Article

Bio-Modified Bitumen: A Comparative Analysis of Algae

Influence on Characteristic Properties
Stavros Kalampokis * , Evangelos Manthos, Avraam Konstantinidis , Christos Kakafikas and Artemis Kalapouti

Civil Engineering Department, Aristotle University of Thessaloniki, GR-54124 Thessaloniki, Greece;

[email protected] (E.M.); [email protected] (A.K.); [email protected] (C.K.);
[email protected] (A.K.)
* Correspondence: [email protected]

Abstract: The main aim of this study was to identify and evaluate the characteristic properties of
bitumen modified with algae. Two types of algae, each with distinct gradation and origin, were
employed for this investigation. For each type of algae (noted as chlorella and microchlorella),
three blends were created with varying algae contents (5%, 10%, and 15% by weight of bitumen),
utilizing a 70/100 reference bitumen as the virgin material and a basis for comparison. The properties
of the blends were investigated using the Penetration, Softening Point, Elastic Recovery, Force
Ductility, Dynamic Viscosity, and Storage Stability tests, both before and after short-term ageing
(TFOT). The test results were then used to calculate the Activation Energy (Ea ), Viscosity-Temperature
Susceptibility (VTS) Index, and Mixing Temperature (Tmixing ), along with their respective Pearson
Correlation Coefficient (PCC) and R2 and p-values. The main finding of the study was that the
addition of a low algae content of 5% caused a change in the classification of the unaged bitumen
from 70/100 to 50/70 according to EN 12591 and thus hardened the reference bitumen. Additionally,
a strong linear statistical correlation was observed between Ea and the VTS index, suggesting that
these values should be considered when characterizing the temperature susceptibility of algae-
modified bitumen.

Citation: Kalampokis, S.; Manthos, E.; Keywords: Biobinder; bio-bitumen; algae; chlorella; microchlorella; bio-modifier
Konstantinidis, A.; Kakafikas, C.;
Kalapouti, A. Bio-Modified Bitumen:
A Comparative Analysis of Algae
Influence on Characteristic Properties. 1. Introduction
Eng 2024, 5, 417–432. https://
Petroleum-derived bitumen is the most widespread material used as a binder in
doi.org/10.3390/eng5010022
pavement construction [1]. The rising financial and environmental costs of all products
Academic Editors: George of the crude oil industry have led to the investigation of alternative biomass-derived
Z. Papageorgiou, Maria Founti materials [2,3]. These materials are examined as potential substitutes for bitumen. Bio-
and George N. Nikolaidis materials can be mixed with bitumen either as solid or liquid components and can be
Received: 12 January 2024
categorized based on the replacement of the original bitumen content as (a) modifiers
Revised: 18 February 2024
(<10% replacement), (b) extenders (25% to 75% replacement) or (c) direct replacements
Accepted: 23 February 2024
(100% replacement) [4]. One of the possible alternatives to conventional bitumen is algae.
Published: 4 March 2024 Algae consists of numerous species, so extensive research needs to be conducted. Greece is
a coastal country where algae exist in abundance. Moreover, algae grow rapidly and do
not need advanced growing techniques, so they may be a feasible modifier in regard to
the production process (equipment, etc.) [5]. In the following paragraph, a review of the
Copyright: © 2024 by the authors. studies examining various algae-modified bitumen and asphalt mixtures is presented.
Licensee MDPI, Basel, Switzerland. As mentioned above, numerous algae species have been assessed as possible alter-
This article is an open access article
native binding materials for asphalt mixtures. For instance, it was found that sargassum-
distributed under the terms and
modified bitumen had higher viscosity and rutting resistance in comparison with unmodi-
conditions of the Creative Commons
fied petroleum-based bitumen, which could improve the high-temperature performance [6].
Attribution (CC BY) license (https://
The same study indicated that a reduction in the sargassum particle size would bring
creativecommons.org/licenses/by/
about an increased specific surface area and thus better cohesion [6]. Furthermore, as
4.0/).

Eng 2024, 5, 417–432. https://doi.org/10.3390/eng5010022 https://www.mdpi.com/journal/eng

Eng 2024, 5 418

the particle size is reduced, the storage instability of bitumen is also reduced up to 3%
content. Above this level of content, segregation is highly likely, regardless of the volu-
metric characteristics of the sargassum particles. The main advantage of this modifier is
its superior decomposition temperature-approximately 320 ◦ C- which is non-comparable
with the required temperatures for the mixing and compaction of asphalt mixtures. The
main concern associated with sargassum is its inability to chemically bind with bitumen.
In other words, this modification is attributed to the physical adsorption of bitumen by
the sargassum particles rather than to the chemical interaction between the two materials.
Another study demonstrated that the optimal content of sargassum powder in bitumen
was 2.5% by weight of bitumen [7]. Up to 2.5%, it affects the bitumen like most powdered
modifiers, i.e., it increases the viscosity, the softening point and the resistance against
permanent deformation and rutting. When surpassing this concentration, a reduction in
the above properties was displayed, which was attributed to a change in the colloidal
system. Specifically, sargassum particles at such high percentages are not distributed
homogeneously in the bitumen, which leads to agglomeration. Consequently, the reverse
effect is observed. Regardless, sargassum powder does not present phase separation up to
4% content by weight when stored at elevated temperatures for extended periods of time,
unlike other powder modifiers, such as crumb rubber. One research study concluded that
unaged, algae-derived bio-oil-modified (microalgae (spirulina) and nanoalgae) bitumen
had a lower complex shear modulus, but after ageing, no significant differences in the G*
values between the reference and the modified bitumen were noticed [8]. From the above it
can be established that although algae bio-oils can reinforce the viscous phase of bitumen
in unaged conditions, this does not necessarily apply for the short- and long-aged states.
The ageing rate of algae bio-oils may sometimes be higher compared to bitumen, so it
may be preferable to incorporate these materials as rejuvenators in reclaimed bitumen. A
major drawback of spirulina algae (microalgae) and nanoalgae is that they tend to produce
excessive fumes that are hazardous to human health when heated at 145 ◦ C or above due
to their high sulfur content. One possible solution would be to include them in Warm
Mix Asphalts (WMA) instead of Hot Mix Asphalts (HMA). Moreover, algae bio-oil has
been found to chemically react with SBS and fortify the SBS network structure present in
bitumen [9]. One of the focal weaknesses of algae bio-oils is that they reduce the interfacial
forces between bio-bitumen and aggregates thus compromising the adhesive properties of
the asphalt mixture [10]. Although the thermochemical use of algae does not compete with
the food industry’s use of algae, there is a specific issue concerning the calorific value of
these materials. Certain types of algae have a high concentration of lipids, which makes
them an ideal raw material for the production of biofuels. For this reason, before using them
in the pavement industry, a process of lipid extraction is preferable. Subsequently, after
this procedure, the waste from biofuel production, which is an oily viscous residue (like
bitumen), can be added to bitumen and asphalt mixtures. In this direction, it was studied
as a bitumen modifier and found to have similar viscoelastic properties to conventional
petroleum-based bitumen. Specifically, the frequency-dependent and time-dependent
viscoelastic characteristics of spirulina-derived biofuel waste were similar to those of un-
modified bitumen [11]. Furthermore, caution needs to be taken during the conversion
of algae into bio-oil. In most studies, hydrothermal liquefaction (HTL) is chosen as the
thermochemical conversion process due to its ability to utilize biomasses with high water
content, unlike others such as fast pyrolysis. During HTL, the experimental conditions
(raw material, temperature, residence time, existence of catalysts, etc.) will determine the
rheological behavior of the bio-oil and, consequently, that of the bio-bitumen. According to
a study, the most suitable temperature of an algae species noted as Scenedesmus sp. HTL
was close to 260 ◦ C [12]. Above this, the water-insoluble solid phase of the converted
Scenedesmus was notably decreased, which negatively affected the dual viscoelastic nature
of the material [12]. In addition to the above study, it has been suggested that a combination
of hydrothermal liquefaction and hydrothermal carbonization at temperatues close to
250–270 ◦ C is ideal spectrum and that, as the reaction time is increased, the complex shear
Eng 2024, 5 419

modulus G* of the product presents a gradual decrease [13]. Two other studies examined
the role of two algae species noted as Spirulina sp. and Scenedesmus sp. as additives to
bitumen [5,14]. The results revealed that Scenedesmus sp. bio-bitumen could potentially be
a direct replacement alternative for the petroleum-based bitumen, whereas Spirulina sp.
bio-bitumen is a better replacement for elastomer modifiers, such as SBS. Moreover, the
implementation of Posidonia oceanica fibers in SMA was investigated, with the optimum
fiber content being 1.5–2% [15]. This concentration improved both the stiffness and the
fatigue life of SMA. If this content is exceeded, the SMA properties will decline rapidly
because of the extensive binder drainage. From the above, it can be deduced that each type
of algae has a different impact on bitumen depending on its origin, its form (powder, fibers,
thermochemically produced bio-oil) and its content.
Chlorella and microchlorella are widespread algae species that have not been studied
extensively as potential bitumen additives. Taking this into consideration, this paper
studies the impact of chlorella and microchlorella on bitumen by examining the chemical
compositions of the above algae species and the characteristic properties of algae-modified
bitumen before and after short-term ageing (TFOT) followed by a statistical analysis.

2. Materials and Methods

In the current study, a conventional 70/100 bitumen served as the reference bitumen
(RB) and the basis for the production of bitumen-algae blends. Two types of algae were
used, having different origins and different maximum particle sizes. Both types of algae
were included in the reference bitumen at three distinct levels of content, i.e., 5%, 10%,
and 15% by weight of bitumen. The characteristic properties of the reference bitumen
and all respective bitumen-algae blends were determined and compared before and after
ageing. These properties were the: penetration, softening point, elastic recovery, force
ductility, dynamic viscosity (Brookfield viscometer), and storage stability. Additionally, the
dynamic viscosity results of the tests were utilized to calculate the Activation Energy (Ea ),
Viscosity-Temperature Susceptibility (VTS) Index and Mixing Temperature (Tmixing ) along
with their respective Pearson Correlation Coefficient (PCC), R2 , and p-values.

2.1. Bitumen
The characteristic properties of the reference bitumen are given in Table 1.

Table 1. Characteristic properties of reference bitumen.

Property Specification Value

Penetration (dmm) EN 1426 [16] 79
Softening Point (◦ C) EN 1427 [17] 49.8
Elastic Recovery (%) EN 13398 [18] 11
Force Ductility (J/cm2 ) EN 13589 & EN 13703 [19,20] 0.844
Dynamic Viscosity (Pa·s) EN 13302 [21] Various 1
1 Dynamic viscosity test was carried out at various temperatures. All results are shown in Section 3.

2.2. Algae
The two algae types utilized in this study were different in origin and maximum
particle size. The first type, denoted as “chlorella” was acquired after cultivation in a
nutrient solution containing the necessary macro and micro nutrients that are essential for
its growth. Upon completion of the cultivation phase, the process involved centrifugation,
filtration, and drying to obtain the dry algae suitable for incorporation into the bitumen
algae-blends. The chlorella grain size was ≤0.5 mm. The second type of algae denoted as
“microchlorella” was a commercial product with a grain size ≤ 0.063 mm.
A view of the chlorella and microchlorella is displayed in Figures 1 and 2. As can be
seen, chlorella is mainly yellow and light brown in color, whereas microchlorella is dark
green. According to images taken by a confocal microscope (×20) (Figure 2), the chlorella
Eng 2024, Eng
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particles
particles had a had tended
more to be more irregularly and angularly shaped, whereas microchlorella
particles a regular and spherical
more regular and sphericalshape. The shape
shape. The shapedifferences between
differences the two
between the two
particles
types types
of algae had
could a more
be regular
attributed andto spherical
the differentshape. The shape
production differences
methods between
chosen for the
each two
types of
of algae
algae could be
could be attributed
attributedtotothe thedifferent
different production
production methods
methods chosen
chosen for for
each each
algae algae
species. species.
algae species.
Before the chlorella
Before and micro-chlorella were mixedmixed with the RB, their chemical com- com-
Before the the chlorella
chlorellaand andmicro-chlorella
micro-chlorellawere were mixedwith withthe theRB,RB,their
theirchemical
chemical
positions were investigated.
positions werewere The results
investigated. The The are shown
results are arein Table
shown 2. According
in Table to Table
2. According 2, chlo-
to Table 2, 2,
chlo-
compositions investigated. results shown in Table 2. According to Table
rella and
rella microchlorella
and microchlorellaare similar
are in
similar regard
in to
regardtheirto macromolecular
their macromolecular composition.
composition.Spe- Spe-
chlorella and microchlorella are similar in regard to their macromolecular composition.
cifically, chlorella
cifically,
Specifically, and microchlorella
chlorella and
chlorella andmicrochlorella consistconsist
microchlorella of crude
consist protein
of crude
crude at percentages
protein
protein atatpercentages of 31.56%
percentages of 31.56%
of 31.56%
and 41.8%,
and respectively.
and 41.8%,
41.8%, TheirTheir
respectively.
respectively. crudecrude
Their carbohydrate
crude carbohydrate
carbohydrate content is almost
content
content identical
is almost
is almost (33.4%
identical
identical and
(33.4%
(33.4% andand
30.2%). It is
30.2%). noteworthy
30.2%). It is noteworthy that
noteworthythat neither bio-modifier
thatneither
neither bio-modifier has
bio-modifier significant
hashas
significant lipid
significant content.
lipidlipid
content. Biomateri-
Biomaterials
content. Biomateri-
als with
als low
with low
with lipid
lipid
low content
content
lipid have
haverelatively
content relatively
have lowcalorific
low
relatively calorific value,
value,
low calorific so they
sovalue,
they soare
are usually
usually
they avoided
areavoided
usually asavoided
raw
as rawas materials
materials forfor biofuel
biofuel production.
production. ThisThis makes
makes them them possible
possible alternatives
alternatives
raw materials for biofuel production. This makes them possible alternatives for use in for usefor
in use in
bitumen
bitumen production.
production.
bitumen TheThe
production.totaltotal
Thesolids,
solids, organic
total organic
solids, content,
content,
organic and moisture
andcontent,
moisture and and
andmoisture
ash ash
content
andcontent
were were were
evaluated
ash content
onlyonly
for chlorella and wereand found
evaluated
evaluated for
only chlorella
for chlorella and to
were be 29.06%,
found
were to be to
found 62.90%, 70.94%
29.06%, 62.90%,
be 29.06%, and 18.44%,
70.94%
62.90%, andrespectively.
70.94% 18.44%,
and 18.44%,
Such high
respectively. Such ash content
high ash indicatesindicates
content high thermal high stability,
thermal so it couldso
stability, beitdeduced
could bethat chlorella
deduced
respectively. Such high ash content indicates high thermal stability, so it could be deduced
is a thermally
that chlorella is a stable material
thermally stable at the usual
material at mixing
the usualand compaction
mixing and temperatures
compaction due to its
tempera-
that chlorella is a thermally stable material at the usual mixing and compaction tempera-
relatively
tures due high ash content [22,23].
turestodueits relatively high ash
to its relatively highcontent [16,17].
ash content [16,17].

(a) (a) (b) (b)

FigureFigure
1. (a) Chlorella
Figure 1. (a)
1. powder
(a) Chlorella
Chlorella (≤0.5 mm)
powder
powder (≤ 0.5and
(≤0.5 mm)
mm)(b) Microchlorella
and
and(b) powder
(b)Microchlorella
Microchlorella (≤0.063
powder
powder mm).mm).
(≤(≤0.063
0.063 mm).

(a) (a) (b) (b)

FigureFigure
2. Confocal
2. microscopy (×20) of(×20)
(a) chlorella powder (≤0.5 mm) (b) microchlorella powder
Figure
(≤0.063(≤0.063 2. Confocal
mm). mm).
microscopy
Confocal microscopy (×20) ofof(a)
(a)chlorella
chlorella powder
powder (≤(≤0.5 mm)
0.5 mm) (b)(b) microchlorella
microchlorella powder
powder
(≤0.063 mm).
Table 2. Chemical
Table characterization
2. Chemical of chlorella
characterization and microchlorella.
of chlorella and microchlorella.
Property
Property Chlorella (%) (%)
Chlorella Microchlorella (%) (%)
Microchlorella
CrudeCrude
protein
protein 31.56 31.56 41.80 41.80
CrudeCrude
carbohydrate
carbohydrate 33.40 33.40 30.20 30.20
Lipid Lipid
content
content 16.60 16.60 14.90 14.90
Eng 2024, 5 421

Table 2. Chemical characterization of chlorella and microchlorella.

Property Chlorella (%) Microchlorella (%)

Crude protein 31.56 41.80
Crude carbohydrate 33.40 30.20
Lipid content 16.60 14.90
Total solids 29.06 N.D.1
Organic content 62.90 N.D.1
Moisture (water content) 70.94 N.D.1
Ash content (oven method) 18.44 N.D.1
1 Not determined.

2.3. Mixing Conditions

In order to establish a proper mixing protocol for the algae-based blends, the relevant
literature was considered [6,7,9,10]. It was observed that there was considerable varia-
tion among researchers regarding the mixing conditions for algae-modified bio-bitumen
(Table 3). Taking the above studies into consideration, the mixing took place at T = 160 ◦ C
for 30 min using a high shear mixer with a rotational speed of 2500 rpm. The mixing
temperature and time were limited to 160 ◦ C and 30 min, respectively, to achieve proper
workability, while also avoiding the excessive oxidation of the bitumen. Since the mix-
ing temperature was lower than the ones presented in Table 3 for powder bio-modifiers,
a higher rotational speed was chosen to compensate for this. Furthermore, the mixing
temperature results in Section 3.6 verify that 160 ◦ C was an appropriate choice for the
mixing temperature.

Table 3. Mixing conditions for algae-modified bitumen from various studies.

Temperature (◦ C) Time (min) Speed (rpm) Phase Reference

180 90 1500 Powder [6]
180 60 1500 Powder [7]
135 30 800 Bio-oil [9]
135 N/A 1 N/A 1 Bio-oil [10]
1 Not available.

3. Results
3.1. Penetration Test
The needle penetration test was carried out at 25 ◦ C in accordance with EN 1426 [16].
Figures 3 and 4 indicate that the addition of microchlorella and chlorella hardened the
reference bitumen. Specifically, increasing contents of algae resulted in lower penetration
values. It is noteworthy that even a small percentage of modification, as low as 5%, caused
a change in category for the reference bitumen from 70/100 to 50/70, in accordance with
the bitumen categories specified in EN 12591 [24]. The hardening effect was also displayed
for the short-term aged algae-modified samples. Short-term aged samples demonstrated
lower penetration values than their unaged counterparts due to the oxidation during the
ageing process, which hardened the bitumen.
Eng
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90
90
79
79
80
80
70
70

(dmm)
60

Penetration(dmm)
60 60
60 54
54 52
52 50
50 50
50
Penetration MCL‐unaged
40
40 MCL‐unaged
35
35 34 34
34 34
30 MCL‐TFOT
MCL‐TFOT aged
aged
30
20
20
10
10
0
0
RB
RB MCL‐5
MCL‐5 MCL‐10
MCL‐10 MCL‐15
MCL‐15
Binder
Binder Type
Type

Figure
Figure3.3.
Figure Penetration
Penetrationofof
3.Penetration MCL-modified
ofMCL-modified
MCL-modified bitumen.
bitumen.
bitumen.

90
90
79
79
80
80
70
70
60
(dmm)

60
Penetration(dmm)

60 56
56
60 54
54 53
53
50
50
Penetration

40 CL‐unaged
CL‐unaged
40 33
33 31
31 29
30 29 CL‐TFOT
CL‐TFOT aged
aged
30
20
20
10
10
0
0
RB
RB CL‐5
CL‐5 CL‐10
CL‐10 CL‐15
CL‐15
Binder
Binder Type
Type

Figure 4. Penetration of CL-modified bitumen.

Figure4.4.Penetration
PenetrationofofCL-modified
CL-modified bitumen.
Figure bitumen.

3.2.
3.2. Softening
3.2. Softening Point
SofteningPoint Test
PointTest
Test
The
Thesoftening
The softeningpoint
softening point
pointtesttest
waswas
test conducted
was conducted
conducted withwith
respect
with to ENto
respect
respect 1427
to EN[17].
EN Figures
1427.
1427. 5 and
Figures
Figures 6
55 and
and 66
demonstrate
demonstrate the gradual increase in the softening point for increasing content in both
demonstrate the the gradual
gradual increase
increase inin the
the softening
softening point
point for
for increasing
increasing content
content in in both
both the
the
the microchlorella-modified
microchlorella-modified and chlorella-modified unaged binders. After short-term
microchlorella-modified and chlorella-modified unaged binders. After short-term ageing,
and chlorella-modified unaged binders. After short-term ageing,
ageing,
the the chlorella-modified blends presented higher softening points than the short-termaged
the chlorella-modified
aged chlorella-modified
reference bitumen.
blends
blends
The
presented
presented higher
higher softening
microchlorella-modified softening
blends
points
points
also
than
than the
displayed theanshort-term
short-term
increase inaged
reference bitumen. The microchlorella-modified blends also displayed an increase in their
their softening point after short-term ageing compared to the reference bitumen, but thetheir
reference bitumen. The microchlorella-modified blends also displayed an increase in
softening point
softening point after
after short-term
short-termthan ageing
ageing compared to the reference bitumen, but the incre-
increment was less pronounced that compared to the reference
of the chlorella-modified bitumen,
blends. but theall
Moreover, incre-
ment was less
mentunmodified pronounced
was less pronounced than that
than that of the
of the chlorella-modified blends. Moreover, all
all aged
aged and bio-modified blends hadchlorella-modified
higher softening pointsblends. Moreover,
than their unaged aged
unmodified
unmodified and and bio-modified blends had higher softening points than their unaged coun-
counterparts. The bio-modified blends
highest resistance had higher
to ageing softening points
was demonstrated than their
by MCL-15 unaged
for which thecoun-
terparts.
terparts. The
softening pointhighest
The increaseresistance
highest resistance to
to ageing
after applying ageing was
was demonstrated
the ageing demonstrated by
by MCL-15
protocol was equal to only for
MCL-15 1 ◦ Cwhich
for (fromthe
which 52 sof-
the sof-
tening
to ◦
53 C).
tening point increase
Thisincrease
point after
is expected applying
to applying
after happen asthe the ageing
ageing protocol
has protocol
ageing a hardeningwas equal
waseffect
equal to only
only 1 °C (from 52
ontobitumen. 1 °C (from 52
to
to 53
53 °C).
°C). This
This is
is expected
expected to
to happen
happen as
as ageing
ageing has
has aa hardening
hardening effect
effect on
on bitumen.
bitumen.
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57.0
57.0
56.0
56.0
55.0
55.0
54.0

°C)
54.0

Temperature( (°C)
53.0
53.0 52.4 53.0
53.0 52.2 52.2 52.4 52.0
52.2 52.2 52.0
Temperature
52.0
52.0 50.8
51.0 50.4 50.8 MCL‐unaged
51.0 50.4 MCL‐unaged
49.8
50.0 49.8 MCL‐TFOT aged
50.0 MCL‐TFOT aged
49.0
49.0
48.0
48.0
47.0
47.0
46.0
46.0
RB MCL‐5 MCL‐10 MCL‐15
RB MCL‐5 MCL‐10 MCL‐15
Binder Type
Binder Type

Figure5.5.Softening
Softening pointofofMCL-modified
MCL-modified bitumen.
Figure 5. Softeningpoint
Figure point of MCL-modified bitumen.
bitumen.

55.0
55.0
54
54.0 54
54.0
53.0
53.0 53.0
53.0 52.4
°C)

52.2 52.4 52.0

Temperature( (°C)

52.2 51.6 52.0

52.0 51.6
52.0
51.0
Temperature

51.0 51.0
51.0 CL‐unaged
49.8 CL‐unaged
50.0 49.8
50.0 CL‐TFOT aged
CL‐TFOT aged
49.0
49.0
48.0
48.0
47.0
47.0
RB CL‐5 CL‐10 CL‐15
RB CL‐5 CL‐10 CL‐15
Binder Type
Binder Type

Figure 6. Softening point of CL-modified bitumen.

Figure6.6.Softening
Figure Softeningpoint
pointofof CL-modified
CL-modified bitumen.
bitumen.

3.3. Elastic
3.3. Elastic RecoveryTest
Test
3.3. ElasticRecovery
Recovery Test
Theelastic
The elasticrecovery
recoverytesttest
waswas carried
carried out
out at ◦ C25
25 at °C according
according to EN[18].
to EN 13398 13398. According
According
The elastic recovery test was carried out at 25 °C according to EN 13398. According
to Table
to Table4,4,the
theelastic
elasticrecovery
recovery demonstrated
demonstrated by by
thethe algae-modified
algae-modified bitumen
bitumen was was similar
similar
to Table 4, the elastic recovery demonstrated by the algae-modified bitumen was similar
to
to the
theelastic
elasticrecovery
recoveryofofthe thereference
referencebitumen
bitumenin both the the
in both unaged andand
unaged short-term agedaged
short-term
to the elastic recovery of the reference bitumen in both the unaged and short-term aged
states.
states.This
Thissuggests
suggeststhat
thatneither
neither chlorella nor
chlorella normicrochlorella
microchlorella powder
powdermanaged
managedto enhance
to enhance
states. This suggests that neither chlorella nor microchlorella powder managed to enhance
the elastic properties of the bitumen. In general, the percentage of the elastic
the elastic properties of the bitumen. In general, the percentage of the elastic recovery recovery of of
the elastic properties
bio-modified samples of the
did not bitumen.
exceed In general, the percentage of the elastic recovery of
10%.
bio-modified samples did not exceed 10%.
bio-modified samples did not exceed 10%.
Table 4. Elastic recovery of unaged and TFOT-aged blends.
Table 4. Elastic recovery of unaged and TFOT-aged blends.
Bitumen/Blend Elastic Recoveryunaged (%) Elastic RecoveryTFOT-aged (%)
Bitumen/Blend Elastic Recoveryunaged (%) Elastic RecoveryTFOT-aged (%)
RB 11 8
RB 11 8
MCL-5 5 10
MCL-5 5 10
MCL-10 5 5
MCL-10 5 5
MCL-15 1 5
MCL-15 1 5
Eng 2024, 5 424

Table 4. Elastic recovery of unaged and TFOT-aged blends.

Bitumen/Blend Elastic Recoveryunaged (%) Elastic RecoveryTFOT-aged (%)

RB 11 8
MCL-5 5 10
MCL-10 5 5
MCL-15 1 5
CL-5 5 10
CL-10 5 10
CL-15 6 10

3.4. Force Ductility Test

The force ductility test is used to characterize the cohesion of modified bitumen and
bituminous binders. According to EN 13589 and EN 13703, the proposed initial testing
temperature is 5 ◦ C [19,20]. Due to the premature brittle cracking of the specimens at
5 and 10 ◦ C, the test was conducted at 15 ◦ C. The results for the unaged and short-term
aged samples are depicted in Tables 5 and 6. Algae addition hardened the bitumen and
reinforced its elastic phase at the expense of the viscous one, which was verified by the
increase in the maximum force and total energy. Chlorella and microchlorella had a similar
effect on the reference bitumen as observed by their similar maximum force and total
energy values. In contrast, the impact of chlorella was more obvious for the short-term
aged samples in comparison with the microchlorella-modified binders. As expected, for
both unmodified and algae-modified bitumen, ageing caused a significant increase in the
maximum force and total energy. This is in agreement with the results of previous research
based on powder-biomodified bitumen [25].

Table 5. Force ductility results of unaged blends.

Bitumen/Blend Maximum Force (N) Total Energy (J/cm2 )

RB 12.10 0.844
MCL-5 14.65 0.951
MCL-10 13.94 1.117
MCL-15 14.69 1.279
CL-5 14.55 1.092
CL-10 13.94 0.961
CL-15 14.75 1.020

Table 6. Force ductility results of TFOT-aged blends.

Bitumen/Blend Maximum Force (N) Total Energy (J/cm2 )

RB 17.12 1.180
MCL-5 17.63 1.356
MCL-10 18.87 1.345
MCL-15 15.71 1.512
CL-5 24.35 1.805
CL-10 24.32 1.979
CL-15 19.50 1.379

3.5. Dynamic Viscosity Test

The dynamic viscosity of the reference and algae-modified blends was determined
in accordance with EN 13302 using a Brookfield viscometer with a No.27 rotating spindle
at 20 rpm [21]. The testing temperature ranged from 130 to 180 ◦ C in steps of 10 ◦ C in
order to cover all bitumen pumping and use-phase temperatures. Figures 7–10 suggest
that the addition of microchlorella and chlorella raised the viscosity of both the unaged
Eng 2024, 5 425

and short-term aged bitumen for all examined temperatures. As the temperature increased,
the differences between the reference bitumen and the bio-modified blends became less
prominent. Significant differences in the dynamic viscosity values were observed between
Eng
Eng 2024,
2024, 5,
5, FOR
FOR PEER
PEER REVIEW
REVIEW 130 ◦ C and 150 ◦ C. The results are in agreement with the literature which suggests that 99
solid-phase modifiers tend to increase the viscosity [26,27].

0.700
0.700
(Pa.s)
Viscosity(Pa.s) 0.600
0.600
0.500
0.500
0.400
DynamicViscosity

0.400
0.300
0.300
0.200
0.200
Dynamic

0.100
0.100
0.000
0.000 130°C
130°C 140°C
140°C 150°C
150°C 160°C
160°C 170°C
170°C 180°C
180°C
RB
RB 0.350
0.350 0.250
0.250 0.175
0.175 0.125
0.125 0.100
0.100 0.075
0.075
MCL‐5
MCL‐5 0.550
0.550 0.375
0.375 0.250
0.250 0.175
0.175 0.150
0.150 0.100
0.100
MCL‐10
MCL‐10 0.550
0.550 0.375
0.375 0.250
0.250 0.175
0.175 0.150
0.150 0.125
0.125
MCL‐15
MCL‐15 0.575
0.575 0.400
0.400 0.275
0.275 0.200
0.200 0.150
0.150 0.125
0.125
Temperature
Temperature (( °C)
°C)

Figure
Figure7.7.
Figure Dynamic
7.Dynamic viscosity
Dynamicviscosity
viscosityofof MCL-modified
MCL-modified
of unaged
unaged
MCL-modified blends.
blends.
unaged blends.

0.700
0.700
0.600
0.600
(Pa.s)
Viscosity(Pa.s)

0.500
0.500
0.400
0.400
DynamicViscosity

0.300
0.300
0.200
0.200
Dynamic

0.100
0.100
0.000
0.000 130°C
130°C 140°C
140°C 150°C
150°C 160°C
160°C 170°C
170°C 180°C
180°C
RB
RB 0.350
0.350 0.250
0.250 0.175
0.175 0.125
0.125 0.100
0.100 0.075
0.075
CL‐5
CL‐5 0.525
0.525 0.350
0.350 0.225
0.225 0.150
0.150 0.125
0.125 0.100
0.100
CL‐10
CL‐10 0.525
0.525 0.375
0.375 0.250
0.250 0.175
0.175 0.125
0.125 0.100
0.100
CL‐15
CL‐15 0.525
0.525 0.350
0.350 0.225
0.225 0.175
0.175 0.125
0.125 0.100
0.100
Temperature
Temperature (( °C)
°C)

Figure 8. Dynamic viscosity of CL-modified unaged blends.

Figure8.8.Dynamic
Dynamicviscosity
viscosity
Figure ofof CL-modified
CL-modified unaged
unaged blends.
blends.
Eng 2024,
Eng2024, 5, FOR PEER REVIEW
5 FOR
2024, 5, 10
Eng PEER REVIEW 426 10

0.700
0.700
0.600

(Pa.s)
0.600

Viscosity(Pa.s)
0.500
0.500
0.400

DynamicViscosity
0.400
0.300
0.300
0.200
Dynamic 0.200
0.100
0.100
0.000
0.000 130°C 140°C 150°C 160°C 170°C 180°C
130°C 140°C 150°C 160°C 170°C 180°C
RB 0.475 0.325 0.200 0.150 0.100 0.075
RB 0.475 0.325 0.200 0.150 0.100 0.075
MCL‐5 0.600 0.400 0.275 0.200 0.150 0.100
MCL‐5 0.600 0.400 0.275 0.200 0.150 0.100
MCL‐10 0.600 0.400 0.275 0.200 0.150 0.125
MCL‐10 0.600 0.400 0.275 0.200 0.150 0.125
MCL‐15 0.675 0.475 0.325 0.225 0.175 0.125
MCL‐15 0.675 0.475 0.325 0.225 0.175 0.125
Temperature ( °C)
Temperature ( °C)

Figure 9. Dynamicviscosity
viscosity of MCL-modified TFOT-aged blends.
Figure9.9.Dynamic
Figure Dynamic viscosityofof
MCL-modified TFOT-aged
MCL-modified blends.
TFOT-aged blends.

0.700
0.700
0.600
0.600
(Pa.s)
Viscosity(Pa.s)

0.500
0.500
0.400
0.400
DynamicViscosity

0.300
0.300
0.200
0.200
Dynamic

0.100
0.100
0.000
0.000 130°C 140°C 150°C 160°C 170°C 180°C
130°C 140°C 150°C 160°C 170°C 180°C
RB 0.475 0.325 0.200 0.150 0.100 0.075
RB 0.475 0.325 0.200 0.150 0.100 0.075
CL‐5 0.650 0.425 0.275 0.200 0.150 0.125
CL‐5 0.650 0.425 0.275 0.200 0.150 0.125
CL‐10 0.650 0.425 0.275 0.200 0.150 0.125
CL‐10 0.650 0.425 0.275 0.200 0.150 0.125
CL‐15 0.700 0.450 0.300 0.225 0.150 0.125
CL‐15 0.700 0.450 0.300 0.225 0.150 0.125
Temperature ( °C)
Temperature ( °C)

Figure 10. Dynamic viscosity of CL-modified TFOT-aged blends.

Figure10.
Figure 10.Dynamic
Dynamicviscosity
viscosityofof CL-modified
CL-modified TFOT-aged
TFOT-aged blends.
blends.

3.6. MixingTemperatures
3.6. Temperatures
3.6.Mixing
Mixing Temperatures
The mixingtemperature
The temperature is is definedas as
thethe optimal temperature of bitumen during
its its
Themixing
mixing temperature defined
is defined as optimal
the optimaltemperature
temperature of bitumen
of bitumen during
during its
mixingprocess
mixing processwith withaggregates
aggregates [21].
[28]. AnAn increment
increment in the
in the temperature
temperature of bitumen
of bitumen leadsleads
mixing process with aggregates [21]. An increment in the temperature of bitumen leads
to
toaadrop
dropininitsitsviscosity
viscosity and
andvice versa.
vice Excessively
versa. Excessively high viscosity
high values
viscosity will will
values not allow
not allow
to a drop in its viscosity and vice versa. Excessively high viscosity values will not allow
the
theaggregates
aggregatestotobebecovered
covered uniformly
uniformly bybythethe
bitumen,
bitumen,whereas
whereas excessively
excessively low low
viscosity
viscosity
the aggregates
values will result toinbethe
covered uniformly
formation of an by the bitumen,
excessively thin filmwhereas
of excessively
bitumen on the low viscosity
surface of of
values will result in the formation of an excessively thin film of bitumen on the surface
values
the will result
aggregates due in
to the formation
bitumen of an excessively
draindown. The mixing thin film of bitumen
temperature can be on the surface of
determined
the aggregates due to bitumen draindown. The mixing temperature can be determined as
thethe
as aggregates
temperature dueattowhich
bitumenthe draindown.
viscosity The mixing temperature ·can be determined as
the temperature at which the viscosity ofof bitumen
bitumen is is equal
equal to to
0.20.2 Pa[21].
Pa.s s [28].
TheThe exact
exact mixing
the temperature at which the viscosity of bitumen is equal to 0.2 Pa.s
mixing temperature of each type of bitumen was calculated via the non-linear, exponential [21]. The exact mixing
temperature of each type of bitumen was calculated via the non-linear, exponential re-
temperature
regression of each
of the dynamictypeviscosity-temperature
of bitumen was calculated via the
scatter plot. Thenon-linear,
specific T exponential
values re-
gression of the dynamic viscosity-temperature scatter plot. The specific mixing Tmixing values are
gression
are of the
displayed dynamic
in Table 7. viscosity-temperature scatter plot. The specific Tmixing values are
displayed in Table 7.
displayed in Table 7.
It can be observed that increasing the algae content by weight of bitumen led to an
It can be observed that increasing the algae content by weight of bitumen led to an
increase in the necessary mixing temperature. The most noteworthy change in the mixing
increase in the necessary mixing temperature. The most noteworthy change in the mixing
temperature per step of added algae (chlorella or microchlorella) was noticed when 5% of
temperature per step of added algae (chlorella or microchlorella) was noticed when 5% of
bio-modifier was incorporated into the bitumen for both types of algae (approximately
bio-modifier was incorporated into the bitumen for both types of algae (approximately
Eng 2024, 5 427

Table 7. Mixing temperature of reference bitumen and algae-modified blends.

Bitumen/Blend Tmixing (◦ C)
RB 146
MCL-5 159
MCL-10 160
MCL-15 163
CL-5 154
CL-10 158
CL-15 158

It can be observed that increasing the algae content by weight of bitumen led to an
increase in the necessary mixing temperature. The most noteworthy change in the mixing
temperature per step of added algae (chlorella or microchlorella) was noticed when 5%
of bio-modifier was incorporated into the bitumen for both types of algae (approximately
between 8 and 13◦ C depending on the type of algae). Above this level of content, the
mixing temperature step increment was minor (up to 4 ◦ C). For both algae-modified blends,
it was seen that the mixing temperatures reached their peaks when 15% of bio-modifier
was mixed into the bitumen (163 and 158 ◦ C for microchlorella and chlorella blends,
respectively). The above results verify that the mixing temperature chosen for the mixing
protocol of bitumen with the algae was correct (160 ◦ C).

3.7. Activation Energy

The activation energy is the energy barrier that the molecules of bitumen need to
overcome to start moving and thus for the bitumen to start flowing [29]. In order to further
investigate the rheological properties of the blends, the activation energy was calculated
according to the Arrhenius equation (Equation (1)) [30,31]:
Ea
n = A · e R· T (1)

where n is the viscosity (Pa·s), Ea is the activation energy (J·mol−1 ), T is the temperature
(Kelvin), R is the universal gas constant (R = 8.314 J·mol−1 ·K−1 ) and A is a pre-exponential
factor. The Arrhenius equation can be transformed into Equation (2) as follows:
 
Ea
ln(n) = + ln( A) (2)
R· T

Graphically, the activation energy can be calculated by multiplying the slope of the
ln(n) versus 1/T plot with the universal gas constant R. The slope of this graph is directly
proportional to the temperature sensitivity of bitumen as explained below. It can be noticed
that the addition of algae caused an increase in the activation energy of the bitumen before
applying the TFOT-ageing protocol (Table 8). However, the opposite phenomenon was
displayed after ageing the samples. Despite the fact that almost all unaged algae-modified
blends were characterized by higher activation energy values than the reference bitumen,
the opposite trend was observed for the short-term aged samples. This trend was more
prominent for the chlorella-modified blends. As expected, the activation energy displayed
an increase after short-term ageing for all blends, except for CL-5 and CL-10 whose values
were almost identical to those of their unaged counterparts. This is expected as ageing
increases the polarity of bitumen compounds and consequently the activation energy [32].
According to the literature, a higher activation energy value is linked to an increased sensi-
tivity to temperature changes [33–35]. Specifically, the lowest temperature susceptibility
was displayed by MCL-10 at both ageing states (45.84 and 48.33 kJ/mol, respectively),
indicating that the performance of this blend was the least temperature-dependent. Con-
sequently, ageing made the samples more sensitive to temperature changes. It can be
summarized that the ageing protocol had a much smaller impact on the bio-modified
bitumen than it did on the reference bitumen in regard to their respective temperature
Eng 2024, 5 428

susceptibilities as demonstrated by the lower activation energies of the bio-modified blends

compared to the reference bitumen after ageing. Overall, these findings underscore the
diverse thermal stabilities of the bitumen blends and emphasize the importance of consider-
ing activation energy changes during aging processes for a comprehensive understanding
of their performance characteristics from a thermodynamical point of view.

Table 8. Activation energy of unaged and TFOT-aged blends.

Bitumen/Blend Ea (unaged) (kJ/mol) Ea (TFOT-aged) (kJ/mol)

RB 46.86 56.68
MCL-5 50.53 53.01
MCL-10 45.84 48.33
MCL-15 47.37 51.20
CL-5 51.34 50.89
CL-10 51.88 50.89
CL-15 50.59 53.04

3.8. VTS Index

Viscosity is a temperature-dependent property, especially for viscoelastic materials
such as bitumen. To establish a relation between the dynamic viscosity of bitumen and the
temperature, the Viscosity Temperature Susceptibility Index (VTS index) was calculated
for all unaged and short-term aged blends (Equation (3)) [36]:

log(log(n1)) − log(log(n2))
VTS = (3)
log( T2) − log( T1)

where T1 and T2 are the two temperatures (in Celsius) from which the VTS index is cal-
culated, and n1 and n2 are the dynamic viscosities at the respective temperatures (cPs).
The VTS index can be calculated for any pair of temperature values. Consequently, the
chosen temperatures were 130 and 180 ◦ C in order to cover all pumping and use-phase
temperatures. Generally, a greater VTS index suggests more temperature-dependent be-
havior and thus higher temperature sensitivity. The analytical results for the unaged and
short-term aged samples are presented in Table 9. The Viscosity Temperature Susceptibility
Index (VTS index) values presented in Table 9 provide crucial insights into the temperature-
dependent viscosity characteristics of the examined bitumen blends. In its unaged state,
MCL-10 exhibited the lowest VTS index at 0.822, indicating the comparatively lower sen-
sitivity of the viscosity to temperature changes versus other blends and confirming the
relative results obtained from the calculation of the activation energies. Notably, even
after TFOT ageing, MCL-10 maintained a consistently lower VTS Index of 0.864, signi-
fying sustained resistance to viscosity alterations. On the other hand, RB demonstrated
a notable increase in the VTS index from 0.938 to 1.094 after short term ageing, suggest-
ing enhanced temperature-dependent behavior and heightened susceptibility to viscosity
changes. Among the chlorella-modified blends, a consistent VTS index between their
unaged and aged states was showcased, emphasizing their stable viscosity performance
across temperature variations.

Table 9. VTS index values of unaged and TFOT-aged blends.

Bitumen/Blend VTS Index (unaged) VTS Index (TFOT-aged)

RB 0.938 1.094
MCL-5 0.968 1.010
MCL-10 0.822 0.864
MCL-15 0.844 0.921
CL-5 0.945 0.903
CL-10 0.945 0.903
CL-15 0.945 0.938
Eng 2024, 5 429

3.9. Statistical Analysis

A statistical analysis was conducted to indentify any correlations between the various
results of the dynamic viscosity test by calculating the Pearson Correlation Coefficient
and the R2 values for every set of Tmixing , Ea , and VTS index results. Smn is the sample
covariance of Xm and Xn (Equation (4)). As demonstrated in Tables 10 and 11, a strong
linear correlation between the VTS index and Ea was displayed. Specifically, the PCC and
R2 values between Ea and the VTS index were 0.85 and 0.72, respectively. The significance
of this correlation was further validated by the p-value which was equal to 0.0001 and thus
much lower than the threshold level of 0.05 based on a confidence level of 95% (Table 12).
The results of the above statistical analysis verify the credibility of Ea and the VTS index to
characterize the temperature sensitivity of not only unmodified asphalt binders, but also
bio-modified ones.
smn
PCCmn = PCCnm = √
√
(4)
smm snn

Table 10. PCC values of reference and bio-modified bitumen.

Tmixing Ea VTS Index

Tmixing 1.00 0.03 −0.42
Ea 0.03 1.00 0.85
VTS Index −0.42 0.85 1.00

Table 11. R2 values of reference and bio-modified bitumen.

Tmixing Ea VTS Index

Tmixing 1.00 0.00 0.18
Ea 0.00 1.00 0.72
VTS Index 0.18 0.72 1.00

Table 12. p-values of reference and bio-modified bitumen.

Tmixing Ea VTS Index

Tmixing N.A. 1 0.16 0.0298
Ea 0.16 N.A. 1 0.0001
VTS Index 0.0298 0.0001 N.A. 1
1 Not applicable.

3.10. Storage Stability Test

The storage stability test was carried out in accordance with EN 13399 for the unaged
algae-modified blends [37]. The test evaluates the tendency of modified bitumen to present
segregation during storage for extended periods of time at elevated temperatures. It can be
noticed that increasing contents of both microchlorella and chlorella led to larger softening
point differences between the top and bottom parts (Table 13). Although smaller particle
sizes allow better mixing and, consequently, dispersion capabilities, chlorella presented
less separation than microchlorella. This could be attributed to the different densities of the
two modifiers. If chlorella presented lower density and bitumen absorption ability than
microchlorella, the buoyancy forces could potentially offset the gravity forces that pull
the particles downwards, thus limiting the separation. Nevertheless, both bio-modifiers
caused significant segregation when incorporated at 10% by weight of bitumen or more,
as observed by the rapid increase in ∆T. Consequently, the replacement content of 5% is
advised as far as storage stability properties are concerned.
Eng 2024, 5 430

Table 13. Storage stability results of algae-modified bitumen.

Bitumen/Blend Difference in Softening Point (◦ C)

MCL-5 1.4
MCL-10 4.2
MCL-15 5.6
CL-5 1.4
CL-10 2.4
CL-15 4.0

4. Conclusions
• Both types of algae had a stiffening effect on the original 70/100 bitumen as noticed
by the decline inthe penetration values and the increase in the softening point.
• Neither bio-modifier had a noticeable impact on the elasticity of the bitumen as all
blends had elastic recovery of up to 10%.
• The addition of algae in the bitumen reinforced its elastic phase. The increment in
both the maximum force and deformation energy indicated a stiffening effect. This
was even more prominent for the short-term aged samples.
• Increasing contents of algae led to increasing dynamic viscosity values and mixing
temperatures.
• Ageing increased the temperature sensitivity of bitumen as demonstrated by the
activation energy and VTS index results.
• Ageing had a much smaller impact on the temperature sensitivity of bio-modified
blends than it did on the reference bitumen.
• A strong statistical correlation was achieved between the activation energy and the
VTS Index. These two values could be utilized to further characterize the temperature
sensitivity of bio-based bitumen.
• Further physicochemical and rheological investigation is required to thoroughly exam-
ine the effect of algae on bitumen before and after short-term and long-term ageing.

Author Contributions: Conceptualization, S.K. and E.M.; methodology, E.M., S.K. and A.K. (Avraam
Konstantinidis); software, S.K.; validation, E.M.; formal analysis, E.M.; investigation, S.K.; resources,
E.M.; data curation, C.K. and A.K. (Artemis Kalapouti); writing—original draft preparation, S.K.;
writing—review and editing, E.M.; visualization, E.M.; supervision, E.M. and S.K.; project adminis-
tration, E.M. All authors have read and agreed to the published version of the manuscript.
Funding: This research received no external funding.
Institutional Review Board Statement: Not applicable.
Data Availability Statement: The data of this research are available upon request.
Conflicts of Interest: The authors declare no conflicts of interest.

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