This work presents a theoretical survey that sheds light on the physical meaning of the gelation index, that is, the main parameter involved in ASTM D5133. More specifically, it is proved that the pulse-shaped region of the gelation curve can be explained as the relief of the supersaturation of the solution, which is a nucleation process that finishes when the saturation ratio takes a value equal to 1. Comparison between experiments and the theoretical approach put forward in this work reveals qualitative agreement. This work also confirms the poor reproducibility of ASTM D4684, which is an alternative test for the evaluation of gelation in engine oils. Particularly, it is shown that the poor reproducibility of this test can be attributed to a systematic error made during the measurements. The lack of accuracy of the temperature, in particular the final test temperature, could be the main cause for discrepancies between laboratories. Finally, it is shown that in order to predict gelation within ASTM D5133, not only must the gelation index be considered, but the gelation index temperature also plays an important role.
Gelation due to the precipitation of paraffins in petroleum oils is a billion dollar problem in the petroleum industry. The most widely known example in this field is the gelation of crude oil during transportation through sub-sea pipelines, which in some cases has caused important remediation cost of pipelines blockages. In the case of lubricant oils, gelation is a latent problem from the massive failure in automotive engines that took place in North America during the winter of 1980-81. In this framework, this work uses a recently developed theoretical survey which has shed light on the physical meaning of the gelation index, that is, the main parameter involved in test ASTM D 5133. This test is commonly used in the petroleum industry for the evaluation of gelation tendency of engine oils at low temperatures. This work analyzes the role played by different parameters (and particularly the induction period and supersaturation ratio) in the theoretical evaluation of the gelation index. In spite of the simplifications used in the theory a qualitative agreement is found when comparing with experimental data, which opens the possibility (after necessary refinements) of a fully predictive theory for nucleation which would be very useful for the petroleum industry. Keywords: Gelation / gelation index / lubricant oils / homogeneous nucleation theory / pour point depressants / Gelierung durch Paraffinausscheidung in Mineralölen bereitet der Erdölindustrie Probleme in Milliardenhöhe. Das bekannteste Beispiel hierfür ist die Gelierung von Rohöl während des Transports durch Unterseepipelines. Dieses Problem hat in einigen Fällen erhebliche Kosten für die Sanierung verstopfter Pipelines verursacht. Im Falle von Schmierölen ist die Gelierung ein latentes Problem, etwa beim massiven Versagen von Automotoren in Nordamerika, das im Winter 1980-81 in besonderem Maße auftrat. Vor diesem Hintergrund nutzt die vorliegende Studie die Ergebnisse einer theoretischen Untersuchung, welche die physikalische Bedeutung des Gelierungsindexes, also des wichtigsten Parameters im Test nach ASTM D 5133, analysiert. Der erwähnte Test kommt in der Erdölindustrie bei der Bewertung der Gelierungstendenz von Motorölen bei Niedrigtemperaturen häufig zum Einsatz. Die vorliegende Studie analysiert die Rolle der verschiedenen Parameter (sowie insbesondere der Induktionszeit und des Übersättigungsgrads) in der theoretischen Bewertung des Gelierungsindexes. Trotz der in der Theorie angesetzten Vereinfachungen kommt es bei einem Vergleich mit den Messdaten zu einer qualitativen Übereinstimmung und diese bietet (nach notwendigen Weiterentwicklungen) die Möglichkeit einer absoluten theoretischen Vorhersage für den Gelierungsprozessbeginn. Letztere wäre für die Erdölindustrie von großem Nutzen.
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