Abstract
Radiation-induced segregation is well known in metals, but has been rarely studied in ceramics. We discover that radiation can induce notable segregation of one of the constituent elements to grain boundaries in a ceramic, despite the fact that the ceramic forms a line compound and therefore has a strong thermodynamic driving force to resist off-stoichiometry. Specifically, irradiation of silicon carbide at 300 °C leads to carbon enrichment near grain boundaries, whereas the enrichment diminishes for irradiation at 600 °C. The temperature dependence of this radiation-induced segregation is different from that shown in metallic systems. Using an ab initio informed rate theory model, we demonstrate that this difference is introduced by the unique defect energy landscapes present in the covalent system. Additionally, we discover that grain boundaries in unirradiated silicon carbide grown by chemical vapour deposition are intrinsically carbon-depleted. The inherent grain boundary chemistry and its evolution under radiation are both critical for understanding the many properties of ceramics associated with grain boundaries.
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Data availability
The data that support the findings of this study are publicly available at https://uwmadison.box.com/v/NM-RISinCeramic.
Code availability
The code used for calculating carbon concentrations at grain boundaries is provided in the Supplementary Information.
References
Van Swygenhoven, H. Grain boundaries and dislocations. Science 296, 66–67 (2002).
Shen, Z., Wagoner, R. H. & Clark, W. A. T. Dislocation and grain boundary interactions in metals. Acta Metall. 36, 3231–3242 (1988).
Allen, T., Lance, M., Meyer, H. & Walker, L. Corrosion of CVD silicon carbide in 500 °C supercritical water. J. Am. Ceram. Soc. 90, 315–318 (2007).
Gleiter, H. Grain boundaries as point defect sources or sinks—diffusional creep. Acta Metall. 27, 187–192 (1979).
Shrader, D. et al. Ag diffusion in cubic silicon carbide. J. Nucl. Mater. 408, 257–271 (2011).
Jiao, Z. & Was, G. S. Novel features of radiation-induced segregation and radiation-induced precipitation in austenitic stainless steels. Acta Mater. 59, 1220–1238 (2011).
Etienne, A., Radiguet, B., Cunningham, N. J., Odette, G. R. & Pareige, P. Atomic scale investigation of radiation-induced segregation in austenitic stainless steels. J. Nucl. Mater. 406, 244–250 (2010).
Field, K. G. et al. Dependence on grain boundary structure of radiation induced segregation in a 9 wt.% Cr model ferritic/martensitic steel. J. Nucl. Mater. 435, 172–180 (2013).
Rehn, L. E., Okamoto, P. R. & Wiedersich, H. Dose dependence of radiation-induced segregation in Ni–1 at% Si. J. Nucl. Mater. 80, 172–179 (1979).
Was, G. S. et al. Assessment of radiation-induced segregation mechanisms in austenitic and ferritic–martensitic alloys. J. Nucl. Mater. 411, 41–50 (2011).
Busby, J., Was, G. & Kenik, E. Isolating the effect of radiation-induced segregation in irradiation-assisted stress corrosion cracking of austenitic stainless steels. J. Nucl. Mater. 302, 20–40 (2002).
Bruemmer, S. M. & Was, G. S. Microstructural and microchemical mechanisms controlling intergranular stress corrosion cracking in light-water-reactor systems. J. Nucl. Mater. 216, 348–363 (1994).
Olesinski, R. W. & Abbaschian, G. J. The C−Si (carbon–silicon) system. Bull. Alloy Phase Diagrams 5, 486–489 (1984).
Katoh, Y., Snead, L. L., Szlufarska, I. & Weber, W. J. Radiation effects in SiC for nuclear structural applications. Curr. Opin. Solid State Mater. Sci. 16, 143–152 (2012).
Mehregany, M. & Zorman, C. A. SiC MEMS: opportunities and challenges for applications in harsh environments. Thin Solid Films 355, 518–524 (1999).
Zheng, M. J., Swaminathan, N., Morgan, D. & Szlufarska, I. Energy barriers for point-defect reactions in 3C-SiC. Phys. Rev. B 88, 1–15 (2013).
Krivanek, O. L. et al. An electron microscope for the aberration-corrected era. Ultramicroscopy 108, 179–195 (2008).
Tan, L., Allen, T. R., Hunn, J. D. & Miller, J. H. EBSD for microstructure and property characterization of the SiC-coating in TRISO fuel particles. J. Nucl. Mater. 372, 400–404 (2008).
Katoh, Y. et al. Current status and critical issues for development of SiC composites for fusion applications. J. Nucl. Mater. 367–370A, 659–671 (2007).
Fu, X.-A., Dunning, J. L., Zorman, C. A. & Mehregany, M. Polycrystalline 3C-SiC thin films deposited by dual precursor LPCVD for MEMS applications. Sens. Actuators A 119, 169–176 (2005).
Kondo, S., Katoh, Y. & Snead, L. L. Analysis of grain boundary sinks and interstitial diffusion in neutron-irradiated SiC. Phys. Rev. B 83, 1–6 (2011).
Wang, X. et al. Evidence for cascade overlap and grain boundary enhanced amorphization in silicon carbide irradiated with Kr ions. Acta Mater. 99, 7–15 (2015).
Jiang, H. & Szlufarska, I. Small-angle twist grain boundaries as sinks for point defects. Sci. Rep. 8, 3736–3749 (2018).
Gao, F., Chen, D., Hu, W. & Weber, W. J. Energy dissipation and defect generation in nanocrystalline silicon carbide. Phys. Rev. B 81, 1–8 (2010).
Ziegler, J. F., Ziegler, M. D. & Biersack, J. P. SRIM—the stopping and range of ions in matter (2010). Nucl. Instrum. Methods Phys. Res. B 268, 1818–1823 (2010).
Stoller, R. E. et al. On the use of SRIM for computing radiation damage exposure. Nucl. Instrum. Methods Phys. Res. B 310, 75–80 (2013).
Tajima, Y. & Kingery, W. D. Grain-boundary segregation in aluminium-doped silicon carbide. J. Mater. Sci. 17, 2289–2297 (1982).
Desu, S. B. & Payne, D. A. Interfacial segregation in perovskites: II, experimental evidence. J. Am. Ceram. Soc. 73, 3398–3406 (1990).
Jiang, C., Zheng, M. J., Morgan, D. & Szlufarska, I. Amorphization driven by defect-induced mechanical instability. Phys. Rev. Lett. 111, 1–5 (2013).
Lucas, G. & Pizzagalli, L. Ab initio molecular dynamics calculations of threshold displacement energies in silicon carbide. Phys. Rev. B 72, 161202(R) (2005).
Snead, L. L. et al. Handbook of SiC properties for fuel performance modeling. J. Nucl. Mater. 371, 329–377 (2007).
Ardell, A. J. & Bellon, P. Radiation-induced solute segregation in metallic alloys. Curr. Opin. Solid State Mater. Sci. 20, 115–139 (2016).
Swaminathan, N., Morgan, D. & Szlufarska, I. Role of recombination kinetics and grain size in radiation-induced amorphization. Phys. Rev. B 86, 1–16 (2012).
Swaminathan, N., Morgan, D. & Szlufarska, I. Ab initio based rate theory model of radiation induced amorphization in β-SiC. J. Nucl. Mater. 414, 431–439 (2011).
Jiang, H., Wang, X. & Szlufarska, I. The multiple roles of small-angle tilt grain boundaries in annihilating radiation damage in SiC. Sci. Rep. 7, 42358 (2017).
Zhang, Y. et al. Ionization-induced annealing of pre-existing defects in silicon carbide. Nat. Commun. 6, 8049 (2015).
Hua, W. et al. Ion-irradiation-induced athermal annealing of helium bubbles in SiC. Nucl. Instrum. Methods Phys. Res. B 268, 2325–2328 (2010).
Park, J. Y. et al. Long-term corrosion behavior of CVD SiC in 360 °C water and 400 °C steam. J. Nucl. Mater. 443, 603–607 (2013).
Liu, C., Xi, J. & Szlufarska, I. Sensitivity of SiC grain boundaries to oxidation. J. Phys. Chem. C. 123, 11546–11554 (2019).
TEAM EBSD Analysis System v.4.5 (Ametek-EDAX, 2017).
OIM Analysis v.8 (Ametek-EDAX, 2017).
Egerton, R. Electron Energy-Loss Spectroscopy in the Electron Microscope (Springer, 2011).
Digital Micrograph v.3.22 (Gatan Inc., 2017).
Jiang, C., Morgan, D. & Szlufarska, I. Structures and stabilities of small carbon interstitial clusters in cubic silicon carbide. Acta Mater. 62, 162–172 (2014).
Katoh, Y., Hashimoto, N., Kondo, S., Snead, L. L. & Kohyama, A. Microstructural development in cubic silicon carbide during irradiation at elevated temperatures. J. Nucl. Mater. 351, 228–240 (2006).
Jiang, H., He, L., Morgan, D., Voyles, P. M. & Szlufarska, I. Radiation-induced mobility of small defect clusters in covalent materials. Phys. Rev. B 94, 024107 (2016).
Liu, C. et al. Evolution of small defect clusters in ion-irradiated 3C-SiC: combined cluster dynamics modeling and experimental study. Acta Mater. 125, 377–389 (2017).
Bockstedte, M., Mattausch, A. & Pankratov, O. Ab initio study of the migration of intrinsic defects in 3C – SiC. Phys. Rev. B 68, 205201 (2003).
Devanathan, R., Weber, W. J. & Gao, F. Atomic scale simulation of defect production in irradiated 3C-SiC. J. Appl. Phys. 90, 2303–2309 (2001).
Swaminathan, N., Kamenski, P. J., Morgan, D. & Szlufarska, I. Effects of grain size and grain boundaries on defect production in nanocrystalline 3C–SiC. Acta Mater. 58, 2843–2853 (2010).
Waite, T. R. General theory of bimolecular reaction rates in solids and liquids. J. Chem. Phys. 28, 103–106 (1958).
Hon, M. H. & Davis, R. F. Self-diffusion of 14C in polycrystalline β-SiC. J. Mater. Sci. 14, 2411–2421 (1979).
Acknowledgements
The authors acknowledge the US Department of Energy Basic Energy Sciences for funding this research (fund number DE-FG02-08ER46493). The authors also acknowledge use of facilities and instrumentation supported by NSF through the University of Wisconsin Materials Research Science and Engineering Center (DMR-1720415). The electron microscopy research was conducted as part of a user project through Oak Ridge National Laboratory’s Center for Nanophase Materials Sciences (CNMS), which is a US Department of Energy Office of Science User Facility.
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I.S. conceived and directed the project, with considerable input from X.W. X.W., P.M.V. and I.S. designed the microscopy experiments. X.W., H.Z. and T.B. prepared the thin foils for the microscopy experiments. H.Z., T.B., Y.G., O.E. and T.K. fabricated the bicrystal SiC sample. H.Z. conducted the correlated tEBSD and TEM analysis. X.W., T.B. and J.I. performed the STEM-EELS measurements and data analysis. H.J. and C.L. carried out MD, DFT and CD calculations. X.W. developed the rate theory model for GB concentration calculations, with input from D.M. and I.S. X.W. and I.S. wrote the manuscript with help from all authors.
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Supplementary Information
Supplementary Notes 1–12, Figs. 1–12, Table 1 and source code of the self-developed algorithm for calculating grain boundary concentrations.
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Wang, X., Zhang, H., Baba, T. et al. Radiation-induced segregation in a ceramic. Nat. Mater. 19, 992–998 (2020). https://doi.org/10.1038/s41563-020-0683-y
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DOI: https://doi.org/10.1038/s41563-020-0683-y
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