Divorced eutectic microstructural NiTiNb shape memory alloy with high recovery rate and recovery stress prepared by laser powder bed fusion

doi:10.1007/s40436-025-00582-9

Abstract

Abstract: NiTiNb is a wide-hysteresis shape memory alloy (SMA) with great application potential in many industries, such as the aerospace and biomedical fields. However, a series of hot working processes, from casting to subsequent hot working processes, such as forging, heat treatment, and machining, are required owing to the limitations of long cycles, high energy consumption, and limited product structure. Meanwhile, during traditional equilibrium solidification, many eutectic structures composed of matrix and β-Nb phase are formed. The plastic deformation of the large β-Nb phase in the eutectic region may seriously deteriorate the shape memory performance. However, the eutectic structure is inherited, and its influence on shape memory properties cannot be eliminated by subsequent traditional hot workings. In this study, considering non-equilibrium solidification in 3D printing, laser powder bed fusion (LPBF) was attempted to rapidly fabricate NiTiNb alloys. Excellent shape memory performance with a divorced eutectic structure could be tailored using suitable LPBF parameters. It was observed that, in terms of the recovery rate, recovery stress, and thermomechanical cycle stability, the LPBF-NiTiNb alloys were superior to the traditional cast, forged, and extruded NiTiNb alloys. The recovery rate of the LPBF-NiTiNb alloy after 6% pre-strain at low temperatures reached approximately 98.8%, which was 21.5% higher than that of the as-cast alloy. The maximum recovery stress of LPBF-NiTiNb alloy reached 420 MPa, which was 55.9% and 15.4% higher than traditional forged and extruded alloys, respectively. The improved shape memory performance was essentially caused by the solidification difference between the non-equilibrium rapidly solidifying additive alloys and equilibrium solidifying as-cast alloys. To reduce costs and shorten fabrication processes using additive manufacturing, this finding provides a new perspective for tailoring the microstructure and improving the shape memory performance of NiTiNb alloys.

The full text can be downloaded at https://doi.org/10.1007/s40436-025-00582-9

Key words: Shape memory alloy (SMA), Laser powder bed fusion (LPBF), NiTiNb, Shape memory properties, Divorced eutectic

Mei-Li Hou, Zhi-Wei Yang, Xin Liu, Jing-Chao Yang, Bao-Hui Zhu, Xin Lin, Heng Li. Divorced eutectic microstructural NiTiNb shape memory alloy with high recovery rate and recovery stress prepared by laser powder bed fusion[J]. Advances in Manufacturing, 2026, 14(3): 639-658.

TrendMD

Add to citation manager EndNote|Reference Manager|ProCite|BibTeX|RefWorks

URL: https://www.aim.shu.edu.cn/EN/10.1007/s40436-025-00582-9

https://www.aim.shu.edu.cn/EN/Y2026/V14/I3/639

References

[1] Yang C, Huang ZY, Chen T et al (2024) Large recoverable strains with high recovery rates via cooperative regulation of texture and precipitation in additive manufactured NiTi alloy. Scr Mater 248: 116122. https://doi.org/10.1016/j.scriptamat.2024.116122
[2] Lu HZ, Ma HW, Cai WS et al (2021) Stable tensile recovery strain induced by a Ni₄Ti₃ nanoprecipitate in a Ni50.4Ti49.6 shape memory alloy fabricated via selective laser melting. Acta Mater 219:117261. https://doi.org/10.1016/j.actamat.2021.117261
[3] Karakoc O, Atli KC, Evirgen A et al (2020) Effects of training on the thermomechanical behavior of NiTiHf and NiTiZr high temperature shape memory alloys. Mater Sci Eng A 794:139857. https://doi.org/10.1016/j.msea.2020.139857
[4] Thomasová M, Seiner H, Sedlák P et al (2017) Evolution of macroscopic elastic moduli of martensitic polycrystalline NiTi and NiTiCu shape memory alloys with pseudoplastic straining. Acta Mater 123:146-156. https://doi.org/10.1016/j.actamat.2016.10.024
[5] Zuo XD, Zhang W, Chen Y et al (2022) Wire-based directed energy deposition of NiTiTa shape memory alloys: microstructure, phase transformation, electrochemistry, X-ray visibility and mechanical properties. Addit Manuf 59:103115. https://doi.org/10.1016/j.addma.2022.103115
[6] Oliveira JP, Shen JJ, Escobar JD et al (2021) Laser welding of H-phase strengthened Ni-rich NiTi-20Zr high temperature shape memory alloy. Mater Des 202:109533. https://doi.org/10.1016/j.matdes.2021.109533
[7] Oliveira JP, Schell N, Zhou N et al (2019) Laser welding of precipitation strengthened Ni-rich NiTiHf high temperature shape memory alloys: microstructure and mechanical properties. Mater Des 162:229-234. https://doi.org/10.1016/j.matdes.2018.11.053
[8] Yang ZW, Li H, Zhang YH et al (2021) Tailoring of microstructure and shape memory properties of hot-forged NiTiNb alloy by multi-pass ECAP at high temperatures. Mater Sci Eng A 828:142011. https://doi.org/10.1016/j.msea.2021.142011
[9] Yang ZW, Li H, Zhang YH et al (2022) ECAP based regulation mechanism of shape memory properties of NiTiNb alloys. J Alloys Compd 897:163184. https://doi.org/10.1016/j.jallcom.2021.163184
[10] Yang ZW, Li H, Zhang YH et al (2022) Comparative study on mechanical and shape memory properties of hot forged NiTiNb in axial and radial direction. Mater Sci Eng A 836:142717. https://doi.org/10.1016/j.msea.2022.142717
[11] Quan D, Hai X (2015) Shape memory alloy in various aviation field. Procedia Eng 99:1241-1246. https://doi.org/10.1016/j.proeng.2014.12.654
[12] Chen X, Chen B, Peng XH et al (2020) Finite element simulation of NiTiNb shape memory alloy pipe-joint subjected to coupled transformation and plastic deformation. Adv Mater Sci Eng 2:1-14. https://doi.org/10.1155/2020/6895850
[13] Bahador A, Hamzah E, Kondoh K et al (2018) Microstructure and superelastic properties of free forged Ti-Ni shape-memory alloy. T Nonferr Metal Soc 28(3):502-514. https://doi.org/10.1016/S1003-6326(18)64683-7
[14] Zhang W, Ao SS, Oliveira JP et al (2020) On the metallurgical joining mechanism during ultrasonic spot welding of NiTi using a Cu interlayer. Scr Mater 178:414-417. https://doi.org/10.1016/j.scriptamat.2019.12.012
[15] Mohd Khalil AN, Azmi AI, Murad MN et al (2018) The effect of cutting parameters on cutting force and tool wear in machining nickel titanium shape memory alloy ASTM F2063 under minimum quantity nanolubricant. Procedia CIRP 77:227-230. https://doi.org/10.1016/j.procir.2018.09.002
[16] Lu HZ, Liu LH, Yang C et al (2022) Simultaneous enhancement of mechanical and shape memory properties by heat-treatment homogenization of Ti₂Ni precipitates in TiNi shape memory alloy fabricated by selective laser melting. J Mater Sci Technol 101:205-216. https://doi.org/10.1016/j.jmst.2021.06.019
[17] Saedi S, Shayesteh Moghaddam N, Amerinatanzi A et al (2018) On the effects of selective laser melting process parameters on microstructure and thermomechanical response of Ni-rich NiTi. Acta Mater 144:552-560. https://doi.org/10.1016/j.actamat.2017.10.072
[18] Saedi S, Turabi AS, Andani MT et al (2017) Texture, aging, and superelasticity of selective laser melting fabricated Ni-rich NiTi alloys. Mater Sci Eng A 686:1-10. https://doi.org/10.1016/j.msea.2017.01.008
[19] Shayesteh Moghaddam N, Saghaian SE, Amerinatanzi A et al (2018) Anisotropic tensile and actuation properties of NiTi fabricated with selective laser melting. Mater Sci Eng A 724:220-230. https://doi.org/10.1016/j.msea.2018.03.072
[20] Wang C, Tan XP, Du Z et al (2019) Additive manufacturing of NiTi shape memory alloys using pre-mixed powders. J Mater Process Technol 271:152-161. https://doi.org/10.1016/j.jmatprotec.2019.03.025
[21] Zhang QQ, Hao SJ, Liu YT et al (2020) The microstructure of a selective laser melting (SLM)-fabricated NiTi shape memory alloy with superior tensile property and shape memory recoverability. Appl Mater Today 19:100547. https://doi.org/10.1016/j.apmt.2019.100547
[22] Alagha AN, Hussain S, Zaki W (2021) Additive manufacturing of shape memory alloys: a review with emphasis on powder bed systems. Mater Des 204:109654. https://doi.org/10.1016/j.matdes.2021.109654
[23] Chen W, Gu DD, Yang JK et al (2022) Compressive mechanical properties and shape memory effect of NiTi gradient lattice structures fabricated by laser powder bed fusion. Int J Extreme Manuf 4(4):045002. https://doi.org/10.1088/2631-7990/ac8ef3
[24] Wei SS, Zhang JL, Zhang L et al (2023) Laser powder bed fusion additive manufacturing of NiTi shape memory alloys: a review. Int J Extreme Manuf 5(3):032001. https://doi.org/10.1088/2631-7990/acc7d9
[25] Sun GA, Wang XL, Wang YD et al (2013) In-situ high-energy synchrotron X-ray diffraction study of micromechanical behavior of multiple phases in Ni₄₇Ti₄₄Nb₉ shape memory alloy. Mater Sci Eng A 560:458-465. https://doi.org/10.1016/j.msea.2012.09.090
[26] Shi H, Frenzel J, Martinez GT et al (2014) Site occupation of Nb atoms in ternary Ni-Ti-Nb shape memory alloys. Acta Mater 74:85-95. https://doi.org/10.1016/j.actamat.2014.03.062
[27] Norouzi-Inallu M, Laitinen V, Poutiainen I et al (2023) Development of a build volume reduction kit for studying epitaxial re-solidification in laser powder bed fusion. IOP Conf Ser: Mater Sci Eng 1296(1):012018. https://doi.org/10.1088/1757-899X/1296/1/012018
[28] Dadbakhsh S, Vrancken B, Kruth JP et al (2016) Texture and anisotropy in selective laser melting of NiTi alloy. Mater Sci Eng A 650:225-232. https://doi.org/10.1016/j.msea.2015.10.032
[29] Yap CY, Chua CK, Dong ZL et al (2015) Review of selective laser melting: Materials and applications. Appl Phys Rev 2(4):041101. https://doi.org/10.1063/1.4935926
[30] Bormann T, Müller B, Schinhammer M et al (2014) Microstructure of selective laser melted nickel-titanium. Acta Mater 94:189-202. https://doi.org/10.1016/j.matchar.2014.05.017
[31] Norouzi-Inallu M, Ghotbi Varzaneh A, Kameli P et al (2024) Transformation behavior and inverse magnetocaloric effect in Ni₄₅Co₅Mn_36.7In_13.3-xGe_xmelt-spun ribbons. Intermetallics 165:108152. https://doi.org/10.1016/j.intermet.2023.108152
[32] Gerstgrasser M, Cloots M, Stirnimann J et al (2021) Focus shift analysis, to manufacture dense and crack-free SLM-processed CM247LC samples. J Mater Process Technol 289:116948. https://doi.org/10.1016/j.jmatprotec.2020.116948
[33] Fu J, Li H, Song X et al (2022) Multi-scale defects in powder-based additively manufactured metals and alloys. J Mater Sci Technol 122:165-199. https://doi.org/10.1016/j.jmst.2022.02.015
[34] Zhao L, Santos Macías JG, Dolimont A et al (2020) Comparison of residual stresses obtained by the crack compliance method for parts produced by different metal additive manufacturing techniques and after friction stir processing. Addit Manuf 36:101499. https://doi.org/10.1016/j.addma.2020.101499
[35] Lee YS, Kirka MM, Ferguson J et al (2020) Correlations of cracking with scan strategy and build geometry in electron beam powder bed additive manufacturing. Addit Manuf 32:101031. https://doi.org/10.1016/j.addma.2019.101031
[36] Tran HT, Chen Q, Mohan J et al (2020) A new method for predicting cracking at the interface between solid and lattice support during laser powder bed fusion additive manufacturing. Addit Manuf 32:101050. https://doi.org/10.1016/j.addma.2020.101050
[37] Gu DD, Hagedorn YC, Meiners W et al (2012) Densification behavior, microstructure evolution, and wear performance of selective laser melting processed commercially pure titanium. Acta Mater 60(9):3849-3860. https://doi.org/10.1016/j.actamat.2012.04.006
[38] Reinhart G, Grange D, Abou-Khalil L et al (2020) Impact of solute flow during directional solidification of a Ni-based alloy: in-situ and real-time X-radiography. Acta Mater 194:68-79. https://doi.org/10.1016/j.actamat.2020.04.003
[39] Pham MS, Dovgyy B, Hooper PA et al (2020) The role of side-branching in microstructure development in laser powder-bed fusion. Nat Commun 11(1):749. https://doi.org/10.1038/s41467-020-14453-3
[40] Mukherjee T, Zuback JS, De A et al (2016) Printability of alloys for additive manufacturing. Sci Rep 6:19717. https://doi.org/10.1038/srep19717
[41] Frenzel J, Wieczorek A, Opahle I et al (2015) On the effect of alloy composition on martensite start temperatures and latent heats in Ni-Ti-based shape memory alloys. Acta Mater 90:213-231. https://doi.org/10.1016/j.actamat.2015.02.029
[42] Chen SG, Gao HJ, Zhang YD et al (2022) Review on residual stresses in metal additive manufacturing: formation mechanisms, parameter dependencies, prediction and control approaches. J Mater Res Technol 17:2950-2974. https://doi.org/10.1016/j.jmrt.2022.02.054
[43] Wang XB, Yu JY, Liu JW et al (2020) Effect of process parameters on the phase transformation behavior and tensile properties of NiTi shape memory alloys fabricated by selective laser melting. Addit Manuf 36:101545. https://doi.org/10.1016/j.addma.2020.101545
[44] Lu HZ, Ma HW, Yang Y et al (2023) Tailoring phase transformation behavior, microstructure, and superelasticity of NiTi shape memory alloys by specific change of laser power in selective laser melting. Mater Sci Eng A 864:144576. https://doi.org/10.1016/j.msea.2022.144576
[45] Hou ML, Gu QF, Yang ZW et al (2025) Enhancing shape memory properties of 3D-printed NiTi alloys by laser powder bed fusion through microstructural control. J Alloys Compd 1010:178029. https://doi.org/10.1016/j.jallcom.2024.178029
[46] He PD, Webster RF, Yakubov V et al (2021) Fatigue and dynamic aging behavior of a high strength Al-5024 alloy fabricated by laser powder bed fusion additive manufacturing. Acta Mater 220:117312. https://doi.org/10.1016/j.actamat.2021.117312
[47] Bermingham MJ, StJohn DH, Krynen J et al (2019) Promoting the columnar to equiaxed transition and grain refinement of titanium alloys during additive manufacturing. Acta Mater 168:261-274. https://doi.org/10.1016/j.actamat.2019.02.020
[48] Liu PW, Wang Z, Xiao YH et al (2019) Insight into the mechanisms of columnar to equiaxed grain transition during metallic additive manufacturing. Addit Manuf 26:22-29. https://doi.org/10.1016/j.addma.2018.12.019
[49] Liu J, To AC (2017) Quantitative texture prediction of epitaxial columnar grains in additive manufacturing using selective laser melting. Addit Manuf 16:58-64. https://doi.org/10.1016/j.addma.2017.05.005
[50] Norouzi-Inallu M, Laitinen V, Vinogradova M et al (2024) Solidification of Ni-Mn-Ga magnetic shape memory alloy built via laser powder bed fusion on a single crystal substrate. J Alloys Compd 998:174907. https://doi.org/10.1016/j.jallcom.2024.174907
[51] DebRoy T, Wei HL, Zuback JS et al (2018) Additive manufacturing of metallic components-process, structure and properties. Prog Mater Sci 92:112-224. https://doi.org/10.1016/j.pmatsci.2017.10.001
[52] Mukherjee T, Zuback JS, De A et al (2016) Printability of alloys for additive manufacturing. Sci Rep 6(1):19717. https://doi.org/10.1038/srep19717
[53] Shi H, Pourbabak S, Humbeeck JV et al (2012) Electron microscopy study of Nb-rich nanoprecipitates in Ni-Ti-Nb and their influence on the martensitic transformation. Scr Mater 67(12):939-942. https://doi.org/10.1016/j.scriptamat.2012.08.020
[54] Otsuka K, Ren X (2005) Physical metallurgy of Ti-Ni-based shape memory alloys. Prog Mater Sci 50(5):511-678. https://doi.org/10.1016/j.pmatsci.2004.10.001
[55] Bhagyaraj J, Ramaiah KV, Saikrishna CN et al (2013) Behavior and effect of Ti₂Ni phase during processing of NiTi shape memory alloy wire from cast ingot. J Alloys Compd 581:344-351. https://doi.org/10.1016/j.jallcom.2013.07.046
[56] Ishida A, Sato M, Ogawa K (2006) Microstructure and shape-memory behavior of annealed Ti_51.5Ni_33.1Cu_15.4 thin films. Philos Mag Lett 86(1):13-20. https://doi.org/10.1080/09500830500482308
[57] Han TY, Liu Y, Liao MQ et al (2022) Refined microstructure and enhanced mechanical properties of AlCrFe₂Ni₂ medium entropy alloy produced via laser remelting. J Mater Sci Technol 99:18-27. https://doi.org/10.1016/j.jmst.2021.05.033