Construction and Building Materials 214 (2019) 187–195

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Construction and Building Materials

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

Nanoindentation characterization of aging gradient of mastic in asphalt

mixtures
Zeheng Yao a, Guilin Lu a, Jun Yang a,⇑, Minghui Gong b,c, Zhiyun Tang a, Jiayue Xue a, Xiaorui Zhang a
a
School of Transportation, Southeast University, 2 Southeast University Road, Nanjing 211189, PR China
b
State Key Laboratory of High Performance Civil Engineering Materials, 118 Liquan Road, Nanjing 211100, PR China
c
Sobute New Materials Co., Ltd, 118 Liquan Road, Nanjing 211100, Jiangsu, PR China

h i g h l i g h t s

Clarify the effects of mixture gradation and polishing on nanoindentation results.

Characterize the age-hardening behavior of asphalt mixtures using nanoindentation.

Describe the vertical aging gradient in asphalt mixtures by nanoindentation.

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

Article history: Understanding the aging behavior of asphalt mixtures is of great significance to the design, construction
Received 23 December 2018 and maintenance of asphalt pavements. Numerous studies have been conducted on the aging phe-
Received in revised form 3 April 2019 nomenon and its effects on mixture properties. However, conventional testing methods focus mainly
Accepted 8 April 2019
on the global view or average value of the performance of aged mixtures, while the inner aging gradients
Available online 20 April 2019
are seldom addressed. The aging gradient, referring to the differences of aging effects in asphalt mixtures
due to different accessibilities to aging conditions, represents the true aging behavior of asphalt mixtures.
Keywords:
Hence, a micromechanical testing technique, nanoindentation, was used in this paper to investigate this
Asphalt mixture
Aging gradient
issue. The effects of mixture gradation and polishing in sample preparation process on nanoindentation
Nanoindentation results were explored first. Then the vertical changes of modulus of asphalt mastic in asphalt mixture
Modulus samples were characterized by nanoindentation to describe the aging gradient in different aged mixture
samples. Dynamic modulus test was also performed for data supplement and comparison. Results show
that gap-graded mixtures are suitable for nanoindentation test and a careful and standard polishing
treatment will not affect the reliability of nanoindentation data. Nanoindentation can well characterize
the age-hardening behavior of asphalt mastic and the aging gradient in long-term aged asphalt mixtures
is approximately in a logarithmic curve form. Nanoindentation modulus results indicate that 8d of lab-
oratory long-term aging in this paper can only affect the upper sections of dense asphalt mixtures.
This paper suggests that nanoindentation can achieve a quantitative, mechanical and precise character-
ization of aging gradient in asphalt mixtures and is therefore promising in further research of asphalt
materials.
Ó 2019 Elsevier Ltd. All rights reserved.

1. Introduction duction (short-term aging) and continuous exposure to environ-

Aging of asphalt pavements and the following performance
deterioration are always key issues in pavement research field.
For asphalt pavements, aging refers to the inevitable chemical,
physical and mechanical changes of asphalt mixtures during pro-
⇑ Corresponding author.
E-mail addresses: yangjun@seu.edu.cn (J. Yang), gongminghui@cnjsjk.cn
(M. Gong), 101101885@seu.edu.cn (X. Zhang).
mental conditions in service (long-term aging) [1]. Aging of
asphalt materials can mainly be divided into three mechanisms:
volatilization, oxidation and steric hardening [2,3], which collec-
tively cause the performance degradation. Generally, aged asphalt
mixtures exhibit higher modulus, reduced moisture, cracking and
fatigue resistance and consequently lower service life. Therefore,
the investigation of aging behavior of asphalt mixtures are of great
significance to the design, construction and maintenance of asphalt
pavements.

https://doi.org/10.1016/j.conbuildmat.2019.04.054
0950-0618/Ó 2019 Elsevier Ltd. All rights reserved.
188 Z. Yao et al. / Construction and Building Materials 214 (2019) 187–195
Extensive studies have been conducted on the aging phe-
nomenon of asphalt materials and its impact on material perfor-
mance [4–7] (In the rest of this paper, aging generally refers to
oxidative aging). However, there are still apparent gaps between
existing research achievements and precise description of aging
behavior of asphalt mixtures. Actually, aging effects inside asphalt
mixtures are not evenly distributed. Obviously, there exists aging
gradient, namely different aging severities, from the surface to
inner part of both field cores and laboratory aging mixtures due
to different accessibilities to aging conditions (temperature, oxy-
gen accessibility and so on). Moreover, only asphalt constituents
are affected in aging process while aggregates remain nearly
unchanged in mixture system. The overlook of those facts may lead
to unreasonable design and maintenance of roads, for example,
excessive milling of asphalt courses. Conventional physical and
mechanical tests focus mainly on macro indicators, such as
strength and deformation, and provide a global view of asphalt
mixture performance. Their results can be seen as an average value
which cover up the presence of aging gradient mentioned above
and therefore fail to characterize the actual aging behavior of
asphalt mixtures. Some researchers examined aged asphalt binder
properties through chemical extraction and recovery to investigate
the aging effects in asphalt mixtures [3,5,8]. For example, Wang
extracted the aged asphalt from different courses and found that
binder aging severity is largely influenced by pavement depth
while showing insensitivity to the cross-sectional location [5].
But this process is destructive and does not account for the effects
of aggregate and filler particles which may not get accurate infor-
mation about the mixture performance [9]. The influence of chem-
ical solvents is also unknown. Considering the aging gradient, Ling
measures the dynamic modulus of top, middle and bottom section
of aged field cores and develops master curves including depth
shift factor [10]. However, in most of the similar research, at least
a 3–6 cm thick slice is taken as a specimen which is insufficient to
describe the consecutive aging gradient. Hence, new experiment
schemes and methods should be developed.
Nanoindentation is a nondestructive testing method focusing
on the measurements of micromechanical properties of multiphase
materials. In a nanoindentation test, a silicon carbide probe with a
radius of several nanometers indents into a specimen and the load-
depth data of the tip during loading and unloading are recorded.
Mathematical models are applied to analyze the load-depth curves
to calculate hardness and modulus of the testing point [11]. With
the help of microscope, the tip can indent into different phases
of composite materials, for example, aggregate and asphalt mastic
phase in asphalt mixtures and then determine their mechanical
properties respectively [12,13].
Nanoindentation is becoming widely used in asphalt research
field. In early research, Jäger used nanoindentation to determine
the viscoelastic properties of B50/B70 asphalt and investigate the
effects of loading rate, maximum load and temperature [14]. Later
Tarefder and other researchers systematically studied the applica-
tion of nanoindentation in asphalt materials and clarified some
experiment details and parameters [15,16]. Some researchers suc-
cessfully applied nanoindentation in research regarding moisture
damage, viscoelasticity, reclaimed asphalt pavement and so on
[17–21]. When it comes to aging research, Tarefder measured the
modulus and hardness data of aged asphalt mastic and aggregate
by nanoindentation and found nanoindentation results show an
agreement with the age-hardening behavior of asphalt mastic
[22]. Ahmad utilized Dynamic Shear Rheometer (DSR) and nanoin-
dentation to characterize the mechanical properties of extracted
asphalt binders. Results indicate that modulus results from
nanoindentation and DSR increase with the air voids of original
aged asphalt mixtures [3]. However, few efforts have been made
to investigate the aging gradient in depth direction in asphalt mix-
tures using nanoindentation or other micromechanical methods.
All existing research indicate that nanoindentation can achieve a
quantitative characterization of micromechanical behavior of
asphalt mixtures and is therefore promising in dealing with this
issue.
In summary, this paper aims to capture the vertical changes of
micromechanical properties in aged asphalt mixtures by nanoin-
dentation to characterize the aging gradient. Before this, the effects
of mixture gradation and polishing in sample preparation process
on nanoindentation results are discussed which is seldom
addressed in existing research. Dynamic modulus test was also
performed for data supplement and comparison. The research will
contribute to a better understanding of aging behavior in asphalt
mixture.
2. Objectives
This paper focuses on the application of nanoindentation in
characterization of aging gradient in asphalt mixtures which may
help better understand the aging behavior of asphalt mixtures
from a novel microscopic view. The objectives are as follows:
1. Clarify the effects of mixture gradation and polishing treat-
ment on nanoindentation results;
2. Characterize the age-hardening behavior of asphalt mixtures
of different air voids and aging levels using nanoindentation test;
3. Describe the aging gradient in different aged asphalt mixtures
through the vertical changes of nanoindentation modulus inside
the mixture samples;
4. Evaluate the laboratory aging effects in asphalt mixtures by
nanoindentation and dynamic modulus test.
3. Experiments
3.1. Nanoindentation analysis
As mentioned above, load-depth curves are recorded in a
nanoindentation test to obtain the micromechanical properties of
specimens. Oliver-Pharr method is a widely-received model used
in analysis of the load-depth curves and the calculation of hardness
and modulus value [11].
Fig. 1(a) shows a diagram of a nanoindentation test. As shown
in Fig. 1(a), an indenter penetrates into the sample surface under
the load P and then reach the maximum depth hmax. hc refers to
the height from the indenter tip to the contact circumference. After
unloading, the indenter is pulled out and the sample surface recov-
ers to a residual depth of hf. Fig. 1(b) is a typical load-depth curve
obtained from a nanoindentation test. It can be divided into three
stages: loading, dwelling and unloading. The dwelling time repre-
sents a stage where the load keeps constant while the indenting
depth continues increasing.
Due to the viscoelasticity and creep behavior of asphalt materi-
als, the indenting depth may keep increasing during the unloading
process, leading to a negative slope of the unloading curve. In this
case, Oliver-Pharr model is no longer applicable. According to Tar-
efder, the introduction and increasing of the dwelling time and
increasing loading rate can eliminate this effect [16]. Extending
the dwelling time can fully release the creep deformation of
asphalt specimens to avoid the viscoelastic behavior in unloading
process. In this case, the reduced modulus Er can be expressed as
[11]:
pffiffiffiffi pffiffiffi
Er ¼ pS=2b A ð1Þ
1 1  v 2s 1  v 2t
¼  ð2Þ
Er Es Et
 Z. Yao et al. / Construction and Building Materials 214 (2019) 187–195 189

100

80

Passing Rate (%)

60
SMA-13
40 AC-13

20

0
0.075 0.15 0.3 0.6 1.18 2.36 4.75 9.5 13.2 16 19 26.5
Sieve Mesh (mm)

Fig. 2. Gradation curves of AC-13 and SMA-13 mixtures.

the effect of air void on aging behavior of asphalt mixtures. Pen70

asphalt, basalt aggregate and limestone filler were used to prepare
all the asphalt mixture samples by gyratory compactor. All the
mixtures are 7.5 kg in weight and 150 mm in radius. No fiber
was added in SMA-13 mixtures to avoid disturbance to nanoinden-
Fig. 1. (a) Diagram of a nanoindentation test; (b) A typical load-depth curve.
tation tests on asphalt mastic. The volumetric properties of all mix-
ture samples are listed in Table 1.

where S is the slope of the unloading curve at h = hmax as shown in 3.2.2. Asphalt mastic
Fig. 1(b). A is the projected area (m2) of the indentation at the con- Smooth surface of specimens are necessary in nanoindentation
tact depth hc. b is the geometry correction factor. Es, ms, Et, mt are test to reduce the errors of testing results. So the nanoindentation
elastic modulus and Poisson’s ratio of the specimen and tip, specimens should be polished before being tested. For asphalt
respectively. materials, the polishing process may disturb the sample surface
The modulus of the specimen can be calculated from the simul- and then bring unknown effects to nanoindentation results. There-
taneous equation of Eqs. (1) and [2]. The contact area A is calcu- fore, asphalt mastic samples are prepared to investigate the effects
lated through the contact depth hc and the known geometry of of polishing because asphalt mastic can form a smooth surface
the indenter. In Oliver-Pharr model, A and hc are defined as: after cooling and hence have no need for polishing before nanoin-
dentation test.
hc ¼ hmax  ePmax =S ð3Þ Pen70 asphalt and limestone filler are used to prepare asphalt
pffiffiffi 2 mastic samples. The maximum particle size of fillers is 0.15 mm
A ¼ 3 3hc tan2 h ð4Þ and the passing rate of 0.075 mm sieve is 80.26%. The filler-
asphalt ratio is 2.08:1 according to the effective asphalt content
where hmax and Pmax are the maximum depth and load of the load-
in the above SMA-13 gradation. Fillers are slowly poured into hot
depth curve, e is a geometric constant and h is the semi-angle of the
asphalt (155 °C) and then mixed for 30 min by a shear device to
tip used. For Berkovich tip (a triangular-pyramid-shaped tip with a
prepare the asphalt mastic.
tip radius of 100 nm) in this research, e = 0.75, h = 65.27°, b = 1.034.
In this article, A for the Berkovich tip is approximated by polynomial
3.2.3. Laboratory aging
fitting in the analysis software:
Although there are many limitations of the laboratory aging
2
A ¼ c0 þ c1 hc þ c2 hc ð5Þ method in AASHTO R30 specification, it is simple to implement
and can provide a general relationship between laboratory and
where c0, c1, c2 are calibration geometric constants. In this paper, field aging behavior [9]. Hence, the oxidative aging treatment in
c0 = 20000, c1 = 2600, c2 = 24. this paper follows the AASHTO protocol [23]. Five levels of aging
treatment are performed as follows:
3.2. Sample preparation
(1) Unaged;
3.2.1. Asphalt mixture (2) Short-term aging (STA): The loose, uncompacted mixtures
Asphalt mixtures of different gradations have totally different are conditioned in a forced-draft oven for 4 h at 135 °C and
structural and mechanical properties, especially in interfacial zone then compacted;
between aggregate and asphalt mastic. It may cause great varia-
tions in nanoindentation results. To investigate the effects of mix-
Table 1
ture gradation, two typical gradations were taken into account for Volumetric properties of mixture samples.
the preparation of asphalt mixtures and nanoindentation samples:
Gradation Asphalt content Height Air voids VMA VFA
a continuous gradation (AC-13) and a gap gradation (SMA-13) as
(%) (mm) (%) (%) (%)
shown in Fig. 2. Finally, SMA-13 was proven to be more suitable
for nanoindentation test in the following sections. After that, AC-13 5.48 167.2 3.0 15.2 80.2
SMA-13 5.63 171.3 3.0 14.9 79.8
SMA-13 mixtures with different air voids (3% and 7%) were pre- SMA-13 5.63 178.8 7.0 18.4 62.0
pared through height control in compacting process to investigate
190 Z. Yao et al. / Construction and Building Materials 214 (2019) 187–195
(3) Long-term aging 2d (LTA-2d): The compacted short-term
aged mixtures are conditioned in a forced-draft oven for
2 days at 85 °C;
(4) Long-term aging 5d (LTA-5d): The compacted short-term
aged mixture are conditioned in a forced-draft oven for
5 days at 85 °C;
(5) Long-term aging 8d (LTA-8d): The compacted short-term
aged mixture are conditioned in a forced-draft oven for
8 days at 85 °C;
All SMA-13 asphalt mixture samples were aged following the
above programme in the same oven. To further simulate the field
aging (only conditioned from the top surface) and raise the vertical
aging gradient in mixture samples, the cylindrical surfaces of the
mixture samples were wrapped by tinfoil before long-term aging
as shown in Fig. 3. Totally 10 kinds of aged mixture samples (2
air voids, 5 aging levels) were prepared for the later nanoindenta-
tion and dynamic modulus test.
3.2.4. Nanoindentation specimen
(1) Asphalt mastic specimen
The asphalt mastic were poured into a mold to form a small
cylinder. Then the cylinder were fixed in epoxy resin to facilitate
the polishing process. The resin specimen was polished using sand-
papers of different grain sizes (mesh number 150–2000). A grind-
ing machine (500 r/min) with water spraying was used to
normalize the polishing process and to minimize the effects of pol-
ishing on samples. The pictures of asphalt mastic specimen before
and after polishing are shown in Fig. 4. The mastic specimen was
tested before and after polishing to reveal the effect of polishing.
(2) Asphalt mixture specimens
As illustrated in Fig. 5, the mixture samples were cored into a
bar (about 1.5 cm in size) and then cut into 1 cm high cubes to pre-
pare the nanoindentation specimens. In this way, the vertical
changes of micromechanical properties in aged asphalt mixtures
can be captured by nanoindentation to achieve the characteriza-
tion of aging gradient. Then, those cubes were also fixed in epoxy
resin and polished. One of the final nanoindentation specimen is
shown in Fig. 5.
Considering the symmetry, only half of the asphalt mixtures
were used to prepare the nanoindentation specimens, namely the
cubes No. 1–8 as shown in Fig. 5. Due to the time and economical
reason, all 8 specimens of LTA-8d mixtures were tested to com-
pletely capture the aging gradient while other aged mixtures only
Fig. 3. Asphalt mixture samples for long-term aging.
Fig. 4. Asphalt mastic specimen: (a) before polishing; (b) after polishing.
have No. 1 and No. 8 cube tested to gain a general understanding.
Hence, totally 32 specimens were tested by nanoindentation.
3.3. Experiments and parameters
3.3.1. Nanoindentation test
A NanoTest instrument (Micro Materials) was used in this
study. The experiment temperature was 25 °C. A Berkovich tip
was selected for nanoindentation testing. The maximum load and
loading rate for the mastic specimen and SMA mixture specimens
were 0.1 mN and 0.01 mN/s according to the pre-experiments to
generate a reasonable indentation depth (no more than the mea-
surement range of 20000 nm). For AC-13 mixture specimens, the
maximum load and loading rate were 2 mN and 0.2 mN/s. The
dwelling time was 200 s to fully release the creep deformation of
mastic phase during loading process to eliminate the effect of its
viscoelastic behavior on load-depth curves. The initial load was
0.02 mN to facilitate the contact between the tip and specimen
surface. Considering that aggregates show insensitivity to aging,
nanoindentation test was only performed on asphalt mastic
around the aggregate-asphalt interface for asphalt mixture speci-
mens. 40 indentations were performed on each mixture specimen
in a matrix of four rows and ten columns to deal with the variabil-
ity of data. For the mastic specimen, there were 24 testing points in
a 4  6 matrix. The testing area and part of the measuring point
array are shown in Fig. 5. The interval between these points was
80 lm to eliminate the effects of residual stresses and indenting
deformations. The unloading sections of load-depth curves were
analyzed using Oliver-Pharr model to calculate the modulus of
the site tested.
3.3.2. Dynamic modulus test
The asphalt mixture samples were also cored and cut into
150 mm in height and 100 mm in diameter for dynamic modulus
test. The experiment was performed at temperatures of 0 °C,
15 °C, 30 °C, 45 °C and frequencies of 25, 10, 5, 1, 0.5, 0.1 Hz to
obtain the master curves. Sinusoidal load was applied for each con-
dition to produce strain amplitudes of about 85–115 le and no
confining pressure was applied.
4. Results and discussion
4.1. Effects of mixture gradation
The scanning images of AC-13 and SMA-13 asphalt mixtures are
shown in Fig. 6. As shown in Fig. 6(a), there are substantial fine
aggregate particles around the aggregate-mastic interface in the
AC-13 mixture. The complex interface brings great difficulties in
nanoindentation test because the indentations may be performed
on small aggregate particles. On the contrary, SMA-13 mixture
 Z. Yao et al. / Construction and Building Materials 214 (2019) 187–195 191

Fig. 5. The preparation of nanoindentation specimens.

Table 2
Nanoindentation modulus of different asphalt mixtures.

Gradation Modulus/GPa CV/%

AC-13 0.576 31.8%
SMA-13 0.021 16.3%

According to Table 2, the nanoindentation modulus of mastic in

Fig. 6. Scanning images: (a) AC-13 mixture; (b) SMA-13 mixture.
exhibits a much clearer interface which is suitable for nanoinden-
tation test.
The nanoindentation load-depth curves and modulus results
are shown in Fig. 7 and Table 2. It is suggested in Fig. 7 that the
nanoindentation curves of AC-13 specimen show higher variabili-
ties in both profile and final depth than SMA-13 specimen. Corre-
spondingly, the nanoindentation modulus of AC-13 specimen
exhibits a greater variation coefficient, though the outliers have
been removed in data analysis. From these points of view, SMA-
13 is more suitable for nanoindentation test.
AC-13 mixture is much higher than SMA-13 mixture. One reason-
able interpretation is the stronger interactions between aggregate
and asphalt in AC-13 mixture due to the higher contents of fine
aggregates and filler particles. It is also inferred that there may
be fine aggregate particles under the testing area of AC-13 speci-
men which leading to higher modulus results. By contrast, the
asphalt mastic in SMA-13 specimen is suggested to be a soft and
well-distributed unity of asphalt and filler particles.
4.2. Effect of polishing
The effect of polishing on nanoindentation results are investi-
gated through the nanoindentation tests on asphalt mastic speci-
men. Fig. 8 shows the microscopy images of testing areas of
asphalt mastic specimen before and after the polishing treatment.
The red mark in the lower right corner of images represents 10 lm.

Fig. 7. Nanoindentation load-depth curves: (a) AC-13 mixture; (b) SMA-13 mixture.
192 Z. Yao et al. / Construction and Building Materials 214 (2019) 187–195
Fig. 8. Microscopy images of test area: (a) before polishing; (b) after polishing.
The white region is asphalt while the black region is the mineral
powder particles with sizes under 0.075 mm. It seems that the
asphalt layer over the specimen surface is partly erased which
reflects the disturbance of polishing process.
The nanoindentation load-depth and creep curves are displayed
in Fig. 9 and modulus results are listed in Table 3. It is found that
there are no significant changes of nanoindentation curves and
modulus results after polishing treatment. It may be attributed to
the fact that the properties of mineral powder-asphalt mixture are
not influenced, though some powder particles are exposed after
polishing. Moreover, the great indenting depth on mastic may also
cover the disturbance to specimen surface. Therefore, it is con-
cluded that the nanoindentation results would not be affected after
a careful and standard polishing treatment.
4.3. Nanoindentation aging results
4.3.1. Aging modulus
Totally 1280 points of 32 aged mixture specimens were tested
in this paper. The modulus of each point was calculated using
Oliver-Pharr method. According to experiment results, the load-
depth curves and calculated modulus of 40 points show limited
variations. It indicates that no apparent interfacial transition zone
(ITZ) was detected. Despite the nature of SMA mixture, it may be
due to the large spacing (80 lm) between testing points. Some
research suggested that the thickness of ITZ is about 20 lm or less
Fig. 9. Nanoindentation curves of asphalt mastic specimen: (a) load-depth curves; (b) creep curves.
Table 3
Nanoindentation modulus results of asphalt mastic specimen.
Treatment Modulus/GPa CV/%
Before polishing 0.010 17.1%
After polishing 0.0096 21.1%
which is much smaller than the indentation interval [24]. There-
fore, the average modulus of 40 points (after removal of a few out-
liers) represents the micromechanical property of asphalt mastic in
each mixture sample.
Nanoindentation modulus of asphalt mastic in the top layer of
different aged mixtures are displayed in Fig. 10. The coefficients
of variation of nearly all specimens are below 20% which verifies
the reasonability of experiment data. It is shown that modulus of
asphalt mastic increases with the aging level, indicating an agree-
ment between nanoindentation results and the age-hardening
behavior of asphalt mastic. After 8d of long-term aging, the modu-
lus of asphalt mastic raises more than 10 times of the original
value. The sharp hardening of asphalt mastic lowers the deforma-
bility of asphalt mixture, which will lead to pavement embrittle-
ment and largely reduced cracking and fatigue resistance.
Modulus result indicates that nanoindentation can achieve a quan-
titative, mechanical and precise characterization of aging in
asphalt mixtures from the micro scale.
 Z. Yao et al. / Construction and Building Materials 214 (2019) 187–195 193

Fig. 10. Nanoindentation modulus of asphalt mastic in top layer of aged mixtures.

4.3.2. Aging gradient

Despite the material properties, the oxidative aging severity in
asphalt mixtures depends largely on the accessibility to oxygen
which is influenced by pressure, percentage of voids and the dis-
tance from the surface. With different oxygen accessibilities, aging
rate varies so that there exists aging gradient inside the aged
asphalt mixture. As illustrated above, nanoindentation modulus
can characterize the age-hardening behavior of asphalt mixtures.
Hence, the vertical aging gradient of different aged asphalt mix-
tures are described through the modulus data as displayed in
Fig. 11.
As mentioned above, only specimens of LTA-8d mixtures were
fully tested by nanoindentation. According to Fig. 11(a), the mod-
ulus data of asphalt mastic in LTA-8d mixtures drop dramatically
with the distance from the surface. It suggests that the modified
laboratory long-term aging treatment in this paper (with tinfoil
wrapped around the mixture samples) only affects the top 2–
3 cm of the 3% air void asphalt mixtures and a little deeper for
7% air void mixtures which can be interpreted by oxygen accessi-
Fig. 12. Master curves of dynamic modulus at 25 °C: (a) Mixtures of 3% air void; (b)
bility. At low air voids, pores in asphalt mixture are mostly discon-
Mixtures of 7% air void.
tinuous and isolated which impedes the oxygen diffusion and
consequently reduces the range of aging effects. Although this
modified aging method cannot achieve a complete aging to the The trends of modulus, or aging gradient as assumed in this
inner part of dense asphalt mixtures, it well matches the actual paper, of LTA-8d mixtures alongside the depth are approximate
field aging effect. to a logarithmic curve as shown in Fig. 11. But no suitable mathe-

Fig. 11. Aging gradient of asphalt mixture samples: (a) Mixtures of 3% air void; (b) Mixtures of 7% air void.
194 Z. Yao et al. / Construction and Building Materials 214 (2019) 187–195
Table 4
Dynamic modulus and top layer nanoindentation modulus of asphalt mixture samples.
3% air void asphalt mixture Dynamic modulus 25 °C, 10 Hz (GPa)
Nanoindentation modulus (GPa)
7% air void asphalt mixture Dynamic modulus 25 °C, 10 Hz (GPa)
Nanoindentation modulus (GPa)
matical fitting was achieved. With the reference of two data points
of LTA-2d and LTA-5d mixtures, their aging gradient are approxi-
mately drawn in dashed lines in Fig. 11. The modulus of asphalt
mastic in top and middle layer of unaged and STA mixtures show
negligible variations. For the latter, it is due to the nearly equiva-
lent aging effects when conditioned in oven with a loose mixture
state. So they are connected by straight dashed lines.
4.4. Dynamic modulus results
The 25 °C master curves of dynamic modulus of aged asphalt
mixtures are constructed by a Sigmoidal model and are displayed
in Fig. 12. For comparison, the dynamic modulus and the top layer
nanoindentation modulus of mixture samples are listed in Table 4.
The master curves of dynamic modulus, as illustrated in Fig. 12,
rise with the aging level of asphalt mixture samples, similarly indi-
cating an age-hardening behavior from the macro view. However,
the uplifts of master curves between different aging levels are
quite minor which partly verifying the conclusion generalized
above that the effects of laboratory aging only appears among
the upper sections of asphalt mixture samples.
Fig. 12 and Table 4 show that dynamic modulus of asphalt mix-
tures of 3% void were higher than that of 7% void mixtures which
can be due to the less compaction of the latter. Although the
nanoindentation modulus of asphalt mastic in LTA-8d mixtures
grows over tenfold, the increase of its dynamic modulus is in a rel-
atively small range. Besides the limited aging effects, it is because
that the overall strength and deformability of asphalt mixture
come from not only the contribution of asphalt mastic, but mainly
that of aggregate skeleton and the interactions (adhesion) between
aggregates and asphalt mastic. The differences of data amplitude in
Table 1 indicate that micro testing methods show more sensibility
to the internal changes of material properties which highlights the
importance of microscopic study. All the above suggests that
nanoindentation can give some novel and detailed insight into
the mechanical behavior of asphalt mixtures rather than a global
view of sample properties.
5. Conclusions
This paper utilized a promising micromechanical testing tech-
nique, nanoindentation, to investigate the aging behavior inside
the asphalt mixtures. The vertical changes of nanoindentation
modulus of asphalt mastic were characterized to describe the aging
gradient in aged asphalt mixtures. Dynamic modulus test was also
conducted to provide an overall view of aged properties of mixture
samples. The main conclusions are as follow:
1. Gap-graded asphalt mixtures are more suitable for nanoinden-
tation test and a careful and standard polishing treatment will
not affect the reliability of nanoindentation results and the
law generalized.
2. Nanoindentation modulus results show a good agreement with
the age-hardening behavior of asphalt mastic.
3. The aging gradient in long-term aged asphalt mixture is approx-
imately in a logarithmic curve form.
Unaged STA LTA-2d LTA-5d LTA-8d
4.014 4.710 5.042 5.411 5.801
0.022 0.061 0.124 0.205 0.304
3.492 3.797 3.984 4.367 4.741
0.019 0.059 0.136 0.219 0.331
4. 8d of laboratory long-term aging in this paper can only affect 2–
3 cm under the surface of dense asphalt mixtures.
5. Nanoindentation can achieve a quantitative, mechanical and
precise characterization of aging gradient in asphalt mixtures
from the micro scale rather than an average value of sample
properties.
Nanoindentation provides a novel insight into the aging behav-
ior of asphalt mixtures. However, only dense asphalt mixtures of
two air voids were tested in this paper. Further research can be
conducted on mixtures of high voidage and different asphalt types.
DSR test can also be combined with nanoindentation to investigate
the aging properties of asphalt mastic specimens to get further
understandings of aging effects.
Conflict of interest statement
None.
Acknowledgments
The authors gratefully acknowledge the financial support of the
National Natural Science Foundation of China [Grant No.
51778140].
References
[1] W.D. Fernández-Gómez, H.R. Quintana, F.R. Lizcano, A review of asphalt and
asphalt mixture aging, Ingenieria e Investigación 33 (1) (2013) 5–12.
[2] J.C. Petersen, A Review of the Fundamentals of Asphalt Oxidation: Chemical,
Physicochemical, Physical Property and Durability Relationships,
Transportation Research Board, Washington, D.C., 2009.
[3] M. Ahmad, H.M. Faisal, U.A. Mannan, R.A. Tarefder, Effects of pore structure on
oxidative aging and related mechanical properties of asphalt concrete,
Construct. Build. Mater. 151 (2017) 636–641.
[4] Y.S. Kumbargeri, K.P. Biligiri, A novel approach to understanding asphalt binder
aging behavior using asphaltene proportion as a performance indicator, J. Test.
Eval. 44 (1S) (2015) 20140490.
[5] P.E.Y. Wang, Y. Wen, K. Zhao, D. Chong, A.S.T. Wong, Evolution and locational
variation of asphalt binder aging in long-life hot-mix asphalt pavements,
Construct. Build. Mater. 68 (15) (2014) 172–182.
[6] M.D.M. Lopes, D. Zhao, E. Chailleux, M. Kane, T. Gabet, C. Petiteau,
Characterization of aging processes on the asphalt mixture surface, Road
Mater. Pav. Design 15 (3) (2012) 477–487.
[7] C.A. Bell, M.J. Fellin, A. Wieder, Field validation of laboratory aging procedures
for asphalt aggregate mixtures (with discussion), J. Assoc. Asphalt Paving
Technol. 63 (1994) 45–80.
[8] Q. Qin, J.F. Schabron, R.B. Boysen, M.J. Farrar, Field aging effect on chemistry
and rheology of asphalt binders and rheological predictions for field aging, Fuel
121 (2) (2014) 86–94.
[9] C. Baek, B.S. Underwood, Y.R. Kim, Effects of oxidative aging on asphalt mixture
properties, Transport. Res. Rec. J. Transport. Res. Board 2296 (4) (2012) 77–85.
[10] M. Ling, X. Luo, F. Gu, R.L. Lytton, Time-temperature-aging-depth shift
functions for dynamic modulus master curves of asphalt mixtures,
Construct. Build. Mater. 157 (2017) 943–951.
[11] W.C. Oliver, G.M.J. Pharr, An improved technique for determining hardness
and elastic modulus using load and displacement sensing indentation
experiments, J. Mater. Res. 7 (6) (1992) 1564–1583.
[12] M.D. Arifuzzaman, Nano-scale Evaluation of Moisture Damage in Asphalt, The
University of New Mexico. ProQuest Dissertations Publishing (2010).
[13] S. Khorasani, E. Masad, E. Kassem, R.K.A. Al-Rub, Nano-mechanical
characterization of mastic, aggregate, and interfacial zone in asphalt
composites, J. Test. Eval. 41 (6) (2013) 924–932.
 Z. Yao et al. / Construction and Building Materials 214 (2019) 187–195
[14] A. Jäger, R. Lackner, J. Eberhardsteiner, Identification of viscoelastic properties
by means of nanoindentation taking the real tip geometry into account,
Meccanica 42 (3) (2007) 293–306.
[15] R.A. Tarefder, A.M. Zaman, W. Uddin, Determining hardness and elastic
modulus of asphalt by nanoindentation, Int. J. Geomech. 10 (3) (2010) 106–
116.
[16] R.A. Tarefder, H. Faisal, Effects of dwell time and loading rate on the
nanoindentation behavior of asphaltic materials, J. Nanomech. Micromech. 3
(2) (2013) 17–23.
[17] R.A. Tarefder, A. Zaman, Characterization of asphalt materials for moisture
damage using atomic force microscopy and nanoindentation, in: K.
Gopalakrishnan, B. Birgisson, P. Taylor, N.O. Attoh-Okine (Eds.),
Nanotechnology in Civil Infrastructure, Springer, Berlin, Heidelberg, 2011,
pp. 237–256.
[18] Z. Yao, H. Zhu, M. Gong, J. Yang, G. Xu, Y. Zhong, Characterization of asphalt
materials’ moisture susceptibility using multiple methods, Construct. Build.
Mater. 155 (2017) 286–295.
195
[19] Y. Veytskin, C. Bobko, C. Castorena, Nanoindentation investigation of asphalt
binder and mastic viscoelasticity, Int. J. Pavement Eng. 17 (4) (2016) 363–376.
[20] M.I. Hossain, H.M. Faisal, R.A. Tarefder, Characterisation and modelling of
vapour-conditioned asphalt binders using nanoindentation, Int. J. Pavement
Eng. 16 (5) (2015) 382–396.
[21] D.M. Abd, H. Al-Khalid, R. Akhtar, Novel methodology to investigate and obtain
a complete blend between rap and virgin materials, J. Mater. Civil Eng. 30 (5)
(2018) 04018060.
[22] R.A. Tarefder, H. Faisal, Nanoindentation characterization of asphalt concrete
aging, J. Nanomech. Micromech. 4 (1) (2014) A4013003.
[23] AASHTO R30. Standard Practice for Mixture Conditioning of Hot Mix Asphalt.
American Association of State Highway and Transportation Officials,
Washington D.C., 1994.
[24] X. Zhu, Y. Yuan, L. Li, Y. Du, F. Li, Identification of interfacial transition zone in
asphalt concrete based on nano-scale metrology techniques, Mater. Design
129 (2017) 91–102.