Atmospheric pressure matrix-assisted laser desorption/ionization mass spectrometry of engine oil additive components.

RATIONALE: The efficiency of lubricants strongly depends on the content of functional additives. In order to assess the chemical and structural changes taking place in the lubricating oil and its additives during operation, it is essential to develop a method for simple and prompt analysis. METHODS: Two single additives as well as a fully formulated engine oil were analysed using an atmospheric pressure matrix-assisted laser desorption/ionization (AP-MALDI) source coupled to a linear trap quadrupole Orbitrap XL hybrid tandem mass spectrometer and compared with results obtained by means of electrospray ionization (ESI) including additional low-energy collision-induced dissociation (LE-CID). The identification of additives directly from technical surfaces was simulated by using steel substrates as AP-MALDI targets with varying roughness. RESULTS: After assessment and selection of the most suited AP-MALDI matrix it was found that pure additives such as calcium sulfonate and zinc dialkyldithiophosphates (ZDDPs) could well be identified with abundant signal intensity based on their elemental composition. Molecular identification was corroborated by LE-CID in ESI mode. Additionally, additives present in the fully formulated commercial oil such as ZDDPs and salicylates could be reliably identified based on the elemental composition of the deprotonated molecules by means of the Orbitrap unit on different substrates including steel surfaces with high roughness. CONCLUSIONS: AP-MALDI is an efficient technique for determination of lubricant additives directly from commercial oil blends. Identification of additive components was also achieved on steel surfaces with high roughness as applied in tribological systems and thus it is expected that it will be possible to assess additive degradation in real applications, enabling more effective and timely maintenance measures.

Formation of Surface Deposits on Steel and Titanium Aviation Fuel Tubes under Real Operating Conditions.

In this study, stainless steel and titanium (Ti) tubes obtained from a turbofan engine after the end of its lifetime were analyzed in order to compare the amount of pyrolytic coke present and its influence on the parent, base material. Various analytical techniques including microhardness and topographical evaluations, optical emission spectrometry (OES), scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDX), Raman spectroscopy, and X-ray photoelectron spectroscopy (XPS) were applied. On steel surfaces, a thick pyrolytic coke deposition layer consisting of carbon and oxygen and also containing elements from the tube material, fuel, and fuel additives was found. The concentration of elements from the pyrolytic coke continuously decreased with distance from the surface of the deposit, while the concentrations of elements from the tube material continuously increased, with the concentrations of elements from the fuel and the fuel additives being relatively constant. With ultrasonic cleaning in distilled water, most of the deposits could be removed. Only carbon-rich patches with a thickness of more than 300 nm remained adhered to the surface and/or had diffused into the original material. On Ti surfaces, the thickness of the C-rich fuel deposit layer was significantly thinner as compared to that on the stainless steel; however, the surface was covered with an ∼3 µm-thick oxide layer, which consisted of elements from the fuel additives. It is believed that the beneficial properties of Ti covered with a thin layer of TiO2, such as low adhesion and/or surface energy, have promoted different deposition mechanisms compared to those of stainless steel and thus prevented pyrolytic coke deposition and the related material deterioration observed on stainless steel.

Modified-Atmospheric Pressure-Matrix Assisted Laser Desorption/Ionization Identification of Friction Modifier Additives Oleamide and Ethoxylated Tallow Amines on Varied Metal Target Materials and Tribologically Stressed Steel Surfaces.

For many tasks in failure and damage analysis of surfaces deteriorated in heavy tribological contact, the detailed characterization of used lubricants and their additives is essential. The objective of the presented work is to establish accessibility of tribostressed surfaces for direct characterization via modified atmospheric pressure-matrix assisted laser desorption/ionization-mass spectrometry (m-AP-MALDI-MS). Special target holders were constructed to allow target samples of differing shape and form to fit into the desorption/ionization chamber. The best results of desorption and ionization on different target materials and varying roughnesses were achieved on smooth surfaces with low matrix/substrate interaction. M-AP-MALDI characterization of tribologically stressed steel surfaces after pin-on-disc sliding wear tests (SRV-tribotests) yielded positive identification of used friction modifier additives. Further structure elucidation by electrospray ionization mass spectrometry (ESI-MS) and measurements of worn surfaces by time-of-flight-secondary ion mass spectrometry (TOF-SIMS) accompanied findings about additive behavior and deterioration during tribological contact. Using m-AP-MALDI for direct offline examinations of worn surfaces may set up a quick method for determination of additives used for lubrication and general characterization of a tribological system.

Surface analysis of different boundary layers on steel discs formed in a lubricated tribocontact during laboratory test compared with field application.

The aim of this study was to gain knowledge of tribological layers on a steel disc. This steel disc has been used in a transmission system in the field. ATF-oil (automatic transmission fluid), which contains different surface-adhering additives, serves as a lubricant and as a cooling fluid in the tribological system. Over time, the tribological characteristics of the system changed. Special interest in this study lies in the modifications of the steel surface. The field-used disc was therefore compared with model tested discs. In a disc-on-disc tribometer, all samples are tested for a short period of time to evaluate the actual condition of the system regarding friction behaviour. Analysis and characterisation of surfaces and layer formation were carried out with, among other techniques, 3D topography, SEM / EDX, AFM, XPS, and ToF-SIMS. Results indicate that in some regions a complex composed tribological layer is formed. Differences were detected between the steel discs used in the field and the model discs. This indicates the problem of evaluation of long-term behaviour exclusively by use of short or accelerated model experiments. A combination of carefully selected and sophisticated analytical methods is necessary to trace small changes of the system.