Skip to main content
SpringerLink
Log in

Understanding reaction sequences and mechanisms during synthesis of nanocrystalline Ti2N and TiN via magnetically controlled ball milling of Ti in nitrogen

  • Polymers
  • Published:
Journal of Materials Science Aims and scope Submit manuscript

Abstract

Mechanically induced reactive synthesis of TiN via magnetically controlled ball milling of titanium under nitrogen gas was investigated using X-ray diffraction, advanced electron microscopy and Raman spectroscopy. Ball milling of titanium powder with nitrogen gas was performed in Uni-Ball-Mill, with external temperature of the vial and initial pressures of the nitrogen gas monitored, while the milled samples were taken out periodically, both before and after detection of an exothermic ignition point. Before ignition, nitrogen-enriched Ti, small proportions of TiN and very minor amounts of Ti2N are formed, in addition to the heavily deformed Ti. Raman spectroscopy revealed the pre-ignition products to include off-stoichiometric nitrides (TiNx) and oxynitride skin (TiOxNy). The formation of the new TiN and Ti2N products before ignition was attributed to the diffusion of highly polarized active N atoms into the mechanically activated clean surfaces of Ti, followed by local reaction. This local reaction is likely promoted by numerous cycles of induced local temperature rise and rapid quenching, large surface area and accumulation of deformation defects. After the exothermic ignition, there was rapid nucleation of new TiN crystals, and simultaneous growth of the pre-existing TiN and the newly formed TiN crystals. This understanding explains the reaction pathways leading to the formation of small proportions of TiN and very minor amounts of Ti2N before ignition and the thin-plated TiN after ignition.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Figure 1
Figure 2
Figure 3
Figure 4
Figure 5
Figure 6
Figure 7
Figure 8

Similar content being viewed by others

References

  1. Gotor FJ, Alcala MD, Real C, Criado JM (2002) Combustion synthesis of TiN induced by high-energy ball milling of Ti under nitrogen atmosphere. J Mater Res 17(7):1655–1663

    Article  Google Scholar 

  2. Chin ZH, Perng TP (1997) In situ observation of combustion to form TiN during ball milling Ti in nitrogen. Appl Phys Lett 75(18):2380–2382

    Article  Google Scholar 

  3. Chin ZH, Perng T (1997) Instant formation of TiN by reactive milling of Ti in nitrogen. Mater Sci Forum 235–238:73–78

    Article  Google Scholar 

  4. Wexler Parker D, Palm V, Calka A (2004) Mechano-synthesis and compaction of titanium–titanium nitride composites. Mater Sci Eng, A 375:905–910

    Article  Google Scholar 

  5. Bhaskar U, Bid S, Satpati B, Pradhan SK (2010) Mechanosynthesis of nanocrystalline titanium nitride and its microstructure characterization. J Alloys Compds 493(1):192–196

    Article  Google Scholar 

  6. El-Eskandarany MS, Sumiyama K, Aoki K, Suzuki K (1992) Morphological and structural evolutions of nonequilibrium titanium-nitride alloy powders produced by reactive ball milling. J Mater Res 7(04):888–893

    Article  Google Scholar 

  7. Calka A (1991) Formation of titanium and zirconium nitrides by mechanical alloying. Appl Phys Lett 59(13):1568–1569

    Article  Google Scholar 

  8. Zhang H, Kisi EH, Myhra S (1996) A solid solution pumping mechanism for the nitrogenation of titanium during mechanical deformation in air. J Phys D Appl Phys 29(5):1367–1372

    Article  Google Scholar 

  9. Zhang F, Kaczmarek WA, Lu L, Lai MO (2000) Formation of titanium nitrides via wet reaction ball milling. J Alloys Compds 307(1–2):249–253

    Article  Google Scholar 

  10. Campbell S, Hofmann M, Calka A (2000) The synthesis of TiN by ball-milling—a neutron diffraction study. Phys B Cond Matter 276:899–900

    Article  Google Scholar 

  11. Wexler D, Calka A, Mosbah AY (2000) Ti–TiN hardmetals prepared by in situ formation of TiN during reactive ball milling of Ti in ammonia. J alloys Compds 309(1):201–207

    Article  Google Scholar 

  12. Sun JF, Wang MZ, Zhao YC, Li XP, Liang BY (2009) Synthesis of titanium nitride powders by reactive ball milling of titanium and urea. J Alloys Compds 482(1):L29–L31

    Article  Google Scholar 

  13. Bolokang AS, Phasha MJ (2010) Formation of titanium nitride produced from nanocrystalline titanium powder under nitrogen atmosphere. Int J Refrac Metals Hard Mater 28(5):610–615

    Article  Google Scholar 

  14. Liu G, Li J, and Chen K (2011) Combustion synthesis of ceramic powders with controlled grain morphologies. Intech open access publisher 49–74

  15. Kaneko K et al (2010) Fabrication and characterization of TiN nanocomposite powders fabricated by DC arc-plasma method. J Alloys Compds 492(1):685–690

    Article  Google Scholar 

  16. Eslamloo-Grami M, Munir ZA (1990) Effect of nitrogen pressure and diluent content on the combustion synthesis of titanium nitride. J Am Ceram Soc 73(8):2222–2227

    Article  Google Scholar 

  17. Mosbah A, Calka A, Wexler D (2006) Rapid synthesis of titanium nitride powder by electrical discharge assisted mechanical milling. J Alloys Compds 424(1):279–282

    Article  Google Scholar 

  18. Takacs L (2002) Self-sustaining reactions induced by ball milling. Prog Mater Sci 47(4):355–414

    Article  Google Scholar 

  19. Ding Z et al (2005) Formation of titanium nitride by mechanical milling and isothermal annealing of titanium and boron nitride. J Alloys Compds 391(1):77–81

    Article  Google Scholar 

  20. Kudaka K, Iizumi K, Sasaki T (1999) Mechanochemical syntheses of titanium carbide, diboride and nitride. J Ceram Soc Jpn 107(11):1019–1024

    Article  Google Scholar 

  21. Suryanarayana C (2001) Mechanical alloying and milling. Prog Mater Sci 46(1):1–184

    Article  Google Scholar 

  22. Schaffer GB, McCormick PG (1989) Combustion synthesis by mechanical alloying. Scripta Metall 23(6):835–838

    Article  Google Scholar 

  23. Schaffer GB, McCormick PG (1991) Anomalous combustion effects during mechanical alloying. Metall Trans A 22(12):3019–3024

    Article  Google Scholar 

  24. Delogu F (2013) Activation of self-sustaining high-temperature reactions by mechanical processing of Ti–C powder mixtures. Scripta Mater 69(3):223–226

    Article  Google Scholar 

  25. Deidda C, Delogu F, Maglia F, Anselmi-Tamburini U, Cocco G (2004) Mechanical processing and self-sustaining high-temperature synthesis of TiC powders. Mater Sci Eng, A 375–377(1–2):800–803

    Article  Google Scholar 

  26. Delogu F, Takacs L (2014) Mechanochemistry of Ti–C powder mixtures. Acta Mater 80:435–444

    Article  Google Scholar 

  27. Yang H, McCormick PG (1993) Synthesis of titanium oxynitride by mechanical milling. J Mater Sci 28(20):5663–5667. doi:10.1007/BF00367844

    Article  Google Scholar 

  28. Calka A, Williams JS (1992) Synthesis of nitrides by mechanical alloying. Mater Sci Forum 88–90:787–794

    Article  Google Scholar 

  29. Rochana P, Lee K, Wilcox J (2014) Nitrogen adsorption, dissociation, and subsurface diffusion on the Vanadium (110) surface: a DFT study for the nitrogen-selective catalytic membrane application. J Phys Chem C 118(8):4238–4249

    Article  Google Scholar 

  30. Hu X, Tu R, Wei J, Pan C, Guo J, Xiao W (2014) Nitrogen atom diffusion into TiO2 anatase bulk via surfaces. Comp Mater Sci 82:107–113

    Article  Google Scholar 

  31. Oghenevweta JE, David W, Calka A (2016) Early stages of phase formation before the ignition peak during mechanically induced self-propagating reactions (MSRs) of titanium and graphite. Scripta Mater 122:93–97

    Article  Google Scholar 

  32. Oghenevweta JE, Wexler D, Calka A (2017) Sequence of phase evolution during mechanically induced self-propagating reaction synthesis of TiB and TiB2 via magnetically controlled ball milling of titanium and boron powders. J Alloys Compds 701:380–391

    Article  Google Scholar 

  33. Ghosh B, Pradhan SK (2010) Microstructure characterization of nanocrystalline TiC synthesized by mechanical alloying. Mater Chem Phys 120(2):537–545

    Article  Google Scholar 

  34. Lutterotti L (2008) Quantitative rietveld analysis in batch mode with Maud. http://www.ing.unitn.it/~maud

  35. Mitchell DRG, Van den Berg JA (2016) Development of an ellipse fitting method with which to analyse selected area electron diffraction patterns. Ultramicroscopy 160:140–145

    Article  Google Scholar 

  36. Mitchell DRG (2008) DiffTools: electron diffraction software tools for DigitalMicrograph™. Micro Res Tech 71(8):588–593

    Article  Google Scholar 

  37. Fecht HJ (1995) Nanostructure formation by mechanical attrition. Nanostruc Mater 6(1–4):33–42

    Article  Google Scholar 

  38. Spengler W, Kaiser R (1976) First and second order Raman scattering in transition metal compounds. Solid State Commun 18(7):881–884

    Article  Google Scholar 

  39. Stoehr M, Shin CS, Petrov I, Greene JE (2011) Raman scattering from TiNx (0.67 ≤ x ≤ 1.00) single crystals grown on MgO (001). J Appl Phys 110(8):083503

    Article  Google Scholar 

  40. Ding ZH, Yao B, Qiu LX, Lv TQ (2006) Raman scattering investigation of nanocrystalline δ-TiNx synthesized by solid-state reaction. J Alloys Compds 421(1):247–251

    Article  Google Scholar 

  41. Dreiling I, Raisch C, Glaser J, Stiens D, Chassé T (2011) Characterization and oxidation behavior of MTCVD Ti–B–N coatings. Surf Coatings Technol 206(2–3):479–486

    Article  Google Scholar 

  42. Constable CP, Yarwood J, Münz WD (1999) Raman microscopic studies of PVD hard coatings. Surf Coatings Technol 116–119:155–159

    Article  Google Scholar 

  43. Spengler W, Kaiser R, Christensen AN, Müller-Vogt G (1978) Raman scattering, superconductivity, and phonon density of states of stoichiometric and nonstoichiometric TiN. Phys Rev B 17(3):1095

    Article  Google Scholar 

  44. Song P, Zhang X, Sun M, Cui X, Lin Y (2012) Graphene oxide modified TiO2 nanotube arrays: enhanced visible light photoelectrochemical properties. Nanoscale 4(5):1800–1804

    Article  Google Scholar 

  45. Takacs L (1996) Combustive mechanochemical reactions with titanium, zirconium and hafnium. Mater Sci Forum 225–227:553–558

    Article  Google Scholar 

  46. Wriedt H, Murray J (1987) The n–ti (nitrogen–titanium) system. Bull Alloy Phase Diagr 8(4):378–388

    Article  Google Scholar 

  47. Moffatt WG (1976) Binary phase diagrams handbook. General Electric, Schenectady

    Google Scholar 

  48. Murray JL, Liao PK, Spear KE (1986) The B–Ti (Boron–Titanium) system. Bull Alloy Phase Diagr 7(6):550–555

    Article  Google Scholar 

  49. Weichert R, Schönert K (1974) On the temperature rise at the tip of a fast running crack. J Mech Phys Solids 22(2):127–133

    Article  Google Scholar 

  50. Schönert K, Weichert R (1969) The heat effect of the fracture in iron and its dependence on the velocity of propagation. Chem Eng Technol 41:295–300

    Google Scholar 

  51. Weichert R, Schönert K (1978) Heat generation at the tip of a moving crack. J Mech Phys Solids 26(3):151–161

    Article  Google Scholar 

  52. Tonejc A, Tonejc AM, Dužević D (1991) Estimation of peak temperature reached by particles trapped among colliding balls in the ball-milling process using excessive oxidation of antimony. Scripta Metall et Mater 25(5):1111–1113

    Article  Google Scholar 

  53. Tonejc A, Stubicar M, Tonejc AM, Kosanović K, Subotić B, Smit I (1994) Transformation of γ-AIOOH (boehmite) and AI(OH)3 (gibbsite) to α-Al2O3 (corundum) induced by high energy ball milling. J Mater Sci Lett 13(7):519–520

    Article  Google Scholar 

  54. Bab M, Mendoza-Zelis L, Damonte L (2001) Nanocrystalline HfN produced by mechanical milling: kinetic Aspects. Acta Mater 49(20):4205–4213

    Article  Google Scholar 

  55. Shih HD, Jona F, Jepsen DW, Marcus PM (1976) Low-energy-electron-diffraction determination of the atomic Arrangement in a Monatomic Underlayer of Nitrogen on Ti (0001). Phys Rev Lett 36(14):798

    Article  Google Scholar 

Download references

Acknowledgements

We thank the Australian Research Council (ARC) Linkage, Infrastructure, Equipment and Facilities (LIEF) Grant Numbers LE120100104, LE0237478 and LE0882613 located at Electron Microscopy Centre (EMC) and Australian National Nanofabrication Facility (ANNF) materials node located at Intelligent Polymer Research Institute (IPRI), University of Wollongong, Australia, for all the equipment uses.

Author information

Authors and Affiliations

  1. Faculty of Engineering and Information Sciences, University of Wollongong, Northfields Avenue, Wollongong, NSW, 2522, Australia

    J. E. Oghenevweta, D. Wexler & A. Calka

Authors
  1. J. E. Oghenevweta
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. D. Wexler
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. A. Calka
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to J. E. Oghenevweta.

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Oghenevweta, J.E., Wexler, D. & Calka, A. Understanding reaction sequences and mechanisms during synthesis of nanocrystalline Ti2N and TiN via magnetically controlled ball milling of Ti in nitrogen. J Mater Sci 53, 3064–3077 (2018). https://doi.org/10.1007/s10853-017-1734-x

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s10853-017-1734-x

Keywords

Search

Navigation