Applied Surface Science 44 (1990) 301-308 301
North-Holland
X-RAY PHOTOELECTRON SPECTROSCOPIC AND X-RAY DIFFRACTOMETRIC
CHARACTERIZATION OF ALKYLIMIDAZOLE FILMS ON COPPER OXIDE
AND ALKYLIMIDAZOLATO COPPER(II) COMPLEXES
S. YOSHIDA, H. ISHIDA *
Department of Macromolecular Science, Case Western Reseroe University, Cleveland, OH 44106, USA
and
J.S. JEN
Research and Development Division, Owens-Corning Fiberglass Corporation, Granville, OH 43023, USA
Received 4 December 1989; accepted for publication 17 February 1990
The molecular structures of 2-undecylimidazole films on copper and copper oxide are studied using XPS with the reference of
synthesized 2-undecylimidazolato copper(II). X-ray diffractograms of synthesized 2-alkylimidazole complexes are studied in order to
understand the molecular structure of alkylirnidazole complexes. The difference in molecular structure between the synthesized
complexes and the films on copper is discussed. The XPS spectra in the Cu2p region indicate Cu(II) complex regardless of the
oxidation state of the copper substrates. The O ls peaks appeared at a binding energy higher than corresponding to oxide indicating
the presence of water or peroxide between the copper ions. A linear relationship between the d(200) spacing of 2-alkylimidazole
complexes and the number of carbons of alkylimidazole complexes indicates the same flat orientation of alkylimidazoles around the
copper ions. The difference between the infrared spectra of imidazole films on copper and synthesized complex is due to the
amorphous structure of the film.
1. Introduction
A good knowledge on the molecular structure
of imidazoles on copper is important for under-
standing the mechanism of corrosion inhibition.
Evaluations of imidazole derivatives as inhibitors
and/or anti-corrosion chemicals have been carried
out in several publications [1-5], from which the
usefulness of the imidazole derivatives was evi-
dent. However, only a few papers [6,7] reported
the molecular structure of imidazole derivatives on
copper. Imidazoles were initially studied because
they possess a similar molecular structure to ben-
zotriazole. Benzotriazole is useful and is widely
used as an inhibitor for copper [8-10]. However,
the molecular structure of benzotriazole is not well
understood in spite of intensive study. Imidazoles
* To whom correspondence should be addressed.
can overcome the disadvantages of benzotriazole:
the loss of anti-corrosion ability in water [11,12].
Copper plate with a benzotriazole pre-treatment
does not show any anti-corrosion effect without
benzotriazole in water [11]. On the other hand,
imidazole pre-treatment indicates an excellent
anti-corrosion effect even in water [12]. Also, a
much faster rate of alkylimidazole film formation,
which is the most important factor for an anti-cor-
rosion film, was reported when compared to ben-
zotriazole [13]. From these points of view, an
extensive study of imidazole derivatives is war-
ranted.
X-ray photoelectron spectroscopy (XPS) is a
useful technique for a surface study as it identifies
not only the surface species, but also its chemical
state. Tompkins and Sharma [6] reported that the
valence state of a Cu-benzimidazole surface com-
pound is cuprous. We used XPS to study 2-unde-
0169-4332/90/$03.50 © 1990 - Elsevier Science Publishers B.V. (North-Holland)