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Toughening oxide glasses through paracrystallization

Nature Materials volume 22, pages 1189–1195 (2023)Cite this article

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Abstract

Glasses, unlike crystals, are intrinsically brittle due to the absence of microstructure-controlled toughening, creating fundamental constraints for their technological applications. Consequently, strategies for toughening glasses without compromising their other advantageous properties have been long sought after but elusive. Here we report exceptional toughening in oxide glasses via paracrystallization, using aluminosilicate glass as an example. By combining experiments and computational modelling, we demonstrate the uniform formation of crystal-like medium-range order clusters pervading the glass structure as a result of paracrystallization under high-pressure and high-temperature conditions. The paracrystalline oxide glasses display superior toughness, reaching up to 1.99 ± 0.06 MPa m1/2, surpassing any other reported bulk oxide glasses, to the best of our knowledge. We attribute this exceptional toughening to the excitation of multiple shear bands caused by a stress-induced inverse transformation from the paracrystalline to amorphous states, revealing plastic deformation characteristics. This discovery presents a potent strategy for designing highly damage-tolerant glass materials and emphasizes the substantial influence of atomic-level structural variation on the properties of oxide glasses.

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Fig. 1: Structure factors and pair distribution functions of the grossular samples.
Fig. 2: Direct structural identification of paracrystalline grossular.
Fig. 3: Mechanical properties of the paracrystalline grossular.
Fig. 4: Toughening mechanism for paracrystalline oxide glass.

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Data availability

The data that support the findings of this study are available from the corresponding authors upon request.

Code availability

The software used for data analysis is available from H.S. upon request.

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Acknowledgements

H.T. thanks the Alexander von Humboldt Foundation for financial support. H.S. was supported by the NSF under grant no. DMR-1611064. W.X. was supported by the National Natural Science Foundation of China (grant no. 12104398) and the China Postdoctoral Science Foundation (grant no. 2021M692840). Nanjing University of Science and Technology thanks the support of the National Natural Science Foundation of China (nos. 92163215, 52174364 and 52101143). Z.Z. acknowledges financial support from the Shanghai Science and Technology Committee, China (no. 22JC1410300), and Shanghai Key Laboratory of Material Frontiers Research in Extreme Environments, China (no. 22dz2260800). This work was also supported by the European Research Council under the European Union’s Horizon 2020 research and innovation programme (proposal no. 787527), the National Nature Science Foundation of China (no. 11804010), Jiangsu Funding Program for Excellent Postdoctoral Talent, and Major Science and Technology Infrastructure Project of Material Genome Big-science Facilities Platform supported by the Municipal Development and Reform Commission of Shenzhen. We acknowledge DESY (Hamburg, Germany), a member of the Helmholtz Association HGF, for the provision of experimental facilities. Parts of this research were carried out at PETRA III beamline P02.1. Beamtime was allocated by an in-house contingent. We thank C. Peng at Zhengzhou Research Institute for Abrasives & Grinding in China for the measurements of hardness and fracture toughness; L. Yuan, R. Njul and T. Withers at BGI for valuable discussions and technical supports; Y. Zhao at Yanshan University in China for the preparation of glass ceramics and standard SENB measurements; and B. Zhang at Chongqing University in China for the in situ TEM tensile tests.

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Authors and Affiliations

  1. Bayerisches Geoinstitut, University of Bayreuth, Bayreuth, Germany

    Hu Tang, Alexander Kurnosov, Fei Wang, Hongzhan Fei, Lin Wang & Tomoo Katsura

  2. Center for High Pressure Science and Technology Advanced Research, Beijing, China

    Hu Tang, Kai Zhang, Tao Liang, Zhidan Zeng, Howard Sheng & Tomoo Katsura

  3. State Key Laboratory of Superhard Materials, Synergetic Extreme Condition High-Pressure Science Center, College of Physics, Jilin University, Changchun, China

    Hu Tang

  4. State Key Laboratory of Physical Chemistry of Solid Surfaces, College of Materials, Xiamen University, Xiamen, China

    Yong Cheng & Ming-Sheng Wang

  5. Academy for Advanced Interdisciplinary Studies & Shenzhen Engineering Research Center for Frontier Materials Synthesis at High Pressures, Southern University of Science and Technology, Shenzhen, China

    Xiaohong Yuan & Songbai Han

  6. National Key Laboratory of Advanced Casting Technologies, MIIT Key Laboratory of Advanced Metallic and Intermetallic Materials Technology, Engineering Research Center of Materials Behavior and Design, Ministry of Education, Nanjing University of Science and Technology, Nanjing, China

    Zhen Chen & Guang Chen

  7. Institute of Light+X Science and Technology, College of Information Science and Engineering, Ningbo University, Ningbo, China

    Wenge Xiao

  8. State Key Lab of Modern Optical Instrumentation, College of Optical Science and Engineering, Zhejiang University, Hangzhou, China

    Wenge Xiao

  9. Deutsches Elektronen-Synchrotron (DESY), Hamburg, Germany

    Henrik S. Jeppesen & Martin Etter

  10. School of Earth Sciences, Zhejiang University, Hangzhou, China

    Hongzhan Fei

  11. Department of Physics and Astronomy, George Mason University, Fairfax, VA, USA

    Howard Sheng

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Contributions

H.T., H.S. and W.X. proposed and supervised the project. H.T., F.W., H.F. and L.W. synthesized the samples. H.T., Y.C., X.Y., K.Z., H.S.J., M.E. and M.-S.W. performed the structure characterizations. H.T., X.Y., A.K., Z.C., W.X., T.L., Z.Z., S.H. and G.C. measured the properties. H.S. performed the theoretical calculations. H.T., H.S., W.X. and T.K. analysed the data and wrote the manuscript, with the contributions of all authors.

Corresponding authors

Correspondence to Hu Tang, Wenge Xiao or Howard Sheng.

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Supplementary Information

Supplementary Figs. 1–17 and Tables 1–3.

Supplementary Video 1

Glassy grossular during in situ tensile test.

Supplementary Video 2

Paracrystalline grossular during in situ tensile test.

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Tang, H., Cheng, Y., Yuan, X. et al. Toughening oxide glasses through paracrystallization. Nat. Mater. 22, 1189–1195 (2023). https://doi.org/10.1038/s41563-023-01625-x

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