CN114574748A - High-entropy alloy coating material with high wear resistance - Google Patents
High-entropy alloy coating material with high wear resistance 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
- C22C30/02—Alloys containing less than 50% by weight of each constituent containing copper
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/06—Making metallic powder or suspensions thereof using physical processes starting from liquid material
- B22F9/08—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying
- B22F9/082—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying atomising using a fluid
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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
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- 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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- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/06—Making metallic powder or suspensions thereof using physical processes starting from liquid material
- B22F9/08—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying
- B22F9/082—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying atomising using a fluid
- B22F2009/0824—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying atomising using a fluid with a specific atomising fluid
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/06—Making metallic powder or suspensions thereof using physical processes starting from liquid material
- B22F9/08—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying
- B22F9/082—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying atomising using a fluid
- B22F2009/0844—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying atomising using a fluid in controlled atmosphere
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Abstract
The invention discloses a TiC enhanced high-entropy alloy coating material with high wear resistance, which comprises high-entropy alloy powder and 20 wt% of TiC powder; the high-entropy alloy material comprises the following components: 14.41 percent of Al, 15.41 percent of Cr, 18.84 percent of Cu, 16.55 percent of Fe and 34.79 percent of Ni. The method for preparing the high-entropy alloy coating by using the material through laser cladding comprises the following steps: preparing high-entropy alloy powder from the high-entropy alloy coating material by a gas atomization method, adding TiC powder, and performing ball milling and powder mixing; and conveying the uniformly mixed alloy powder to the surface of the matrix by using a powder feeder, and carrying out laser cladding to obtain a cladding coating combined with the matrix material. The invention utilizes the laser cladding technology to improve the hardness and the wear resistance of the material by changing the content of TiC, meets the performance requirements of key wear-resistant parts of agricultural machinery, and can be widely applied to high-end agricultural machinery.
Description
Technical Field
The invention relates to the technical field of metal alloy material coatings, in particular to a high-wear-resistance laser cladding high-entropy alloy coating material.
Background
Unlike conventional alloys having one or two main elements, High Entropy Alloys (HEA) are alloys containing a plurality of main alloying elements, which are not based on main components but are composed of five or more main elements in equimolar or near equimolar ratios, and the concentration of each element cannot be less than 5% and more than 35%, and the structure of HEA is generally composed of a simple face-centered-cubic (FCC), a body-centered-cubic (BCC), a Hexagonal Closed (HCP) solid solution phase, and an FCC, BCC, or HCP mixture, rather than intermetallic compounds and other complex structures. The high-entropy alloy is a novel metal material, has comprehensive excellent performance, is obviously superior to the characteristics of conventional metal materials in the aspects of hardness, wear resistance, thermal stability and the like, and has important application prospect in the fields of high-temperature-resistant alloys, wear-resistant alloys, corrosion-resistant alloys and the like.
The laser cladding technology for preparing the high-entropy alloy coating is one of the most main ways for realizing the performance of the high-entropy alloy. In laser cladding, firstly, alloy powder is conveyed to the surface of a matrix through a powder feeder, then the powder is melted at high temperature by laser, and the high-entropy alloy coating is prepared through rapid cooling. Compared with the traditional high-entropy alloy preparation method, the laser cladding technology has the characteristics of high energy density, high cooling speed, low coating dilution rate and the like, and has the characteristics of almost no any limitation on powder selection, large thickness range of a cladding layer and the like.
The high-entropy alloy has higher hardness and wear resistance, and the method is a main way for improving the hardness and wear resistance of the laser cladding high-entropy alloy coating by changing the component proportion of the high-entropy alloy or carrying out proper heat treatment on the high-entropy alloy. Al (Al)1.8CrCuFeNi2The high-entropy alloy is of a single body-centered cubic structure and has excellent performances in the aspects of hardness, strength, toughness, wear resistance and the like. Al is prepared by smelting in a traditional electric arc furnace1.8CrCuFeNi2The high-entropy alloy is easy to have the problems of component inclusion, element segregation and the like, and the prepared alloy has a simple appearance and is difficult to meet the requirements of industrial parts with complex appearances. Compared with the traditional high-entropy alloy smelting process, the selective laser smelting forming high-entropy alloy is not controlled by the shape of a part, and the high-entropy alloy with fine structure, uniform components and no segregation can be obtained due to the characteristic of rapid solidification forming. Selective laser melting formingAl1.8CrCuFeNi2Research on high-entropy alloy organization and performance (master thesis, Plumbum preparatium) uses selective laser melting to form high-entropy alloy, but selective laser melting is a forming method of metal parts, cannot be applied to preparation of high-entropy alloy coatings on substrates, and further cannot be used for large-scale production. And selective laser melting Al1.8CrCuFeNi2The wear resistance of the high-entropy alloy needs to be further improved.
Disclosure of Invention
In view of the prior art, the invention aims to provide a high-entropy alloy coating material with high wear resistance. The invention improves the hardness and the wear resistance of the alloy coating by adding 20 wt% of TiC powder and utilizing the laser cladding technology.
In order to realize the purpose, the invention adopts the following technical scheme:
the invention provides a high-entropy alloy coating material with high wear resistance, which comprises a high-entropy alloy coating material and TiC powder accounting for 20 wt% of the high-entropy alloy coating material;
the high-entropy alloy coating material comprises the following raw materials in percentage by mass:
Al 14.41％、Cr 15.41％、Cu 18.84％、Fe 16.55％、Ni 34.79％；
the purity of the Al, Cr, Cu, Fe and Ni metal simple substances is not less than 99%.
In a second aspect of the invention, the method for preparing the high-entropy alloy coating by laser cladding of the high-entropy alloy coating material with high wear resistance is provided, and comprises the following steps:
(1) preparing the high-entropy alloy coating material with high wear resistance by a gas atomization method to obtain high-entropy alloy powder, and then adding TiC powder to perform ball milling to obtain high-wear-resistance high-entropy alloy powder;
(2) and (3) conveying the high-wear-resistance high-entropy alloy powder obtained in the step (1) to the surface of the matrix by using a powder feeder, and performing laser cladding to obtain a cladding coating combined with the matrix material.
Preferably, in the step (1), the temperature of the gas atomization is about 1500 ℃, and the pressure of the gas atomization is 4.5 MPa.
Preferably, in step (2), the laser beam spot diameter is
The laser power is 1100W, 1500W or 2100W, and the lap joint rate is 50%.
Preferably, in the step (2), the defocusing amount is 12mm, the scanning speed is 10mm/s, and the powder feeding speed is 1.3 r/min.
In a third aspect of the invention, the high-wear-resistance high-entropy alloy coating prepared by the method is provided.
Preferably, the thickness of the high-wear-resistance high-entropy alloy coating is 1.5 mm.
In a fourth aspect of the invention, the application of the high-wear-resistance high-entropy alloy coating in improving the wear resistance of mechanical equipment is provided.
Preferably, the mechanical equipment is a blade of a harvester, a wool shearing machine, a rotary cultivator and the like, a spindle of a cotton picker, a plough side plate, a feed pelleting press die, a feed crusher hammer, a plough share or a rotary cultivator curved blade.
The invention has the beneficial effects that:
(1) the invention is obtained by reasonable component design, reduces the production cost and obviously improves the hardness and the wear resistance of the high-entropy alloy. The laser cladding process adopting the coaxial powder feeding mode is adopted in the experiment, the powder utilization rate of the coaxial powder feeding is higher, and because the laser beam and the powder are simultaneously sent out, the cross powder laying can greatly reduce the oxidation of the coating powder and reduce the cracking of the surface material. By utilizing the laser cladding process technology, the good metallurgical bonding of the coating and the substrate can be realized, and the coating has excellent performances of high hardness and wear resistance.
(2) The material prepared by the method obviously improves the hardness and wear resistance of the matrix alloy, meets the performance requirements of key wear-resistant parts of agricultural machinery, and can be widely applied to high-end agricultural machinery.
Drawings
FIG. 1 is an XRD pattern of a 20% TiC coating;
as can be seen from the figure: after addition of 20% TiC, the phase structure of the coating is simple BCC + TiC phase.
FIG. 2 is a gold phase diagram of a 20% TiC coating, (a) at 100 times magnification, and (b) at 400 times magnification;
it can be seen from the macroscopic (100 times) metallographic picture in the figure that a significant large precipitated phase appears, and the precipitated phase is dendritic-like in shape, and the whole phase particles are large in block head and concentrated in distribution. When a high-power (400 times) gold phase diagram is observed, the grain boundary of the coating is relatively coarse, the crystallinity of the coating is relatively poor, and the shape of the grains is relatively small dendritic crystals.
FIG. 3 is a plot of the element area scan of a 20% TiC coating;
as can be seen from the figure: the elements concentrated at the precipitated second phase are C, Ti elements, and in the range of the non-precipitated phase, Al, Cr, Cu, Fe and Ni elements are uniformly distributed, and are doped with a trace amount of C, Ti elements, and the doped C, Ti elements are mainly distributed in the grain boundary of the non-precipitated phase.
FIG. 4 is a metallographic picture of a coating containing 10% TiC, at (a) a magnification of 100 and (b) a magnification of 400;
FIG. 5 is a metallographic picture of a coating containing 30% TiC, at (a) a magnification of 100 and (b) a magnification of 400;
FIG. 6 is the BCC phase hardness values for the coatings of examples and comparative examples 1-3;
FIG. 7 is the surface topography of the 20% TiC (a) and 30% TiC (b) coatings;
FIG. 8 is a graph of the profile of the coating in longitudinal section and elemental distribution after addition of 20% TiC.
Detailed Description
It should be noted that the following detailed description is exemplary and is intended to provide further explanation of the disclosure. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs.
As described in the background section, Al1.8CrCuFeNi2The high-entropy alloy has excellent performances in the aspects of hardness, strength and the like, but the Al1.8CrCuFeNi2 high-entropy alloy prepared by the traditional electric arc furnace smelting easily has the problems of component inclusion, element segregation and the like, andthe prepared alloy has simple appearance and is difficult to meet the requirement of industrial parts with complex appearance. How to further increase Al1.8CrCuFeNi2The wear resistance of the high-entropy alloy coating does not appear in the prior art1.8CrCuFeNi2High entropy alloy as coating and how to improve further Al1.8CrCuFeNi2The wear resistance of the high-entropy alloy is reported.
Based on the above, the invention aims to provide a TiC reinforced high-entropy alloy coating material with high wear resistance. According to the invention, the 65Mn steel is coated by a laser cladding method to obtain the coating material with high wear resistance, so that the wear resistance of the matrix alloy is effectively improved. The ceramic phase materials being of a wide variety, e.g. TiB, TiB2、TiC、WC、Al2O3、B4C. AlN, TiN, etc., but the inventors found through studies that not all ceramic phase materials can strengthen Al1.8CrCuFeNi2The wear resistance of high entropy alloys, while Al can be significantly enhanced by the addition of an appropriate amount of TiC1.8CrCuFeNi2The wear resistance of the high-entropy alloy laser cladding coating and the bonding performance of the cladding coating and the base material.
In order to improve the wear resistance of the coating of the laser cladding high-entropy alloy, some material particles for enhancing the performance are added into the high-entropy alloy, so that a strengthening phase with greatly improved hardness and wear resistance is formed. Ceramic materials are superior to high-entropy alloys and are hot spots for adjusting strength-plasticity matching in high-entropy alloy systems in recent years, so that the high-entropy alloys can be strengthened by adding ceramic particles. TiC particles with a simple cubic lattice of the NaCl type possess a very high hardness (over 3000 HV) and a low density (4.93 g/cm) in various ceramic-based reinforcing phases3) Meanwhile, the excellent composition structure of the alloy can be used as a high-quality nucleation core in an alloy system to promote the grain refinement. And the high hardness and the high melting point of the TiC particles enable the TiC particles to be nailed among crystal grains, so that the TiC particles play a role in solid solution strengthening, and the hardness and the wear resistance of the material are greatly improved. Therefore, in the invention, the TiC ceramic powder with 200 meshes, which has the same grain diameter as the high-entropy alloy powder, is selected as the reinforcing material.
In one embodiment of the present invention, a method for producing a high wear resistance coating is provided, comprising the steps of: 1. designing and preparing a TiC enhanced high-entropy alloy coating sample; 2. analyzing the tissue structure of the coating; 3. the hardness of the coating and the substrate was tested using an MH-5 Vickers hardness tester. 4. And testing the wear resistance of the coating and the substrate by a wear tester.
1. Design and preparation of TiC enhanced high-entropy alloy coating sample
Selecting Al, Cr, Cu, Fe and Ni metal simple substances with the purity of not less than 99 percent, preparing and smelting the simple substances into alloy melt in proportion, preparing alloy powder by a gas atomization method, and mixing TiC powder by using a vacuum ball-milling mixer to form Al with the TiC mass fraction of 20 percent1.8CrCuFeNi2+ TiC powder; and conveying the mixed powder on the surface of the matrix, simultaneously melting the powder and the matrix by using laser, and cladding the powder on the surface of the matrix to form the wear-resistant coating.
2. Analysis of the texture of the coating
Elemental and microstructural analysis was performed using a metalloscope microscope (CK-500), Scanning Electron Microscope (SEM) and energy spectrometer (EDS).
3. Testing the hardness of the coating and the substrate by using MH-5 Vickers hardness tester
And (3) preparing the small sample into a metallographic sample by using resin metallographic embedding liquid, and polishing by using a polishing machine (MPD-1) to ensure that the surface is smooth. And corroding the surface of the treated metallographic specimen by using aqua regia solution for 15s, and then detecting the hardness by using an MH-5 Vickers hardness tester.
4. Testing the wear resistance of the coating and the substrate by a wear tester
And (3) carrying out a friction and wear test on the sample and the matrix under a test force of 100N by using a wear testing machine, carrying out dry friction by using a ring block, wherein the lower friction sample is a No. 45 steel ring-shaped material with the diameter of 40mm, and weighing the wear loss of the sample and the matrix after the friction and wear test by using an electronic balance.
In order to make the technical solutions of the present application more clearly understood by those skilled in the art, the technical solutions of the present application will be described in detail below with reference to specific embodiments.
The test materials used in the examples and the verification examples of the present invention are conventional in the art and are commercially available.
Example (b): preparation of high-wear-resistance high-entropy alloy coating
1) According to the contents of Al, Cr, Cu, Fe and Ni in the coating components, preparing and smelting the Al, Cr and Ni into an alloy melt according to the mass percentages of 14.41 percent, 15.41 percent, 18.84 percent, 16.55 percent and 34.79 percent of Ni, preparing alloy powder by a gas atomization method, wherein the atomization temperature is about 1500 ℃, the atomization pressure is about 4.5MPa, and the equipment model is YC2017-0062# vacuum gas atomization equipment. The powder has good fluidity, uniform element distribution and excellent physical properties. Adding TiC powder, mixing the powder for 36h under a vacuum condition by using a YC2019-0061# vacuum ball-milling mixer at the rotating speed of 3000r/min to form Al with the TiC mass fraction of 20%1.8CrCuFeNi2+ TiC powder;
2) putting the mixed alloy powder into a dryer for drying at the heating rate of 4 ℃/min for 1h to obtain dry powder, wherein the drying aims to remove residual moisture in the powder, prevent the influence on flowability due to the moisture of the powder and reduce the influence on experimental results due to the oxidation caused by the moisture;
3) the invention adopts a coaxial powder feeding mode, dry powder is put into a powder feeding barrel, and the powder is cladded on the surface of 65Mn steel by laser to form a wear-resistant coating. The specific process of cladding the powder on the surface of the substrate by laser is that the diameter of a laser beam spot is
The lapping rate is 50%, the defocusing amount is 12mm, the scanning speed is 10mm/s, the powder feeding speed is 1.3r/min, double-layer laser cladding (cladding one layer after cladding one layer) is carried out, the laser power is 1100w, and the cladding thickness is about 1.5mm (double-layer thickness).
Phase analysis:
the surface of the coating obtained in this example was polished flat with sandpaper and then cleaned with ultrasonic oscillation. The coating was phase analyzed using an X-ray diffractometer (XRD, Empyrean) in the netherlands. The main test parameters of the equipment are as follows: co Kalpha radiation with the wavelength of 1.789A, the scanning speed of 4/min, the scanning angle of 20-110 degrees, the tube voltage of 35kV and the tube current of 50 mA.
As can be seen from fig. 1: the sharp peaks on the XRD curves indicate that the coating consists of a simple BCC solid solution + TiC. In addition, the half height width of the diffraction peak is larger, and the peak value is obviously lower, which means that the overall crystallinity is lower and the grain size is smaller.
Metallographic analysis:
the coating prepared in this example was sequentially ground with 400, 800, 1200, 1500, 3000, 5000 mesh water-ground sandpaper, and finally polished on a wool felt to remove scratches on the surface. After the surface of the sample is smooth, aqua regia (HCL: HNO) is used33: 1) the etching was carried out for 15 seconds. Metallographic structure of the sample elemental and microstructural analysis was performed using an optical metallographic microscope (CK-500), Scanning Electron Microscope (SEM) and energy spectrometer (EDS).
Fig. 2 shows that there are obvious large precipitated phases in the solid solution phase from the macroscopic metallographic picture, the shape of the precipitated phases is dendritic-like, and the overall phase particles are large in block heads and relatively concentrated in distribution. As can be seen from the high-power gold phase diagram, the BCC solid solution phase grain boundary in the coating is obvious, and the grains are smaller dendrites. The TiC is dissolved in the high-entropy alloy to form a reinforced coating, but when the TiC content in the high-entropy alloy is too high to be saturated, a high-hardness phase is precipitated, and the phase is TiC.
Fig. 3 is a surface scanning distribution diagram of coating elements, and it can be seen from the diagram that the element concentrated at the second phase precipitation is C, Ti element, which is the same as the result of XRD diffraction pattern analysis in fig. 1, and the phase can significantly improve the wear resistance of the surface. Besides, in the range of the non-precipitated phase, we can see that the distribution of the elements of Al, Cr, Cu, Fe and Ni is very uniform, and a trace amount of C, Ti element is doped in the elements, and the doped C, Ti element is mainly distributed in the grain boundary of the non-precipitated phase.
Comparative example 1
The difference from the examples is that the addition amount of TiC powder accounts for 10% of the total mass of the high-entropy alloy material.
FIG. 4 is a metallographic picture of a coating containing 10% TiC, from which it is evident that the grains of the coating are uniformly distributed without any other precipitated phases at a TiC content of 10 wt%. As can be seen from the high-power gold phase diagram, the BCC solid solution phase grain boundary in the coating is not obvious, and the crystal grains are elongated and isometric crystals.
Comparative example 2
The difference from the embodiment is that the addition amount of TiC powder accounts for 30% of the total mass of the high-entropy alloy material.
FIG. 5 is a metallographic picture of a coating layer comprising 30 wt% of TiC, in which it is evident that the precipitated phases become smaller, the overall shape is more elongated, the distribution is more dispersed, but the content is significantly increased, as can be seen from the macroscopic metallographic picture. As can be seen from the high-power gold phase diagram, the distribution of the crystal grains is more regular than 20%, and the crystallinity of the coating is increased to some extent and gradually becomes into a metallographic form mainly comprising long equiaxed crystals.
Comparative example 3
The difference from the examples is that no TiC powder was added.
As can be seen from fig. 2, 4 and 5, the coatings of examples and comparative example 2 both included BCC phase and precipitated phase. The higher the TiC content, the more precipitated phases and the higher the coating hardness, but as can be seen from FIG. 7, the coating of 30% TiC has cracks and obvious defects. It is shown that the coating is not only very hard, but also defect free when the TiC content is 20 wt%.
Further examining the bonding of the coating and the substrate prepared in the examples, FIG. 8 is a longitudinal sectional profile and an elemental profile of the coating after adding 20% TiC, and the surface scanning elemental analysis on the right side is a corresponding 500-fold profile. The gradual change process of the substrate, the transition zone and the coating can be obviously seen from the figure. The distribution of the elements is analyzed from bottom to top, and the elements have obvious diffusion tendency in the period from the base body to the transition layer, which fully shows that the atoms of each element can move and diffuse due to the formation of a molten pool in the cladding process, and the kinetic energy for moving the atoms is provided by heat, so that the element bonding state is good, and the excellent metallurgical bonding can be kept.
Test example 1: testing the hardness of the high-entropy alloy coating and the substrate by using MH-5 Vickers hardness tester
Measuring the hardness values of the coating and the substrate by using an MH-5 Vickers hardness tester; the load of MH-5 Vickers hardness tester was set to 9.8N, and the loading time was set to 15 s. And (3) selecting 20 points at different positions with the distance of 2mm on the center line of the sample for measurement, recording data, removing 5 maximum values and 5 minimum values of the obtained data, finally calculating the average value of the remaining 10 points, and respectively measuring the microhardness values of the coating and the substrate.
FIG. 6 shows the BCC phase hardness values of the coatings of examples and comparative examples 1 to 3, and it can be seen from the figure that the microhardness value of the substrate is 352.7HV, and the BCC phase hardnesses of the high-entropy alloy coatings respectively added with 10% of TiC, 20% of TiC and 30% of TiC are 642.7HV, 947.9HV and 969.6HV, and it can be seen from the figure that after TiC is added, the surface hardnesses of the three coatings are greatly improved relative to the substrate, the hardness improvement range of the 30% TiC high-entropy alloy coating with the highest hardness reaches 174.9%, the 10% TiC high-entropy alloy coating with the lowest hardness is also improved 82.2%, the high-entropy alloy coating with the highest overall hardness is the high-entropy alloy coating added with 30% of TiC reinforcing phase, and the addition of TiC reinforcing phases with different contents actually improves the hardness of the overall coating.
When the addition amount of TiC is increased to 20%, a new phase is precipitated, the hardness value of the new phase is very high, the phase is analyzed to be a TiC intermetallic compound, wherein the hardness value of the precipitated phase with the TiC content of 20% reaches 2645.4HV, and the hardness of the precipitated phase with the TiC content of 30% reaches 3408.5HV, because more TiC is accumulated in the precipitated phase along with the increase of the TiC content, the thickness of the precipitated phase is increased, the compression of microhardness diamond is prevented, and the side length of a compression surface is only within 10 mu m under the load of 100N, and the microhardness is extremely high. In the high-entropy alloy integral coating with the TiC content of more than 20%, the precipitated reinforcing phases are uniformly distributed, and the wear resistance of the coating can be remarkably improved due to the generated integral effect.
Test example 2: testing the wear resistance of the high-entropy alloy coating and the matrix by a wear testing machine
The coatings and the matrix of the examples and the comparative examples 1 to 3 are respectively subjected to a frictional wear test under a test force of 100N by a wear testing machine, a ring block is adopted for dry friction, the loading time is respectively 30min and 120min, the frictional wear in a short time and the frictional wear in a long time are respectively represented, the sample to be tested is an upper sample, the scale of the upper sample is a cuboid with the size of 30mm 7mm 6mm, the lower sample is 45# steel with the diameter of 40mm, the ring block combination meets the national standard GB/T12444.2-1990 of the frictional wear sample, the wear of the sample and the matrix after the frictional wear test is weighed by an electronic balance, and the obtained result is shown in Table 1.
Table 1: amount of wear of substrate and coating
Table 1 shows the wear loss of the substrate and the coating with 10%, 20% and 30% TiC added in the ring block dry friction test, and the wear results show that after TiC is added, the wear loss of the coating is greatly reduced in both 30min and 120min, when the TiC content is increased from 10% to 20%, the wear loss of the coating is obviously reduced, the wear resistance is obviously improved, when the TiC content is increased from 20% to 30%, the wear loss is not obviously changed in 30min, and when the TiC content is decreased in 120min, the wear loss is slightly reduced. According to metallographic pictures and XRD diffraction pattern observation, obvious precipitated phases begin to appear in the coating with 20% TiC, which is also the root cause of great reduction of the wear of the coating with the content TiC. Compared with the coating with 20% of TiC, when the TiC is increased to 30%, although more precipitated phases exist, the hardness of the coating is higher and the abrasion loss is lower, because the TiC content is too high, obvious cracks are generated on the surface of the coating, and therefore, analysis of various factors shows that the coating with the addition of 20% of TiC has the best abrasion resistance.
The above description is only a preferred embodiment of the present application and is not intended to limit the present application, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, improvement and the like made within the spirit and principle of the present application shall be included in the protection scope of the present application.
Claims (10)
1. A high-wear-resistance TiC-reinforced high-entropy alloy coating material through laser cladding is characterized by comprising the high-entropy alloy coating material and 20 wt% of TiC powder;
the high-entropy alloy coating material comprises the following raw materials in percentage by mass:
Al 14.41％、Cr 15.41％、Cu 18.84％、Fe 16.55％、Ni 34.79％；
the purity of the Al, Cr, Cu, Fe and Ni metal simple substances is not less than 99%.
2. The method for preparing the high-wear-resistance high-entropy alloy coating by laser cladding the high-wear-resistance TiC-reinforced high-entropy alloy coating material of claim 1, which is characterized by comprising the following steps:
(1) preparing the high-entropy alloy coating material with high wear resistance of claim 1 into high-entropy alloy powder by a gas atomization method, and then adding TiC powder to perform ball milling to obtain uniform high-wear-resistance high-entropy alloy powder;
(2) and (3) conveying the high-wear-resistance high-entropy alloy powder obtained in the step (1) to the surface of the matrix by using a powder feeder, and performing laser cladding to obtain a cladding coating combined with the matrix material.
3. The method according to claim 2, wherein in the step (1), the temperature of the gas atomization is about 1500 ℃, and the pressure of the gas atomization is 4.5 MPa.
4. The method of claim 2, wherein in the step (1), the ball milling is performed for 36h under vacuum.
5. The method of claim 2, wherein in step (2), the laser beam spot diameter is
mm, laser power 1100W, and lap joint rate 50%.
6. The method according to claim 2, wherein in the step (2), the defocusing amount is 12mm, the scanning speed is 10mm/s, and the powder feeding speed is 1.3 r/min.
7. The high-wear-resistance high-entropy alloy coating prepared by the method of any one of claims 2 to 6.
8. The high-wear-resistance high-entropy alloy coating layer according to claim 7, wherein the thickness of the high-wear-resistance high-entropy alloy coating layer is 1.5 mm.
9. Use of the high wear-resistant high entropy alloy coating of claim 7 or 8 for improving wear resistance of mechanical equipment.
10. Use according to claim 9, wherein the mechanical device is a blade of a harvester, a shearer, a rotocultivator or the like, a spindle of a cotton picker, a plow plate, a feed pellet mill die, a feed grinder hammer, a ploughshare or a rotary tiller blade.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115747602A (en) * | 2022-11-16 | 2023-03-07 | 南京农业大学 | High-wear-resistance soil-contacting cutter of cultivation machine and preparation method thereof |
| CN115772627A (en) * | 2022-11-27 | 2023-03-10 | 重庆大学 | High-temperature AlCrTiNiY eutectic high-entropy alloy wear-resistant cladding layer |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103484810A (en) * | 2013-09-23 | 2014-01-01 | 河海大学 | Plasma cladding in-situ synthesized TiB2-TiC-TiN reinforced high-entropy alloy coating material and preparation method thereof |
| CN104651828A (en) * | 2013-11-22 | 2015-05-27 | 沈阳工业大学 | Powder for high-entropy alloy-based composite material modified layer prepared on ferrous alloy surface |
| US20170314097A1 (en) * | 2016-05-02 | 2017-11-02 | Korea Advanced Institute Of Science And Technology | High-strength and ultra heat-resistant high entropy alloy (hea) matrix composites and method of preparing the same |
| CN111005019A (en) * | 2019-11-07 | 2020-04-14 | 中南大学 | Method for preparing TiC/TiB wear-resistant coating in situ through laser cladding |
-
2022
- 2022-03-08 CN CN202210227687.7A patent/CN114574748A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103484810A (en) * | 2013-09-23 | 2014-01-01 | 河海大学 | Plasma cladding in-situ synthesized TiB2-TiC-TiN reinforced high-entropy alloy coating material and preparation method thereof |
| CN104651828A (en) * | 2013-11-22 | 2015-05-27 | 沈阳工业大学 | Powder for high-entropy alloy-based composite material modified layer prepared on ferrous alloy surface |
| US20170314097A1 (en) * | 2016-05-02 | 2017-11-02 | Korea Advanced Institute Of Science And Technology | High-strength and ultra heat-resistant high entropy alloy (hea) matrix composites and method of preparing the same |
| CN111005019A (en) * | 2019-11-07 | 2020-04-14 | 中南大学 | Method for preparing TiC/TiB wear-resistant coating in situ through laser cladding |
Non-Patent Citations (2)
| Title |
|---|
| YANGCHUAN CAIA ET AL.: "Fracture and wear mechanisms of FeMnCrNiCo +x(TiC) composite high-entropy alloy cladding layers", 《APPLIED SURFACE SCIENCE》 * |
| 孔丹: "选区激光熔化成形Al1.8CrCuFeNi2高熵合金组织和性能研究", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115747602A (en) * | 2022-11-16 | 2023-03-07 | 南京农业大学 | High-wear-resistance soil-contacting cutter of cultivation machine and preparation method thereof |
| CN115747602B (en) * | 2022-11-16 | 2024-04-16 | 南京农业大学 | High-wear-resistance soil contact cutter for cultivation machinery and preparation method thereof |
| CN115772627A (en) * | 2022-11-27 | 2023-03-10 | 重庆大学 | High-temperature AlCrTiNiY eutectic high-entropy alloy wear-resistant cladding layer |
| CN115772627B (en) * | 2022-11-27 | 2023-08-15 | 重庆大学 | High-temperature AlCrTiNiy eutectic high-entropy alloy wear-resistant cladding layer |
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