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Modeling the final sintering stage of doped ceramics: mutual interaction between grain growth and densification

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Abstract

Applying the thermodynamic extremal principle, a model for grain growth and densification in the final stage of sintering of doped ceramics was derived, with segregation-dependent interfacial energies and mobilities (or diffusivities). The model demonstrated an interdependence between the driving forces of grain growth and densification during sintering evolution, observed because the surface energy contributes positively to the driving force of grain growth while the GB energy negatively to the driving force of densification. The model was tested in alumina as a host system, and calculations demonstrate that dopants with more negative GB (or surface) segregation enthalpy or which cause lower GB diffusion coefficient can induce higher relative densities at a given grain size. Comparatively studying yttria- and lanthana-doped alumina, the lanthana doping showed significantly enhanced sintering attributed to the larger La3+ radius causing a more negative GB segregation energy. This present model is expected to help dopant designing to improve control over sintering.

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Notes

  1. Here, ignoring the difference in atomic volume between the three different regions, then the molar fraction will be equivalent to the volume fraction.

  2. For ceramics (ionic compounds), the diffusion path of the dopant cation should be consistent with the host cation, since the cations generally occupy the same sub-lattice. For the case of isovalent doping, where the same electrostatic interaction acts on these two types of cations, the variation of the surrounding environment due to segregation would produce a similar effect on the diffusion of the host cation and that of the dopant cation. For aliovalent doping, the dopant cation may exhibit different dependence of diffusion on segregation compared to the host cation since, although the dopant cation passes through the same diffusion path as the host cation, the difference in electrostatic interactions due to their own charge differences may have a more pronounced effect on diffusion.

  3. The relative density during the final stage of sintering is usually above 90%.

  4. Model calculations show that, at moderate levels of GB segregation and surface segregation (ΔH GBseg  = ΔH sseg  = −40 kJ mol−1) with T = 1300 °C and x B = 1×10−3, when D GBB0  > 0.02D GB0, solute drag will not exert any observable effect on grain growth and densification.

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Acknowledgements

The authors are grateful to the financial support of National Basic Research Program of China (No. 2011CB610403), the Natural Science Foundation of China (Nos. 51134011 and 51431008), the Fundamental Research Fund of Northwestern Polytechnical University (No. JC20120223), and the China National Funds for Distinguished Young Scientists (No. 51125002). M. M. Gong is thanked for the financial supports of the Doctorate Foundation of Northwestern Polytechnical University (CX201204) and of China Scholarship Council. R. H. R. Castro is thanked for the financial support of the National Science Foundation (DMR 1609781).

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Gong, M.M., Castro, R.H.R. & Liu, F. Modeling the final sintering stage of doped ceramics: mutual interaction between grain growth and densification. J Mater Sci 53, 1680–1698 (2018). https://doi.org/10.1007/s10853-017-1617-1

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