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Recent developments in diesel fuel injection equipment coupled with moves to using ULSD and biodiesel blends has seen an increase in the number of reports, from both engine manufacturers and fleet operators, regarding fuel system deposit issues. Preliminary work performed to characterise these deposits showed them to be complicated mixtures, predominantly carbon like but also containing other possible carbon precursor materials. This paper describes the application of the combination of hydropyrolysis, gas chromatography and mass spectrometry to the analysis of these deposits. It also discusses the insights that such analysis can bring to the constitution and origin of these deposits.

The increased severity and prevalence of insoluble deposits formed on fuel injectors in gasoline direct injection (GDI) engines precipitates negative environmental, economic and healthcare impacts. A necessary step in mitigating deposits is to unravel the molecular compositions of these complex layered materials. But very little molecular data has been acquired. Mass spectrometry shows promise but most techniques require the use of solvents, making them unsuited for analyzing insoluble deposits. Here, we apply the high mass-resolving power and in-situ analysis capabilities of 3D OrbitrapTM secondary ion mass spectrometry (3D OrbiSIMS) to characterize deposits formed on the external tip and internal needle from a GDI injector. This is the first application of the technique to study internal GDI deposits. Polycyclic aromatic hydrocarbons (PAHs) are present up to higher maximum masses in the external deposit.

The recent developments in diesel fuel injection equipment coupled with the moves in the US to using ULSD and biodiesel blends has seen an increase in the number of reports from both engine manufacturers and fleet operators regarding fuel system deposit formation issues. These deposits not only form on and within the fuel injectors but they also form elsewhere in the fuel system, due to fuel recirculation. These will eventually accumulate in the fuel filters. Historically, diesel fuel system deposits have been attributed to contamination of the fuel or the degradation of the fuel with age. Such age related degradation has been attributed to oxidation of the fuel via well documented pathways, although the initiation of this process is still poorly understood. Papers at recent SAE meetings in Florence, San Antonio, Rio de Janeiro, San Diego and Kyoto have addressed many of these causes.

Since 2009, there has been a rise in deposits of various types found in diesel fuel injection systems. They have been identified in the filter, the injector tip and recently inside the injector. The latter internal diesel injector deposits (IDIDs) have been the subject of a number of recent publications, and are the subject of investigations by CRC (Central Research Council Diesel Performance Group-Deposit Panel Bench/ Rig Investigation sub panel) in the US and CEN (Committee European de Normalisation TC19/WG24 Injector Deposit Task Force) and CEC (Coordinating European Council TDFG-110 engine test) in Europe. In the literature one of the internal injector deposit types, amide lacquers, has been associated with a poorly characterised noncommercial low molecular weight polyisobutylene succinimide detergent which also lacked provenance.

The effect of legislation in driving towards lower emissions has seen significant changes in injector design, (common- rail) and fuel composition (ULSD). This has led to numerous reports of deposits throughout the vehicle diesel system, filters, tanks, pumps and injectors. In recent examples, deposits internal to the fuel injector on the needle have become prevalent and characterisation of the deposits on the injector needle has become an industry priority. A number of studies have made progress on this but the deposits have proven difficult to fully characterise and often have an ineradicable nature, which makes analysis other than in situ difficult. This paper will describe for the first time the application of a number of surface techniques, in combination which not only provide characterisation data but also the ability to provide cross-sectional lifts out of the sample, which may then be the subject of further analysis.