[en] Grain boundaries (GBs) generally exhibit complex structural and compositional features that significantly affect material hardness. Here, we establish a methodology to correlate the local hardness contributions of the GBs with their frequency distribution and their structural and compositional characteristics, using a submicron WC–Co cemented carbide as a model. An exceptional local hardness of (14.68 ± 0.12) GPa is observed from a 90° WC{0001}/WC{101¯0} GB, unlike the low contributions from other WC/WC GBs. This is linked to pronounced Cr and Co segregation at this GB, due to Cr affinity at the WC{0001}/Co and WC{101¯0}/Co phase boundaries and Co infiltration during liquid-phase sintering. Density functional theory results indicate that a large lattice mismatch, strong W–C covalent bonding, and Cr and Co accumulation increase the elastic strain field, resulting in strong atomic distortion near the interface and contributing to exceptional strengthening. Our findings highlight the critical influence of GB complexities on material hardness.
Disciplines :
Materials science & engineering
Author, co-author :
Chen, Hansheng ; School of Aerospace, Mechanical and Mechatronic Engineering, The University of Sydney, Sydney, Australia ; Australian Centre for Microscopy and Microanalysis, The University of Sydney, Sydney, Australia
Zhou, Haoruo; School of Aerospace, Mechanical and Mechatronic Engineering, The University of Sydney, Sydney, Australia ; Australian Centre for Microscopy and Microanalysis, The University of Sydney, Sydney, Australia
Cui, Xiangyuan; School of Aerospace, Mechanical and Mechatronic Engineering, The University of Sydney, Sydney, Australia ; Australian Centre for Microscopy and Microanalysis, The University of Sydney, Sydney, Australia
Czettl, Christoph; CERATIZIT Austria GmbH, Reutte, Austria
Weirather, Thomas ; CERATIZIT Austria GmbH, Reutte, Austria
Pachlhofer, Julia; CERATIZIT Austria GmbH, Reutte, Austria
Mueller, Pauline; CERATIZIT Austria GmbH, Reutte, Austria
Teppernegg, Tamara; CERATIZIT Austria GmbH, Reutte, Austria
USELDINGER, Ralph ; University of Luxembourg > Faculty of Science, Technology and Medicine (FSTM) > Department of Engineering (DoE) ; CERATIZIT Luxembourg S.à.r.l., 101 Route de Holzem, 8232 Mamer, Luxemburg
Primig, Sophie ; School of Materials Science & Engineering, UNSW Sydney, Australia
Ringer, Simon P. ; School of Aerospace, Mechanical and Mechatronic Engineering, The University of Sydney, Sydney, Australia ; Australian Centre for Microscopy and Microanalysis, The University of Sydney, Sydney, Australia
External co-authors :
yes
Language :
English
Title :
Effect of WC/WC grain boundary misorientation angle on the local hardness in WC–Co cemented carbides
The authors acknowledge the facilities, the scientific, and technical assistance provided at Sydney Microscopy & Microanalysis (SMM) and the Sydney Manufacturing Hub (SMH), which are Core Research Facilities at the University of Sydney. We particularly acknowledge Drs. Takanori Sato, Magnus Garbrecht, Vijay Bhatia, Jiangtao Qu, Ranming Niu, Hongwei Liu, Ehsan Farabi, Mrs. Ashalatha Indiradevi, and Ms. Zhifei Zhu. SMM is the university's node of Microscopy Australia. This work was supported by the Australian Research Council (LP190100850). This work was supported by computational resources provided by the Australian Government through the National Computational Infrastructure (NCI, Gadi), and by the Sydney Informatics Hub (the University of Sydney).
Wu, D., Zhang, J., Huang, J.C., Bei, H., Nieh, T.G., Grain-boundary strengthening in nanocrystalline chromium and the Hall–Petch coefficient of body-centered cubic metals. Scr. Mater. 68:2 (2013), 118–121.
Hussein, A., Krom, A.H.M., Dey, P., Sunnardianto, G.K., Moultos, O.A., Walters, C.L., The effect of hydrogen content and yield strength on the distribution of hydrogen in steel: a diffusion coupled micromechanical FEM study. Acta Mater., 209, 2021, 116799.
Cao, W., Kundu, A., Yu, Z., Harmer, M.P., Vinci, R.P., Direct correlations between fracture toughness and grain boundary segregation behavior in ytterbium-doped magnesium aluminate spinel. Scr. Mater. 69:1 (2013), 81–84.
Arafin, M.A., Szpunar, J.A., A new understanding of intergranular stress corrosion cracking resistance of pipeline steel through grain boundary character and crystallographic texture studies. Corros. Sci. 51:1 (2009), 119–128.
Ye, X., Yan, F., Schäfer, L., Wang, D., Geßwein, H., Wang, W., Chellali, M.R., Stephenson, L.T., Skokov, K., Gutfleisch, O., Raabe, D., Hahn, H., Gault, B., Kruk, R., Magnetoelectric tuning of pinning-type permanent magnets through atomic-scale engineering of grain boundaries. Adv. Mater. (Weinheim), 33(5), 2021, e2006853 -n/a.
Petch, N., The cleavage strength of polycrystals. J. Iron Steel Inst. 174 (1953), 25–28.
Hall, E., The deformation and ageing of mild steel: III discussion of results. Proc. Phys. Soc. Sec. B, 64(9), 1951, 747.
Saylor, D.M., Morawiec, A., Rohrer, G.S., The relative free energies of grain boundaries in magnesia as a function of five macroscopic parameters. Acta Mater. 51:13 (2003), 3675–3686.
García, J., Collado Ciprés, V., Blomqvist, A., Kaplan, B., Cemented carbide microstructures: a review. Int. J. Refract. Hard Met. 80 (2019), 40–68.
Shing, T., Luyckx, S., Northrop, I., Wolff, I., The effect of ruthenium additions on the hardness, toughness and grain size of WC–Co. Int. J. Refract. Hard Met. 19:1 (2001), 41–44.
Zeng, H., Liu, W., Wei, C., Influence of Ru on the microstructure and performance of WC-Co cemented carbides. Mater. Sci. Technol. 38:13 (2022), 940–946.
Luyckx, S., Alli, M.Z., Comparison between V8C7 and Cr3C2 as grain refiners for WC-Co. Mater. Des. 22:6 (2001), 507–510.
Tian, H., Zhang, M., Peng, Y., Du, Y., Zhou, P., Sintering behavior and mechanical properties of Cr3C2 doped ultra-fine WC-Co cemented carbides: experment guided with thermodynamic calculations. Int. J. Refract. Hard Met. 78 (2019), 240–246.
Tian, H., Peng, Y., Du, Y., Zhang, Y., Zhang, S., Zheng, J., Optimization of the mechanical properties of ultra-fine WC-Co-Cr3C2 cemented carbides via an approach based on thermodynamic calculations and characterization of the experimental results by the Weibull distribution. Calphad, 70, 2020, 101778.
Henjered, A., Hellsing, M., Andrén, H.-O., Nordén, H., Quantitative microanalysis of carbide/carbide interfaces in WC–Co-base cemented carbides. Mater. Sci. Technol. 2:8 (1986), 847–855.
Vicens, J., Benjdir, M., Nouet, G., Dubon, A., Laval, J., Cobalt intergranular segregation in WC-Co composites. J. Mater. Sci. 29 (1994), 987–994.
Christensen, M., Wahnström, G., Strength and reinforcement of interfaces in cemented carbides. Int. J. Refract. Hard Met. 24:1–2 (2006), 80–88.
Christensen, M., Wahnström, G., Effects of cobalt intergranular segregation on interface energetics in WC–Co. Acta Mater. 52:8 (2004), 2199–2207.
Zhou, X., Ahmadian, A., Gault, B., Ophus, C., Liebscher, C.H., Dehm, G., Raabe, D., Atomic motifs govern the decoration of grain boundaries by interstitial solutes. Nature Commun, 14(1), 2023, 3535.
Herbig, M., Raabe, D., Li, Y., Choi, P., Zaefferer, S., Goto, S., Atomic-scale quantification of grain boundary segregation in nanocrystalline material. Phy. Rev. Lett., 112(12), 2014, 126103.
Kalidindi, S.R., Vachhani, S.J., Mechanical characterization of grain boundaries using nanoindentation. Curr. Opin. Solid State Mater. Sci. 18:4 (2014), 196–204.
Perdew, J.P., Burke, K., Ernzerhof, M., Generalized gradient approximation made simple. Phys. Rev. Lett., 77(18), 1996, 3865.
Kresse, G., Furthmüller, J., Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set. Phys. Rev. B, 54(16), 1996, 11169.
Lay, S., Evaluation of slip transfer through WC grain boundaries in cemented carbides. Int. J. Refract. Hard Met., 99, 2021, 105584.
Elizalde, M., Ocaña, I., Alkorta, J., Sánchez-Moreno, J., Mechanical strength assessment of single WC-WC interfaces present in WC-Co hardmetals through micro-beam bending experiments. Int. J. Refract. Hard Met. 72 (2018), 39–44.
Cui, X.-Y., Ringer, S.P., On the nexus between atom probe microscopy and density functional theory simulations. Mater. Charact. 146 (2018), 347–358.
Luo, Z., Hu, C., Xie, L., Nie, H., Xiang, C., Gu, X., He, J., Zhang, W., Yu, Z., Luo, J., A highly asymmetric interfacial superstructure in WC: expanding the classic grain boundary segregation and new complexion theories. Mater. Horiz. 7:1 (2020), 173–180.
Yang, C., Hu, C., Xiang, C., Nie, H., Gu, X., Xie, L., He, J., Zhang, W., Yu, Z., Luo, J., Interfacial superstructures and chemical bonding transitions at metal-ceramic interfaces. Sci. Adv., 7(11), 2021, eabf6667.
Exner, H., Physical and chemical nature of cemented carbides. Int. Met. Rev. 24:1 (1979), 149–173.
Yousfi, M., Norgren, S., Andrén, H.-O., Falk, L., Chromium segregation at phase boundaries in Cr-doped WC-Co cemented carbides. Mater. Charact. 144 (2018), 48–56.
Zhong, Y., Shaw, L.L., Growth mechanisms of WC in WC–5.75 wt% Co. Ceram. Int. 37:8 (2011), 3591–3597.
Fransson, E., Gren, M., Wahnström, G., Complexions and grain growth retardation: first-principles modeling of phase boundaries in WC-Co cemented carbides at elevated temperatures. Acta Mater., 216, 2021, 117128.
