CN111085689B - FeCoCrNi series high-entropy alloy selective laser melting in-situ additive manufacturing method and product - Google Patents
FeCoCrNi series high-entropy alloy selective laser melting in-situ additive manufacturing method and product Download PDFInfo
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Abstract
The invention provides a FeCoCrNi series high-entropy alloy selective laser melting in-situ additive manufacturing method, which comprises the following steps of: step 1, mixing mixed simple substance metal powder with M-X alloy powder and/or N-Y alloy powder, wherein the mixed simple substance metal powder at least comprises two of three kinds of metal simple substance powder of Fe, Co and Ni, the M metal element in the M-X alloy powder is a metal element with the highest melting point in the high-entropy alloy, the N metal element in the N-Y alloy powder is a metal element with the lowest melting point in the high-entropy alloy, X and Y are at least one metal element in the mixed simple substance metal powder, and the mole numbers of the metal elements in the mixed metal powder are the same; and 2, performing laser additive manufacturing by using laser 3D printing equipment to obtain the FeCoCrNi series high-entropy alloy. The product has good forming effect and no air holes and macrocracks.
Description
Technical Field
The invention belongs to the technical field of alloy materials, and particularly relates to a FeCoCrNi series high-entropy alloy selective laser melting in-situ additive manufacturing method and a product.
Background
High-entropy alloy has excellent mechanical properties and corrosion resistance, and is widely researched by the material field in recent years. However, the high-entropy alloy system is huge, and the specific formation mechanism and strengthening mechanism of the high-entropy alloy system are not completely clear, and still need to be researched and explored for a long time. The mode for preparing the high-entropy alloy sample is mainly vacuum arc fusion casting, but the mode can prepare the sample with a very simple geometric shape and cannot prepare the sample with a complex shape. Compared with vacuum arc casting, in recent years, laser additive manufacturing has strong adaptability to the geometric shape of a processed part, and can prepare parts with complex geometric structures, so that the laser additive manufacturing is gradually the key point of research in the material field. Laser additive manufacturing has two major branches, Laser Melting Deposition (LMD) and Selective Laser Melting (SLM). The LMD technology is fast in forming speed and large in size, but is poor in forming precision and generally requires post-machining treatment. Compared with the LMD technology, the SLM technology has extremely high precision of manufactured parts, and the machining error is usually within 30 microns. The principle is that laser is used as a heat source, and a geometric slicing mode is adopted to spread powder layer by layer for printing. Therefore, the SLM technology will become the main manufacturing method of future high-entropy alloy complex and precise components, and is worthy of further research on the forming mechanism and method thereof.
At present, the high-entropy alloy has various types, and the common elements are as many as 13. However, according to the summary, the four elements of Fe, Co, Cr and Ni account for more than 70% of the elements used in all the high-entropy alloys at present, so the research on FeCoCrNi high-entropy alloys is the most basic research in the field of high-entropy alloys and is the premise for solving the more complex strengthening mechanism of the FeCoCrNi high-entropy alloys and elements.
However, the existing domestic additive manufacturing powder production system is not complete, and the alloy powder for FeCoCrNi series high-entropy alloy additive manufacturing needs huge waste of capacity for customization. And the components of the alloy powder are fixed, which is not beneficial to the component adjustment in the alloy development process. The direct use of elemental powders for in-situ SLM manufacturing also faces the problems of large differences in melting points and boiling points of the individual elemental powders and many defects. Therefore, the novel FeCoCrNi series high-entropy alloy in-situ SLM manufacturing method can greatly accelerate the development speed of the high-entropy alloy and reduce the production cost. The method has important significance for the perfection of a high-entropy alloy theoretical system and the development of an SLM technology.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, provides a selective laser melting in-situ additive manufacturing method and product of FeCoCrNi high-entropy alloy, improves the alloy development efficiency, obtains a compact high-entropy alloy structure, makes the in-situ synthesis of the high-entropy alloy by using an SLM (selective laser melting) become possible, and obtains a product with good mechanical properties.
The invention is realized by the following technical scheme:
a FeCoCrNi series high-entropy alloy selective laser melting in-situ additive manufacturing method comprises the following steps:
step 1, mixing raw materials, and matching alloy powder or simple substance metal powder with the alloy powder to obtain high-entropy alloy powder, so that the melting points of all component powders in the high-entropy alloy powder tend to be similar, and the mole numbers of all metal elements in the high-entropy alloy powder are the same;
2, performing additive manufacturing, namely polishing the surface of a substrate by using a stainless steel material until the surface of the substrate is free of oxides, cleaning oil stains and dirt on the surface by using an organic solvent, performing surface sand blasting treatment by using a sand blasting machine, putting the high-entropy alloy powder obtained after the step 1 into a printer bin, constructing a block body with a preset size, setting an interlayer rotation angle to be 65-70 degrees to release residual stress, performing laser walking off-line programming, vacuumizing the printing bin before printing, wherein the oxygen content is lower than 500ppm, the laser power is 180-400W, the exposure time is 30-70 mu s, the linear point distance is 20-70 micrometers, performing argon atmosphere protection, printing to obtain a sample with a preset size, and cooling along with the bin;
in the above technical scheme, in the step 1, raw materials are mixed, mixed simple substance metal powder and M-X alloy powder and/or N-Y alloy powder and/or X-Y alloy powder are mixed to obtain high-entropy alloy powder, the mixed metal powder is dried in a vacuum dryer, and is sealed and stored after being dried, the mixed simple substance metal powder at least comprises two of three kinds of simple substance metal powder of Fe, Co and Ni, the M-X alloy powder is alloy powder formed by an M metal element and X, the M metal element is a metal element with the highest melting point in the high-entropy alloy, wherein X is at least one metal element appearing in the mixed simple substance metal powder, the N-Y alloy powder is alloy powder formed by an N metal element and Y, and the N metal element is a metal element with the lowest melting point in the high-entropy alloy, wherein Y is at least one metal element appearing in the mixed simple substance metal powder, and the mole numbers of all the metal elements in the mixed metal powder are the same;
in the technical scheme, in the step 1, the mixed simple substance metal powder, the M-X alloy powder, the N-Y alloy powder and the X-Y alloy powder are all spherical powders, the granularity of the spherical powder is 0-64 μ M, the mixed simple substance metal powder and the M-X alloy powder and/or the N-Y alloy powder and/or the X-Y alloy powder are mixed in a three-dimensional mixer for 2-4 hours, the rotating speed of a cylinder body is 20-40 r/min, the uniformly mixed spherical powder is dried in a vacuum dryer for 5-10 hours at the temperature of 50-100 ℃, the vacuum degree is less than the absolute pressure of 10KPa, and the spherical powder is sealed and stored after being dried;
in the technical scheme, the substrate is made of 316L stainless steel and has the size of 250 multiplied by 15 mm.
In the above technical scheme, the substrate surface is polished by an angle grinder in the step 2 until no oxide exists, and oil stains and dirt on the surface are respectively cleaned by acetone and alcohol.
In the above technical solution, in step 2, laser additive manufacturing is performed by using an AM-400 laser 3D printing device manufactured by renishao corporation.
In the above technical solution, the sample specification in the step 2 is 5 × 5 × 5 mm.
In the technical scheme, in the step 2, laser additive manufacturing is performed by using AM-400 laser 3D printing equipment produced by Renisshaw-Quantam, a block body with the size of 5mm multiplied by 5mm is constructed in Renisshaw-Quantam, the rotation angle between layers is set to be 67 degrees so as to release residual stress, laser walking off-line programming is automatically performed by software, a printing bin is vacuumized before printing, the oxygen content is lower than 200ppm, the laser power is 180-200W, the exposure time is 50-70 mu s, the line dot spacing is 30-50 micrometers, the protective gas is argon, and a printed sample is cooled for 2 hours along with the bin.
In the above technical solution, in the step 1, the M-X alloy powder is Ni20Cr80、Ni30Cr70、Ni50Cr50、Ni15Cr85、Ni25Cr75、Ni35Cr65、Co35Cr65The N-Y alloy powder is Mn75Fe25、Mn60Fe40、Mn75Fe25、Al35Fe65At least one of, the X-Y alloy powder is Ti60Al40。
The FeCoCrNi high-entropy alloy prepared by the laser additive manufacturing method according to the technical scheme.
The invention has the advantages and beneficial effects that:
the material prepared by the method has high molding efficiency, and the part model is not restricted by the process and can be used for preparing parts with complex shapes. Secondly, unlike traditional subtractive manufacturing, the selective laser melting in-situ additive manufacturing method is one of laser additive manufacturing. The near-net-shape forming of the material can be realized, and the production cost of parts is greatly reduced.
The laser additive manufacturing of FeCoCrNi series high-entropy alloy can be successfully carried out by using the method. The sample has good forming effect, no air holes and macrocracks, good density and uniform tissue. The energy spectrometer is used for component detection, and the result shows that the components of the formed part are similar to those of the powder material, and the situation of large-amount element burning loss does not occur.
The method can greatly reduce the production and research and development cost of FeCoCrNi series high-entropy alloy. At present, the FeCoCrNi series high-entropy alloy amorphous grade needs to be customized into powder in production and research and development, has extremely high cost and needs to be customized again if component modification is needed. The powder and the binary alloy powder used in the method are common powder in the market, and the price is low. Also, the composition modification is easy to perform by the present method.
According to the method, the metal simple substance powder and the alloy powder are mixed to prepare the raw material powder for selective laser melting in-situ additive manufacturing, the problems of unmelted metal particles and air holes generated in the process of printing the mixed powder by completely using the metal simple substance powder are solved by printing, and the problems that the effective sectional area is reduced due to the fact that the air holes are generated by the gasification of the unmelted high-melting-point metal particles and the low-melting-point metal, so that the material strength is reduced due to cracks and the like are solved.
Drawings
FIG. 1 is a scanning electron micrograph of a sample after printing in comparative example step 2;
FIG. 2 is an EDS profile of a Cr element energy spectrum of a sample printed in comparative example step 2;
FIG. 3 is a scanning electron microscope image of a sample after completing printing in step 2 of example 1 of the present invention;
FIG. 4 is a surface distribution diagram of Cr, Fe, Co and Ni elements in a sample printed in step 2 of example 1 (EDS surface distribution diagram);
a: spectral surface distribution diagram of Cr element, b: the spectrum surface distribution diagram of the Fe element, C: spectrum surface distribution diagram of Co element, D: the spectral surface distribution diagram of the Ni element.
FIG. 5 shows a sample after printing in step 2 of example 1 of the present invention
For a person skilled in the art, other relevant figures can be obtained from the above figures without inventive effort.
Detailed Description
In order to make the technical solution of the present invention better understood, the technical solution of the present invention is further described below with reference to specific examples.
Comparative example: high-entropy alloy selective laser melting in-situ additive manufacturing by directly mixing metal simple substance powder serving as raw material
Step 1, 560g of Fe, 590g of Co, 520g of Cr and 590g of 590gNi elementary substance metal spherical powder (the particle size of the powder is 15-48 microns) with the purity of 99.9% is placed into a three-dimensional mixer to be mixed for 2-4 hours, the rotating speed of a cylinder body is 20-40 r/min, the uniformly mixed spherical powder is dried for 5-10 hours in a vacuum dryer at the temperature of 50-100 ℃ and the vacuum degree of 10KPa below the absolute pressure, and the spherical powder is sealed and stored after drying.
And 2, selecting 316L stainless steel as the substrate, wherein the size is 250mm multiplied by 15 mm. And (3) cleaning the greasy dirt and the smudged dirt on the surface respectively by using acetone and alcohol. The surface blasting treatment was performed using a sandblaster. The method comprises the steps of printing by using AM-400 laser 3D printing equipment produced by Renisshaw-Quantam, constructing a block body with the size of 5mm multiplied by 5mm in Renisshaw-Quantam with the power of 180-200W, enabling an interlayer rotation angle of 67 degrees to release residual stress, enabling exposure time to be 50-70 mu s and line point distance to be 30-50 micrometers, vacuumizing a printing bin before printing, enabling oxygen content to be lower than 500ppm, adopting argon protection, and cooling a printed test piece for 2 hours along with the bin.
Due to the large difference of the melting points of the metal simple substances (table 1), various defects such as unmelted particles, pores and the like (as shown in fig. 1) often occur in the production process and cannot be eliminated through process adjustment. The unmelted grains and pores also cause a reduction in the effective area of the sample in the direction of residual stress, thereby causing cracking (see fig. 1). The unmelted particles were found to be elemental particles of Cr by surface scan analysis (see fig. 2).
The differences between the melting points of the Cr simple substance and the Fe, Co and Ni simple substances in the FeCoCrNi simple substance mixed powder are all over 300 ℃. Therefore, in the printing process, the heat input is low enough to melt the elemental Fe, Co and Ni, but not melt the elemental Cr to form unmelted particles, and the heat input is high enough to completely melt the elemental Cr, so that the elemental Fe, Co and Ni can be evaporated due to overheating, and the gas can not overflow the molten pool to generate pores. Therefore, a printed matter having no or few defects cannot be obtained by directly using the single substance mixed powder.
TABLE 1 melting Point (. degree. C.) of Fe, Co, Cr, Ni simple substance
Therefore, in the invention, the metal element with higher melting point and/or the metal element with lower melting point in the high-entropy powder are added and mixed in the form of alloy powder, so that the melting points of the powders tend to be similar, and the metal element which cannot be melted or the gasified metal element is prevented from being generated when the same heat is input. In the specific embodiment, the metal with the highest melting point and the metal with the lowest melting point are combined to form alloy powder, the metal with the highest melting point and the metal with the middle melting point are combined to form alloy powder, the metal with the lowest melting point and the metal with the middle melting point are combined to form alloy powder, or the metal with the higher melting point and the metal with the lower melting point are combined to form alloy powder, so that the melting points of the powders are close to each other as a whole.
Example one
A FeCoCrNi series high-entropy alloy selective laser melting in-situ additive manufacturing method comprises the following steps:
step 1, mixing raw materials, namely 560g of Fe, 590g of Co simple substance metal spherical powder (the particle size of the powder is 15-48 microns) and 1110gNi with the purity of 99.9%50Cr50Putting the alloy spherical powder (the particle size of the powder is 15-48 microns) into a three-dimensional mixer, mixing for 4 hours, drying the uniformly mixed spherical powder in a vacuum dryer at the temperature of 50 ℃ and the vacuum degree of less than 10KPa absolute pressure at the rotation speed of 20r/min of a cylinder, and sealing and storing after drying.
2, additive manufacturing, namely polishing the surface of a substrate by using an angle grinder until no oxide exists, respectively cleaning oil stain and dirt on the surface by using acetone and alcohol, performing surface sand blasting by using a sand blasting machine, putting the mixed metal powder obtained after the step 1 is finished into a printer bin, performing laser additive manufacturing by using AM-400 laser 3D printing equipment produced by Renisshaw-Quantam, constructing a block body with the size of 5mm x 5mm in Renisshaw-Quantam, setting the rotation angle between layers to be 67 degrees to release residual stress, automatically performing laser walking off-line programming by software, vacuumizing the printing bin before printing, enabling the oxygen content to be lower than 200ppm, enabling the laser power to be 180-200W, enabling the exposure time to be 50-70 mus, enabling the line point distance to be 30-50 micrometers, and protecting argon gas, the argon flow was 15L/min and the printed sample was cooled with the bin for 2 hours.
After the printed sample is analyzed by a Scanning Electron Microscope (SEM), the result is shown in figure 3, the tissue of the sample is uniform, and no macroscopic defect occurs.
Fig. 4 was analyzed and evaluated, and the phenomenon and the obtained conclusion are discussed. According to the energy spectrum surface distribution diagram (figure 4), Fe and Co elements are slightly enriched at the bottom of the molten pool, and Cr and Ni elements are not enriched. On the whole, the four elements are uniformly distributed, and Fe, Co-poor, Cr-poor and Ni-poor regions are not seen.
Fig. 5 is a photograph of a printed sample, showing that the forming effect is good, the mark is clear and visible, and the edge angle of the sample is clear without adhesive powder.
The area energy spectrum detection is carried out on the sample (Table 2), and the detection result shows that the components are uniform and the situation of burning loss of a large amount of elements does not occur.
TABLE 2 regional energy Spectrum detection (at%)
In this embodiment, Fe and Co elemental metal powders and nichrome powders are mixed to prepare a raw material powder for selective laser melting in-situ additive manufacturing, and the raw material powder is printed, so that the problems of unmelted Cr particles and pores generated in the printing process of the mixed powder completely using the elemental metal powders are solved, and the problem of cracks caused by reduction of effective cross-sectional area due to the unmelted Cr particles and pores is solved. The test piece printed by the embodiment has uniform structure, fine crystal grains and no defect.
The unit prices of common simple substance powder, alloy powder and high-entropy alloy powder in the market are shown in table 3 (the unit prices of all manufacturers are slightly different). The simple substance powder and the binary alloy powder are widely applicable and are usually produced in batches, so the cost is lower. However, the high-entropy alloy powder is usually sold only by scientific research institutions and needs to be customized according to components, 1-2 ten thousand yuan is usually needed for one-time furnace opening of smelting and powder making, the labor cost is about 5000-8000 yuan, and the cost of the powder is added, so that the unit price of the high-entropy alloy powder is extremely high. It can be seen that the use of this method for powder preparation will result in substantial cost savings.
TABLE 3 unit price (Yuan/Kg) of spherical atomized powder
Example two
A FeCoCrNi series high-entropy alloy selective laser melting in-situ additive manufacturing method comprises the following steps:
step 1, mixing raw materials, namely 560g of Fe, 590g of Co and 442.5gNi elementary substance metal spherical powder (the particle size of the powder is 15-48 microns) with the purity of 99.9%, and 667.5gNi20Cr80And (3) placing the alloy spherical powder (the particle size of the powder is 15-48 microns) into a three-dimensional mixer, mixing for 2 hours, drying the uniformly mixed spherical powder in a vacuum dryer for 5 hours at the temperature of 100 ℃ and the vacuum degree of less than 10KPa absolute pressure at the rotation speed of 40r/min of a cylinder, and sealing and storing after drying.
2, additive manufacturing, namely polishing the surface of a substrate by using an angle grinder until no oxide exists, respectively cleaning oil stain and dirt on the surface by using acetone and alcohol, performing surface sand blasting by using a sand blasting machine, putting the mixed metal powder obtained after the step 1 is finished into a printer bin, performing laser additive manufacturing by using AM-400 laser 3D printing equipment produced by Renisshaw-Quantam, constructing a block body with the size of 5mm x 5mm in Renisshaw-Quantam, setting the rotation angle between layers to be 67 degrees to release residual stress, automatically performing laser walking off-line programming by software, vacuumizing the printing bin before printing, enabling the oxygen content to be lower than 200ppm, enabling the laser power to be 180-200W, enabling the exposure time to be 50-70 mus, enabling the line point distance to be 30-50 micrometers, and protecting argon gas, the argon flow was 15L/min and the printed sample was cooled with the bin for 2 hours.
EXAMPLE III
A FeCoCrNi series high-entropy alloy selective laser melting in-situ additive manufacturing method comprises the following steps:
step 1, mixing raw materials, namely 560g of Fe, 590g of Co, 337.1gNi elementary substance metal spherical powder (the particle size of the powder is 15-48 microns) with the purity of 99.9%, and 772.9gNi30Cr70Putting the alloy spherical powder (the particle size of the powder is 15-48 microns) into a three-dimensional mixer, mixing for 3 hours at the rotating speed of 30r/min, and putting the uniformly mixed spherical powder into a vacuum mixerAnd drying in an air dryer for 8 hours at the temperature of 80 ℃ and the vacuum degree of less than 10KPa absolute pressure, and sealing and storing after drying.
2, additive manufacturing, namely polishing the surface of a substrate by using an angle grinder until no oxide exists, respectively cleaning oil stain and dirt on the surface by using acetone and alcohol, performing surface sand blasting by using a sand blasting machine, putting the mixed metal powder obtained after the step 1 is finished into a printer bin, performing laser additive manufacturing by using AM-400 laser 3D printing equipment produced by Renisshaw-Quantam, constructing a block body with the size of 5mm x 5mm in Renisshaw-Quantam, setting the rotation angle between layers to be 67 degrees to release residual stress, automatically performing laser walking off-line programming by software, vacuumizing the printing bin before printing, enabling the oxygen content to be lower than 200ppm, enabling the laser power to be 180-200W, enabling the exposure time to be 50-70 mus, enabling the line point distance to be 30-50 micrometers, and protecting argon gas, the argon flow was 15L/min and the printed sample was cooled with the bin for 2 hours.
Example four
A selective laser melting in-situ additive manufacturing method for FeCoCrNiMn high-entropy alloy comprises the following steps:
step 1, mixing raw materials, namely 373.3g of Fe, 590g of Co and 442.5gNi of elementary metal spherical powder (the particle size of the powder is 15-48 microns) with the purity of 99.9%, 736.7gMn75Fe25、667.5gNi20Cr80And (3) placing the alloy spherical powder (the particle size of the powder is 15-48 microns) into a three-dimensional mixer, mixing for 3 hours, drying the uniformly mixed spherical powder in a vacuum dryer for 8 hours at the temperature of 80 ℃ and the vacuum degree of less than 10KPa absolute pressure at the rotation speed of 30r/min of a cylinder, and sealing and storing after drying.
2, additive manufacturing, namely polishing the surface of a substrate by using an angle grinder until no oxide exists, respectively cleaning oil stain and dirt on the surface by using acetone and alcohol, performing surface sand blasting by using a sand blasting machine, putting the mixed metal powder obtained after the step 1 is finished into a printer bin, performing laser additive manufacturing by using AM-400 laser 3D printing equipment produced by Renisshaw-Quantam, constructing a block body with the size of 5mm x 5mm in Renisshaw-Quantam, setting the rotation angle between layers to be 67 degrees to release residual stress, automatically performing laser walking off-line programming by software, vacuumizing the printing bin before printing, enabling the oxygen content to be lower than 200ppm, enabling the laser power to be 180-200W, enabling the exposure time to be 50-70 mus, enabling the line point distance to be 30-50 micrometers, and protecting argon gas, the argon flow was 15L/min and the printed sample was cooled with the bin for 2 hours.
EXAMPLE five
A FeCoCrNi high-entropy alloy selective laser melting in-situ additive manufacturing method comprises the following steps:
step 1, mixing raw materials, namely 560gFe with the purity of 99.9%, 272.3gCo, 590gNi elementary substance metal spherical powder (the particle size of the powder is 15-48 microns) and 837.7gCo35Cr65And (3) placing the alloy spherical powder (the particle size of the powder is 15-48 microns) into a three-dimensional mixer, mixing for 3 hours, drying the uniformly mixed spherical powder in a vacuum dryer for 8 hours at the temperature of 80 ℃ and the vacuum degree of less than 10KPa absolute pressure at the rotation speed of 30r/min of a cylinder, and sealing and storing after drying.
2, additive manufacturing, namely polishing the surface of a substrate by using an angle grinder until no oxide exists, respectively cleaning oil stain and dirt on the surface by using acetone and alcohol, performing surface sand blasting by using a sand blasting machine, putting the mixed metal powder obtained after the step 1 is finished into a printer bin, performing laser additive manufacturing by using AM-400 laser 3D printing equipment produced by Renisshaw-Quantam, constructing a block body with the size of 5mm x 5mm in Renisshaw-Quantam, setting the rotation angle between layers to be 67 degrees to release residual stress, automatically performing laser walking off-line programming by software, vacuumizing the printing bin before printing, enabling the oxygen content to be lower than 200ppm, enabling the laser power to be 180-200W, enabling the exposure time to be 50-70 mus, enabling the line point distance to be 30-50 micrometers, and protecting argon gas, the argon flow was 15L/min and the printed sample was cooled with the bin for 2 hours.
EXAMPLE six
FeCoCrNiAlTi high-entropy alloy selective laser melting in-situ additive manufacturing methodThe method has the advantages that the melting points of Cr and Ti in the FeCoCrNiAlTi high-entropy alloy are high, the melting point of Al is low, and Co can be used simultaneously35Cr65Alloy powder, Ti60Al40Alloy powder and Al35Fe65The alloy is subjected to raw material mixing, and comprises the following steps:
step 1, mixing raw materials, namely 213.3gFe with the purity of 99.9%, 272.3gCo, 590gNi elementary substance metal spherical powder (the particle size of the powder is 15-48 microns) and 837.7gCo35Cr65、630gTi60Al40、436.7gAl35Fe65And (3) placing the alloy spherical powder (the particle size of the powder is 15-48 microns) into a three-dimensional mixer, mixing for 3 hours, drying the uniformly mixed spherical powder in a vacuum dryer for 8 hours at the temperature of 80 ℃ and the vacuum degree of less than 10KPa absolute pressure at the rotation speed of 30r/min of a cylinder, and sealing and storing after drying.
2, additive manufacturing, namely polishing the surface of a substrate by using an angle grinder until no oxide exists, respectively cleaning oil stain and dirt on the surface by using acetone and alcohol, performing surface sand blasting by using a sand blasting machine, putting the mixed metal powder obtained after the step 1 is finished into a printer bin, performing laser additive manufacturing by using AM-400 laser 3D printing equipment produced by Renisshaw-Quantam, constructing a block body with the size of 5mm x 5mm in Renisshaw-Quantam, setting the rotation angle between layers to be 67 degrees to release residual stress, automatically performing laser walking off-line programming by software, vacuumizing the printing bin before printing, enabling the oxygen content to be lower than 200ppm, enabling the laser power to be 180-200W, enabling the exposure time to be 50-70 mus, enabling the line point distance to be 30-50 micrometers, and protecting argon gas, the argon flow was 15L/min and the printed sample was cooled with the bin for 2 hours.
The invention has been described in an illustrative manner, and it is to be understood that any simple variations, modifications or other equivalent changes which can be made by one skilled in the art without departing from the spirit of the invention fall within the scope of the invention.
Claims (8)
1. A FeCoCrNi series high-entropy alloy selective laser melting in-situ additive manufacturing method comprises the following steps:
step 1, mixing raw materials, mixing mixed simple substance metal powder with M-X alloy powder and/or N-Y alloy powder and/or X-Y alloy powder to obtain high-entropy alloy powder, drying the mixed metal powder in a vacuum dryer, sealing and storing after drying is finished, wherein the mixed simple substance metal powder at least comprises two of three kinds of simple substance metal powder of Fe, Co and Ni, the M-X alloy powder is alloy powder formed by M metal elements and X, the M metal elements are metal elements with the highest melting point in the high-entropy alloy, X is at least one metal element in the mixed simple substance metal powder, the N-Y alloy powder is alloy powder formed by N metal elements and Y, and the N metal elements are metal elements with the lowest melting point in the high-entropy alloy, wherein Y is at least one metal element appearing in the mixed simple substance metal powder, and the mole numbers of all the metal elements in the mixed metal powder are the same;
and 2, performing additive preparation, namely polishing the surface of the substrate by using a stainless steel material until the surface of the substrate is free of oxides, cleaning oil stains and dirt on the surface by using an organic solvent, performing surface sand blasting treatment by using a sand blasting machine, putting the high-entropy alloy powder obtained after the step 1 into a printer bin to construct a block with a preset size, setting an interlayer rotation angle to be 65-70 degrees to release residual stress, performing laser walking off-line programming, vacuumizing the printing bin before printing, wherein the oxygen content is lower than 500ppm, the laser power is 180-400W, the exposure time is 30-70 mu s, the linear point distance is 20-70 micrometers, performing argon atmosphere protection, printing to obtain a sample with a preset size, and cooling along with the bin.
2. The selective laser melting in-situ additive manufacturing method for FeCoCrNi series high-entropy alloys, as claimed in claim 1, wherein in step 1, the mixed elemental metal powder, the M-X alloy powder, the N-Y alloy powder and the X-Y alloy powder are all spherical powders, the particle size of the spherical powders is in the range of 0 to 64 μ M, the mixed elemental metal powder and the M-X alloy powder and/or the N-Y alloy powder and/or the X-Y alloy powder are mixed in a three-dimensional mixer for 2 to 4 hours at a cylinder rotation speed of 20 to 40r/min, the uniformly mixed spherical powders are dried in a vacuum dryer for 5 to 10 hours at a temperature of 50 to 100 ℃ and a vacuum degree of less than an absolute pressure of 10KPa, and the spherical powders are sealed and stored after being dried.
3. The selective laser melting in-situ additive manufacturing method for FeCoCrNi high-entropy alloys according to claim 1, wherein in the step 2, the substrate is made of 316L stainless steel and has the size of 250 x 15 mm.
4. The selective laser melting in-situ additive manufacturing method for FeCoCrNi high-entropy alloys according to claim 1, wherein in the step 2, the surface of the substrate is polished by an angle grinder until no oxide exists, and oil stains and dirt on the surface are cleaned by acetone and alcohol respectively.
5. The method for manufacturing the FeCoCrNi series high-entropy alloy selected area through laser melting in-situ additive manufacturing according to claim 1, wherein in the step 2, laser additive manufacturing is performed by adopting an AM-400 laser 3D printing device manufactured by Renissha corporation, a block body with the size of 5mm x 5mm is built in Renisshaw-QuantAM, an interlayer rotation angle is set to 67 degrees to release residual stress, laser walking off-line programming is automatically performed by software, a printing cabin is vacuumized before printing, the oxygen content is lower than 200ppm, the laser power is 180-200W, the exposure time is 50-70 μ s, the linear point distance is 30-50 micrometers, the protective gas is argon, and a printed sample is cooled for 2 hours along with the cabin.
6. The selective laser melting in-situ additive manufacturing method for FeCoCrNi high-entropy alloys according to claim 1, wherein in the step 1, the M-X alloy powder is Ni20Cr80、Ni30Cr70、Ni50Cr50、Ni15Cr85、Ni25Cr75、Ni35Cr65、Co35Cr65At least one of (1).
7. The selective laser melting in-situ additive manufacturing method for FeCoCrNi high-entropy alloys according to claim 1, wherein in the step 1, the N-Y alloy powder is Mn75Fe25、Mn60Fe40、Mn75Fe25、Al35Fe65At least one of (1).
8. The selective laser melting in-situ additive manufacturing method for FeCoCrNi high-entropy alloys according to claim 1, wherein in the step 1, the X-Y alloy powder is Ti60Al40。
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| CN112267056A (en) * | 2020-10-23 | 2021-01-26 | 鑫精合激光科技发展（北京）有限公司 | High-entropy alloy component and manufacturing method thereof |
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| CN115533111B (en) * | 2022-10-11 | 2024-03-29 | 浙江工业大学 | High-specific-surface-area high-entropy alloy nano powder and preparation method thereof |
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104308153A (en) * | 2014-10-27 | 2015-01-28 | 西安交通大学 | High-entropy alloy hot-end part manufacturing method of turbine engine on basis of selective laser melting |
| CN106756407A (en) * | 2016-12-07 | 2017-05-31 | 徐轶 | A kind of CrMnFeCoNiZr high-entropy alloys and preparation method thereof |
| CN107130124A (en) * | 2017-04-21 | 2017-09-05 | 北京科技大学 | A kind of method that increases material manufacturing technology shapes high-entropy alloy |
| CN107151755A (en) * | 2017-05-11 | 2017-09-12 | 浙江大学 | A kind of method for the high-entropy alloy for preparing close-packed hexagonal structure |
| CN107214336A (en) * | 2017-06-16 | 2017-09-29 | 东北大学 | The method that a kind of utilization selective laser smelting technology prepares 24CrNiMo Pattern Bainite Alloy steel |
| KR20170123968A (en) * | 2016-04-29 | 2017-11-09 | 한국과학기술원 | In-situ strengthened high entropy powder, alloy thereof and method of manufacturing the same |
| CN107971490A (en) * | 2017-11-10 | 2018-05-01 | 南京航空航天大学 | A kind of increasing material preparation method of surface high-entropy alloy gradient metallurgy layer |
| CN108118338A (en) * | 2018-01-04 | 2018-06-05 | 苏州科技大学 | A kind of method of high-frequency induction heating cladding TiC enhancings high-entropy alloy coating |
-
2018
- 2018-10-23 CN CN201811237707.9A patent/CN111085689B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104308153A (en) * | 2014-10-27 | 2015-01-28 | 西安交通大学 | High-entropy alloy hot-end part manufacturing method of turbine engine on basis of selective laser melting |
| KR20170123968A (en) * | 2016-04-29 | 2017-11-09 | 한국과학기술원 | In-situ strengthened high entropy powder, alloy thereof and method of manufacturing the same |
| CN106756407A (en) * | 2016-12-07 | 2017-05-31 | 徐轶 | A kind of CrMnFeCoNiZr high-entropy alloys and preparation method thereof |
| CN107130124A (en) * | 2017-04-21 | 2017-09-05 | 北京科技大学 | A kind of method that increases material manufacturing technology shapes high-entropy alloy |
| CN107151755A (en) * | 2017-05-11 | 2017-09-12 | 浙江大学 | A kind of method for the high-entropy alloy for preparing close-packed hexagonal structure |
| CN107214336A (en) * | 2017-06-16 | 2017-09-29 | 东北大学 | The method that a kind of utilization selective laser smelting technology prepares 24CrNiMo Pattern Bainite Alloy steel |
| CN107971490A (en) * | 2017-11-10 | 2018-05-01 | 南京航空航天大学 | A kind of increasing material preparation method of surface high-entropy alloy gradient metallurgy layer |
| CN108118338A (en) * | 2018-01-04 | 2018-06-05 | 苏州科技大学 | A kind of method of high-frequency induction heating cladding TiC enhancings high-entropy alloy coating |
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