This paper is a review of the technical approaches taken at Toyota Central R&D Labs. (TCRDL) toward the surface and micro-analysis of organic materials. For organic microanalysis techniques, which are suitable for analysis of the degradation of organic materials, a depth analysis technique using micro-IR and a distribution analysis technique using derivatization-XMA have been developed. The former technique provides a great deal of information about organic chemical structure and the latter has higher sensitivity and higher lateral resolution than micro-IR. For organic surface analysis techniques, which are suitable for the analysis of adhesion and lubrication, a new method for time-of-flight mass spectrometry (TOF-SIMS) and a new type of surface analysis using a combination of SEIRA and ATR have been developed. Looking ahead to future trends, it is anticipated that "organic surface and micro-analysis" will evolve into "organic nanoanalysis", which will permit nanometer-order lateral and depth resolution, via the application of two approaches for extending the applicability of conventional organic analysis techniques to smaller scales, and for extending the applicability of nanometer scale analysis techniques to organic chemical analysis.

　
Motoyasu Sugiura, Atsushi Murase, Keiko Fukumoto,
Takuya Mitsuoka, Masao Tsuji

A new analytical method, referred to as "Derivatization-Electron Probe X-ray Micro-analysis (Derivatization-XMA)", has been developed to determine the distribution of 0.1 % order functional groups in polymers with μm level lateral resolution. Also, the optimal reaction conditions that make it possible to selectively derivatize the vinyl groups, carboxyl groups, carbonyl groups, hydroxyl groups and epoxy groups have been found. This method first derivatizes the functional groups in a polymer using a reagent with an indicator element highly sensitive to XMA, and moreover, with high selectivity to the functional group, and then measures the distribution of the indicator elemens by XMA, thus obtaining the distribution of the original functional groups. The fundamental performance of XMA in analyzing derivatized polymers has been investigated. The results showed that the detection limit was 0.05 % and the lateral resolution was 3 μm. In addition, the depth profile of the vinyl groups in an amine-degraded polyvinylchloride sheet was analyzed using this method. Since the depth profiles agreed well with those obtained by micro-IR spectroscopy, the reliability of measuring the distribution of functional groups by this method was confirmed. By this method, the sensitivity was 30 times higher, and the lateral resolution was 4 times higher than those obtained by micro-IR spectroscopy. Actual application to the depth analysis of degraded polymers has proved that this method is useful for the characterization of polymers and the study of polymer degradation.

Atsushi Murase, Toshihide Ohmori

The adsorption of model compounds of lubricant additives onto ferrous materials was investigated using time-of-flight secondary ion mass spectrometry (TOF-SIMS). Nineteen types of model compounds, including phosphates, carboxylic acids, alcohols, amines, and esters, were subjected to lubrication tests. The TOF-SIMS spectra of the friction surfaces after hexane washing indicated that amines were physically adsorbed, carboxylic acids and esters were chemically adsorbed, and phosphates were tribochemically reacted onto friction surfaces. For alcohols, which showed no lubricity, no adsorbed component was detected on the friction surfaces by TOF-SIMS. From the results of investigation of correlation between the TOF-SIMS data and lubrication properties, it was possible to discuss the relationships between the results of TOF-SIMS analysis and lubrication properties such as friction coefficient and wear scar width when making comparisons among similar types of lubricant additives or investigating chemical changes of friction surfaces during lubrication tests.