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Journal of Materials Science

, Volume 49, Issue 21, pp 7597–7603 | Cite as

Re-oxidation mechanism and kinetics of fine scale Ti-Magnéli phases in fibre form using thermo-gravimetric analysis

  • Vaia Adamaki
  • Frank Clemens
  • John Taylor
  • Tim J. Mays
  • Christopher R. Bowen
Original Paper

Abstract

This paper describes the manufacture and properties of fine scale (Ø 260 μm) and dense (>96 % theoretical density) fibres consisting of Magnéli (TinO2n-1) phases for sensing and energy storage applications. In order to understand their operational limits, the re-oxidation of the Magnéli phases in air was examined using thermo-gravimetric analysis at temperatures up to 900 °C under a variety of heating rates. The material was characterised before and after re-oxidation via X-ray diffraction and scanning electron microscopy. The re-oxidation of the Magnéli phases was observed to begin at 650 °C, and the kinetics of the process was studied using the iso-conversional method. The calculated activation energy was consistent with Jander’s three-dimensional diffusion model, where oxidation is limited by diffusion of oxygen through a layer of the oxidised product. An activation energy of 0.71 eV was obtained from kinetic analysis of the thermogravimetry data, which is in agreement with previous work on electrical conduction of Magnéli phases using impedance spectroscopy.

Keywords

TiO2 TiO2 Powder Cathodic Protection Energy Storage Application Carbon Black Powder 
These keywords were added by machine and not by the authors. This process is experimental and the keywords may be updated as the learning algorithm improves.

Notes

Acknowledgements

Adamaki acknowledges funding by the European Union Seventh Framework Programme (FP7/2007-2013) under the Grant Agreement no. CP-TP 229099-2 as part of the ‘MesMesh’ project. Bowen acknowledges funding from the European Union’s Seventh Framework Programme (FP7/2007-2013)/ERC Grant Agreement No. 320963 on Novel Energy Materials, Engineering, Science and Integrated Systems (NEMESIS).

References

  1. 1.
    Pfaff G, Reynders P (1999) Angle-dependent optical effects deriving from submicron structures of films and pigments. Chem Rev 99:963–1981CrossRefGoogle Scholar
  2. 2.
    Vannoort R (1987) Titanium: the implant material of today. J Mater Sci 22:3801–3811CrossRefGoogle Scholar
  3. 3.
    Bañares MA (2011) Operando spectroscopy: the knowledge bridge to assessing structure–performance relationships in catalyst nanoparticles. Adv Mater 23:5293–5301CrossRefGoogle Scholar
  4. 4.
    Chen G, Waraksa CC, Cho H, Macdonald DD, Mallouka TE (2003) EIS studies of porous oxygen electrodes with discrete particles. J Electrochem Soc 150:E423CrossRefGoogle Scholar
  5. 5.
    Fox MA, Dulay MT (1993) Heterogeneous photocatalysis. Chem Rev 93(1):341–357CrossRefGoogle Scholar
  6. 6.
    Fujishima A, Honda K (1972) Electrochemical photolysis of water at a semiconductor electrode. Nature 238:37–38CrossRefGoogle Scholar
  7. 7.
    Oregan B, Gratzel M (1991) A low-cost, high-efficiency solar-cell based on dye-sensitized colloidal TiO2 films. Nature 353:737–740CrossRefGoogle Scholar
  8. 8.
    Korotcenkov G (2007) Metal oxides for solid-state gas sensors: what determines our choice? Mat Sci Eng 139:1–23CrossRefGoogle Scholar
  9. 9.
    Radecka M, Rekas M (2002) Charge and mass transport in ceramic TiO2. J Eur Ceram Soc 22:2001–2012CrossRefGoogle Scholar
  10. 10.
    Nowotny MK, Bogdanoff P, Dittrich T, Fiechter S, Fujishima A, Tributsch H (2010) Observations of p-type semiconductivity in titanium dioxide at room temperature. Mater Lett 64:928–930CrossRefGoogle Scholar
  11. 11.
    Nowotny J, Bak T, Nowotny MK, Sheppard LR (2007) Titanium dioxide for solar-hydrogen II. Defect chemistry. Int J Hydrog Energy 32:2630–2643CrossRefGoogle Scholar
  12. 12.
    Seebauer EG, Kratzer MC (2006) Charged point defects in semiconductors. Mater Sci Eng 55:57–149CrossRefGoogle Scholar
  13. 13.
    Hayfield PCS (2002) Development of a new material-monolithic Ti4O7 ebonex ceramic. R Soc Chem, Thomas Graham HouseGoogle Scholar
  14. 14.
    Andersson S, Magneli A (1956) Diskrete titanoxyd phasen im zusammensetzungs bereich TiO1.75-TiO1.90. Naturwissenschaften 43:495–496CrossRefGoogle Scholar
  15. 15.
    Liborio L, Mallia G, Harrison N (2009) Electronic structure of the Ti4O7 Magnéli phase. Phys Rev 79:245133CrossRefGoogle Scholar
  16. 16.
    Harada S, Tanaka K, Inui H (2010) Thermoelectric properties and crystallographic shear structures in titanium oxides of the Magneli phases. J Appl Phys 108:083703CrossRefGoogle Scholar
  17. 17.
    Walsh FC, Wills RGA (2010) The continuing development of Magnéli phase titanium sub-oxides and Ebonex® electrodes. Electrochim Acta 55:6342–6351CrossRefGoogle Scholar
  18. 18.
    Smith JR, Walsh FC, Clarke RL (1998) Reviews in applied electrochemistry. Number 50-electrodes based on Magneli phase titanium oxides: the properties and applications of Ebonex (R) materials. J Appl Electrochem 28:1021–1033CrossRefGoogle Scholar
  19. 19.
    Kitada A, Hasegawa G, Kobayashi Y, Kanamori K, Nakanishi K, Kageyama H (2012) Selective preparation of macroporous monoliths of conductive titanium oxides TinO2n–1 (n = 2, 3, 4, 6). J Am Chem Soc 134:10894–10898CrossRefGoogle Scholar
  20. 20.
    Li X, Zhu AL, Qu W, Wang H, Hui R, Zhang L, Zhang J (2010) Magneli phase Ti4O7 electrode for oxygen reduction reaction and its implication for zinc-air rechargeable batteries. Electrochim Acta 55:5891–5898CrossRefGoogle Scholar
  21. 21.
    Gardon M, Dosta S, Guilemany JM, Kourasi M, Mellor B, Wills R (2013) Improved, high conductivity titanium sub-oxide coated electrodes obtained by atmospheric plasma spray. J Power Sources 238:430–434CrossRefGoogle Scholar
  22. 22.
    Heiber J, Clemens F, Graule T, Hulsenberg D (2005) Thermoplastic extrusion to highly-loaded thin green fibres containing Pb(Zr, Ti)O3. Adv Eng Mater 7:404–408CrossRefGoogle Scholar
  23. 23.
    Adamaki V, Clemens F, Ragulis P, Pennock SR, Taylor J, Bowen CR (2014) Manufacturing and characterization of Magneli phase conductive fibres. J Mater Chem A 2:8328–8333CrossRefGoogle Scholar
  24. 24.
    BSI, 1993, “Advanced technical ceramics — Monolithic ceramics — General and textural properties “ Part 2: Determination of density and porosity, BSI 10-1999Google Scholar
  25. 25.
    Vyazovkin S, Wight CA (1997) Kinetics in solids. Annu Rev Phys Chem 48:125–149Google Scholar
  26. 26.
    Słoczyński J (1996) Kinetics and mechanism of reduction and reoxidation of the alkali metal promoted vanadia-titania catalysts. Appl Catal 146(2):401–423CrossRefGoogle Scholar
  27. 27.
    Prudenziati M, Morten B, Travan E (2003) Reduction process of RuO2 powders and kinetics of their re-oxidation. Mater Sci Eng 98:167–176CrossRefGoogle Scholar
  28. 28.
    Jander W (1927) Z Anorg Chem 1:163Google Scholar
  29. 29.
    Ginstling AM, Brounshteim BI (1950) J Appl Chem USSR 23:1327Google Scholar
  30. 30.
    Regonini D, Adamaki V, Bowen CR, Pennock SR, Taylor J, Dent ACE (2012) AC electrical properties of TiO2 and Magnéli phases, TinO2n−1. Solid State Ionics 229:38–44CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media New York 2014

Authors and Affiliations

  • Vaia Adamaki
    • 1
  • Frank Clemens
    • 2
  • John Taylor
    • 3
  • Tim J. Mays
    • 4
  • Christopher R. Bowen
    • 1
  1. 1.Materials Research Centre, Department of Mechanical EngineeringUniversity of BathBathUK
  2. 2.High Performance CeramicsEMPA Materials Science and TechnologyZurichSwitzerland
  3. 3.Department of Electronic and Electrical EngineeringUniversity of BathBathUK
  4. 4.Department of Chemical EngineeringUniversity of BathBathUK

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