Journal of Materials Science

, Volume 53, Issue 19, pp 13432–13441 | Cite as

Mechanical activation of pre-alloyed NiTi2 and elemental Ni for the synthesis of NiTi alloys

  • X. Zhao
  • F. Neves
  • J. B. Correia
  • K. Liu
  • F. M. Braz Fernades
  • V. Koledov
  • S. von Gratowski
  • S. Xu
  • J. Huang
Mechanochemical Synthesis


This work reports on an efficient powder metallurgy method for the synthesis of NiTi alloys, involving mechanical activation of pre-alloyed NiTi2 and elemental Ni powders (NiTi2–Ni) followed by a press-and-sinter step. The idea is to take advantage of the brittle nature of NiTi2 to promote a better efficiency of the mechanical activation process. The conventional mechanical activation route using elemental Ti and Ni powders (Ti–Ni) was also used for comparative purposes. Starting with (NiTi2–Ni) powder mixtures resulted in the formation of a predominant amorphous structure after mechanical activation at 300 rpm for 2 h. A sintered specimen consisting mainly of NiTi phase was obtained after vacuum sintering at 1050 °C for 0.5 h. The produced NiTi phase exhibited the martensitic transformation behavior. Using elemental Ti powders instead of pre-alloyed NiTi2 powders, the structural homogenization of the synthesized NiTi alloys was delayed. Performing the mechanical activation at 300 rpm for the (Ti–Ni) powder mixtures gave rise to the formation of composite particles consisting in dense areas of alternate fine layers of Ni and Ti. However, no significant structural modification was observed even after 16 h of mechanical activation. Only after vacuum sintering at 1050 °C for 6 h, the NiTi phase was observed to be the predominant phase. The higher reactivity of the mechanically activated (NiTi2–Ni) powder particles can explain the different sintering behavior of those powders compared with the mechanically activated (Ti–Ni) powders. It is demonstrated that this innovative approach allows an effective time reduction in the mechanical activation and of the vacuum sintering step.



XZ, KL, and JH acknowledge the support of the Fundamental Research Funds for the Central Universities [FRF-IC-15-005], China. FBF acknowledge funding of CENIMAT/i3N by FEDER funds through the COMPETE 2020 Programme and National Funds through FCT—Portuguese Foundation for Science and Technology under the Project UID/CTM/50025/2013. V.K. and S. G. are grateful to support of RSF Project No 17-19-01748. The authors acknowledge MIDAS Project No 612585 “MIDAS—Micro and Nanoscale Design of Thermally Actuating Systems” Marie Curie Actions, FP7-PEOPLE-2013-IRSES.

Compliance with ethical standards

Conflict of interest

The authors declare that they have no conflict of interest.


  1. 1.
    Wu SK, Lin HC, Chen CC (1999) A study on the machinability of a Ti49.6Ni50.4 shape memory alloy. Mater Lett 40:27–32CrossRefGoogle Scholar
  2. 2.
    Grummon DS, Shaw JA, Gremillet A (2003) Low-density open-cell foams in the NiTi system. Appl Phys Lett 82:2727–2729CrossRefGoogle Scholar
  3. 3.
    Biswas A (2005) Porous NiTi by thermal explosion mode of SHS: processing, mechanism and generation of single phase microstructure. Acta Mater 53:1415–1425CrossRefGoogle Scholar
  4. 4.
    Yuan B, Zhang XP, Chung CY, Zeng MQ, Zhu M (2006) A comparative study of the porous TiNi shape memory alloys fabricated by three different processes. Metall Mater Trans A 37:755–761CrossRefGoogle Scholar
  5. 5.
    Chen G, Cao P, Edmonds N (2013) Porous NiTi alloys produced by press-and-sinter from Ni/Ti and Ni/TiH2 mixtures. Mat Sci Eng A 582:117–125CrossRefGoogle Scholar
  6. 6.
    Xu JL, Bao LZ, Liu AH, Jin XF, Luo JM, Zhong ZC, Zheng YF (2015) Effect of pore sizes on the microstructure and properties of the biomedical porous NiTi alloys prepared by microwave sintering. J Alloys Compd 645:137–142CrossRefGoogle Scholar
  7. 7.
    Zaki HHM, Abdullah J (2014) Comparison studies on solid state diffusion of Ni–Ti and Ni–TiH2 under CaH2 reducing environment. Mater Lett 121:36–39CrossRefGoogle Scholar
  8. 8.
    Otsuka K, Wayman CM (1999) Shape memory materials. Cambridge University Press, CambridgeGoogle Scholar
  9. 9.
    Nishida M, Wayman CM, Honma T (1986) Precipitation processes in near-equiatomic TiNi shape memory alloys. Metall Trans A 17:1505–1515CrossRefGoogle Scholar
  10. 10.
    Chang LC, Read TA (1951) Plastic deformation and diffusionless phase changes in metals—the gold–cadmium beta phase. JOM 3:47–52CrossRefGoogle Scholar
  11. 11.
    Duerig TW (1994) Present and future applications of shape memory and superelastic materials. In: 1st International conference on shape memory and superelastic technologies, Pacific Grove, California, USA, 7–10 March, pp 31–42Google Scholar
  12. 12.
    Bertheville B, Bidaux JE (2005) Enhanced powder sintering of near-equiatomic NiTi shape-memory alloys using Ca reductant vapor. J Alloys Compd 387:211–216CrossRefGoogle Scholar
  13. 13.
    Bertheville B (2006) PM processing of single-phase NiTi shape memory alloys by VPCR process. Mater Trans 47:698–703CrossRefGoogle Scholar
  14. 14.
    Zaki HHM, Abdullah J (2016) The role of CaH2 in preventing oxidation for the production of single-phase NiTi alloy in solid state. J Alloys Compd 655:364–371CrossRefGoogle Scholar
  15. 15.
    Bhosle V, Baburaj EG, Miranova M, Salama K (2003) Dehydrogenation of TiH2. Mater Sci Eng A 356:190–199CrossRefGoogle Scholar
  16. 16.
    Li BY, Rong LJ, Li YY (2000) Synthesis of porous Ni–Ti shape-memory alloys by self-propagating high-temperature synthesis: reaction mechanism and anisotropy in pore structure. Acta Mater 48:3895–3904CrossRefGoogle Scholar
  17. 17.
    Robertson IM, Schaffer GB (2010) Comparison of sintering of titanium and titanium hydride powders. Powder Metall 53:12–19CrossRefGoogle Scholar
  18. 18.
    Maziarz W, Dutkiewicz J, Humbeeck JV, Czeppe T (2004) Mechanically alloyed and hot pressed Ni–49.7Ti alloy showing martensitic transformation. Mater Sci Eng A 375:844–848CrossRefGoogle Scholar
  19. 19.
    Siegmann S, Halter K and Wielage B (2002) Vacuum plasma sprayed coatings and freestanding parts of Ni–Ti shape memory alloy. In: ITSC 2002 international thermal spray conference, Essen, Germany, March 2002, pp 357–361Google Scholar
  20. 20.
    Suryanarayana C (2001) Mechanical alloying and milling. Prog Mater Sci 46:1–184CrossRefGoogle Scholar
  21. 21.
    Schüller E, Bram M, Buchkremer HP, Stöver D (2004) Phase transformation temperatures for NiTi alloys prepared by powder metallurgical processes. Mater Sci Eng A 378:165–169CrossRefGoogle Scholar
  22. 22.
    Terayama A, Kyogoku H, Sakamura M, Komatsu S (2006) Fabrication of TiNi powder by mechanical alloying and shape memory characteristics of the sintered alloy. Mater Trans 47:550–557CrossRefGoogle Scholar
  23. 23.
    Yurko GA, Barton JW, Parr JG (1959) The crystal structure of Ti2Ni. Acta Crystallogr A 12:909–911CrossRefGoogle Scholar
  24. 24.
    Wang HW, Liu YF (2002) Microstructure and wear resistance of laser clad Ti5Si3/NiTi2 intermetallic composite coating on titanium alloy. Mater Sci Eng A 338:126–132CrossRefGoogle Scholar
  25. 25.
    Neves F, Martins I, Correia JB, Oliveira M, Gaffet E (2007) Reactive extrusion synthesis of mechanically activated Ti–50Ni powders. Intermetallics 15:1623–1631CrossRefGoogle Scholar
  26. 26.
    Schwarz RB, Petrich RR, Saw CK (1985) The synthesis of amorphous Ni–Ti alloy powders by mechanical alloying. J Non-Cryst Solids 76:281–302CrossRefGoogle Scholar
  27. 27.
    Chen G, Cao P (2013) NiTi powder sintering from TiH2 powder: an in situ investigation. Metall Mater Trans A 44:5630–5633CrossRefGoogle Scholar
  28. 28.
    Neves F, Braz Fernandes FM, Martins I, Correia JB, Oliveira M, Gaffet E, Wang T-Y, Lattemann M, Suffner J, Hahn H (2009) The transformation behaviour of bulk nanostructured NiTi alloys. Smart Mater Struct 18:115003CrossRefGoogle Scholar
  29. 29.
    Otsuka K, Ren X (2005) Physical metallurgy of TiNi-based shape memory alloys. Prog Mater Sci 50:511–678CrossRefGoogle Scholar
  30. 30.
    Gasperini AAM, Machado KD, Buchner S, Lima JC, Grandi TA (2008) Influence of the temperature on the structure of an amorphous Ni46Ti54 alloy produced by mechanical alloying. Eur Phys J B64:201–209CrossRefGoogle Scholar
  31. 31.
    Saito T, Takasaki A (2009) The influence of chemical composition on shape memory effect of TiNi bulk alloy produced by mechanical alloying. Trans Mater Res Soc Jpn 34:403–406CrossRefGoogle Scholar
  32. 32.
    Wang KY, Shen TD, Wang JT, Quan MX (1993) Characteristics of the mechanically-alloyed Ni60Ti40 amorphous powders during mechanical milling in different atmospheres. J Mater Sci 28:6474–6478. CrossRefGoogle Scholar
  33. 33.
    Takasaki A (1998) Mechanical alloying of the Ti–Ni system. Phys Status Solidi a 169:183–191CrossRefGoogle Scholar
  34. 34.
    Mousavi T, Karimzadeh F, Abbasi MH (2008) Synthesis and characterization of nanocrystalline NiTi intermetallic by mechanical alloying. Mater Sci Eng A 487:46–51CrossRefGoogle Scholar
  35. 35.
    Ghadimi M, Shokuhfar A, Rostami HR, Ghaffari M (2012) Effects of milling and annealing on formation and structural characterization of nanocrystalline intermetallic compounds from Ni–Ti elemental powders. Mater Lett 80:181–183CrossRefGoogle Scholar
  36. 36.
    Chen G, Liss KD, Cao P (2014) In situ observation and neutron diffraction of NiTi powder sintering. Acta Mater 67:32–44CrossRefGoogle Scholar
  37. 37.
    Karolus M, Panek J (2016) Nanostructured Ni–Ti alloys obtained by mechanical synthesis and heat treatment. J Alloys Compd 658:709–715CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media, LLC, part of Springer Nature 2018

Authors and Affiliations

  1. 1.School of Materials Science and EngineeringUniversity of Science and Technology BeijingBeijingChina
  2. 2.Unidade de Energias Renováveis e Integração de SistemasLaboratório Nacional de Energia e GeologiaLisbonPortugal
  3. 3.CENIMAT/i3N, Faculdade de Ciências e TecnologiaUniversidade Nova de LisboaLisbonPortugal
  4. 4.Kotelnikov Institute of Radio Engineering and Electronics of the Russian Academy of SciencesMoscowRussia
  5. 5.Departament de FísicaUniversitat de les Illes BalearsPalma de MallorcaSpain

Personalised recommendations