MULTI-COMPONENT HIGH ENTROPY ALLOY WITH NANOSCALE ATOMIC SELF-ORDERING STRUCTURE AND PREPARATION METHODS THEREOF
20240344183 ยท 2024-10-17
Inventors
Cpc classification
C22C30/00
CHEMISTRY; METALLURGY
B22F10/28
PERFORMING OPERATIONS; TRANSPORTING
Y02P10/25
GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
International classification
C22C30/00
CHEMISTRY; METALLURGY
B22F10/28
PERFORMING OPERATIONS; TRANSPORTING
Abstract
The present invention uses additive manufacturing technology to develop a new L1.sub.2 reinforced multi-component high entropy alloy, which has high density and excellent strength and ductility mechanical properties. The selective laser melting process employed in crafting these multi-component high entropy alloys renders them safer, more cost-effective, and significantly reduces processing time, thus positioning them as highly competitive offerings within the market.
Claims
1. A multi-component high entropy alloy with nanoscale atomic self-ordering structure, comprising a composition of cobalt (Co), nickel (Ni), chromium (Cr), aluminum (Al), titanium (Ti), molybdenum (Mo), tantalum (Ta), and niobium (Nb), wherein the multi-component high entropy alloy is represented by the formula:
Co.sub.aNi.sub.bCr.sub.c Al.sub.d Ti.sub.eMo.sub.f Ta.sub.gNb.sub.h, where a, b, c, d, e, f, g, h, correspond to the atomic percentage of metal elements and, 10a70, 10b50, 0.1c20, 0.1d20, 0.01e10, 0.01f10, 0.1g10, 0.01h10, and wherein the multi-component high entropy alloy is a near-void-free alloy, and the multi-component high entropy alloy exhibits the nanoscale atomic self-ordering structure with dimensions ranging from 1 to 5 nm, wherein the multi-component high entropy alloy has a relative density of at least 95% compared to a reference material.
2. The multi-component high entropy alloy of claim 1, wherein the composition comprises 30-50 at. % cobalt (Co), 20-40 at. % Ni, 1-15 at. % Cr, 1-15 at. % Al, 0.1-5.0 at. % Ti, 0.5-5 at. % Mo, 0.5-5 at. % Ta, and 0.1-5 at. % Nb.
3. The multi-component high entropy alloy of claim 1, wherein the composition comprises 36-45 at. % Co, 26-32 at. % Ni, 7-12 at. % Cr, 8-13 at. % Al, 0.5-3 at. % Ti, 0.6-2.5 at. % Mo, 0.7-2.6 at. % Ta, and 0.7-2.2 at. % Nb.
4. The multi-component high entropy alloy of claim 1, wherein the multi-component high entropy alloy has diffraction angles (2) at which the peaks occur in the X-ray diffraction (XRD) pattern as follows: 43.53, 50.52, 74.55, 90.35, and 95.70.
5. The multi-component high entropy alloy of claim 1, wherein the multi-component high entropy alloy has a size distribution ranging from 10 m to 100 m.
6. The multi-component high entropy alloy of claim 1, wherein the multi-component high entropy alloy has an ultimate tensile strength of at least 1 GPa.
7. The multi-component high entropy alloy of claim 1, wherein the multi-component high entropy alloy has a uniform elongation of at least 15.0% under tension at ambient temperature.
8. The multi-component high entropy alloy of claim 1, wherein the multi-component high entropy alloy has a sphericity of at least 90%.
9. A method for preparing a multi-component high entropy alloy, comprising: weighting and blending metal powders to obtain a mixture; degassing and slagging the mixture to obtain a composition; forming an alloy liquid in a vacuum induction furnace and casting the liquid into an alloy ingot; processing the alloy ingot into spherical alloy powder; and melting and solidifying the spherical alloy powder by selective laser to obtain the multi-component high entropy alloy with a nanoscale atomic self-ordering structure with dimensions ranging from 1 to 5 nm.
10. The method of claim 9, wherein the metal powders comprise 10-70 at. % cobalt (Co), 10-50 at. % Ni, 0.1-20 at. % Cr, 0.1-20 at. % Al, 0.01-10 at. % Ti, 0.01-10 at. % Mo, 0.1-10 at. % Ta, and 0.01-10 at. % Nb.
11. The method of claim 9, wherein the metal powders comprise 30-50 at. % cobalt (Co), 20-40 at. % Ni, 1-15 at. % Cr, 1-15 at. % Al, 0.1-5.0 at. % Ti, 0.5-5 at. % Mo, 0.5-5 at. % Ta, and 0.1-5 at. % Nb.
12. The method of claim 9, wherein step of degassing and slagging the mixture to obtain a composition occurs in an inert atmosphere and is conducted at a working temperature in a range of 1500 C. to 1600 C.
13. The method of claim 12, wherein step of degassing and slagging the mixture to obtain a composition is conducted for 5-10 minutes.
14. The method of claim 9, wherein the temperature within the vacuum induction furnace is controlled at 1400 C. to 1450 C.
15. The method of claim 9, wherein step of processing the alloy ingot into spherical alloy powder is carried out using plasma rotation click atomization, and the step occurs at a working speed of 40,000 rpm to 50,000 rpm and a working pressure of 6 MPa to 10 MPa.
16. The method of claim 9, wherein the multi-component high entropy alloy has a size distribution ranging from 10 m to 100 m.
17. The method of claim 9, wherein the multi-component high entropy alloy has a sphericity of at least 90%.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
[0030] Embodiments of the invention are described in more details hereinafter with reference to the drawings, in which:
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DETAILED DESCRIPTION
[0053] In the following description, multi-component high entropy alloys (HEAs) and their preparation process are set forth as preferred examples. It will be apparent to those skilled in the art that modifications, including additions and/or substitutions may be made without departing from the scope and spirit of the invention. Specific details may be omitted so as not to obscure the invention; however, the disclosure is written to enable one skilled in the art to practice the teachings herein without undue experimentation.
[0054] Additive Manufacturing (AM), also known as 3D printing, uses computer-aided design (CAD), material processing, and molding techniques to fabricate specialized materials layer by layer using software and numerical control systems based on digital model files. A method of directly manufacturing 3D solid parts identical to corresponding digital models. It has the characteristics of a simple process, a short processing cycle, and high material utilization rate. This makes it possible to manufacture complex structural parts, which cannot be realized due to the constraints of traditional manufacturing methods in the past, and topological optimization of the model structure could be carried out according to the needs.
[0055] L1.sub.2 is a crystal structure that is often used as a strengthening mechanism in alloys. It consists of a face-centered cubic (FCC) lattice with ordered arrangements of atoms, which can enhance the mechanical properties of the material. In the context of multi-component Co-rich high entropy alloys, L1.sub.2 refers to the ordered arrangement of atoms in the crystal structure of the alloy that provides enhanced mechanical properties, such as increased strength and hardness.
[0056] The present invention utilizes 3D printing, specifically its extreme printing parameters, in conjunction with the composition of cobalt (Co), nickel (Ni), chromium (Cr), aluminum (Al), titanium (Ti), molybdenum (Mo), tantalum (Ta), and niobium (Nb) to develop a new L1.sub.2 reinforced multi-component Co-rich high entropy alloy (MCoHEA), which is a nearly void-free HEAs, and has high density and excellent strength and ductility mechanical properties. In the SLM process, a high-energy laser beam is precisely directed onto metal powder, selectively melting it layer by layer. This controlled melting process gradually builds up a three-dimensional object with high precision and intricate detail. The working principle of SLM revolves around precise computer control of both the positioning and intensity modulation of the laser beam throughout each layer-building phase. This intricate process ensures that the laser beam is accurately directed onto specific areas of the metal powder bed, melting it according to the digital design. By controlling the laser's intensity, the amount of energy delivered to the powder can be finely adjusted, allowing for the precise melting and solidification required to build up complex three-dimensional objects with exceptional accuracy and structural integrity.
[0057] The HEAs are characterized by high-density nanoscale atomic self-ordering (NS-ASO) structures. Such NS-ASO structures facilitates the overcoming of barriers susceptible to cracking often observed in precipitate-strengthened alloys with a high (Al+Ti+Nb+Ta) content exceeding 6.0 wt. %, while also fully guaranteeing the strengthening effect of the ordered precipitates. Additionally, these structures maintain a high work hardening rate and plastic deformation capacity. These findings provide an efficient routine to fabricate near-void-free alloys with an exceptional 99.998% relative density. They exhibit unprecedented isotropy in mechanical properties, boasting impressive strengths of approximately 1.54 GPa and a uniform elongation as high as approximately 22.5% under tension at ambient temperature.
[0058] In one embodiment, the composition of the multi-component high entropy alloy includes 10-70 at. % cobalt (Co), 10-50 at. % nickel (Ni), 0.1-20 at. % chromium (Cr), 0.1-20 at. % aluminum (Al), 0.01-10.0 at. % titanium (Ti), 0.01-10 at. % molybdenum (Mo), 0.1-10 at. % tantalum (Ta), and 0.01-10 at. % niobium (Nb).
[0059] Preferably, the composition of the multi-component high entropy alloy includes 30-50 at. % cobalt (Co), 20-40 at. % nickel (Ni), 1-15 at. % chromium (Cr), 1-15 at. % aluminum (Al), 0.1-5.0 at. % titanium (Ti), 0.5-5 at. % molybdenum (Mo), 0.5-5 at. % tantalum (Ta), and 0.1-5 at. % niobium (Nb).
[0060] In one embodiment, the present invention provides a more diverse range of high-entropy alloys with a molecular formula of Co.sub.aNi.sub.bCr.sub.cAl.sub.d Ti.sub.eMo.sub.fTa.sub.gNb.sub.h, where a, b, c, d, e, f, g, h, correspond to the atomic percentage of metal elements and, 36a45, 26b32, 7c12, 8d13, 0.5e3, 0.6f2.5, 0.7g2.6, 0.7h2.2.
[0061] Preferably, the composition of HEAs includes Co.sub.43.1Ni.sub.28.8Cr.sub.10.2Al.sub.10.0Ti.sub.2.1Nb.sub.2.2Ta.sub.1.5Mo.sub.2.1.
[0062] The addition of Ni serves to widen the phase region while also inhibiting the formation of harmful intermetallic phases. The addition of Al and Cr can improve oxidation resistance and maintain low / lattice mismatches. The use of Ti, Mo, Ta, and Nb is to replace the high-density W, which can reduce the mass density without destroying the microstructure of /.
[0063] The HEA also feature an outstanding work-hardening capacity of approximately 530 megapascals. The ultrahigh strength primarily originates from the ordering strengthening, while substantial ductility is attributed to a progressive work-hardening mechanism regulated by the coherent NS-ASO architectures.
[0064] The present invention also provides a method for preparing the multi-component high entropy alloy, including: [0065] (1) weighting and blending designated elemental metal powders of Co, Ni, Cr, Al, Ti, Mo, Ta, and Nb according to their atomic percentages in the molecular formula; [0066] (2) performing degassing and slagging processes to achieve the desired composition; [0067] (3) forming an alloy liquid within a vacuum induction furnace and subsequently casting the liquid into an alloy ingot. [0068] (4) transforming the alloy ingot into spherical alloy powder using plasma rotation click atomization technology at a working speed of 40,000 rpm to 50,000 rpm and a working pressure of 6 MPa to 10 MPa. [0069] (5) melting and solidifying the spherical alloy powder by selective laser to produce a multi-component high entropy alloy with high-density nanoscale atomic self-ordering structure, which has high density and excellent strong plastic energy.
[0070] The raw materials are fully matured, available at an inexpensive price, and the milling technology has been proficiently mastered.
[0071] Compared with traditional processing methods such as casting and forging, laser 3D printing technology can quickly achieve near net forming. The technology has simple process flow, low cost and short production cycle.
[0072] The resulting multi-component high entropy alloy has a particle size distribution between 10 m to 100 m, with an average particle size ranging from 10 m to 50 m. The sphericity of the spherical powder is greater than 90%.
[0073] In one embodiment, the resulting multi-component high entropy alloy has a particle size distribution between 15 m to 80 m, with an average particle size ranging from 20 m to 40 m. The sphericity of the spherical powder is greater than 92.5%.
[0074] Preferably, the resulting multi-component high entropy alloy has a particle size distribution between 20 m to 65 m, with an average particle size ranging from 28 m to 37 m. The sphericity of the spherical powder is greater than 95%.
[0075] In one embodiment, the resulting multi-component high entropy alloy has a density of at least 90%, a strength of at least 1 GPa, and a uniform elongation of at least 15.0%.
[0076] In one embodiment, the resulting multi-component high entropy alloy has a density of at least 95%, a strength of at least 1.2 GPa, and a uniform elongation of at least 20.0%.
[0077] Preferably, the resulting multi-component high entropy alloy has a density of 99.997%, a strength of up to 1.5 GPa, and a uniform elongation of up to 22.5%.
[0078] The excellent strength-ductility matching means that the multi-component high entropy alloy (e.g., MCoHEA) can provide higher safety, more beneficial to energy conservation and emission reduction. In addition, additive manufacturing technology can prepare a variety of complex shape structural parts, which can significantly shorten the preparation cycle, save raw materials and costs, and realize large-scale production.
EXAMPLE
Example 1
Characterization of HEA Powders Processed Through SLM
[0079] The HEA powders were produced using gas atomization method, achieving good sphericity and a particle size distribution of D (10)=22.26, D (50)=35.16, and D (90)=48.34. Electron backscatter diffraction (EBSD) analysis revealed that a polycrystalline morphology with an average grain size of approximately 7 m, and a random orientation distribution can be found (
[0080] Through preliminary experiments based on the normalized equivalent energy density, the parameters were optimized (Energy density of 64.59 J/mm.sup.3, power of 285 W, scanning rate of 950 mm/s) for fabricating the cuboid samples using selective laser melting (SLM) (
TABLE-US-00001 TABLE 1 the optimized processing parameters of laser-powder bed fusion (L-PBF) Processing parameters Laser power (W) 270 Scan speed (mm/s) 950 Layer thickness (m) 40 Hatch spacing (m) 110 Scan pattern Layer to layer rotation Rotation angle () 67
[0081] Although cracks and voids were detected in the as-printed HEAs using microcomputed tomography (-CT) and metallographic methods (
TABLE-US-00002 TABLE 2 Comparison of the relative density between the present NS- ASO HEA and other as-printed alloys reported in prior art Relative AM Density Detection Alloy method (%) method This work NS-ASO HEA SLM 99.998 3D CT Superalloy IN713LC SLM 99.92 OM IN738LC SLM Cracked OM GH4099 SLM 99.7 OM CMSX-4 SLM Cracked OM GH99 SLM 99.57 OM Haynes282 SLM 99.98 OM K418 SLM 99.7 OM Rene77 SLM 99.93 OM GH3536 SLM 99.91 OM SBCoNi10C SLM 99.85 OM CM247LC SLM Cracked SEM IN939 SLM Cracked SEM MAR M-247 SLM Cracked SEM M3 SLM Cracked SEM Rene 108 SLM Cracked SEM Hastelloy X SLM 99.9 Archimedes IN625 SLM 99.95 Archimedes GTD222 SLM 99.8 Archimedes GH5188 SLM 99.53 Archimedes HEA AlCoCrFeNi.sub.2.1 SLM 99.5 AlCrFeNiV SLM 99.88 OM AlCrCuFeNix SLM 99.7 OM FeNiCoAlTaB SLM 99.8 OM (FeCoNi).sub.85.84Al.sub.7.07Ti.sub.7.09 SLM 99.95 Archimedes Al.sub.0.3CoCrFeNiCu SLM 99.08 Archimedes TiNbTaZrMo SLM 99.7 Archimedes (FeCoNi).sub.86Al.sub.7Ti.sub.7 SLM 99.43 Archimedes Al.sub.0.2Co.sub.1.5CrFeNi.sub.1.5Ti.sub.0.3 SLM 97 OM+ Archimedes FeCoCrNi SLM 99.01 Archimedes CoCrFeNiTi SLM 99.3 Archimedes CoCrFeNiMn SLM 99.2 Archimedes Fe.sub.50Mn.sub.30Co.sub.10Cr.sub.10 SLM 99.4 Archimedes NiCrFeCoMo.sub.0.2 SLM 99.12 Archimedes Co.sub.1.5CrFeNi.sub.1.5Ti.sub.0.5Mo.sub.0.1 SLM 99.3 Archimedes CoCrNi SLM 99.7 3D CT Titanium Ti1Al8V5Fe SLM 99.38 OM alloy Ti35Nb7Zr-5Ta SLM 99.87 OM Ti6Al2Sn4Zr2Mo SLM 99.5 Archimedes Ti6Al2Zr1Mo1V SLM 99.5 Archimedes Ti5.5Al3.4Sn3.0Zr SLM 99.34 Archimedes 0.7Mo0.3Si0.4Nb 0.35Ta Ti15A SLM 99.98 Archimedes TiTa SLM 99.9 Archimedes Ti5Al5Mo5V SLM 99.9 Archimedes 3Cr1Zr Aluminium 2024Al SLM 97.5 OM alloy 7075Al SLM 99.5 OM AlCuMg SLM 96.7 OM Ti/AlCuMg SLM 99.7 OM AlSi7Mg0.3 SLM 99.8 Archimedes 7075Al SLM 97.2 Archimedes A357 SLM 99.79 Archimedes AlSi10Mg SLM 98.5 Archimedes AA6061 SLM 97.6 Archimedes AlSi12 SLM 99.97 3D CT
[0082] The present invention further addresses common defects encountered during the 3D printing process, such as lack of fusion (LoF) defects and the occurrence of keyholes. LoFs refer to the situation where materials in the 3D printing process do not fully fuse together to form a continuous structure. This can lead to poor adhesion between material layers, impacting the overall strength and performance of the printed object. Keyholes, on the other hand, are holes formed during the 3D printing process due to excessive printing speed or improper material flow. These holes typically have a keyhole shape and may affect the appearance and surface quality of the printed object. Referring to
[0083] These results indicates that the multi-component high entropy alloy with NS-ASO structure (NS-ASO HEAs) effectively resolved the typical cracking problems typically associated with precipitate-strengthened superalloys containing FCC and L1.sub.2 with (Al+Ti+Nb+Ta)>6.0 wt. %.
[0084] Furthermore, representative engineering components such as an octet-truss micro lattice and prototype turbine blades with thin, overhanging platforms were successfully printed (
[0085] Following that, the basic microstructure of the as-printed NS-ASO HEAs was analyzed. The as-printed HEAs exhibited a polycrystalline morphology under EBSD, with no significant texture observed (
Example 2
Atomic-Scale Chemical Composition of the Printed HEAs
[0086] In this example, three-dimensional atom probe tomography (3D-APT, spatial resolution of approximately 1 nm) was used to evaluate the atomic-scale chemical composition of our as-printed HEAs. Turning to
[0087] Referring to
TABLE-US-00003 TABLE 3 Chemical compositions of the present NS-ASO HEA measured by 3D-APT Co Ni Al Cr Ti Nb Ta Mo DC1 43.48 1.62 30.16 1.24 10.09 0.80 10.55 0.81 1.64 0.39 1.43 0.13 1.91 0.40 2.00 0.98 DC2 43.99 2.04 27.52 1.54 10.17 1.02 10.43 1.03 2.20 0.61 2.05 0.53 1.74 0.46 2.21 1.00 DC3 43.09 2.08 29.57 1.72 10.37 1.17 11.03 1.18 1.72 0.52 1.94 0.42 1.95 0.55 2.07 0.18 DC4 43.23 2.16 27.91 0.48 10.21 0.89 10.96 0.48 1.64 0.21 2.06 0.23 1.90 0.25 2.07 0.23
[0088] Turning to
[0089] The main issue with as-printed precipitate-hardened alloys lies in the balance between strength and ductility, alongside the anisotropic mechanical properties observed in both building direction (BD) and scanning direction (SD).
[0090] Referring to
[0091] Additionally, Outs versus uniform elongation curves were plotted and compared with those of as-printed alloys featuring FCC-type, FCC+BCC-type, FCC+L1.sub.2-type, FCC+HCP-type, FCC+BCC+HCP-type, and FCC+ other structures (i.e., carbides, ceramic, etc.)-type alloys. The results illustrated the exceptional combination of high strength and large ductility exhibited by the NS-ASO HEAs of the present invention, surpassing those of state-of-the-art as-printed alloys (
TABLE-US-00004 TABLE 4 Room temperature tensile properties of other as-printed alloys reported in prior art Uniform .sub.uts elongation Materials (MPa) (%) Ti3.5Cu LMD 1180 2.1 Ti6.5Cu 1073 5.5 Ti8.5Cu 867 10.5 Ti644.5%316L SLM 1297 8.8 Ti6Al-4V SLM with 1137 3.0 ultrasound SLM 1015 3.7 without ultrasound Ti6Al4V SLM-V 1219 1.9 SLM-H 1269 2.0 Ti6Al4V SLM-V 1166 1.7 SLM-H 1206 2.6 Ti6Al4V SLM 1300 3.0 1272 3.3 1252 3.4 1150 3.5 1028 6.3 Ti6Al4V SLM 1115 2.5 Ti6Al4V SLM 1095 4.5 Ti6Al4V SLM 1090 4.5 1149 5.4 1165 5.2 CoCrNi LAAM 873.5 43 Fe.sub.26.13Co.sub.23.1Ni.sub.23.29Cr.sub.25.78Si.sub.1.36C.sub.0.34 SLM 907 22 (CoCrFeMnNi).sub.99C.sub.1 SLM 840 21 Al.sub.0.5Cr.sub.0.9FeNi.sub.2.5V.sub.0.2 SLM 1057 27 Co.sub.32.4Ni.sub.11.7W.sub.4.4Cr.sub.3.3Ta.sub.1.5 SLM 1270 11.5 AlCoCrFeNi.sub.2.1 SLM 1418 3.19 AlCrCuFeNi.sub.3.0 SLM 957 14.3 AlCoCrFeNi CCW- 975 3.11 AAM Al.sub.0.25FeMnNiCrCu.sub.0.5 LMD 1052 24.5 Al.sub.36.67Ni.sub.33.79Fe.sub.17.28Cr.sub.8.28Co.sub.4.99 WAAM 880 10 AlCoCrFeNi.sub.2.1 SLM 1640 7.5 Fe.sub.49.5Mn.sub.30Co.sub.10Cr.sub.10C.sub.0.5 SLM 1000 28 Fe.sub.40Mn.sub.20Co.sub.20Cr.sub.15Si.sub.5 L-PBF 980 24 Fe.sub.40Mn.sub.20Co.sub.20Cr.sub.15Si.sub.5B.sub.4C 1200 5 Al.sub.0.2Co.sub.1.5CrFeNi.sub.1.5Ti.sub.0.3 SLM 1042 20.58 (FeCoNi).sub.86Al.sub.7Ti.sub.7 SLM 1090 28 Co.sub.1.5CrFeNi.sub.1.5Ti.sub.0.5Mo.sub.0.1 SLM 1178 20 Co.sub.19.96Cr.sub.20.31Fe.sub.20.18Ni.sub.20.07Mn.sub.19.48 + SLM 1100 5.5 TiN(12 wt. %) (CoCrFeMnNi).sub.99C.sub.1 SLM 989 11 (FeCoCrNi).sub.98.5Si.sub.1.5 SLM 815 23.5 (CoCrFeMnNi).sub.99C.sub.1 SLM 995 13 Ni.sub.20.7Cr.sub.19.8Mn.sub.18.7Co.sub.20.9Fe.sub.19.9 + L-PBF 940 30 1 wt. % AlCoCrFeNi2.1 SLM 1600 10 AlCoCrFeNi.sub.2.1 LMD 965 12.5 1100 21 Al1.2CoCrFeNi.sub.2.1 PPA- 985 6 AM Ni.sub.6Cr.sub.4WFe.sub.9Ti SLM 966 11 Al.sub.0.5CrCoFeNi SLM 865 16 FeCoCrNiMo.sub.0.3 L-PBF 955 36 AlCoCrFeNi.sub.2.1 SLM 1260 21 1280 20 1355 8.5 1441 5 1489 4.8 (FeCoNi).sub.86Al.sub.7Ti.sub.7 SLM 1010 18.5 VCoNi LMD 1219 19 1354 14.8 1463 11 1539 9 EP718 SLM 845 27 MM509 SLM 1436 4.3 K468 EHLMD 880 30 Hastelloy X SLM 935 13 IN100 Micro- 1030 9 LAAM Inconel718 SLM 1033 25 Inconel718 SLM 947 17 Inconel718 EBM 908 12.4 SLM 1026 20 Inconel738 SLM 1592 6 1290 11.3 Inconel625 Additive 1072 21 Friction Stir Inconel625 SLM 835 40 Inconel625 SLM 1041 33.1 Inconel625 PMAM 834 17 855 31 CMSX-4 EBM 930 5 Hastelloy X + TiC SLM 849 15 IN738LC EBM 1185 11.5 1074 9.5 GH3536 LSF 855 18 Ni.sub.50.34(Co, Cr).sub.20(Al, Ti).sub.20(Hf, Mo, DED 1096 24 Nb).sub.9.2(Si, C).sub.0.46 Co28Cr6Mo SLM 1260 12.7 Fe.sub.19Ni.sub.5Ti steel DED 1300 7 AISI4340-H SLM 1510 4.5 AISI4340-V 1474 4.8 AISI8620-H 1400 3.0 AISI8620-V 1384 4.3 AISI4140-H 1110 2.5 AISI4140-V 1080 2.2 AISI 420 LAAM 1573 10 300M SLM-V 1218 8 SLM-H 1119 8.4 15-5PH SLM 1413 21 15-5 PH SLM 1424 7.1 18Ni-300 SLM-H 1224 6 SLM-V 1194 4 18Ni-300 SLM-V 1007 4 SLM-H 1005 2 ER120S-G CMT- 1000 8.8 WAAM-H CMT- 1040 6.3 WAAM-V SS411 SLM-H 892 9.5 SLM-V 864 10.5
[0092] In addition to the mechanical properties, the low cyclic fatigue (LCF) resistance of the present as-printed NS-ASO HEA was also evaluated, as shown in
[0093] An in-depth investigation of the compositional features and atomic structure of the HEA powders was initiated using APT and HAADF-STEM.
[0094] Additionally, Scheil-Gulliver analysis was employed to model the non-equilibrium solidification process, and Differential Scanning calorimetry (DSC) was utilized for enhanced insights (
where f.sub.s is the fraction solid, and T is the temperature.
[0095] The HEA exhibited a smaller Scheil freezing range of about 240 K and a CSI value, even lower than readily printable IN718 and IN625 superalloys. STEM-EDS results showed there were no elemental segregation at the grain boundary and formation of FCC+L1.sub.2 eutectic phases with low-melting point (
[0096] Additionally, the TEM and EDS results presented in
TABLE-US-00005 TABLE 5 Chemical compositions of the BCC and HCP phases precipitated in the NS-ASO HEA measured by STEM-EDS Co Ni Al Cr Ti Nb Ta Mo BCC 35.64 0.77 26.98 0.62 20.10 0.65 5.89 0.67 3.99 0.23 3.36 0.81 2.83 0.13 1.19 0.35 HCP 46.85 1.92 17.99 1.26 3.80 0.54 11.69 1.67 3.64 0.11 8.38 1.12 2.63 0.68 5.03 0.48
[0097] Next, an exploration into the origins of the excellent strength-ductility synergy in the as-printed HEA was undertaken. The as-printed NS-ASO HEA exhibited a distinctive two-stage work-hardening behavior, characterized by a significantly higher work-hardening rate and a consistent work-hardening exponent across a wider strain range. The dynamic evolution of the deformation microstructure under varying strains was meticulously characterized using electron backscatter diffraction (EBSD), transmission electron microscopy (TEM), and neutron diffraction. At approximately 5% strain, many dislocations and antiphase boundary (APB) were observed, and the dislocation slipping in the appearance of extended stacking faults (SFs) was activated (
[0098] Additionally, planar dislocations and stacking faults (SFs) crossing the cell boundary were detected in the initial stage of deformation (
[0099] Turning to
Example 3
Preparation of MCoHEA-1
[0100] The composition of MCoHEA-1 is as follows: 39-44 at. % cobalt (Co), 28-32 at. % nickel (Ni), 9-12 at. % chromium (Cr), 10-13 at. % aluminum (Al), 0.5-1.5 at. % titanium (Ti), 1.2-2.5 at. % molybdenum (Mo), 1.3-2.2 at. % tantalum (Ta), and 0.8-1.2 at. % niobium (Nb).
[0101] MCoHEA-1 was prepared as follows: [0102] (1) weighting and blending designated elemental metal powders of Co, Ni, Cr, Al, Ti, Mo, Ta, and Nb to obtain a mixture. [0103] (2) degassing and slagging the mixture to reach a composition. [0104] (3) forming an alloy liquid in a vacuum induction furnace and casting the liquid into an alloy ingot. [0105] (4) processing the obtained alloy ingot into spherical alloy powder using plasma rotation click atomization technology occurs at a working speed of 40,000 rpm to 50,000 rpm and a working pressure of 6 MPa to 10 MPa. [0106] (5) melting and solidifying the spherical alloy powder by selective laser to produce a multi-component high entropy alloy with high-density nanoscale atomic self-ordering structure, which has high density and excellent strong plastic energy.
[0107] The morphology evaluation was conducted by SEM.
[0108]
[0109] The sphericity of the powder is more than 95% when laser melting is performed using the following parameters: laser power of 315 W, scanning speed of 750 mm/s, scanning thickness of 40 m, and input energy density of 95.45 J/mm.sup.3. these particles are roughly round in shape, like a ball. They may have a smooth surface or be covered in small protrusions.
[0110] In one embodiment, the particle shape is not limited to spherical.
[0111] The density, tensile strength and uniform elongation of the MCoHEA-1 were also tested. The printed MCoHEA-1 has a density of 95.5%, a tensile strength of 1.36 GPa, and a uniform elongation of 15.1%.
Example 4
Preparation of MCoHEA-2
[0112] The composition of MCoHEA-2 is as follows: 38-43 at. % cobalt (Co), 26-29 at. % nickel (Ni), 8-11 at. % chromium (Cr), 8-12 at. % aluminum (Al), 1.2-2.1 at. % titanium (Ti), 1.6-2.6 at. % molybdenum (Mo), 1.5-2.1 at. % tantalum (Ta), and 1.1-2.1 at. % niobium (Nb).
[0113] The preparation method of MCoHEA-2 is the same as that of MCoHEA-1, the only difference is that the atomic percentages used are different.
[0114] The morphology evaluation was conducted by SEM.
[0115] The sphericity of the powder is more than 95% when laser melting is performed using the following parameters: laser power of 270 W, scanning speed of 950 mm/s, scanning thickness of 40 m, and input energy density of 64.59 J/mm.sup.3. These particles are roughly round in shape, like a ball. They may have a smooth surface or be covered in small protrusions.
[0116] The density, tensile strength and uniform elongation of the MCoHEA-2 were also tested. The printed MCoHEA-2 has a density of 99.997%, an ultimate tensile strength (UTS) of 1.50 GPa, and a yield strength (YS) of 970 MPa. Also,
[0117] In one embodiment, the as-built sample was subjected to aging heat treatment (1050 C. for 30 minutes plus 800 C. for 4 hours, AC) in ambient temperature. After heating, the microstructure morphology changed from
Example 5
Preparation of MCoHEA-3
[0118] The composition of MCoHEA-3 is as follows: 38-43 at. % cobalt (Co), 26-29 at. % nickel (Ni), 8-11 at. % chromium (Cr), 8-12 at. % aluminum (Al), 1.2-2.1 at. % titanium (Ti), 1.6-2.6 at. % molybdenum (Mo), 1.5-2.1 at. % tantalum (Ta), and 1.1-2.1 at. % niobium (Nb).
[0119] The preparation method of MCoHEA-3 is the same as that of MCoHEA-1, the only difference is that the atomic percentages used are different.
[0120] The morphology evaluation was conducted by SEM.
[0121] The sphericity of the powder is more than 95% when laser melting is performed using the following parameters: laser power of 270 W, scanning speed of 950 mm/s, scanning thickness of 40 m, and input energy density of 64.59 J/mm. these particles are roughly round in shape, like a ball. They may have a smooth surface or be covered in small protrusions.
[0122] The as-built sample was subjected to aging heat treatment (800 C. for 4 h, AC) in ambient temperature. The uniform elongation was measured to be about 11.8%, as shown in
[0123] Micro-CT analysis, or micro computed tomography analysis, is a non-destructive imaging technique that uses X-rays to create high-resolution, three-dimensional images of small objects or samples. During micro-CT analysis, the sample is placed inside the scanner, which rotates and takes a series of X-ray images from different angles. These images are then reconstructed into a 3D image using computer algorithms. The histogram displays the distribution of data based on the EqDiameter variable, with the relative frequency of each data point being represented by the height of the bars. Referring to
INDUSTRIAL APPLICABILITY
[0124] Multi-principal element high entropy alloys are expected to have a wide range of potential applications in aerospace, automotive, nuclear engineering and other fields. The multi-component high entropy alloy of the present invention fabricated through selective laser melting offers enhanced safety, affordability, and reduced processing time, thus presenting significant competitiveness within the market. This nanoscale atomic self-ordering strategy provides a new pathway to design ultrastrong-yet-ductile alloys with near-zero void, which can also be feasibly applied to many other alloy systems like superalloys, steels, and aluminum alloys for extensive engineering applications.
[0125] The foregoing description of the present invention has been provided for the purposes of illustration and description. It is not intended to be exhaustive or to limit the invention to the precise forms disclosed. Many modifications and variations will be apparent to the practitioner skilled in the art.
[0126] The embodiments were chosen and described in order to best explain the principles of the invention and its practical application, thereby enabling others skilled in the art to understand the invention for various embodiments and with various modifications that are suited to the particular use contemplated.
Definition
[0127] The term at. % used herein refers to atomic percent. For example, if a sample contains 80 atoms of element A and 20 atoms of element B, the atomic percent of element A would be 80 at. %, and the atomic percent of element B would be 20 at. %.
[0128] The term multi-component alloy used herein is a type of alloy that is composed of three or more different elements in varying proportions. Multi-component alloys can include binary, ternary, quaternary, and even higher-order combinations of elements.
[0129] The term relative density, also known as specific gravity, is the ratio of the density of a material to the density of a reference material under specified conditions. It is typically expressed as a percentage. A relative density of 100% indicates that the material has the same density as the reference material under the given conditions. If the relative density is greater than 100%, it means the material is denser than the reference material, and if it is less than 100%, it means the material is less dense than the reference material.
[0130] The term near-void-free refers to the condition in which a material contains almost no pores or voids. In metallic materials, pores or voids are typically considered undesirable defects as they can lead to degradation in mechanical properties such as strength and toughness. Therefore, near-void-free indicates that the number of pores present in the material is very minimal, approaching zero or zero, ensuring that the material maintains high quality and reliability.
[0131] Throughout this specification, unless the context requires otherwise, the word comprise or variations such as comprises or comprising, will be understood to imply the inclusion of a stated integer or group of integers but not the exclusion of any other integer or group of integers. It is also noted that in this disclosure and particularly in the claims and/or paragraphs, terms such as comprises, comprised, comprising and the like can have the meaning attributed to it in U.S. Patent law; e.g., they allow for elements not explicitly recited, but exclude elements that are found in the prior art or that affect a basic or novel characteristic of the present invention.
[0132] Furthermore, throughout the specification and claims, unless the context requires otherwise, the word include or variations such as includes or including, will be understood to imply the inclusion of a stated integer or group of integers but not the exclusion of any other integer or group of integers.
[0133] As used herein and not otherwise defined, the terms substantially, substantial, approximately and about are used to describe and account for small variations. When used in conjunction with an event or circumstance, the terms can encompass instances in which the event or circumstance occurs precisely as well as instances in which the event or circumstance occurs to a close approximation. For example, when used in conjunction with a numerical value, the terms can encompass a range of variation of less than or equal to +10% of that numerical value, such as less than or equal to +5%, less than or equal to +4%, less than or equal to +3%, less than or equal to +2%, less than or equal to +1%, less than or equal to +0.5%, less than or equal to +0.1%, or less than or equal to +0.05%.
[0134] References in the specification to one embodiment, an embodiment, an example embodiment, etc., indicate that the embodiment described can include a particular feature, structure, or characteristic, but every embodiment may not necessarily include the particular feature, structure, or characteristic. Moreover, such phrases are not necessarily referring to the same embodiment. Further, when a particular feature, structure, or characteristic is described in connection with an embodiment, it is submitted that it is within the knowledge of one skilled in the art to affect such feature, structure, or characteristic in connection with other embodiments whether or not explicitly described.
[0135] In the methods of preparation described herein, the steps can be carried out in any order without departing from the principles of the invention, except when a temporal or operational sequence is explicitly recited. Recitation in a claim to the effect that first a step is performed, and then several other steps are subsequently performed, shall be taken to mean that the first step is performed before any of the other steps, but the other steps can be performed in any suitable sequence, unless a sequence is further recited within the other steps. For example, claim elements that recite Step A, Step B, Step C, Step D, and Step E shall be construed to mean step A is carried out first, step E is carried out last, and steps B, C, and D can be carried out in any sequence between steps A and E, and that the sequence still falls within the literal scope of the claimed process. A given step or sub-set of steps can also be repeated. Furthermore, specified steps can be carried out concurrently unless explicit claim language recites that they be carried out separately.
[0136] Other definitions for selected terms used herein may be found within the detailed description of the present invention and apply throughout. Unless otherwise defined, all other technical terms used herein have the same meaning as commonly understood to one of ordinary skill in the art to which the present invention belongs.