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Abstract
Ultraviolet ray (UV) absorbing coating consisting of a complex oxide of cerium and titanium was deposited on glass via the solgel
process. Addition of TiO2 to CeO2 changed the crystallinity and coordination state of CeO2 and improved UV absorption. Formation of a
double-layered coating comprised of outer CeO2TiO2 layer and inner TiO2SiO2 layer diminished the interference coloring and improved
the adhesion of the coating to the glass substrate. The double layer coated glass shows high UV-shielding properties without visible light
absorption and excellent durability against chemical and physical attacks. Therefore, it has been widely used in automobile windows. q 1999
Elsevier Science S.A. All rights reserved.
Keywords: Solgel process; Ultraviolet absorption; Optical coating; Spin-coating
1. Introduction
2. Experimental
0040-6090/99/$ - see front matter q 1999 Elsevier Science S.A. All rights reserved.
PII: S 0040-609 0(98)01779-9
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3. Results
3.1. CeO2TiO2 UV absorbing coating
Fig. 1 shows the UV transmittance of glasses coated with
various CeO2TiO2 binary compositions. Film thickness
was 160 nm for all coatings. The addition of TiO2 to CeO2
lowers UV transmittance in the composition range of CeO2/
TiO2 $1 and shows its minimum at around 40 mol%.
Although it was reported [4] that CeO2 precipitates in a
solution of the molar ratio of CeO2 =TiO2 1, no precipitation
occurred in any ratios of CeO2/TiO2 solutions used in this
experiment. Acetylacetone and polyethyleneglycol added to
Fig. 4. SEM surface photographs of CeO2TiO2 coatings treated at 7008C for (a) 3 and (b) 60 min.
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Table 1
EXAFS results
Sample
Coordination number of Ce
distance to
neighboring
O 22 (nm)
CeO2
CeO2TiO2
8.0 (standard)
6.2
0.234 ^ 0.002
0.233 ^ 0.002
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Fig. 7 shows the refractive indices of various compositions of TiO2SiO2 coatings. The coating with molar ratio of
TiO2/SiO2 33:67 had the refractive index of 1.76.
Fig. 8 shows the reection spectra of the glass coated with
UV absorbing layer with and without an inner layer of
which the refractive index and the optical thickness are
1.76 and 125 nm, respectively. The inner layer reduces
reectance and prevents the glass from exhibiting a reection coloring. Moreover, this inner layer plays a very important role for strengthening the adhesion between the coating
and the substrate as shown in Fig. 9. The insertion of the
inner layer increases the number of surface active hydroxyl
groups [5] which can bond with the hydroxyl groups in the
UV absorbing layer. Fig. 10 shows the cross-sectional SEM
image of the double layer coated UV-shielding glass.
4. Application of UV-shielding glass to automobile
windows
Test condition
Results
Abrasion
Acid
Alkali
Humidity
Heating
Weathering
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5. Conclusions
Ultraviolet rays shielding CeO2TiO2 coatings on glass
were prepared by the solgel process. UV absorption of
CeO2 was improved with the changes of crystallinity and
coordination state by adding TiO2. The inner layer
composed of TiO2SiO2 applied between the substrate and
CeO2TiO2 coating prevented the glass from exhibiting
interference coloring and improved the adhesion of coatings
to the substrate. This double-layered UV-shielding coating
on glass is useful for protecting human bodies and materials
from the harmful effects of UV and shows excellent durability. The coated glass is widely used in the automobile industry.
References
[1] Executive Summary of the Environmental Assessment of Ozone
Depletion, 1991.
[2] C.A. Hampel, Glass Ind. 41 (2) (1960) 82.
[3] A. Makishima, H. Kubo, K. Wada, Y. Kitami, T. Shimohira, J. Am.
Ceram. Soc. 69 (6) (1986) C127.
[4] M.A. Sainz, A. Duran, J.M. Fernandez Navarro, J. Non-Cryst. Solids
121 (1990) 315.
[5] F. Gunji, T. Yoneda, T. Morimoto, New Glass 11 (4) (1996) 49.