Skip to main content

Thank you for visiting nature.com. You are using a browser version with limited support for CSS. To obtain the best experience, we recommend you use a more up to date browser (or turn off compatibility mode in Internet Explorer). In the meantime, to ensure continued support, we are displaying the site without styles and JavaScript.

  • Article
  • Published:

Three-dimensional printing of multicomponent glasses using phase-separating resins

Nature Materials volume 19, pages 212–217 (2020)Cite this article

Subjects

Abstract

The digital fabrication of oxide glasses by three-dimensional (3D) printing represents a major paradigm shift in the way glasses are designed and manufactured, opening opportunities to explore functionalities inaccessible by current technologies. The few enticing examples of 3D printed glasses are limited in their chemical compositions and suffer from the low resolution achievable with particle-based or molten glass technologies. Here, we report a digital light-processing 3D printing platform that exploits the photopolymerization-induced phase separation of hybrid resins to create glass parts with complex shapes, high spatial resolutions and multi-oxide chemical compositions. Analogously to conventional porous glass fabrication methods, we exploit phase separation phenomena to fabricate complex glass parts displaying light-controlled multiscale porosity and dense multicomponent transparent glasses with arbitrary geometry using a desktop printer. Because most functional properties of glasses emerge from their transparency and multicomponent nature, this 3D printing platform may be useful for distinct technologies, sciences and arts.

This is a preview of subscription content, access via your institution

Access options

Buy this article

  • Purchase on Springer Link
  • Instant access to full article PDF
Buy now

Prices may be subject to local taxes which are calculated during checkout

Fig. 1: DLP 3D printing of phase-separating resins.
Fig. 2: Resin composition determines the degree of phase separation during DLP printing.
Fig. 3: Light-controlled pore size in 3D printed glass objects.
Fig. 4: Boro-phospho-silicate (BPS) glasses obtained by 3D printing of phase-separating resins.

Similar content being viewed by others

Data availability

The datasets generated during and/or analysed during the current study are available from the corresponding authors on reasonable request.

Code availability

The *.stl and encoded microstructure print files are available from the corresponding authors on reasonable request.

References

  1. Pfaender, H. G. Schott Guide to Glass (Springer, 2012).

  2. Pilkington, L. A. B. Review lecture: the float glass process. Proc. R. Soc. Lond. A 314, 1–25 (1969).

    Article  CAS  Google Scholar 

  3. Hale, D. Strengthening of silicate glasses by ion exchange. Nature 217, 1115 (1968).

    Article  CAS  Google Scholar 

  4. Klein, J. et al. Additive manufacturing of optically transparent glass. 3D Print. Addit. Manuf. 2, 92–105 (2015).

    Article  Google Scholar 

  5. Nguyen, D. T. et al. 3D‐printed transparent glass. Adv. Mater. 29, 1701181 (2017).

    Article  Google Scholar 

  6. Destino, J. F. et al. 3D printed optical quality silica and silica–titania glasses from sol–gel feedstocks. Adv. Mater. Technol. 3, 1700323 (2018).

    Article  Google Scholar 

  7. Luo, J. et al. Additive manufacturing of transparent soda-lime glass using a filament-fed process. J. Manuf. Sci. Eng. 139, 061006 (2017).

    Article  Google Scholar 

  8. Kotz, F. et al. Three-dimensional printing of transparent fused silica glass. Nature 544, 337–339 (2017).

    Article  CAS  Google Scholar 

  9. Liu, C., Qian, B., Ni, R., Liu, X. & Qiu, J. 3D printing of multicolor luminescent glass. RSC Adv. 8, 31564–31567 (2018).

    Article  CAS  Google Scholar 

  10. Bártolo, P. J. Stereolithography: Materials, Processes and Applications (Springer, 2011).

  11. Wong, K. V. & Hernandez, A. A review of additive manufacturing. ISRN Mech. Eng. 2012, 208760 (2012).

  12. Wu, C., Luo, Y., Cuniberti, G., Xiao, Y. & Gelinsky, M. Three-dimensional printing of hierarchical and tough mesoporous bioactive glass scaffolds with a controllable pore architecture, excellent mechanical strength and mineralization ability. Acta Biomater. 7, 2644–2650 (2011).

    Article  CAS  Google Scholar 

  13. Tesavibul, P. et al. Processing of 45S5 Bioglass® by lithography-based additive manufacturing. Mater. Lett. 74, 81–84 (2012).

    Article  CAS  Google Scholar 

  14. Zocca, A. et al. SiOC ceramics with ordered porosity by 3D-printing of a preceramic polymer. J. Mater. Res. 28, 2243–2252 (2013).

    Article  CAS  Google Scholar 

  15. Eckel, Z. C. et al. Additive manufacturing of polymer-derived ceramics. Science 351, 58–62 (2016).

    Article  CAS  Google Scholar 

  16. Zanchetta, E. et al. Stereolithography of SiOC ceramic microcomponents. Adv. Mater. 28, 370–376 (2016).

    Article  CAS  Google Scholar 

  17. Schmidt, J. & Colombo, P. Digital light processing of ceramic components from polysiloxanes. J. Eur. Ceram. Soc. 38, 57–66 (2018).

    Article  Google Scholar 

  18. Brinckmann, S. A. et al. Stereolithography of SiOC polymer‐derived ceramics filled with SiC micronwhiskers. Adv. Eng. Mater. 20, 1800593 (2018).

    Article  Google Scholar 

  19. Cooperstein, I., Shukrun, E., Press, O., Kamyshny, A. & Magdassi, S. Additive manufacturing of transparent silica glass from solutions. ACS Appl. Mater. Interfaces 10, 18879–18885 (2018).

    Article  CAS  Google Scholar 

  20. Sanchez, C., Julián, B., Belleville, P. & Popall, M. Applications of hybrid organic–inorganic nanocomposites. J. Mater. Chem. 15, 3559–3592 (2005).

    Article  CAS  Google Scholar 

  21. Nakanishi, K. & Soga, N. Phase separation in silica sol–gel system containing polyacrylic acid. I. Gel formation behavior and effect of solvent composition. J. Non-Cryst. Solids 139, 1–13 (1992).

    Article  CAS  Google Scholar 

  22. Rabinovich, E. Preparation of glass by sintering. J. Mater. Sci. 20, 4259–4297 (1985).

    Article  CAS  Google Scholar 

  23. Zhu, J., Chen, L. Q., Shen, J. & Tikare, V. Coarsening kinetics from a variable-mobility Cahn–Hilliard equation: application of a semi-implicit Fourier spectral method. Phys. Rev. E 60, 3564–3572 (1999).

    Article  CAS  Google Scholar 

  24. Baret, G., Madar, R. & Bernard, C. Silica‐based oxide systems. I. Experimental and calculated phase equilibria in silicon, boron, phosphorus, germanium and arsenic oxide mixtures. J. Electrochem. Soc. 138, 2830–2835 (1991).

    Article  CAS  Google Scholar 

  25. Klenin, V. J. & Shmakov, S. L. Features of phase separation in polymeric systems: cloud-point curves (discussion). Univers. J. Mater. Sci. 1, 39–45 (2013).

    Google Scholar 

  26. Dougherty, R. & Kunzelmann, K.-H. Computing local thickness of 3D structures with ImageJ. Microsc. Microanal. 13, 1678–1679 (2007).

    Article  Google Scholar 

Download references

Acknowledgements

This research was supported by the Swiss National Science Foundation through the National Centre of Competence in Research for Bio-Inspired Materials. Additional support by the Swiss Competence Center for Energy Research (SCCER—Capacity Area A3: Minimization of Energy Demand) and the Swiss National Science Foundation (consolidator grant no. BSCGIO_157696) is also acknowledged. The authors thank D. Naselli for helpful discussions and A. Lauria for support with the photoluminescence measurements.

Author information

Author notes

  1. These authors contributed equally: David G. Moore, Lorenzo Barbera.

Authors and Affiliations

  1. Complex Materials, Department of Materials, ETH Zurich, Zurich, Switzerland

    David G. Moore, Lorenzo Barbera, Kunal Masania & André R. Studart

Authors
  1. David G. Moore
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Lorenzo Barbera
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Kunal Masania
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. André R. Studart
    View author publications

    You can also search for this author in PubMed Google Scholar

Contributions

D.G.M., L.B., K.M. and A.R.S. conceived the idea together and designed the experiments. For the experimental work, D.G.M. focused more on the alkoxide chemistry, L.B. developed the sintering procedure and K.M. programmed the 3D printing microstructure. All the remaining experimental work was carried out by D.G.M., L.B. and K.M. D.G.M., L.B., K.M. and A.R.S. conducted the analysis and co-wrote the paper. All authors discussed the results and their implications, and revised the manuscript at all stages.

Corresponding authors

Correspondence to Kunal Masania or André R. Studart.

Ethics declarations

Competing interests

The authors have filed patent application EP18191209.8 related to this work.

Additional information

Publisher’s note Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Supplementary information

Supplementary Information

Supplementary Table 1, Supplementary Figs. 1–7 and Supplementary references.

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Moore, D.G., Barbera, L., Masania, K. et al. Three-dimensional printing of multicomponent glasses using phase-separating resins. Nat. Mater. 19, 212–217 (2020). https://doi.org/10.1038/s41563-019-0525-y

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1038/s41563-019-0525-y

This article is cited by

Search

Advanced search

Quick links

Nature Briefing

Sign up for the Nature Briefing newsletter — what matters in science, free to your inbox daily.

Get the most important science stories of the day, free in your inbox. Sign up for Nature Briefing