CN108560032B - Preparation method and application of chromium-rich compound layer on surface of nickel-based superalloy - Google Patents
Preparation method and application of chromium-rich compound layer on surface of nickel-based superalloy Download PDFInfo
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- CN108560032B CN108560032B CN201810477182.XA CN201810477182A CN108560032B CN 108560032 B CN108560032 B CN 108560032B CN 201810477182 A CN201810477182 A CN 201810477182A CN 108560032 B CN108560032 B CN 108560032B
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Abstract
The invention provides a method for preparing a chromium-rich compound layer on the surface of a nickel-based high-temperature alloy, which is used for improving the surface hardness and the high-temperature oxidation resistance of the nickel-based high-temperature alloy. The nickel-based high-temperature alloy is used as a cathode, stainless steel is used as an anode, and pulse direct-current voltage is applied between the two electrodes at room temperature. Electric powerThe pressure is 300-400V, the duty ratio is 20-50%, and the electrolyte comprises the following components in percentage by mass: 45-80% of glycerol, 5-20% of ethylene glycol, 5-20% of sodium bicarbonate and 5-20% of deionized water. The method has simple process and low cost, and the hardness of the prepared chromium-rich layer can reach more than 1000 HV, which is about three times of that of the alloy matrix; the oxidation weight gain rate constant in air at 900 deg.C is 2.27X 10‑2‑3.15×10‑2g/m2H, 1/3-1/2 for matrix only.
Description
Technical Field
The invention belongs to the technical field of metal material surface modification, and relates to a method for preparing a chromium-rich compound layer on the surface of a nickel-based high-temperature alloy by utilizing a cathode plasma discharge phenomenon, which is used for improving the surface hardness and the high-temperature oxidation resistance of the nickel-based high-temperature alloy.
Background
The nickel-based high-temperature alloy has good high-temperature oxidation resistance, corrosion resistance and fatigue resistance as well as higher high-temperature strength and creep strength, and is widely used as high-temperature structural materials of aircraft engines, spacecrafts, naval vessels and industrial gas turbines, such as turbine blades, guider blades, turbine discs, combustion chambers and the like. In recent years, the emergence of aircraft engines in service for a long time and industrial gas turbines requiring higher-load power generation have put higher demands on various properties of nickel-based superalloy materials. However, in the preparation process of the nickel-based superalloy, metallurgical defect black spots are often generated due to inaccurate control of technical parameters, the high-temperature performance of the material is seriously influenced, and higher production cost needs to be invested for upgrading smelting equipment and perfecting a smelting process, so that the wider application of the alloy is limited. Therefore, it is of great significance to develop a nickel-based superalloy with higher performance and reduce the preparation cost thereof.
The nickel-base high-temperature alloy generally contains more than ten elements, wherein chromium mainly plays a role in oxidation resistance and corrosion resistance, and other elements mainly play a role in strengthening. The prior strengthening method of the nickel-based superalloy mainly comprises solid solution strengthening and dispersion strengthening. Wherein the solid solution strengthening is to add tungsten, molybdenum and cobalt into the nickel-based superalloyChromium and vanadium, and the like, which are alloying elements having a radius close to that of nickel, can be dissolved in a nickel matrix in a large amount without new phases. The high-temperature strength of the solid solution strengthened nickel-based high-temperature alloy Haynes230 produced in China at 1100 ℃ is about 90 MPa (Tangjia Wu, Li jin shan, Wu Sha, etc. the performance research and material report of the solid solution strengthened high-temperature alloy Ni-20Cr-18W-Mo, 2012, 26(8): 1-4), while the high-temperature strength of the Haynes230 alloy developed in the United states at 1100 ℃ can reach 135 MPa. Besides adding a large amount of refractory alloy elements such as tungsten, chromium and the like to improve the strength of a matrix, the alloy also adds a small amount of carbon element to form carbide to prevent grain growth and strengthen grain boundaries. Dispersion strengthening is achieved by mechanically alloying ultra-fine oxide particles, e.g. Y2O3、Al2O3The alloy is distributed in the alloy matrix in an equal dispersion way to generate the strengthening effect. Therefore, the carbon element and the oxygen element play an important role in improving the high-temperature performance of the nickel-based alloy.
The cathode plasma electrolysis is a new metal surface modification technology, and the technology uses the treated metal workpiece as the cathode and stainless steel or graphite as the anode, and the metal workpiece and the stainless steel or graphite are immersed in a specific electrolyte, and a certain voltage is applied between the two electrodes, and the electrolyte used is usually composed of organic matters such as methanol, glycol, glycerol and the like and a small amount of inorganic conductive media. At a critical voltage, the electrolyte gas film surrounding the cathode surface is broken down, a plasma discharge phenomenon occurs, and a local high temperature is accompanied. Meanwhile, the organic electrolyte is decomposed into a large amount of active carbon and oxygen particles in a plasma state, and the active particles bombard the surface of the cathode under the action of a high electric field and local high temperature and quickly diffuse towards the direction of the metal matrix to form a carbon and oxygen permeation layer or a compound layer. The whole process is carried out in normal-temperature electrolyte and in an atmospheric environment, and the method has the advantages of simple equipment, low cost, high treatment efficiency and wide application prospect. Patent 201310301580.3 discloses a method for preparing a diamond-like composite carburized layer on the surface of steel, the effective components of the electrolyte are glycerol, ethanol and sodium carbonate, the discharge treatment time is 0.5-5 minutes, and the hardness of the carburized layer prepared can reach more than 600 HV, which is much higher than that of the steel matrix.
Disclosure of Invention
The invention adopts a cathode plasma electrolysis technology, takes nickel-based high-temperature alloy as a cathode, takes organic matters such as glycerol and the like as electrolyte, utilizes the violent plasma discharge on the surface of the cathode to generate a large amount of activated carbon and oxygen particles to regulate and control the surface element components, and forms a film layer rich in chromium-containing carbide and oxide on the surface of the alloy. The carbide and the oxide in the chromium-rich layer can play a remarkable role in strengthening, and the surface hardness and the high-temperature oxidation resistance of the nickel-based high-temperature alloy are improved, so that the service life of the nickel-based high-temperature alloy part is prolonged. The method for simultaneously preparing chromium carbide and oxide on the surface of the nickel-based superalloy to obtain the strengthening effect is not reported at present.
In order to achieve the purpose, the invention discloses the following technical contents:
the electrolyte for preparing the chromium-rich compound layer on the surface of the nickel-based superalloy is characterized by comprising the following components in percentage by mass: 45-80% of glycerol, 5-20% of ethylene glycol, 5-20% of sodium bicarbonate and 5-20% of deionized water.
The invention further discloses a preparation method of the chromium-rich compound layer with low cost and capable of strengthening the surface of the nickel-based superalloy, which comprises the following process steps:
the method comprises the following steps: preparing an electrolyte for cathode plasma electrolysis, wherein the electrolyte comprises the following components in percentage by mass: 45-80% of glycerol, 5-20% of ethylene glycol, 5-20% of sodium bicarbonate and 5-20% of deionized water;
step two: performing surface pretreatment on a nickel-based high-temperature alloy sample, polishing the alloy surface step by using 400#, 800# and 1500# sandpaper, ultrasonically cleaning for 10 min by using alcohol, and then drying the sample;
step three: the pretreated nickel-based high-temperature alloy sample is taken as a cathode, stainless steel is taken as an anode, and the nickel-based high-temperature alloy sample and the stainless steel are immersed into an electrolytic tank containing prepared electrolyte together, 300-400V pulse direct current voltage is applied between two electrodes under the room temperature condition, the duty ratio is set to be 20-50%, bright plasma arc discharge light can be generated on the surface of the cathode sample in the treatment process, and the power supply can be turned off after the treatment time of 2-10 min is maintained in the state. After the nickel-based high-temperature alloy sample is treated by adopting the steps, a chromium-rich compound layer with the thickness of 5-20 microns can be obtained on the surface of the alloy.
The invention further discloses application of the chromium-rich compound layer prepared by the method in improving the surface performance of the nickel-based high-temperature alloy. The experimental result shows that the hardness of the chromium-rich compound layer can reach over 1000 HV, which is about three times of that of the alloy matrix; the oxidation weight gain rate constant in air at 900 deg.C is 2.27X 10-2- 3.15×10-2g/m2H, 1/3-1/2 of the matrix only, reaching a complete oxidation resistance level. Therefore, the chromium-rich compound layer prepared by the method can effectively improve the service performance of the nickel-based high-temperature alloy.
The invention is characterized in that:
(1) the method fully utilizes the composition characteristics of the nickel-based high-temperature alloy, and the activated carbon and oxygen particles generated by the decomposition of the organic electrolyte react with chromium elements in the alloy to generate carbide and oxide, and are deposited on the surface of the alloy to form a chromium-rich layer, so that the surface hardness and the high-temperature oxidation resistance of the nickel-based high-temperature alloy are obviously improved.
(2) The electrolyte used for cathode plasma electrolysis has wide sources, is common chemical reagents and has low cost.
(3) The whole treatment process is carried out at normal temperature and in the atmospheric environment, and the method has the advantages of simple process, strong repeatability and high production efficiency. (4) The process can be used for various grades of nickel-based high-temperature alloy materials, and is particularly suitable for nickel-based high-chromium-content alloy materials
High temperature alloy.
Drawings
FIG. 1 is a scanning electron micrograph of a cross-section of a chromium-rich layer prepared on the surface of an Inconel 690 nickel-based superalloy by the method of the present invention, the chromium-rich layer having a thickness of about 10 μm;
fig. 2 is an XRD spectrum of the chromium-rich compound layer from which it can be determined that chromium-rich layers contain chromium carbides and oxides.
Detailed Description
The invention is described below by means of specific embodiments. Unless otherwise specified, the technical means used in the present invention are well known to those skilled in the art. In addition, the embodiments should be considered illustrative, and not restrictive, of the scope of the invention, which is defined solely by the claims. It will be apparent to those skilled in the art that various changes or modifications in the components and amounts of the materials used in these embodiments can be made without departing from the spirit and scope of the invention. The following examples are provided in accordance with the electrolyte system and process steps described herein.
Example 1
The Inconel 690 nickel-based superalloy is used as a cathode, stainless steel is used as an anode, and sand paper (400) is used firstly#、800#、1500#) And (3) polishing the alloy sample, ultrasonically cleaning the alloy sample for 10 min by using alcohol, and drying the alloy sample. Then preparing an electrolyte: 795 ml of glycerin, 180 ml of ethylene glycol, 400 g of sodium bicarbonate and 400 ml of deionized water. The two electrodes are immersed in an electrolytic bath containing the electrolyte, 300V pulse direct current voltage is applied, the duty ratio is set to be 20%, and the treatment time is 2 min. After the treatment is finished, the power supply is turned off, and a chromium-rich compound layer with the thickness of about 5 mu m can be obtained.
Example 2
The Inconel 690 nickel-based superalloy is used as a cathode, stainless steel is used as an anode, and sand paper (400) is used firstly#、800#、1500#) And (3) polishing the alloy sample, ultrasonically cleaning the alloy sample for 10 min by using alcohol, and drying the alloy sample. Then preparing an electrolyte: glycerol 952 ml, ethylene glycol 90 ml, sodium bicarbonate 300 g, deionized water 400 ml. Immersing two electrodes in an electrolytic bath containing the electrolyte, applying 360V pulse direct current voltage, setting the duty ratio to be 30%, and setting the treatment time to be 5 min. After the treatment, the power supply is turned off, and a chromium-rich compound layer with the thickness of about 10 mu m can be obtained. (as shown in FIG. 1).
Example 3
Firstly, using Inconel 690 nickel-based high-temperature alloy as a cathode and stainless steel as an anodeSand paper (400)#、800#、1500#) And (3) polishing the alloy sample, ultrasonically cleaning the alloy sample for 10 min by using alcohol, and drying the alloy sample. Then preparing an electrolyte: 1270 ml of glycerol, 90 ml of ethylene glycol, 200 g of sodium bicarbonate and 100 ml of deionized water. The two electrodes are immersed in an electrolytic bath containing the electrolyte, 400V pulse direct current voltage is applied, the duty ratio is set to be 50%, and the treatment time is 10 min. After the treatment is finished, the power supply is turned off, and a chromium-rich compound layer with the thickness of about 20 mu m can be obtained.
Example 4
Samples of the chromium-rich compound layers obtained in examples 1-3 were designated as S1, S2, and S3, and were subjected to microhardness testing and high-temperature oxidation testing, respectively, and compared with the alloy matrix. The microhardness measurements for each sample were averaged three times and the results are shown in table 1. The high-temperature oxidation performance test is carried out at 900 ℃ in the air, the oxidation time is 100 h, the sample is taken out and weighed once every 10 h, the relation curve of the weight gain value of the unit area of the sample and the oxidation time is measured, the oxidation weight gain rate constant is calculated, and the calculation result is shown in table 2.
TABLE 1 microhardness test results for Ni-based superalloy substrates and three chromium rich layer samples
TABLE 2 calculation of the oxidation weight gain rate constants of the nickel-base superalloy substrate and the three chromium-rich layer samples
As can be seen from tables 1 and 2, compared with the untreated alloy matrix, after the alloy is subjected to cathode plasma electrolytic treatment by adopting the method provided by the invention, the microhardness of the obtained chromium-rich compound layer sample is increased and can reach more than 1000 HV, which is about three times of that of the alloy matrix; the oxidation weight gain rate constant in air at 900 deg.C is 2.27X 10-2- 3.15×10-2g/m2H, of the base body only1/3-1/2, which shows that the surface hardness and the high temperature oxidation resistance of the nickel-based superalloy are greatly improved. Therefore, the method is a low-cost method capable of effectively improving the service performance of the nickel-based superalloy.
The above embodiments are merely illustrative of the technical ideas and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and not to limit the protection scope of the present invention. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.
Claims (2)
1. A method for preparing a chromium-rich compound layer on the surface of a nickel-based superalloy by using an electrolyte for preparing the chromium-rich compound layer on the surface of the nickel-based superalloy is characterized by comprising the following steps:
the method comprises the following steps: preparing an electrolyte: the weight percentages are respectively as follows: 45-80% of glycerol, 5-20% of ethylene glycol, 5-20% of sodium bicarbonate and 5-20% of deionized water;
step two: performing surface pretreatment on a nickel-based high-temperature alloy sample, polishing the alloy surface step by using 400#, 800# and 1500# sandpaper, ultrasonically cleaning for 10 min by using alcohol, and then drying the sample;
step three: taking the pretreated nickel-based high-temperature alloy sample as a cathode, taking stainless steel as an anode, immersing the nickel-based high-temperature alloy sample and the stainless steel into an electrolytic bath containing electrolyte together, applying 300-400V pulse direct current voltage between two electrodes under the room temperature condition, wherein the duty ratio is 20-50%, the treatment time is 2-10 min, then turning off a power supply, and preparing a chromium-rich compound layer with the thickness of 5-20 microns on the surface of the nickel-based high-temperature alloy, wherein the surface hardness of the chromium-rich compound layer is more than 1000 HV.
2. Use of a chromium-rich compound layer prepared by the method of claim 1 for improving the surface properties of a nickel-base superalloy; wherein the improvement of the surface property of the nickel-base superalloy refers to: the surface hardness and the high temperature oxidation resistance of the nickel-based high-temperature alloy.
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