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Tribol Lett (2011) 41:463470 DOI 10.

1007/s11249-010-9734-x

ORIGINAL PAPER

Atomic Force Microscopy and Thermo-Rheological Characterisation of Lubricating Greases


nchez J. M. Franco C. Valencia M. C. Sa C. Gallegos F. Urquiola R. Urchegui

Received: 10 February 2010 / Accepted: 3 December 2010 / Published online: 14 December 2010 Springer Science+Business Media, LLC 2010

Abstract In this work, non-perturbed microstructures of several commercial and model lubricating greases, differing in nature and concentration of the thickener agent, were examined using the atomic force microscopy (AFM) technique. Grease microstructure mainly depends on the nature of the thickener employed and, also, on thickener concentration and viscosity of the base oil. Thermal-induced changes in the viscoelastic response of lubricating greases have been investigated by using different rheological techniques in a temperature range of 0175 C. Small-amplitude oscillatory shear (SAOS) measurements were carried out to determine the mechanical spectra of the different samples studied. Lubricating grease rheological thermal susceptibility was analysed by following the evolution of the plateau modulus with temperature. SAOS functions dramatically decrease, in most cases, above a characteristic temperature, which depends on nature and/or concentration of the thickener used and therefore on grease microstructure. The thermo-mechanical reversibility of grease microstructure has been studied by carrying out triple-step-shear stress tests (shear stresses inside and outside of the linear viscoelasticity range), at different temperatures. The degree of lubricating grease non-reversible structural breakdown, which increases with temperature, depends on the shear stress applied above the linear viscoelasticity limits.

Keywords Atomic force microscopy Lubricating grease Microstructure Rheology Temperature

1 Introduction Lubricating greases are, in general, highly structured colloidal dispersions of a thickening agent, usually a metal soap, in lubricant oil [15]. Fatty acid soaps of lithium, calcium, sodium, aluminium and barium are most commonly used as thickeners. This component is added to confer the consistency of greases, preventing loss of lubricant under operating conditions and avoiding the penetration of contaminants, such as solid particles and water, without a signicant reduction of the lubricating properties. Greases are the preferred lubricant in hardto-reach places, for mechanically rubbing or dynamic systems. Many important functional properties such as their ability to ow under external forces, mechanical stability under shearing, thermal susceptibility, dripping and spattering, etc, depend on the nature of its components and the presence of some performance additives [2, 5]. The thickener forms an entanglement network, which traps the oil and confers the appropriate rheological behaviour to the grease [4]. Consequently, suitable structural and physical properties may be reached from a proper selection of the ingredients but, also, from process optimisation, as was previously reported [6]. In this sense, it is relevant to understand how the development of grease microstructure contributes to several functional properties and, particularly, to the rheological characteristics of lubricating greases [7]. The thermo-rheological behaviour of lubricating greases under working conditions may be responsible for softening or bleeding causing grease to ow away from contact areas

nchez J. M. Franco (&) C. Valencia C. Gallegos M. C. Sa a Qu mica, Facultad de Ciencias Departamento de Ingenier Experimentales, Campus de El Carmen, Universidad de Huelva, 21071 Huelva, Spain e-mail: franco@uhu.es F. Urquiola R. Urchegui Verkol Lubricantes, S.A., Barrio Zalain, 42, 31780 Bera, Navarra, Spain

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[8] or an improvement in the replenishment of the grease into the contact zone decreasing starvation [9], depending on the lubrication mechanism. On the other hand, the rheology of lubricating greases is important not only under working operation, being responsible for preventing loss of lubricating under static conditions or acting as an effective sealing agent. These rheological properties in quasiunperturbed conditions are determined by the microstructure induced by the thickener dispersed in the base oil. Moreover, the rheological response of greases under high shear rate situations, as for instance those achieved in bearing lubrications, may be modelled from the characterisation of the linear viscoelastic behaviour by applying a factorable non-linear viscoelasticity model as previously shown by Madiedo et al. [10]. In general, the microstructure of lubricating greases depends on the type and concentration of the thickener soap, as well as on the nature and viscosity of the base oil employed. Thus, for instance, lithium lubricating greases typically consist of a ne dispersion of the crystallized lithium soap in the mineral or synthetic oil, usually in the form of long, twisted and well-entangled bres [3, 1113]. These bres arrange themselves to form a characteristic microstructure, resulting from physical interactions between colloidal particles and oil medium [12]. Other types of thickener agents crystallize as rods, spheres or platelet congurations [3, 11]. Traditionally, the analysis of grease microstructure has been characterised through TEM and SEM techniques [11, 14]. The most common criticism associated to SEM or TEM observations is that both techniques are vacuum based, and grease sample has to be submitted to either a freezing treatment or oil removing, thus distorting the original microstructure. Up to now, little work has been carried out on the characterisation of grease

microstructure by means of atomic force microscopy (AFM) [1517]. In spite of some experimental difculties, this technique provides a great advantage. Thus, grease samples do not need to be perturbed to carry out suitable microstructural observations [16, 17], since the experiments can be performed under atmospheric pressure. In this paper, different microstructures presented by a set of commercial and model lubricating greases were examined using the AFM technique. This microstructure was related to both some compositional variables and the resulting thermo-rheological behaviour.

2 Experimental 2.1 Materials Six lubricating grease samples differing in composition were analysed from a rheological and microstructural point of view. Lubricating greases C1C4 were commercial products manufactured by Verkol S.A. (Spain). Samples M1 and M2 were model lubricating greases manufactured in a 25 kg size pilot plant, following the Verkol S.A. property method. Table 1 shows some compositional and technical data for all the samples studied. 2.2 Atomic Force Microscopy Microstructural characterisation of lubricating greases was carried out by means of AFM, using a multimode AFM connected to a Nanoscope IV scanning probe microscope controller (Digital Instruments, Veeco Metrology Group Inc., Santa Barbara, CA). All the observations were performed in the tapping mode, using Veeco NanoprobeTM

Table 1 Main compositional and technical data for the lubricating greases studied Lubricating grease Thickener type % Thickener (w/w) Base uid Polymeric additive Lubricating oil viscosity at 40 C, ASTM D-445 (mm2/s) Dropping point, ASTM D-566 (C) Consistency, NLGI Grade Worked penetration, ASTM D-217 (dmm) C1 Lithium 12hydroxystearate 14.2 Mineral No 100 190 3 227 C2 Lithium 12hydroxystearate 7.6 Mineral No 150 200 2 271 C3 Lithium complex 13.6 Mineral/ synthetic No 26 263 2 275 C4 M1 M2 Lithium complex 16.5 Synthetic Yes 32 274 2 268

Calcium sulphonate Lithium complex complex 32.1 Mineral No 400 249 2 287 16.1 Synthetic No 32 294 2 270

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tips, in Phase Imaging, where the cantilever oscillates at its resonant frequency. The amplitude was used as a feedback signal. 2.3 Rheological Tests The rheological characterisation was performed in both a controlled-stress (RS150 from Haake, Germany) and a controlled-strain (ARES, Rheometric Scientic, UK) rheometer, in a temperature range between 0 and 175 C. Small amplitude oscillatory shear tests, inside the linear viscoelasticity range, were carried out in a frequency range between 0.01 and 100 rad/s, using a plateplate geometry (35 mm diameter, 1 mm gap). Strain or stress sweep tests, at the frequency of 1 Hz, were previously performed on each sample to determine the linear viscoelasticity range. Rheo-destruction measurements were also performed in oscillatory mode, following the evolution of the complex modulus when a step-shear stress outside the linear viscoelasticity range was applied on the lubricating grease sample, at different temperatures (25, 70 and 110 C), and the subsequent recovery when a step-shear stress inside the linear region was again restored. Electric and forced convection ovens, with environmental chambers that enclose the sample, were used to control the temperature in the controlled-stress and controlled-strain rheometers, respectively. At least two replicates of each test were carried out on fresh samples. 2.4 Penetration and Mechanical Stability Tests The lubricating greases were worked 60 strokes in a Mechanical Stability Tester and penetration values were determined using a Koehler Penetrometer model K 95500 following the ASTM D-217 standard. Classical consistency NLGI grade was established according to these penetration values [3].

3 Results and Discussion 3.1 AFM Observations Atomic force microscopy (AFM) is not a simple technique, particularly for studying the microstructure of lubricating greases. Some experimental problems, which may distort structural data, are derived from the textural and rheological properties of these materials when using the contact mode. Thus, Hurley and Cann [15] pointed out that they were not able to obtain good observations of untreated lubricating greases by using the AFM contact mode. They used the non-contact mode to successfully examine nonwashed samples, although some discrepancies in both types

of observations were detected. However, suitable microstructural observations were previously obtained with lithium greases by using the tapping mode, once the sample was heated up to a temperature below the dropping point and, then, cooled down to room temperature in order to obtain a very smooth surface [16, 17]. This protocol was followed in this study. All observations were carried out by using tapping mode in phase imaging. The phase lag is dependent on several parameters such as grease composition, adhesion, friction and viscoelastic properties. Figure 1ad shows AFM micrographs for different commercial lubricating greases. Typical entangled brous microstructures were observed in lithium greases. Samples C1 and C2 are lithium lubricating greases differing in soap content (see Table 1). As can be observed in the phase images shown in Fig. 1ab, sample C1, with higher soap content, shows thicker and more entangled and densely arranged bres than grease C2. Moreover, bres in C1 appear clearly more agglomerated, yielding large hollow spaces among them, where the oil is trapped. A lower density of bres, and not so agglomerated, is noticed in the case of grease C3 (Fig. 1c), which contains a lithium complex soap concentration similar to grease C1, although manufactured with a blend of mineral and synthetic oils of lower viscosity (Table 1). On the contrary, as expected, a completely different microstructure was observed for grease C4, based on a complex calcium sulphonate thickener, at high concentration (32.1% w/w). In this case, the structure consists of a ne dispersion of spherical and agglomerated particles (Fig. 1d) with average size around 0.23 lm. The inuence of temperature on the microstructure of lubricating greases was analysed on a model lithium complex grease manufactured with a low-viscosity synthetic oil (M1). Thus, Fig. 2a, b shows AFM images of this sample obtained at 25 C and 75 C, respectively. Similar microstructural arrangements are clearly observed, due to the fact that this temperature window is not particularly wide for a typical lubricating grease. However, it can be noticed that highly entangled and agglomerated bres are apparent at 25 C, whilst lower density of bres and less agglomerated, yielding larger hollow spaces among them, are apparent at 75 C, which may be attributed to a higher solvency of the base oil. Unfortunately, phase images cannot be obtained at higher temperatures, due to an excessive softening of the sample that induces sticking of the tip to the sample. 3.2 Small-Amplitude Oscillatory Shear (SAOS) Tests Figures 3 and 4 show the evolution of the storage (G0 ) and loss (G00 ) moduli with frequency, within the linear viscoelasticity range, for two selected lubricating grease formulations, in a temperature window of 0175 C. As can

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466 Fig. 1 AFM micrographs (window size 20 lm) for selected commercial lubricating greases: a C1; b C2; c C3; d C4

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be observed, the values of the storage modulus, G0 , are always higher than those found for the loss modulus, G00 , in the whole frequency range studied. G0 slightly evolves with frequency, with a slope that increases with temperature, whilst G00 usually shows a minimum value, which tends to vanish as temperature increases. These results mainly correspond to the plateau region of the mechanical spectrum, typical of highly entangled systems [18], and support the idea that lubricating greases are highly structured systems, as has been previously discussed. In addition, there is a tendency to a crossover between both viscoelasticity functions at low frequencies, more apparent at the highest temperatures, evidencing the beginning of the terminal or viscous region. Regarding the inuence of temperature on the linear viscoelastic functions, both G0 and G00 decrease as temperature increases, although this decay depends on the nature of the thickener used. Thus, for instance, the SAOS functions of the lithium grease C1 (Fig. 3) are almost unaffected by temperature below 50 C, and then progressively decrease. On the contrary, the calcium sulphonate grease C4 shows a decrease in the values of both linear viscoelasticity functions up to 100 C, which dramatically drop at 125 C (Fig. 4).

The characteristic parameter of the plateau region of the mechanical spectrum previously mentioned is the plateau modulus, Go N, dened, for polymeric materials, as the extrapolation of the contribution of the entanglements to G0 at high frequencies [19], which may be considered as a measure of the aggregation number among the dispersed structural units and, consequently, related to the strength of the microstructural network. The temperature dependence on the plateau modulus, Go N, with temperature, for the commercial and model lubricating greases studied, is shown in Figs. 5 and 6. As can be observed, the abovementioned dependence dramatically changes at a characteristic temperature, which depends on the nature of the lubricating grease studied. Table 2 shows the values of this characteristic temperature (Tc) and the slopes (S1 and S2) of the two regions below and above this temperature, which are related to the thermal susceptibility of the grease in the respective temperature windows. Commercial lithium grease C1 shows the lowest characteristic temperature and, also, the lowest value of the slope in the rst region, S1. As was previously mentioned, SAOS functions for this sample were almost constant at low temperature. On the contrary, lithium grease C2, having lower soap concentration and, also, lower values of SAOS functions than C1, shows a

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0 C 50 C 100 C 150 C 25 C 75 C 125 C 175 C
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Fig. 3 Frequency dependence of the storage and loss moduli for lubricating grease C1, at different temperatures
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Fig. 4 Frequency dependence of the storage and loss moduli for lubricating grease C4, at different temperatures
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sample C1 sample C2 sample C3 sample C4 linear fittings

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Fig. 2 AFM micrographs (window size 20 lm) for a model lubricating grease (M1), at different temperatures: a 25 C; b 75 C

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continuous decrease in Go N, being the slope in the whole temperature range studied similar to that found for lithium grease C1 in the second temperature region, S2. On the other hand, lubricating grease C3, which contains a lithium complex soap, displays a very similar behaviour to that found with sample C2 in a wide temperature window, although, in this case, a dramatic increase in the slope of the plateau modulus versus temperature is found at the highest temperatures studied (150175 C). Grease C3 also exhibits intermediate Go N values than those found for C1 and C2 samples, respectively, which can be attributed to an

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Fig. 5 Temperature dependence of the plateau modulus for the commercial lubricating greases studied (samples C1C4)

intermediate degree of bres agglomeration. Finally, as expected attending to its microstructure, calcium sulphonate lubricating grease C4 shows a quite different

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sample M1 sample M2 linear fittings

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ageing of a lithium lubricating grease, at 120 C, caused clumping and agglomeration of the thickener particles and, eventually, the bre network was fully destroyed. Although the inuence of temperature on grease microstructure, in a limited temperature range, can be deduced from the micrographs shown in Fig. 2, unfortunately, the AFM technique used in this work does not allow direct suitable morphological observations above the characteristic temperature previously discussed. 3.3 Rheo-Destruction and Recovery Tests

o GN (Pa)

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Fig. 6 Temperature dependence of the plateau modulus for the model lubricating greases studied (samples M1 and M2)

behaviour. Thus, Go N steadily decreases up to a temperature of around 100 C, and then a dramatic drop (almost one decade) in the plateau modulus is noticed. After Tc, this lubricating grease shows the lowest value of the slope S2. Figure 6 shows the evolution of Go N with temperature for two model greases thickened with a complex lithium soap. Concerning complex lithium grease M1, the slope below the characteristic temperature (130 C) is quite similar to that obtained for the commercial lubricating grease C3, having the same thickener. However, M1 thermal susceptibility, S2, is much lower above Tc, probably due to its higher soap concentration (16.1 vs. 13.6%). Including a polymeric additive in a grease formulation seems to affect, in a qualitative manner, the inuence of temperature on o Go N. Thus, GN slightly increases with temperature for grease M2 below Tc, temperature signicantly lower than that obtained for the polymer-free formulation. Above Tc, Go N values remain almost constant. The overall results presented are in general agreement et al. with those reported in the literature. Thus, Couronne [20] studied the inuence of thermal degradation on the rheological and physico-chemical characteristics of lithium lubricating greases, indicating that thermally aged greases showed lower values of their rheological functions, due to the degradation of the microstructural network into isolated bres. Similarly, Hurley and Cann [15], using scanning electron and atomic force microscopes, found that thermal

When an external stress beyond the limits of the linear viscoelasticity range is applied on a lubricating grease, a microstructural modication, which may be partially irreversible, is induced [21]. Consequently, grease non-linear viscoelastic and viscous functions, at constant shear strain/ rate, will decrease with shear time. The degree of irreversible structural breakdown is governed, among other factors, by temperature, elapsed time and shear strain/stress applied on the sample [21, 22]. Figure 7 shows results obtained from triple-step-shear stress tests in oscillatory shear carried out on selected lubricating grease samples. As can be observed, the complex modulus decreases when a

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stress programme 5-500-5 Pa 5-1000-5 Pa 5-2000-5 Pa

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Fig. 7 Evolution of the complex modulus with time, during triplestep-shear stress tests in oscillatory shear, for lubricating grease M1, at 70 C. (Step 1: shear stress inside the linear viscoelasticity region; Step 2: shear stress outside the linear viscoelasticity region; Step 1: shear stress inside the linear viscoelasticity region)

Table 2 Lubricating grease characteristic temperatures and plateau modulus versus temperature slopes of the two regions below and above the corresponding characteristic temperature Lubricating grease Characteristic temperature (C) Thermal susceptibility, S1 (1/C) Thermal susceptibility, S2 (1/C) C1 50 -1.6 9 10-4 -4.4 9 10-3 C2 -3.2 9 10-3 C3 149 -3.8 9 10-3 -1.8 9 10-2 C4 100 -2.4 9 10-2 -9.3 9 10-4 M1 130 -5.3 9 10-3 9.6 9 10-4 M2 75 1.5 9 10-3 -9.8 9 10-4

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469 Table 4 Rheological destruction and recovery percentages, during triple-step-shear-stress tests in oscillatory shear, for grease sample M2 Stress-step test (Pa) 1050010 Temperature (C) 25 70 10100010 110 25 70 110 10200010 25 70 110 Rheo-destruction (%) 78.8 93.0 99.2 98.1 99.4 99.9 99.3 99.9 99.9 Recovery (%) 91.9 76.7 70.5 66.1 56.1 37.2 57.3 14.1 8.5

stress outside the linear viscoelasticity range is applied, and subsequently recovers when a shear stress inside the linear region is, once again, restored. As expected, the complex modulus values are lower as the magnitude of the stress applied increases, as a consequence of a much larger structural breakdown. The percentage of lubricating grease rheo-destruction and reversible structural breakdown can be quantied as follows: %Rheo-destruction
G o G1 100 Go

1 2

G G 1 %Recovery 2 100 G G 1 o

being G o ; G1 and G2 the values of the complex modulus in the linear viscoelastic region (rst stepstress), after the application of a stress value outside the linear viscoelastic range (second stepstress), and after restoring the initial stress value (third stepstress), respectively. Rheo-destruction and recovery percentages are listed in Tables 3 and 4, as a function of temperature, for both model lubricating grease formulations, M1 and M2, respectively. As can be observed, in most cases, rheodestruction percentage is close to 100%, and increases with both stress magnitude and temperature. Moreover, the nal value of the complex modulus after the third step-stress (stress inside the linear viscoelasticity region) is always inferior to that shown by the original sample (complex modulus values after the rst step-stress), which indicates a certain degree of irreversible structural modication in the samples, enhanced, as expected, by increasing stress and temperature. Figure 8 shows the AFM image of sample M1 submitted to a stress programme of 10100010 Pa in a rheo-destruction test, which illustrates the effect of a relatively high shear stress on grease microstructure. As can be clearly observed, the new shear-induced microstructure consists of more agglomerated shorter bres and much larger hollow spaces among them, than those found in the

Fig. 8 AFM micrograph (window size 20 lm) for lubricating grease sample M1 submitted to stress programme of 10100010 Pa in a rheo-destruction test

Table 3 Rheological destruction and recovery percentages, during triple-step-shear-stress tests in oscillatory shear, for grease sample M1 Stress-step test (Pa) 1050010 Temperature (C) 25 70 110 10100010 25 70 110 10200010 25 70 110 Rheo-destruction (%) 89.5 99.6 99.8 99.5 100 99.9 100 100 100 Recovery (%) 73.1 31.1 66.0 53.4 43.7 27.3 22.8 19.1 7.6

non-perturbed microstructure (see Fig. 2a). Finally, the addition of a polymeric thickener to a model grease formulation does not generally modify rheo-destruction percentages, excepting for the lowest stress applied in the non-linear viscoelastic range (i.e. 500 Pa). On the contrary, this polymeric thickener usually improves recovery percentages (decreased irreversible rheo-destruction).

4 Conclusions The non-perturbed microstructure of different lubricating grease samples was analysed by means of the AFM technique. Grease microstructure mainly depends on the nature

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Tribol Lett (2011) 41:463470 5. Gow, G.: In: Mortier, R.M., Orszulik, S.T. (eds.) Chemistry and Technology of Lubricants, pp. 306319. Blackie Academic & Professional, London (1997) nchez, M.C., 6. Franco, J.M., Delgado, M.A., Valencia, C., Sa Gallegos, C.: Mixing rheometry for studying the manufacture of lubricating greases. Chem. Eng. Sci. 60, 24092418 (2005) nchez, M.C., Valencia, C., Franco, J.M., 7. Delgado, M.A., Sa Gallegos, C.: Relationship among microstructure, rheology and processing of a lithium lubricating grease. Chem. Eng. Res. Des. 83, 10851092 (2005) 8. US Army Corps of Engineers.: Engineering and Design-Lubricants and Hydraulic Fluids. US Army Corps of Engineers. Washington DC, 5.4 (1999) 9. Cann, P.M.: Starved grease lubrication of rolling contacts. Tribol. Trans. 42, 867873 (1999) 10. Madiedo, J.M., Franco, J.M., Valencia, C., Gallegos, C.: Modeling of the non-linear rheological behavior of a lubricating grease at low-shear rates. J. Tribol. 122, 590596 (2000) 11. Shuff, P.J., Clarke, L.J.: Imaging of lubricating oil insolubles by electron-microscopy. Tribol. Int. 24, 381387 (1991) nchez, M.C., Franco, J.M., 12. Delgado, M.A., Valencia, C., Sa Gallegos, C.: Inuence of soap concentration and oil viscosity on the rheology and microstructure of lubricating greases. Ind. Eng. Chem. Res. 45, 19021910 (2006) 13. Moreno, G., Valencia, C., de Paz, M.V., Franco, J.M., Gallegos, C.: Use of reactive diisocyanate-terminated polymers as rheology modiers of lubricating greases. Ind. Eng. Chem. Res. 45, 40014010 (2006) 14. Mansot, J.L., Terech, P., Martin, J.M.: Structural investigation of lubricating greases. Colloids Surf. 39, 321333 (1989) 15. Hurley, S., Cann, P.: Examination of grease structure by SEM and AFM techniques. NLGI Spokesm 65, 1726 (2001) 16. Moreno, G., Valencia, C., de Paz, M.V., Franco, J.M., Gallegos, C.: Rheology and microstructure of lithium lubricating greases modied with a reactive diisocyanate-terminated polymer: inuence of polymer addition protocol. Chem. Eng. Process. 47, 528538 (2008) 17. Moreno, G., Valencia, C., Franco, J.M., Gallegos, C., Diogo, A., Bordado, J.A.C.: Inuence of molecular weight and free NCO content on the rheological properties of lithium lubricating greases modied with NCO-terminated prepolymers. Eur. Polym. J. 44, 22622274 (2008) 18. Ferry, J.D.: Viscoelastic Properties of Polymers, 3rd edn. Wiley, New York (1980) 19. Baumgaertel, M., De Rosa, M.E., Machado, J., Masse, M., Winter, H.H.: The relaxation-time spectrum of nearly monodisperse polybutadiene melts. Rheol. Acta 31, 7582 (1992) , I., Vergne, P., Mazuyer, D., Truong-Dinh, N., Girodin, 20. Couronne D.: Effects of grease composition and structure on lm thickness in rolling contact. Tribol. Trans. 46, 3136 (2003) nchez, M.C., Franco, J.M., 21. Delgado, M.A., Valencia, C., Sa Gallegos, C.: Thermorheological behaviour of a lithium lubricating grease. Tribol. Lett. 23, 4754 (2006) 22. Krasnokutskaya, M.E., Nakaonechnaya, M.B., Sinitsyn, V.V., Prokopchuk, V.A., Mnishchenko, G.G.: Inuence of temperature on mechanical stability of lubricating greases. Chem. Technol. Fuels Oils 18, 7376 (1982)

of the thickener agent employed, and, also, on thickener concentration and viscosity of the base oil. In the case of lithium soap-based greases, the higher the soap content more entangled and agglomerated bres appear in grease microstructure. Lower density of bres and less agglomerated, yielding larger hollow spaces among them, are noticed as temperature increases. On the other hand, the microstructure of the complex calcium sulphonate soap-based grease consists of a ne dispersion of spherical, and agglomerated, particles. The values of the linear viscoelasticity moduli of the lubricating grease samples studied dramatically decrease, in most cases, above a characteristic temperature, which depends on the nature and/or concentration of the thickener used and therefore on the resulting microstructure. Higher values of the linear viscoelastic functions were found for lithium greases showing more agglomerated bres. Lubricating grease rheological thermal susceptibility was analysed by following the evolution of the plateau modulus with temperature. The complex calcium sulphonate soap-based grease displays a thermo-rheological behaviour quite different to those found for lithium greases, as a result of a very different microstructure. The thermo-mechanical reversibility of lubricating grease microstructure was studied by carrying out triple-step-shear stress tests in oscillatory shear (shear stresses inside and outside the linear viscoelasticity range), at different temperatures. The degree of lubricating grease non-reversible structural breakdown, which increases with temperature, depends on the shear stress applied above the linear viscoelasticity limits. Including a polymeric additive in a grease formulation signicantly dampens its non-reversible shearinduced structural breakdown.
Acknowledgments This work is part of the research project AVI2015 (CENIT programme, sponsored by CDTI-MCI, Spain). The authors gratefully acknowledge its nancial support.

References
1. Kuhn, E.: Zur Tribologie der Schmierfette. Verlag, Renningen (2009) 2. Sacchettini, M., Magnin, A., Piau, J.M., Pierrard, J.M.: Characterization of lubricating grease in transient viscometric ows. J. Theor. Appl. Mech. 4, 165199 (1985) 3. NLGI: NLGI Lubricating Greases Guide. National Lubricating Greases Institute, Kansas City, MO (1994) 4. Mas, R., Magnin, A.: Rheology of colloidal suspensions-case of lubricating greases. J. Rheol. 38, 889908 (1994)

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