Fuel 87 (2008) 30183023

Contents lists available at ScienceDirect

Fuel
journal homepage: www.fuelrst.com

Asphalt rheology evolution through thermo-oxidation (aging) in a rheo-reactor

X.A. Vargas a,c,*,1, N. Afanasjeva b,2, M. lvarez c,3, P.H. Marchal a,1, L. Choplin a,1
a b c

GEMICO-ENSIC, 1, Rue Grandville, BP 20451, F-54001 Nancy cedex, France Departamento de Qumica, Universidad del Valle, Calle 13 No. 100-00, Cali, Colombia GIAS (Grupo de Investigacin en Asfaltos), Universidad Industrial de Santander, Carrera 27 Calle 9, Bucaramanga, Colombia

a r t i c l e

i n f o

a b s t r a c t
In this research we present the results of thermo-oxidation process of Colombian asphalt in a rheo-reactor. The viscosity and the particle size distribution of asphaltenes aggregates increased with the temperature of the thermo-oxidation process, demonstrating changes of the microstructure of the asphalt. The evolution of the elastic and viscous modules for aging asphalt in the rheo-reactor in the range of frequency examinated, they showed a relation of the type: G00 (x) $ G0 (x) $ xn. This behavior with G00 > G0 (weak gel structure) is related to a greater connectivity of molecules and conrms the changes generated by aging process. 2008 Elsevier Ltd. All rights reserved.

Article history: Received 20 August 2007 Received in revised form 7 December 2007 Accepted 28 April 2008 Available online 23 May 2008 Keywords: Rheo-reactor Thermo-oxidation Aging asphalt

1. Introduction Asphalt, a by-product of petroleum crude oils vacuum distillation, is essentially used as a binder with mineral aggregates in order to obtain asphalt concretes for uses in paving applications. Generally, asphalt is an extremely complex mixture of more than one thousand of different types of hydrocarbons, linear or cyclic, parafnic, aromatic or naphtenic, saturated or unsaturated, with or without functional groups or heteroatoms, such as oxygen, nitrogen and sulfur. The molecular weights of these various constituents uctuate between 600 and 2000 Daltons. Asphalt is therefore considered as a colloidal dispersion, with large molecular aggregates called asphaltenes forming the disperse phase (with an average size of 100 nm) and the saturated parafns, aromatic oils and resins constitute the continuous (liquid) phase, also called the maltenes [1]. The macroscopic properties of this dispersion are largely dependent on the temperature and on the volume fraction of asphaltenes [2,3]. At low volume fractions and temperature around 60 C and above, the viscous behavior is essentially Newtonian and the viscosity increases with the volume fraction of solute particles according to a RoscoeBrinkman type equation [1,4]

g0 g0;m 1

ueff um

2:5

* Corresponding author. Address: GIAS (Grupo de Investigacin en Asfaltos), Universidad Industrial de Santander, Carrera 27 Calle 9, Bucaramanga, Colombia. Tel.: +57 7 6344746x2533; fax: +57 7 6350540. E-mail address: xiomarandrea@yahoo.es (X.A. Vargas). 1 Tel.: +33 0 383175010; fax: +33 0 383175319. 2 Tel.: +57 2 3212100 (A.A) 25360. 3 Tel.: +57 7 6344746x2533; fax: +57 7 6350540. 0016-2361/$ - see front matter 2008 Elsevier Ltd. All rights reserved. doi:10.1016/j.fuel.2008.04.026

where um is the maximum packing volume fraction of asphaltenes, g0,m is the viscosity of the maltene continuous phase and ueff, the effective volume fraction of peptized asphaltenes (the asphaltene core is surrounded by a solvation shell of resins). Above 60 C, the solute particles freely diffuse within the sheared asphalt, and there is a competition between Brownian motion and hydrodynamic forces, resulting in a Newtonian behavior. Below 60 C, the solute particles motion is only induced by the applied shear and the Brownian motion contribution vanishes. This results in a drastic change in the rheological behavior of asphalts with the appearance of viscoelastic effects. In addition, due to the fact that the parameters of Eq. (1) are temperature-dependent, the time-temperature superposition principle no longer applies. This change of rheological behavior of asphalts at temperatures around 60 C has been called the a-relaxation [2]. Asphalts appear to be extremely sensitive to oxidation; as a consequence, different testing procedures have been developed to simulate the aging process. The most used testing procedures are known as the thin lm oven test (TFOT, ASTM D 1754) and the rolling thin lm oven test (RTFOT, ASTM D 2872). Both testing procedures operate at 163 C. In both cases, it is however hard to believe that the testing procedures are able to simulate real mixing conditions [57]. In this paper, we will examine how the rheological properties of asphalts can be modied by thermo-oxidation using a rheo-reactor, in other words a mini-reactor installed on a rheometer, an array in which it will be possible to reproduce real mixing conditions (macromixing and constant renewal of the free surface),

X.A. Vargas et al. / Fuel 87 (2008) 30183023

3019

and at the same time to expose the free surface of the asphalt contained is this reactor to a constant gas (oxygen, oxygen enriched air, or air) ow rate under given temperature conditions, with the purpose of direct measurement in situ and the deepening in the knowledge of the aging process in asphalts. The rheological properties of the thermo-oxidized asphalts will then be compared with those of both a specic asphalt material and the same asphalt having been submitted to the standard TFOT testing procedure. 2. Experimental The asphalt used in this study comes from a Colombian crude oil produced at the Complejo Industrial de Barrancabermeja renery and will be denominated CIB. It has a penetration of 70/ 90 (ASTM D 5-86). This asphalt, submitted to an aging procedure according to the ASTM D 1754 standard (TFOT), will be denominated CIB-TFOT. The same asphalt CIB was also submitted to thermo-oxidative conditions under real mixing conditions in a rheo-reactor (Fig. 1). We used oxygen to assure oxidative atmosphere in the rheo-reactor. The asphalt was exposed to the oxygen ow rate on the top part of the vessel since the good top-to-bottom axial circulation of the helical ribbon impeller ensures a permanent renewal of the free surface of the asphalt. In all the cases, the oxygen ow rate was constant (1000 ml/min). The temperatures used were 100 C, 160 C, 200 C and 250 C. The thermo-oxidized asphalts were denominated CIB-100, CIB-160, CIB-200 and CIB-250 respectively. The choice of 160 C was dictated by the fact that this temperature is close to the temperature of the TFOT test and also to the temperatures in real mixing and handling operations of asphalts. The two other temperatures were chosen for evaluating the effect of particularly high temperature conditions. The rheo-reactor (Fig. 1) consists of a cylindrical vessel (43 mm of diameter and 75 ml of effective volume) equipped with a double helical ribbon impeller (40 mm of diameter and 45 mm of height). This impeller type is a close-clearance impeller, known to be one of the most appropriate choice for macromixing highly viscous materials. This impeller conguration allows a quite good top-to-bottom axial circulation of the material and therefore ensures a permanent renewal of the free surface in the rheo-reactor. This

vessel-impeller combination is installed on a RDA II rheometer (Rheometric Scientic, now TA Instruments, USA). The vessel is connected to the motor of the rheometer and the impeller to the stress transducer. A analytical method, based on a Couette analogy, allows to quantitatively analyze torque-rotational speed data in order to extract absolute rheological data in this non-conventional geometry, for instance (effective or apparent) viscous rheograms as well as mechanical spectra [810]. The rheo-reactor is equipped with forced convection-oven and temperature control is ensured. The thermocouple located in the rheo-reactor allows to measure the temperature of the asphalt (thermo-oxidation temperature). The rheo-reactor was instrumented with an electronic mass ow controller (5850 E series, Brooks Instruments) for controlling the oxygen ow rate (1000 ml/min) through the forced convection-oven of the RDA II rheometer. The thermo-oxidation protocol was as follows: 75 ml of asphalt, previously heated at 110 C, was introduced in the rheo-reactor, and then, the temperature was progressively increased up to the temperature of thermo-oxidation. Then, a given rotational speed (of the vessel) was xed, corresponding to an effective shear rate and the gas ow rate through the forced convection-oven was started for a period of time of the order of 7000 s. During the thermo-oxidation process under controlled macromixing conditions, the effective viscosity was recorded. After this thermo-oxidation process, the temperature was slowly reduced to a temperature between 40 and 80 C. Then, a complete rheological characterization was undertaken in the rheo-reactor: viscous rheogram and mechanical spectrum in the linear viscoelastic domain previously determined with a strain sweep at frequency of 1 rad/s. The asphaltenes were extracted from the asphalt CIB using 100 ml n-heptane (n-C7) per gram added to the asphalt. The mixture was subjected to digestion with stirring for 1 h and then ltered with a lter paper of 0.02 lm pore. The asphaltenes remaining in the lter paper were continually washed with n-C7 until the ltrate became colorless. Additionally, particle size distribution measurements of asphaltenes precipitated in n-heptane solvent, of original CIB asphalt and the CIB-250 asphalt thermooxidized in the rheo-reactor was determined in an equipment of laser diffraction technology (Mastersizer 2000, Malvern

Fig. 1. Rheo-reactor for asphalt thermo-oxidation.

3020

X.A. Vargas et al. / Fuel 87 (2008) 30183023

Instruments), with an interval of measurement from 0.02 lm to 2000 lm. The measures were made at room temperature. The used dispersing means were ethanol with a refractive index of 1.46. The density and the refractive index of the asphaltenes were 1200 kg/ m3 and 1.70 respectively. 3. Results and discussion In Fig. 2, we report the mechanical spectrum of the original CIB asphalt obtained at 60 C, in the linear viscoelastic domain, in two different geometries: parallel plates with a gap of 1 mm and the double helical ribbon-cylindrical vessel conguration of the rheoreactor, showing a very good agreement, in other words, the Couette analogy is successfully veried. At this temperature and in this range of frequency, we observe that the terminal region (G0 $ x2 and G00 $ x) is reached, and that a Newtonian viscous behavior is exhibited by the original CIB asphalt. This is also conrmed by a Black diagram representation, illustrated in Fig. 3, (Black diagram also demonstrates that there are no inertial effects with the double helical ribbon-cylindrical vessel conguration). For 60 C and 70 C, the phase angle is very close to 90. On the other hand, for temperature lower than 60 C, a signicant reduction of the phase angle indicates that the asphalt exhibits a viscoelastic behavior in the same frequency range and that the a-relaxation occurs at a temperature around 60 C, in agreement with all reported literature information. The onset of viscoelastic behavior is hardly seen in the classical viscous rheogram, even at 40 C, as illustrated in the Fig. 4, where we reported viscosity versus shear stress data. We can observe at this temperature a slight shear-thinning behavior. In Fig. 5, we report the follow-up of the relative effective viscosity during the thermo-oxidation process in the rheo-reactor, when oxygen is used and the effective shear rate is 300 s1. No evolution is observed at 100 C, whereas a signicant increase in viscosity (more than 30% over the rst 7000 s) is observed at 160 C. The kinetics of the thermo-oxidation process in the rheo-reactor is inuenced by the mixing conditions, in other words by the imposed value of the rotational speed of the vessel, which corresponds to an effective shear rate. Fig. 6 illustrates the differences in the viscous behavior of the asphalts, after a thermo-oxidation process at different temperatures and macromixing conditions (through different values of the effective shear rate) during a period of time of the order of 7000 s. All the data have been obtained after the temperature has been reduced to a value of 60 C, in the rheo-reactor. When we
10 4
G' G" Double helical ribbon Parallel plates Double helical ribbon Parallel plates

90
40C 50C

88

60C 70C

PhaseAngle []

86

90.0 88.75 87.5

Phase Angle( )

84

86.25

Double helical ribbon Parallel plates

60C

82

[]

85.0

83.75 82.5 81.25 80.0 10 0

10 1 10 2 10 3 10 4

G* [Pa]

80 10

100

1000

10000

100000

1000000

G* [Pa]
Fig. 3. Black diagrams (phase angle versus complex modulus G*) of initial CIB asphalt for different temperatures.

10000
100C 80C 70C 60C 50C 40C

1000

Viscosity [Pa-s]

100

10

1 1 10 100 1000 10000

Stress [Pa]
Fig. 4. Viscous rheograms (viscosity versus shear stress) of initial CIB asphalt at different temperatures.

1.4 1.35 1.3

CIB-160 oxygen and 300 s-1 CIB-100 oxygen and 300 s-1

10 3

10 2

1.25

10

Viscosity

G' ( ) [Pa] G" ( ) [Pa]

1.2 1.15 1.1 1.05 1 0.95

10 0

10 -1

10 -1

10 0

10 1

Freq [rad/s]

10 10 2

-2

0.9 0

1000

2000

3000

4000

5000

6000

7000

8000

Time [s]
Fig. 5. Comparison between thermo-oxidation kinetics of CIB asphalt in the rheoreactor (effective shear rate: 300 s1, and the gas used was pure oxygen) at two temperatures: 100 C and 160 C.

Fig. 2. Comparison of mechanical spectra of initial CIB asphalt at 60 C obtained with a parallel plates geometry and in the rheo-reactor equipped with a double helical ribbon impeller.

X.A. Vargas et al. / Fuel 87 (2008) 30183023

3021

10000
CIB-Initial CIB-TFOT CIB-160 30 s-1 CIB-160 300 s-1 CIB-200 CIB-250

1000

100

10

100

1000

10000

Stress [Pa]
Fig. 6. Viscous rheogram (viscosity versus shear stress) of initial CIB asphalt as compared with those corresponding to CIB-TFOT and CIB thermo-oxidized in different conditions.

compare the viscous rheogram for CIB-160, it is clear that the thermo-oxidation process at the higher value of the effective shear rate induces an increase in the viscosity of the material. Obviously, there is a better renewal of the free surface in the rheo-reactor when the effective shear rate during the process is increased. Also, in this Fig. 6, we can compare at a temperature of 60 C the viscous behavior of the asphalt submitted to a TFOT (standard) aging procedure. There is a clear difference in the efciency of the thermooxidation process between the TFOT procedure and the one which makes use of the rheo-reactor, the difference in viscosity being close to one order of magnitude. The difference in viscosity is even more pronounced when the temperature during the thermo-oxidation process is increased. The data for CIB-200 and CIB-250 correspond to a value of the effective shear rate in the rheo-reactor equal to 300 s1, therefore to relatively efcient macromixing conditions. We have calculated the activation energy from values of viscosity at temperatures of 40, 50, 60, 70, 80 and 100 C (Fig. 7), for the asphalts after the TFOT testing procedure and the thermo-oxidation process in the rheo-reactor and the data are reported in Table 1. The concomitant increases in both the viscosity and the activation energy with the temperature of the thermo-oxidation process
14 12 10
CIB- initial CIB-TFOT CIB-160 CIB-200 CIB-250

ln Viscosity (Pa.s)

8 6 4 2 0 0.0026

reect some changes at the level of the microstructure of the asphalt. It is known that the thermo-oxidation process or aging phenomenon generates an increase in the effective volume fraction of the asphaltenes, in other words, the solvation shell of resins surrounding the asphaltene cores increases in size and generates a more compact structure. The increase in the content of asphaltenes in percentage by weight (%w/w) of the samples of asphalt: CIB-250, CIB-160, CIBTFOT with respect to CIB-initial (8% w/w) was: 16%, 12.3% and 9% respectively, which explains the observed behavior and demonstrates the inuence of aging on the chemical composition of asphalt and consequently in its rheological behavior. It is noted that the reported content of asphaltenes of CIB-250 is twice the content in the CIB-initial and there is a marked difference in the asphaltenes content of CIB-160 and CIB-TFOT. Additionally, the particle size distribution of asphaltene aggregates after precipitation in n-heptane solvent between the original CIB asphalt and the CIB asphalt thermo-oxidized in the rheo-reactor at 250 C is shown in Fig. 8. The increase in the content of asphaltenes and the shift of the size distribution towards higher size values strengthens the idea of an increase of the effective volume fraction of the asphaltenes due to the aging. The average value of the Sauter diameter (D32) of the aggregates increases from 30 to 60 lm approximately. This is sufcient enough to signicantly enhance the effective volume fraction, and therefore the viscosity. The precipitation of asphaltenes with n-heptane can remove non-polar molecules of high molecular weight contained in asphaltenes and this also inuences the rheological behavior, but precipitates the components that are highly polar and of low solubility. However, this procedure is useful for comparative purposes because it makes evident the increase in polar compounds due to the aging of the asphalt, which promote strong molecular interactions that inuence the rheological behavior of the asphalt, and increase the molecular size distribution of the asphaltenes. The results of the study of thermo-oxidation under natural conditions in tropical climate, showed a similar behavior for the aged CIB asphalt during 36 months [11]. The asphaltenes content precipitated in n-heptane solvent from CIB asphalt, increased in 13.04% and 19.6% (%w/w) after 24 and 36 months, respectively, with respect to CIB-initial (7.7% w/w). Furthermore, the experimental results of size distribution of asphaltenes from aged CIB asphalt in a rheo-reactor (Fig. 8) are consistent with the results of X-ray diffraction of the same aged CIB asphalt under natural weather conditions, and were used for the calculation of crystallite parameters (proposed by Yen et al. [12]) of the obtained asphaltenes, on the basis of crystallite parameters. The average diameter of the aromatic sheets (La) changed from 17.37 to 26.77 , the layer distance between aromatics sheets (dm) changed from 3.63 to 3.56 , the distance between the saturated portions of the molecules (dc), changed from 4.7 to 5.14 , and the number of aromatic sheets in a stacked cluster (M) changed from 4.77 to 7.52 after 36 months of aging [11]. These results suggest that the aging phenomenon promotes changes in the structure of asphalt that are reected in the rheological behavior and the aging procedure in a rheo-reactor can adequately represents the aging of asphalt under natural conditions.

Viscosity [Pa-s]

Table 1 Activation energy for initial CIB and thermo-oxidized CIB asphalts ASPHALT Activation energy (kJ/mol) 117 121 133 139 145

0.0027

0.0028

0.0029

0.003

0.0031

0.0032

0.0033

1/ T (1/K)
Fig. 7. Dependency of the temperature of the viscosity for initial CIB asphalt, CIBTFOT and CIB asphalts thermo-oxidized in the rheo-reactor at 160 C, 200 C and 250 C.

CIB- initial CIB-TFOT CIB-160 CIB-200 CIB-250

3022

X.A. Vargas et al. / Fuel 87 (2008) 30183023

9
Asphaltene CIB-initial

10 6
Asphaltene CIB-250 CIB-initial CIB-TFOT CIB-160 CIB-200 CIB-250

8 7 6

10 5

Volume (%)

5 4 3 2 1 0 1

10 4

G' ( ) [Pa]

10 3

10 2

10

100

1000

10000

Particle size (m)

Fig. 8. Comparison of particle size distribution for aggregates of asphaltene (in n-heptane) between initial CIB asphalt and thermo-oxidized CIB-250 asphalt.

10 -1

10 0

10 1

10 2

10 1

Freq [rad/s]
Fig. 10. Elastic modulus as a function of frequency at 40 C for initial CIB asphalt and several CIB asphalts, thermo-oxidized in different conditions.

The structural changes induced by the thermo-oxidation process are better illustrated through the Black diagram representation shown in Fig. 9, in which we compare the initial CIB asphalt and the same asphalt thermo-oxidized at 250 C in the rheo-reactor. It can be deduced from these results, that the a-relaxation is shifted towards higher temperatures for aged asphalts, for instance around 80 C in the CIB-250 case. The change of the curvature for high values of the complex modulus G* can suggest the existence of several mechanisms of relaxation and structural changes in the material probably due to the aging. Therefore, it is necessary to study in depth this aspect. The evolution of the elastic modulus G0 is illustrated in Fig. 10, where all data have been obtained at 40 C. The TFOT testing procedure does not modify signicantly the G0 dependence with frequency as compared with the initial CIB asphalt, contrarily to the aging procedure realized in the rheo-reactor at equivalent temperature conditions (160 C). For CIB-200 and CIB-250 asphalts, in the range of frequency examined, G00 x $ G0 $ x0.83 y G00 x $ G0 $ x0.81, respectively (Fig. 11), similar behaviors have been reported for modied asphalts by other authors [13,14]. This behavior with G00 > G0 in this frequency window, is equivalent to that of a weak gel structure and conrms the changes in structure generated by the thermo-oxidation process. The gel-type behaviour of aged asphalt is related to a greater connectivity of molecules of the material as result of the
90

10 7
G'

CIB-200 CIB-250
G"

CIB-200 CIB-250

10 6

G' ( ) [Pa]
10 5

G" ( ) [Pa]
10 4 10 3

10 -1

10 0

10 1

10 2

Freq [rad/s]
Fig. 11. Comparison of mechanical spectra at 40 C for CIB asphalts thermo-oxidized in the rheo-reactor at 200 C and 250 C.

1.8

80C
1.6 1.4
85
CIB-Initial 40C CIB-Initial 50C CIB-Initial 60C CIB-Initial 70C CIB-250 40C CIB-250 50C CIB-250 60C CIB-250 70C CIB-250 80C

70C

60C

50C

40C

1.2 1

PhaseAngle []

n
0.8 0.6 0.4 0.2 0
CIB initial CIB TFOT CIB-160 Asphalt CIB-200 CIB-250

80

75

70

65 10

100

1000

10000

100000

1000000

10000000

Fig. 12. Comparison of the values of the n-exponent at different temperatures for the asphalt: CIB-initial, CIB-TFOT, CIB-160, CIB-200 and CIB-250.

G* [Pa]
Fig. 9. Comparison between black diagrams for initial CIB asphalt and thermooxidation CIB-250 asphalt at different temperatures.

increase of the molecular interactions, but not strictly with a transition of liquid state to solid.

X.A. Vargas et al. / Fuel 87 (2008) 30183023

3023

Consequently, the viscoelastic behaviour of CIB asphalt can be represented by a power law model in the experimental frequency window (G0 (x) $ xn, G00 (x) $ x1). The effect of temperature in the exponent n is presented in Fig. 12. The behaviour suggests that the thermo-oxidation process induces a structuring effect of asphalt, more pronounced at higher temperatures, which is consistent with an increase in the polar compounds content.

Acknowledgements Financial support provided by Instituto Colombiano para el Desarrollo de la Ciencia y la Tecnologa Francisco Jos de Caldas (Colciencias, Colombia) and the French Embassy in Colombia through the BONPLAN program is gratefully acknowledged. References

4. Conclusions The thermo-oxidation process induces structural changes in the asphalt, at the level of the asphaltene aggregates and their solvation shell, as evidenced by the changes in viscous rheograms and mechanical spectra on one hand, and, on the other hand, in the size distribution of the asphaltenes aggregates and the increase in the asphaltene content. The resulting structure of the thermo-oxidized asphalt is that of a weak gel and the a-relaxation process has been shifted towards higher temperature as compared with initial asphalt. The change of the exponent n is an indicator of the evolution of the viscoelastic behavior due to changes in the structure of the aged asphalt, which are promoted by the thermo-oxidation process and by a temperature reduction. The thermo-oxidation process carried out in a rheo-reactor has been shown to be efcient for simulate the aging of asphalts, principally because the macromixing that occurs in the rheo-reactor can be made effectively. From the experimental results obtained during thermo-oxidation process, we can conclude that high processing temperature inuences the structural changes of asphalt. The imposed effective shear rate during the aging process seems to greatly inuence the viscous behavior of the material, under the same temperature conditions for the thermo-oxidation process. No signicant differences were found concerning the linear viscoelastic properties of the asphalt submitted to TFOT as compared to initial asphalt, contrarily to the results obtained in the rheo-reactor at the same temperature conditions.

[1] Lesueur D, Gerard JF, Claudy P, Letoffe JM, Planche JP, Martin D. A structurerelated model to describe asphalt linear viscoelasticity. J Rheol 1996;40: 81336. [2] Lesueur D. La Rhologie des bitumes: principes et modication. Rhologie 2002;2:130. [3] Brl B, Ramond G, Such C. Relations composition-structure-proprits des bitumes routiers. Etat des recherches au LCPC BL 148 1987; Art 3179. [4] Storm DA, Sheu EY, Barresi RJ, Detar MM. Colloidal properties of asphaltenes in vacuum residue. Proc Chem Bitumen 1991;2:81341. [5] Sirin O, Tia M, Ruth B. Evaluation of an improved rotavapor aging apparatus using a morton ask for simulation of hot-mixing on modied asphalts. Annual meeting of the transportation research board, Washington, DC; 2000. [6] Shalaby A. Modelling short-term aging of asphalt binders using the rolling thin lm oven test. Can J Civil Eng 2002;29:13544. [7] Vassiliev NY, Davison RR, Glover CHJ. Development of a stirred airow test procedure for short-term aging of asphaltic materials. Transport Res Record 2002;1810:2532. [8] Choplin L, Marchal PH. Rheo-reactor for in situ rheological follow-up of chemical or physical processes. Ann Trans Nordic Rheol Soc 1999;7:512. [9] At-kadi A, Marchal PH, Chrissemant AS, Bousmina M, Choplin L. Quantitative analysis ofm Mixer-type rheometers using Couette analogy. Can J Chem Eng 2002;80:116674. [10] Lacoste C, Choplin L, Cassagnau P, Michel A. Rheology innovation in the study of mixing conditions of polymer blends during chemical reaction. Appl Rheol 2005;15:31425. [11] Afanasjeva N, lvarez M. Estudio del envejecimiento de los asfaltos bajo la accin de algunos factores climticos; 2004. ISBN 958-3371351. [12] Yen YF, Erdman JG, Pollack SS. Investigation of the structure of petroleum asphaltenes by X-ray diffraction. Anal Chem 1961;33(11):158794. [13] Garcia-Morales M, Partal P, Navarro FJ, Martnez-Boza F, Gallegos C. Linear viscoelasticity of recycled EVA-modied bitumens. Energy Fuel 2004;18: 35764. [14] Giavarini C, Mastroni D, Scarsella M, Barr L, Espinat D. Macrostructure and rheological properties of chemically modied residues and bitumens. Energy Fuel 2000;14:40295.