*Article* **Low-Temperature Rheology and Thermoanalytical Investigation of Lubricating Greases: Influence of Thickener Type and Concentration on Melting, Crystallization and Glass Transition**

**Andreas Conrad 1,\*, Annika Hodapp 2, Bernhard Hochstein 2, Norbert Willenbacher 2 and Karl-Heinz Jacob 1**


**Abstract:** This study investigates crystallization, melting and glass transition of Li- and Ca-12- hydroxystearate greases in relation to the pour point of the corresponding oils. The base oils for the greases are mineral oil, polyalphaolefin, alkylated naphthalene, propylene glycol, and trimellitate. For the mineral oil-based greases the crystallization temperature *T*c increases and the melting temperature *T*m decreases upon addition of thickener. The pour point of the mineral oil then is 3 K below *T*c and does not properly define the lowest application temperature for mineral oil (MO) based greases. Both thickeners induce a small increase of the glass transition temperature (1–3 K) of the synthetic oils polyalphaolefin, alkylated naphthalene, propylene glycol. The pour point of the base oils correlates well with the onset of the glass transition in the corresponding grease indicated by a sharp increase in grease viscosity. Pure trimellitate with unbranched alkyl chains does not crystallize upon cooling but shows noticeable supercooling and cold crystallization. As the percentage of thickener in corresponding greases increases, more oil crystallizes upon cooling 20 K above the crystallization temperature of the trimellitate without thickener (−44 ◦C). Here, the thickener changes the crystallization behavior from homogeneous to heterogeneous and thus acts as a crystallization nucleus. The pour point of the base oil does not provide information on the temperature below which the greases stiffen significantly due to crystallization.

**Keywords:** lubricating grease; heterogeneous crystallization; glass transition; rheology; differential scanning calorimetry (DSC)
