Skip to main content
SpringerLink
Log in

Decolorization of high refractive index glass based on SiO2-(BaO + ZrO2)-TiO2 using transition metal oxides

  • Original Article
  • Published:
Journal of the Korean Ceramic Society Aims and scope Submit manuscript

Abstract

High refractive index glasses based on SiO2-(BaO + ZrO2)-TiO2 were synthesized for road sign applications with nd > 1.9. Although the refractive index increased with the addition of TiO2, visible transmittance was deteriorated with colorization of the glasses with increasing TiO2. Visible light absorption by the multi-valenced Ti-ions within the glass matrix was responsible for the change in color and transmittance. To improve transmittance and guarantee the retro-reflectivity of the glass beads, various transition metal oxides (TMOs) CuO, NiO, MnO and CoO were introduced for color control. The transmittance change with various TMOs was monitored, and a glass with CoO showed a noticeable change in color as well as an increase in transmittance. The valence change of Ti-ions was inspected by XPS, photo-luminescence (PL) and photo-luminescence excitation (PLE) spectra of the glasses, to elucidate the color change.

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

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6
Fig. 7
Fig. 8
Fig. 9

Similar content being viewed by others

References

  1. L.A. Ivanov, D.V. Kiesewetter, N.N. Kiselev, V.I. Malyugin, V.A. Slugin, Measurement of retroreflection by glass beads for road marking. Proc. SPIE. 6251, 62510U (2006)

    Article  Google Scholar 

  2. T. Grosges, Retro-reflection of glass beads for traffic road stripe paints. Opt. Mater. Express. 30, 1549–1554 (2008)

    Article  Google Scholar 

  3. J.T. Lee, T.L. Maleck, W.C. Taylor, Pavement marking material evaluation study in Michigan. ITE J. Inst. Transp. Eng. 69, 44–51 (1999)

    Google Scholar 

  4. T. Schnell, F. Aktan, Y.C. Lee, Nighttime visibility and retroreflectance of pavement markings in dry, wet, and rainy conditions. Transp. Res. Rec. 1824, 144–155 (2003)

    Article  Google Scholar 

  5. D.M. Burns, T.P. Hedblom, T.W. Miller, Modern pavement marking systems: relationship between optics and nighttime visibility. Transp. Res. Rec. 2056, 43–51 (2008)

    Article  Google Scholar 

  6. S.Y. Shin, J.I. Lee, W.J. Chung, S.H. Cho, Y.G. Choi, Assessing the refractive index of glass beads for use in road-marking applications via retroreflectance measurement. COPP. 3(5), 415–422 (2019)

    CAS  Google Scholar 

  7. S.Y. Shin, J.I. Lee, W.J. Chung, Y.G. Choi, Correlations between refractive index and retrorflectance of glass beads for use in road-marking applications under wet conditions. COPP. 3(5), 423–428 (2019)

    CAS  Google Scholar 

  8. C. Karras, D. Litzkendorf, S. Grimm, K. Schuster, W. Paa, H. Stafast, Nonlinear refractive index study on SiO2-Al2O3-La2O3 glasses. Opt. Mater. Express. 4(10), 2066–2077 (2014)

    Article  Google Scholar 

  9. K. Yoshimoto, A. Masuno, H. Inoue, Y. Watanabe, Thermal stability, optical transmittance, and refractive index dispersion of La2O3-Nb2O5-Al2O3 glasses. J. Am. Ceram. Soc. 98(2), 402–407 (2015)

    Article  CAS  Google Scholar 

  10. K. Yoshimoto, A. Masuno, M. Ueda, H. Inoue, H. Yamamoto, T. Kawashima, Thermal and optical properties of La2O3-Ga2O3-(Nb2O5 or Ta2O5) ternary glasses. J. Am. Ceram. Soc. 101(8), 3328–3336 (2018)

    Article  CAS  Google Scholar 

  11. R.C. Turnbull, W.G. Lawrence, The role of titania in silica glasses. J. Am. Ceram. Soc. 35(2), 48–53 (1952)

    Article  CAS  Google Scholar 

  12. S. Karlsson, L.G. Back, P. Kidkhunthod, K. Lundstedt, L. Wondraczek, Effect of TiO2 on optical properties of glasses in the soda-lime-silicate system. Opt. Mater. Express. 6(4), 1198–1216 (2016)

    Article  CAS  Google Scholar 

  13. K. Moringa, H. Yoshida, H. Takebe, Compositional dependence of absorption spectra of Ti3+ in silicate, borate, and phosphate glasses. J. Am. Ceram. Soc. 77(12), 3113–3118 (1994)

    Article  Google Scholar 

  14. L.H.C. Andrade, S.M. Lima, A. Novatski, A.M. Neto, A.C. Bento, M.L. Baesso, F.C.G. Gandra, Y. Guyot, G. Boulon, Spectroscopic assignments of Ti3+ and Ti4+ in titanium-doped OH− free low-silica calcium aluminosilicate glass and role of structural defects on the observed long lifetime and high fluorescence of Ti3+ ions. Phys Rev. B. 78(22), 224202 (2008)

    Article  Google Scholar 

  15. A. Terczyńska-Madej, K. Cholewa-Kowalska, M. Łączka, Coordination and valence state of transition metal ions in alkali-borate glasses. Opt. Mater. 33(12), 1984–1988 (2011)

    Article  Google Scholar 

  16. A. Terczyńska-Madej, K. Cholewa-Kowalska, M. Łączka, The effect of silicate network modifiers on colour and electron spectra of transition metal ions. Opt. Mater. 32(11), 1456–1462 (2010)

    Article  Google Scholar 

  17. A. Wannagon, N. Mishima, T. Wakasugi, R. Ota, J. Fukunaga, Formation and thermal stability of gels in the SiO2-TiO2-ZrO2 system. J. Ceram. Soc. Jpn. 105(1227), 940–946 (1997)

    Article  CAS  Google Scholar 

  18. S. Samal, S. Kim, H. Kim, Effects of filler size and distribution on viscous behavior of glass composites. J. Am. Ceram. Soc. 95(5), 1595–1603 (2012)

    Article  CAS  Google Scholar 

  19. H. Tandon, T. Chakraborty, V. Suhag, A new scale of atomic static dipole polarizability invoking other periodic descriptors. Am. J. Math. 57(9), 2142–2153 (2019)

    CAS  Google Scholar 

  20. V. Dimitrov, T. Komatsu, Electronic polarizability optical basicity and non-linear optical properties of oxide glasses. J. Non. Cryst. Solids. 249(2–3), 160–179 (1999)

    Article  CAS  Google Scholar 

  21. V. Dimitrov, T. Komatsu, Electronic polarizability and average single bond strength of ternary oxide glasses with high TiO2 contents. Phys. Chem. Glasses – Eur J. Glass Sci. Tech. B 52, 225–230 (2011)

    CAS  Google Scholar 

  22. C.G. Lee, J.H. Park, H.U. Oh, Abrasion-resistant road markings for improved durability lane to wear simulators test. Int. J. Highw. Eng. 13(3), 75–82 (2011)

    Article  Google Scholar 

  23. Y. Fujimoto, M. Nakatsuka, Spectroscopic properties and quantum yield of Cu-doped SiO2 glass. J. Lumin. 75(3), 213–219 (1997)

    Article  CAS  Google Scholar 

  24. A. Thulasiramudu, S. Buddhudu, Optical characterization of Mn2+, Ni2+ and Co2+ ions doped zinc lead borate glasses. J. Quant. Spectrosc. Radiat. Transf. 102(2), 212–227 (2006)

    Article  CAS  Google Scholar 

  25. X. Duan, D. Yuan, X. Cheng, X. Wang, Optical absorption of Co2+ in gel-derived aluminosilicate glass-ceramics. Opt. Mater. 28(10), 1152–1155 (2006)

    Article  CAS  Google Scholar 

  26. A.M. Malyarevich, I.A. Denisov, K.V. Yumashev, O.S. Dymshits, A.A. Zhilin, U. Kang, Cobalt-doped transparent glass ceramic as a saturable absorber Q switch for erbium: glass lasers. Appl. Opt. 40(24), 4322–4325 (2001)

    Article  CAS  Google Scholar 

  27. Y. Yang, P. Gao, X. Ren, L. Sha, P. Yang, J. Zhang, Y. Chen, L. Yang, Massive Ti3+ self-doped by the injected electrons from external Pt and the efficient photocatalytic hydrogen production under visible-Light. Appl. Catal. B 218, 751–757 (2017)

    Article  CAS  Google Scholar 

  28. F. Farges, G.E. Brown Jr., A. Navrotsky, H. Gan, J.J. Rehr, Coordination chemistry of Ti (IV) in silicate glasses and melts: II. Glasses at ambient temperature and pressure. Geochim. Cosmochim. Acta. 60(16), 3039–3053 (1996)

    Article  CAS  Google Scholar 

  29. E. Fargin, C. Duchesne, R. Olazcuaga, G. Le Flem, C. Cartier, L. Canioni, P. Segonds, L. Sarger, A. Ducasse, XANES and EXAFS study of glasses of the TiO2-Na2O-P2O5 system. J. Non Cryst. Solids. 168(1–2), 132–136 (1994)

    Article  CAS  Google Scholar 

  30. M.E. Khan, M.M. Khan, B.K. Min, M.H. Cho, Microbial fuel cell assisted band gap narrowed TiO2 for visible light-induced photocatalytic activities and power generation. Sci. Rep. 8(1), 1–12 (2018)

    Google Scholar 

  31. N. Wei, H. Cui, Q. Song, L. Zhang, X. Song, K. Wang, Y. Zhang, J. Li, J. Wen, J. Tian, Ag2O nanoparticle/TiO2 nanobelt heterostructures with remarkable photo-response and photocatalytic properties under UV, visible and near-infrared irradiation. Appl. Catal. B 198, 83–90 (2016)

    Article  CAS  Google Scholar 

  32. X. Han, X. Feng, Y. Kang, S. Guo, Y. Li, Intervalence charge transfer transition of Co2+-Ti4+ ion pair in α-Al2O3: Co, Ti crystal. J. Alloys Compd. 768, 1058–1063 (2018)

    Article  CAS  Google Scholar 

  33. N. Iwamoto, H. Hidaka, Y. Makino, State of Ti3+ ion and Ti3+-Ti4+ redox reaction in reduced sodium silicate glasses. J. Non Cryst. Solids. 58(1), 131–141 (1983)

    Article  CAS  Google Scholar 

Download references

Acknowledgements

This work was supported by Kongju National University in 2020 and the Technology Innovation Program (10063275, Development and evaluation of high refractive index (nd>1.9) glass beads for road marking) funded By the Ministry of Trade, Industry & Energy (MOTIE, Korea).

Author information

Authors and Affiliations

  1. Institute for Rare Metals and Division of Advanced Materials Engineering, Kongju National University, 1223-24 Cheonan-daero, Seobuk-gu, Cheonan, Chungnam, 31080, Republic of Korea

    Jung Hee Lee, Hansol Lee & Woon Jin Chung

  2. Department of Materials Science and Engineering, Korea Aerospace University, Goyang, 10540, Republic of Korea

    Yong Gyu Choi

  3. R&D New Business Division Team, Unique Technology Integral Corporation, Yesan, 32446, Republic of Korea

    In Gun Kim

Authors
  1. Jung Hee Lee
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Hansol Lee
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Yong Gyu Choi
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. In Gun Kim
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Woon Jin Chung
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Woon Jin Chung.

Additional information

Publisher's Note

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

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Lee, J.H., Lee, H., Choi, Y.G. et al. Decolorization of high refractive index glass based on SiO2-(BaO + ZrO2)-TiO2 using transition metal oxides. J. Korean Ceram. Soc. 59, 514–526 (2022). https://doi.org/10.1007/s43207-022-00187-z

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s43207-022-00187-z

Keywords

Search

Navigation