Construction and Building Materials 421 (2024) 135691

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Construction and Building Materials

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

Use of sugarcane molasses for preparation of bio-asphalt: Effect of source

Dheeraj Mehta , Nikhil Saboo *
Indian Institute of Technology Roorkee, India

A R T I C L E I N F O A B S T R A C T

Keywords: Demand for asphalt binder is on rampant rise due to overpopulation and rapid urbanization. Non-renewability
Asphalt binder and fluctuating price of asphalt binder have prompted research efforts in the direction of sustainable flexible
Sugarcane molasses pavements using bio-asphalt. This study is aimed to evaluate the feasibility and source variability of sugarcane
Rheology
molasses (SM) as a partial replacement of asphalt binder. Three sources of SM were used in the study. A series of
FTIR
conventional, chemical, rheological, and storage tests were conducted. The optimum dosage of SM for partial
replacement was found to be 30% by weight of asphalt binder. Fourier transform infrared spectroscopy (FTIR)
results revealed the possibility of chemical interaction between SM and asphalt binder. Through rheological
mastercurves, it was found that the addition of SM, regardless of the dosage, improved permanent deformation
characteristics. The segregation test results indicated adequate thermal storage stability of bio-asphalts. Further,
statistical analysis showed that the source of SM had no significant impact on the physical and rheological
characteristics of the bio-asphalt. Cost analysis showed that 30% incorporation of SM could lower the cost of
asphalt production by 20–30%.

1. Introduction
Asphalt concrete, used in the surface, binder, and base layers of
flexible pavement, has gained popularity owing to its excellent ride­
ability, recyclability, stability, and possibility of convenient mainte­
nance [1]. The focus on the development of road infrastructure along
with pavement maintenance generates huge demand for asphalt con­
crete, and therefore asphalt binder. Asphalt binder, which is extracted
from crude oil, is a non-renewable material. Fluctuating oil prices and
the increasing demand of this fossil fuel derived material requires search
for an alternative material for production of asphalt concrete. Addi­
tionally, the extraction process takes a heavy toll on the environment, in
the form of emissions. Therefore, the pavement industry is seeking
sustainable green alternatives to substitute asphalt binder partially/fully
in flexible pavement.
Among the sustainable avenues being explored, bio-asphalt has
gained wide spread attention due to its renewable nature [2,3].
Bio-asphalt is a mixture of conventional asphalt binder and bio-binder
(e.g., bio-oil, heavy oil, cooking oil, etc.). The feedstock for bio-oil
mostly comprises of renewable sources such as wood biomass, animal
manure, plants, waste oils, etc. [4]. Biomass conversion to bio-oils is
conducted through biochemical, thermochemical, and mechanical
extraction techniques [5,6]. The biochemical method of conversion
requires the application of bacteria and fungus to convert the biomass
into bio-oil. Mechanical extraction involves squeezing of the feedstock
through mechanical procedures. Thermochemical conversion, on the
other hand, can be carried out through pyrolysis, combustion, lique­
faction, and gasification [7]. Pyrolysis, which is conducted in the
absence of oxygen, is widely adopted due to the increased yield, flexi­
bility in operation, lower catalyst cost, and versatility in handling a wide
variety of feedstocks [6,8]. The compatibility between bio-oil and
asphalt binder is attributed to similar chemical characteristics
comprising of elements such as carbon, hydrogen, nitrogen, and oxygen
[9]. Typically, bio-oil contains higher oxygen, equivalent hydrogen, and
slightly lower carbon component in comparison to asphalt binder [4].
The composition of bio-oil is a function of a wide variety of factors, such
as pyrolysis temperature, biomass source, moisture content of biomass,
type of reactor, bed type, etc. [8]. Such variables lead to variation in the
performance of the resultant bio-asphalt. Generally, it has been found
that most of the bio-oils lower the viscosity of the bio-asphalt, leading to
insufficient high temperature performance [10]. Additionally, the
presence of light oil components may increase the susceptibility of the
bio-asphalt to aging [11]. The machinery and plant required for the
extraction of bio-oil necessitate huge investment and operational costs
[12]. Therefore, bio-renewable materials that could be directly incor­
porated in the base asphalt binder will be beneficial. One such material

* Corresponding author.
E-mail address: nikhil.saboo@ce.iitr.ac.in (N. Saboo).

https://doi.org/10.1016/j.conbuildmat.2024.135691
Received 17 January 2024; Received in revised form 16 February 2024; Accepted 1 March 2024
Available online 6 March 2024
0950-0618/© 2024 Elsevier Ltd. All rights reserved.
D. Mehta and N. Saboo
of interest is sugarcane (Saccharum officinarum L.) molasses.
Sugarcane molasses (SM) is obtained as a byproduct of the sugar
refining industry. SM is a dark brown thick liquid containing sugars.
Typically, the composition of SM comprises of 76% of dry matter (DM),
sucrose (42.4–55.2%), glucose (2.6–8%), fructose (5.3–10.9%), ash
(10–16%), and trace quantities of organic acids, polysaccharide, oligo­
saccharide, crude protein, potassium, and nitrogen compounds [13,14].
Some attempts to utilize sugarcane molasses in asphalt binder have been
reported. A recent study by Phuc Le [15] found that the addition of SM
leads to improved rutting characteristics. Hareru and Ghebrab [16]
researched the effects of moisture (in SM) on the properties of modified
asphalt binder. The study concluded that the addition of SM results in
improved rheological behavior and could be a viable solution for
partially replacing asphalt binder. Saboo et al. [17] concluded that 25%
SM (by weight of base asphalt binder) as a replacement of asphalt binder
could result in improved permanent deformation characteristics and
fatigue resistance. Further, Gürü et al. [18] found that the addition of
sugar beet molasses improved the stripping resistance of modified
asphalt mixtures. In summary, researchers are in agreement to partially
substitute asphalt binder with SM. However, concerns related to source
variability of sugarcane molasses have not been studied with enough
rigor. The molasses composition is a function of type of soil, climatic
conditions, and maturity of cane. Additionally, sugar manufacturing
process differs from plant to plant. Molasses composition is also a
function of technology applied, type of input material, moisture content,
topography, etc. [19,20]. To be a viable solution from a field-applicable
point of view, the source of sugarcane molasses ideally should not affect
the performance of the produced bio-asphalt. Based on the literature
survey and the identified problem statement, this study was undertaken
to assess the effect of source of sugarcane molasses on the characteristics
of bio-asphalt produced by partial replacement of asphalt binder with
SM.
2. Materials
2.1. Asphalt binder
Viscosity grade-40 (VG40) was used as the control binder in the
study. This asphalt binder was selected owing to its wide application in
India. The basic properties of VG40, as per the standard specification
[21], are presented in Table 1. Additionally, the high temperature per­
formance grade of VG40, evaluated as per AASHTO M320 [22], was
found to be PG 70-XX.
2.2. Sugarcane molasses (SM)
SM is a thick dark liquid of brown tint, containing sugars, and having
small percentage of moisture. The composition of sugarcane molasses
mainly comprises of sucrose, inverted sugar (fructose+ glucose), un-
fermentable sugar, along with other organic substances [19,20]. The
molecular structure of these components is shown in the Fig. 1a. The
physical appearance of SM obtained from three different sugarcane in­
dustries (with varying geographical locations) is depicted in Fig. 1b.
These sources were tagged as S1, S2, and S3. The basic properties of SM
are presented in Table 2. Brix is a measure of dissolved solids. A higher
Table 1
Basic properties of VG40 binder.
S No. Characteristic Value Specification
1. Penetration at 25◦ C, 100 g, 5 s, 0.1 mm 41 IS 1203
2. Absolute viscosity at 60◦ C, Poises 421.98 IS 1206 (Part 2)
3. Flash point (Cleveland open cup), ◦ C 285 IS 1448 [P: 69]
4. Solubility in trichloroethylene, percent 99.95 IS 1216
5. Softening point (R&B), ◦ C 52.4 IS 1205
Tests on residue from rolling thin film oven test:
6. Ductility at 25◦ C, cm IS 1208
>100
2
Construction and Building Materials 421 (2024) 135691
value of brix signifies higher sucrose content [23]. The average specific
gravity and moisture content was found to be 1.403 g/cm3 and 14.98%,
respectively. The pH value indicates that SM has acidic nature.
2.3. Production of bio-asphalt
SM was partially replaced at concentrations of 10%, 20%, and 30%
by weight of the asphalt binder. The next higher dosage (40%) was not
considered based on the criteria of workability. The presence of mois­
ture in SM leads to foaming when the mixture of SM and asphalt binder
is heated. At 40% dosage, the foaming in the binder was found to reduce
the workability of blend. As will be discussed later, with increase in the
dosage of SM, the flowability of the bio-asphalt reduces. Additionally, in
the hot mix plant, such characteristics will hinder the pumping of the
binder. The asphalt binder tank should be operated at a lower capacity
to allow for the expansion of binder. The operating capacity is a direct
function of the amount of SM present in the bio-asphalt. With the in­
crease in the replacement dosage, the tank capacity will reduce.
Considering these two aspects, 30% was considered to be the maximum
permissible dosage. The preparation procedure of bio-asphalt was
established through several trials in the laboratory. The blending pa­
rameters, including blending temperature, speed, and shear rate, were
fixed to obtain a visually homogenous blend. The base binder (VG40 in
this case) was heated around 130–140◦ C followed by the addition of SM.
The mixture of VG40 and SM was blended at 500 rpm for 15 mins. The
prepared bio-asphalts are coded as shown in Table 3.
3. Experimental methods
A series of conventional, chemical, rheological, and storage tests
were undertaken to assess the performance of bio-asphalt. Fig. 2 pre­
sents the experimental methodology adopted for the present study.
3.1. Physical behaviour
Though the conventional physical experiments are becoming obso­
lete for characterization of asphalt binders, they provide quick insight
into the stiffness of the binder. For comparison, penetration, and soft­
ening point of the prepared bio-asphalt, as per IS 1203 [24] and IS 1205
[24], respectively, were measured. SM has unique characteristics in
comparison to asphalt binder. The inclusion of SM in the asphalt binder
may change its density, which will further impact the mix design of the
asphalt mixture. Therefore, the specific gravity of the bio–asphalts was
evaluated as per IS 1202 [24]. SM is water soluble due to the presence of
disaccharides. Therefore, the blend of SM and asphalt binder is expected
to get separated in the presence of moisture. The concern related to this
dissolvability was addressed by performing a simple water immersion
test. A fixed weight of bio-asphalt (2 gms) was taken and immersed in a
beaker full of water. Quantification was made via visual observation of
the beaker to track the color change after 24 hrs. As mentioned previ­
ously, presence of SM in bio-asphalt leads to foaming at elevated tem­
peratures. Such behaviour is anticipated to affect the workability during
the preparation of the asphalt mixture. To study the flowability of the
bio-asphalt, an unconventional method was used in this study using a tar
viscometer (Fig. 3).100 gm of sample was introduced in the tar cup
having an orifice opening of fixed diameter. An oil bath was used as the
heating medium to maintain the test temperature of 130◦ C. The sample
was allowed to flow through an orifice and collected using a measuring
cylinder. The time taken in seconds to collect 50 cm3 of sample through
the orifice was recorded. The values obtained for bio-asphalts were
compared with VG40 for indirectly assessing the workability
characteristics.
3.2. FTIR
Fourier transform infrared spectroscopy (FTIR) is widely used for
D. Mehta and N. Saboo Construction and Building Materials 421 (2024) 135691

Fig. 1. (a) Molecular structure sucrose, fructose, and glucose (b) physical appearance of sugarcane molasses.

mixture was dropped on KBr powder, thoroughly mixed, and hydrauli­

Table 2
cally pressed to obtain thin pellets. The pellets produced were kept in a
Properties of sugarcane molasses.
draft oven for a period of 10 minutes to eliminate the interference of
Source ◦
Brix Specific gravity (g/cc) Moisture content (%) pH solvent. The pellets were allowed to cool and introduced in the pellet
S1 78 1.402 15.42 4.72
S2 74 1.375 17.53 4.80
S3 84 1.433 12.01 4.95

Table 3
Coding of bio-asphalts.
Source Sugarcane molasses (% by weight of asphalt) ID

S1 10 SM 10 S1
20 SM 20 S1
30 SM 30 S1
S2 10 SM 10 S2
20 SM 20 S2
30 SM 30 S2
S3 10 SM 10 S3
20 SM 20 S3
30 SM 30 S3

identification of chemical and molecular structure of asphalt binder

[25]. A transmission based FTIR (Thermo-scientific Nicolet Summit LITE
iD1) was used in this study. The sample was prepared by dissolving 1 gm
of binder in 10 ml of toluene solution. Next, a small amount of this Fig. 3. Test setup of flowability.

Fig. 2. Experimental flowchart.

3
D. Mehta and N. Saboo
holder where infrared beam is allowed to penetrate the sample. Similar
procedure has been used by previous researchers [25,26]. Each sample
was subjected to thirty scans at 4 cm− 1 resolution. The spectra were
recorded at a wavenumber range of 400–4000 cm− 1. Four replicates for
each sample were tested for repeatability.
3.3. Separation test
As two different materials are being mixed to prepare the bio-
asphalt, it is important to ensure that the mixture remains stable
under prolonged storage at high temperatures. The storage stability of
the bio-asphalts was measured using the separation test [27]. The pre­
pared bio-asphalt was poured in an aluminum tube of standard dimen­
sion, sealed, and was allowed to stand vertically at 140◦ C for 48 hours.
This was followed by freezing the binder at a temperature of –10◦ C for
4 hours. Further, the tube was cut horizontally into three equal parts.
The difference in the softening point of the top and bottom samples was
calculated and used to quantify the storage stability. As per standards,
the difference in softening point should be less than 3◦ C to ensure sta­
bility of the blend [28]. It should be noted that the conventional sepa­
ration test is done at 163◦ C. A lower temperature was chosen for the
prepared bio-asphalts due to the foaming characteristic which will
interfere with the conditioning process. Additionally, this study rec­
ommends that at the hot mix plant the bio-asphalt should be pumped
and mixed with the aggregates at lower temperatures than conven­
tionally used. This justifies the use of 140◦ C in lieu of 163◦ C.
3.4. Rheological tests
The rheological characterization was done using a dynamic shear
rheometer (DSR) (Anton paar- MCR 302). Frequency sweep (0.1 rad/s to
100 rad/s) test was conducted within a temperature range of 10◦ C -
80◦ C (at 10◦ C intervals) using a parallel plate geometry. For the tem­
perature range of 10◦ C - 30◦ C, 8 mm diameter spindle with 2 mm plate
gap was employed, whereas 25 mm diameter plate with 1 mm plate gap
was utilized for 40◦ C - 80◦ C. Two replicates for each test condition were
tested. Complex shear modulus (|G*|) master curves, based on the time-
temperature superposition principle (TTSP), were plotted at a reference
temperature of 40◦ C. 40◦ C represents the average of the temperature
range used for the frequency sweep test and was thus chosen for
comparing the binders. Arrhenius equation [29,30] was used to obtain
the shift factors. Christensen, Anderson and Marasteanu (CAM) model
[31,32] was used to fit the complex shear modulus |G*| and quantify the
stiffness characteristics of the binders [33]. The Arrhenius equation and
Fig. 4. (a) Variation of softening point (b) Variation of Penetration.
4
Construction and Building Materials 421 (2024) 135691
CAM model used in this study can be mathematically represented as
follows:
1 1
Log aT = C( − ) (1)
T Tref
fc − w
G∗ = Gg [1 + ( )v ] v (2)
f
R=
log2
(3)
v
Where G∗ is the complex shear modulus; Gg is the glassy modulus; fc is
the frequency at cross point; f is the reduced frequency; w, v are the
shape parameters; R is the rheological index.
4. Results and discussions
4.1. Effect of SM on physical properties
Fig. 4a shows the variation of softening point with increasing dosage
of SM. The softening point difference of SM 30 S1, SM 30 S2, and SM 30
S3 was found to be 1◦ C, 2◦ C, and 2.15 ◦ C higher than the control binder,
respectively. In terms of effect of source, the softening point difference
of all three SM source, varied in the close range of 1◦ C – 2.15◦ C. Overall,
it was found that increase in SM content increased the softening point
difference, indicating stiffening effect of SM. The variation in penetra­
tion corresponding to dosage and source of SM is shown in the Fig. 4b.
As can be seen, the penetration of all bio-asphalts decreased with in­
crease in the dosage of SM. The penetration value of all bio-asphalts
ranged between 32 dmm to 40 dmm. The penetration value of SM 30
was 17% lower than the control binder. Irrespective of the source, the
addition of sugarcane molasses reduced the penetration by approxi­
mately 15%. The increment of softening point difference and reduction
in penetration could be attributed to the presence carbohydrates (su­
crose, glucose, and fructose) in SM. As reported by [34] the polymeri­
sation of carbohydrates results in resinification within the base asphalt
binder which leads to increase in the stiffness. However, it must be noted
that the nature of interaction of SM and base binder is a complex phe­
nomenon and is not clearly understood [35].
The results of specific gravity of control binder, sugarcane molasses,
and bio-asphalts are shown in the Fig. 5a. As seen, SM has higher specific
gravity than the control binder. The specific gravity of bio-asphalts ex­
hibits increasing trend as the dosage of SM increases. The average spe­
cific gravity of bio-asphalt with 30% SM was found to be 1.06. VG40,
used in this study, had a specific gravity of 1.03. This indicate that in an
D. Mehta and N. Saboo
Fig. 5. (a) Specific gravity results of SM modified asphalt binder (b) Water dissolvability test of bio-asphalt with S1.
asphalt mixture SM 30 will occupy about 97% of the volume of VG40.
With approximately 10% volume of asphalt binder in the mix, this dif­
ference will increase the air-voids about 0.3%. In other words, for a fixed
air-void content (of say 4%) the optimum asphalt binder content will
increase by 0.1% (approximately). Such considerations should be taken
into account while carrying out the cost-benefit analysis. In regard to the
impact of SM source, it was observed that there was negligible variation
in specific gravity.
The results of dissolvability test are shown through Fig. 5b. As can be
seen, no separation between VG40 and SM is observed, irrespective of
the dosage of SM. The presence of carbohydrates in sugarcane molasses
interacts with the phenolic group of asphalt binder resulting in the
formation of compound(s) completely insoluble in water [35].
In the flowability experiment, the time taken by the binder to fill the
50 ml beaker increased with the increase in the dosage of SM. This is
attributed to the formation of interconnected bubbles (during foaming)
within bio-asphalt blocking the orifice flow. In comparison to VG40, the
time taken by SM 10, SM 20, and SM 30 were 0.20 sec, 0.42 sec, and
0.60 sec higher, respectively (Fig. 6). The longer time could be corre­
lated to pumpability in the hot mix plant. However, it must be noted that
the foaming attributes of bio-asphalt are dependent on the temperature
and dosage of SM. The source of SM had marginal impact on the flow­
ability characteristics. Plant application will throw more light into the
effect of such behaviour on the production of asphalt mixtures. Notably,
Fig. 6. Results of flowability test.
5
Construction and Building Materials 421 (2024) 135691
a recent plant execution [36] with 25% SM showed no hindrance in the
production process.
4.2. FTIR spectra of sugarcane molasses
The FTIR spectra of sugarcane molasses from three sources (SM 1, SM
2, SM 3) are shown in Fig. 7. As can be seen, the FTIR spectra of all three
sources showed similar trend. Various distinct peaks, identifying the
presence of specific functional groups, could be observed. The strong
and broad peak between 3200 and 3600 cm− 1 corresponds to O-H and
N-H stretching vibrations. The peak at 2931 cm− 1 is attributed to C-H
bond stretching [37]. The next peaks at 1620 cm− 1 and 1415 cm− 1 are
associated with asymmetrical and symmetrical -COO- stretching of
carboxylic group, respectively [38,39]. The region between 720 and
862 cm− 1 shows several peaks which are attributed to C-H bending vi­
brations. Table 4 present the details of these functional groups available
in sugarcane molasses. In summary, sugarcane molasses mainly consists
of aromatics, alcohols, polymeric O-H, amines, nitrogen compounds,
water, carboxylic acids, and alkanes.
cm-1
Fig. 7. Spectra of sugarcane molasses.
D. Mehta and N. Saboo Construction and Building Materials 421 (2024) 135691

Table 4 Table 5
Functional groups of sugarcane molasses. Prominent peaks of VG 40, SM 30, and SM 60.
Wavenumbers Functional Groups Compound Class Wavenumber VG 40 SM 30 SM 60 Compound class
cm¡1
3421 + + + O-H
3421 O-H stretching, N-H stretching Polymeric O-H, 2950 + + + Asymmetric stretching of C–H in CH3
NH2, Water 2923 + + + Asymmetric stretching of C–H in CH2
2930 C-H stretching Alkanes 2868 + + + Symmetric stretching of C–H in CH3
1620, 1415 asymmetrical -COO- stretching, Carboxylic 2851 + + + Symmetric stretching of C–H in CH2
symmetrical -COO- stretching 1743 + + + C–
–O stretching
1097 S–
–O Sulfoxides 1600 + + + –C stretching
C–
1050 C-O Stretching Primary alcohol 1458 + + + Asymmetric bending of CH3
862–720 C-H plane bending Aromatics 1376 + + + Symmetric bending of CH3
1032 + + + S–
–O stretching vibrations
726 + + + Long alkyl chain groups
4.3. FTIR spectra of bio-asphalt
+ Present

To understand the chemical interaction (if any) between VG40 and

interaction during the preparation of bio-asphalt where alkanes react
30% SM, it was important to understand the change in the chemical
with oxygen. The other noticeable variation was at 3421 cm− 1, where a
characteristic of the bio-asphalt with varying dosage of SM. This would
lower peak in SM 30 compared to base binder was observed (Fig. 8b).
help in analyzing the transition in the extent of interaction between the
The lower peak could be attributed to degradation of sugars [41] and
base binder and SM. Another blend (SM 60) with a higher dosage of
interaction between alcohol and oxygen during the preparation of
sugarcane molasses (60% replacement of asphalt binder) was prepared
blends [16]. Compared with the base binder (VG40), significant differ­
for this purpose. The overlapped spectra are shown in the Fig. 8a. As can
ence occurred in the band range of 1380–1440 cm− 1, where new char­
be seen, the spectrum of SM 60 was identical to SM, indicating domi­
acteristic peak at 1410 cm− 1 was found, as shown in Fig. 9a. No such
nance of SM due to higher percentage of replacement. The changes in
peak was observed in the spectrum of VG40, indicating that the new
the functional groups of bio-asphalt(s) were compared with FTIR spectra
formation is attributed to the presence of SM. The peak is attributed to
of VG40 and SM. As can be seen, the FTIR absorbance spectra trend was
symmetric deformation of C-H and O-H, and C-O stretching of phenolic
different for SM, bio-asphalt, and VG40. The common functional groups
group (O-H) [42,43]. Similarly, as seen in Fig. 9b, the characteristic peak
identified from absorbance spectra of VG 40, SM 30, and SM 60 are
at 925 cm− 1 belongs to SM, which was absent in VG 40.
tabulated in Table 5. The bands at 3200–3600 cm− 1 are attributed to
Further, in the band range 1000–1150 cm− 1, numerous peaks of
intramolecular hydrogen bond O-H stretching. Further, the peaks cor­
VG40 disappeared and converged into a single broad peak in SM 30, as
responding to 2950 and 2923 cm− 1, representing asymmetric stretching
shown in the Fig. 10a. Several additional absorbance bands were
of C–H in CH3 and CH2, were found. Likewise, the peaks at 2868 and
observed between 730 and 780 cm− 1 (Fig. 10b). These bands are asso­
2851 cm− 1 are attributed to symmetric stretching of C–H in CH3 and
ciated to the out of plane C-H bending vibrations in alkenes and aro­
CH2, respectively. The peaks at 1743 and 1600 cm− 1 indicate existence
matics. These bands could be due to the absorbance of aromamins, in
of carbonyl and aromatics (C– –C stretching) [40]. The asymmetric and
which oxidation of alcohol results in aldehyde. The aldehyde bonds
symmetric bends of CH3 are shown at band of 1458 and 1376 cm− 1. The
(C––O) replaced the O-H bonds of alcohol [16]. Based on the above
sulfoxide peak at 1032 cm− 1 indicates vibrations of S– –O, whereas the
discussion, the certainty of chemical interaction between sugarcane
peak at 726 cm− 1 represents the presence of long alkyl chain groups in
molasses and asphalt binder could be witnessed. Interestingly, a
saturates (i.e., more than four carbon atoms in row) [25].
noticeable difference (as discussed above) was found between the
The emergence, disappearance, or shift in the peaks indicate the
spectra of SM 30 and SM 60. This can be attributed to the extent of
interaction of sugarcane molasses and the base binder. As can be seen in
resinification occurring in the bio-asphalt due to the increase in the
Fig. 8a, the spectra of SM and VG40 have obvious differences. The SM
dosage of SM. At lower dosages, the amount of resins being formed does
spectra is dominated by the presence of aromatics, polymeric O-H, NH2,
not create any imbalance in the chemical structure (asphaltene-maltene
and sulfoxide groups, while VG40 has C-H dominant structure. The
ratio) of the asphalt binder. Thus, up to 30% replacement, evident dif­
disappearance of peak at 2930 cm− 1 for SM 30, indicates chemical
ference between VG40 and SM 30 was seen from the FTIR peaks. It is

1
Fig. 8. (a) Overlapped spectra of SM, VG 40, SM 30, and SM 60 (b) Peak variation at 3421 cm− of VG 40 and SM 30.

6
D. Mehta and N. Saboo
Fig. 9. Spectra of (a) 1200–1600 cm−
Fig. 10. Spectra of (a) 900–1300 cm−
hypothesized that beyond 30%, unreacted products of SM in the base
binder alters the characteristics of the bio-asphalt. The unreacted com­
ponents shift the behavior of the bio-asphalt (as was seen in the case of
SM 60) towards SM. This argument requires further investigation as the
determination of exact nature of chemical functionalities reaction be­
tween the two components is a challenging task.
4.4. Effect of sugarcane molasses on rheological properties
Fig. 11 shows the complex shear modulus (G*) master curves of
control and bio-asphalts at a reference temperature of 40◦ C. The dif­
ference in the variation of stiffness with the change in the dosages and
source of SM was compared with the base binder (VG40). As can be seen,
irrespective of source, bio-asphalts have similar trend to that of base
binder. For comparison, three domains of frequency corresponding to
slow, medium, and fast-moving traffic (0.1, 1, and 10 Hz) were selected.
At lower frequencies (representing high temperature), the addition of
SM displayed higher G* values. For instance, SM 30 S1 and SM 30 S3
showed an improvement of 66% in G* value compared with base binder,
whereas SM 30 S2 exhibited an increase of 26%. The lower rate of
increment in SM 2 could be linked to the presence of higher moisture
content which interferes and hinders the stiffness gain. The higher
complex shear modulus at lower frequency implies that the addition of
SM will enhance the resistance to permanent deformation. This
7
Construction and Building Materials 421 (2024) 135691
1 1
area (b) 900–1000 cm− area.
1 1
area (b) 720–780 cm− area.
improvement is attributed to the interaction between the phenolic group
of asphalt binder with carbohydrates present in SM, resulting in for­
mation compounds capable of imparting hardness to the bio-asphalt [34,
35,44]. At intermediate frequency, the G* of SM 30 S1, SM 30 S2, and
SM 30 S3 was found to be 60%, 26%, and 66% higher than the base
asphalt binder, respectively. In higher frequency domain, all
bio-asphalts showed similar trend as that of VG40. Regardless of the
source, the increase in dosage of SM resulted in an increase of G* values.
The CAM model (Eq. 2) was chosen to fit the master curves. Gg was
taken as 1×109 Pa for all the materials [33]. Table 6, depicts CAM model
parameters, where w and v are the shape parameters of the model. The
parameter w is associated with the rate at which complex shear modulus
converges to asymptotes (viscous or elastic) [33,45]. It was observed
that the addition of SM decreased the value of w, implying that the
behaviour of bio-asphalts will be more elastic and less brittle at inter­
mediate loading conditions. The decrement also indicates less sensitivity
of bio-asphalts to frequency. The v value is used to compute rheological
index, R, which is associated with the width of the relaxation spectrum.
Rheological index is defined as the distance between glassy modulus
(Gg) and complex shear modulus (G*) at the crossover point. Rheological
index is a measure of change in modulus with respect to loading time. In
the CAM model, a higher value of R is associated with smaller width of
relaxation [33]. As seen in the Table 6, as the dosage of SM increases,
lower R values are obtained, implying reduced sensitivity to the
D. Mehta and N. Saboo Construction and Building Materials 421 (2024) 135691

Fig. 11. Master curves of SM modified bio-asphalt.

SM increases the rutting factor also increases. For instance, at 70◦ C, the
Table 6
rut factor of SM 10 S3, SM 20 S3, and SM 30 S3 was found to be 10%,
CAM model parameters.
18% and 42% higher than the base binder. This enhanced permanent
Model Parameters VG 40 SM 10 S1 SM 20 S1 SM 30 S1 deformation characteristics could be attributed to stiffening effect
v 0.1501 0.1515 0.1558 0.1651 imparted by SM. The gummy interaction can be linked to presence of
w 1.204 1.200 1.184 1.143 sucrose, resulting in highly cohesive and adhesive properties [34].
R 2.006 1.988 1.932 1.823
Interestingly for SM S1 and S2, the rut factor decreased at 10% incor­
VG 40 SM 10 S2 SM 20 S2 SM 30 S2
v 0.1501 0.1504 0.1551 0.1664
poration of SM, whereas for SM 3 the value increased. This decrease
w 1.204 1.198 1.182 1.131 might be due to readjustment of water molecules present in SM. As
R 2.006 2.002 1.941 1.809 indicated in Table 2, the moisture content of SM 1 and SM 2 was
VG 40 SM 10 S3 SM 20 S3 SM 30 S3 marginally higher than the SM 3. The relative improved performance of
0.1501 0.1514 0.1615 0.1669
SM 3 in comparison to SM 1 and SM 2 is due to the presence of higher
v
w 1.204 1.201 1.163 1.143
R 2.005 1.988 1.864 1.803 concentration of total soluble solids (sucrose, fructose, and glucose). As
shown in Table 2, SM 3 has highest ◦ brix followed by SM 1 and SM 2.
Brix is a measure of sucrose or sugar content. A higher value of brix
frequency. signifies higher sucrose content. According to George [34] the intro­
Rutting factor (G*/sinδ) was measured at 10 rad/sec to characterize duction of sucrose in asphalt results in an increment in stiffness. G*/sinδ
the permanent deformation characteristics of bio-asphalts. According to values also represents high temperature performance grade. As seen the
Superpave binder specification, the value of G*/sinδ should be greater Fig. 13, the addition of SM up to 20% yield similar grade as base binder
than 1.0 kPa in unaged condition and 2.2 kPa in short-term aged con­ (PG 70). The SM 30 modification of all three sources observed a grade
dition to ensure satisfactory rut performance. In this study, only the increment from PG 70 to PG 76. However, it was found that the true fail
unaged binders were tested and compared corresponding to the limiting temperature of all bio-asphalts irrespective of source varied within a
criteria. Fig. 12 shows the variation of G*/sinδ with respect to temper­ close range of 72–78◦ C.
ature, source, and dosage. In general, the rutting factor of the base Further, statistical analysis was carried out using two-way ANOVA
binder and bio-asphalts decreases with the increase in temperature. At a with a confidence interval of 95%. The statistical significance of SM
particular temperature, from Fig. 12c, it can be seen that as the dosage of

8
D. Mehta and N. Saboo
Fig. 12. Variation of G*/sinδ with respect to temperature, source, and dosage.
Fig. 13. True fail temperature of bio-asphalt.
dosage (10, 20, 30%) and source (S1, S2, S3) on the rutting factor was
examined and the results are presented in Table 7. The independent
variables were SM dosage and source, whereas rut factor was considered
as the dependent variable. The obtained p-values were compared with
α=0.05 (α denotes reliability) to perform the significance analysis. The
9
Construction and Building Materials 421 (2024) 135691
results indicated that the SM dosage (p=0.01<0.05) does have a sig­
nificant effect on the rutting factor. Whereas, the source (p=0.14>0.05)
was found to have no significant influence on the rutting factor. Statis­
tical test results confirm that SM source will not affect the performance
of bio-asphalts.
4.5. Effect of sugarcane molasses on thermal storage stability
Table 8 presents the results of the separation test of bio-asphalt using
top and bottom softening point (◦ C). Regardless of the source, the dif­
ference in top and bottom softening point increased with increase in SM
dosage. For example, the ΔTR&B of SM 10 S3, SM 20 S3, SM 30 S3
reached 0.3◦ C, 0.8◦ C, and 1.30◦ C respectively. This variation could be
attributed to the presence of organic compounds in SM altering the
chemical composition under longer storage at elevated temperature,
resulting change in softening [27,46]. The softening point of bottom
section accumulated larger values than the top section. The softening
point of top and bottom section for source S3, at replacement level of
30%, was 55.10◦ C and 56.40◦ C respectively. The higher softening in
lower portion may be due to settlement of higher molecular weight
compounds. In terms of variation among SM sources, the bio-asphalts
with S1 and S3 showed higher softening point difference compared to
S2. The higher softening point difference between top and bottom sec­
tion could be attributed higher ◦ brix of S1 and S3. The higher ◦ brix
implies higher number of soluble solids resulting in the marginal in­
crease in ΔTR&B. According to Indian specification of polymer modified
D. Mehta and N. Saboo Construction and Building Materials 421 (2024) 135691

Table 7
Two-way ANOVA test results.
Source of Variation SS DF MS F-value p-value F-critical Significant effect

SM dosage 12.2423 2 6.1211 15.4624 0.01 6.9442 Yes

SM source 2.5781 2 1.2890 3.2563 0.14 6.9442 No
Error 1.5834 4 0.3958
Total 16.4039 8

SS: sum of squares; DF: degree of freedom; MS: mean square; p: significance probability

• The softening point difference of all bio-asphalts varied in the close

Table 8
range of 1◦ C to 2.15◦ C. The penetration of all bio-asphalts decreased
Thermal storage stability test results.
with increase in the dosage of SM. The polymerisation of carbohy­
Source Designation Top (◦ C) Bottom (◦ C) Difference (◦ C) |ΔTR&BI drates results in resinification within the base asphalt binder leads to
TR&Bt TR&Bb
increased stiffness. Source of SM was insensitive to the change in the
VG-40 56.90 57.05 0.15 values of softening point difference and penetration.
S1 SM 10 53.60 54.05 0.45
• Through flowability experiment, it was found that the addition of SM
SM 20 54.05 55.15 1.10
SM 30 56.90 58.25 1.35
increased the time taken by the binder to fill the 50 ml due to the
S2 SM 10 54.50 54.75 0.25 presence of sight moisture leading to formation of interconnected
SM 20 55.25 55.55 0.30 bubbles. Upto 30% replacement, the workability of asphalt mix will
SM 30 56.05 57.10 1.05 not get affected. Further field trials are required to confirm the re­
S3 SM 10 54.15 54.45 0.30
sults presented in this study.
SM 20 54.55 55.35 0.80
SM 30 55.10 56.40 1.30 • FTIR spectrum of sugarcane molasses indicated the presence of ar­
omatics, alcohols, polymeric O-H, amines, nitrogen compounds,
water, carboxylic acids, and alkanes. The chemical interaction be­
bitumen [28] the maximum softening point difference should be less tween SM and asphalt binder was observed via emergence, disap­
than 3◦ C. It can be observed that all binders tested passed this criteria, pearance, and shift in peaks of spectra.
implying adequate thermal storage stability contributing to homoge­ • Master curves showed that at lower frequency the addition of SM
nous properties during storage, transportation, and laying. displayed higher G* values with an approximate increase of 66% for
SM 30 in comparison with base binder. Rutting factor (G*/sinδ) was
5. Cost effectiveness analysis found to increase with increase in dosage. For instance, at 70◦ C, the
rut factor of SM 10 S3, SM 20 S3, and SM 30 S3 was found to be 10%,
The cost of conventional asphalt is approximately Rs 60,000 ($ 722) 18% and 42% higher than the base binder implying improved per­
per ton while the cost of sugarcane molasses is Rs 5000 ($ 60) per ton manent deformation characteristics.
[47]. Considering a replacement of 30% asphalt binder the cost of • The variance analysis results showed that the SM source had insig­
bio-asphalt per ton will amount to Rs 43,500 ($ 524). In terms of cost nificant impact on physical and rheological properties of bio-
saving, there is a direct reduction of 27.5%. Considering the variability asphalts.
in pavement thickness and density of the mix, it can be concluded that • Segregation test results showed that all bio-asphalts have adequate
approximately 20–30% reduction in the cost of asphalt mix per lane per thermal storage stability as per (IS 15462–2019) contributing to
km can be expected. In addition, due to the foaming effect the produc­ homogenous properties during storage, transportation, and laying.
tion, mixing, and compaction temperature is expected to decrease • The incorporation of SM resulted in lowering of cost by 20–30%
leading to reduced fuel consumption. promoting sustainable development goals.
The cost of asphalt mixture is directly proportional to cost of mineral
aggregate and asphalt binder. In the case of bio-asphalt the comparison In summary, it is practically feasible to utilize the sugarcane
of cost between asphalt mixtures produced using conventional asphalt molasses as a partial replacement of asphalt binder.
binder and bio-asphalt can be made by comparing the cost of respective
binders. Since the production of bio-asphalt does not require any addi­ Funding information
tional arrangement no additional cost will be incurred.
No funding information is available
6. Conclusions
CRediT authorship contribution statement
Use of SM as a partial replacement of asphalt binder can offer sig­
nificant advancements in the quest for achieving sustainability in
Dheeraj Mehta: Writing – review & editing, Writing – original draft,
pavement construction. However, limited studies have delved into the
Investigation, Formal analysis, Data curation, Conceptualization. Nikhil
assessment of bio-asphalt prepared with SM. This study is a step to un­
Saboo: Writing – review & editing, Writing – original draft, Supervision,
derstand the use of SM in the preparation and performance of bio-
Formal analysis, Conceptualization.
asphalt. In this direction, three sources of SM and one base binder
were utilized to prepare bio-asphalt at replacement levels of 10%, 20%,
and 30%. A criterion based on physical and rheological properties was Declaration of Competing Interest
proposed to assess the maximum allowable dosage of SM. Further, FTIR
study was undertaken to ascertain the form of interaction between SM The authors declare that they have no known competing financial
and the base binder. Based on the experimental investigation and interests or personal relationships that could have appeared to influence
resulting analysis, the following conclusions can be drawn from the the work reported in this paper.
study:
Data availability

All data, models, and code generated or used during study appear in

10
D. Mehta and N. Saboo
the article. Data will be made available on request.
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