Hardness augmentation engineering of TiFe2 with doping design and single-crystal realization

Xinyang Tan; Hongxiong Liu; Tingping Hou; Sicong Zhu; Gengping Jiang; Dong Zhang; Junwen Duan; Xuan Liang; Wuming Liu; Kaiming Wu

doi:10.59717/j.xinn-mater.2025.100140

The Innovation Materials > 2025 Vol. 3 > No. 3 > 100140

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Hardness augmentation engineering of TiFe₂ with doping design and single-crystal realization

1.
The State Key Laboratory of Refractories and Metallurgy, Joint International Research Laboratory of Refractories and Metallurgy, Ministry of Education, China, Hubei Province Key Laboratory of Systems Science in Metallurgical Process, International Research Institute for Steel Technology, Collaborative Innovation Center for Advanced Steels, Wuhan University of Science and Technology, Wuhan 430081, China
2.
Beijing National Laboratory for Condensed Matter Physics, Institute of Physics, Chinese Academy of Sciences, Beijing 100190, China
3.
These authors contributed equally

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Corresponding authors: houtingping@wust.edu.cn (T.P.H.); wliu@iphy.ac.cn (W.M.L.); wukaiming@wust.edu.cn (K.M.W.)
Received Date: December 10, 2024

Accepted Date: May 29, 2025

Published Online: June 05, 2025

The Innovation Materials 3(3), https://doi.org/10.59717/j.xinn-mater.2025.100140 | Cite this article

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PUBLIC SUMMARY
1. The strengthening effect of silicon on the mechanical properties of TiFe₂ was demonstrated.
  
  Single-crystal samples were successfully prepared, and their mechanical properties were measured.
  
  The significant increase in hardness is attributed to the enhancement of interatomic covalent bonding.

ABSTRACT

ABSTRACT

As a critical reinforcing phase in high-entropy alloy matrix and coating materials, enhancing the hardness of TiFe₂ significantly improves the upper limits of alloy performance through low-concentration doping. However, the mechanism by which doping alters macroscopic hardness through the disturbance of electronic structure remains unclear. Furthermore, there is a lack of robust experimental evidence to substantiate the hardness enhancements predicted by theoretical calculations. This investigation assessed the strengthening effect of silicon (Si) on the hardness of TiFe₂ through both calculations and experiments. First-principles calculations indicated that Si alloying enhances the structural stability and hardness of TiFe₂. The mechanisms underlying the notable increase in hardness due to Si were thoroughly investigated from the perspective of bonding characteristics. Si alloying disrupted the original symmetric electronic structure and increased the prevalence of directional covalent bonds. Successful single-crystal preparation experiments confirmed the stability of the doped structure. The results of nano-hardness testing address the deficiency of accurate experimental data on hardness enhancement. This study provides a systematic approach to improving the mechanical properties of TiFe₂ and offers new insights into the development of advanced materials with enhanced hardness.
- Doping design /
- Hardness augmentation engineering /
- Electronic structure modulation /
- TiFe₂ /
- First-principles calculations

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REFERENCES

[1]	Guo Y., Wang H. and Liu Q. (2020). Microstructure evolution and strengthening mechanism of laser-cladding MoFe_xCrTiWAlNb refractory high-entropy alloy coatings. J. Alloys Compd. 834:155147. DOI:10.1016/j.jallcom.2020.155147 View in Article CrossRef Google Scholar
[2]	Moon, J., Jo, H. H., Park S. J., et al. (2021). Ti-bearing lightweight steel with large high temperature ductility via thermally stable multi-phase microstructure. Mater. Sci. Eng. A 808:140954. DOI:10.1016/j.msea.2021.140954 View in Article CrossRef Google Scholar
[3]	Rabadia C. D., Liu Y. J., Chen L. Y., et al. (2019). Deformation and strength characteristics of Laves phases in titanium alloys. Mater. Design 179:107891. DOI:10.1016/j.matdes.2019.107891 View in Article CrossRef Google Scholar
[4]	Wang H. M., Cao F., Cai L. X., et al. (2003). Microstructure and tribological properties of laser clad Ti₂Ni₃Si/NiTi intermetallic coatings. Acta Mater. 51:9. DOI:10.1016/s1359-6454(03)00465-8 View in Article CrossRef Google Scholar
[5]	Xiang K., Chen L. Y., Chai L., et al. (2020). Microstructural characteristics and properties of CoCrFeNiNb_x high-entropy alloy coatings on pure titanium substrate by pulsed laser cladding. Appl. Surf. Sci. 517:146214. DOI:10.1016/j.apsusc.2020.146214 View in Article CrossRef Google Scholar
[6]	Wang D., van der Wee E. B., Daniele Z., et al. (2021). Quantitative 3D real-space analysis of Laves phase supraparticles. Nat. Commun. 12:3980. DOI:10.1038/s41467-021-24227-0 View in Article CrossRef Google Scholar
[7]	Wang D., Tonnishtha D., van der Wee E. B., et al. (2021). Binary icosahedral clusters of hard spheres in spherical confinement. Nat. Phys. 17:128−134. DOI:10.1038/s41567-020-1003-9 View in Article CrossRef Google Scholar
[8]	Hynninen A. P., Thijssen J. H. J., Vermolen E. C. M., et al. (2007). Self-assembly route for photonic crystals with a bandgap in the visible region. Nat. Mater. 6:202−205. DOI:10.1038/nmat1841 View in Article CrossRef Google Scholar
[9]	Shevchenko E. V., Talapin D. V., Kotov N. A., et al. (2006). Structural diversity in binary nanoparticle superlattices. Nature 439:55−59. DOI:10.1038/nature04414 View in Article CrossRef Google Scholar
[10]	Edalati P., Floriano R., Mohammadi A., et al. (2020). Reversible room temperature hydrogen storage in high-entropy alloy TiZrCrMnFeNi. Scr. Mater. 178:387−390. DOI:10.1016/j.scriptamat.2019.12.009 View in Article CrossRef Google Scholar
[11]	Wan C., Jiang X., Yin X., et al. (2020). High-capacity Zr-based AB₂-type alloys as metal hydride battery anodes. J. Alloys Compd. 828:154402. DOI:10.1016/j.jallcom.2020.154402 View in Article CrossRef Google Scholar
[12]	Wijayanti I. D., Denys R., Suwarno et al. (2020). Hydrides of Laves type Ti-Zr alloys with enhanced H storage capacity as advanced metal hydride battery anodes. J. Alloys Compd. 828:154354. DOI:10.1016/j.jallcom.2020.154354 View in Article CrossRef Google Scholar
[13]	Zhu Y. Y., Yang X. S., Xu Z. L., et al. (2024). Development of AB₂-type TiZrCrMnFeCoV intermetallic high-entropy alloy for reversible room-temperature hydrogen storage. J. Energy Storage 75:109553. DOI:10.1016/j.est.2023.109553 View in Article CrossRef Google Scholar
[14]	Tang X., Sepehri Amin H., Terada N., et al. (2022). Magnetic refrigeration material operating at a full temperature range required for hydrogen liquefaction. Nat. Commun. 13:1817. DOI:10.1038/s41467-022-29340-2 View in Article CrossRef Google Scholar
[15]	Wakefield J. P., Kang M., Neves P. M., et al. (2023). Three-dimensional flat bands in pyrochlore metal CaNi₂. Nature 623:301−306. DOI:10.1038/s41586-023-06640-1 View in Article CrossRef Google Scholar
[16]	Enz C. P. and Matthias B. T. (1978). P-State Pairing and the Ferromagnetism of ZrZn₂. Science 201:828−829. DOI:10.1126/science.201.4358.828 View in Article CrossRef Google Scholar
[17]	Jiang K., Liu R., Chen K. et al. (2013). Microstructure and tribological properties of solution-treated Tribaloy alloy. Wear 307:22−27. DOI:10.1016/j.wear.2013.08.018 View in Article CrossRef Google Scholar
[18]	Ramkumar K. R., Nagini M., Ravi R., et al. (2023). High-temperature wear behavior of Tribaloy 400 deposited 17-4 PH stainless steel using spark plasma sintering. Surf. Coat. Tech. 463:129528. DOI:10.1016/j.surfcoat.2023.129528 View in Article CrossRef Google Scholar
[19]	Renz A., Prakash B., Hardell J., et al. (2018). High-temperature sliding wear behaviour of Stellite^®12 and Tribaloy^®T400. Wear 402-403:148−159. DOI:10.1016/j.wear.2018.02.013 View in Article CrossRef Google Scholar
[20]	Pennell S. M., Chappuis B., Carpenter J. A., et al. (2023). Hierarchically porous Iron alloys with high sintering resistance during cyclic steam oxidation and hydrogen reduction. Adv. Funct. Mater. 33:2307470. DOI:10.1002/adfm.202307470 View in Article Google Scholar
[21]	Chen S., Aitken Z. H., Pattamatta S., et al. (2021). Simultaneously enhancing the ultimate strength and ductility of high-entropy alloys via short-range ordering. Nat. Commun. 12:4953. DOI:10.1038/s41467-021-25264-5 View in Article CrossRef Google Scholar
[22]	Lee S. I., Ha T., Lee Y. S., et al. (2021). EBSD microstructural analysis of AB-type TiFe hydrogen storage alloys. Mater. Charact. 178:111276. DOI:10.1016/j.matchar.2021.111276 View in Article CrossRef Google Scholar
[23]	Ma E. and Wu X. (2019). Tailoring heterogeneities in high-entropy alloys to promote strength-ductility synergy. Nat. Commun. 10:5623. DOI:10.1038/s41467-019-13311-1 View in Article CrossRef Google Scholar
[24]	Ye X. C., Wang T., Xu Z. Y., et al. (2020). Effect of Ti content on microstructure and mechanical properties of CuCoFeNi high-entropy alloys. Int. J. Min. Met. Mater. 27:1326−1331. DOI:10.1007/s12613-020-2024-1 View in Article CrossRef Google Scholar
[25]	Cui P., Ma Y. M., Zhang L. J., et al. (2018). Effect of Ti on microstructures and mechanical properties of high entropy alloys based on CoFeMnNi system. Mater. Sci. Eng. A 737:198−204. DOI:10.1016/j.msea.2018.09.050 View in Article CrossRef Google Scholar
[26]	Liang H., Gao B. Y., Li Y. N., et al. Microstructures and wear resistance of Al_1.5CrFeNiTi_0.5 and Al_1.5CrFeNiTi_0.5W_0.5 high entropy alloy coatings manufactured by laser cladding. Mater. Sci. Forum 956:154-159 (2019). DOI:10.4028/www.scientific.net/MSF.956.154. View in Article Google Scholar
[27]	Wang H. B., Liu Q. B., Guo Y. X., et al. (2019). MoFe_1.5CrTiWAlNb_x refractory high-entropy alloy coating fabricated by laser cladding. Intermetallics 115:106613. DOI:10.1016/j.intermet.2019.106613. View in Article Google Scholar
[28]	Hall E. O. (1954). Variation of Hardness of Metals with Grain Size. Nature 173:948−949. DOI:10.1038/173948b0 View in Article CrossRef Google Scholar
[29]	Li K., Wang X., Zhang F., et al. (2008). Electronegativity identification of novel superhard materials. Phys. Rev. Lett. 100:235504. DOI:10.1103/PhysRevLett.100.235504 View in Article CrossRef Google Scholar
[30]	Sun G., Feng X., Wu X., et al. (2022). Is hardness constant in covalent materials. J. Mater. Sci. Tech. 114:215−221. DOI:10.1016/j.jmst.2021.10.032 View in Article CrossRef Google Scholar
[31]	Li Z. H., Wang Y. J., Ma M. D., et al. (2023). Ultrastrong conductive in situ composite composed of nanodiamond incoherently embedded in disordered multilayer graphene. Nat. Mater. 22:42−49. DOI:10.1038/s41563-022-01425-9 View in Article CrossRef Google Scholar
[32]	Qiu K. L., Hou J. P., Chen S., et al. (2023). Self-healing of fractured diamond. Nat. Mater. 22:1317. DOI:10.1038/s41563-023-01656-4 View in Article CrossRef Google Scholar
[33]	Kim S. H., Kim H. and Kim N. J. (2015). Brittle intermetallic compound makes ultrastrong low-density steel with large ductility. Nature 518:77−79. DOI:10.1038/nature14144 View in Article CrossRef Google Scholar
[34]	Liang J. S., Wan Y. Y., Lv H. F., et al. (2024). Metal bond strength regulation enables large-scale synthesis of intermetallic nanocrystals for practical fuel cells. Nat. Mater. 23:1259. DOI:10.1038/s41563-024-01901-4 View in Article CrossRef Google Scholar
[35]	Wei H. T., DeSantis D., Wei W., et al. (2017). Dopant compensation in alloyed CH₃NH₃PbBr_3-xCl_x perovskite single crystals for gamma-ray spectroscopy. Nat. Mater. 16:826−833. DOI:10.1038/nmat4927 View in Article CrossRef Google Scholar
[36]	Niu W. Z., Feng J., Chen J. F., et al. (2024) High-efficiency C3 electrosynthesis on a lattice-strain-stabilized nitrogen-doped Cu surface. Nat. Commun. 15:7070. DOI:10.1038/s41467-024-51478-4. View in Article Google Scholar
[37]	Szlawska M. and Kaczorowski D. (2013). Single-crystal growth of f-electron intermetallics in a tetra-arc czochralski furnace. Acta Phys. Pol. A 124:336−339. DOI:10.12693/APhysPolA.124.336 View in Article CrossRef Google Scholar
[38]	Kresse G. and Furthmüller J. (1996). Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set. Phys. Rev. B 54:18. DOI:10.1016/0927-0256(96)00008-0 View in Article CrossRef Google Scholar
[39]	Perdew J. P., Burke K., Ernzerhof M. (1996). Generalized gradient approximation made simple. Phys. Rev. Lett. 77:4. DOI:10.1103/PhysRevLett.77.3865 View in Article CrossRef Google Scholar
[40]	Perdew J. P., Chevary J. A., Vosko S. H., et al. (1992). Atoms, molecules, solids, and surfaces: Applications of the generalized gradient approximation for exchange and correlation. Phys. Rev. B Condens Matter. 46:6671−6687. DOI:10.1103/physrevb.46.6671 View in Article CrossRef Google Scholar
[41]	Hill R. (1952). The elastic behaviour of a crystalline aggregate. Proc. Phys. Soc. A 65:6. DOI:10.1088/0370-1298/65/5/307 View in Article CrossRef Google Scholar
[42]	Pelloth J., Brand R. A., Keun W. (1995). Local magnetic properties of the Fe₂Ti Laves phase. J. Magn. Magn. Mater. 140:59−60. DOI:10.1016/0304-8853(94)00836-1 View in Article CrossRef Google Scholar
[43]	Wertheim G. K., Wernick J. H. and Sherwood R. C. (1970). Model for the Composition-Dependent Ferromagnetic to Antiferromagnetic Transition in Fe₂Ti. J. Appl. Phys. 41:1325−1326. DOI:10.1063/1.1658924 View in Article CrossRef Google Scholar
[44]	Tian Y. F., Zhang P. Y., Zhang W., et al. (2024). Iron alloys of volatile elements in the deep Earth’s interior. Nat. Commun. 15:3320. DOI:10.1038/s41467-024-47663-0 View in Article CrossRef Google Scholar
[45]	Friedrich R., Usanmaz D., Oses C., et al. (2019). Coordination corrected ab initio formation enthalpies. npj Comput. Mater. 5:59. DOI:10.1038/s41524-019-0192-1 View in Article CrossRef Google Scholar
[46]	Nong Z. S., Cui P. C., Zhu J. C., et al. (2013). A first-principles study on the structural, elastic and electronic properties of the C14 Laves phase compounds TiX₂ (X=Cr, Mn, Fe). Phys. B 419:11−18. DOI:10.1007/s11771-017-3560-3 View in Article CrossRef Google Scholar
[47]	Gong X. G., Cui C., Yu Q., et al. (2020). First-principles study of phase stability and temperature-dependent mechanical properties of (Cr, M)₂₃C₆ (M = Fe, Mo) phases. J. Alloys Compd. 824:153948. DOI:10.1016/j.jallcom.2020.153948 View in Article CrossRef Google Scholar
[48]	Lv Z. Q., Wang B., Sun S. H., et al. (2015). Effect of atomic sites on electronic and mechanical properties of (Fe, Mo)₆C carbides. J. Alloys Compd. 649:1089−1093. DOI:10.1016/j.jallcom.2015.06.249 View in Article CrossRef Google Scholar
[49]	Gusev V. V., Adamson D., Deligkas A., et al. (2023). Optimality guarantees for crystal structure prediction. Nature 619:68−72. DOI:10.1038/s41586-023-06071-y View in Article CrossRef Google Scholar
[50]	Otero-de-la-Roza A., Abbasi-Pérez D. and Luaña V. (2011). Gibbs2: A new version of the quasiharmonic model code. II. Models for solid-state thermodynamics, features and implementation. Comput. Phys. Commun. 182:2232−2248. DOI:10.1016/j.cpc.2011.05.009 View in Article CrossRef Google Scholar
[51]	Chong X., Hu M. Y., Wu P., et al. (2019). Tailoring the anisotropic mechanical properties of hexagonal M₇X₃ (M=Fe, Cr, W, Mo; X=C, B) by multialloying. Acta Mater. 169:193−208. DOI:10.1016/j.actamat.2019.03.015 View in Article CrossRef Google Scholar
[52]	Parvinian S., Sievers D. E., Garmestani H., et al. (2021). Evaluation of the influence of B and Nb microalloying on the microstructure and strength of 18% Ni maraging steels (C350) using hardness, spherical indentation and tensile tests. Acta Mater. 215:117071. DOI:10.1016/j.actamat.2021.117071 View in Article CrossRef Google Scholar
[53]	Senkov O. N., Rao S., Chaput K. J., et al. (2018). Compositional effect on microstructure and properties of NbTiZr-based complex concentrated alloys. Acta Mater. 151:201−215. DOI:10.1016/j.actamat.2018.03.065 View in Article CrossRef Google Scholar
[54]	Li Y. F., Gao Y. M., Xiao B., et al. (2010). Theoretical study on the stability, elasticity, hardness and electronic structures of W-C binary compounds. J. Alloys Compd. 502:28−37. DOI:10.1016/j.jallcom.2010.04.184 View in Article CrossRef Google Scholar
[55]	Li Y. Y., Duan Y. H., Peng M. J., et al. (2023). Structural, elastic, and thermal properties of TM₅Si₃C (TM = Ti, Cr, Y) carbides from first-principles calculations. Vacuum 218:112616. DOI:10.1016/j.vacuum.2023.112616 View in Article CrossRef Google Scholar
[56]	Li P., Ma L. S., Peng M. J., et al. (2018). Elastic anisotropies and thermal conductivities of WB₂ diborides in different crystal structures: A first-principles calculation. J. Alloys Compd. 747:905−915. DOI:10.1016/j.jallcom.2018.03.109 View in Article CrossRef Google Scholar
[57]	Jian Y. X., Huang Z. F., Xing J. D., et al. (2019). Phase stability, mechanical properties and electronic structures of Ti-Al binary compounds by first principles calculations. Mater. Chem. Phys. 221:311−321. DOI:10.1016/j.matchemphys.2018.09.055 View in Article CrossRef Google Scholar
[58]	Ji J. S., Bu H. Y., Duan Y. H., et al. (2023). Electronic, elastic and thermal properties of hexagonal TM₅Si₃N investigated by first-principles calculations. Vacuum 214:112232. DOI:10.1016/j.vacuum.2023.112232 View in Article CrossRef Google Scholar
[59]	Bai H. X., Duan Y. H., Qi H. R., et al. (2024). Anisotropic elastic and thermal properties and damage tolerance of CrH: A first-principles calculation. Vacuum 222:112962. DOI:10.1016/j.vacuum.2024.112962 View in Article CrossRef Google Scholar
[60]	Sun Y., Yang A. C., Duan Y. H., et al. (2022). Electronic, elastic, and thermal properties, fracture toughness, and damage tolerance of TM₅Si₃B (TM = V and Nb) MAB phases. Int. J. Refract. Met. Hard Mater. 103:105781. DOI:10.1016/j.ijrmhm.2022.105781 View in Article CrossRef Google Scholar
[61]	Wu Y., Ma L. S., Zhou X. L., et al. (2022). Insights to electronic structures, elastic properties, fracture toughness, and thermal properties of M₂₃C₆ carbides. Int. J. Refract. Met. Hard Mater. 109:105985. DOI:10.1016/j.ijrmhm.2022.105985 View in Article CrossRef Google Scholar
[62]	Yang A. C., Duan Y. H., Li C. J., et al. (2022). Theoretical explorations of structure, mechanical properties, fracture toughness, electronic properties, and thermal conductivity of Ag-doped η΄-Cu₆Sn₅. Intermetallics 141:107437. DOI:10.1016/j.intermet.2021.107437 View in Article CrossRef Google Scholar
[63]	Simunek A. and Vackar J. (2006). Hardness of covalent and ionic crystals: first-principle calculations. Phys. Rev. Lett. 96:085501. DOI:10.1103/PhysRevLett.96.085501 View in Article CrossRef Google Scholar
[64]	Vecchio K., Curtarolo S., Kaufmann K. et al. (2024). Fermi energy engineering of enhanced plasticity in high-entropy carbides. Acta Mater. 276:120117. DOI:10.1016/j.actamat.2024.120117 View in Article CrossRef Google Scholar
[65]	Hu H., Wu X. Z., Wang R., et al. (2016). Phase stability, mechanical properties and electronic structure of TiAl alloying with W, Mo, Sc and Yb: First-principles study. J. Alloys Compd. 658:689−696. DOI:10.1016/j.jallcom.2015.10.270 View in Article CrossRef Google Scholar
[66]	Mao Q. Q., Mu X., Deng K., et al. (2023). Multisite synergism-induced electron regulation of high-entropy alloy metallene for boosting alkaline hydrogen evolution reaction. Adv. Funct. Mater. 33:2304963. DOI:10.1002/adfm.202304963 View in Article CrossRef Google Scholar

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Tan X., Liu H., Hou T., et al. (2025). Hardness augmentation engineering of TiFe2 with doping design and single-crystal realization. The Innovation Materials 3:100140. https://doi.org/10.59717/j.xinn-mater.2025.100140

Tan X., Liu H., Hou T., et al. (2025). Hardness augmentation engineering of TiFe₂ with doping design and single-crystal realization. The Innovation Materials 3:100140. https://doi.org/10.59717/j.xinn-mater.2025.100140

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Hardness augmentation engineering of TiFe₂ with doping design and single-crystal realization

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Hardness augmentation engineering of TiFe₂ with doping design and single-crystal realization