CN117488160A - Co-ordinated L1 2 Phase-reinforced high-strength cavitation-corrosion-resistant multi-principal element alloy, and preparation method and application thereof - Google Patents
Co-ordinated L1 2 Phase-reinforced high-strength cavitation-corrosion-resistant multi-principal element alloy, and preparation method and application 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
- C22C30/00—Alloys containing less than 50% by weight of each constituent
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
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Abstract
The invention discloses a common L1 2 Phase-reinforced high-strength cavitation-corrosion-resistant multi-principal element alloy, and a preparation method and application thereof. The chemical components of the multi-principal element alloy of the present invention include, in atomic percent (at.%): 33-40% of Ni, 25-29% of Co, 25-29% of Cr, 3-6% of Al and 4-6% of Ti. The microstructure of the alloy comprises an FCC matrix phase and uniformly distributed spherical L1 2 The nano precipitated phase has excellent room temperature tensile mechanical properties and shows excellent cavitation-corrosion resistance in 3.5wt.% NaCl solution. The multi-principal element alloy disclosed by the invention has excellent performance, meets the urgent requirements of structure-function integrated materials, has a wide application prospect, and has the advantages of simple process and low manufacturing cost because the multi-principal element alloy can be prepared by a casting method.
Description
Technical Field
The invention belongs to the technical field of advanced metal materials, and in particular relates to a common L1 2 Phase-reinforced high-strength cavitation-corrosion-resistant multi-principal element alloy, and a preparation method and application thereof.
Background
Multiple principal componentsGold is an alloy with unique atomic structural characteristics, which is formed by mixing a plurality of alloy elements in equal atomic ratios or approximate equal atomic ratios, and shows excellent properties which are incomparable with the traditional alloy, such as high strength, high hardness, corrosion resistance, oxidation resistance, irradiation resistance, excellent electromagnetic properties and the like. As-cast NiCoCr and other atomic ratio multi-element alloys are single FCC solid solution phases, and have extremely excellent impact toughness and corrosion resistance, but the yield strength of the alloy is relatively low under the room temperature condition, so that the application of the CoCrNi multi-element alloy in industry is greatly limited. The strength of the CoCrNi multi-principal element alloy is improved while good plasticity is maintained, and the synergistic improvement of strength and plasticity is realized, so that the CoCrNi multi-principal element alloy is the most critical research target at present. At present, researchers try to control the structure and mechanical properties of CoCrNi multi-element alloy by alloying Al and Ti elements, and reveal the rule and mechanism of influence of the alloying elements on the structure and mechanical properties of the multi-element alloy system. Lu Yiping et Al (Lu W, luo X, yang Y, materials Chemistry and Physics.2019,238: 121841.) from university of Conn's university, by adding an Al element to NiCoCrAl x (x=0 to 30 at.%) multi-principal alloys were studied. The results show that NiCoCrAl with FCC+BCC dual phase structure 19 The alloy has the best performance, and the compression yield strength, the breaking strength and the elongation reach 1226MPa,2542MPa and 21.97 percent respectively. Yang Tao et al (Y.L.Zhao a, T.Yang a, Y.Tong, acta materials, 2017, 138:72-82.) from university of hong Kong City studied the rolled annealed state (CoCrNi) 94 Al 3 Ti 3 The phase composition, microstructure and mechanical property of the multi-principal element alloy show that the addition of Al and Ti elements can obviously improve the mechanical property of the alloy, and the yield strength of the alloy is improved by 70 percent compared with that of the CoCrNi multi-principal element alloy, so that the strengthening effect is obvious. The research results fully prove that the strength of the CoCrNi-based multi-element alloy can be effectively improved by introducing Al and Ti elements and reasonably regulating the composition proportion of the Al and Ti elements, and the plasticity is maintained within an acceptable range. However, in introducing L1 2 Precipitation of the phase is also accompanied by formation of other secondary phases, such as brittle Heusler phases, laves phases and cellular L1 formed at grain boundaries 2 And (3) phase (C). The presence of these second phases is an alloyThe mechanical properties of (2) are adversely affected and need to be considered and controlled in the alloy design. In addition, most of the existing alloys with excellent performance rely on long-process thermo-mechanical processing technologies, such as cold rolling, hot rolling, annealing and the like, and the long-process processing processes are time-consuming, labor-consuming and production cost-increasing, and if an as-cast alloy or an as-cast+short-process heat treatment which can be directly put into use can be developed, the production efficiency can be effectively improved, and the economic advantage is further achieved.
Critical components (such as a propeller, a rudder, a turbine and the like) of ships, chemical machinery, ocean platforms and the like are in a severe environment in seawater for a long time, wherein the seawater is a natural electrolyte with complex components, and the seawater is corroded by microorganisms and chloride ions in the seawater after being soaked in the seawater for a long time, so that the critical components are seriously damaged. In addition, waves, tidal water and the like in the marine environment can generate low-frequency reciprocating impact stress on the metal components, and cavitation can seriously reduce the performance of the material and reduce the service life of the material. Cavitation is the repeated impact to the material surface due to collapse of bubbles on the surface of the flow-through member, which causes fatigue damage to the material and further degradation. In practical industrial application, most of the equipment used in the ocean is made of nickel-aluminum bronze and stainless steel, but the seawater cavitation corrosion resistance of the two materials is close to the bottleneck, and the upgrading or updating of key equipment such as ships, ocean platforms and the like is hindered. In addition, the frequent damage and replacement of ship components bring about huge economic loss to the industry. Therefore, development of a novel alloy material having both excellent mechanical properties and excellent cavitation-corrosion resistance to seawater is highly demanded.
The invention selects Al and Ti elements as alloying elements, researches phase composition, microstructure, room temperature mechanical property and cavitation erosion resistance and screens out coherent L1 through alloy component design and accurate regulation and control 2 Phase strengthened high strength and high toughness cavitation erosion-corrosion resistant multi-element alloy. The NiCoCrAlTi multi-principal element alloy component with the best comprehensive performance is searched, the requirement of the structural-functional integrated alloy material for key parts such as ships, ocean platforms and the like is met, and the NiCoCrAlTi multi-principal element alloy component is expected to be applied to the aspect of replacing the traditional material for the overcurrent parts, and has huge application prospect.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a nano precipitated phase reinforced high-strength high-toughness corrosion-resistant coherent L1 2 Phase-strengthened high-strength cavitation-corrosion-resistant multi-principal element alloy and a preparation method thereof. The invention is based on a NiCoCr single-phase FCC alloy system, selects Al and Ti elements as alloying elements, and regulates and controls the atomic percentages of the Ni element, the Al element and the Ti element in the multi-principal element alloy through alloy component design and accurate regulation and control to obtain common L1 with excellent mechanical property and good cavitation erosion resistance at the same time 2 Phase-strengthened high-strength cavitation-corrosion-resistant multi-principal element alloy material. Research on phase composition, microstructure, room temperature mechanical property and cavitation erosion resistance and screening out coherent L1 2 Phase strengthened high strength and high toughness cavitation erosion-corrosion resistant multi-element alloy. The NiCoCrAlTi multi-principal element alloy component with the best comprehensive performance is searched, the technical problem that the mechanical performance and cavitation erosion resistance and the like are not matched in the existing alloy design is solved, and the requirements of structural-functional integrated alloy materials of key parts such as ships, ocean platforms and the like are met.
Another object of the invention is to produce coherent L1 by casting 2 Phase-reinforced high-strength high-toughness cavitation-corrosion-resistant multi-principal element alloy material;
a further object of the present invention is to combine L1, which is high in toughness and cavitation-erosion resistance 2 The phase reinforced high-strength and high-toughness cavitation-corrosion-resistant multi-principal element alloy is used for preparing cavitation-corrosion-resistant key parts.
The aim of the invention is achieved by the following technical scheme:
co-ordinated L1 2 A phase strengthened, high strength, cavitation-corrosion resistant multi-principal component alloy, the composition of the material comprising, in atomic percent (at.%): 33-40% of Ni, 25-29% of Co, 25-29% of Cr, 3-6% of Al and 4-6% of Ti.
Preferably, the consensus L1 2 The phase-reinforced high-strength cavitation-corrosion-resistant multi-principal element alloy consists of the following components in percentage by atom: 33-40% of Ni, 25-28% of Co, 25-28% of Cr, 3-6% of Al and 4-6% of Ti.
Preferably, the consensus L1 2 The phase composition of the phase reinforced high-strength cavitation erosion-corrosion-resistant multi-principal element alloy is FCC matrix phase and L1 2 Nano precipitated phase, co-operating L1 2 The nano precipitated phase is dispersed and distributed in the FCC matrix phase, and the grain boundary has no second phase, wherein the FCC matrix phase is rich in Ni-Co-Cr element, L1 2 The nano precipitated phase component is (Ni, co, cr) 3 (Ti,Al)。
Preferably, the consensus L1 2 The phase-strengthened high-strength, cavitation-corrosion-resistant multi-element alloy has excellent cavitation-corrosion resistance, and cavitation-corrosion resistance weight loss in a 3.5wt.% NaCl solution is not higher than 1.9mg/10h.
Preferably, the consensus L1 2 The phase reinforced high-strength and cavitation erosion-resistant multi-principal element alloy has excellent mechanical properties, the room temperature tensile yield strength is 800-950 MPa, the tensile strength is 1000-1250 MPa, and the elongation after breaking is 14-30%.
The above-mentioned coherent L1 2 The preparation method of the phase-reinforced high-strength cavitation-corrosion-resistant multi-principal-element alloy is carried out by casting.
Preferably, the casting method is a vacuum magnetic suspension smelting method, comprising the following steps:
(1) According to the common rule L1 2 Preparing raw materials of the phase-reinforced high-strength cavitation-corrosion-resistant multi-principal element alloy by atomic percent;
(2) Carrying out vacuum magnetic suspension smelting on the raw materials prepared in the step (1), cooling, and taking out cast ingots;
(3) Repeatedly carrying out vacuum magnetic suspension smelting on the cast ingot in the step (2) for 3-5 times, and turning over the cast ingot before smelting each time.
Further preferably, the parameters of the vacuum magnetic levitation melting in the steps (2) and (3) are as follows: the temperature rising rate is 10-20 ℃/min, the smelting temperature is 1500-2600 ℃ and the smelting time is 40-60 min.
Further preferably, the cooling time in the step (2) is 30-60 min.
Further preferably, the feedstock of step (1) comprises a pure metal of Ni, co, cr, al and Ti or a master alloy comprising Ni, co, cr, al and Ti; the purity of the pure metal of Ni, co, cr, al and Ti or the master alloy comprising Ni, co, cr, al and Ti is above 99.9 wt.%. Aims to avoid influencing alloy performance due to impurities and the like in the smelting process.
Further preferably, the vacuum environment of the vacuum magnetic suspension smelting in the steps (2) and (3) is that the reverse charging protective atmosphere is 0.03-0.10 MPa after the vacuum is pumped to 0.005-0.008 Pa.
More preferably, the protective atmosphere is argon.
The nano precipitated phase reinforced high-strength high-toughness cavitation-corrosion-resistant coherent L1 2 The application of the phase reinforced high-strength and cavitation-corrosion-resistant multi-principal element alloy in preparing cavitation-corrosion-resistant and/or corrosion-resistant parts.
Compared with the prior art, the invention has the following advantages:
(1) According to the invention, the multi-principal element alloy with good corrosion resistance is obtained by reasonable proportioning by utilizing the characteristics of good oxidation resistance and corrosion resistance of elements such as Ni, co, cr, al, ti. The nickel-aluminum bronze alloy has more outstanding corrosion resistance than the traditional common nickel-aluminum bronze material in severe working environment of seawater, has cavitation corrosion resistance-corrosion weight loss of not more than 1.9mg/10h in 3.5wt.% NaCl solution, and has mass loss of 5.7mg/10h under the same test condition.
(2) The invention is realized by the method of the common L1 2 Component regulation of phase-reinforced high-strength cavitation-corrosion-resistant multi-principal element alloy, and introduction of spherical L1 into FCC matrix phase 2 The nano precipitated phase is used for improving the mechanical property of the alloy material, the designed alloy material has the room temperature tensile yield strength of 800-950 MPa, the ultimate tensile strength of 1000-1250 MPa and the elongation after fracture of 14-30%, and can meet the urgent requirements of the alloy material with integrated structure and function of key components such as ships, ocean platforms and the like.
(3) The invention can obtain the multi-principal element alloy with high strength and toughness and corrosion resistance meeting the requirements by using the casting method, has simple preparation process, short flow and low energy consumption, and has good development prospect.
Drawings
FIG. 1 shows XRD patterns of Ni-Co-Cr-Al-Ti multi-principal component alloys prepared in examples 1-3 of the present invention.
FIG. 2 is a drawing of Ni prepared in example 1 of the present invention 35 Co 27.5 Cr 27.5 Al 5 Ti 5 BSE and TEM pictures of multi-principal element alloys.
FIG. 3 is a drawing of Ni prepared in example 2 of the present invention 33 Co 28 Cr 28 Al 3 Ti 6 BSE and TEM pictures of multi-principal element alloys.
FIG. 4 is a drawing of Ni prepared in example 3 of the present invention 40 Co 25 Cr 25 Al 6 Ti 4 BSE and TEM pictures of multi-principal element alloys.
FIG. 5 is a comparative example 1Ni of the present invention 31.4 Co 31.3 Cr 31.3 Al 3 Ti 3 Comparative example 2Ni 44 Co 23 Cr 23 Al 7 Ti 3 And comparative example 3Ni 36 Co 26 Cr 25 Al 4 Ti 9 XRD pattern of the multi-principal component alloy.
FIG. 6 is a comparative example 1Ni of the present invention 31.4 Co 31.3 Cr 31.3 Al 3 Ti 3 BSE pictures of multi-principal alloys.
FIG. 7 is a comparative example 2Ni of the present invention 44 Co 23 Cr 23 Al 7 Ti 3 BSE pictures of multi-principal alloys.
FIG. 8 is a comparative example 3Ni of the present invention 36 Co 26 Cr 25 Al 4 Ti 9 BSE and TEM pictures of multi-principal element alloys.
FIG. 9 is a plot of tensile stress versus strain at room temperature for the high strength and cavitation-erosion resistant multi-master alloys prepared in examples 1-3 and the multi-master alloys of comparative examples 1-3 of the present invention.
FIG. 10 is a cavitation-corrosion weight loss comparison plot of the high strength and cavitation-corrosion resistant multi-master alloys prepared in examples 1-3 of the present invention and the multi-master alloys of comparative examples 1-3 in 3.5wt.% NaCl solution.
Detailed Description
The following description of specific embodiments of the invention will be given in connection with examples, it being evident that the embodiments described are part of the embodiments of the invention, to which the practice and protection of the invention are not limited. It should be noted that the following descriptions and processes, unless specifically stated otherwise, are all possible embodiments or examples which may be realized or understood by those skilled in the art with reference to the present technology without inventive effort.
The structural characterization, mechanical property and cavitation erosion resistance test information of the high-strength high-toughness cavitation erosion-resistance multi-principal element alloy and the comparative alloy prepared by the invention are as follows:
(1) And (3) phase analysis: phase identification was performed using a Bruker-D8 Advance, germany type Cu K alpha ray diffractometer, with a scan angle ranging from 20℃to 100℃at a speed of 2℃per minute.
(2) Microstructure: the high strength and cavitation-corrosion resistant multi-principal component alloys prepared by the present invention and the multi-principal component alloys of comparative examples 1 and 2 were examined for their microstructures at different magnification using a scanning electron microscope (SEM, NOVANANOSEM, usa) and a transmission electron microscope (FEI Talos F200X).
(3) Mechanical properties: the mechanical property test was carried out by room temperature tensile test, and 3 tests were carried out for each alloy.
(4) Cavitation and cavitation-erosion resistance: cavitation and cavitation-corrosion experiments were performed on an ultrasonic vibration cavitation tester with reference to the GB/T6383-2009 standard, with a test solution of 3.5wt.% NaCl solution.
Further details are provided below in connection with specific examples.
Example 1
The vacuum magnetic suspension smelting is adopted to prepare a high-strength cavitation-corrosion-resistant multi-principal element alloy with enhanced nano precipitated phase, and the alloy has good casting performance and comprehensive mechanical property, and the chemical components are as follows, in atom percent, 35 percent of Ni; 27.5% of Co; 27.5% of Cr; 5% of Al; 5% of Ti. The method specifically comprises the following steps:
(1) Sample preparation: ni, co, cr, al, ti granular pure metal raw material with purity higher than 99.9wt.% is selected. Before batching, the raw materials are polished by sand paper to remove oxide films on the surface layer, then surface impurities are cleaned by ultrasonic waves, the atomic ratio is converted and calculated into the percentage of the mass of each element to the total mass during batching, and then the percentage of the mass of each element is weighed by a high-precision electronic balance.
(2) Vacuumizing: the hearth is cleaned, and the influence of other impurities is reduced. And then placing the prepared metal raw materials into a crucible in the order of lower low melting point and upper high melting point, so as to avoid volatilization and splashing of the low melting point metal in the smelting process as much as possible. The furnace door is closed after the crucible is loaded, the tightness of the furnace chamber is ensured, the vacuum pumping is started, and high-purity argon (0.07 MPa) is filled after the high vacuum is pumped to 0.005 Pa. In order to reduce the oxygen content in the furnace chamber as much as possible, the steps of vacuumizing and filling argon are repeated twice.
(3) Smelting: the heating rate is 15 ℃/min, the smelting is started after the heating is carried out to 1950 ℃, the smelting time is 60min, the cast ingot is taken out after the cast ingot is cooled to the room temperature along with the furnace, the cast ingot is turned over and then is charged again, and in order to ensure the uniformity of alloy components, the smelting step is repeated for 3 times.
(4) Shaping: pouring the molten metal into a graphite die after the alloy is smelted for 3 times, cooling to room temperature along with a furnace, and taking out an ingot to obtain the multi-principal element alloy ingot required by final research.
The multi-principal element alloy in this example was subjected to phase analysis to obtain an X-ray diffraction pattern as shown in FIG. 1, and the XRD results were combined with the BSE and TEM pictures of FIG. 2, ni prepared in this example 35 Co 27.5 Cr 27.5 Al 5 Ti 5 The multi-principal element alloy consists of an FCC matrix phase and L1 2 The nanometer precipitated phase is composed of spherical nanometer precipitated phases which are uniformly distributed in the interior of the crystal grains. Since the precipitated phase is in the nano-size scale, the whole appearance of the alloy is presented as an equiaxed crystal structure. The room temperature tensile results are shown in FIG. 9, and the multi-element alloy prepared in this example has a room temperature tensile yield strength of 916MPa, an ultimate tensile strength of 1220MPa, and an elongation after break of 21.5%. For Ni in this embodiment 35 Co 27.5 Cr 27.5 Al 5 Ti 5 Cavitation-corrosion test was conducted on the multi-principal component alloy, and the experimental results are shown in FIG. 10, and the mass of the multi-principal component alloy prepared in this example was reduced by 1.1mg after cavitation-corrosion in 3.5wt.% NaCl solution for 10 hours, which proves that the multi-principal component alloy prepared in example 1The multi-principal component alloy exhibits excellent cavitation-erosion resistance.
Example 2
Preparing a multi-principal element alloy with cavitation erosion resistance, good casting performance and comprehensive mechanical property by adopting vacuum induction melting, wherein the chemical components are 33% of Ni in atomic percent; 28% of Co; 28% of Cr; 3% of Al; 6% of Ti. The method specifically comprises the following steps:
(1) Sample preparation: ni, co, cr, al, ti granular pure metal raw material with purity higher than 99.9wt.% is selected. Before batching, the raw materials are polished by sand paper to remove oxide films on the surface layer, then surface impurities are cleaned by ultrasonic waves, the atomic ratio is converted and calculated into the percentage of the mass of each element to the total mass during batching, and then the percentage of the mass of each element is weighed by a high-precision electronic balance.
(2) Vacuumizing: the hearth is cleaned, and the influence of other impurities is reduced. And then placing the prepared metal raw materials into a crucible in the order of lower low melting point and upper high melting point, so as to avoid volatilization and splashing of the low melting point metal in the smelting process as much as possible. The furnace door is closed after the crucible is loaded, the tightness of the furnace chamber is ensured, the vacuum pumping is started, and high-purity argon (0.07 MPa) is filled after the high vacuum is pumped to 0.005 Pa. In order to reduce the oxygen content in the furnace chamber as much as possible, the steps of vacuumizing and filling argon are repeated twice.
(3) Smelting: the heating rate is 15 ℃/min, the smelting is started after the heating is carried out to 1950 ℃, the smelting time is 60min, the cast ingot is taken out after the cast ingot is cooled to the room temperature along with the furnace, the cast ingot is turned over and then is charged again, and in order to ensure the uniformity of alloy components, the smelting step is repeated for 3 times.
(4) Shaping: pouring the molten metal into a graphite die after the alloy is smelted for 3 times, cooling to room temperature along with a furnace, and taking out an ingot to obtain the multi-principal element alloy ingot required by final research.
The multi-principal element alloy of this example was subjected to phase analysis to obtain an X-ray diffraction pattern as shown in FIG. 1, and combined with BSE and TEM images of FIG. 3 to prepare Ni 33 Co 28 Cr 28 Al 3 Ti 6 The multi-principal element alloy consists of an FCC matrix phase and L1 2 Precipitated phase composition, spherical nano-precipitationThe outlet phase is uniformly distributed in the interior of the crystal grains. Since the precipitated phase is in the nano-size scale, the whole appearance of the alloy is represented by an equiaxed dendritic structure. The room temperature tensile result is shown in FIG. 9, and the yield strength is 863MPa, the tensile strength is 1124MPa, and the elongation after breaking is 23.2%. Cavitation-erosion test results As shown in FIG. 10, the multi-principal component alloy was reduced in mass by 1.7mg after cavitation-erosion in 3.5wt.% NaCl solution for 10 hours, demonstrating example 2Ni 33 Co 28 Cr 28 Al 3 Ti 6 The multi-principal element alloy has excellent cavitation erosion resistance and corrosion resistance.
Example 3
Preparing a multi-principal element alloy with cavitation erosion resistance, good casting performance and comprehensive mechanical property by adopting a vacuum induction melting method, wherein the chemical components are calculated as (at%) Ni is 40%; 25% of Co; 25% of Cr; 6% of Al; 4% of Ti. The specific preparation process comprises the following steps:
(1) Sample preparation: ni, co, cr, al, ti granular pure metal raw material with purity higher than 99.9wt.% is selected. Before batching, the raw materials are polished by sand paper to remove oxide films on the surface layer, then surface impurities are cleaned by ultrasonic waves, the atomic ratio is converted and calculated into the percentage of the mass of each element to the total mass during batching, and then the percentage of the mass of each element is weighed by a high-precision electronic balance.
(2) Vacuumizing: the hearth is cleaned, and the influence of other impurities is reduced. And then placing the prepared metal raw materials into a crucible in the order of lower low melting point and upper high melting point, so as to avoid volatilization and splashing of the low melting point metal in the smelting process as much as possible. The furnace door is closed after the crucible is loaded, the tightness of the furnace chamber is ensured, the vacuum pumping is started, and high-purity argon (0.07 MPa) is filled after the high vacuum is pumped to 0.005 Pa. In order to reduce the oxygen content in the furnace chamber as much as possible, the steps of vacuumizing and filling argon are repeated twice.
(3) Smelting: the heating rate is 15 ℃/min, the smelting is started after the heating is carried out to 1950 ℃, the smelting time is 60min, the cast ingot is taken out after the cast ingot is cooled to the room temperature along with the furnace, the cast ingot is turned over and then is charged again, and in order to ensure the uniformity of alloy components, the smelting step is repeated for 3 times.
(4) Shaping: pouring the molten metal into a graphite die after the alloy is smelted for 3 times, cooling to room temperature along with a furnace, and taking out an ingot to obtain the multi-principal element alloy ingot required by final research.
The multi-principal element alloy in this example was subjected to phase analysis to obtain an X-ray diffraction pattern of FIG. 1, and a microstructure of FIG. 4 was combined to obtain Ni as prepared 40 Co 25 Cr 25 Al 6 Ti 4 The multi-principal element alloy consists of FCC matrix phase and L1 2 The precipitated phase is composed of spherical nano precipitated phases which are uniformly distributed in the interior of the crystal grains. Since the precipitated phase is in the nano-size scale, the whole appearance of the alloy is represented by an equiaxed dendritic structure. The room temperature tensile result is shown in FIG. 9, and the yield strength is 836MPa, the tensile strength is 1043MPa, and the elongation after breaking is 14.9%. Cavitation-erosion test results are shown in FIG. 10, ni 40 Co 25 Cr 25 Al 6 Ti 4 The mass of the multi-principal element alloy is reduced by 1.9mg after cavitation erosion in 3.5wt.% NaCl solution for 10 hours, and the cavitation erosion resistance of the material is proved to be very excellent.
To better illustrate the comprehensive mechanical properties and cavitation-corrosion resistance of the Ni-Co-Cr-Al-Ti series block multi-principal element alloy of the invention, ni is used 31.4 Co 31.3 Cr 31.3 Al 3 Ti 3 、Ni 44 Co 23 Cr 23 Al 7 Ti 3 (FCC matrix phase+BCC second phase) and Ni 36 Co 26 Cr 25 Al 4 Ti 9 The (FCC matrix phase + eta second phase) multi-principal alloys were used as comparative example 1, comparative example 2 and comparative example 3, respectively.
Comparative example 1
Selecting Ni, co, cr, al, ti pure metal raw materials or master alloy with purity of more than 99.9wt.% as raw materials, and adding 31.4% of Ni according to the atomic percentage; 31.3% of Co; 31.3% of Cr; 3% of Al; 3% of Ti. Selecting a granular pure metal raw material with purity higher than 99.9 wt%, polishing the raw material with sand paper to remove an oxide film on the surface layer before batching, cleaning surface impurities with ultrasonic waves, converting atomic ratio into weight percentage of each element to total weight during batching, and weighing with a high-precision electronic balanceAmount of the components. The hearth is cleaned, and the influence of other impurities is reduced. And then placing the prepared metal raw materials into a crucible in the order of lower low melting point and upper high melting point, so as to avoid volatilization and splashing of the low melting point metal in the smelting process as much as possible. The furnace door is closed after the crucible is loaded, the tightness of the furnace chamber is ensured, the vacuum pumping is started, and high-purity argon (0.07 MPa) is filled after the high vacuum is pumped to 0.005 Pa. In order to reduce the oxygen content in the furnace chamber as much as possible, the steps of vacuumizing and filling argon are repeated twice. And (3) starting smelting, wherein the heating rate of heating is 15 ℃/min, starting smelting after heating to 1950 ℃, the smelting time is 60min, taking out the cast ingot after the cast ingot is cooled to room temperature along with a furnace, overturning the cast ingot, and re-charging the cast ingot, and repeating the smelting step for 3 times to ensure the uniformity of alloy components. Pouring molten metal into a graphite die after smelting for 3 times, cooling to room temperature along with a furnace, taking out an ingot, and finally obtaining Ni 31.4 Co 31.3 Cr 31.3 Al 3 Ti 3 Multi-principal element alloy ingot casting.
Ni in comparative example 31.4 Co 31.3 Cr 31.3 Al 3 Ti 3 As can be seen from the XRD pattern of FIG. 5 and the BSE pattern of FIG. 6, the multi-principal element alloy exhibits an FCC matrix phase +L1 2 Precipitated phase structure due to L1 2 The precipitated phase has a small size, and is not observed in BSE pictures, and is expressed as an FCC equiaxed crystal structure. Ni (Ni) 31.4 Co 31.3 Cr 31.3 Al 3 Ti 3 As shown in FIG. 9, the multi-element alloy has a yield strength of 540MPa, a tensile strength of 748MPa, and an elongation after breaking of 40.9%, and when the Co and Cr elements are higher and the same as the Ni element, the enhancement effect caused by adding Al and Ti elements is generally limited, and the improvement of the yield strength of the alloy is very limited. Cavitation-corrosion mass loss of the comparative multi-principal element alloy in 3.5wt.% NaCl solution was examined using an ultrasonic vibration cavitation tester, and the result showed that the cumulative mass loss (3.6 mg) after cavitation for 10 hours was significantly greater than that of the coherent L1 of the present invention 2 The phase strengthened high strength, cavitation erosion-corrosion resistant multi-principal component alloy is shown in figure 10.
Comparative example 2
Selecting Ni, co, cr, al, ti pure metal raw materials or master alloy with purity of more than 99.9wt.% as raw materials, wherein the raw materials comprise 44% of Ni by atom percent; 23% of Co; 23% of Cr; 7% of Al; ti 3% of the formulation (not within the atomic percentage range specified in the claims of the present invention). Selecting a granular pure metal raw material with the purity higher than 99.9wt.%, polishing the raw material with sand paper to remove an oxide film on the surface layer before batching, cleaning surface impurities with ultrasonic waves, converting the atomic ratio into the mass percentage of each element in the total mass during batching, and weighing by using a high-precision electronic balance. The hearth is cleaned, and the influence of other impurities is reduced. And then placing the prepared metal raw materials into a crucible in the order of lower low melting point and upper high melting point, so as to avoid volatilization and splashing of the low melting point metal in the smelting process as much as possible. The furnace door is closed after the crucible is loaded, the tightness of the furnace chamber is ensured, the vacuum pumping is started, and high-purity argon (0.07 MPa) is filled after the high vacuum is pumped to 0.005 Pa. In order to reduce the oxygen content in the furnace chamber as much as possible, the steps of vacuumizing and filling argon are repeated twice. And (3) starting smelting, wherein the heating rate of heating is 15 ℃/min, starting smelting after heating to 1950 ℃, the smelting time is 60min, taking out the cast ingot after the cast ingot is cooled to room temperature along with a furnace, overturning the cast ingot, and re-charging the cast ingot, and repeating the smelting step for 3 times to ensure the uniformity of alloy components. Pouring molten metal into a graphite die after smelting for 3 times, cooling to room temperature along with a furnace, taking out an ingot, and finally obtaining Ni 44 Co 23 Cr 23 Al 7 Ti 3 Multi-principal element alloy ingot casting.
Ni in comparative example 44 Co 23 Cr 23 Al 7 Ti 3 From the observation of the microstructure of the multi-principal element alloy, it is apparent from the XRD pattern of FIG. 5 and the BSE pattern of FIG. 7 that the alloy exhibits a FCC matrix phase and a BCC second phase structure with a small BCC phase content. As shown in FIG. 9, the tensile strength at room temperature is 531MPa, the tensile strength is 836MPa, the elongation after breaking is 32.1%, and the comparison shows that the common L1 of the invention is increased along with the increase of the Al content 2 The phase-reinforced high-strength high-toughness cavitation-corrosion-resistant multi-principal element alloy has a small amount of BCC phase, and the strength is obviously reduced. Comparative example Ni was tested using an ultrasonic vibration cavitation tester 35 Co 27.5 Cr 27.5 Al 7 Ti 3 Cavitation-corrosion mass loss of the multi-principal element alloy in 3.5wt.% NaCl solution, and the result shows that the accumulated mass loss (4.2 mg) after cavitation corrosion for 10 hours is obviously larger than the coherent L1 of the invention 2 The phase strengthened high strength, cavitation erosion-corrosion resistant multi-principal component alloy is shown in figure 10.
Comparative example 3
Selecting Ni, co, cr, al, ti five pure metal raw materials or master alloy with purity of more than 99.9wt.% as raw materials, wherein the raw materials comprise 36 atomic percent of Ni; 26% of Co; 25% of Cr; 4% of Al; ti 9% of the formulation (not within the atomic percent range specified in the claims of the present invention). Selecting a granular pure metal raw material with the purity higher than 99.9wt.%, polishing the raw material with sand paper to remove an oxide film on the surface layer before batching, cleaning surface impurities with ultrasonic waves, converting the atomic ratio into the mass percentage of each element in the total mass during batching, and weighing by using a high-precision electronic balance. The hearth is cleaned, and the influence of other impurities is reduced. And then placing the prepared metal raw materials into a crucible in the order of lower low melting point and upper high melting point, so as to avoid volatilization and splashing of the low melting point metal in the smelting process as much as possible. The furnace door is closed after the crucible is loaded, the tightness of the furnace chamber is ensured, the vacuum pumping is started, and high-purity argon (0.07 MPa) is filled after the high vacuum is pumped to 0.005 Pa. In order to reduce the oxygen content in the furnace chamber as much as possible, the steps of vacuumizing and filling argon are repeated twice. And (3) starting smelting, wherein the heating rate of heating is 15 ℃/min, starting smelting after heating to 1950 ℃, the smelting time is 60min, taking out the cast ingot after the cast ingot is cooled to room temperature along with a furnace, overturning the cast ingot, and re-charging the cast ingot, and repeating the smelting step for 3 times to ensure the uniformity of alloy components. Pouring molten metal into a graphite die after smelting for 3 times, cooling to room temperature along with a furnace, taking out an ingot, and finally obtaining Ni 36 Co 26 Cr 25 Al 4 Ti 9 Multi-principal element alloy ingot casting.
Ni in comparative example 36 Co 26 Cr 25 Al 4 Ti 9 Microstructure of multi-principal element alloyFrom the XRD pattern of FIG. 5, in combination with the BSE and TEM images of FIG. 8, the alloy exhibits FCC matrix phase and eta second phase structure with less eta phase content. As shown in FIG. 9, the tensile strength at room temperature is 630MPa, the tensile strength is 925MPa, the elongation after breaking is 7.5%, and the comparison shows that the coherent L1 of the invention is increased along with the increase of the Ti content 2 The phase-reinforced high-strength cavitation-corrosion-resistant multi-principal element alloy has a small amount of eta phase, and the strength and the plasticity are obviously reduced. Comparative example Ni was tested using an ultrasonic vibration cavitation tester 36 Co 26 Cr 25 Al 4 Ti 9 Cavitation-corrosion mass loss of the multi-principal element alloy in 3.5wt.% NaCl solution, and the result shows that the accumulated mass loss (3.8 mg) after cavitation corrosion for 10 hours is obviously larger than the coherent L1 of the invention 2 The phase strengthened high strength, cavitation erosion-corrosion resistant multi-principal component alloy is shown in figure 10.
The above description shows that even though the types of the components used for preparing the multi-principal component alloy are the same as the present invention, if the atomic percentages of the components are out of the ranges specified in the present invention, the mechanical properties of the alloy are significantly deteriorated, mainly because other secondary phases are formed which are detrimental to the mechanical properties. Too much Al element promotes the formation of the second BCC phase, while too much Ti element promotes the formation of the eta phase, both phases being brittle phases. In addition, the presence of the second phase can lead to excessive phase interfaces in the material where cracks can propagate in the cavitation-corrosion environment, ultimately leading to spalling of the surface.
The above examples are preferred embodiments of the present invention, and materials, characteristics, etc. well known in the art will not be described in detail. It should be noted that modifications and improvements can be made by those skilled in the art without departing from the invention, and these should also be considered as the scope of the invention, which does not affect the effectiveness and practicality of the implementation of the invention. The protection scope of the invention is subject to the claims, and the specific embodiments and the like in the description can be used for explaining the claims.
Claims (10)
1. Co-ordinated L1 2 Phase strengthThe high-strength and high-toughness cavitation-corrosion-resistant multi-principal element alloy is characterized by comprising the following components in percentage by atom: 33-40% of Ni, 25-29% of Co, 25-29% of Cr, 3-6% of Al and 4-6% of Ti.
2. The co-ordinates L1 of claim 1 2 The phase-reinforced high-strength and cavitation-corrosion-resistant multi-principal element alloy is characterized in that: the alloy consists of the following components in percentage by atom: 33-40% of Ni, 25-28% of Co, 25-28% of Cr, 3-6% of Al and 4-6% of Ti.
3. The co-ordinates L1 of claim 1 2 The phase-reinforced high-strength and cavitation-corrosion-resistant multi-principal element alloy is characterized in that: the coherent L1 2 The phase composition of the phase reinforced high-strength high-toughness cavitation-corrosion-resistant multi-principal element alloy is FCC matrix phase and coherent L1 2 Nano precipitated phase, co-operating L1 2 The nano precipitated phase is dispersed and distributed in the FCC matrix phase, and the grain boundary has no second phase, wherein the FCC matrix phase is rich in Ni-Co-Cr elements and has the same L1 2 The metering of nano precipitated phase is (Ni, co, cr) 3 (Ti,Al)。
4. The co-ordinates L1 of claim 1 2 The phase-reinforced high-strength and cavitation-corrosion-resistant multi-principal element alloy is characterized in that: the coherent L1 2 The phase reinforced high-strength and cavitation erosion-resistant multi-principal element alloy has excellent mechanical properties, the room temperature tensile yield strength is 800-950 MPa, the ultimate tensile strength is 1000-1250 MPa, and the elongation after breaking is 14-30%.
5. The co-ordinates L1 of claim 1 2 The phase-reinforced high-strength and cavitation-corrosion-resistant multi-principal element alloy is characterized in that: the coherent L1 2 The phase-strengthened high-strength, cavitation-corrosion-resistant multi-element alloy has excellent cavitation-corrosion resistance, and the accumulated mass loss after cavitation-corrosion in a NaCl solution of 3.5wt.% for 10 hours is not higher than 1.9mg.
6. A coherent L1 according to any one of claims 1 to 5 2 The preparation method of the phase-reinforced high-strength cavitation-corrosion-resistant multi-principal-element alloy is characterized by comprising the step of casting.
7. The co-ordinates L1 of claim 6 2 The preparation method of the phase-reinforced high-strength cavitation-corrosion-resistant multi-principal-element alloy is characterized by comprising the following steps of:
(1) According to the common rule L1 2 Preparing raw materials of the phase-reinforced high-strength cavitation-corrosion-resistant multi-principal element alloy by atomic percent;
(2) Carrying out vacuum magnetic suspension smelting on the raw materials prepared in the step (1), cooling, and taking out cast ingots;
(3) Repeatedly carrying out vacuum magnetic suspension smelting on the cast ingot in the step (2) for 3-5 times, and turning over the cast ingot before smelting each time.
8. The co-ordinates L1 of claim 7 2 The preparation method of the phase-reinforced high-strength cavitation-corrosion-resistant multi-principal-element alloy is characterized in that the parameters of the vacuum magnetic suspension smelting in the steps (2) and (3) are as follows: the temperature rising rate is 10-20 ℃/min, the smelting temperature is 1500-2100 ℃ and the smelting time is 40-60 min.
9. The co-ordinates L1 of claim 7 2 The preparation method of the phase-reinforced high-strength cavitation-corrosion-resistant multi-principal-element alloy is characterized in that the raw material in the step (1) comprises pure metals of Ni, co, cr, al and Ti or intermediate alloys of Ni, co, cr, al and Ti; the purity of the pure metal of Ni, co, cr, al and Ti or the master alloy comprising Ni, co, cr, al and Ti is above 99.9 wt.%;
and (3) vacuumizing the vacuum environment of 0.005-0.008 Pa and reversely filling a protective atmosphere of 0.03-0.10 MPa in the vacuum magnetic suspension smelting in the steps (2) and (3).
10. A coherent L1 according to any one of claims 1 to 5 2 Phase reinforced high strength and toughness, and resistanceUse of cavitation-erosion multi-principal component alloys in the manufacture of cavitation-erosion resistant and/or corrosion resistant components.
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