Materials Today: Proceedings 65 (2022) 1861–1866

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Materials Today: Proceedings

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Use of nano-materials to enhance the properties of asphalt mixes

Bhupendra Singh a,⇑, Deepak Prasad b, Aashutosh Kumar b, Baljeet Yadav C
a
Civil and Infrastructure Engineering, Indian Institute of Technology Jodhpur, 342037, India
b
Civil Engineering, National Institute of Technology Patna, 800005, India
C
Civil Engineering, Rajkiya Engineering College Mainpuri, 205001, India

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

Article history: Nanotechnology is being used in different aspects of life to solve different problems. Highway researchers
Available online 20 May 2022 and practitioner are also using nano-materials to modify asphalt binders. Studies associated with the use
of nano-materials in pavement construction are still very limited. In order to make this more applicable
Keywords: in the field, there is a need of more studies on this topic. The current study investigates the influence of
Nano-materials the nano-based chemical warm mix additive zycotherm on the characteristics of asphalt mixes. In the
Zycotherm study zycotherm was added into the mix in different proportions and the properties of the asphalt mixes
Moisture damage resistance
were examined. In order to assess the moisture damage resistance of the mix, parameters like retained
Asphalt mix
marshall stability (RMS) and tensile strength ratio (TSR) were calculated. Based on the results of these
tests, comparisons are made and conclusions are presented in this paper.
Copyright Ó 2022 Elsevier Ltd. All rights reserved.
Selection and peer-review under responsibility of the scientific committee of the International Confer-
ence on Advances in Construction Materials and Structures.

1. Introduction many kinds of nanomaterials to enhance asphalt mix performance.

Some studies have used Nano-metal oxides, i.e. ZnO, TiO2 and SiO2,
Moisture damage is one of the biggest issues which is faced by which are found to enhance the rutting performance of the asphalt
the flexible pavements constructed using asphalt binders. Many of mix but do not improve the fatigue performance [7,8]. On the other
the researchers have used different modifiers to tackle this prob- hand, some studies have used nano-inorganic materials, like nano-
lem and found varying success. Most popularly used asphalt binder clays and carbon nano-tubes (CNT). These materials are found to
modifiers are polymer modifiers. Numerous research works has improve rutting and fatigue performances of the asphalt binders
shown that polymer modifiers are very effective in enhancing the [9,10]. Chemical nano-materials are another type of asphalt modi-
moisture resistance of asphalt binder and asphalt mix [1–6]. But fier which are gaining popularity among the researchers as they
polymer modifiers increases the production cost of the asphalt are easily availability and easier to utilise in asphalt modification.
mixes which makes it unsuitable for small projects. Polymer mod- Some of the previous researches have studied the use of chemical
ification also increases the manufacturing temperature of the nanomaterial like zycosoil and zycotherm, which are found useful
asphalt mix which further increases the cost and also increases in enhancing the performance of the asphalt binder and mixes
the amount of greenhouse gases produced during the pavement [1,11]. Although the researchers are studying the use of nanomate-
construction. So, now researchers are exploring new and innova- rials to modify asphalt binders but more studies are needed to be
tive materials such as nanomaterials to enhance moisture damage carried out to give the confidence to the practitioners to utilise
resistance and improve the characteristics of the asphalt binders nanomaterial modified asphalt binders in the field.
and mixes. Apart from moisture damage resistance, researchers
and practitioners are employing nanotechnology to overcome chal-
lenges caused by rising traffic, heavier axle loads, and severe 2. Background literature
weather conditions. In the recent past, several studies have used
In recent times, a number of researchers have studied the use of
⇑ Corresponding author. nanomaterials in concrete mixtures [12] as well as in asphalt mix-
E-mail addresses: [email protected], [email protected],
tures as asphalt binder modifier. Khodaii et al. [13] studied the use
[email protected] (B. Singh), [email protected] (D. Prasad), of zycosoil and concluded that coating the aggregate surface with
[email protected] (A. Kumar), [email protected] (B. Yadav). zycosoil lowers the moisture susceptibility of the asphalt mixes.

https://doi.org/10.1016/j.matpr.2022.05.043
2214-7853/Copyright Ó 2022 Elsevier Ltd. All rights reserved.
Selection and peer-review under responsibility of the scientific committee of the International Conference on Advances in Construction Materials and Structures.
B. Singh, D. Prasad, A. Kumar et al. Materials Today: Proceedings 65 (2022) 1861–1866

Moghadas Nejad et al. [14] also found the similar results in their needed in this direction to study it with different materials, which
study. Behbahani et al.[15] found 4.5% of zycosoil (4.5%) enhances will give confidence to practitioners to use it in the field.
the moisture damage resistance of the asphalt mixtures. Likewise,
Ziari et al. [16] in their study concluded use of zycosoil improves 3. Objectives of the study
rutting performance of the asphalt mixes. Teppala et al. [17]. used
zycosoil as the modifier with crumb rubber modified bitumen and Based on the study of past literature, the goal of current work is
found it to be effective in improving the performance of the dense to examine the consequences of using nano-modifier i.e.,
bituminous macadam. Dam et al. [18] concluded that zycosoil zycotherm on asphalt mix characteristics and finding out the opti-
reduces the stripping of asphalt mix and improves the quality flex- mum dosage of modifier to be used.
ible pavement. In their studies, various researchers have varied the
dosage of nanomaterials. For instance, Dam et al. [18] applied 0.02,
4. Materials and methodology
0.03 and 0.04% of zycosoil with 5.1% of bitumen content. Sarkar
et al. [19] studied the performance of stone and brick aggregate
The base binder used for this work was viscosity graded VG-30
by soaking them into a solution of 1 kg zycosoil: 400 L water and
bitumen. Zycotherm as a nanomaterial, shown in Fig. 1., was used
then spraying the mix of 5% by weight of aggregate on oven dried
in this work. Zycotherm works on a silane-based technology. It
aggregates. Ibrahim et al. [20] applied zycotherm both on asphalt
forms water-repulsive hydrophobic zone on a molecular level
and asphalt mixes and observed that zycotherm provide resistance
which improves the performance as well as moisture damage
to asphalt concrete mix against rutting, moisture damage, fatigue
resistance of the bituminous mix. The dosage of zycotherm was
and temperature cracking. Saha et al [11] used the inferior quality
varied from 0, 0.1, 0.2 and 0.3% and asphalt mix were prepared.
aggregate with zycosoil solution and found out it to be effective in
Based on the results attained from different tests, optimum dosage
enhancing the characteristics of the asphalt mixture. Singh et al [1]
was found out. The basic characteristics of zycotherm are given in
studied the use of zycotherm with polymer modified binders
Table 1. The experimental program of the study was started by
(PMB) and found it to be decreasing the production temperature
conducting conventional tests were conducted on bitumen and
of the asphalt mixes. Therefore, from the above literature review
aggregates. Table 2 and 3 provide the conventional test results of
it can be concluded that chemical nanomaterials are effective in
bitumen and aggregates respectively. As per criteria set by
improving the properties of aggregates and mixes. More work
MORT&H [21], the aggregate properties were found satisfactory.
Fig. 2 provide a block diagram, showing the investigational plan
followed in this work.

5. Results and discussion of the study

In this work Marshall Stability, retained Marshall Stability, Indi-

rect tensile strength and modified Lottman tests have been carried
out on the asphalt mixes containing varying nano-modifier
dosages. The results obtained from these tests are discussed in this
section.
The gradation of aggregate used to prepare asphalt mix samples
is presented in Fig. 3.

Table 3
Aggregate Properties.

Tests Standard Standard Values Obtained

Used (MORTH, 2013) [21] Values
Specific gravity of coarse IS-2386, – 2.70
Fig. 1. Zycotherm.
aggregates part III [27]
Specific gravity of fine IS-2386, – 2.712
aggregates part III [27]
Impact Value IS-2386, Max 27% 16.44%
Table 1 part IV [28]
Nano Modifier Properties. Los Angeles Abrasion IS-2386, Max 35% 14.75%
part IV [28]
Properties Values
Crushing Strength IS-2386, – 10.25%
Specific gravity 0.97 part IV [28]
State Liquid Flakiness and Elongation IS-2386, Max 35% 22.45%
Colour Pale yellow Index (Combined) part I [29]
Odour Odourless Water Absorption IS-2386, Max 2% 0.62%
Freezing point 5 °C part III [27]

Table 2
Asphalt binders Properties.

Tests Standard Used Standard Values (IS: 73, 2013) [22] Obtained values
Penetration Value IS 1203 [23] 45 mm (min.) 53 mm
Softening Point IS 1205 [24] 47 °C (min.) 49 °C
Absolute Viscosity at 60 °C IS 1206 (Part 2) [25] 2400–3600 Poise 2760 Poise
Ductility IS 1208 [26] – 62 cm

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B. Singh, D. Prasad, A. Kumar et al. Materials Today: Proceedings 65 (2022) 1861–1866

Fig. 2. Experimental Plan.

Marshall Stability test used to find out optimum binder content

(OBC) and evaluate strength of the bituminous mix. OBC was found
out by preparing the asphalt mix samples with varying asphalt
content from 3.5% to 6% by weight of aggregate with increments
of 0.5%. Compaction of the samples was done by giving it 75 blows
on each face to simulate heavy traffic condition. OBC was worked
out at 4% air void. OBC was found out for different samples con-
taining varying nano-modifier dosage (by weight of bitumen).
OBC values for different asphalt mix samples prepared using differ-
ent modifier content have been given in Table 4.
From Table 4, it can be seen that adding modifier decreases OBC
values of asphalt mixes. For 0.1% modifier, OBC was marginally
increased but decreased for other two modifier contents. OBC
was found to be lowest for 0.2% of modifier. Marshall stability
and flow values of asphalt mix containing different % of modifier
are shown in Fig. 4(a). Stability values of the samples first
increased with increasing modifier dosage. At 0.2% highest stability
value was obtained which decreased marginally at 0.3% dosage.
Fig. 3. Aggregate gradation. Overall, the stability values of asphalt binders were found to be
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B. Singh, D. Prasad, A. Kumar et al. Materials Today: Proceedings 65 (2022) 1861–1866

Table 4 The average Marshall Stability values obtained from these two
Optimum Binder Content with Varying Nano Modifier Content. groups were recorded and RMS values were calculated using the
Modifier content (%) Optimum bitumen content (%) following relationship (eq. (1)):
0 4.65
0.1 4.68
RetainedMarshall StabilityðRMSÞ
0.2 4.55 Marshall Stability of 24 hours conditioned specimen
0.3 4.62 
Marshall Stability of 30minutesconditioned specimen
 100 ð1Þ
Higher RMS values indicate higher moisture damage resistance
increasing with the addition of modifier. This increase in stability and vice-versa. Retained Marshall stability values of samples con-
values can be credited to the alkoxy groups of silane which are pre- taining different modifier content are represented in Fig. 5(a). Here,
sent in the nano molecules. These alkoxy groups form siloxane retained stability values increased with increasing dosage of mod-
bonds (Si-O-Si) by chemically reacting with hydroxyl (OH) groups ifier up to 0.2%. After that at 0.3% modifier content. RMS value
presents in the aggregates. Siloxane bonds are known to be one of decreased slightly but the value was better than base sample. So,
the most resilient bonds and this increases the overall stability of nano-modifier increased moisture damage resistance of the
the asphalt mix [1]. When the modifier is increased beyond 0.2%, asphalt mixtures.
a slight decrease in the stability value is observed that is the indi- Indirect Tensile Strength (ITS) test is carried by applying load on
cation of the extra modifier present in the mix. a vertical diametrical plane of a cylindrical asphalt mix sample. The
Marshall Quotient (MQ) is a parameter which can be used as an load is applied using two curved strips having the same radius of
indicator of shear resistance and rutting resistance of the asphalt curvature as specimens. As a result of this loading configuration,
mix. Mathematically, the Marshall Quotient is computed by divid- constant tensile stress is created perpendicular to the applied
ing the asphalt mix’s stability value by its flow value. In present load’s direction, resulting in specimen failure by splitting across -
study MQ values of different asphalt mix samples prepared (at the vertical diametrical plane.
OBC) using different modifier dosages were compared. From the ITS is an assessment of the tensile properties of asphalt mixes
comparison it was observed that addition of nanomaterial which further correlates with the cracking of the pavement. A
improved the MQ of asphalt mix samples. Samples prepared using higher ITS value indicates higher low temperature cracking resis-
0.2% modifier showed highest MQ values which slightly decreased tance. Moreover, a higher value indicates that the mix will be able
at 0.3% modifier content. MQ values of asphalt mixes has been to withstand greater tensile strains before failure. To evaluate the
graphically presented in Fig. 4(b). moisture resistance of the asphalt mix, the tensile strength ratio
When it comes to the bituminous pavements, moisture damage (TSR) was calculated using modified Lottman test.
is one of the biggest reasons of pavement failure [30]. Moisture Mathematically, the TSR value of asphalt mix is obtained by
resistance of the asphalt mix is an indicator of its durability. Thus, dividing ITS values of conditioned samples by those of the uncon-
to assess the consequence of nano-modifier on the moisture dam- ditioned samples. The samples were conditioned by keeping them
age resistance of mixes, Retained Marshall Stability (RMS) values in water for 24 h at temperature of 60 °C and then curing them for
were calculated. For conducting the test, six asphalt mix samples 2 h at 25 °C before performing the test. ITS and TSR results of are
were prepared at OBC and separated into two groups of three sam- presented in Fig. 5(b).
ples in each. Samples from one of the groups were used for Mar- The results revealed that modifier improved both ITS and TSR
shall Stability test after immersing them in water at a values. Like Marshall and RMS values ITS and TSR value also
temperature of 60 °C for 30 min. The specimen from the other showed best outcome at 0.2% modifier content. This improved
group were tested by immersing them in water for 24 h at temper- behaviour can be the result of molecular level hydrophobic layer
ature of 60 °C. that nano-modifier (zycotherm) creates around the aggregates.

Fig. 4. (a) Marshall stability and flow value of asphalt mixes; (b) Marshall quotient values of asphalt mixes.

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B. Singh, D. Prasad, A. Kumar et al. Materials Today: Proceedings 65 (2022) 1861–1866

Fig. 5. (a) RMS; (b) ITS and TSR values of the asphalt mixes.

Organofunctional silanes have both organic and inorganic phases. 3. Different percentages of modifier were used and from the
The inorganic component of the couple bonds with the hydroxy- results it can be said that 0.2% modifier content is the optimum
lated agent on the aggregate surface, while the organic part con- content for enhancing the strength and moisture damage resis-
denses during hydrolysis in the presence of water and is turned tance of asphalt mixture.
into siloxane, which is hydrophobic in nature. When the tempera-
ture rises during mixing and compaction, the hydrogen bond Current study can be further stretched by using different binder,
breaks, resulting in the formation of H2O and covalently bonded aggregate type and aggregate gradation to study the effect of nano-
metallosiloxane. This results in the formation of a cross-linked material on asphalt binder properties.
siloxane (Si-O-Si) coating on the surface of the aggregate. [14,31].
This improves overall coating and bonding of aggregate and
Declaration of Competing Interest
bitumen which further results in better performance of the mix.
Base sample was found to be having TSR value lower than 80%
The authors declare that they have no known competing finan-
which makes it unsuitable to be used in the areas which are prone
cial interests or personal relationships that could have appeared
to cracking. Modified mixes were found to possess TSR values
to influence the work reported in this paper.
greater than 80% with mix containing 0.2% modifier showing the
highest value. At 0.3% modifier content ITS and TSR values
decreased a little but overall modifier was found to be improving Acknowledgements
the performance of the mix. Greater TSR values also indicate
greater moisture resistance of the mix. All persons who have made substantial contributions to the
Results of all the tests conducted on asphalt mix i.e. Marshall work reported in the manuscript (e.g., technical help, writing and
stability, RMS, ITS and TSR, indicated that asphalt mix properties editing assistance, general support), but who do not meet the cri-
increased with the inclusion of nano-modifier. For all the tests, teria for authorship, are named in the Acknowledgements and have
0.2% of modifier gave highest values which also indicates better given us their written permission to be named. If we have not
performance. Parameters values declined with further rise in mod- included an Acknowledgements, then that indicates that we have
ifier content. So, centred on this trend it is concluded that 0.2% is not received substantial contributions from non-authors.
the optimum modifier content.
References
6. Conclusions
[1] B. Singh, N. Saboo, P. Kumar, Pet. Sci. Technol. 35 (2017) 1648–1654.
[2] B. Singh, N. Saboo, P. Kumar, J. Transp. Eng. Part B Pavements 143 (2017)
Present study examined the influence of chemical nano mate- 04017017.
rial on the properties of asphalt mixes. In the study three different [3] N. Saboo, P. Kumar, Constr. Build. Mater. 96 (2015) 632–640.
dosage of chemical nano modifier (zycotherm) was used to prepare [4] S.S. Awanti, M.S. Amarnath, A. Veeraragavan, J. Mater. Civ. Eng. 20 (2008) 327–
330.
asphalt mix samples. These samples were tested and following [5] F. Cardone, G. Ferrotti, F. Frigio, F. Canestrari, Constr. Build. Mater. 71 (2014)
conclusions were made: 435–443.
[6] B. Singh, P. Kumar, Constr. Build. Mater. 205 (2019) 633–641.
[7] G.H. Shafabakhsh, O.J. Ani, Constr. Build. Mater. 98 (2015) 692–702.
1. Nano modifier was found to be improving Marshall stability and
[8] C. Fang, R. Yu, S. Liu, Y. Li, J. Mater. Sci. Technol. 29 (2013) 589–594.
ITS values of the base mix. [9] A.N. Amirkhanian, F. Xiao, S.N. Amirkhanian, Int. J. Pavement Res. Technol. 4
2. Modifier formed a hydrophobic layer around the aggregate sur- (2011) 281–286.
face of the aggregate this layer improved the bonding between [10] A.N. Amirkhanian, F. Xiao, S.N. Amirkhanian, J. Test. Eval. 39 (2011) 583–591.
[11] A. Saha, B. Singh, S. Biswas, Eur. Transp. Eur. 65 (2017) 1–12.
aggregate and binder which improves the moisture resistance [12] J.A. Abdalla, B.S. Thomas, R.A. Hawileh, J. Yang, B.B. Jindal, E. Ariyachandra,
of the mix. This was observed in RMS and TSR Values. Clean. Mater. (2022) 100061.

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[13] A. Khodaii, V. Khalifeh, M.H. Dehnad, G.H. Hamedi, J. Mater. Civ. Eng. 26 (2014) [23] IS 1203, Indian Standard Method for Testing Tar and Bituminous Materials :
259–266. Determination of Penetration, New Delhi, India, 1978.
[14] P. Mirzababaei, F. Moghadas Nejad, K. Naderi, Road Mater, Pavement Des. 21 [24] IS 1205, Methods for Testing Tar and Bituminous Materials : Determination of
(2020) 570–585. Softening Point, New Delhi, India, 1978.
[15] H. Behbahani, H. Ziari, N. Kamboozia, A.M. Khaki, S.M. Mirabdolazimi, Constr. [25] IS 1206 (Part II), Methods for Testing Tar and Bituminous Materials :
Build. Mater. 78 (2015) 60–68. Determination of Viscosity (Part II: Absolute Viscosity), New Delhi, India, 1978.
[16] H. Ziari, H. Behbahani, N. Kamboozia, M. Ameri, Constr. Build. Mater. 101 [26] IS 1208, Indian Standard Method for Testing Tar and Bituminous Materials :
(2015) 752–760. Determination of Ductility, New Delhi, India, 1978.
[17] B.R. Teppala, C.B. Mishra, A. Sinha, D. Kumar, Int. J. Innov. Res. Sci. Eng. Technol. [27] IS 2386 (Part III), Methods of Test for Aggregates for Concrete, Part 3: Specific
03 (2014) 16489–16494. Gravity, Density, Voids, Absorption and Bulking, New Delhi, India, 1963.
[18] T. Dam, V. Khambhayta, D. Makwana, S.K. Jadav, B.R. Teppala, P.C.B. Mishra, J. [28] IS 2386 (Part IV), Indian Standard Method of Test for Aggregates for Concrete,
Mech. Civ. Eng 11 (2014) 10–15. Part IV : Mechanical Properties, New Delhi, India, 1963.
[19] D. Sarkar, M. Pal, A. Sarkar, Int. J. Civ. Environ. Eng. 8 (2014) 1302–1306. [29] IS 2386 (Part I), Methods of Test for Aggregates for Concrete, Part I: Particle
[20] I. Ibrahim, H.N.A. Mehan, Open, J. Civ. Eng. 5 (2015) 419. Size and Shape, New Delhi, India, 1963.
[21] MORT&H, Specification for Road and Bridge Work, New Delhi, India, 2013. [30] B. Singh, S. Jain, Road Mater. Pavement Des. (2021) 1–17.
[22] IS 73, Indian Standard Paving Bitumen-Specification (Fourth Revision), New [31] B. Singh, P. Kumar, Int. J. Pavement Eng. (2021) 1–15.
Delhi, India, 2013.

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