Skip to main content

Advertisement

SpringerLink
Log in

In situ TEM investigation of the oxide/metal interface during the annealing of anodically formed titanium dioxide nanotubes

  • Ceramics
  • Published:
Journal of Materials Science Aims and scope Submit manuscript

Abstract

Titanium dioxide nanotubes (NTs) anodically grown on a titanium metal substrate are of great interest to many fields due to their unique physiochemical properties and electrochemical behavior. For many applications, a heat treatment is required to impart the NTs with a useful crystalline structure. The exact processes which occur in NTs during this high-temperature transformation, including the anatase-to-rutile transition (ART), were not well understood. Previous studies conducted to understand this phenomenon largely made use of conventional materials characterization techniques on annealed NTs attached to the titanium substrate. Therefore, it was challenging to determine if and/or how the substrate influenced the ART. In this study, in situ transmission electron microscopy was used to observe the morphological and phase changes occurring at the oxide/metal interface of anodically formed NTs during annealing. Samples were prepared both with and without the substrate to understand the effects of the substrate on phase changes within the NTs. These investigations revealed that when the substrate is present, the oxide/metal interface is a bilayer structure in which the ART is initiated from the upper layer of the interface while hydride and nitride precipitation occurs in the bottom layer. At elevated temperatures (> 500°C), the substrate undergoes spalling and loses its ordered morphology and crystallinity. When the NTs are not attached to the substrate, there is no evidence of ART or precipitation. These findings highlight the crucial role that the titanium substrate plays in the morphological and phase transformation of NTs during annealing.

Graphical Abstract

In situ transmission electron microscopy (enabled observation of the changes occurring at the oxide/metal interface during annealing. In situ TEM identified the oxide/metal interface as the epicenter of the morphological and crystal phase transformation. The in situ TEM investigation revealed the influence of substrate on anatase to rutile phase transformation.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Figure 1
Figure 2
Figure 3
Figure 4
Figure 5
Figure 6
Figure 7
Figure 8

Similar content being viewed by others

Data availability

Not Applicable.

References

  1. Andrzejczuk M, Rasiński M, Roguska A et al (2019) An electron microscopy three-dimensional characterization of titania nanotubes. Microsc Res Tech 82:173–177. https://doi.org/10.1002/jemt.23093

    Article  CAS  Google Scholar 

  2. Carlson K, Elliott C, Walker S et al (2016) An effective, point-of-use water disinfection device using immobilized black TiO2 Nanotubes as an electrocatalyst. J Electrochem Soc 163:H395–H401. https://doi.org/10.1149/2.0651606jes

    Article  CAS  Google Scholar 

  3. Roguska A, Belcarz A, Zalewska J et al (2018) Metal TiO2 nanotube layers for the treatment of dental implant infections. ACS Appl Mater Interfaces 10:17089–17099. https://doi.org/10.1021/acsami.8b04045

    Article  CAS  Google Scholar 

  4. Smith YR, Ray RS, Carlson K et al (2013) Self-ordered titanium dioxide nanotube arrays: anodic synthesis and their photo/electro-catalytic applications. Mater Basel 6:2892–2957. https://doi.org/10.3390/ma6072892

    Article  CAS  Google Scholar 

  5. Huber JM, Carlson KL, Conroy-Ben O et al (2016) Development of a field enhanced photocatalytic device for biocide of coliform bacteria. J Environ Sci China 44:38–44. https://doi.org/10.1016/j.jes.2015.08.023

    Article  CAS  Google Scholar 

  6. Naldoni A, Altomare M, Zoppellaro G et al (2019) Photocatalysis with reduced TiO2: from black TiO2 to cocatalyst-free hydrogen production. ACS Catal 9:345–364. https://doi.org/10.1021/acscatal.8b04068

    Article  CAS  Google Scholar 

  7. Beeman MG, Nze UC, Sant HJ et al (2018) Electrochemical detection of E. Coli O157:H7 in water after electrocatalytic and ultraviolet treatments using a polyguanine-labeled secondary bead sensor. Sens Switz 18:1497. https://doi.org/10.3390/s18051497[12]

    Article  Google Scholar 

  8. Bai J, Zhou B (2014) Titanium dioxide nanomaterials for sensor applications. Chem Rev 114:10131–10176. https://doi.org/10.1021/cr400625j

    Article  CAS  Google Scholar 

  9. Kirkey A, Li J, Sham TK (2019) Low temperature amorphous to anatase phase transition of titanium oxide nanotubes. Surf Sci 680:68–74. https://doi.org/10.1016/j.susc.2018.10.012

    Article  CAS  Google Scholar 

  10. Feng H, Xu Z, Ren L et al (2018) Activating titania for efficient electrocatalysis by vacancy engineering. ACS Catal 8:4288–4293. https://doi.org/10.1021/acscatal.8b00719

    Article  CAS  Google Scholar 

  11. Hanaor DAH, Sorrell CC (2011) Review of the anatase to rutile phase transformation. J Mater Sci 46:855–874. https://doi.org/10.1007/s10853-010-5113-0

    Article  CAS  Google Scholar 

  12. Zerjav G, Zizek K, Zavasnik J, Pintar A (2022) Brookite vs. rutile vs. anatase: what’s behind their various photocatalytic activities? J Environ Chem Eng 10:107722. https://doi.org/10.1016/j.jece.2022.107722

    Article  CAS  Google Scholar 

  13. Wang X, Hu H, Yang Z et al (2015) Visible light-active sub-5 nm anatase TiO2 for photocatalytic organic pollutant degradation in water and air, and for bacterial disinfection. Catal Commun 72:81–85. https://doi.org/10.1016/j.catcom.2015.09.014

    Article  CAS  Google Scholar 

  14. Tominaka S, Ishihara A, Nagai T, Ota KI (2017) Noncrystalline titanium oxide catalysts for electrochemical oxygen reduction reactions. ACS Omega 2:5209–5214. https://doi.org/10.1021/acsomega.7b00811

    Article  CAS  Google Scholar 

  15. Zhou Y, Fichthorn KA (2012) Microscopic view of nucleation in the anatase-to-rutile transformation. J Phys Chem C 116:8314–8321. https://doi.org/10.1021/jp301228x

    Article  CAS  Google Scholar 

  16. Castrejón-Sánchez VH, López R, Ramón-González M et al (2019) Annealing control on the anatase/rutile ratio of nanostructured titanium dioxide obtained by sol-gel. Crystals 9:22. https://doi.org/10.3390/cryst9010022

    Article  CAS  Google Scholar 

  17. Jarosz M, Syrek K, Kapusta-Kołodziej J et al (2015) Heat treatment effect on crystalline structure and photoelectrochemical properties of anodic TiO2 nanotube arrays formed in ethylene glycol and glycerol based electrolytes. J Phys Chem C 119:24182–24191. https://doi.org/10.1021/acs.jpcc.5b08403

    Article  CAS  Google Scholar 

  18. Hurum DC, Agrios AG, Gray KA et al (2003) Explaining the enhanced photocatalytic activity of Degussa P25 mixed-phase TiO2 using EPR. J Phys Chem B 107:4545–4549. https://doi.org/10.1021/jp0273934

    Article  CAS  Google Scholar 

  19. Li J, Wang Z, Wang J, Sham TK (2016) Unfolding the anatase-to-rutile phase transition in TiO2 nanotubes using X-ray spectroscopy and spectromicroscopy. J Phys Chem C 120:22079–22087. https://doi.org/10.1021/acs.jpcc.6b07613

    Article  CAS  Google Scholar 

  20. Zhang H, Banfield JF (2000) Understanding polymorphic phase transformation behavior during growth of nanocrystalline aggregates: Insights from TiO2. J Phys Chem B 104:3481–3487. https://doi.org/10.1021/jp000499j

    Article  CAS  Google Scholar 

  21. Luo Z, Poyraz AS, Kuo CH et al (2015) Crystalline mixed phase (anatase/rutile) mesoporous titanium dioxides for visible light photocatalytic activity. Chem Mater 27:6–17. https://doi.org/10.1021/cm5035112

    Article  CAS  Google Scholar 

  22. Talla A, Suliali NJ, Goosen WE et al (2022) Effect of annealing temperature and atmosphere on the structural, morphological and luminescent properties of TiO2 nanotubes. Phys B Condens Matter 640:414026. https://doi.org/10.1016/j.physb.2022.414026

    Article  CAS  Google Scholar 

  23. Tang C, Zhou D, Zhang Q (2012) Synthesis and characterization of Magneli phases: Reduction of TiO2 in a decomposed NH3atmosphere. Mater Lett 79:42–44. https://doi.org/10.1016/j.matlet.2012.03.095

    Article  CAS  Google Scholar 

  24. Colombo JS, Malik H, Caranto CA et al (2022) Highly targeted electrochemical disruption of microbes with minimal disruption to pulp cells. J Dent 125:104241. https://doi.org/10.1016/J.JDENT.2022.104241

    Article  CAS  Google Scholar 

  25. Pan X, Yang MQ, Fu X et al (2013) Defective TiO2 with oxygen vacancies: Synthesis, properties and photocatalytic applications. Nanoscale 5:3601–3614. https://doi.org/10.1039/c3nr00476g

    Article  CAS  Google Scholar 

  26. Yang Y, Kao LC, Liu Y et al (2018) Cobalt-doped black tio2nanotube array as a stable anode for oxygen evolution and electrochemical wastewater treatment. ACS Catal 8:4278–4287. https://doi.org/10.1021/acscatal.7b04340

    Article  CAS  Google Scholar 

  27. Mangum JS, Garten LM, Ginley DS, Gorman BP (2020) Utilizing TiO2 amorphous precursors for polymorph selection : an in situ TEM study of phase formation and kinetics. J Am Ceram Soc 103(4):2899–2907. https://doi.org/10.1111/jace.16965

    Article  CAS  Google Scholar 

  28. Diebold U (2003) The surface science of titanium dioxide. Surf Sci Rep 48:53–229. https://doi.org/10.1016/s0167-5729(02)00100-0

    Article  CAS  Google Scholar 

  29. Jaroenworaluck A, Regonini D, Bowen CR, Stevens R (2010) A microscopy study of the effect of heat treatment on the structure and properties of anodised TiO2 nanotubes. Appl Surf Sci 256:2672–2679. https://doi.org/10.1016/j.apsusc.2009.09.078

    Article  CAS  Google Scholar 

  30. Mohammadpour A, Kar P, Wiltshire DB et al (2015) Electron Transport, Trapping and Recombination in Anodic TiO2 Nanotube Arrays. Curr Nanosci 11:593–614. https://doi.org/10.2174/1573413711666150415230019

    Article  CAS  Google Scholar 

  31. Wetchakun N, Incessungvorn B, Wetchakun K, Phanichphant S (2012) Influence of calcination temperature on anatase to rutile phase transformation in TiO2 nanoparticles synthesized by the modified sol-gel method. Mater Lett 82:195–198. https://doi.org/10.1016/j.matlet.2012.05.092

    Article  CAS  Google Scholar 

  32. Byrne C, Fagan R, Hinder S et al (2016) New approach of modifying the anatase to rutile transition temperature in TiO2 photocatalysts. RSC Adv 6:95232–95238. https://doi.org/10.1039/c6ra19759k

    Article  CAS  Google Scholar 

  33. Wang G, Wang H, Ling Y et al (2011) Hydrogen-treated TiO2nanowire arrays for photoelectrochemical water splitting. Nano Lett 11:3026–3033. https://doi.org/10.1021/nl201766h

    Article  CAS  Google Scholar 

  34. Malik H, Barrera K, Mohanty S, Carlson K (2020) Enhancing electrochemical properties of TiO2 nanotubes via engineered defect laden crystal structures. Mater Lett 273:127956. https://doi.org/10.1016/j.matlet.2020.127956

    Article  CAS  Google Scholar 

  35. Hyam RS, Lee J, Cho E et al (2012) Effect of annealing environments on self-organized TiO2 nanotubes for efficient photocatalytic applications. J Nanosci Nanotechnol 12:8908–8912. https://doi.org/10.1166/jnn.2012.6734

    Article  CAS  Google Scholar 

  36. Albu SP, Tsuchiya H, Fujimoto S, Schmuki P (2010) TiO2 nanotubes–annealing effects on detailed morphology and structure. Eur J Inorg Chem 2010:4351–4356. https://doi.org/10.1002/ejic.201000608

    Article  CAS  Google Scholar 

  37. Fang D, Luo Z, Huang K, Lagoudas DC (2011) Effect of heat treatment on morphology, crystalline structure and photocatalysis properties of TiO2 nanotubes on Ti substrate and freestanding membrane. Appl Surf Sci 257:6451–6461. https://doi.org/10.1016/j.apsusc.2011.02.037

    Article  CAS  Google Scholar 

  38. Satoh N, Nakashima T, Yamamoto K (2013) Metastability of anatase: Size dependent and irreversible anatase-rutile phase transition in atomic-level precise titania. Sci Rep 3:1959. https://doi.org/10.1038/srep01959

    Article  Google Scholar 

  39. Malik H, Sarkar S, Mohanty S, Carlson K (2020) Modelling and synthesis of Magnéli phases in ordered titanium oxide nanotubes with preserved morphology. Sci Rep 10:8050. https://doi.org/10.1038/s41598-020-64918-0

    Article  CAS  Google Scholar 

  40. Tian X, Cook C, Hong W et al (2019) In Situ TEM study of the amorphous-to-crystalline transition during dielectric breakdown in TiO2 film. ACS appl mater interfaces 11(43):40726–40733. https://doi.org/10.1021/acsami.9b08146

    Article  CAS  Google Scholar 

  41. Chang J, Tseng Y, Ho A, Lo H (2022) Materials characterization In situ TEM investigation of indium oxide / titanium oxide nanowire heterostructures growth through solid state reactions. Mater Charact 187:111832. https://doi.org/10.1016/j.matchar.2022.111832

    Article  CAS  Google Scholar 

  42. Straubinger R, Beyer A, Volz K (2016) Preparation and loading process of single crystalline samples into a gas environmental cell holder for in situ atomic resolution scanning transmission electron microscopic observation. Microsc Microanal 22:515–519. https://doi.org/10.1017/S1431927616000593

    Article  CAS  Google Scholar 

  43. Schaffer M, Schaffer B, Ramasse Q (2012) Sample preparation for atomic-resolution STEM at low voltages by FIB. Ultramicroscopy 114:62–71. https://doi.org/10.1016/j.ultramic.2012.01.005

    Article  CAS  Google Scholar 

  44. Zhong XL, Schilling S, Zaluzec NJ, Burke MG (2016) Sample preparation methodologies for in situ liquid and gaseous cell analytical transmission electron microscopy of electropolished specimens. Microsc Microanal 22:1350–1359. https://doi.org/10.1017/S1431927616011855

    Article  CAS  Google Scholar 

  45. Briant CL, Wang ZF, Chollocoop N (2002) Hydrogen embrittlement of commercial purity titanium. Corros Sci 44:1875–1888. https://doi.org/10.1016/S0010-938X(01)00159-7

    Article  CAS  Google Scholar 

  46. Chen X, Liu L, Yu PY et al (2017) Increasing solar absorption for photocatalysis with black hydrogenated titanium dioxide nanocrystals. Science 331:746–750

    Article  Google Scholar 

Download references

Acknowledgements

We would like to thank Randy Polson (Nanofab, University of Utah) for preparing the FIB samples. We would like to thank Rainer Straubinger (Protochips, Inc., Morrisville, NC, USA) for assisting with the FIB procedure. This work made use of University of Utah USTAR shared facilities supported, in part, by the MRSEC Program of the NSF under Award No. DMR-1121252.

Funding

This work was made possible by the support of the National Science Foundation (NSF # 1706283). Additionally support was provided by the United States Government and the American people through the United States Agency for International Development (USAID). The contents are the sole responsibility of the University of Utah and do not necessarily reflect the views of USAID or the United States Government. This material is based upon work supported by the National Science Foundation Graduate Research Fellowship Program under Grant No. GR09557. Any opinions, findings, and conclusions or recommendations expressed in this material are those of the author(s) and do not necessarily reflect the views of the National Science Foundation. Acquisition of the heatable gas cell sample holder was supported by a DURIP grant from the Air Force Office of Scientific Research (AFOSR grant FA9550-16-1-0501).

Author information

Authors and Affiliations

  1. Department of Chemical and Materials Engineering, University of Nevada, Reno, Reno, NV, 89509, USA

    Hammad Malik, Jerry R. Howard & Krista Carlson

  2. NanoFab Surface Analysis Lab, University of Utah, Salt Lake City, UT, 84112, USA

    Brian Van Devener

  3. Department of Chemical Engineering, Department of Materials Science Engineering, University of Utah, Salt Lake City, UT, 84112, USA

    Swomitra Kumar Mohanty

Authors
  1. Hammad Malik
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Jerry R. Howard
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Brian Van Devener
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Swomitra Kumar Mohanty
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Krista Carlson
    View author publications

    You can also search for this author in PubMed Google Scholar

Contributions

HM contributed to Conceptualization, Methodology, Investigation, Analyzing, Writing original draft. JRH contributed to Figures, Reviewing, Editing. BVD contributed to Conceptualization, Methodology, TEM experiments. SK contributed to Reviewing, Resources. KC contributed to Supervision, Methodology, Revising, Editing, Investigation.

Corresponding author

Correspondence to Krista Carlson.

Ethics declarations

Conflict of Interest

The authors declare that they have no conflicts of interest related to this work.

Supplementary material

Supplementary material (in situ TEM investigation of anodically formed Titanium oxide nanotube-substrate interface during annealing) is available in the online version of this article at http://dx.doi.org/10.1007/s12274-***-****-* (automatically inserted by the publisher).

Ethical approval

Not Applicable.

Additional information

Handling Editor: Christopher Blanford.

Publisher's Note

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

Supplementary Information

Below is the link to the electronic supplementary material.

Supplementary file 1 (DOCX 3287 KB)

Rights and permissions

Springer Nature or its licensor (e.g. a society or other partner) holds exclusive rights to this article under a publishing agreement with the author(s) or other rightsholder(s); author self-archiving of the accepted manuscript version of this article is solely governed by the terms of such publishing agreement and applicable law.

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Malik, H., Howard, J.R., Van Devener, B. et al. In situ TEM investigation of the oxide/metal interface during the annealing of anodically formed titanium dioxide nanotubes. J Mater Sci 58, 15588–15602 (2023). https://doi.org/10.1007/s10853-023-09005-1

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s10853-023-09005-1

Search

Navigation