International Journal of Applied Chemistry ISSN 0973-1792 Volume 5 Number 3 (2009) pp. 169179 Research India Publications http://www.ripublication.com/ijac.

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A Comparison of the Composition and Rheology of Trinidad Lake Asphalt and Trinidad Petroleum Bitumen
Rean Maharaj University of Trinidad and Tobago OMeara Industrial Estate, OMeara, Arima, Trinidad & Tobago, W. I. Corresponding author E-mail: rean.maharaj@utt.edu.tt

Abstract The composition and rheological properties of naturally occurring Trinidad Lake Asphalt (TLA) and Trinidad Petroleum Bitumen (TPB) have been investigated. The rheology study highlighted the superior rheological properties of TLA, (high G* and low phase angle). Fractionation of TLA revealed that its asphaltene content was significantly higher than TPB and other asphalt materials and the levels of asphaltenes, naphthalene aromatics and polar aromatics were similar. These observations coupled with TLAs higher concentration of key functional groups can account for its unique physical properties however the higher degree of unsaturation associated with TLA was contradictory. TLA contained 35.3% wt inorganic material which was characterized as kaolinitic in nature and is believed to play a key role in the chemistry of TLA that results in the materials superior properties. Keywords: Trinidad Lake Asphalt; rheological properties; fractionation; functional groups; kaolinitic

Introduction
Bitumen as defined by the British Standards Institution is a viscous liquid, or a solid, consisting essentially of hydrocarbons and their derivatives, which is soluble in trichloroethylene and is substantially non-volatile and softens gradually when heated. It is black or brown in colour and possesses waterproofing and adhesive properties. It is obtained by refinery processes from petroleum, and is also found as a natural deposit or as a component of naturally occurring asphalt, in which it is associated with mineral matter (British Standards Institution, 1989). The most famous natural

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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 a mixture of bitumen, water and very fine mineral matter. 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 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 and Elliott, 2008). Asphalt is thought of as a colloidal system similar to petroleum, the difference being that the lighter molecules have been removed from asphalt. In a colloidal chemistry context, three types of asphalts are recognized: sol type; sol-gel type; and gel type. In crude oil, asphaltenes are present as discrete or colloidally dispersed particles in the oily phase. As the various low boiling and intermediate petroleum oils are removed during the distillation process, the smaller particles of asphaltenes micelles mass together to form larger clusters. Therefore, the colloidal dispersions (asphalts) are made up of high molecular weight hydrocarbons (asphaltenes) in a dispersion medium of gas oil (low molecular weight saturated and aromatic hydrocarbons and resins (Pfeiffer, 1950). The chemical composition of asphalt determines the physical, flow (rheological) and colloidal properties, and durability characteristics of asphalt and its end uses. The relationship between the differences in the quality of asphalt (different compositions) from different sources and the resulting performance qualities is well known (Knotnerus, 1972; Griffen et al., 1959; Peters, 1975; Petersen, 1984; Andersen et al., 2001; Trejo et al., 2004; Oyenkunle, 2006; Oyenkunle, 2007). The purpose of this study is to analyze and compare the composition and rheological properties of the natural Trinidad Lake Asphalt (TLA) and Trinidad Refinery Bitumen (TPB) in an effort to better understand the unique qualities of TLA.

Experimental
Separation of Bitumen material into Organic and Inorganic Constituents This method follows the ASTM D2172-81 procedure. The sample material (250g) was extracted with 1500mL of trichloroethylene by agitating in a flask for 1 hour. After centrifugation the solution was washed through glass microfibre filters with a pore size of 0.8m. The impure inorganic component was collected, dried and weighed, then allowed to soak in 35% hydrogen peroxide (2 mL per gram of residue) for 2 hours with occasional stirring. This was then washed with dilute hydrochloric acid (2M), and the residue was dried and reweighed.

Fractionation of the Organic Component of Asphalt The ASTM D4124-84 method separates the pure bitumen into four fractions: saturates, naphthene aromatics, polar aromatics and asphaltenes. The method basically involved the removal of the n-heptane insoluble asphaltenes from the material followed by separation of the remaining petrolenes using a chromatographic column

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containing 500grams of calcined F-20 alumina into the three defined fractions according to ASTM D4124-84 method. Qualitative and Quantitative Analysis of Functional Groups The qualitative and quantitative analysis of the functional groups present in TLA and TPB was determined using Infrared Spectroscopy (Petersen, 1975; Petersen, 1986; Petersen et al. 1975). The prepared samples were analyzed using the Nicolet Avatar Fourier Transform Infra Red Spectrometer (FTIR) using the Attenuated Total Reflectance (ATR) sampling accessory. Analysis of the Inorganic Component contained in Trinidad Lake Asphalt. (a) Qualitative Analysis using X-Ray Diffraction (XRD) A Bruker AXS Model D5005 X-ray diffractometer (Physics Department, University of the West Indies, St. Augustine) operated at 40 kV and 20 Ma was used to characterize the mineral matter contained in the TLA samples. Samples for XRD were dusted onto microscope slides coated with petroleum jelly. The data was analyzed using the instruments Diffrac Plus software. (b) Quantitative Analysis of Inorganic Component of Trinidad Lake Asphalt using X-Ray Fluorescence (XRF). Approximately 15 gm of previously dried sample of the material was pressed using a Graseby Press for 20 seconds at 20 tons load/force. The sample was then analyzed using a ARL 8620 X-Ray Fluorescence (XRF) Spectrometer. (Trinidad Cement Limited Laboratory Facility, Claxton Bay, Trinidad). The data was analyzed using the WIN XRF Software feature of the instrument.

Rheology
Samples were analyzed using a Controlled Dynamic Shear Rheometer (ATS RheoSystems). The test geometries were plateplate (diameters 25mm and 1mm gap) Viscosity measurements were conducted in the temperature range 20C 140 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

TLA was initially separated using the ASTM D 2172-81. The inorganic and organic (bitumen) content was found to be 35.3% and 56.9% respectively which compared favourably with previous work done (Attwooll and Broome, 1962; Chattergoon et al., 1986) which found the inorganic content to be in the range of 35-36% and the bitumen content to be 55% -56%. The bitumen content obtained was slightly higher than expected. The slightly higher value can be attributed to the possibility of very fine inorganic particles (<0.8m) passing through the filter paper into the bitumen filtrate. The difference was attributed mainly to organic matter that was not

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bituminous in nature as well as some porphyrin compounds that may have remained undissolved by trichloroethylene (Chattergoon et al., 1986). The ASTM D 4124-86 Fractionation procedure was employed for determining asphalt composition based on fractionation of the bitumen into four generic components. The only adjustment to the method involved the use of a UV lamp to more accurately establish the cut-off points between the fractions as they elute. Its use stems from the fact that the naphthalene aromatic fraction was highly UV active unlike the polar aromatic fraction. Figure 1 shows the results obtained for the fractionation of TLA and TPB and compares these values with other asphalt materials. The data shows that the saturate content of all the materials were of a similar magnitude and all of the materials had a similar naphthalene aromatic to polar aromatic ratio. In TLA the asphaltene content is significantly higher than other asphalts and in fact the asphaltenes, naphthalene aromatics and polar aromatics existed at similar levels. The relative amount of the polar aromatic fraction was relatively lower than the other materials. Corbett (1970) offered an explanation on the relationship between the

Figure 1: Results of Fractionation of TLA and TPB.

physical properties of the asphalt and the four fractions obtained. The saturates and naphthalene aromatics exist as liquids and probably the soft and plasticizing components of the material and imparts fluidity within the material unlike the asphaltenes and the polar aromatics which are hard components and are plasticized by the saturates and the naphathalene aromatics. The polar aromatics impart ductility and the asphaltenes function as solution thickeners. He also concluded that the saturates

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and the naphthalene aromatics in conjunction with the asphaltenes produce the complex flow properties. In summary he concluded each fraction or it is logical to assume that the overall physical properties of one asphalt are thus dependent upon the combined effect of these fractions and the proportions in which they are present. The saturates and naphthalene aromatics have relatively low viscosities and softening points relative to the asphaltenes and the polar aromatics. They in conjunction with the asphaltenes improve the temperature susceptibility, the shear susceptibility and increase the flow resistance of the material. Polar aromatics in conjunction with asphaltenes are generally Newtonian and results in lower temperature susceptibility and flow resistance. The presence of the polar aromatics alone influences the ductility. High viscosity relative to penetration occurs due to the combination of naphthalene aromatics with the asphaltenes as all other combinations result in low viscosities. For this reason the asphalt is considered to be a system consisting of a liquid phase of saturates and naphthalene aromatics acting as plasticizers for the solid asphaltenes and polar aromatics. The unique combination of the four fractions of TLA has been associated with the materials low flow resistance (penetration value (0.4mm)) (Attwooll and Broome), high temperature and shear susceptability as well as its viscoelastic rheological properties (Chattergoon et al., 1986). Fourier Transform Infra Red Spectroscopy using Attenuated Total Reflectance (FTIR/ATR) was used for the qualitative and quantitative analysis of functional groups present in TLA and TPB (Petersen, 1975; Petersen, 1986; Petersen et al. 1975). The FTIR interferogram for TLA and TPB were very similar with regards to the presence of various functional groups within both materials. Figure 2 shows a FTIR/ATR interferogram of unmodified TLA.

Figure 2: FTIR/ATR Interferogram for an unmodified TLA.

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Identifiable peaks were observed for aliphatic CH2 and CH3 stretch, carbonyl and carboxyl stretch, pyrrolic NH stretch and sulphoxide stretch. In addition absorbance for free OH and phenolic OH stretches were observed. The weak absorbance bands observed at 3500 cm-1 is attributed to the stretching frequencies of N-H and O-H chemical bonds. The aromatic C-H stretching and methylene vibrations are observed at around 3000cm-1 and 2900cm-1 respectively. The peaks at 2730cm-1 are due to the C-H stretching for the aldehyde functional groups. The presence of this group is confirmed by the peaks around 1700 cm-1 which are caused by C=O stretching for aldehyde and ketone groups. Conjugated systems show C=C stretching around 1600 cm-1. The peak is more prominent for TLA than Trinidad Petroleum Bitumen and indicates a higher degree of unsaturation associated with the organic molecules in TLA compared to TPB. The infrared technique employed also allowed for the quantitative analysis of the compound types absorbing in the carbonyl region of the IR spectra including carboxylic acids, dicarboxylic acid anhydrides, 2- quinolone type. The absorption bands of these functional groups are masked by the intense band of ketones formed on oxidation. The basis of this method was to react the anhydrides and 2-quinilone types with specific chemical reagents which would as a result of the chemical reaction either shift or change the absorption band so that the bands can be isolated and measured. This analytical method was applied to Trinidad Lake Asphalt and Trinidad Petroleum bitumen and the concentration of the functional group types discussed determined and is shown in the Table 1 below.

Table 1: Compositional analysis of Functional groups in TLA and TPB. Free Acid TLA TPB 111.8 121.4 Ketone 487.6 346.2 Dicarboxylic Anhydride 124.6 135.5 2-Quinolone 13.92 11.39 Sulphoxide 296.44 265.50

The results show that TLA contains a greater proportion of these functional groups compared to TPB. Ketones are the major oxidation product formed in both the natural asphalt and bitumen samples. Carboxylic acid anhydrides, free acids and sulphoxides are not naturally occurring compounds but are artifacts of the oxidation process associated with the aging process. Relatively little 2-quinolone type compounds were present in the materials and unlike the other functional groups qualitatively measured 2-quinolone type compounds are naturally occurring and do not form as a result of oxidation processes. Figure 3 shows the corresponding XRD patterns obtained for the inorganic material extracted from TLA. The XRD pattern indicated the inorganic material removed from the TLA is kaolinitic with the presence of Quartz and Illite.

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Figure 3: X-Ray Diffraction Pattern for the Inorganic Fraction of TLA.

The results obtained from the X-Ray Fluorescence study of the inorganic content of TLA confirm the findings of the XRD analysis. Table 2 shows the quantitative chemical analysis of the TLA inorganic extract as well as that of two naturally occurring clays in Trinidad namely Valencia and Longdenville clays. The aluminium oxide content of the asphalt extract was significantly lower than that of the clays but it had the highest quartz content.

Table 2: Composition of Inorganic Fraction of TLA and two naturally occurring Trinidad clays. SiO2 (%) 76.04 68.99 67.86 Al2O3 (%) 6.43 10.85 15.85 Fe2O3 (%) 2.70 6.77 1.91 CaO (%) 6.34 6.32 6.29

TLA Inorganic Longendenville Clay Valencia Clay

Rheology is that part of science that is interested in the description of the mechanical properties of different materials under various deformation conditions when they simultaneously perform the capability to flow and accumulate recoverable deformation; in this case, the rheological properties of bituminous blends are measured using the DSR and variations in the complex modulus and phase angles were observed. The Complex modulus represents stiffness, whilst phase angle is

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normally used to demonstrate the viscoelastic response of bituminous materials. Higher values of phase angle indicate a tendency towards more viscous behaviour, whilst lower values indicate more elastic response. The elastic behaviour (lower phase angle) is generally associated with high stiffness and increased brittleness; while the viscous response (higher phase angle) reflects high ductility and low stiffness. Figures 4 and 5 show the variation of the phase angle and G* with frequency at different temperatures for TPB and TLA respectively. TLA exhibited lower phase angles and higher G* values than TPB over the temperature range. At 333K and at a frequency of 4.0 Hz, TPB was almost completely viscous (phase angle 88.4 degrees) whereas the phase angle for TLA was 54.2 degrees. At these conditions of temperature and frequency, G* for TLA was approximately 2000 times that of TPB. These observations are consistent with the superior physical properties of TLA as the material was significantly stiffer and more elastic material than TPB. As expected the phase angles for TPB and TLA increased and the values of G* decreased with increasing temperature. For example at a load frequency of 15.9Hz the phase angle for TPB increased from between 18 to 86.4 and the G* values decreased 36 times as the temperature moved from 293K to 333K whereas for TLA it increased from between 35.5 to 79.4 and the G* values decreased 50 times as the temperature increased from 333K to 383K. The materials moved from exhibiting an elastic response to an almost viscous liquid. The effect of the load frequency was more pronounced at lower temperatures and affected the phase angle and G* as the response tended to be more elastic and stiffer with increased load frequency.

Figure 4: Variation of G* and Phase angle with Frequency at different temperatures for Bitumen.

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Figure 5: Variation of G* and Phase angle with frequency at different temperatures for TLA.

Conclusion
The results of the rheology study clearly described the superior rheological properties of TLA compared to a rypical refinery bitumen as TPB. Its relatively high complex modulus, G*, and its relatively low phase angle can be attributed to its composition. The asphaltene content in TLA is significantly higher than TPB and other asphalt materials and the asphaltene to naphthalene aromatic to polar aromatic ratio was approximately equal to one. TLA had a higher concentration of key functional groups. These functional groups identified have the ability to form strong association complexes, and the extent to which these groups are formed on aging ultimately has a significant effect on the physical properties and durability of asphalt. It is these polar constituents of asphalt containing the heteroatoms that adhere to the interfacial surface of the aggregate. It is this asphalt-aggregate interaction that affects the adhesion of asphalt to aggregates and determines the strength between them and the ultimate strength of the material. On the other hand, the higher degree of unsaturation associated with TLA and the associated lower degree of molecular interactions within the material suggest however that the material should have inferior physical properties compared with TPB and other materials of similar chemical compositions. This contradiction clearly suggests that there exists another factor to account for its unique properties. TLA was found to contain 35.3% wt inorganic material which was further shown to be kaolinitic in nature. The author believes that the inorganic clay material plays a crucial role in the rheological properties of the TLA by influencing the colloidal characteristics of the material and/or demonstrating bridging characteristics at the asphalt-aggregate interface in pavements. These theories form the basis for ongoing research.

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Acknowledgements
The author wishes to thank the laboratory staff at Trinidad Cement Limited and Dr. J Knight of the Department of Physics, University of the West Indies for their assistance.

References
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