Construction and Building Materials 214 (2019) 178–186

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Construction and Building Materials

journal homepage: www.elsevier.com/locate/conbuildmat

Evaluation of the durability of asphalt concrete modified with

nanomaterials using the TEAGE aging method
João Miguel Lopes Crucho a,⇑, José Manuel Coelho das Neves a, Silvino Dias Capitão a,b,
Luís Guilherme de Picado-Santos a
a
CERIS, Instituto Superior Técnico, Universidade de Lisboa, Av. Rovisco Pais 1, 1049-001 Lisboa, Portugal
b
Instituto Politécnico de Coimbra, Instituto Superior de Engenharia de Coimbra, Rua Pedro Nunes, 3030-199 Coimbra, Portugal

h i g h l i g h t s

The modification of asphalt concrete with nanomaterials was studied.

The nanomaterials used were: nanosilica, zero-valent nanoiron and nanoclay bentonite.

For the simulation of aging due to environmental conditions the TEAGE method was used.

Nanosilica and nanoclay modifications improved the aging resistance of the mixture.

Nanosilica and nanoclay modifications enhanced performance under aged conditions.

a r t i c l e i n f o a b s t r a c t

Article history: Aging phenomenon has a key role in the deterioration of the asphalt mixtures performance. The modifi-
Received 30 October 2018 cation of asphalt binders with nanomaterials that can retard the aging process can be of great interest for
Received in revised form 25 January 2019 the paving industry. This study evaluates the durability of asphalt mixtures modified with three types of
Accepted 15 April 2019
nanomaterials: nanosilica, nanoiron and nanoclay. The mixtures were conditioned to accelerated aging
and tested for stiffness, fatigue and indirect tensile strength. After testing the mixtures, the binders were
recovered and characterized. The results showed that the modifications with nanosilica and nanoclay
Keywords:
improved the aging resistance of the mixture indicating enhanced durability.
Aging simulation
Asphalt mixtures
Ó 2019 Elsevier Ltd. All rights reserved.
TEAGE
Nanoclay
Nanosilica
Nanoiron

1. Introduction
Asphalt pavements serve the majority of the road networks. The
increase in traffic and traffic loads observed over the years puts
additional pressure on the traditional asphalt binders, which seem
to no longer ensure satisfactory performance during the desired
service life. The use of modified binders, generally with polymers,
became more frequent. In recent years, the modification of the
asphalt binder using nanomaterials revealed capacity to improve
the mechanical performance of the asphalt mixture [1–3]. In addi-
tion, there is also an expectation that the use of nanomaterials may
improve the durability of the asphalt mixture, or in different
⇑ Corresponding author.
E-mail addresses: joao.crucho@tecnico.ulisboa.pt (J.M.L. Crucho), jose.manuel.
neves@tecnico.ulisboa.pt (J.M.C. Neves), capitao@isec.pt (S.D. Capitão),
luispicadosantos@tecnico.ulisboa.pt (L.G. Picado-Santos).
words, enhance the resistance to aging [4]. The number of studies
involving nanomodified mixtures is still limited, and there is also
an important lack of studies regarding the performance over the
service life, i.e. characterization under aged conditions, and the
consequent evaluation of their durability. Amongst the nanomate-
rials, the nanoclays [5–18] and nanosilica [4,19–26] are the most
studied materials for asphalt binders modification.
The studies on the modification of asphalt binders with nanosil-
ica, standard silicon dioxide, found the following effects on the bin-
der: decrease in penetration, increase in softening point, higher
complex modulus and lower phase angle [22,26–28]. The modified
binders presented better fatigue resistance in dynamic shear
rheometer (DSR) tests [21,24]. Regarding the behavior under low
temperature, some authors [21,23,26,27] found the modification
to cause higher creep stiffness and lower creep rate (m-value) in
bending beam rheometer (BBR) tests, indicating worst perfor-
mance. Concerning asphalt mixtures, the modification with

https://doi.org/10.1016/j.conbuildmat.2019.04.121
0950-0618/Ó 2019 Elsevier Ltd. All rights reserved.
 J.M.L. Crucho et al. / Construction and Building Materials 214 (2019) 178–186
nanosilica lead to higher Marshall stability, higher indirect tensile
strength (ITS), improved water sensitivity, higher stiffness modu-
lus and lower permanent deformation [4,20,21,25,29–33].
The modification of asphalt mixtures with nanosilica can be
beneficial for improving the mixture aging resistance
[4,21,22,26]. When properly dispersed, the presence of these
nanoparticles can slow the polymer’s aging process [21]. Studies
about the properties and rheology of modified asphalt binder
found that the introduction of nanosilica improved the viscosity
aging index and led to reductions in the rheology aging index
and carbonyl index (evaluated using FTIR spectrums), indicating
a delay in the oxidative aging process [22,26]. A study evaluating
the effect of aging on a nanosilica modified mixture [4], concluded,
from the computation of an aging index based on laboratory tests,
that the long-term aging was reducing with the increase of
nanosilica content.
Clays are naturally occurring layered mineral silicates. The
nanometric dimension of the nanoclay is the thickness of its sili-
cate layers of about 1–2 nm. Authors studying nanoclays, gener-
ally, focused on bentonite which is mostly constituted of
montmorillonite (smectite group), pure montmorillonite (calcium
or sodium montmorillonite) and organically modified clays. The
variety of nanoclay materials and asphalt binders to be modified,
standard or polymer modified, led to some variability in the
obtained effects. Regarding the effects of the nanoclay modification
on the properties of the asphalt binder, generally, authors report:
reduction of penetration, increase in softening point, increase in
viscosity, increase in complex shear modulus and decrease in
phase angle [8,10,14,15,18,26,28,34–37]. The effects of the nan-
oclay modification on the performance of the asphalt mixture
properties were: improved water sensitivity, higher stiffness mod-
ulus, better fatigue resistance and lower permanent deformation
[7–9,12,13,17,30,38–40]. The modification of nanoclays with
organic modifiers was justified by the expectation of obtaining
exfoliated structures in the final modified binder, thus achieving
higher performance improvements. The raw nanoclays, in their
hydrophilic natural form, can be more difficult to disperse into
the asphalt matrix and may form only intercalated structures
[41]. Generally, the modified nanoclays caused higher effects on
the modified binder, however, authors that studied asphalt binder
modification with raw nanoclays also reported positive effects,
occasionally even better than the modified nanoclays
[15,16,18,35,42].
Several authors [14,18,42–46] already highlighted the potential
of the nanoclays to enhance the aging resistance of the asphalt bin-
ders. Such effect can depend on the neat asphalt binder to be mod-
ified [47]. Studies regarding the aging of asphalt binders under
rolling thin-film oven (RTFO), thin-film oven (TFO), pressure aging
vessel (PAV) and ultraviolet (UV) radiation [14,43,44] found that
the modifications with nanoclays lead to: lower viscosity aging
index, higher retained penetration, lower softening point incre-
ment and higher ductility retention rate. Results of DSR tests also
suggested that the presence of nanoclays effectively reduced the
thermo-oxidative aging of the binder, as the nanoclay modified
binders presented lower aging factor [42,45]. Zare-Shahabadi and
coworkers [18] performed BBR tests on PAV-aged samples of neat
and two modified asphalt binders, one with raw bentonite and
other with organically-modified bentonite (obtained by ion
exchange with octadecylammonium salt), and concluded that the
first caused a decrease in creep stiffness and a increase in the m-
value, and the second caused a decrease in creep stiffness and also
a decrease in the m-value. The authors suggest that the clay plate-
lets prevented the oxidation of the asphalt matrix and volatiliza-
tion of light oil molecules. A study about the effect of
nanomaterials on aging and water sensitivity of asphalt mixtures
found that the use of raw nanoclay improved water sensitivity
179
under all aging conditions, as well as presented better aging index
based on the ITS results of unaged and aged specimens [39].
The zero-valent nanoiron, or nano zero-valent iron, is a ferrous
powder of non-valent chain, mostly iron particles and iron oxides.
The high reactivity and specific surface of these nanoparticles
allowed their use in reduction technologies, as ground-water
remediation and wastewater treatment [48,49]. The modification
of asphalt binder with zero-valent nanoiron leads to lower pene-
tration values and to an increase in softening point and viscosity
[30]. Regarding the asphalt mixtures, the modification with
nanoiron particularly enhanced water sensitivity [30,50]. The
nanoiron modification also presented better affinity aggregate-
binder and lower permanent deformation [30].
There is an expectation that the use of nanoiron will improve the
aging resistance of the asphalt mixture. The nanoiron has a reducing
activity and due to the high specific surface of the nanoparticles, it
can rapidly oxidize to iron oxides thus reducing the effective con-
centration of dissolved oxygen in the asphalt mixture. The effects
of the of the nanoiron modification on the aging of the asphalt mix-
ture are still not clear. A study that conducted ITS tests in unaged
and aged specimens found that the nanoiron modified mixture
had aging index values slightly higher than the neat mixture [39].
Such results indicate worse aging resistance, nevertheless such con-
clusion based only in one specific test can be premature.
It can be concluded that the effects on mechanical performance
and aging resistance will be dependent on the type of nanomaterial
used in the asphalt binder modification. The aging phenomenon
influences the chemistry and rheology of the asphalt binder, lead-
ing to a degradation of its properties [51]. The aging of the asphalt
binder occurs mostly due to oxidation and volatilization of its com-
ponents [52]. Concerning rheology, aging causes an increase in
complex shear modulus and creep stiffness, and a decrease in
phase angle and creep rate (m-value) [53–55]. The aged asphalt
binder becomes stiffer and more brittle [56–58], presenting an
increase in viscosity and softening point and a decrease in penetra-
tion [59]. The effect of aging on the asphalt mixtures is similar,
leading to an increase of stiffness modulus and decrease of phase
angle [60], thus, being associated with several pavement dis-
tresses, such as fatigue cracking, top-down cracking, aggregates’
stripping and raveling [60–62].
To evaluate in laboratory the aging of asphalt pavements, the
simulation of aging in compacted asphalt mixtures would be
preferable and more representative than the simulation of aging
in the binder separately or in loose (uncompacted) asphalt mix-
ture. The morphology of the compacted asphalt mixture, particu-
larly the air-voids content, configuration and interconnectivity,
have an important role in accelerating/retarding the aging process
[63]. Regarding the field aging caused by environmental condi-
tions, several authors already highlighted the importance of UV
radiation [64–72] and moisture damage [73–76].
The objective of this study is to evaluate the influence of three
different nanomodifications in durability and long-term perfor-
mance of asphalt mixtures. The nanomaterials selected for this
study were nanosilica, nanoiron (zero-valent iron) and nanoclay
(hydrophilic bentonite). To simulate in laboratory the aging of
the compacted asphalt mixture was used the Técnico accelerated
aging (TEAGE), method that was described and compared with
LTOA in Crucho et al., 2018 [77]. This method was tuned to simu-
late seven years of aging due to environmental conditions in Lisbon
area. An experimental program was implemented to characterize
the mechanical performance of the aged mixtures, including: stiff-
ness, fatigue resistance, indirect tensile strength and characteriza-
tion of the recovered binders. The obtained results were compared
with the characterization of mechanical performance of the
unaged mixtures published in a previous work of the authors
[30]. To quantify the effects in durability, it was determined the
180 J.M.L. Crucho et al. / Construction and Building Materials 214 (2019) 178–186
aging sensitivity of the obtained performance indicators and com-
puted a global aging index.
2. Materials and methods
2.1. Materials and sample preparation
To allow a proper comparison of results, the materials used in this study and the
methods used for the production of the asphalt mixtures were the same that were
used on the previous study about the mechanical performance of nanomodified
asphalt concrete (AC) under unaged conditions [30]. Thus, the materials used in this
study were: neat asphalt binder 35/50 penetration grade; granitic aggregates; lime-
stone filler; and nanomaterials to modify the asphalt binder. The studied mixture
corresponds to a gap-graded AC14 surf 35/50 according to the European normative
EN 13108-1, which aggregate gradation is presented in Fig. 1.
The nanomaterials used in this study were: nanosilica (NSIL), zero-valent
nanoiron (NZVI) and nanoclay bentonite (NCBT). The NSIL, is silicon dioxide, SiO2,
has an average particle size of 70 nm, a specific surface of 64 m2/g and pH in the
range of 6.5–7.5. The NZVI is mostly iron nanoparticles, Fe (65%–80%), and iron oxi-
des, FeO and Fe3O4 (20%–35%). It has an average particle size of 50 nm, a specific
surface higher than 25 m2/g and alkaline properties (pH from 11 to 12). The NCBT
is hydrophilic bentonite, H2Al2O6Si, that has a nanometric dimension in the thick-
ness of its silicate layers of about 1–2 nm and has a pH in the range of 6–9. The neat
asphalt binder was modified using the dry blending method, as used in the previous
study [30], that consists in adding the nanoparticles into the heated asphalt binder
(at 160 °C) and apply mechanical stirring at 2000 rpm during 60 min. To promptly
evaluate the proper dispersion of the nanoparticles in the asphalt binder, the soft-
ening point temperature of samples collected from the top and bottom of the mod-
ified binder blend was compared. All modifications presented small differences
(0.4 °C, 2.3 °C and 0.1 °C, for nanosilica, nanoiron and nanoclay, respectively), thus,
the mechanical stirring process was considered acceptable. Each nanomodified bin-
der has 4% nanomaterial content (in mass of the final binder).
In total, four mixtures of the type AC14 were produced according with the bin-
der being used: not modified (neat 35/50 asphalt binder); NSIL modified; NZVI
modified; and NCBT modified. All the blends were produced using a laboratory
mixer (EN 12697-35), considering a binder content of 4.5% and the mixing and com-
paction temperatures were 164 °C and 154 °C, respectively. The optimum binder
content previously determined, 4.5%, was set for the neat AC14 using the Marshall
method and then the same was considered in the production of all the other mix-
tures. This assumption allows a better evaluation of the effects of the nanomodifi-
cations as the binder type is the only variable. Cylindrical specimens (63.5 mm
height and 101.5 mm diameter) were produced using the impact compactor apply-
ing 50 blows on each side (EN 12697-30). Prismatic specimens
(5 cm  30 cm  40 cm) were produced using the roller compactor (EN 12697-33)
and sawed into prismatic beams (5 cm  5 cm  40 cm). The produced mixtures
presented similar properties: bulk density of 2.390 Mg/m3, 3.6% void content and
14% voids in mineral aggregate (VMA). After production, the compacted specimens
were conditioned for accelerated aging simulation in TEAGE according to the
described in the following section.
2.2. Aging conditioning
The TEAGE method was used to simulate in laboratory the aging of the AC mix-
tures. This method aims to simulate aging due to the exposure to environmental
conditions for a certain period of time, using available weather data of the service
100
90 Upper limit
80 Gradation
Lower limit
Percent passing
70
60
50
40
30
20
10
0
100 10 1 0.1 0.01
Sieve size (mm)
Fig. 1. AC14 aggregate gradation.
location. In this study the data acquired by the weather station of Instituto Superior
Técnico, located in Lisbon, was used to determine the total energy received due to
solar radiation and precipitation. Lisbon receives an annual energy of 5.7 GJ/m2
due to solar radiation and has 40 days per year with precipitation higher than
5 mm. The TEAGE method proposes an equivalency between the energy received
by solar radiation and the applied UV radiation, as well as between the number
of days with precipitation higher than 5 mm, considered to be enough to cause
some surface water flow, and the application of watering drying cycles.
The TEAGE prototype was tuned to simulate seven years of Lisbon environmen-
tal conditions. The prototype was set to apply UV radiation continuously during
30 days, with no rest periods, and a combination of four watering/drying cycles
per day with 40 min immersion per cycle. The prototype also includes a group of
cooling fans that continuously induce an air draft, preventing the specimens to
reach temperatures higher than 60 °C. A more detailed description of the TEAGE
method and its effects can be found elsewhere [77].
The TEAGE prototype enables a more realistic simulation of the field aging due
to environmental conditions and allows some equivalency between the condition-
ing process and field service age. The exposure to UV radiation and the water wash-
ing effect caused a visible change on the coloration of the asphalt mixtures (Fig. 2),
similar to the observed in aged asphalt pavements. The method also induces an
aging gradient through the depth of the specimen, being the top surface more
severely aged than in-depth [77].
2.3. Test methods
The main focus of the experimental study (Fig. 3) was to evaluate the mechan-
ical performance of the neat and nanomodified AC mixtures after being subjected to
accelerated aging in laboratory. The aged AC mixtures were tested for stiffness, fati-
gue resistance and indirect tensile strength. After the fatigue tests, the binders were
recovered and tested for fundamental characterization: penetration and softening
point. As the TEAGE conditioning causes an aging gradient in the depth of the spec-
imens the binder recovery was performed in two different sections of the speci-
mens (Fig. 4): top section, from the UV exposed surface till middle depth of the
specimen; and base section, from middle-depth till bottom of the specimen.
Toluene was the solvent used in the process of binder recovery.
The test methods were selected according to the current European standards
(Table 1). The stiffness and fatigue resistance tests were conducted in the four-
point bending beam equipment. The temperature selected for these tests was
20 °C as it is a temperature fairly representative of the Portuguese in-service condi-
tions and also commonly used in these type of tests [78]. The stiffness results are
the average of 10 individual specimens per mixture. In the fatigue tests a total of
18 specimens per mixture were tested and the adopted failure criterion was a
50% reduction of the initial stiffness modulus determined at the 100th load cycle.
The indirect tensile strength tests were also used to evaluate the water sensitivity
by calculating the ITSR. ITSR is the ratio between the ITS of conditioned (wet) spec-
imens, by immersion in water at 40 °C for approximately 70 h (ITSwet), and the ITS
Fig. 2. Color of the AC specimens before (left) and after (right) TEAGE conditioning.
 J.M.L. Crucho et al. / Construction and Building Materials 214 (2019) 178–186 181

Fig. 3. Experimental plan.

Table 1
Test methods and conditions.

Test Standard Method Conditions

Stiffness EN 12697-26 Four-point 20 °C; 1, 3, 5, 10, 20
top bending and 30 Hz; 50 lm/m
Fatigue resistance EN 12697-24 Four-point 20 °C; 10 Hz; 150,
bending 250 and 350 lm/m
Indirect tensile EN 12697-23 Diametral 15 °C
base strength compression
Water sensitivity EN 12697-12 Method A (ITSR) 15 °C
Binder recovery EN 12697-3 Rotary –
evaporator
Fig. 4. Designation of binder recovery locations in the TEAGE-aged specimens. Softening point EN 1427 Ring and ball –
Penetration EN 1426 Needle 25 °C
penetration

of unconditioned (dry) specimens (ITSdry). The ITS results are the average of at least
three individual specimens per group.
To evaluate the effect of the nanomodifications on the aging resistance, the test
results of the aged mixtures were compared with the test results of the mechanical The variation between unaged and aged conditions can be simply designated as
performance obtained under unaged conditions published in a previous study of the aging sensitivity. A high aging sensitivity indicates that the aging process had a dra-
authors [30]. This effect can be quantified by the variation that the experimental matic effect in that parameter. On the other hand, an aging sensitivity near zero
parameters suffered with the aging process regarding their initial (unaged) value. indicates that the aging process had no effect in that parameter.
182 J.M.L. Crucho et al. / Construction and Building Materials 214 (2019) 178–186

3. Results and discussion 10000

Stiffness modulus (MPa)

Neat - unaged
3.1. Evaluation of binder behavior NSIL - unaged
NZVI - unaged
Table 2 presents the results of penetration and softening point NCBT - unaged
of the fresh and recovered binders. The samples designated as fresh Neat - aged
binders were collected prior to the asphalt mixture production. The NSIL - aged

samples designated TEAGE-aged were recovered from the aged NZVI - aged

specimens following the fatigue tests, and according to the location NCBT - aged

scheme presented in Fig. 4. 1000

1 10 100
As expected, the recovered binders presented lower penetration
Frequency (Hz)
and higher softening point than the correspondent fresh binders.
The hardening of the binder was caused by the processes of mixing, Fig. 5. Stiffness modulus under unaged and aged conditions.
compaction and TEAGE aging. Also, as previously highlighted, the
TEAGE method induces an aging gradient through the depth of
the specimens, thus the binders recovered from the top sections 30
were more severely aged than the binders recovered from the base Neat - unaged
section. Considering the average value (between top and base sec- 25

Phase angle (º)

NSIL - unaged
tions) of the aged specimens, the neat binder presented a 45% NZVI - unaged
decrease in penetration and a 26% increase in softening point. 20
NCBT - unaged
The modification with nanosilica presented a 24% decrease in pen- Neat - aged
15
etration and a 21% increase in softening point while the modifica- NSIL - aged
tions with nanoiron and nanoclay behaved similarly to the neat
10 NZVI - aged
binder. These results suggest that nanosilica modification is suffer-
NCBT - aged
ing less hardening effect, i.e. aging. Nevertheless, looking to the 5
results of the fresh binders, if compared to the neat binder the 1 10 100
nanosilica modification itself had already caused a considerable Frequency (Hz)
reduction in penetration and increase in softening point, thus it
is not possible to immediately conclude that aging resistance is Fig. 6. Phase angle under unaged and aged conditions.

being improved.
range, showing a reduction if compared with the neat mixture of
9% at 1 Hz to 5% at 30 Hz.
3.2. Evaluation of asphalt mixture performance
To understand if the nanomodifications gave some contribution
to aging resistance, the results of stiffness modulus and phase
3.2.1. Stiffness
angle at unaged and aged conditions were compared and the aging
The stiffness modulus and the phase angle obtained from the
sensitivity (variation of the parameter regarding its unaged value)
stiffness tests are presented in Figs. 5 and 6, respectively. As
was computed (Figs. 7 and 8). The positive or negative contribution
expected, each aged mixture presented an increase in the stiffness
of the nanomodifications is evaluated according the aging sensitiv-
modulus and a reduction in the phase angle if compared with the
ity of the neat AC that is considered as reference. The aging sensi-
results of the correspondent unaged mixture. Under aged condi-
tivity of the neat AC and nanosilica were very similar, presenting
tions, the modification with nanoiron presented the highest stiff-
fairly close values for both stiffness modulus and phase angle.
ness modulus across the entire frequency range, followed by the
The modification with nanoiron had the highest values in every
modifications with nanosilica and nanoclay, and finally, the neat
parameter and frequency, clearly indicating that the aging resis-
AC presented the lowest stiffness modulus. Compared with the
tance was not being improved. Nanoclay modification showed a
stiffness modulus of the neat AC, the increase observed in stiffness
higher aging sensitivity concerning the stiffness modulus but
modulus of the nanomodified mixtures was dependent on the test
lower concerning the phase angle, thus the outcome is not obvious.
frequency. At the lowest frequency (1 Hz) the increase in stiffness
modulus were 10%, 16% and 6% for the modifications with nanosil-
ica, nanoiron and nanoclay, respectively. At the highest frequency 3.2.2. Fatigue
(30 Hz) the increase in stiffness modulus were 0%, 10% and 1% The aged mixtures presented worse fatigue resistance if com-
for the modifications with nanosilica, nanoiron and nanoclay, pared with the fatigue resistance obtained under unaged condi-
respectively. Concerning the phase angle, except some variation tions. As highlighted previously by the recovered binder tests
at the low frequencies, the modification with nanoclay presented and the mixtures stiffness tests, the aging process leads to the
values similar to the neat AC. The modifications with nanosilica hardening of the asphalt binder, consequently, the asphalt mixture
and nanoiron presented similar phase angle across the frequency becomes stiffer and more brittle, thus a reduction of the fatigue

Table 2
Characterization of the fresh and recovered binders.

Modification Penetration (101 mm) Softening point (°C)

fresh binder TEAGE-aged fresh binder TEAGE-aged
top base average top base average
Neat 41.3 20.3 25.0 22.7 55.7 72.3 68.0 70.2
NSIL 25.0 18.7 19.3 19.0 59.3 72.7 70.3 71.5
NZVI 35.7 19.3 19.7 19.5 56.5 72.1 69.6 70.8
NCBT 40.1 19.3 23.7 21.5 57.7 73.8 68.5 71.2
 J.M.L. Crucho et al. / Construction and Building Materials 214 (2019) 178–186 183

sented 8% and 14% increase, respectively. Regarding aging sensitiv-

Stiffness mod. aging sensitivity

80
ity, the aging process caused a reduction of strains e4 and e6. The
70 reduction of e6 was 15%, 11%, 20% and 9% for neat, nanosilica,
60 nanoiron and nanoclay, respectively. The reduction of e4 was 24%
Neat
50 for nanosilica, and more homogenous among neat, nanoiron and
(%)

NSIL nanoclay, of 11%, 14% and 12%, respectively.

40
NZVI Considering as reference the aging sensitivity of the neat AC, the
30
NCBT modification with nanoiron presented higher aging sensitivity on
20
both, e4 and e6, indicating that the aging resistance was not being
10 improved. On the other hand, particularly regarding lower strain
0 levels, the modification with nanoclay presented lower aging sen-
1 Hz 3 Hz 5 Hz 10 Hz 20 Hz 30 Hz sitivity combined with longer fatigue life under unaged conditions.
Although the effects were more moderate, similar conclusions can
Fig. 7. Aging sensitivity in stiffness modulus.
be withdrawn for the nanosilica modification.

3.2.3. Indirect tensile strength

Phase angle aging sensivity (%)

-80 The effect of aging in the indirect tensile strength is presented in

-70
-60
-50
-40
-30
-20
-10
0 and nanoclay, respectively. The increase in ITS of the water sensitiv-
1 Hz 3 Hz
Fig. 8. Aging sensitivity in phase angle.
resistance was expected. Fig. 9 presents the fatigue lines plotted in
a log-log space. The fatigue lines were drawn according to the
regression described by Eq. (1):
e ¼ a  Nb
where e is the applied strain (lm/m), N is the number of loading
cycles, a and b are the regression coefficients. Table 3 presents the
fatigue complementary results: a and b – regression coefficients,
e4 – the strain correspondent to a fatigue life of 104 cycles, e6 –
the strain correspondent to a fatigue life of 106 cycles, the slope
of the fatigue law, and R2 – coefficient of determination.
Under aged conditions, the nanoclay modification had the best
performance, followed by the nanosilica modification, and finally
the neat AC and nanoiron modification. At the higher strain,
350 lm/m, the neat, nanosilica and nanoiron presented very simi-
lar behavior. At the lower strain, 150 lm/m, compared to the neat
AC, the modification with nanoiron presented a slightly worst fati-
gue resistance but nanosilica presented some improvement.
Concerning the parameter e6, that is frequently used to compare
different mixtures, relatively to the neat AC, under aged conditions,
the nanoiron had 3% reduction, while nanosilica and nanoclay pre-
Table 4 where are shown the results of ITSdry, ITSwet and ITSR. Com-
pared with the unaged specimens, the correspondent aged speci-
Neat mens presented higher ITS values. The ITS increases with the
NSIL aging period because of the hardening experienced by the binders
NZVI during the aging process [79]. This result is in good agreement with
the findings of the characterization of the recovered binders and
NCBT
stiffness tests. The increase in ITS of the unconditioned specimens
(ITSdry) was 59%, 27%, 75% and 23% for neat, nanosilica, nanoiron
5 Hz 10 Hz 20 Hz 30 Hz ity conditioned specimens (ITSwet) was 69%, 36%, 54% and 42% for
neat, nanosilica, nanoiron and nanoclay, respectively.
Regarding the ITSR, although some variations were observed,
the aging process did not affect this ratio significantly. A figure
around an increase of 10% was reached. However, sometimes it
could happen a slight decrease in ITSR, much probably related with
samples’ properties variation that induces more/less increase for
ITS (dry and wet) figures and then a different trend for the ratio
ð1Þ wet/dry. Nevertheless, the variations of ITSR caused by aging were
complying with the repeatability criterion (approximately 15%)
mentioned in EN 12697-12. For the cases of nanosilica and nan-
oclay, the increase in ITS caused by aging was smaller than the
observed with the neat mixture – lower aging sensitivity, suggest-
ing that some improvement in aging resistance has occurred.
Concerning the effect of the nanomodifications, the conclusions
obtained with the unaged specimens are valid for the aged mix-
tures as well. Compared with the neat AC, the nanomodified mix-
tures presented higher ITSdry, ITSwet, and ITSR, either for unaged,
either for aged specimens. Under aged conditions the mixture
modified with nanosilica presented the highest ITSR, and also the
highest ITSdry and ITSwet values, 27% and 56% higher than the neat
AC, respectively. Similar trend was observed with the nanoiron and
nanoclay modified mixtures, presenting higher ITSdry and ITSwet
values, 15% and 37%, for nanoiron, and 12% and 31%, for nanoclay,
respectively.

3.3. Analysis of aging

1E+03
Neat - unaged
The evaluation of the mechanical performance of the modified
NSIL - unaged
mixtures under unaged conditions was presented in a previous
Strain (µm/m)

NZVI - unaged
work [30], where the comparison of mechanical performance
NCBT - unaged
among different mixtures was done using the global performance
Neat - aged
index (GPI) suggested by Martinho et al., 2017 [80]. However,
NSIL - aged
under aged conditions, the GPI is not adequate because some
NZVI - aged
parameters (e.g. stiffness modulus and indirect tensile strength)
NCBT - aged
suffer an increase in their values due to the hardening effect caused
1E+02
1E+03 1E+04 1E+05 1E+06 1E+07 by aging, thus a higher aging sensitivity can be misunderstood as
Number of cycles (N) an improvement in performance.
The durability of an AC mixture is highly related to its aging
Fig. 9. Fatigue lines under unaged and aged conditions. sensitivity, thus, to give a better insight of the improvements
184 J.M.L. Crucho et al. / Construction and Building Materials 214 (2019) 178–186

Table 3
Fatigue complementary results.

Aging Mod. a b e4 (lm/m) e6 (lm/m) slope R2

unaged Neat 1559.46808 0.16110 354 168 6.21 0.94
NSIL 2114.85998 0.18058 401 175 5.54 0.95
NZVI 1526.20286 0.15714 359 174 6.36 0.95
NCBT 1674.28543 0.16132 379 180 6.20 0.98
TEAGE (7 years) Neat 1502.13323 0.17001 314 143 5.88 0.80
NSIL 1191.63811 0.14786 305 155 6.76 0.86
NZVI 1546.07314 0.17435 310 139 5.74 0.88
NCBT 1382.41660 0.15465 333 163 6.47 0.93

Table 4 GPI (%)

Indirect tensile strength tests results.
60 70 80 90 100
Aging Modification ITSdry (kPa) ITSwet (kPa) ITSR (%) 0
unaged Neat 1287 739 57
10
NSIL 2050 1433 70 Neat
NZVI 1357 1116 82
20

GAI (%)
NCBT 1879 1154 61 NSIL
TEAGE (7 years) Neat 2052 1253 61
30
NSIL 2604 1952 75
NZVI
NZVI 2368 1722 73
40
NCBT 2303 1642 71
NCBT
50

attained regarding aging resistance, a global aging index (GAI) is
proposed. The GAI computes the equivalent to a weighted aging
sensitivity. GAI is the weighted sum of the variations caused by
aging in the selected parameters, Eq. (2).
 aged  AC and finally the nanoiron. As the nanoiron presents a GAI higher
X P unaged 
 i;j  Pi;j  than the neat AC, the nanomodified mixture is more prone to
GAIi ¼ wj    100
j¼1;2;3
 Punaged 
i;j
Pi,j is the value of parameter j for the mixture i. The mixtures
considered were: (1) neat, (2) nanosilica, (3) nanoiron and (4) nan-
oclay. The selected parameters were: (1) Sm – stiffness modulus at
10 Hz, (2) e6 – strain for one million cycles fatigue life and (3) ITS –
indirect tensile strength. The parameters’ weights (wj) considered
for GAI computation were: Sm 40%, e6 20% and ITS 40%. The selec-
tion of the parameters and attributed weights is qualitative and
based on what was considered by the authors the most important
aging effects on a surface course. In fact, it is believed that Sm and
ITS represent very well together the most part (80% for the sum of
the two parameters) of the rigidity increase due to aging of an
asphalt concrete for the surface course, leaving for e6 the remain-
ing representative part (20%) because, in a certain extent, it stands
for the lack of flexibility related to aging. The higher the parame-
ters’ variations caused by the aging process, the higher the GAI
score. If the GAI score is low, near 0%, the mixture has suffered
no change in the considered parameters, presenting virtually no
loss in its initial performance. Fig. 10 presents the ranking obtained
according to the GAI. The modifications with nanosilica and nan-
60
53%
50
Sm
40 36%
29.8
GAI (%)
60
Fig. 11. Global analysis of performance and aging sensitivity.
oclay presented the lowest aging sensitivity, followed by the neat
ð2Þ aging.
The combination of GPI and GAI is useful to compare perfor-
mance and durability among different mixtures. The qualitative
nature of global indexes as the GPI or the GAI can have some influ-
ence on the outcome, for example, by adjusting the parameters’
weights or selecting a different set of parameters. For the studied
mixtures, the effect was limited, as the relative ranking of the mix-
tures remained the same after conducting a sensitivity analysis on
the chosen parameters’ weights. Fig. 11 presents a global analysis
of the mixtures, considering the previously determined GPI [30]
and GAI scores. The modification with nanosilica had the best
result in both indexes, showing improved initial performance and
indicating better durability. The modification with nanoclay pre-
sented a similar behavior, although, if compared with nanosilica,
the improvement in initial performance was more modest. The
modification with nanoiron presented an improvement in initial
performance but worse durability, revealing to be not interesting
for asphalt mixture modification.
4. Conclusions
The paper has evaluated the durability of asphalt concrete mod-
ified with different nanomaterials: nanosilica, zero-valent
nanoiron and nanoclay. The neat and nanomodified asphalt con-
crete mixtures were aged to an equivalent of seven years of expo-
sure to environmental conditions in Lisbon area, using the TEAGE

25%
method [77]. An experimental study was performed to obtain a
30
22% characterization of the mechanical performance of the mixtures
23.8
20 4.0 9.0 ITS under aged conditions. The aged mixtures were tested for stiffness,
10.8 1.9 fatigue resistance and indirect tensile strength. The correspondent
10 3.0 2.3 18.9 recovered binders were tested for penetration and softening point.
14.6
9.2 8.5 The obtained results were compared with a previous study regard-
0
Neat NSIL NZVI NCBT
ing the characterization of the same nanomodified mixtures under
unaged (fresh) conditions, allowing the analysis of aging sensitivity
Fig. 10. Ranking of the mixtures according to GAI. and computation of a global aging index.
 J.M.L. Crucho et al. / Construction and Building Materials 214 (2019) 178–186
The following main conclusions are drawn from the laboratory
study:

The aging process affected the performance of the mixtures pro-
voking a hardening effect. All the aged mixtures presented a
stiffer and more brittle behavior as highlighted by the deter-
mined test parameters that evolved as expected: increase in
stiffness modulus, reduction in phase angle, reduction in fatigue
resistance and increase in indirect tensile strength.

The modification with nanosilica enhanced aging resistance and
led to superior mechanical performance under aged conditions.
This modification presented the lowest score in the global aging
index (14% less compared with the neat AC). Regarding the
mechanical performance under aged conditions, the modifica-
tion with nanosilica had better results in all the tests: higher
stiffness modulus, lower phase angle, higher fatigue resistance,
higher ITS and better water sensitivity.

The modification with zero-valent nanoiron presented higher
aging sensitivity and limited effects regarding the mechanical
performance under aged conditions. This modification had the
highest global aging index (17% more compared with the neat
AC), indicating inferior durability. Under aged conditions, this
modification presented better performance in ITS and water
sensitivity, consistent with the previously found under unaged
conditions. Nevertheless, the fatigue resistance had worsened,
possibly, partially explained by the abrupt increase of stiffness
modulus observed.

The modification with nanoclay enhanced aging resistance and
presented improvements in the mechanical performance under
aged conditions. Compared to the neat AC, this modification
presented lower global aging index (11% less). Regarding the
mechanical performance under aged conditions, the modifica-
tion with nanoclay presented improvements in all tests: higher
stiffness modulus, lower phase angle, higher fatigue resistance,
higher ITS and better water sensitivity.
A global analysis of the mechanical performance and durability
indicates that the modifications with nanosilica and nanoclay were
adequate to improve the mechanical performance during service
life and enhance aging resistance of the asphalt mixtures.
Conflict of interest
None.
Acknowledgments
This work was supported by the Portuguese national funding
agency for science, research and technology (FCT) under the MIT
Portugal Program – Transportation Systems, through the doctoral
degree grant SFRH/BD/51938/2012. This support is gratefully
acknowledged. The authors would like to thank to meteo|Técnico
for providing the weather data and to NANO IRON for supplying
the zero-valent iron nanoparticles.
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