Infrared Spectra of U.S. Automobile Original Finishes. VII. Extended Range FT‐IR and XRF Analyses of Inorganic Pigments In Situ—Nickel Titanate and Chrome Titanate

Edward M. Suzuki · Martin X. McDermot

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Cultural Heritage Materials Analysis Spectroscopy and Chemometric Analyses Pigment Synthesis and Properties

Abstract

The identification, analysis, and occurrence in U.S. automobile original finishes (1974-1989) of Nickel Titanate (yellow) and Chrome Titanate (yellow-orange) are described in this report. The titanate pigments are based on the rutile (titanium dioxide) structure and there are only minor differences between the infrared absorptions of rutile and the titanates. Titanate pigment absorptions in paint spectra can thus be easily mistaken for those of rutile. Each of the titanates, however, contains two elements in addition to titanium that can serve to distinguish them using elemental analyses. Fourier transform infrared (4000-220 cm(-1)) and X-ray fluorescence instruments were used in combination for the in situ analysis of the titanates. In addition to titanium, nickel, and antimony, the three main detectable elements comprising Nickel Titanate, all of the commercial products of this pigment that were examined also contained impurities of zirconium, niobium, and usually lead. These elements were also detected in most of the monocoats in which Nickel Titanate was identified, as well as in the Chrome Titanate pigments, and the zirconium to niobium ratio was found to exhibit a wide variation. Nickel Titanate is a relatively common pigment that was identified in nearly three dozen U.S. automobile yellow nonmetallic monocoats (1974-1989), while Chrome Titanate appears to have been used in only a few yellow and orange nonmetallic monocoats. The use of the titanate pigments likely increased after this time period as they were replacements for lead chromate pigments (last used in a U.S. automobile original finish in the early 1990s), and are more amenable for use in basecoat/clearcoat finishes than in monocoats. Minor distortions of the infrared absorptions of rutile, anatase, and the titanates obtained using accessories with diamond windows were noted, and their origins are discussed.

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References

2000Analysis of pigments and inks on oil paintings and historical manuscripts using total reflection x-ray fluorescence spectrometry 1999Pigment investigation of a late-medieval manuscript with total reflection X-ray fluorescence and micro-Raman spectroscopy 2001In Situ Identification and Analysis of Automotive Paint Pigments Using Line Segment Excitation Raman Spectroscopy: I. Inorganic Topcoat Pigments 1999Identification of organic pigments in coatings: applications to red automotive topcoats 1993Analytical characterization of artists' pigments used in old and modern paintings by total-reflection X-ray fluorescence 1996Infrared Spectra of U.S. Automobile Original Topcoats (1974–1989): I. Differentiation and Identification Based on Acrylonitrile and Ferrocyanide C≡N Stretching Absorptions 1997Infrared Spectra of U.S. Automobile Original Topcoats (1974–1989): III. In Situ Identification of Some Organic Pigments Used in Yellow, Orange, Red, and Brown Nonmetallic and Brown Metallic Finishes—Benzimidazolones 1996Infrared Spectra of U.S. Automobile Original Topcoats (1974–1989): II. Identification of Some Topcoat Inorganic Pigments Using an Extended Range (4000-220 cm−1) Fourier Transform Spectrometer

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