Abstract
X-ray photoelectron spectroscopy (XPS) and x-ray absorption spectroscopy (XAS) measurements were made on thin film (∼1000 Å) sol-gel adhesion promoting surface treatments. These silicon/zirconium-containing sol-gel coatings are possible replacement processes for traditional surface preparations that use environmentally undesirable and potentially toxic materials. The sol-gels were waterborne mixtures formulated with tetra-n-propoxyzirconium (TPOZ) and a silane, either 3-glycidoxypropyl-trimethoxysilane (GTMS) or 3-aminopropyl-triethoxysilane (APS). Results show that dried sol-gel powders formulated with TPOZ or TPOZ + GTMS have longer Zr—O bond lengths (∼2.18 Å, CN 7 or 8) than the TPOZ + silane + metal substrate samples (∼2.10 Å, CN 6). The fraction (+/− 0.10) of Zr in a short bonded 6-fold site is highest (0.80) for TPOZ + (APS or GTMS) on (Ti or Al), at an intermediate value (0.40) for TPOZ on Ti and low (0.10) for the powders. For sol-gels deposited on a metal substrate, there are indications of a chemical bond between the thin film sol-gel and the metal substrate. The TPOZ + APS coatings on Ti data suggest that this Zr—O—Ti bond is present with a Zr—Ti separation of ∼3.5 Å. Only subtle differences were observed in the near-neighbor bonding due to curing treatment variations from room temperature to ∼125°C, alloy substrate variations (Ti-6Al-4V/Al 2024), and age of the deposited sol-gel coating (up to 1 year).
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References
K.Y. Blohowiak, J.H. Osborne, K.A. Krienke, and D.F. Sekits, Nonchemical surface treatment for titanium alloys, Final Report Contract Number F33615-92-D-5812, Air Force Wright Laboratory, April 1996; (b) K.Y. Blohowiak, K.A. Krienke, and D.F. Sekits, Optimization and scale-up of sol-gel technology for preparation of titanium for adhesive bonding, Final Report Contract Number F33615-95-D-5615, Air Force Wright Laboratory, February 1997.
J.D. McCullough and K.N. Trueblood, Acta Cryst. 12, 507 (1959).
H.J. Rossell, Nature 283, 282 (1980).
J. Singer and D.T. Cromer, Acta Cryst. 12, 719 (1959).
C. Sanchez and M. In, J. Non-Cryst. Sol. 147 & 148, 1 (1992).
G.A. Novak and G.V. Gibbs, Am. Min. 56, 791 (1971).
R.W. Wyckoff, Crystal Structures. Vol. II (Interscience, New York 391, 1963).
Von H.J. Deiseroth und Hk. Muller-Buschbaum, Zeitschrift fur anorganische und allgemeine Chemie, 375, 150 (1970).
S.I. Zabinsky, J.J. Rehr, A. Ankudinov, R.C. Albers, and M.J. Eller, Phys. Rev. B52, 2995 (1995).
D.C. Koningsberger and R. Prins, X-rays Absorption: Principles, Applications, Techniques of EXAFS, SEXAFS and XANES (Wiley-Intersciences, Chichester, 1988).
F.W. Lytle, in Applications of Synchrotron Radiation edited by H. Winick, D. Xian, M. Ye, and T. Huang (Gordon and Breach, New York, 1989), p. 135.
W.H. McMaster, N. Kerr-Del Grande, H.H. Mallet, and H.H. Hubbell, Compilation of X-ray Cross-Sections (National Technical Information Service, Springfield, Ohio 1969).
B. Ravel, ATOMS2.46, Software from University ofWashington Physics Dept., November, 1995.
F. Lytle, D. Sayers, and E. Stern, Physica B158, 701 (1989).
D. Peter, T.S. Ertel, and H. Bertagnolli, J. Sol-Gel Sci. and Tech. 3, 91 (1994).
D. Peter, T.S. Ertel, and H. Bertagnolli, J. Sol-Gel Sci. and Tech. 5, 5 (1995).
K. Okasaka, H. Nasu, and K. Kamiya, J. Non-Cryst. Sol. 136, 103 (1991).
S. Moon, M. Fujino, H. Yamashita, and M. Anpo, J. Phys. Chem B101, 369 (1997).
T. Lopez, J. Navarrete, R. Gomez, O. Novaro, F. Figueras, and H. Armendariz, Appl. Catal. A: General 125, 217 (1995).
O. Stachs, V. Petkov, B. Himmel, and T. Gerber, SSRL Activity Report, (Stanford University, Palo Alto, 1995), p. 175.
A. Helmerich, F. Raether, D. Peter, and H. Bertagnolli, J. Matl. Sci. 29, 1393 (1994).
A. Mosset, P. Baules, P. Lecante, J. Trombe, H. Ahamdane and F. Bensamka, J. Mater. Chem. 6(9), 1527 (1996).
A. Douy and J. Landon, Fourth Euro Ceramics-Vol. 1, edited by C. Galassi (Gruppo Editoriale Faenza Editrice S.p.A. 1995), p. 139.
F.A. Cotton and G. Wilkinson, Advanced Inorganic Chemistry, (John Wiley & Sons, New York, 1980).
R. Shannon and C. Prewitt, Acta Cryst. B25, 925 (1969).
F. Farges and G. Calas, Am. Min. 76, 60 (1991).
M. Plueddeman, Silane Coupling Agents (Plenum, New York, 1991), p. 139.
C.J. Brinker and G. Scherer, Sol-Gel Chemistry (Wiley, New York, 1991).
W. Noll, Chemistry and Technology of Silicones (Academic Press, New York, 1968).
G. Antonioli, P. Lottici, I. Manzini, G. Gnappi, A. Montenero, F. Paloschi, and P. Parent, J. Non-Cryst. Sol. 177, 179 (1994).
L. Esquivias, C. Barrera-Solano, M. Pinero, and C. Prieto, J. Alloys and Compounds 239, 71 (1996).
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Greegor, R., Blohowiak, K., Osborne, J. et al. X-Ray Spectroscopic Investigation of the Zr-Site in Thin Film Sol-Gel Surface Preparations. Journal of Sol-Gel Science and Technology 20, 35–50 (2001). https://doi.org/10.1023/A:1008772532638
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DOI: https://doi.org/10.1023/A:1008772532638