涂层的氧化层致密，具有优良的保护性，因此本发明制备的新型Co基高温合金涂层具有良好的高温抗氧化性能和耐腐蚀性。
The invention discloses a novel Co-based superalloy coating with anti-corrosion and high-temperature oxidation resistance and a preparation method thereof. Co-based and the new Co-based coatings of the present invention were prepared on Q235 by plasma cladding technology, and the performance of the coatings was compared by calculating dilution rate, electrochemical experiments and oxidation experiments. The results show that the corrosion resistance of the new Co-based superalloy coating with 0.5wt% Y2O3 is much higher than that of the Co - based superalloy coating without Y2O3 . Cyclic oxidation is carried out at 1000°C, and the oxide layer of the Co-based superalloy coating with 0.5wt% Y 2 O 3 added is dense and has excellent protection, so the new Co-based superalloy coating prepared by the present 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 novel Co-based high-temperature alloy coating with corrosion resistance and high-temperature oxidation resistance 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 novel Co-based high-temperature alloy coating with corrosion resistance and high-temperature oxidation resistance and a preparation method thereof, and aims to prepare a Co-based alloy coating which has large area, good combination with a Q235 matrix and low cost, meets the high-temperature resistance and oxidation resistance requirements on the surface of Q235 with low cost.
The invention is realized by the following technical scheme:
corrosion resistanceThe novel Co-based high-temperature alloy coating with corrosion resistance and high-temperature oxidation resistance 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% Y2O3And the balance being Co.
Further, the coating element 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, 0.5 wt% Y2O3And 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 high-temperature alloy is positive, the addition of Si inhibits the outward diffusion of metal ions and the inward diffusion of oxygen ions, and the existence of Si promotes Cr2O3So that continuous Cr can be rapidly formed2O3And 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 Y2O3Contains rare earth element Y, so that it not only can strengthen alloy, but also can greatly improve its oxidation resistance. Thus, Y is added to the Co-based superalloy2O3The 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 added2O3Is favorable for the corrosion resistance and high-temperature oxidation resistance of the Co-based high-temperature alloy coating, and proper amount of Y2O3The 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 Y2O3But rather coarsens the grains and excess Y during high temperature oxidation2O3Will react with Cr2O3Formation of YCrO3The 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 coating2O3Should not be too high, so that Y is added2O3The 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 8-9r/s, the protective gas flow is 4-10L/min, the welding speed is 3-4mm/s, the progressive distance is 2.5-3mm, 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, and the model is 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 Y2O3Y in the coating layer2O3The particles can be used as oxides, especially Cr2O3Thereby promoting Cr2O3Is performed. At Y2O3In an alloy with a content of 0.5 wt.%, more spinel oxide, i.e. NiCr, is formed during the oxidation cycle2O4And CoCr2O4And the presence of spinel oxides reduces oxidationThe rate. Furthermore, Y2O3The 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 0.5 wt% of Y2O3Cross-sectional SEM images of Co-based superalloy coatings.
FIG. 4 shows no addition of Y2O3Adding 0.5 wt% of Y2O3And adding 1 wt% of Y2O3SEM image of the near surface of the Co-based superalloy coating.
FIG. 5 shows no addition of Y2O3Adding 0.5 wt% of Y2O3And adding 1 wt% of Y2O3Polarization curve of the Co-based superalloy coating.
FIG. 6 shows no addition of Y2O3Adding 0.5 wt% of Y2O3And adding 1 wt% of Y2O3The weight gain curve of the Co-based superalloy at 1000 ℃ cyclic oxidation and (G)+)2And oxidation time.
FIG. 7 shows no addition of Y2O3Adding 0.5 wt% of Y2O3And adding 1 wt% of Y2O3Cross-sectional SEM images of Co-based superalloys at 1000 deg.c cyclic oxidation.
FIG. 8 shows no addition of Y2O3Adding 0.5 wt% of Y2O3And adding 1 wt% of Y2O3The 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
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 120min 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 Y2O3Homogenizing 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, properly adjusting experimental parameters to prepare a novel Co-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
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 0.5 wt% of Y2O3Based on CoThe SEM image of the section of the high-temperature alloy coating shows that the coating is tightly combined with the substrate without cavities and gaps, which indicates that 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, 0.5 wt% of Y is added2O3The 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 0.5 wt% of Y is added2O3The coating surface is denser.
Cutting the sample into 10X 3mm blocks according to the electrochemical test standard, welding 20cm 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 begins to be measured, the sample is soaked in the corrosion solution until the open-circuit self-corrosion potential is stable, the scanning speed in the experimental process is 0.5mV/s, and the scanning range is-2V- + 2V.
Y is added in the invention2O3The corrosion resistance of the post-coating is improved, wherein 0.5 wt% of Y is added in the electrochemical corrosion of the novel Co-based high-temperature alloy coating2O3The 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
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+)2Graph with time t. It can be seen that 0.5 wt% Y is added2O3The oxidation performance of the novel Co-based coating is the best.
FIG. 7 is an oxidized cross-sectional view of the coating with the addition of 0.5 wt% Y2O3Y in the coating2O3The particles can be used as oxides, especially Cr2O3Thereby promoting Cr2O3Is performed. As can be seen in the figure, at Y2O3In an alloy with a content of 0.5 wt.%, more spinel oxide, i.e. NiCr, is formed during the oxidation cycle2O4And CoCr2O4. The results show that the presence of spinel oxide reduces the oxidation rate. Furthermore, Y2O3The addition of (2) improves the adhesion and spalling resistance of the oxide skin, and reduces the Cr-poor area. While adding 1 wt% of Y2O3In the coating, the oxidation resistance is rather lowered because a sufficient amount of Y is added to the coating2O3High-temperature oxidation at later stage can generate YCrO3，YCrO3Compressive stress was generated on the matrix phase grains (YCrO was not found in XRD analysis)3A peak, because there is no peak on XRD when the solubility of this phase in the heterogeneous mixture is lower than the limit of XRD detection), the scale tends to crack and peel with the accumulation of stress, resulting in deterioration of the oxidation resistance of the coating layer. Thus, 0.5 wt% of Y is optionally added2O3The 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 (6)
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