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Large-scale engineered synthesis of BaTiO3 nanoparticles using low-temperature bioinspired principles

Nature Protocols volume 6, pages 97–104 (2011)Cite this article

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Abstract

We report here a robust, large-scale synthesis of BaTiO3 nanopowders using a bioinspired process that first was developed on a much smaller scale. The most advantageous points of this protocol are that it takes place at nearly room temperature (25 °C), overcomes many limitations encountered in other scale-up processes (such as the need for external drivers, e.g., heat, radiation or pressure), bypasses the use of surfactants and templates and does not necessitate pH adjustment. The use of a single-source, bimetallic alkoxide with the vapor diffusion of a hydrolytic catalyst (H2O) provides the necessary conditions for facile crystallization and growth of small, well-defined BaTiO3 nanoparticles at mild temperatures, yielding batches of up to 250 ± 5 g in a green process. Extension of this method to kilogram-scale production of BaTiO3 nanocrystals in semicontinuous and continuous processes is feasible.

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Figure 1: Schematic representation of the reactor platform used in this protocol.
Figure 2: The scale-up platform and Viscoklick attachment.
Figure 3: Comparative torque data from heated (red) 125 ± 5 g and unheated (blue) 125 ± 5 g syntheses.
Figure 4: Structural characterization of the nanopowder manufactured using the reactor platform described in Figure 1.
Figure 5: XRD analysis monitoring the structural evolution on gradual sintering of the product from 30 to 700 °C (heating rate 50 °C per min, dwell time 25 min, after which XRD data was collected).
Figure 6: Proposed continuous-flow automated scale-up plant (currently under investigation).

References

  1. Cha, J.N. et al. Biomimetic synthesis of ordered silica structures mediated by block copolypeptides. Nature 403, 289–292 (2000).

    Article  CAS  Google Scholar 

  2. Morse, D.E. Silicon biotechnology: harnessing biological silica production to construct new materials. Trends Biotechnol. 17, 230–232 (1999).

    Article  CAS  Google Scholar 

  3. Bieri, C. et al. Micropatterned immobilization of a G protein-coupled receptor and direct detection of G protein activation. Nat. Biotechnol. 17, 1105–1108 (1999).

    Article  CAS  Google Scholar 

  4. Pum, D. & Sleytr, U.B. The application of bacterial S-layers in molecular nanotechnology. Trends Biotechnol. 17, 8–12 (1999).

    Article  CAS  Google Scholar 

  5. Arai, Y. et al. Tying a molecular knot with optical tweezers. Nature 399, 446–448 (1999).

    Article  CAS  Google Scholar 

  6. Seeman, N.C. et al. New motifs in DNA nanotechnology. Nanotechnology 9, 257–273 (1998).

    Article  CAS  Google Scholar 

  7. Montemagno, C. & Bachand, G. Constructing nanomechanical devices powered by biomolecular motors. Nanotechnology 10, 225–231 (1999).

    Article  CAS  Google Scholar 

  8. Mehta, A.D. et al. Single-molecule biomechanics with optical methods. Science 283, 1689–1698 (1999).

    Article  CAS  Google Scholar 

  9. Mao, C. et al. A nanomechanical device based on the B-Z transition of DNA. Nature 397, 144–146 (1999).

    Article  CAS  Google Scholar 

  10. Gao, H. et al. Materials become insensitive to flaws at nanoscale: lessons from nature. Proc. Natl. Acad. Sci. USA 100, 5597–5600 (2003).

    Article  CAS  Google Scholar 

  11. Mann, S. Biomineralization: Principles and Concepts in Bioinorganic Materials Chemistry (Oxford University Press, 2001).

  12. Darder, M., Aranda, P. & Ruiz-Hitzky, E. Bionanocomposites: a new concept of ecological, bioinspired, and functional hybrid materials. Adv. Mater. 19, 1309–1319 (2007).

    Article  CAS  Google Scholar 

  13. Sheet, L.L. Nano manufacturing equipment and materials for electronics. Technical Proceedings of the 2007 Nanotechnology Conference and Trade Show. Santa Clara, California, USA 4, 52–53 (2007).

    Google Scholar 

  14. Beaucage, G. et al. Aero-sol-gel reactor for nano-powder synthesis. J. Nanopart. Res. 1, 379–392 (1999).

    Article  CAS  Google Scholar 

  15. Sentein, C. et al. Dispersion and stability of TiO2 nanoparticles synthesized by laser pyrolysis in aqueous suspensions. J. Phys. Conf. Ser. 170 doi:10.1088/1742-6596/170/1/012013 (2009).

  16. Yamauchi, Y. et al. Aerosol-assisted fabrication of porous silica spheres with a hierarchical pore system through multicomponent assembly. Chem. Lett. 38, 78–79 (2009).

    Article  CAS  Google Scholar 

  17. Didenko, Y.T. & Suslick, K.S. Chemical aerosol flow synthesis of semiconductor nanoparticles. J. Am. Chem. Soc. 127, 12196–12197 (2005).

    Article  CAS  Google Scholar 

  18. Lester, E. et al. Scale up production of nanoparticles using hydrothermal synthesis. Technical Proceedings of the 2007 Nanotechnology Conference and Trade Show. Santa Clara, California, USA 4, 316–319 (2007).

    Google Scholar 

  19. Blood, P. et al. Tailored nanoparticulate metal/metal oxides from a continuous supercritical water reactor. Proceedings of the 7th World Congress of Chemical Engineering. Glasgow, Scotland 84111/1–84111/9 (2005).

    Google Scholar 

  20. Park, J. et al. Ultra-large-scale syntheses of monodisperse nanocrystals. Nat. Mater 3, 891–895 (2004).

    Article  CAS  Google Scholar 

  21. Hu, Y. & Chen, J.-F. Synthesis and Characterization of semiconductor nanomaterials and micromaterials via Gamma-irradiation route. J. Cluster Sci. 18, 371–387 (2007).

    Article  CAS  Google Scholar 

  22. Strouse, G.F., Gerbec, J.A. & Donny, M. Method for the Large-scale, Safe, Convenient, Reproducible, Energy-Conserving Synthesis of Highly-Dispersive Inorganic Colloidal Nanoparticles Application for US Patent no. 10945053; Continuation-in-part of US Ser. no. 103,159 (The Regents of the University of California, 2007).

  23. Sumerel, J.L. et al. Biocatalytically templated synthesis of titanium dioxide. Chem. Mater. 15, 4804–4809 (2003).

    Article  CAS  Google Scholar 

  24. Kisailus, D. et al. Enzymatic synthesis and nanostructural control of gallium oxide at low temperature. Adv. Mater. 17, 314–318 (2005).

    Article  CAS  Google Scholar 

  25. Brutchey, R.L. & Morse, D.E. Silicatein and the translation of its molecular mechanism of biosilicification into low temperature nanomaterial synthesis. Chem. Rev. 108, 4915–4934 (2008).

    Article  CAS  Google Scholar 

  26. Schwenzer, B. et al. Kinetically controlled vapor-diffusion synthesis of novel nanostructured metal hydroxide and phosphate films using no organic reagents. J. Mater. Chem. 16, 401–407 (2006).

    Article  CAS  Google Scholar 

  27. Zhou, Y. et al. Efficient catalysis of polysiloxane synthesis by silicatein alpha requires specific hydroxy and imidazole functionalities. Angew. Chem. Int. Ed. 38, 780–782 (1999).

    Article  CAS  Google Scholar 

  28. Cha, J.N. et al. Silicatein filaments and subunits from a marine sponge direct the polymerization of silica and silicones in vitro. Proc. Natl. Acad. Sci. USA 96, 361–365 (1999).

    Article  CAS  Google Scholar 

  29. Kisailus, D. et al. Functionalized gold nanoparticles mimic catalytic activity of a polysiloxane-synthesizing enzyme. Adv. Mater. 17, 1234–1239 (2005).

    Article  CAS  Google Scholar 

  30. Brutchey, R.L. & Morse, D.E. Template-free, low-temperature synthesis of crystalline barium titanate nanoparticles under bio-inspired conditions. Angew. Chem. Int. Ed. 45, 6564–6566 (2006).

    Article  CAS  Google Scholar 

  31. Brutchey, R.L. et al. Positive temperature coefficient of resistivity in donor-doped BaTiO3 ceramics derived from nanocrystals synthesized at low temperature. Adv. Mater. 20, 1029–1033 (2008).

    Article  CAS  Google Scholar 

  32. Beier, C.W., Cuevas, M.A. & Brutchey, R.L. Room-temperature synthetic pathways to barium titanate nanocrystals. Small 4, 2102–2106 (2008).

    Article  CAS  Google Scholar 

  33. Rao, Y. & Wong, C.P. Material characterization of a high-dielectric-constant polymer-ceramic composite for embedded capacitor for RF applications. J. Appl. Polym. Sci. 92, 2228–2231 (2004).

    Article  CAS  Google Scholar 

  34. Salaoru, I. & Paul, S. Non-volatile memory device-using a blend of polymer and ferroelectric nanoparticles. J. Optoelectron. Adv. Mater. 10, 3461–3464 (2008).

    CAS  Google Scholar 

  35. Livingston, F.E. et al. Bio-inspired synthesis and laser processing of nanostructured barium titanate thin films: implications for uncooled IR sensor development. Proc. SPIE 7321 doi:10.1117/12.818170 (2009).

  36. Yu, J. & Chu, J. Nanocrystalline barium titanate. in Encyclopedia of Nanoscience and Nanotechnology, Vol. 6 (ed. Nalwa, H.S.) 389–416 (American Scientific Publishers, 2004).

  37. Huybrechts, B., Ishizaki, K. & Takata, M. The positive temperature coefficient of resistivity in barium titanate. J. Mater. Sci. 30, 2463–2474 (1995).

    Article  CAS  Google Scholar 

  38. Hsieh, C.-L. et al. Three-dimensional harmonic holographic microcopy using nanoparticles as probes for cell imaging. Opt. Express 17, 2880–2891 (2009).

    Article  CAS  Google Scholar 

  39. Garcia Carrodeguas, R., Vazquez Lasa, B. & San Roman del Barrio, J . Injectable acrylic bone cements for vertebroplasty with improved properties. J. Biomed. Mater. Res. B 68B, 94–104 (2003).

    Article  Google Scholar 

  40. Bowen, C.R. & Topolov, V.Y. Piezoelectric activity and sensitivity of novel composites based on barium titanate-hydroxyapatite composite ceramics. Key Eng. Mater. 334–335 (Part 2, Advances in Composite Materials and Structures): 1113–1116 (2007).

    Article  Google Scholar 

  41. Mimura, K.-i. et al. Synthesis of transparent and field-responsive BaTiO3 particle/organosiloxane hybrid fluid. Angew. Chem. Int. Ed. 49, 4902–4906 (2010).

    Article  CAS  Google Scholar 

  42. Furukawa, Y. & Mutsaers, C.A.H.A. Semiconductor Device with a Superparaelectric Gate Insulator. Application for US Patent no. 11722518 (Koninklijke Philips Electronics, 2006).

    Google Scholar 

  43. Huang, L. et al. High K capacitors and OFET gate dielectrics from self-assembled BaTiO3 and (Ba,Sr)TiO3 nanocrystals in the superparaelectric limit. Adv. Funct. Mater. 20, 554–560 (2010).

    Article  CAS  Google Scholar 

  44. Hayashi, H. et al. Hydrothermal synthesis of BaTiO3 nanoparticles using a supercritical continuous flow reaction system. J. Cryst. Growth 312, 1968–1972 (2010).

    Article  CAS  Google Scholar 

  45. Xie, Y. et al. Low temperature synthesis of tetragonal BaTiO3 by a novel composite-hydroxide-mediated approach and its dielectric properties. J. Eur. Ceram. Soc. 30, 699–704 (2010).

    Article  Google Scholar 

  46. Wei, X. et al. Room-temperature synthesis of BaTiO3 nanoparticles in large batches. J. Am. Ceram. Soc. 91, 3774–3780 (2008).

    Article  CAS  Google Scholar 

  47. Blanchard, J. et al. Structural characterization of titanium oxo-polymers synthesized in the presence of protons or complexing ligands as inhibitors. J. Non Cryst. Solids 265, 83–97 (2000).

    Article  CAS  Google Scholar 

  48. Zhang, H.-L. & Morse, D.E. Kinetically controlled catalytic synthesis of highly dispersed metal-in-carbon composite and its electrochemical behavior. J. Mater. Chem. 19, 9006–9011 (2009).

    Article  CAS  Google Scholar 

  49. Shiratori, Y. et al. Raman scattering studies on nanocrystalline BaTiO3 part II—consolidated polycrystalline ceramics. J. Raman Spectrosc. 38, 1300–1306 (2007).

    Article  CAS  Google Scholar 

  50. Smith, M.B. et al. Crystal structure and the paraelectric-to-ferroelectric phase transition of nanoscale BaTiO3. J. Am. Chem. Soc. 130, 6955–6963 (2008).

    Article  CAS  Google Scholar 

  51. Brinker, C. & Scherer, G. Sol-Gel Science: The Physics and Chemistry of Sol-Gel Processing (Academic Press, 1990).

Download references

Acknowledgements

This work was supported by contracts from the Power and Energy Division of the US Army's Communications-Electronics Research, Development and Engineering Center (CERDEC); by grants from the US Army Research Office through Grant DAAD19-03-D-0004 to the Institute for Collaborative Biotechnologies and (for support of D.E.M. and M.L.) the US Department of Energy (DEFG03-02ER46006); and by the facilities of UCSB's Materials Research Laboratory (through the National Science Foundation's Materials Research Science and Engineering Centers (MRSEC) Program Grant no. DMR05-20414). We thank Dr. E.J. Plichta, Chief of the Power Division at CERDEC and M. Hendrickson, Chief Engineer at CERDEC, for their vision and support. We also thank R. Bock and S. Kramer for technical assistance.

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Authors and Affiliations

  1. Institute for Collaborative Biotechnologies, University of California, Santa Barbara, Santa Barbara, California, USA

    Teyeb Ould-Ely, Matthew Luger, Lyle Kaplan-Reinig, Krisztian Niesz & Daniel E Morse

  2. California NanoSystems Institute, University of California, Santa Barbara, Santa Barbara, California, USA

    Teyeb Ould-Ely, Krisztian Niesz & Daniel E Morse

  3. Materials Research Laboratory, University of California, Santa Barbara, Santa Barbara, California, USA

    Teyeb Ould-Ely, Krisztian Niesz & Daniel E Morse

  4. Department of Molecular, Cellular and Developmental Biology, University of California, Santa Barbara, Santa Barbara, California, USA

    Teyeb Ould-Ely, Krisztian Niesz & Daniel E Morse

  5. Department of Chemical Engineering, University of California, Santa Barbara, Santa Barbara, California, USA

    Matthew Luger, Lyle Kaplan-Reinig & Michael Doherty

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  1. Teyeb Ould-Ely
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Contributions

All authors contributed equally to this work. T.O.-E. wrote the main paper, conceived and engineered all the scale-up reactors, and executed experimental work with the assistance of M.L., L.K.-R. and K.N. All authors discussed the results and implications, and edited and commented on the manuscript at all stages. M.D. and D.E.M. directed this collaborative research.

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Correspondence to Daniel E Morse.

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Ould-Ely, T., Luger, M., Kaplan-Reinig, L. et al. Large-scale engineered synthesis of BaTiO3 nanoparticles using low-temperature bioinspired principles. Nat Protoc 6, 97–104 (2011). https://doi.org/10.1038/nprot.2010.138

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