International Journal of Applied Chemistry ISSN 0973-1792 Volume 7 Number 1 (2011) pp. 18 Research India Publications http://www.ripublication.com/ijac.

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The Viscoelastic Properties of Trinidad Lake AsphaltUsed Engine Oil Blends

D. Singh Ackbarali1 and Rean Maharaj2 Centre of Process Engineering University of Trinidad and Tobago, OMeara Industrial Estate OMeara, Arima, Trinidad & Tobago, W. I. E-mail:1dimple.singh@utt.edu.tt, 2rean.maharaj@utt.edu.tt

Abstract In this study the influence of different amounts of Used Engine Oil (UEO) on the rheological properties of Trinidad Lake Asphalt (TLA) was studied. The results showed that UEO has the potential to modify the rheological properties of TLA and the abundance of UEO in Trinidad renders the material attractive for expanding or improving the use of TLA. The incremental addition of UEO, up to 30% UEO to TLA resulted in a general decrease in the values of dynamic shear modulus, G, the loss modulus, G as well as the complex modulus, G* (stiffness). This decrease can be associated with an increase solvency of the maltenes in TLA thus reducing the cross-linkages and resulting in a material of lower stiffness. The increasing addition of UEO to TLA resulted in a viscosity maximum (highest phase angle) for the blends containing 10-20% UEO and further additions resulted in a decrease in the viscosity, with a viscosity minimum (lowest phase angle) occurring at 25% UEO. Keywords: TLA, Used Engine Oil, rheological properties, complex modulus, phase angle.

Introduction
Asphalts and bitumen are both used together with mineral aggregates to construct roads. In fact asphalt is used as the surfacing material in over 96% of the pavements in the world (NCAT, 1999). The performance of these road pavements depend on the properties of the asphalt and the bitumen which are the only deformable components in the mixture. Both these systems have thermal susceptibilities and often experience low temperature cracking in cold environments as most bitumen have been shown to

D. Singh Ackbarali and Rean Maharaj

exhibit an apparent glass temperature near zero degrees Celsius and hence its physical behaviour moves from ductile to brittle, (Kortschot et al., 1984). The cracking phenomenon is attributed to thermal shrinkage stresses and further damage occurs due to weathering, moisture damage, frost heave, heavy traffic or embrittlement due to the chemical oxidation of functional groups within the asphalt. Engineers are required to also develop asphalt mixes that provide pavement stability during the high temperature periods to avoid creep and distortion of the material. These limitations can be overcome and the properties significantly modified by blending a polymeric material with asphalt and bitumen for improving the viscoelastic behavior while maintaining their own advantages, (Fawcett et al., 2002, Masson et al., 2001, Blanco et al., 1995, Wen et al., 2001, Lu et al., 2000, Singh et al., 2003, Maharaj et al., 2009a; 2009b). The inclusion of other polymer material such as commercial waxes into asphalt concrete mixtures have also been proven to have better resistance to rutting, (Edwards et al., 2006). Asphalt pavements that contain diesel contaminated soil have been known to resist deformation and require little maintenance after years of use, (Schoenberger et al., 1999). The inclusion of oil shale in asphalt concrete mixes has provided these mixes with higher ability to withstand deformation than the standard mix, (Katamine, 2000). Oil in bitumen and asphalt was found to have a detrimental effect with regards to the quality of the asphaltic material as it leads to reduced adhesiveness to the aggregates leading to stripping and ravelling (Villanueva et al, 2008 and Katamine 2000). However previous research (Maharaj, 2009) has demonstrated that the influence of additives on the rheological properties of bituminous materials cannot be easily generalized but is dependent on the composition of the bituminous materials. There exists a clear relationship between the differences in the quality of asphalt (different compositions) from different sources and the resulting performance qualities. Consequently bitumen and asphalt materials may interact with additives differently. This was confirmed by a recent study by Borhan et al., 2009, who evaluated the application of used cylinder oil in the preparation of asphalt concrete and its effect on the mechanical properties of the modified mixtures. The results confirmed that the effects of the used cylinder oil in asphalt concrete mixes is dependent on the quantity of used oil added to the blends and on the chemistry of the interaction between the used oil and the asphalt. Used oil is the single largest environmentally hazardous recyclable material (MARRC, 2001) and a spill of used oil as small as one litre can potentially contaminate a million litres of fresh water. Most developing countries struggle to properly manage their used engine oil due to inadequate collection services and limited utilization of recycling. This waste material imposes a significant economic cost for collection and disposal and results in long term liabilities. In many cases used motor engine oil is disposed of in drains, rivers and state lands. The most famous natural deposit of lake asphalt is the Trinidad Lake Asphalt (TLA), which occurs naturally in the form of a 100 acre lake located on the island of Trinidad in the West Indies. The material basically comprises of a unique mixture of bitumen and mineral matter which was found to be kaolinitic in nature (Maharaj, 2009). TLA is well known for its consistent properties, stability and durability, and is widely used for bridge and airport applications where high stability surfaces are

The Viscoelastic Properties of Trinidad Lake

required. TLA is a well established commercial product and typically, a 50:50 blend of TLA and bitumen is adopted in the production of TLA modified mastic asphalt, (Widyatmoko, 2008). This study intends to investigate the influence of Used Engine Oil (UEO) on the rheological properties of TLA and hence evaluate its potential reuse in the preparation of asphalt concrete.

Experimental
Materials and preparation of samples A gallon of Used Engine Oil (UEO) was obtained from a service station and blended in Trinidad Lake Asphalt (TLA) in proportions up to 30%. Aluminium cans of approximately 500cm3 were filled with 250260 g of asphalt and put in a thermoelectric heater Thermo Scientific Precision (Model 6555) where the temperature was raised to 200 C. A digital IKA (Model RW20D) high shear mixer was then immersed in the can and set to 3000 rpm. The UEO was added gradually while the system was kept at a temperature of 2001 C. Each TLA-UEO blend was formed from 0, 5, 10, 15, 20, 25 and 30% of UEO by weight. At the end of mixing, each blend was split into different cans and transferred to an oven at 200 C, under static conditions and in an oxygen-free environment. After the desired period of curing, the cans were taken out and the molten mixtures were then cast into a ring stamp with 25 mm diameter and 1 mm thickness for subsequent rheological testing. Before testing, the samples were cooled at room temperature and stored in a Fisher Isotemp freezer at 20 C. Rheological Measurements The rheological characterization of the various asphalt blends were studied using an oscillatory Dynamic Shear Rheometer (ATS RheoSystems) operated within the linear domain under strain control. The test geometries were plateplate (diameters 25mm and 1mm gap). Viscosity measurements were conducted in the temperature range 40 C 120 C and frequency range was 0.1 15.91 Hz. The maximum strain was kept below the limit of the linear viscoelastic region.

Results and Discussion

DSR rheological properties of Trinidad asphalt materials at temperatures from high to intermediate values are an important consideration in understanding pavement distress characteristics such as pavement deformation (including rutting and shearing) (Lavin, 2003). Deformation in asphalt material consists of three types, instant elastic recoverable strain, delayed elastic recoverable strain, and permanent non-recoverable strain (or viscous flow). Most critical among these is viscous flow which results in permanent deformation in traffic asphalt pavement due to repeated loading forces. The complex shear modulus, G*, represents the total resistance of the asphalt/bitumen sample to deformation caused by repeated pulses of small angle oscillations by the plates of the

D. Singh Ackbarali and Rean Maharaj

DSR. The phase angle or the phase lag () is a measure of the degree of the elasticity of the material. A totally viscous material has a phase difference of between shear stress and strain curves of frequency of 90, an elastic material would have no phase difference. High values of G* and are desirable for a material with rutting resistance and low values of G* and for fatigue cracking resistance (Asphalt Institution, 1997). G is the elastic or storage modulus and G is the viscous or loss modulus. The physical interpretation of the two moduli is as follows: The elastic modulus (also known as the storage modulus since elastic behaviour implies the storage of deformational energy) G is the in-phase component of the stress and is concerned with elastic nature of the material; The viscous modulus G (also known as the loss modulus since viscous deformation results in the dissipation of energy) is the out-ofphase component of the stress and characterizes the viscous nature of the material. Figure 1 shows the variation of the dynamic shear storage modulus, (G) and the loss modulus (G) with the frequency () at 60 C for TLA and TLA-UEO blends containing 0%, 10% and 30% UEO. The graph shows that the values of G and G were higher in pure TLA than TLA-UEO blends. At a shear frequency of 10Hz the G and G values were ten times higher for TLA than the TLA-UEO blend containing 10% UEO. The crossover shear frequency for TLA was observed between 5 and 10Hz compared to a value of < 1Hz for the TLA-UEO blend containing 10% UEO. From a theoretical perspective for liquid-like fluids, the storage modulus is much lower than the loss modulus; for solid-like fluids G ' ( ) >> G '' ( ) and G ' ( ) is nearly independent of frequency. Real complex fluids often show behaviour intermediate between the solid-like and liquid-like fluids. At low frequency the material is liquidlike, i.e. G<<G, whereas at high frequency G > G. At the cross-over point of Gand G there is a transition from liquid-like to solid-like fluids. For a blend, a corresponding crossover is seen in the steady state shear viscosity curve from a plateau liquid-like to a shear thinning solid-like region. The crossover shear rate c in steady state shearing is numerically equal to crossover frequency c in oscillatory shearing, both c and c are approximately equal to the inverse of the fluids characteristic relaxation time, c1 c1 These observations is consistent with work by Raghavan and Kaler (2001) and Cates (1990) indicating that this observation can be associated with a decrease the relaxation times tR decreased and can be associated with a decrease in the average worm length. The average worm length is a thermodynamic property and affects the dynamics of micellar stress relaxation. The relaxation time is determined as the net of the competition between the micellar breaking (tB) and chain repetition (trep) processes, a Maxwellian behaviour. Figure 2 shows the effect of the % composition of UEO on the rheological properties of TLA at a fixed frequency of 0.4Hz and a temperature of 313K. The trends in the rheological parameters obtained indicated an unusual function of % composition of UEO. Values of G and G* slightly decreased and G showed a slight increase with the addition of 5% UEO added. This was followed by a pronounced decrease in G, G and G* with the addition of up to 10% UEO followed by an incremental increase between 15% and 20% UEO after which the parameters

The Viscoelastic Properties of Trinidad Lake

dropped to a minima occurring at approximately 26% UEO. The values of G and G at the minima are approximately 1000 times smaller than those obtained for pure TLA.

Figure 1: Variation of the dynamic shear storage modulus, (G) and the loss modulus (G) with the frequency () at 60 C for TLA and TLA-UEO blends.

Figure 2: Variation of the dynamic shear storage modulus (G), complex modulus (G*) and the loss modulus (G) with % TLA-UEO at 0.4Hz and 313K.

Previous work done by Borhan et al. (2009) and Raghavan and Kaler (2001) recorded similar observations and suggested that the observations can be attributed to the composition of the blends. Asphaltic materials consist of asphaltenes that are complex in nature and are dispersed in low molecular weight hydrocarbon, known as maltenes. Maltenes maintain the stability of asphaltene dispersion and act as a solvent for any material added. Thus the addition of the UEO to the asphalt reduced the solvency of the maltenes; softened the crosslinks that are required to be strong and resulted in the Asphalt-UEO reduced ability to withstand elongation. Figure 3 shows the variation of G* with frequency for the various TLA-UEO blends. The stiffness (G*) increased as the load frequency increased for all the TLAUEO blends. For example increasing the load frequency from 0.1Hz to 15.9Hz of a TLA blend containing 20% UEO resulted in an increase of 34.4 times in the G*.

D. Singh Ackbarali and Rean Maharaj

Figure 3: The effect of increasing UEO% on Complex Modulus of the TLA Blend for different frequencies at 313K.

The effect of the addition of UEO to TLA on the phase angle produced interesting results. The viscosity of the material increased (higher phase angle) with % UEO until a maxima at 20%. Further addition of resulted in a viscousity minima at 25% UEO.

Figure 4: The effect of increasing UEO% on Phase Angle of the TLA Blend for different frequencies at 313C.

Conclusion
The addition of UEO in TLA resulted in changes in the rheological properties of the materials and confirmed previous findings that the rheology of asphaltic materials is composition dependent. Values of the dynamic shear storage modulus, (G) and the loss modulus, (G) in TLA and TLA blends decreased with increasing percentage of UEO. The observations can be attributed to a decrease in the solvency of the maltenes which results in the blends reduced ability to withstand elongation. This was evident as the addition of UEO to TLA resulted in a decrease in the values of G* and hence the stiffness of the blend. G* of each blend also decreased when load frequency and temperature was decreased. The effect of the addition of UEO to TLA on the phase angle resulted in an increase in the viscosity of the material

The Viscoelastic Properties of Trinidad Lake

(higher phase angle) which plateaued between 10-20% UEO. Further addition of UEO resulted in a decrease in the viscoelastic response with a minima observation at 25% UEO. Variations of the rheological properties reflect variations in the mechanical properties of the various blends. Blends with relatively lower G* and higher phase angles are more ductile and flexible resulting in a more crack resistant material whereas blends with relatively higher G* and lower phase angles are more elastic and deformation resistant. The results therefore confirm that from a rheological perspective UEO has the potential to be used as a modifier of TLA and renders this abundant waste material environmentally attractive for expanding the use of TLA.

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