Hardening and Ageing of Bituminous Materials

in Hot Arid Climates

1 Introduction

Ageing and hardening of bituminous materials are considered to be the main factors contributing to
the performance and durability of bituminous pavements in the long term. In its applications,
bitumen is used to coat aggregate particles in thin films. It makes an excellent binder because it is
adhesive, cohesive, self-healing, resistant to abrasion and waterproof. With age the bitumen suffers
a gradual loss of these desirable properties. This lessening of effectiveness is caused by hardening
which is the result of continued exposure to heat, light, air and moisture, which are always present
in the environment.

One of the main challenges facing workers in the pavement industry is the prediction of long term
behaviour of the pavement structure based on binder and mix properties. In recent years, there have
been numerous reported complaints about the quality of bituminous pavements because of
premature ageing problems in different parts of the world (Omar et al, 1994; Smith et al, 1990;
Guan and Ruth, 1990 and Page et. al, 1985). The problem comes from the fact that bitumen
hardening increases the mix stiffness and lowers the cracking strain, making the pavement surface
vulnerable to cracking. This problem could be avoided by limiting the strains to an acceptable level
corresponding to the degree of binder hardening attained during the life of the pavement. However,
this can only be achieved by altering the foundation support or the thickness of the bituminous
layer. In a situation where thermal cracking prevails, this solution will not be valid. Only lower
viscosity or less hardening of the bitumen binder will be beneficial in reducing the potential of
thermal cracking. It is generally accepted that bitumen hardening is a good relative measure of
asphalt durability (Kemp and Predoehl, 1981).

Hardening of bitumen binders occurs in three different stages at different rates; in storage; during
hot mixing and compaction and ageing in service. There are several variables which contribute to
the hardening of bitumens such as plant operations, field operations, aggregates and bitumen
characteristics. The hardening of bitumen binder takes place due to the action of different reactions

1
that occur in service and result in loss of its desirable properties. These reactions are summarised
by Richardson (1994) as:

(a) Oxidation (a process involving the loss of electrons, generally with the gain of oxygen
or loss of hydrogen)

(b) Volatilisation (the loss of lighter constituents)

(c) Thixotropy (an isothermal gel-sol transformation brought about by shaking or other
mechanical means e. g. a gel on shaking may form a sol which rapidly sets again when
allowed to stand)

(d) Syneresis (the separation of liquid from gel or jelly-like substance on standing)

(e) Polymerisation (the formation of large molecules, comprising repeated structural units).

In general, it is agreed that the hardening of the binder in service is due in large part to oxidation
and volatilisation, and to a lesser degree to thixotropy, syneresis and polymerisation.

Most of the research in this subject has concentrated on the first two stages of hardening which take
place during the time of construction. Those efforts resulted in a number of specifications and
standard testing procedures like the Thin Film Oven Test (TFOT) which aims to control the quality
of bitumen binders to be used in paving mixes. The last stage hardening mentioned above, which is
ageing of the binder in service, has not received the required attention yet. However, the Strategic
Highway Research Program (SHRP) for Long-Term Pavement Performance (LTPP) studies
launched in the USA is expected to fill this research need. Nevertheless, there are other parts of the
world with different climates which need special studies. Laboratory investigations will not be
enough and field studies are required. Unfortunately they take a long time and are very costly.
Common durability tests such as immersion compression, or Marshall immersion tests do not
provide good correspondence with performance (Craus et al., 1981). The Roster finger printing
procedure, Hethaus method, Vanadium content, rotating thin film (RTF) durability test, weathering
plate durability test and others were evaluated and deemed inadequate in accurately predicting the
field ageing effects (Kemp and Predoehl, 1981). The poor correlation between mixture fatigue
resistance and asphalt viscosity projected from RTF and original bitumen data suggests that it may
be dangerous to predict long-term durability from short term hardening characteristics (Santucci
and Schmidt, 1969). However, penetration and viscosity of recovered bitumens correlate well with
the fatigue resistance of mixtures. Although not definitive, the results of chromatography tests,
show promise for predicting in-service performance of bituminous materials (Davis and Petersen,
1967). Although the results of many investigations have not solved the problem of test
requirements for rational specifications, they do provide insight into the variables which influence

TE610 - Hardening and Ageing of Bituminous Materials in Hot Arid Climates 2

age hardening and performance of bituminous concrete pavements.

In this study special consideration is given to long-term hardening of bitumen binders in hot arid
climates. Binder hardening in this climate is most influenced by thermal oxidation and
volatilisation which are caused by high temperatures and high rate of exposure to sun radiation.
Earlier research (Dickinson, 1980) showed that the thermal oxidation is approximately doubled for
every 10° C rise in temperature. Thus the rate of hardening in service depends, to a large extent, on
the pavement temperature system. Hardening of the surface is generally greater due to the higher
temperature and ultraviolet radiation (Kumar and Goetz, 1977). Other investigators showed that the
top 1/4 in of the pavement was found to have a viscosity 50% greater than at depths of 1/2 in
(Coons and Wright, 1968). Hardening is influenced by the percent of air voids content and mixture
permeability. Pavements with lateral cracking and high air voids had a greater degree of hardening
and oxidation than uncracked pavements with low voids (Gietz and Lamb, 1968).

Based on the background given above, the investigation of bitumen hardening in hot arid climates
was carried out using two different approaches: monitoring the loss of volatile compounds and
measuring the apparent viscosity of the bitumen binder. Firstly, a chemical analysis was carried out
to study the hardening mechanisms of the binder in service by following up the loss of volatile
compounds from the bitumen material. The analysis was designed to monitor the loss of volatiles
with both the duration and degree of exposure. Secondly, a series of viscosity tests was conducted
on field samples using the Sliding Plate Viscometer. The aim was to suggest a simple routine test
for assessing the ageing and hardening of the binder in service.

The ensuing portion of this chapter will present details of the testing programs and analysis of the
obtained results.

2 Monitoring the loss of volatile compounds in bitumen binders

The objective of this analysis is to consider one of the factors giving rise to hardening of asphalt in
hot climates, namely loss of volatile components of the bitumen binder due to evaporation.
Samples were obtained from a number of highways in Southern Libya, a typical hot arid climate
(see Chapter 3). The samples ranged in age from zero to eight years. The loss of volatile
compounds was evaluated by chemical analysis of the extracted binder.

The composition of asphalt binder is very complex, consisting of hydrocarbons of widely varying
types and molecular weights. A number of methods and techniques have been tried for the
fractionation and analysis of bituminous materials (Traxler 1961 and Churchill et al., 1995).
Sample preparation is important in order to minimise matrix interference. There has been much
TE610 - Hardening and Ageing of Bituminous Materials in Hot Arid Climates 3
study of the separation of bitumen, mostly using silica column chromatography. However, this
method is very tedious. The extraction time is reduced if solid phase extraction is used instead to
separate the bitumen into fractions. Further more, the separation of each component may be
achieved by using capillary gas chromatography.

The analysis of volatile compounds was carried out in a stepwise manner. Firstly, the sample was
extracted using a Soxhlet extraction apparatus with normal heptane solvent to extract the bitumen
from the matrix. Secondly the bitumen was separated using solid phase extraction (sep-pak) with
three different eluents; normal heptane, toluene and a mixture of toluene with dichloromethene
(1:2). Each fraction from the solid phase extraction was run on a capillary gas column with a BP 10
megabore column 0.5 mm, 25 m length. This column is equivalent to the OV1701 (BP Ltd., 1970).

2.1 Experimental procedure

The procedure used is illustrated in Figure 1. As common to most methods, asphaltenes are
precipitated/separated initially with a paraffin solvent at high dilution ratio, by the principle of
disparity of molecule size and type between solvent and asphaltenes (Bunger and Li, 1981).
Normal heptane is preferred for this step because of its purity and other properties that permit
filtration steps without precipitation of wax components. It is also used in a standard test for
asphaltene content of bitumen. The chromatographic step that follows involves the use of silica
active gel (sep-pak) and elution solvent polarity. This step permits the separation of components of
different polarity. Furthermore, each component is pre-concentrated in the nitrogen stream, which
is then run into capillary gas chromatography.

2.1.1 Samples
Asphalt concrete samples were collected from actual pavements in the Southern part of Libya (the
Sahara Desert). Four roads were selected as shown in Table 1. The asphalt binder used in the
analyses was extracted from the top 20 mm of the road surface.

2.1.2 Soxhlet extraction

The sample was ground into small pieces. Then an accurately weighed amount of bitumen sample
(approx. 50 gr.) was extracted using Soxhlet apparatus with 150 ml of heptane for 6 hours. The
extractant was diluted into 250 ml.

TE610 - Hardening and Ageing of Bituminous Materials in Hot Arid Climates 4

 ORIGINAL BITUMEN

Heptane Extraction

(undissolved) (dissolved)

Asphaltenes Fraction Petrolenes Fraction

and residue
Silica Gel Column
(Sep-Pak)

Heptane Eluate Toluene Eluate Toluene:Dichloromethylene

Fraction Fraction (1:2) Fraction

GC GC GC

Components Components Components

Figure 1. The diagram of bitumen separations

2.1.3 Solid phase extraction

Prior to the extraction of bitumen, the sep-pak was wetted using normal heptane solvent. To obtain
the first fraction, 5 ml of the extractant was eluted into the sep-pak and 25 ml of normal heptane
were added. The second and third fractions were obtained by adding 30 ml of toluene and 30 ml of
a mixture of toluene and dichloromethylene (1:2) into the same sep-pak consecutively. Thus, each
fraction was 30 ml. However, the major volatile compounds were contained in the heptane fraction.
No volatile compounds were found in the toluene/dichloromethene fraction. Therefore, the
subsequent analysis was focused entirely on the heptane fraction.

TE610 - Hardening and Ageing of Bituminous Materials in Hot Arid Climates 5

 Table 1 Roads selected for the study

Age (years) Location Description

0 Alfugaha-Tripoli/Sabha road 2-Lane main rural highway

1 Sabha (Street No. 18) 2-Lane urban Street

4 Traghen-Ghoddua road 2-Lane main rural highway

8 Tazerbo-Jalu/Kufra road 2-Lane main rural highway

2.1.4 Typical temperature programme

The temp. was programmed as a series of increasing ramps and intervals as shown in Figure 2.

270°C (2 minutes)

10°C/minute
200°C (2 minutes)

10°C/minute
60°C (2 minutes)

Figure 2 Temperature program

2.1.5 Optimum parameters for gas chromatography

Gas chromatography (GC) analysis was performed using:

• The column was BP 10, equivalent to OV1701, contained 86% dimethylsiloxane and
14% cyanoprophylphenyl. It is moderately polar (Figure 3), column length 25 m and
inner diameter 0.5 mm.

• The electrometer and detector were Carlo Erba Strumentazione model 180 with split
injection port and flame ionisation detector.

• The recorder was a Hewlett Packard 3390 A Integrator

TE610 - Hardening and Ageing of Bituminous Materials in Hot Arid Climates 6

 CN
CH3
(CH)23

Si O Si

CH3

86% 14%

Figure 3 The Chemical Structure of BP 10

2.1.6 Internal standard

Internal standards were alkanes that had the carbon numbers C9-C19, C22, C24 and C30. The
concentration of each component was 25 ppm. The qualitative identification was conducted by
comparing the retention times of standards and samples, under the same gas chromatography
conditions. This mixture was eluted without interfering with the bitumen sample. The spiking
technique was used to confirm the aforementioned identifications. The quantitative analysis of each
component was conducted by comparing between the standards and samples peak area.

2.2 Results and discussion

2.2.1 Soxhlet extraction

The bitumen sample was extracted from the sample matrix using normal heptane solvent. The
percentage of bitumen that was dissolved in normal heptane represented the total volatile
compounds in the sample. In addition, there are some non-volatile components with high molecular
weight that dissolved in the normal heptane. The extraction result is shown in Table 2. The
percentages of bitumen were plotted against time (years) as shown in Figure 6.4. The percentage of
bitumen decreased sharply from 0 to 1 years, and then slowly from 1 to 8 years. These rates of
decline indicate rapid loss of the volatile compounds from the top surface layer during the first year
by the processes of evaporation and oxidation. The loss will continue in the following years but at
a slower rate. It is expected that the loss in the lower layers will be less than the top layer during
TE610 - Hardening and Ageing of Bituminous Materials in Hot Arid Climates 7
the first year but will continue in the following years.

Table 2 Results of extraction

Sample age Sample weight Sample residue Sample extract Extract
(Years) (gr.) (gr.) (gr.) percentage

0 49.93 46.98 3.05 6.11

1 49.96 47.00 2.30 4.6

4 50.01 47.89 2.13 4.25

8 50.02 48.09 1.94 3.87

10
9
8
Extract %

7
6
5
4
3
2
1
0
0 1 2 3 4 5 6 7 8
Time (years)

Figure 4 Percentage of extract against age

2.2.2 Analysis of volatile compounds in bitumen

The chromatograms of the heptane fraction for 0, 1, 4 and 8 years are shown in Figures 5a to 5d
respectively. These chromatograms show that the bitumen contained some very complex
components. The major components are alkane compounds that were identified using internal
standards. Each peak area in the chromatogram was calculated using a Hewlett Packard 3390 A
Integrator. Theoretically, the peak areas are proportional to the concentration of volatile
compounds in the sample. The different volatile compounds contained in the heptane fraction for 0
to 8 years are shown as peak areas in Table 3 and were plotted against the carbon number, as
TE610 - Hardening and Ageing of Bituminous Materials in Hot Arid Climates 8
shown in Figure 6. The area bars in the horizontal axis represent the relative concentration of each
volatile compound for different years. Figure 6 shows that, the volatile compounds with carbon 13
and 37 disappeared during the first year and could not be found in the samples for 1 to 8 years,
whereas other hydrocarbon compounds like carbon 15 could no longer be found after 1 year.
Generally, the concentration of each volatile compound decreased with service time by different
rates depending on the properties of each compound. The peak areas of the different compounds
are summed for each age in Table 3. It is assumed that the total for year 0 is proportional to the
total volatile compounds at the start of service life. On this basis the volatile compounds remaining
after 1, 4 and 8 years may be expressed as a percentage of the total at year 0. These percentages are
plotted in Figure 7. These results indicate that the heptane fraction of the binder will lose about
62% of its volatile compounds in 1 year and about 98% in 4 years.

However, in analytical chemistry terms, the techniques used in this analysis still need to be
improved for complete separation of bitumen constituents and more precise analysis. The
chromatogram of bitumen analysis shows the solvent peak to be too wide, indicating a slow
evaporation of the sample. The analysis could possibly be improved by increasing the temperature
of the injector port, but for this analysis is limited by the maximum temperature of the BP10
column which is 300° C. In addition, the detector was noisy when the temperature of injector port
increased to over 275° C. The baseline of the chromatograms is observed to rise around the middle,
which implies that the samples contained some unresolved material compounds. An attempt was
made to insert glass wool in the glass liner to trap particulates and non-volatile compounds into the
capillary column. In addition, the sample was retained in the injector port longer so that the
evaporation of the sample could be better controlled for reproducibility. Also it was ensured that
the sample reached the column in a gas phase. However, the results generated from this attempt
were less than ideal. The experiment could possibly be improved by using another inlet system
that prevents non-volatile compounds and unresolved materials from entering into the column.

TE610 - Hardening and Ageing of Bituminous Materials in Hot Arid Climates 9

 Figure 5a Chromatograms for the heptane fraction of 0 year

Figure 5b Chromatograms for the heptane fraction of 1 year

TE610 - Hardening and Ageing of Bituminous Materials in Hot Arid Climates 10

 Figure 5c Chromatograms for the heptane fraction of 4 years

Figure 5d Chromatograms for the heptane fraction of 8 years

TE610 - Hardening and Ageing of Bituminous Materials in Hot Arid Climates 11

 Table 3 Calculated peak areas of volatile compounds
Carbon Retention Peak areas in integration units
number time (min) Time (years)
0 1 4 8
C13 9.460 9791 0 0 0
C14 10.920 10161 5300 0 0
C15 12.330 24779 11489 0 0
C16 13.660 44455 13534 5799 8989
C17 14.930 61190 23284 11054 6983
C18 16.130 84353 38317 15482 12270
C19 16.860 109570 100300 11260 13142
C20 18.860 85000 37559 10916 6861
C21 20.320 91046 40355 13754 10490
C22 21.610 187480 71620 5467 14606
C23 22.780 307360 120510 16059 14479
C24 23.860 385370 184010 14561 16699
C25 24.850 527110 293180 18732 12880
C26 25.790 627870 359430 27411 23408
C27 26.780 711090 381510 12352 10169
C28 27.940 811460 539030 8855 12532
C29 29.320 867870 407390 12482 12628
C30 30.990 1287300 499580 6679 6646
C31 33.050 1287800 382190 0 0
C32 34.460 1305000 395770 0 0
C33 35.550 843630 178050 0 0
C34 36.650 1138700 167080 0 0
C35 38.730 452710 47712 0 0
C36 39.760 186020 53593 0 0
C37 42.620 101090 0 0 0
Total 11548205 4350793 190863 182782
% of volatile 100 37.68 1.65 1.58

TE610 - Hardening and Ageing of Bituminous Materials in Hot Arid Climates 12

 C37

C35

C33

C31

C29
Carbon number

C27

C25

C23

C21

C19

C17

C15

C13

0% 25% 50% 75% 100%

Peak area %

Figure 6 Relative volatile concentration for different years

TE610 - Hardening and Ageing of Bituminous Materials in Hot Arid Climates 13

 100
90
80

Remaining volatile %
70
60
50
40
30
20
10
0
0 1 2 3 4 5 6 7 8
Service age (years)

Figure 7 Remaining volatile compounds for different years as percentage of

year 0.

3 Measurement of the viscosity of bitumen binders in hot arid climates

The specification for bitumen binders used in pavement construction is based mainly on the
rheological properties of the material. The most relevant specification relates to the viscosity.
Agencies working in the pavement industry use different measures for viscosity. It is reported
directly as absolute viscosity or kinematic viscosity, and some times indirectly as penetration or
softening point. However, viscosity is a well known property of bitumen binders, and its
measurement is common in most of the laboratories dealing with bitumen and highway materials.
Its magnitude is comprehended by all researchers and engineers working in the field. Hence,
expressing the hardening of bitumens in terms of viscosity will be a good way of presenting the
analysis of this problem. It was decided to carry out a series of tests to measure the viscosity of the
binders involved in this study using two different methods; the sliding plate viscometer and the

TE610 - Hardening and Ageing of Bituminous Materials in Hot Arid Climates 14

Rheometer. Details and results of these tests are presented in the following sections.

3.1 Specimens for viscosity measurement

As already explained in the introduction to this chapter (§ 1) the aim was to study the hardening of
the bitumen binder in service by investigating the influence of both the duration and degree of
exposure. Field samples of different ages (0 to 8 years) were collected from the area selected for
the case study. Each sample was sawn into slices of 15 mm thick through its depth. For the
extraction and recovery of the bitumen binder from the sample a special procedure described by the
Australian Road Research Board (ARR No. 66) was adopted, the only exception being that the
solvent specified for binder extraction (benzene) was substituted with toluene in order to comply
with permissible stack emission requirements. Using about 100 grams of the bituminous mixture is
enough for recovering the needed material (about 2 grams) for preparing the test specimens for both
the sliding plate viscometer test and the Rheometer test.

3.2 Measuring the apparent viscosity of bitumen binder using the sliding plate
viscometer

The apparent viscosity of the bitumen binder was determined using a Stanhope Seta sliding plate
viscometer according to the procedure detailed in the Aust. Road Research Report ARR No 59.

The mean of three determinations is reported as the apparent viscosity (log Pa.s units) at a
temperature of 45° C and shear rate of 5x10-3 s-1. A few specimens were tried at a temperature of
25° C. One specimen only, the top surface specimen of 8 years old, could not be tested at the
conditions specified above even by reducing the shear rate to 2x10-3s-1 and using the largest weight.
Extrapolating the results available the approximate apparent viscosity was 7.27 (log Pa.s units).

The results are given in Table 4. Figures 8 and 9 show the change of binder viscosity with age
and depth respectively.

The results show that the viscosity of the binder increases rapidly with service age. The viscosity-
age change follows a certain rate, that reflects the combined influence of both the environment and
the degree of exposure (depth below surface) of the bituminous material on the process of
hardening. In other words, hardening of the bitumen binder in this kind of environment (hot arid
climate) takes place mainly by two process; volatilisation and oxidation. These hardening
processes are increased by solar radiation, pavement temperature and the presence of oxygen. The
change of binder viscosity with age shown in Figure 9 may be expressed by the following

TE610 - Hardening and Ageing of Bituminous Materials in Hot Arid Climates 15

 Table 4 Apparent viscosity of the binder as measured by sliding plate
viscometer at 45°° C
Apparent viscosity (log Pa.s);
Sample
depth At temperature of 45°C and shear rate 5x10-3s-1

(mm) 0 year 1 year 2 years 4 years 8 years

7.5 4.68 5.37 5.64 6.06 7.27

25.5 4.52 4.7 5.35 5.31 6.61

43.5 4.47 4.57 5.06 5.29 6.76

ηb (log Pa.s)
8
measured
linear fit d = 25.5 mm

7
d = 7.5 mm

d = 43.5 mm
5

4
0 2 4 6 8
Age, N (years)

Figure 8 Change of binder viscosity with service age; different depths at 45° C
and shear rate of 5x10-3s-1.

TE610 - Hardening and Ageing of Bituminous Materials in Hot Arid Climates 16

 ηb (log Pa.s)
8

8 years

4 years
6
2 years

1 year

5
0 year

4
0 10 20 30 40
Depth, d (mm)

Figure 9 Change of binder viscosity with pavement depth; different ages at 45°
C and shear rate of 5x10-3s-1.

relation:

log η = log η + β.N

b o ............................................................................................( 1)

where:

ηb = viscosity of bitumen at given age

ηo = viscosity of bitumen at age = 0 year

N = service age in years

β = ageing factor; the rate of change of viscosity with service time

The ageing factor β was found to decrease slightly with pavement depth. e.g. it was 0.30 at depth of

TE610 - Hardening and Ageing of Bituminous Materials in Hot Arid Climates 17

7.5 mm, 0.29 at 25.5 mm and 0.28 at 43.5 mm.

The process of hardening follows a certain regime that can be explained with the aid of Figure 9 in
the following steps:

• At the beginning of service life (age = 0 years), no hardening has taken place and the
gradient of viscosity profile through the pavement depth is minimal. In theory there
should be no difference in viscosity values through the layer depth, but the slight
difference shown in Figure 9 for age = 0 year could be accounted for by the hardening
that takes place during laying and compaction of the pavement and not to the
environmental effect. The other possibility for this initial hardening is that the tested
samples for age zero were taken some time after the actual date of construction.

• In the following years, hardening takes place due to the effect of environmental factors
such as solar radiation, temperature and circulation of oxygen. The two main processes
responsible for hardening in the hot arid climate are volatilisation and oxidation. In
both processes the upper layers of pavement are more exposed to the environmental
factors causing these processes, hence the viscosity at top layers increases more rapidly
then that of lower layers. The gradient of viscosity-depth profile becomes steeper (see
curves of 1, 2 and 4 years in Figure 9).

• As bituminous mixtures get older, most of the volatile compounds in the top layers are
evaporated and the rate of viscosity increase becomes less compared to that of lower
layers where more volatiles still exist and the rate of hardening is faster. Thus the
viscosity-depth profile becomes flatter again.

Figure 10 shows the change of binder viscosity with layer depth for age of 4 years at two
temperatures (25° C and 45° C). This figure shows the significant drop in viscosity with the
increase of temperature. The hardening gradient through pavement depth does not change
significantly with the change of temperature. Measurement of the apparent viscosity of bitumen
binders at a temperature of 45° C was recommended by the testing procedure adopted for this study
(ARR No. 66). Since the aim was to enable measurements to be done on hardened bitumens and
due to the difficulty experienced in this study in testing older specimens (8 years at 7.5 mm), it
would be desirable to raise the testing temperature, for example to 60° C.

TE610 - Hardening and Ageing of Bituminous Materials in Hot Arid Climates 18

 8

25° C

7
Vb (log Pa.s)

45° C
5

4
0 10 20 30 40 50
Depth, d (mm)

Figure 10 Change of binder viscosity with pavement depth; age of 4 years at

25° C, 45° C and shear rate of 5x10-3s-1.

This analysis showed that the measurement of viscosity is a good approach to investigate and
evaluate the in-service hardening of bitumen binders. The sliding plate viscometer is an affordable
means of testing the apparent viscosity of bitumen binders using very small field specimens. This
procedure could be improved by testing at higher temperature such as 60° C to cover a wider range
of hardened binders.

3.3 Measuring of bitumen viscosity using the Rheometer

The Rheometer test was explained in detail in § 5.2. One of the measurements obtained from the
Rheometer test is the viscosity of the bitumen binder. Viscosity was measured at various
temperatures and different depths of the pavement layer. Figure 11 shows examples of the
obtained results, where the binder viscosity is plotted against the change of temperature. As
expected the viscosity increases with service age and decreases with temperature. The linear
relationship between “log ηb” and temperature drop made it possible to predict the viscosity of the
bitumen binder at other temperatures. Table 5 shows the values of Rheometer viscosity for

TE610 - Hardening and Ageing of Bituminous Materials in Hot Arid Climates 19

different service ages at 45° C in (log Pa.s) units.

ηb (log Pa.s)
9
d = 7.5 mm
8 years
t = 1 sec
8 strain = 2%
4 years
7 2 years
0 year
6

2
10 20 30 40 50 60 70 80
Temperature, T (° C)

Figure 6.11 Binder viscosity vs temperature for different ages; (Rheometer test
at d=7.5 mm, t=1 sec and strain = 2%)

Table 5 Apparent viscosity of the binder as measured by the Rheometer at 45°°

C, t= 1 sec and strain = 2%

Layer depth Bitumen viscosity (log Pa.s)

(mm) 0 year 2 years 4 years 8 years

7.5 4.509 5.014 5.409 6.806

25.5 4.431 4.905 5.162 6.383

43.5 4.263 4.808 5.038 6.165

TE610 - Hardening and Ageing of Bituminous Materials in Hot Arid Climates 20

 ηb (log Pa.s)
7
T = 45° C
t = 1 sec d = 22.5 mm

6
d =7.5 mm

d = 43.5 mm
5

4
0 2 4 6 8
Age, N (years)

Figure 12 Change of binder viscosity with service age at different layers; (t=1
sec and T= 45° C)
η b (log Pa.s)
8
T =45° C
t =1 sec

7 8 years

4 years

2 years
5
0 year

4
0 10 20 30 40
Depth, d (mm)

Figure 13 Change of binder viscosity with layer depth at different ages; (t=1
sec and T = 45° C)

TE610 - Hardening and Ageing of Bituminous Materials in Hot Arid Climates 21

For the sake of comparison, binder viscosity measured by the Rheometer was plotted against
service age and layer depth in Figures 13 and 14 respectively. Since the viscosity in the
Rheometer test is determined in dynamic mode at a certain loading, binder viscosity with service
age shown in Figure 12 is similar to that shown in Figure 9 as obtained from the viscometer test,
and relation 1 can be used to predict the viscosity from data obtained by the Rheometer test. The
ageing factor β was found to be slightly different from that calculated using the viscometer results,
Table 6 shows values of β as obtained by both methods.

In the case of the hardening profile through the pavement depth, trends shown in Figure 13 based
on viscosity results obtained from the Rheometer test are similar to those explained above in the
case of viscometer results (see Figure 9).

Table 6 Ageing factor β at different layer depths and 45°° C

Sample depth β)
Ageing factor (β

(mm) From Viscometer data From Rheometer data

7.5 0.300 0.287

25.5 0.289 0.241

43.5 0.287 0.232

3.4 Discussion of viscosity results

Results obtained by both methods, the viscometer and the Rheometer, correlate very well as shown
in Figure 14. Both procedures can be used to follow up the in-service hardening of the bituminous
pavement by measuring the viscosity of field samples. The Rheometer test gives more data by
testing at a wide range of variables such as temperature, rate of loading and strain, but it is
relatively expensive, sophisticated and not common in highway and bitumen laboratories. The
sliding plate viscometer gives viscosity results at limited variables, but is simple, affordable and its
results are comprehended by a wide range of researchers and highway engineers.

Analysis of viscosity results obtained by testing field samples of bitumen binders shows very clear
trends for their ageing and in-service hardening, caused by environmental factors. It will be useful
to adopt viscosity as a measurement of the in-service hardening of bitumen binders for use in
further evaluation processes. Moreover, viscosity may be used to estimate the stiffness modulus
TE610 - Hardening and Ageing of Bituminous Materials in Hot Arid Climates 22
of the binder which is then used to calculate thermal stresses and to check the strength of the
mixture.

Estimating the stiffness modulus of the bitumen binder from viscosity measurement may be done by
using a suitable correlation between stiffness and viscosity. This kind of correlation is discussed in
Chapter 5 (§5.2.4.4), and a typical correlation is given in Figure 5.13. Similarly, viscosity
measured by the sliding plate viscometer may be correlated to that measured by the Rheometer. As
an example using the current data of viscosity measured at 45° C a similar correlation is given in
Figure 14. The correlation factor or relation depends on the rheology of the bitumen binder itself
and on the environment in which it has been used. In addition, the correlation is affected by the
temperature at which the measurements were made.

ηb (log Pa.s); by Rheometer

8
d = 7.5 mm
T = 45° C

Vrheo = 0.9016V visc + 0.1052

R2 = 0.9613

4
4 5 6 7 8

ηb (log Pa.s); by Viscometer

Figure 14 Correlation of viscosity results obtained by the sliding plate

viscosity test and the Rheometer test

TE610 - Hardening and Ageing of Bituminous Materials in Hot Arid Climates 23

4 Assessment of binder hardening in hot arid climates

Analysis of the loss of volatile compounds of the binder and the measurements of viscosity
presented in this Chapter provide support for the theory that rapid ageing and hardening of
bituminous pavements in hot arid climates is significantly affected by volatilisation. The
chromatographic analysis showed a rapid loss of the volatile compounds in the bitumen which is
responsible for the fluidity and adhesion of the material.

Measurement of viscosity showed a significant and rapid increase in the viscosity of the binder.
Results presented in Table 4 showed that viscosity of the binders in the Sahara desert increased
about 5 times in the first year of service, 9 times in two years, 24 times in four years and up to 390
times in eight years. It was not found possible to compare these findings directly with available
data for other parts of the world with different climatic conditions, because of the diversity of
measuring procedures and variables. However, some individual comparisons are made as follows:

• In Kenya the viscosity of bitumen binder in two years of service was found to be 5.25
log Pa.s as reported by H R Smith et al (1990). For the same service age (2 years) it was
5.64 log Pa.s in the Sahara desert, which is about 2.5 times that of Kenya.

• In Saskatchewan, Canada, data given by Culley (1969) showed that, the viscosity of the
bitumen binder doubled in one year of service. In the Sahara desert the viscosity
increased 5 times in the same period of time.

• In Pennsylvania, the viscosity of bitumen took 7 years to reach twice its original value
(Sandvig et al, 1968). In same period of time (7 years) viscosity of bitumen in Sahara
desert increased by about 200 times.

These extreme records of loss of volatiles, viscosity and stiffness modulus are attributed mainly to
the severe environment of the region under investigation. Sun radiation and high pavement
temperatures are the major factors contributing to the rapid ageing and hardening of the bitumen
binder in hot arid climates.

5 Conclusions

Results of both investigations presented in this chapter, the chromatographic analysis of volatile
compounds in bitumen and viscosity measurements, showed that bituminous binders in hot arid
climates are subjected to a rapid process of hardening reflected in the high loss of volatile
compounds from the binder and a significant increase of their viscosity. This early hardening and

TE610 - Hardening and Ageing of Bituminous Materials in Hot Arid Climates 24

ageing of the binder increases the mix stiffness to high levels making it vulnerable to thermal
cracking. The main results of these analyses may be summarised in the following conclusions:

• The chromatographic analysis showed that, the heptane fraction of the bitumen binder
in the top 20 mm of the pavement surface may have lost about 62% of its volatile
compounds during the first year and up to 98% in 4 years.

• Binder viscosity increased rapidly with increase in service age. The increase follows a
logarithmic function controlled by an ageing factor which is attributed to the climatic
conditions and the rheological characteristic of the bitumen.

• Hardening of the bitumen binder shows a viscosity depth profile. The gradient of the
viscosity-depth profile follows a typical history regime.

• Measurement of binder viscosity showed a significant increase of viscosity of the

bitumens in hot arid climates (Sahara desert) compared with those in other parts of the
world of different climates.

• Viscosity proved to be a good parameter for investigation and evaluating the in-
service hardening of the bitumen binders.

• Using the Rheometer it is possible to test very small specimens of recovered binder at
a wide range of variables obtaining extensive rheological data for viscosity and
stiffness modulus. The test is relatively expensive, sophisticated and not common in
the highway and bitumen laboratories.

• The sliding plate viscometer gives viscosity results at limited variables, but it is
simple, affordable and its results are comprehended by a wide range of researchers and
highway engineers.

• There was a reasonable correlation between viscosity results obtained from the
Rheometer test and the sliding plate viscometer test. There was also a reasonable
correlation between measured viscosity and stiffness of the bitumen binder and it is
dependent on both the bitumen rheology and the environmental conditions of the site.

• A complementary rheological examination of the bitumen showed that the increase in

its stiffness modulus and viscosity was broadly consistent with the reduction in
volatile compounds.

ηb = viscosity of bitumen at given age

TE610 - Hardening and Ageing of Bituminous Materials in Hot Arid Climates 25

 ηo = viscosity of bitumen at age = 0 year

N = service age in years

β = ageing factor; the rate of change of viscosity with service time

TE610 - Hardening and Ageing of Bituminous Materials in Hot Arid Climates 26