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Effect of Silica Additive on the Anatase‐to‐Rutile Phase Transition
Author(s) -
Okada Kiyoshi,
Yamamoto Nobuo,
Kameshima Yoshikazu,
Yasumori Atsuo,
MacKenzie Kenneth J. D.
Publication year - 2001
Publication title -
journal of the american ceramic society
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.9
H-Index - 196
eISSN - 1551-2916
pISSN - 0002-7820
DOI - 10.1111/j.1151-2916.2001.tb00882.x
Subject(s) - anatase , rutile , crystallinity , materials science , calcination , x ray photoelectron spectroscopy , fourier transform infrared spectroscopy , crystallization , amorphous solid , titanium , silicon , analytical chemistry (journal) , inorganic chemistry , mineralogy , chemical engineering , photocatalysis , crystallography , catalysis , chemistry , organic chemistry , metallurgy , engineering , composite material
The effect of SiO 2 addition on the anatase‐to‐rutile phase transition was investigated by DTA, XRD, FTIR, and XPS. TiO 2 xerogels containing SiO 2 up to 20 mol% were prepared by mixing and hydrolyzing titanium tetraisopropoxide (TTIP) and tetraethylorthosilicate (TEOS) with HNO 3 as a catalyst. With increased amounts of SiO 2 in the xerogels, the following results were obtained: (1) the crystallization temperature of anatase increased from 415°C in pure TiO 2 to 609°C in 20‐mol%‐SiO 2 ‐containing xerogel in the DTA curves; (2) the formation temperature of rutile, according to quantitative XRD analysis, increased with increased SiO 2 content up to 5 mol% SiO 2 but became constant at higher SiO 2 contents; (3) the crystallinity of anatase became lower; and (4) the lattice parameter a of the anatase decreased slightly, but the parameter c decreased greatly up to 20 mol% SiO 2 . Although the added silicon atoms were considered from these results to be incorporated into the amorphous TiO 2 and anatase structures, the 29 Si MAS NMR spectra of the xerogels containing 10 mol% SiO 2 showed only tetrahedral silicon, with no indication of silicon in octahedral coordination. When calcined at higher temperatures, the xerogel showed polymerization of the SiO 4 tetrahedra in the NMR spectra and the Si–O–Si vibration in the FTIR spectra. The chemical composition of the xerogel surfaces, measured using XPS, showed increased SiO 2 content with increased calcining temperature, indicating the expulsion of silicon from inside the particles to form an amorphous SiO 2 surface layer. The formation of this amorphous SiO 2 surface layer was considered to be important in retarding the anatase‐to‐rutile phase transition by suppressing diffusion between anatase particles in direct contact and limiting their ability to act as surface nucleation sites for rutile. These effects of silicon additions were similar to those observed in the γ‐Al 2 O 3 ‐ to‐α‐Al 2 O 3 transition.