2019

Vol.:(0123456789)
1 3
Arabian Journal for Science and Engineering
https://doi.org/10.1007/s13369-019-04028-w
RESEARCH ARTICLE - CIVIL ENGINEERING
Replacement of Limestone with Volcanic Stone in Asphalt Mastic Used
for Road Pavement
Haibin Li1
· Wenjie Wang1
· Wenbo Li1
· Assaad Taoum2
· Guijuan Zhao1
· Ping Guo3
Received: 3 April 2019 / Accepted: 2 July 2019
© King Fahd University of Petroleum & Minerals 2019
Abstract
Volcanic stones are a kind of natural materials, and they will occupy large amounts of land resources which brings a lot of
inconvenience to local residents and traffic. Meanwhile, the annual demand for limestone in the world is about 1.2 billion tons
and high-quality limestone has low natural resources and low production volume. In order to comply with the current green
eco-friendly pavement concept, this paper aims to study the use of volcanic rocks in place of limestone in road pavement con-
struction as a way of utilizing available natural mineral resource to reduce the problematic over-dependence on limestone. In
this paper, asphalt mastics with different dosages of ground volcanic stone and limestone powder were produced. Combining
macro and micro-methods, the applicability of volcanic stone was analyzed and evaluated from the aspects of basic perfor-
mance experiments, X-ray photoelectron spectroscopy, scanning electron microscopy and infrared spectroscopy. The results
clearly showed that the volcanic stone powder could get better distribution and better high-temperature performance in the
asphalt mastic than limestone powder. It contained Si and much higher content of
SiO2, Al2O3, Fe2O3, Na2O and
K2O which
promoted chemical reactions with the asphalt, making it more compatible with asphalt than limestone powder. Based on the
results of this study, it can be concluded that volcanic stone could effectively replace some limestone usage in the asphalt
pavement field which will in return reduce the occupation of land resources and provide a new choice for the limestone.
Keywords Road asphalt · Asphalt mastic · Volcanic stone · Limestone powder · Asphalt mastic properties
1 Introduction
With rapid development of economy, science and technol-
ogy, the requirements of asphalt pavement for high-temper-
ature stability, low-temperature crack resistance and water
stability were constantly increasing in order to achieve high
quality and long service life [1]. To overcome these prob-
lems, many modifiers were used in asphalt, in which the
most common ones were organic modifiers and inorganic
modifiers [2]. Organic modifiers had disadvantages such as
high cost, complicated operation and difficult production
processes which significantly limited their use [3]. Inor-
ganic modifiers were regarded as inert fillers, which affected
their dispersion in the asphalt and the interfacial chemistry
between filler and the asphalt. In fact, inorganic modifiers
could improve the performance of asphalt binder by enhanc-
ing the mastication of asphalt and aggregates [4, 5]. Moreo-
ver, the asphalt modified with inorganic materials had the
characteristics of simple production process, low price and
good performance, which is consistent with China’s national
requirements [6].
* Haibin Li
lihaibin1212@126.com
Wenjie Wang
wwj19930710@163.com
Wenbo Li
yalwb@qq.com
Assaad Taoum
assaad.taoum@utas.edu.au
Guijuan Zhao
guijuanzhao@126.com
Ping Guo
guoping8088@163.com
1
School of Architecture and Civil Engineering, Xi’an
University of Science and Technology, Xi’an 710054, China
2
School of Engineering, University of Tasmania, Hobart,
Australia
3
Xi’an Highway Research Institute, Xi’an 710054, China

1 3
For common inorganic materials, fly ash and limestone
powder were frequently used in highway engineering. Stud-
ies have shown that although limestone is the largest amount
used in road engineering, it is only present as an inert filler
in asphalt [7, 8]. Franesqui [9] found the higher resistance to
water action of asphalt rubber mixtures with high-porosity
marginal volcanic aggregates. Liu [10] found that volcanic
ash filler could further enhance the mechanical properties of
Styrene–Butadiene–Styrene (SBS) modified asphalt mixture
via a solid filler-SBS-binder system formed within mastics
due to the complex topography and porous structure of vol-
canic ash. Liu [11] studied four kinds of asphalt concrete
with nano-scale volcanic ash fine fillers, which proved that
the shape of the strain curve in the stable cycle can be inde-
pendent of the load size and the aggregate skeleton. Han [12]
studied the road performance and modification mechanism
of composite modified asphalt mixture with volcanic ash
and SBS and concluded that it was feasible for volcanic ash
to replace the limestone powder as a modifier of asphalt
mixture. Chen [13, 14] conducted a research on the road per-
formance of volcanic ash asphalt mastic, in which he showed
that natural volcanic ash could significantly improve the
high-temperature stability of asphalt mixture and the low-
temperature performance of asphalt mastic. Moreover, it was
established by Hu [15, 16] that fine volcanic ash could qual-
ify as a filler modifier for asphalt mixture and it significantly
improved asphalt pavement performance and reduced project
cost. Kong [17] studied comparative evaluation of designing
asphalt treated base mixture with composite aggregate types.
The research showed that composite aggregate will change
the volumetric properties of composite asphalt mixtures.
The incorporation of alkaline coarse aggregates or surface
roughness coarse aggregates on the aggregate can improve
the mechanical properties of asphalt treated base.
As a natural building material, volcanic rocks were
widely distributed in the world. If volcanic rocks were used
as road construction materials, the economic benefits were
considerable. At present, domestic research reports on vol-
canic ash modified asphalt concrete were limited, the adapt-
ability and its modification effect of volcanic ash for asphalt
mixture as a modifier was still in the exploration stage. In
this paper, the technical feasibility of using volcanic rocks
as a filler-type modifier to improve asphalt was studied. The
asphalt binder with different dosages of ground volcanic
stone and limestone powder were produced after which they
were macroscopically evaluated from the aspects of basic
performance experiments. Microscopic analysis was also
carried out by X-ray photoelectron spectroscopy, scanning
electron microscopy and infrared spectroscopy. Therefore,
this study provided an innovative method for utilizing vol-
canic stone in the asphalt pavement field. The service quality
of asphalt mastic will be improved, and it will be in line with
the objective of green materials utilization and reduce the
occupation of land resources.
2 Materials
2.1 Asphalt
The virgin asphalt (VA) used in this study was Kunlun 70#
asphalt produced by Chinese Petroleum. The basic proper-
ties of the VA are shown in Table 1.
2.2 Volcanic Stone Powder
The basalts volcanic group was mainly distributed on the
Jingmu fault zone of the Tantalum fault system located at
Changle County, east of China. This volcanic group formed
mainly in the late Tertiary–early Quaternary, including the
Miocene, Pliocene, and Pleistocene. The crater was round or
oval in shape and the section was concave. The basalts vol-
canic stones had existed for hundreds of years which brought
a lot of inconvenience to transportation.
The volcanic rocks of the basalts volcanic group had
developed alkaline basalts which were mostly alkaline
olivine basalt, bixonite and olive nepheline. The rocks,
as shown in Figs. 1 and 2, were black, gray-brown, dense
Table 1 Basic properties of VA used in this study
Catego-
ries
Penetration
(25 °C)/0.1 mm
Softening
point/°C
Ductility
(10 °C)/cm
Viscosity
VA 68.2 47.8 46.9 475
Fig. 1 Volcanic stone origin

1 3
blocks, columnar joints, reticular joints and porous amyg-
dala structures.
In order to evaluate the applicability of the volcanic
stones, samples were collected randomly every 10 meters.
The particle size of the stones is controlled below 30 cm
as shown in Fig. 3, and the process was repeated several
times. The collected stones were then mixed evenly and
non-volcanic stones were discarded from the mix. After
this process, the volcanic stone powder (VSP) was pro-
duced based on the following steps:
1. The crusher was used to break the volcanic rock into
gravel below 4.75 mm;
2. The crushed volcanic rocks were poured into the Los
Angeles shelf-type abrasion tester for 4.5 h;
3. After the Los Angeles abrasion test, the ground stone
residue was filtered along with the powder using a sieve
with particle size of 0.075 mm. The powder left behind
after filtration was the volcanic stone powder required
for the test as shown in Fig. 4.
2.3 Limestone Powder
The limestone powder was commonly used in road construc-
tion field. In this paper, two types of limestone powders
were used, limestone powder M and limestone powder B,
to explain their consistency of components.
M was produced in Ankang City located in the middle of
China. It belonged to the north-eastern margin of the Qin-
ling trough fold system and the Hannan ancient road in the
northern part of the Yangzi quasi-station of the geotectonic
position. It consists of the east–west Qinling trough fold and
the northwest-oriented Dabashan arc fold belt. As shown
in Fig. 5, most of the limestone used to produce powder M
was white.
B was produced in Yanshan City (1000 km away from
Ankang). The Yanshan Mountains are one of the famous
Fig. 2 Volcanic stone topography
Fig. 3 Volcanic stone
Fig. 4 Volcanic stone powder
Fig. 5 Limestone from Ankang

1 3
mountains in northern China. It started from Yanghe in the
west to the dam on the plateau in the north. Yanshan had a
complex geological structure and rich limestone formations.
The selected limestone which was used to produce powder
B is shown in Fig. 6.
The processing method of the limestone powder was
consistent with the processing method of the volcanic stone
powder. The basic properties of the volcanic stone powder
and limestone powder are shown in Table 2. As it could be
seen from Table 2, the volcanic stone powder and both lime-
stone powders had a similar thermal stability (Figs. 7, 8).
The density, specific surface area, and volume specific
surface area of the VSP, M and B are measured and reported
in Table 3. As it could be seen from Table 3, the physical
properties were similar; however, VSP had much larger vol-
ume specific surface area than M and B.
2.4 Chemical Properties Test
In this study, the chemical composition of VSP, M and B
were tested using X-ray Photoelectron Spectroscopy (Fig. 9)
in order to illustrate the elemental difference. The test results
showed that the VSP contained various oxides, such as
SiO2,
Al2O3, Fe2O3, Na2O, K2O, CaO and MgO, as well as the
non-metallic element Si. On the other hand, M and B did
not contain the non-metallic element Si, and their content
of SiO2, Al2O3, Fe2O3, Na2O and
K2O were significantly
smaller than that of VSP. The test data is shown in Table 4.
The elements difference was also a deciding factor of
VSP, M and B in the road construction field. As shown in
Table 4, the VSP contained active oxides
SiO2, Al2O3 and Si
which could facilitate the occurrence of reactions between
VSP and asphalt binder. These basic oxides reacted with
the bitumen acid and the bitumen anhydride to improve the
Fig. 6 Limestone from Yanshan
Table 2 Basic properties of the volcanic stone powder and limestone
powder
Categories Hydrophilic coefficient Heating stability
VSP 0.611 Color unchanged
M 0.667 Color unchanged
B 0.632 Color unchanged
Fig. 7 Limestone powder M from Ankang
Fig. 8 Limestone powder B from Yanshan
Table 3 Physical properties of volcanic stone powder and limestone
powders
Categories Apparent den-
sity (g/cm3
)
Specific surface
area (m2
/g)
Volume specific
surface area
(m2
/L)
VSP 2.78 1.68 4.31
M 2.73 1.29 3.30
B 2.75 1.47 3.53

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adhesion of the bitumen [18, 19]. It again proved the suit-
ability of the VSP as a filler in asphalt mixture.
2.5 Comparison of Different Limestone Powders
Infrared spectroscopy has extensive practicability in the
field of chemical structure analysis of modified asphalt, and
can provide rich structural component information [20, 21].
Infrared spectroscopy mainly reverses the change of char-
acteristic peaks in different cases, and reverses the change
of functional groups by the change of characteristic peaks
[22]. Based on this, changes in the chemical structure of the
bitumen can be studied.
As shown in Fig. 10, the characteristic peaks of the VA
and the two kinds of limestone powder asphalt mastics
were basically the same. The wavelength of 1375 cm−1
was
the symmetric bending vibration absorption peak of
CH3,
which was the characteristic peak of VA. The wavelength of
1450 cm−1
was a peak formed by the superposition of
CH2
bending vibration and
CH3 asymmetric bending vibration.
This peak indicated that the asphalt contained long-chain
alkanes, aromatics and hydrocarbons. The wavelength of
1600 cm−1
was a peak formed by C=C stretching, which
was an aromatic compound in the pitch.
As shown in Fig. 10, it showed that the particle size
of M and B was in the range of 1300–2000 cm−1
and
3300–4000 cm−1
. The absorption peak amplitude was small,
but the wavelength vibration range was wide. These features
distinguished whether the asphalt contained an important
sign of minerals. The wavelength of 1450 cm−1
was carbon-
ate, indicating that the asphalt contained calcium carbonate.
The wavelength of 1000 cm−1
was silicate, but the char-
acteristic peak was not obvious, which indicated that the
asphalt contained a small amount of silicate. The results of
Fig. 9 XPS for analysis of volcanic stone powder and limestone pow-
der components
Table 4 Chemical composition
analysis of volcanic stone
powder and limestone powders
Categories SiO2 (%) Al2O3 (%) Fe2O3 (%) Na2O (%) K2O (%) CaO (%) MgO (%) Si (%)
VSP 33.53 14.21 8.37 3.56 2.35 4.55 3.52 11.47
M 10.67 0.02 0.04 0.01 0.04 31.96 14.63 0.00
B 9.42 0.05 0.08 0.12 0.02 29.64 11.24 0.00
Fig. 10 Infrared spectroscopy
analysis of asphalt mastic with
limestone powder and VA

1 3
infrared spectrum were consistent with that of the XR com-
ponent detection. Moreover, the change of frequency at dif-
ferent absorption peaks of M and B were basically the same
which showed the similar mineral composition in the asphalt
mastics according to the qualitative analysis. All the results
indicated that the limestone powder in different regions had
almost the same elemental composition and would have a
little effect on the asphalt mastic. Therefore, the limestone
powder M was selected as a control to verify the effective-
ness of VSP in asphalt mastic.
3 Experimental Procedures
3.1 Preparation of Asphalt Mastic
The asphalt mastic was prepared as described below:
1. The asphalt was heated to 150 °C and kept at a constant
temperature for about 1 h until it reached a flowing state
and became easy to stir. Next, the VSP was dried to a
constant weight at a temperature of 105 °C, and then
mixed with the asphalt at 150 °C;
2. Prior to the experiment, the quality of the dried VSP
was determined. After the VSP and M were added into
the asphalt, as shown in Figs. 11 and 12, the asphalt
mastic was stirred for 20 min using an electric whisker
with speed of 2000 r/min until the powder particles
were almost distributed in the asphalt and no bubbles
appeared on the surface;
3. The temperature was maintained at 150 °C while stirring
in order to improve the activation reaction of VSP and
M. In order to ensure the even mixing between limestone
powders and asphalt, the asphalt mastic was quickly put
into the incubator for insulation. In the case where the
blended asphalt mastic was not tested immediately, it
was mixed again before reuse.
3.2 Physical Properties Test
In order to test the basic physical properties of asphalt mas-
tic, the penetration at 25 °C, softening point, ductility at
10 °C and rotational viscosity at 135 °C were conducted
according to the JTG E20 T0604-2011, JTG E20 T0606-
2011, JTG E20 T0605-2011 and JTG E20 T0625-2011,
respectively. All the tests were similar with ASTM D5,
ASTM D36, ASTM D113 and ASTM D4402. The ductility
test of asphalt mastic at 10 °C is shown in Fig. 13.
3.3 Penetration Index of Asphalt Mastic
The penetration index evaluation of asphalt mastic mainly
referred to the test procedure of China Highway Engineering
Asphalt and Asphalt Mixture (JTG E20-2011). The main
indicators of this standard were similar to the American
ASTM standards [23, 24].
(1) Temperature sensitivity
Fig. 11 Asphalt mastic with volcanic stone powder
Fig. 12 Asphalt mastic with limestone powder

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The temperature sensitivity of asphalt mastic is one of the
most important indicators to evaluate the asphalt mixture
performance. Presently, there are mainly three methods for
measuring the temperature sensitivity of asphalt, namely vis-
cosity-temperature index method, penetration-temperature
index method and penetration index method. In this paper,
the measured penetration-temperature index method was
used to evaluate the performance of asphalt mastic with VSP.
The prepared asphalt mastic with VSP and M were meas-
ured for penetration under three temperature conditions
(15 °C, 25 °C and 30 °C). The experimental data are linearly
analyzed using Eq. (3.1).
where a—Penetration-temperature sensitivity coefficient,
K—constant obtained by linear regression, T—temperature
The penetration index PI is obtained using Eq. (3.2):
where A—Penetration-temperature sensitivity coefficient.
(2) High-temperature stability
The equivalent softening point (T800) was used as an indi-
cator for evaluating the high-temperature stability of asphalt.
The higher the index value was, the more stable the high-
temperature performance was [25]. The calculation method
was as follows:
where A—penetration-temperature sensitivity coefficient,
K—constant obtained by linear regression.
(3) Low-temperature performance
Since the low-temperature failure form of asphalt tended
to be brittle failure, it was extremely difficult to measure
[26–29]. Therefore, the equivalent brittle point (T1.2) was
(3.1)
lg P = AT + K
(3.2)
PI =
(20 − 500A)
(1 + 50A)
(3.3)
T800 =
(lg 800 − K)
A
used as the index for evaluating the low-temperature perfor-
mance of asphalt. The equation for calculating the equivalent
brittle point (T1.2) was as follows:
where A—penetration-temperature sensitivity coefficient,
K—constant obtained by linear regression
3.4 Scanning Electron Microscope (SEM)
In order to evaluate the performance of asphalt mastic with
VSP and M, the microscopic aspects should first satisfy the
conditions for the firm bonding of the asphalt to the surface
of the filler. Studies had shown that the irregular shape and
distribution characteristics of fine particles in asphalt mas-
tic could affect the mechanical properties of asphalt binder
[30, 31]. In this paper, asphalt mastics with VSP and M
were separately investigated by SEM. The process of sample
preparation and coating of conductive materials is shown
in Fig. 14.
4 Results and Discussion
The penetration index (PI), softening point, viscosity at
135 °C and ductility at 10 °C of asphalt mastic with VSP
and M were analyzed to evaluate the modification effect. The
test setups were shown in Fig. 15. The test results are shown
in Table 5. In the Fig. 16, the red dotted line represented
the value of corresponding VA, and the black dotted line
represented 6% VSP.
4.1 Softening Point
From Fig. 16, it could be seen that the softening point of
asphalt mastic with VSP and M had both gradually increased
with the dosage increment. Compared to the VA, the soften-
ing point of asphalt mastic with 4% VSP increased from 52.1
to 54.5 °C. It also increased from 52.1 to 59.5 °C with 5%
(3.4)
T1.2 =
(lg 1.2 − K)
A
Fig. 13 Ductility test of asphalt
mastic at 10 °C

1 3
Fig. 14 Sample preparation
process in SEM test
Table 5 Test results of asphalt
mastic with VSP and M
Categories Penetration/0.1 mm Softening point
(°C)
Ductility
(10 °C)/cm
Viscosity
(135 °C)
mPa s
15 °C 25 °C 30 °C
VA 23.4 65.4 109.4 52.1 46.95 475
4% VSP 20.7 54.8 94.1 54.5 10.00 557
5% VSP 21.2 56.3 98.2 59.5 10.50 571
6% VSP 20.9 51.6 81.9 61.3 11.10 586
4% M 23.1 60.5 98.4 54.5 12.05 545
5% M 22.2 62.2 101.0 55.5 13.90 552
6% M 21.6 53.7 88.6 59.5 11.70 562
Fig. 15 Basic physical proper-
ties tests of asphalt mastic

1 3
VSP and from 52.1 to 61.3 °C with 6% VSP. The increase
extent was 14.2% and 17.6%, respectively. All the softening
point with M was lower than that of asphalt mastic with VSP.
When the dosages were the same, the asphalt mastic with
VSP had higher-temperature performance than that of VA
and asphalt mastic with M. Therefore, it can be concluded
that VSP and M could affect the viscosity of asphalt mastic
and make it much harder, which was beneficial to the tem-
perature sensitivity. Figure 16 also shows that the VSP was
better than M in improving high-temperature performance
of the asphalt mastic.
4.2 Ductility at 10 °C
Figure 17 indicates that the ductility of asphalt mastic with
VSP and M had both gradually decreased with the dosage
increment. Compared to the VA, the ductility of asphalt
mastic with 4% VSP decreased from 46.95 to 11.1 cm. It
dropped from 46.95 to 10.5 cm with 5% VSP and to 10 cm
with 6% VSP. The decrease rates were 77.6% and 78.7%,
respectively. All ductility of M was higher than that with
VSP. It decreased by 74.4% and 75.1%, respectively. Fig-
ure 17 also shows the asphalt mastic with VSP was almost
similar to that with A in improving the low-temperature
performance.
4.3 Viscosity at 135 °C
Figure 18 reveals that the viscosities of asphalt mastic
with VSP and M at 135 °C had both gradually increased
with the dosage increment. Compared to VA, the viscos-
ity of asphalt mastic with 4% VSP increased from 475 to
557 mPa s. It increased from 475 to 571 mPa s with 5% VSP
and to 586 mPa s with 6% VSP. The increase was 20.2% and
23.4%, respectively. The viscosities of asphalt mastic with
M increased by 16.2% and 18.3%, respectively. All viscosi-
ties of asphalt mastic with M were lower than those with
VSP. The viscosity of asphalt mastic with VSP was slightly
larger than that with the same content of M. It could make
the asphalt mastic much more viscous.
4.4 Penetration
Penetration comparisons of asphalt mastic with VSP and M
are represented in Fig. 19.
It could be seen from Fig. 19 that when the temperature
rose, the penetration value of the asphalt mastic gradu-
ally increased. Compared with VA, the penetration value
of asphalt mastic with VSP and M reduced. As seen in
Fig. 19c, the penetration of 6% VSP was 81.9 mm, the
penetration of VA was 109.4 mm, and the decreased rate
of penetration was 25%. While the decreased rate of pen-
etration with 6% M was 19%. It could be seen that vol-
canic stone powder had a greater influence on penetration.
Fig. 16 Softening points of asphalt mastics with VSP and M
Fig. 17 Ductility comparison of asphalt mastics with VSP and M at
10 °C
Fig. 18 Viscosity comparison of asphalt mastics with VSP and M at
135 °C

1 3
Moreover, it had different effect of the same powder con-
tent on asphalt mastic under different temperature. When
the temperature was 15 °C, the penetration of asphalt
mastic with 5% VSP decreased from 23.4 to 23.1 mm.
When it was 25 °C, the penetration decreased from 65.4
to 56.3 mm increasing its decline ratio to 13.9%. But when
the temperature was 30 °C, penetration decreased from
109.4 to 98.2 mm whereby the decline ratio decreased to
10.2%.
4.5 Penetration Index (PI)
The data according to Table 5 are calculated using Eqs. (3.2),
(3.3) and (3.4), respectively, and the results are shown in
Table 6.
Table 6 shows that the coefficient A of asphalt mastic
with VSP was between 0.0395 and 0.0439, which illustrated
that the asphalt mastic with VSP had good performance
and was not sensitive to temperature. This proved that the
Fig. 19 Penetration comparison of asphalt mastics with VSP and M
Table 6 Calculation results of
penetration index of VA and
different asphalt mastics
Categories K A PI T800 T1.2 R
VA 0.7648 0.0403 − 0.0481 53.07 − 17.02 0.9996
4% VSP 0.6666 0.0436 − 0.5660 51.64 − 13.47 0.9995
5% VSP 0.6605 0.0439 − 0.6103 51.08 − 13.88 0.9997
6% VSP 0.7269 0.0395 0.0840 55.09 − 16.40 0.9992
4% M 0.7342 0.0420 − 0.3226 51.30 − 13.47 0.9994
5% M 0.6885 0.0439 − 0.6103 50.45 − 13.24 0.9987
6% M 0.7216 0.0409 − 0.1478 53.34 − 15.71 0.9993

1 3
performance of asphalt mastic with the VSP would be more
stable during the construction process if the temperature
changed significantly.
The PI index not only reflects the sensitivity of penetra-
tion, but also reflects the type of asphalt colloidal structure.
When the PI value is between − 2 and 2, the asphalt state
is between the sol type (Newtonian body) and the gel type
(non-Newtonian body). The type of colloidal structure of
asphalt will change with the change of dosage and this will
affect the high- and low-temperature performance of asphalt.
The closer the asphalt state is to the sol type, the better the
high-temperature performance of the asphalt. The closer the
asphalt state is to the gel type, the better the low-temperature
performance of the asphalt. As shown in Fig. 20, the high-
temperature performance of asphalt mastic with VSP was
better than that with M. When the dosage was less than 5%,
the PI value decreased. It proved that the mineral was melted
into the asphalt but did not reach saturation. When the dos-
age was higher than 5%, the PI value increased. This showed
that the mineral in the asphalt had reached a saturated state.
As the mineral dosage continued to increase, the minerals
could not blend into the asphalt. This situation would not
only affect the uniform dispersion of the asphalt and filler,
but also destroy the stable state of the asphalt mastic. It
caused the PI value to drop. When the dosage was 5%, the
PI values were the same which indicated that the different
asphalt mastics had the same low-temperature performance.
From the point of view of chemical adsorption, when
the content of the mineral powder increases, the surface of
the mineral powder has a large surface energy, which will
adsorb the mineral powder in the asphalt, which increases
the asphaltene. Therefore, when there is not enough mineral
powder in the asphalt to adsorb the mineral powder to make
it form a good adsorption layer with the asphalt, and the
strong cohesive force is generated, the mineral powder is
easily separated from the asphalt. The degree of segregation
of powder and asphalt increases (PI value decreases),
proving that the more the mineral powder modifier is not
blended, the better it is and when it exceeds a certain range,
it is possible to negatively affect its compatibility with modi-
fied asphalt.
The comparison of the equivalent softening point (T800)
of asphalt mastic with VSP and M is shown in Fig. 21. When
dosages were less than 5%, both the T800 values decreased
with increase in dosage. When dosages were more than 5%,
both the T800 values had opposite trend. Moreover, the T800
values of asphalt mastic with VSP were higher than that with
M. This showed that asphalt mastic with VSP had higher-
temperature performance under the same conditions. The
comparison curve of the T1.2 of asphalt mastic with VSP
and M is shown in Fig. 22. When the dosage was less than
5%, the T1.2 values of asphalt mastic with VSP and M gradu-
ally increased. When the dosage was more than 5%, the T1.2
value had the opposite trend with increase in dosage. When
the dosage was 5%, the two asphalt mastics had similar low-
temperature performance. It was also illustrated that the T1.2
of asphalt mastic with VSP and M was higher than that of
VA.
In summary, when the dosage was 5%, the high-tempera-
ture performance of the VSP asphalt mastic was better than
that of the M asphalt mastic, and the low-temperature per-
formance of both of them was not much different.
4.6 Infrared Spectroscopy Experiment
Asphalt mastic is a uniform dispersion system composed of
asphalt and filler. Its mixing uniformity has a direct impact
on the asphalt pavement performance. In this paper, the
chemical structure of VSP asphalt mastic and limestone
asphalt mastic was studied by infrared spectroscopy, and
the reasons for the changes were analyzed.
Fig. 20 PI comparison curves of asphalt mastic with VSP and M Fig. 21 T800 comparison of Asphalt mastic with VSP and M

1 3
As shown in Fig. 23, when the wavelength was
1000–1200 cm−1
, the peak of VSP was wider and larger than
that of M. The VSP produced a new mixed absorption peak.
The information of each superimposed functional group
could not be directly obtained from Fig. 23. Peak-saturation
was performed using Peakfit software prior to analysis of
chemical products [32, 33]. The peaks were fitted to VSP
and M with wavelengths ranging from 1000 to 1200 cm−1
.
As shown in Fig. 24, the superimposed peaks at
1000–1200 cm−1
in the VSP could be divided into three
peaks at 1050 cm−1
, 1100 cm−1
and 1170 cm−1
. The cor-
relation coefficient after fitting was greater than 0.96,
which proved that there was a good fitting effect. The
wavelengths of 1050 cm−1
and 1170 cm−1
were anhydrides
while a wavelength of 1100 cm−1
was a sodium carboxylate
(CH3COONa). The in situ peak of VSP consisted of these
three peaks. It illustrated the reaction of a basic oxide with
a bitumen anhydride to form a sodium carboxylate
As shown in Fig. 25, the peak after fitting the M peak
was coincident with the original peak position. There was
not superimposed peak. The wavelengths of 1050 cm−1
and
1170 cm−1
were anhydrides. These proved that limestone
asphalt mastic was simply blended into the asphalt and did
not undergo any chemical reaction.
4.7 SEM Imaging Results
The SEM images of asphalt mastic with VSP and M are
shown in Fig. 26. It could be seen that the interface of the
asphalt with M was very clear and the interface with VSP
was lightly blurred. The magnification in Fig. 26c and d was
450 times and there were more wrinkles in the asphalt inter-
face. A large part of the limestone powder was not melted
into the asphalt. Most of the VSP was covered by asphalt and
there were fewer free VSP particles which demonstrated that
the VSP was more compatible with asphalt than limestone
powder. From the 1000 times magnification SEM images,
it could be seen more clearly that the asphalt mastic inter-
face with VSP was much smoother and had less wrinkles.
Compared with M, it could be inferred that some chemical
reaction occurred besides physical swelling, which made the
interface of asphalt mastic with VSP much smoother.
From previous analysis of material properties, the appar-
ent density, specific surface area and volume specific surface
area of VSP were larger than that of limestone powder M,
which made it much more compatible with asphalt. Mean-
while, the volcanic stone powder contained Si and much
Fig. 23 Infrared spectroscopy
analysis of asphalt mastic and
VA
Fig. 22 T1.2 comparison of asphalt mastic with VSP and M

1 3
higher content of
SiO2, Al2O3, Fe2O3, Na2O and
K2O. All
these elements promoted chemical reactions with asphalt
during swelling. For example, volcanic stone powder con-
tains a large amount of basic metal ions and metal com-
pounds such as
K1+
, Fe3+
, and
Na1+
. These metal cations
will react with asphaltic acid and asphaltic acid anhydride.
The chemical reaction formula is:
The Si element is an inorganic non-metallic element
and does not undergo an acid–base reaction. From the
viewpoint of chemical adsorption, when the volcanic ash
contains a large amount of active Si and
SiO2, the sur-
face of the Si element has a large surface energy. These
surface energies will adsorb the oil in the asphalt, which
will reduce the content of saturated phenol and aromatic
phenol and increase the content of asphaltene. A new
colloidal equilibrium system will be established in the
asphalt due to adsorption. This changes the properties
(4.1)
En+
+ R-COOH → (R-COO)nE + H2 ↑
of the asphalt itself. Adsorption does not only make the
volcanic stone powder more stable and compatible with
the asphalt, but also increase the adhesion of the asphalt.
Meanwhile, Limestone powder mainly contains CaO and
MgO, which are chemically stable and difficult to dis-
solve, so it is difficult for them to sufficiently combine
well with asphalt.
In order to further verify the reaction effect of the basic
oxide and the asphaltic acid anhydride in the asphalt, the
acid value of the asphalt and the asphalt mastic were tested,
respectively, according to the ASTM D 664
As can be seen from Table 7, the VSP acid value was
lower. It demonstrated that the basic oxide in VSP could
react with asphaltic acid and asphaltic acid anhydride, which
reduced the acid value of the asphalt. The acid value of VA
was not much different from the M. This indicated that the
substance in M did not react with the asphaltic acid and
asphaltic acid anhydride.
It again demonstrated that volcanic stone could be used
in road engineering by grounding it into powder. It also
provided a utilization method for volcanic stone and a new
substitute for limestone powder.
5 Conclusions
In this study, some conventional and specific experiments
were conducted to evaluate the improvement properties
of asphalt mastic with volcanic stone power. Based on the
experiments results and analysis from different powder types
and contents, the following conclusions can be drawn.
1. The asphalt mastic with VSP had better basic perfor-
mance than that with limestone powder. The high-
temperature performance of asphalt mastic with VSP
increased by 17.6% and they had almost the same low-
temperature performance. Meanwhile, the volcanic stone
powder could provide better bonding effect for asphalt
than limestone powder.
2. The dispersion state of asphalt mastic with VSP was sol
type, but asphalt mastic with limestone powder was gel
type. During the construction process, asphalt mastic
with VSP had much more stable temperature sensitivity.
The VSP was more conducive to improve the tempera-
ture performance of asphalt than limestone powder from
the results of T1.2 and T800.
3. The volcanic stone powder contained unique Si element
and much higher content of
SiO2, Al2O3, Fe2O3, Na2O
and K2O. All those elements could promote chemical
reactions with asphalt during swelling, which made the
VSP much more compatible with asphalt. Limestone
Fig. 24 Asphalt mastic with VSP peak fitting map
Fig. 25 Asphalt mastic with M peak fitting map

1 3
powder mainly contained CaO and MgO, which were
difficult to dissolve and combine well with asphalt.
4. It demonstrated that volcanic stone powder could replace
part of limestone powder as the inorganic filler. It also
illustrated that VSP were not only the simple inert fill-
Fig. 26 SEM images of asphalt mastic with VSP and M

1 3
ers but also could improve the asphalt performance by
enhancing the cementation effect.
Acknowledgements The project was supported by the Shaanxi Sci-
ence and Technology Project (No. 2018SF-364), Shaanxi Transporta-
tion Science and Technology Project (No. 17-12K), and the Funda-
mental Research Funds for the Central Universities of China (Nos.
310831153409, 300102218502 and 300102318401).
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(mL mol/
(L g))
VA 3.23
VSP 2.49
M 3.10

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