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Nano Research 2019, 12(11): 2889-2893 https://doi.org/10.1007/s12274-019-2531-4
Research Article | Issue | Published: 19 October 2019

Real time imaging of two-dimensional iron oxide spherulite nanostructure formation

Show Author's Information Wenjing Zheng1,2,  Matthew R. Hauwiller2,3,  Wen-I Liang2,4,  Colin Ophus5,  Peter Ercius5,  Emory M. Chan5,  Ying-Hao Chu4,  Mark Asta2,6,  Xiwen Du1( ),  A. Paul Alivisatos2,3,7,  Haimei Zheng2,6( )
Institute of New-Energy MaterialsSchool of Materials Science and EngineeringTianjin UniversityTianjin300350China
Materials Sciences DivisionLawrence Berkeley National LaboratoryBerkeleyCA94720USA
Department of ChemistryUniversity of CaliforniaBerkeleyBerkeleyCA94720USA
Department of Materials Science and Engineering"National Chiao Tung University"Hsinchu30010Taiwan, China
The Molecular FoundryLawrence Berkeley National LaboratoryBerkeleyCA94720USA
Department of Materials Science and EngineeringUniversity of CaliforniaBerkeleyBerkeleyCA94720USA
Kavli Energy NanoScience InstituteUniversity of California-Berkeley and Lawrence Berkeley National LaboratoryBerkeleyCA94720USA
Keywords:
liquid cell transmission electron microscopy (TEM), iron oxide, in situ TEM, spherulite nanostructures
Topics:
Growth kineticsHigh resolution transmission electron microscopyMagnettiteNanostructures
Cite this article:
Zheng W, Hauwiller MR, Liang W-I, et al. Real time imaging of two-dimensional iron oxide spherulite nanostructure formation. Nano Research, 2019, 12(11): 2889-2893. https://doi.org/10.1007/s12274-019-2531-4
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Abstract Full text Electronic supplementary material About this article

The formation of complex hierarchical nanostructures has attracted a lot of attention from both the fundamental science and potential applications point of view. Spherulite structures with radial fibrillar branches have been found in various solids; however, their growth mechanisms remain poorly understood. Here, we report real time imaging of the formation of two-dimensional (2D) iron oxide spherulite nanostructures in a liquid cell using transmission electron microscopy (TEM). By tracking the growth trajectories, we show the characteristics of the reaction front and growth kinetics. Our observations reveal that the tip of a growing branch splits as the width exceeds certain sizes (5.5–8.5 nm). The radius of a spherulite nanostructure increases linearly with time at the early stage, transitioning to nonlinear growth at the later stage. Furthermore, a thin layer of solid is accumulated at the tip and nanoparticles from secondary nucleation also appear at the growing front which later develop into fibrillar branches. The spherulite nanostructure is polycrystalline with the co-existence of ferrihydrite and Fe3O4 through-out the growth. A growth model is further established, which provides rational explanations on the linear growth at the early stage and the nonlinearity at the later stage of growth.


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Abstract
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Electronic supplementary material
About this article

Real time imaging of two-dimensional iron oxide spherulite nanostructure formation

Show Author's information Wenjing Zheng1,2, Matthew R. Hauwiller2,3, Wen-I Liang2,4, Colin Ophus5, Peter Ercius5, Emory M. Chan5, Ying-Hao Chu4, Mark Asta2,6, Xiwen Du1( ), A. Paul Alivisatos2,3,7, Haimei Zheng2,6( )
Institute of New-Energy MaterialsSchool of Materials Science and EngineeringTianjin UniversityTianjin300350China
Materials Sciences DivisionLawrence Berkeley National LaboratoryBerkeleyCA94720USA
Department of ChemistryUniversity of CaliforniaBerkeleyBerkeleyCA94720USA
Department of Materials Science and Engineering"National Chiao Tung University"Hsinchu30010Taiwan, China
The Molecular FoundryLawrence Berkeley National LaboratoryBerkeleyCA94720USA
Department of Materials Science and EngineeringUniversity of CaliforniaBerkeleyBerkeleyCA94720USA
Kavli Energy NanoScience InstituteUniversity of California-Berkeley and Lawrence Berkeley National LaboratoryBerkeleyCA94720USA

Abstract

The formation of complex hierarchical nanostructures has attracted a lot of attention from both the fundamental science and potential applications point of view. Spherulite structures with radial fibrillar branches have been found in various solids; however, their growth mechanisms remain poorly understood. Here, we report real time imaging of the formation of two-dimensional (2D) iron oxide spherulite nanostructures in a liquid cell using transmission electron microscopy (TEM). By tracking the growth trajectories, we show the characteristics of the reaction front and growth kinetics. Our observations reveal that the tip of a growing branch splits as the width exceeds certain sizes (5.5–8.5 nm). The radius of a spherulite nanostructure increases linearly with time at the early stage, transitioning to nonlinear growth at the later stage. Furthermore, a thin layer of solid is accumulated at the tip and nanoparticles from secondary nucleation also appear at the growing front which later develop into fibrillar branches. The spherulite nanostructure is polycrystalline with the co-existence of ferrihydrite and Fe3O4 through-out the growth. A growth model is further established, which provides rational explanations on the linear growth at the early stage and the nonlinearity at the later stage of growth.

Keywords: liquid cell transmission electron microscopy (TEM), iron oxide, in situ TEM, spherulite nanostructures

References(52)

1

Geveling, N. N.; Maslenkov, S. B. Solidification of eutectic Ni-Ni3Ti alloys. Met. Sci. Heat Treat. 1976, 18, 755–760.
DOI Google Scholar
2

Crist, B.; Schultz, J. M. Polymer spherulites: A critical review. Prog. Polym. Sci. 2016, 56, 1–63.
DOI Google Scholar
3

Kolosov, V. Y.; Shvamm, K. L.; Gainutdinov, R. V.; Tolstikhina, A. L. Combined TEM-AFM study of "transrotational" spherulites growing in thin amorphous films. Bull. Russ. Acad. Sci. : Phys. 2007, 71, 1442–1446.
DOI Google Scholar
4

Sasaki, N.; Murakami, Y.; Shindo, D.; Sugimoto, T. Computer simulations for the growth process of peanut-type hematite particles. J. Colloid Interface Sci. 1999, 213, 121–125.
DOI Google Scholar
5

Fowler, A. D.; Berger, B.; Shore, M.; Jones, M. I.; Ropchan, J. Supercooled rocks: Development and significance of varioles, spherulites, dendrites and spinifex in Archaean volcanic rocks, Abitibi Greenstone belt, Canada. Precambrian Res. 2002, 115, 311–328.
DOI Google Scholar
6

Davis, B. K.; McPhie, J. Spherulites, quench fractures and relict perlite in a late Devonian rhyolite dyke, Queensland, Australia. J. Volcanol. Geotherm. Res. 1996, 71, 1–11.
DOI Google Scholar
7

Hutter, J. L.; Bechhoefer, J. Three classes of morphology transitions in the solidification of a liquid crystal. Phys. Rev. Lett. 1997, 79, 4022–4025.
DOI Google Scholar
8

Hutter, J. L.; Bechhoefer, J. Morphology transitions in diffusion-and kinetics-limited solidification of a liquid crystal. Phys. Rev. E 1999, 59, 4342–4352.
DOI Google Scholar
9

Hutter, J. L.; Bechhoefer, J. Banded spherulitic growth in a liquid crystal. J. Cryst. Growth 2000, 217, 332–343.
DOI Google Scholar
10

Kim, Y. Y.; Ribeiro, L.; Maillot, F.; Ward, O.; Eichhorn, S. J.; Meldrum, F. C. Bio-inspired synthesis and mechanical properties of calcite-polymer particle composites. Adv. Mater. 2010, 22, 2082–2086.
DOI Google Scholar
11

Toda, A.; Okamura, M.; Taguchi, K.; Hikosaka, M.; Kajioka, H. Branching and higher order structure in banded polyethylene spherulites. Macromolecules 2008, 41, 2484–2493.
DOI Google Scholar
12

Maxfield, J.; Mandelkern, L. Crystallinity, supermolecular structure, and thermodynamic properties of linear polyethylene fractions. Macromolecules 1977, 10, 1141–1153.
DOI Google Scholar
13

Voigt-Martin, I. G.; Mandelkern, L. A quantitative electron microscopic study of the crystallite structure of molecular weight fractions of linear polyethylene. J. Polym. Sci. Ploym. Phys. Ed. 1984, 22, 1901–1917.
DOI Google Scholar
14

Magill, J. H. Review spherulites: A personal perspective. J. Mater. Sci. 2001, 36, 3143–3164.
DOI Google Scholar
15

Keith, H. D.; Padden, F. J. Jr. Spherulitic crystallization from the melt. Ⅱ. Influence of fractionation and impurity segregation on the kinetics of crystallization. J. Appl. Phys. 1964, 35, 1286–1296.
DOI Google Scholar
16

Asta, M.; Hoyt, J. J.; Karma, A. Calculation of alloy solid-liquid interfacial free energies from atomic-scale simulations. Phys. Rev. B 2002, 66, 100101(R).
DOI Google Scholar
17

Karma, A.; Rappel, W. J. Numerical simulation of three-dimensional dendritic growth. Phys. Rev. Lett. 1996, 77, 4050–4053.
DOI Google Scholar
18

Karma, A.; Rappel, W. J. Quantitative phase-field modeling of dendritic growth in two and three dimensions. Phys. Rev. E 1998, 57, 4323–4349.
DOI Google Scholar
19

Langer, J. S. Instabilities and pattern formation in crystal growth. Rev. Mod. Phys. 1980, 52, 1–28.
DOI Google Scholar
20

Morris, J. R. Complete mapping of the anisotropic free energy of the crystal-melt interface in Al. Phys. Rev. B 2002, 66, 144104.
DOI Google Scholar
21

Mullins, W. W.; Sekerka, R. F. Stability of a planar interface during solidification of a dilute binary alloy. J. Appl. Phys. 1964, 35, 444–451.
DOI Google Scholar
22

Mullins, W. W.; Sekerka, R. F. Morphological stability of a particle growing by diffusion or heat flow. J. Appl. Phys. 1963, 34, 323–329.
DOI Google Scholar
23

Plapp, M.; Karma, A. Multiscale random-walk algorithm for simulating interfacial pattern formation. Phys. Rev. Lett. 2000, 84, 1740–1743.
DOI Google Scholar
24

Plapp, M.; Karma, A. Multiscale finite-difference-diffusion-monte-carlo method for simulating dendritic solidification. J. Comput. Phys. 2000, 165, 592–619.
DOI Google Scholar
25

Provatas, N.; Goldenfeld, N.; Dantzig, J. Efficient computation of dendritic microstructures using adaptive mesh refinement. Phys. Rev. Lett. 1998, 80, 3308–3311.
DOI Google Scholar
26

Sun, D. Y.; Asta, M.; Hoyt, J. J. Kinetic coefficient of Ni solid-liquid interfaces from molecular-dynamics simulations. Phys. Rev. B 2004, 69, 024108.
DOI Google Scholar
27

Sun, D. Y.; Mendelev, M. I.; Becker, C. A.; Kudin, K.; Haxhimali, T.; Asta, M.; Hoyt, J. J.; Karma, A.; Srolovitz, D. J. Crystal-melt interfacial free energies in hcp metals: A molecular dynamics study of Mg. Phys. Rev. B 2006, 73, 024116.
DOI Google Scholar
28

Turing, A. M. The chemical basis of morphogenesis. Philos. Trans. Roy. Soc. B: Biol. Sci. 1952, 237, 37–72.
DOI Google Scholar
29

Sperling, L. H. Introduction to physical polymer science, 4th ed.; John Wiley & Sons: Hoboken, New Jersey, USA, 2006.
30

Magill, J. H.; Plazek, D. J. Physical properties of aromatic hydrocarbons. Ⅱ. Solidification behavior of 1, 3, 5-tri-α-naphthylbenzene. J. Chem. Phys. 1967, 46, 3757–3769.
DOI Google Scholar
31

Muthukumar, M. Commentary on theories of polymer crystallization. Eur. Phys. J. E 2000, 3, 199–202.
DOI Google Scholar
32

Gránásy, L.; Pusztai, T.; Tegze, G.; Warren, J. A.; Douglas, J. F. Growth and form of spherulites. Phys. Rev. E 2005, 72, 011605.
DOI Google Scholar
33

Aaronson, H. I.; Spanos, G.; Masamura, R. A.; Vardiman, R. G.; Moon, D. W.; Menon, E. S. K.; Hall, M. G. Sympathetic nucleation: An overview. Mater. Sci. Eng. B 1995, 32, 107–123.
DOI Google Scholar
34

Ferrone, F. A.; Hofrichter, J.; Sunshine, H. R.; Eaton, W. A. Kinetic studies on photolysis-induced gelation of sickle cell hemoglobin suggest a new mechanism. Biophys. J. 1980, 32, 361–380.
DOI Google Scholar
35

Ferrone, F. A.; Hofrichter, J.; Eaton, W. A. Kinetics of sickle hemoglobin polymerization: Ⅱ. A double nucleation mechanism. J. Mol. Biol. 1985, 183, 611–631.
DOI Google Scholar
36

Samuel, R. E.; Salmon, E. D.; Briehl, R. W. Nucleation and growth of fibres and gel formation in sickle cell haemoglobin. Nature 1990, 345, 833–835.
DOI Google Scholar
37

Galkin, O.; Vekilov, P. G. Mechanisms of homogeneous nucleation of polymers of sickle cell anemia hemoglobin in deoxy state. J. Mol. Biol. 2004, 336, 43–59.
DOI Google Scholar
38

Liao, H. G.; Zheng, H. M. Liquid cell transmission electron microscopy. Annu. Rev. Phys. Chem. 2016, 67, 719–747.
DOI Google Scholar
39

Kim, B. J.; Tersoff, J.; Kodambaka, S.; Reuter, M. C.; Stach, E. A.; Ross, F. M. Kinetics of individual nucleation events observed in nanoscale vapor-liquid-solid growth. Science 2008, 322, 1070–1073.
DOI Google Scholar
40

Harutyunyan, A. R.; Chen, G. G.; Paronyan, T. M.; Pigos, E. M.; Kuznetsov, O. A.; Hewaparakrama, K.; Kim, S. M.; Zakharov, D.; Stach, E. A.; Sumanasekera, G. U. Preferential growth of single-walled carbon nanotubes with metallic conductivity. Science 2009, 326, 116–120.
DOI Google Scholar
41

Ross, F. M. Opportunities and challenges in liquid cell electron microscopy. Science 2015, 350, aaa9886.
DOI Google Scholar
42

Zheng, H. M.; Smith, R. K.; Jun, Y. W.; Kisielowski, C.; Dahmen, U.; Alivisatos, A. P. Observation of single colloidal platinum nanocrystal growth trajectories. Science 2009, 324, 1309–1312.
DOI Google Scholar
43

Liao, H. G.; Cui, L. K.; Whitelam, S.; Zheng, H. M. Real-time imaging of Pt3Fe nanorod growth in solution. Science 2012, 336, 1011–1014.
DOI Google Scholar
44

Liao, H. G.; Zherebetskyy, D.; Xin, H. L.; Czarnik, C.; Ercius, P.; Elmlund, H.; Pan, M.; Wang, L. W.; Zheng, H. M. Facet development during platinum nanocube growth. Science 2014, 345, 916–919.
DOI Google Scholar
45

Wang, Y.; Peng, X. X.; Abelson, A.; Xiao, P. H.; Qian, C.; Yu, L.; Ophus, C.; Ercius, P.; Wang, L. W.; Law, M. et al. Dynamic deformability of individual PbSe nanocrystals during superlattice phase transitions. Sci. Adv. 2019, 5, eaaw5623.
DOI Google Scholar
46

Hauwiller, M. R.; Zhang, X. W.; Liang, W. I.; Chiu, C. H.; Zhang, Q.; Zheng, W. J.; Ophus, C.; Chan, E. M.; Czarnik, C.; Pan, M. et al. Dynamics of nanoscale dendrite formation in solution growth revealed through in situ liquid cell electron microscopy. Nano Lett. 2018, 18, 6427–6433.
DOI Google Scholar
47

Yang, J.; Zeng, Z. Y.; Kang, J.; Betzler, S.; Czarnik, C.; Zhang, X. W.; Ophus, C.; Yu, C.; Bustillo, K.; Pan, M.; et al. Formation of two-dimensional transition metal oxide nanosheets with nanoparticles as intermediates. Nat. Mater. 2019, 18, 970–976.
DOI Google Scholar
48

Baumgartner, J.; Dey, A.; Bomans, P. H. H.; Le Coadou, C.; Fratzl, P.; Sommerdijk, N. A. J. M.; Faivre, D. Nucleation and growth of magnetite from solution. Nat. Mater. 2013, 12, 310–314.
DOI Google Scholar
49

Tronc, E.; Belleville, P.; Jolivet, J. P.; Livage, J. Transformation of ferric hydroxide into spinel by iron(Ⅱ) adsorption. Langmuir 1992, 8, 313–319.
DOI Google Scholar
50

Benner, S. G.; Hansel, C. M.; Wielinga, B. W.; Barber, T. M.; Fendorf, S. Reductive dissolution and biomineralization of iron hydroxide under dynamic flow conditions. Environ. Sci. Technol. 2002, 36, 1705–1711.
DOI Google Scholar
51

Hansel, C. M.; Benner, S. G.; Neiss, J.; Dohnalkova, A.; Kukkadapu, R. K.; Fendorf, S. Secondary mineralization pathways induced by dissimilatory iron reduction of ferrihydrite under advective flow. Geochim. Cosmochim. Acta 2003, 67, 2977–2992.
DOI Google Scholar
52

Müller, C.; Aghamohammadi, M.; Himmelberger, S.; Sonar, P.; Garriga, M.; Salleo, A.; Campoy-Quiles, M. One-step macroscopic alignment of conjugated polymer systems by epitaxial crystallization during spin-coating. Adv. Funct. Mater. 2013, 23, 2368–2377.
DOI Google Scholar
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Publication history
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Acknowledgements

Publication history

Received: 12 August 2019
Revised: 16 September 2019
Accepted: 27 September 2019
Published: 19 October 2019
Issue date: November 2019

Copyright

© Tsinghua University Press and Springer-Verlag GmbH Germany, part of Springer Nature 2019

Acknowledgements

Acknowledgements

This project was supported by the U.S. Department of Energy (DOE), Office of Science, Office of Basic Energy Sciences (BES), Materials Sciences and Engineering Division under Contract No. DE-AC02-05-CH11231 within the in-situ TEM (KC22ZH) program. Work at the Molecular Foundry was supported by the Office of Science, Office of Basic Energy Sciences, of the U.S. Department of Energy under Contract No. DE-AC02-05CH11231. We acknowledge Gatan Inc. for the advanced K2 IS camera and Dr. Ming Pan and Dr. Cory Czarnik for their help with part of experimental set up in this work. W. J. Z. acknowledges the support from Tianjin University Graduate School International Academic Exchange Fund. M. R. H. was funded by KAUST project under H. M. Z. at UC Berkeley.

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