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Future Directions for Applications of Bio-Oils in the Asphalt

Industry: A Step to Sequester Carbon in Roadway Infrastructure
Abolhasan Ameri, Hamzeh F. Haghshenas, and Elham H. Fini*

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ABSTRACT: The global emphasis on sustainability and net zero carbon roads combined
with the increased cost of crude oil has necessitated the application of new environmentally
friendly alternatives to the bitumen used in asphalt by the pavement industry. Physical aging,
chemical aging, and moisture damage are three important matters encountered in the
pavement industry that are harmful for asphalt; bio-oils can decelerate the rates of physical
aging and chemical aging in virgin bitumen, and bio-oils can substantially improve virgin
bitumen’s resistance to moisture damage. Bio-oils can also restore properties in environ-
mentally damaged asphalt up to a certain limit of aging. The main goal of this review is a
comprehensive analysis of the literature about the potential of bio-oils produced from different
biomass sources to influence the physical aging, chemical aging, and moisture damage of
asphalt. Considering that bitumen’s physical aging is highly impacted by the bitumen’s wax
content, this review also covers the effect of wax inherently present in bitumen or wax added
to bitumen as a modifier. It is concluded that the chemical composition of a bio-oil has a
significant impact on the bio-oil’s ability to protect or recover the bitumen’s original properties. Phenolic compounds found in bio-
oils have antiaging effects while bio-oils’ acidic compounds may lead to moisture susceptibility.According to the literature, most bio-
oils have positive effects only in a specific range of temperatures: low, intermediate, or high. Complete miscibility and dispersion of a
bio-oil in the asphalt matrix also have a significant influence on making a bio-oil an effective modifier. Generally, bio-oils are
promising as sustainable, carbon-neutral, cost-effective alternatives to replace or modify conventional bitumen in the pavement
industry. This review has identified the following critical research gaps: (1) the lack of standard methods for evaluating and reporting
the performance characteristics of each bio-oil in bitumen; (2) the lack of long-term field performance data on bio-oils to support
comprehensive life-cycle assessments and life-cycle analyses; (3) high variation among bio-oils made from the same feedstock
through different processing methods, leading to variation in performance characteristics; (4) the lack of accurate technoeconomic
analysis on industrial bio-oils to facilitate entry of bio-oils into the asphalt market.

1. INTRODUCTION aging. Either of these mechanisms results in increasing the

With the current emphasis on sustainability and carbon bitumen’s viscosity, molecular weight, and softening point
neutrality combined with the increased number of vehicles while decreasing the bitumen’s penetration ductility and its
and the depletion of the world’s oil reserves, the use of bio-oils capacity for stress relaxation.6−9 The presence of moisture in
to fully or partially replace bitumen in roadway construction asphalt causes a reduction in the durability and strength of the
has gained significant attention. Bitumen has several important asphalt. Water can weaken the bonds between bitumen and
properties that make it useful for significant applications; it is aggregate, deteriorating the adhesion between them and finally
impenetrable to water, highly adhesive, and has a high stripping the bitumen from aggregates.10
softening point.1,2 When a surface of asphalt pavement is There have been many studies on the development and
exposed to environmental conditions, hardening of the application of modifiers and additives to improve bitumen’s
bitumen can have negative effects on the asphalt’s performance properties and hinder the harmful consequences of physical
and lead to premature cracking.3 Unlike chemical aging, aging, chemical aging, and exposure to moisture. Bio-oils are
physical aging is reversible; however, both forms of aging
negatively affect pavement performance. Physical aging, which
is mostly associated with the crystallization of wax (inherent or Received: November 11, 2022
added), increases the bitumen’s stiffness,4 leading to cracks on Revised: March 7, 2023
the asphalt surface.5 In contrast to physical aging, chemical Published: March 22, 2023
aging is irreversible, and it influences the rheological properties
of bitumen. The oxidation of bitumen and the evaporation of
volatile compounds are the two main mechanisms of chemical

© 2023 American Chemical Society https://doi.org/10.1021/acs.energyfuels.2c03824

4791 Energy Fuels 2023, 37, 4791−4815
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sustainable alternatives to be added to bitumen to improve its 2. BIO-OILS

physical, chemical, thermal, and rheological properties. Bio-oils
Shortages of petroleum and the depletion of petroleum
are not harmful for the environment, are cost-effective, and can
resources have caused the substitution of alternatives such as
be produced from agricultural or industrial wastes.11 Bio-oils
bio-oils for petroleum.12 Bio-oils can be produced from
from different sources and with different functional groups
biomass as a renewable energy that is both clean and cost-
reveal the role of bitumen chemistry on the behavior of asphalt.
effective. Using waste materials for the production of bio-oils
This review focuses on three areas: the physical hardening
helps the environment and the material life cycle.13 The CO2
that is induced by inherent and/or added wax in bitumen; the
chemical aging of bitumen; and moisture damage to asphalt. emissions from the process of biomass conversion are
This review presents a comprehensive overview of the use of negligible and could be minimized by recycling the CO2 into
bio-oils in bitumen and discusses the effects of bio-oils on the plants.14
physical hardening of bitumen, the chemical aging of bitumen, 2.1. Biomass Sources of Bio-Oils. There are many
and the moisture damage of asphalt. The literature review industrial, organic, and agricultural resources for biomass, such
performed for this study resulted in the number of articles as wood waste, animal wastes, agricultural crops, and aquatic
shown in Figure 1. As shown, the papers investigated can be plants.15 Bio-oils could be used in bitumen in several ways:
without treatment, dewatered, or modified with sulfur.16
Biomass is sufficiently abundant to be used as a raw material
for the production of bio-oils. Biomass is generally categorized
into herbs, wood, human wastes, animal wastes, and
agricultural wastes. The lignocellulosic composition of a
biomass has a direct impact on the physicochemical properties
of the bio-oil produced. The main constituents of lignocellu-
losic compounds are lignin, cellulose, and hemicellulose. Each
of these biomasses has been used to produce bio-oil: almond
shell,17 beechwood,17 birch,18 coconut husk,18 corncob,17 corn
stover,19 Douglas fir,20 empty fruit bunch,17 European birch,19
fir,18 hardwood,21 hazelnut seed coat,21 hazelnut shell,17
Monterey pine,20 oil palm shell,22 olive husk,17 peanut
shell,18 pine bark,18 softwood,21 sugar cane bagasse,19 swine
waste,19 switchgrass,19,23 tobacco leaf,21 tobacco stalk,21 walnut
Figure 1. Number of articles in the literature in each of four shell,18 wheat straw,17 white poplar,24 white spruce,19 white
categories. willow,20 and wood bark.21
2.2. Production Methods of Bio-Oils. Bio-oils can be
produced from biomass through either biochemical processes
(such as fermentation, anaerobic digestion, and composting)
grouped into four categories: bio-oils’ source and composition, or thermochemical processes (such as combustion, gasification,
bio-oils’ effect on physical hardening, bio-oils’ effect on liquefaction, pyrolysis, carbonization, and supercritical oxida-
chemical aging, and bio-oils’ effect on moisture damage. tion).25 Liquefaction consists of a mixture of physical and
Our examination of the related literature led to very few chemical reactions. It uses a catalyst to enhance the
review studies of the use of bio-oils in asphalt, with no decomposition of macromolecules using thermal energy.
comprehensive state-of-the-art review identifying research gaps Conversion of macromolecules to small molecules occurs
and barriers to entry. This is attributed to the fact that the use through reactions such as dehydration, cracking, and
of bio-oils in asphalt is relatively new. Bio-oil applications in hydrolysis. Liquefaction can be divided into two categories:
asphalt were promoted by industry’s emphasis on recycling of direct liquefaction, and indirect liquefaction. In pyrolysis,
aged asphalts combined with the effectiveness of selected bio- biomass molecules convert or decompose to smaller molecules
oils to facilitate the recycling of aged asphalt. Therefore, we by heat absorption. Pyrolysis has the advantage of direct
believe the outlook of this review paper can be significant to production of liquid products from biomass. It is typically
this emerging technology and associated industries. This performed in a fluid bed reactor.
2.3. Composition of Bio-Oils. The main atoms in bio-oils
review has identified the following critical research gaps: (1)
are carbon, hydrogen, nitrogen, and oxygen. The molecules of
the lack of standard methods for evaluating and reporting the
bio-oils are mainly alcohols, aldehydes, esters, acids, phenols,
performance characteristics of each bio-oil in asphalt; (2) the
ketones, furan, and lignin-derived oligomers.26,27 A bio-oil can
lack of long-term field-performance data on bio-oils to support be used in three ways: as a modifier added to bitumen (usually
comprehensive life-cycle assessments and life-cycle analyses; below 10 wt %), as an extender for bitumen (between 25 and
(3) high variation among bio-oils made from the same 75 wt %), or as an alternative to bitumen (replacement for
feedstock through different processing methods, leading to 100% of bitumen). All of these forms involve substitution for
variation in performance characteristics; (4) the lack of petroleum-based bitumen.28 So, part of the weight percentage
accurate technoeconomic analysis on industrial bio-oils to of bitumen would be bio-oil as a binder, thereby reducing the
facilitate entry of bio-oils into the asphalt market. Addressing amount of bitumen needed. The addition of the appropriate
these gaps along with issuing carbon certificates on each bio-oil percentage of bio-oil to bitumen has great importance to
can facilitate the widespread application of bio-oils in the obtain the best enhancement in performance of the asphalt
asphalt market while promoting carbon sequestration, resource pavement.29 Bio-oils can also be used as rejuvenators.30
conservation, and sustainability. Rejuvenators based on algae, animal waste, or vegetable oil
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are usually in liquid form, and their introduction to aged alkane.59,60 The concerning wax crystallization is often
asphalt could help revitalize aged asphalt. Bio-oil from oak attributed to wax-based additives, which are macro-crystalline
wood is a bitumen replacer with properties similar to those of wax.61 In contrast, the wax inherent in bitumen is mostly the
bitumen; bio-oil from oak wood can be modified by polymers microcrystalline type.62
or rubber, and it is resistant to thermal cracking.31 There are conflicting opinions in the literature about the
Bio-oils are compatible with bitumen and can be mixed with influence of wax on bitumen’s properties. Factors that
it to affect various factors such as reducing the energy required influence bitumen’s properties include the amount of wax
for mixing and compaction of asphalt.32 Bio-oils can enhance present in the bitumen and the chemical composition and
bitumen’s properties and reduce a bituminous mixture’s cost, structure of wax and bitumen. During the aging process of
mixing time, aging, and stiffness.33 Based on the literature, bio- bitumen, the polarity and aromaticity of bitumen molecules
oils have positive effects at low and intermediate temperatures; increase because of oxidation of the bitumen. As a result,
however, they have a negative influence at high temperatures, asphaltenes aggregation will increase.58,63,64 Wax in the liquid
which could be addressed by the addition of polymers to the phase reduces the stiffness of bitumen, but if wax changes to a
bio-oils.34 Bitumen consists of four main components: solid state, it makes the bitumen stiffer.65 At intermediate
saturates (8%−10%), aromatics (41%−55%), resins (25%− temperatures, the wax crystal size reduces the influence on the
28%), and asphaltenes (10%−20%).26 softening point, causing the bitumen to have more
susceptibility to rutting.58,64 At higher wax content, bitumen
3. PHYSICAL AGING OF BITUMEN shows more elastic behavior as the temperature drops; this
The type of bitumen used in asphalt affects the aging rate of shows that wax-modified bitumen is stiffer at low temper-
bituminous composites used in asphalt pavements.35 There are atures.66 The presence of a high content of wax in bitumen
other factors that also influence the aging process: temper- could reduce the bitumen adhesion, augment the physical
ature; rainfall; solar radiation; and mixture properties such as hardening of bitumen,67,68 and weaken the bitumen’s
void content and permeability, type of aggregates, thickness of healing.69
the binder layer, storage time, and plant type.36,37 One type of Lamperti et al. showed that the type of the wax affects the
aging is short-term aging, which is related to the amount of adhesion of bitumen.69 However, another study showed no
bitumen hardening during asphalt’s manufacturing stage and reduction in adhesion by the addition of 5 wt % wax to
during asphalt’s placement and compaction.38 Bitumen bitumen.70 Some researchers have used wax as an additive to
hardens for three main reasons: evaporation of volatile bitumen to improve its characteristics. Their reasoning is that
compounds, chemical aging (also referred to as bitumen wax reduces the bitumen’s viscosity at higher temperatures and
oxidation), and physical aging (also referred to as physical helps improve the flow of bitumen, enhancing its work-
hardening).39−41 The distinction of physical hardening ability.71,72 Edwards et al. showed that the addition of wax to
compared to the other two is that it is a reversible process bitumen would not have a negative influence on the fracture
and does not affect the chemical composition of the bitumen.42 temperature, but the addition of wax to bitumen increased the
Physical hardening is mainly induced by wax crystallization in stress at an asphalt fracture because of the lower air-void
maltene.43 Even though the chemical composition of bitumen content of wax-based additives such as FT-paraffin and
is not changed in this process, bitumen’s rheological properties polyethylene wax.73 The addition of wax increases the stiffness
are highly impacted.44 Bitumen chemical aging mainly occurs of bitumen to different extents according to the type of
by oxidation; however, aromatization, carbonation, and chain additive.74 Bitumen containing wax showed different physical
scission are among other contributing mechanisms.45−48 hardening relative to wax-free bitumen, which showed a
Physical aging occurs along with increased stiffness of constant creep response.73 Yi-qiu et al. investigated the effects
bitumen after a long period of storage under isothermal of Sasobit as a wax additive on the properties of bitumen. They
conditions.49 Severe cracking will occur in the asphalt because reported that the penetration grade of bitumen decreased after
of embrittlement.50 This may result from a combination of mixing Sasobit with the bitumen. However, the softening point
bitumen and aggregate or from a specific type of bitumen. The of bitumen increased, indicating lower susceptibility to rutting
cracking causes drastic problems specifically in cold and high- at high temperatures. The viscosity of the wax-modified binder
altitude areas.51,52 decreased with increasing temperature. The addition of wax
The degree of physical aging depends on the amount of leads to higher values of antirutting factor, higher complex
crystallized fractions in the bitumen below and above the glass moduli, and lower phase angles, all of which show better
transition temperature, Tg, and the length of formed chains. rutting resistance.68 The presence of wax in bitumen causes
Among the latter fractions are wax, whose crystallization results lower ductility and lower viscosity relative to bitumen without
in an increased viscosity in bitumen.53 This phenomenon will wax. Wax crystallization in wax-rich bitumen results in a loss of
increase the creep stiffness and reduce the penetration index.3 ductility in the bitumen.75 This is attributed to an increase in
Reheating and/or mixing the bitumen can recover the the peak load of failure (which shows the load at which the
bitumen’s original properties.54 Other parameters such as sample breaks) and an increase in fracture energy at higher wax
sol−gel transition, asphaltenes aggregation, wax crystallization, content.58
and the collapse of free volume also promote the aging and In another study, it was shown that various kinds of wax
hardening process.49,55−57 additives did not have any unfavorable effects on rutting
There is a difference between wax additives and the wax resistance at high temperatures.76 The results of the dynamic
inherent in bitumen. The n-alkanes in wax additives usually creep test showed that polyethylene wax did not stiffen the
have a higher melting point (70−145 °C) than the wax bitumen at higher temperatures. Some types of waxy additives
inherent in bitumen (20−40 °C).58 The number of carbon showed higher hardening effects on bitumen. They had no
atoms in n-alkane affects the aggregation behavior of positive effect on the aging properties of bitumen.76 The
asphaltenes molecules in the mixture of asphaltenes and n- presence of wax in bitumen along with asphaltenes molecules
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could shift bitumen from sol-type to gel-type because of of bitumen. Also, wax caused a reduction of the interaction
crystalline behavior of the solid phase. The molecules in between resins molecules and PPA because of the scattering of
paraffinic waxes are less polar, so their interactions with resins molecules.87
bitumen components are weaker.61 In contrast, amidic waxes Some researchers think that stress relaxation could prevent
are more polar and can have more interactions with maltenes the physical aging of bitumen. The test used for physical aging
and greater influence on rheological properties. At lower of asphalt is the thermal stress restrained-specimen test
temperatures, the structure of the wax preserves its solid state (TSRST). Its disadvantage is that it measures thermal stress
and does not have any special effect on bitumen properties. (which is dependent on various parameters) instead of a direct
Increasing the temperature changes the structure to liquid measurement of stiffness. An alternative method is using an
phase, and the viscoelastic characteristics of the bitumen will asphalt thermal cracking analyzer (ATCA). Judycki et al.
be affected because of the mobility of molecules.61 At higher claimed that different stiffness improvements were observed in
temperatures, the wax becomes melted, the structure is lost, hardening of various mixtures. They showed that the tensile
and the properties would be the same as the base bitumen.61 strength of asphalt was related to low-temperature cracks in
The effect of a wax additive on the properties of bitumen at pavement.88 Lu and Redelius investigated the effect of the wax
different temperatures was investigated by Samieadel et al. content of bitumen on its physical aging and other character-
They showed that increasing the wax content could raise the istics such as temperature cracking, water sensitivity, and
values of the creep stiffness modulus and make the binder rutting. Their results demonstrated that the presence of wax
stiffer at low temperatures. Wax crystallization is another point would affect the physical aging at low temperatures. For
that causes cracks at the surface of asphalt and makes bitumen instance, a higher fracture temperature was observed for waxy
more brittle.64 bitumen. On the other hand, the presence of wax in bitumen
There are three orientations for wax: T-shape, parallel, and had no effect on water sensitivity or rutting. They commented
displaced parallel. Wax as an n-paraffin has a structure of that the wax’s nature and the bitumen’s chemical composition
layered packs. The most important layer cells (subcells) in wax are the main parameters that influenced the asphalt’s
crystallization are the first two layers.77 The wax crystal has an performance.89 McKay et al. measured the physical aging of
important role in the formation of bee-like structures. Bee size bitumen to investigate the effects of aggregate on the rate and
has a significant effect on the stiffness, deformation, and amount of embrittlement. The results revealed that the
viscosity of asphalt.77 Sometimes bee structures may be hardening of oxidized bitumen could be altered by the
composed of wax crystals through nonpolar interactions presence of aggregates. The addition of aggregates to asphalt
between them, and a small amount of wax plays a role as a
and the composition of aggregates did not influence catalyzing
nucleation center. Another viewpoint says that a bee structure
the aging process. Other factors such as poor compaction,
is a solid-like deposit from the coprecipitation of wax and
overheating bitumen, overloading on the structure, and
asphaltenes. In this hypothesis, the nucleation center would be
moisture effectively cause physical aging.90
an asphaltenes molecule and the interactions are between polar
3.1. Solutions. Raouf and Williams used bio-oil from
asphaltenes and nonpolar waxes. The presence of wax has an
switchgrass as an alternative for bitumen binder. Their results
unfavorable effect on the π-stacking interactions of asphaltene
molecules or sheets. Pahlavan et al. showed that paraffin wax showed that the bio-oil had the same behavior as a neat
would destabilize the interaction of asphaltenes-asphaltenes bitumen. Increasing the temperature decreased the viscosity of
and wax-asphaltenes molecules, and bee structures would not the mixture. The activation energy and the viscosity’s
be created because of the hypothesized interactions between susceptibility to temperature were higher after the addition
wax and asphaltenes.78 The binding energy between wax of bio-oil, which indicates that switchgrass bio-oil is more
molecules is higher than for a wax-asphaltenes complex, which susceptible to temperature. The blends showed more New-
shows that wax prefers to aggregate with wax molecules instead tonian behavior by increasing temperature, and they
of asphaltenes molecules. This strengthens the hypothesis of approached pseudoplastic fluid behavior at low temperatures.
bee formation from wax crystallization.79,80 Increasing the wax Generally, the researchers found that this bio-oil had similar
dosage raised the amount of wax diffused into the asphalt rheological properties to the base bitumen.91 They also applied
matrix.64 Bitumen’s original composition as well as its oakwood bio-oil to improve bitumen’s rheological properties.
crystallinity81 and wax content has a special effect on the The results were similar to those of their previous study for
degree of wax’s influence on bitumen properties. The wax switchgrass bio-oil.92 Mills-Beale et al. analyzed the possibility
content of the bitumen and its crystallized fraction can be of using swine manure to improve the rheological properties of
determined using methods such as distillation, extraction, and bitumen. Tests using a dynamic shear rheometer, a Superpave
liquid chromatography.82 The hydrophobicity of asphalt is rotational viscometer, a bending beam rheometer, and a
influenced by the addition of wax, which leads to a reduction of Fourier-transform infrared spectroscope were conducted for
surface free energy and increased wettability of the binder.83 characterization of the modified bitumen. The viscosity of the
Kim et al. showed that the addition of wax to bitumen reduced bitumen was reduced after the addition of bio-oil. The phase
the viscosity. The addition of wax also had an effect on angle and complex module were also lower for modified
increasing rutting resistance. They concluded that wax- binder. A decrease in creep stiffness resulted in improvement
modified bitumen could be recycled better in cold regions.84 of thermal cracking.93 Yang et al. evaluated the application of a
Similar results can be found in other studies.85,86 bio-oil from waste wood as an alternative to bitumen. Various
A wax additive can have an impression on the effect of other tests were carried out to analyze stiffness, tensile strength,
additives and modifiers to bitumen. For instance, when using rutting resistance, and fatigue performance. The addition of
polyphosphoric acid (PPA) as an additive, the addition of wax bio-oil enhanced fatigue performance, had little effect on
could moderate the interactions between bitumen and PPA. tensile strength, and had no influence on rutting resistance and
Wax reduces the influence of PPA on increasing the elasticity the dynamic modulus.94
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Guarin et al. used each of rapeseed oil and fish oil as a operative temperature. The crossover temperature and bitu-
modifier for bitumen to enhance its rheological and chemical men stiffness were not considerably affected by this additive.
behavior in a bituminous mixture. The main compound in fish The effective concentration of this compound was higher than
oil is ethyl ester; the main compound in rapeseed oil is fatty 5 wt %. The last three types of additives were derivatives from
acid methyl ester. Both oils caused draining down of the tall oils. They decreased the operative temperature because of
bitumen by covering the aggregate particles and preventing their lower viscosity compared with the original bitumen. Also,
bonding between bitumen and stones. The researchers they reduced the binder stiffness, but it had no effect on
introduced several factors such as large air voids and light, temperature susceptibility. Increasing their dosage dominantly
rounded aggregate particles. Bitumen modified with bio-oils influenced the viscosity parameter.101
demonstrated higher mass loss and there was no difference in Elkashef et al. enhanced the fatigue and low-temperature
their rheological behavior before and after aging. The oils characteristics of asphalt pavements by the addition of
increased the softening and decreased adhesion of the rejuvenators. They showed that the chemical composition of
bitumen.95 the rejuvenator had a great influence on its performance. Also,
Fernandes et al. assessed the behavior of bitumen after they investigated the effect of the thermal properties of
partial replacement of bitumen by waste motor oil, styrene− additives on the rheological behavior of the asphalt.102
butadiene−styrene (SBS), and ground tire rubber; the results Alamawi et al. studied the effect of a palm kernel oil polyol
showed that the performance of modified binder improved biobinder on the physical, thermal, and chemical behavior of
relative to conventional bitumen. Resistance to rutting and bitumen. Bitumen with biobinders showed lower mixing and
resistance to fatigue cracking were better in the modified compaction temperatures compared with bitumen without bio-
mixture; as a result, its durability increased. Waste motor oil oil. There was no significant difference in the thermal
and SBS demonstrated better resistance to fatigue cracking; susceptibility of modified binders and unmodified binders,
waste motor oil and ground tire rubber had better resistance to while bitumen with a biobinder showed higher values of
rutting and resistance to stiffness.96 activation energy.28
Yang et al. studied the effect of bio-oil rejuvenators Li et al. modified bitumen with a bio-oil from seaweed. The
produced from the pyrolysis of municipal solid waste on the concentration of bio-oil to obtain the best results was 20 wt %
rheological and aging properties of bitumen. The aging process of the total mass of bitumen. The bio-oil was added to bitumen
did not affect the composition of the modified bitumen with modified by SBS. Because of the similar chemistry of bio-oil
bio-oils. Increasing the temperature and shear rate resulted in and virgin bitumen, the bio-oil could improve the bitumen’s
decreasing viscosity. The modified bitumen’s dynamic viscosity performance in areas such as high-temperature rutting
decreased because of the decomposition of organic agglomer- resistance and low-temperature resistance to embrittlement,
ates in the solids during accelerated aging. This pyrolysis oil especially in harsh environments for road pavements.103
could be used in the bitumen as a substitute for the light Sun et al. investigated the influence of bio-oil from waste
fraction.97 cooking oil on the chemical and rheological characteristics of a
Sun et al. used a byproduct of the biodiesel refining process polymer-modified bitumen. The polymer was SBS. The
from waste cooking oil as a bio-oil in a substitution for addition of bio-oil decreased the activation energy and
bitumen. The free-radical polymerization method was used to viscosity of polymer-modified bitumen. The new mixture had
convert low-molecular-weight bio-oil to high molecular weight. a lower construction temperature. Bio-oil affected the low-
They obtained the optimal mass of bio-oil along with the temperature cracking resistance by reducing the shear modulus
accelerator and initiator. The produced bio-oil was more and increasing the bending creep compliance. However, it did
expensive than the base bitumen and it was not cost-effective not have an affirmative effect on the rutting resistance at high
to totally replace the bitumen, so the bio-oil should be a partial temperature. Generally, this polymer-modified bitumen with
substitution for bitumen.98 bio-oil is recommended for application in cold regions.104
Oldham et al. showed that restoration of properties in aged, Yu et al. used epoxidized vegetable oil as a biorejuvenator to
oxidized bitumen could be accomplished using swine-manure study its regenerating effects on aged bitumen compared with
bio-oil as a cost-effective rejuvenator. Bitumen’s stiffness and soft bitumen and warm-mix asphalt. They performed softening
viscosity were reduced by increasing the additive dosage from point, rotational viscometer, penetration, dynamic shear
5 to 30 wt %, while the strain at failure and the m-value rheometer, and bending beam rheometer tests for this target.
increased.99 Fini et al. used biobinder from swine manure to The biorejuvenator showed the best effect among three
improve the rheological properties of bitumen. They additives; i.e., soft bitumen and Evotherm-DA. However, it did
concluded that this bio-oil could lower the compaction not influence well at low temperatures.105
temperature, resulting in better workability. Reducing carbon Ingrassia et al. studied the effect of wood bio-oil in a
emissions and reducing the consumption of fossil fuel were bituminous mixture to improve its chemical, rheological, and
other advantages of swine-manure bio-oil.100 morphological characteristics. The doses used for wood bio-oil
Grilli et al. tested each of five derivatives from pine trees as were 0, 5, 10, and 15 wt %. Wood bio-oil is mainly composed
an additive to bitumen. The first derivative was the distilled of esters. Its addition caused a reduction of saturates,
resins of pine. It had no influence on operative temperature, aromatics, and asphaltenes and an increase in the amount of
but it increased the stiffness. Increasing the additive resins. Its blending with bitumen was only physical, without
concentration resulted in higher values of the complex any chemical reaction. The bio-oil increased the penetration
modulus, higher crossover temperature, greater elasticity and decreased the softening point and viscosity, which shows
behavior, and more susceptibility to temperature. A lower Newtonian behavior. In the presence of bio-oil, the complex
dosage of this compound had no significant effect on bitumen modulus decreased and the phase angle increased. However,
properties. The second derivative was obtained from the the bio-oil did not affect the temperature susceptibility of the
distillation of terpenes. It reduced bitumen’s viscosity and mixture.106
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Hajikarimi et al. investigated the effect of various bio-oils the interaction between bitumen and biomodified nano-
derived from swine manure, miscanthus pellet, corn stover, and particles through hydrogen bonding, dipole−dipole interac-
wood pellet on the rheological properties of bitumen at low tion, and dispersive force.113
temperatures. The results of experiments and modeling Abele et al. used rapeseed oil as a rejuvenator for bitumen
showed that the recovery ratios and mechanical behavior of that was modified with ethylene-octane and SBS copolymers.
biomodified bitumen were higher than bitumen without bio- Rapeseed oil is a kind of fatty acid methyl ester. The functional
oils. However, the source of the bio-oil had a specific effect on groups of saturated fatty acid (C=O) and ester (C−O) could
the extent of the improvement in bitumen performance.107 be observed in its structure. Tests performed with a dynamic
Liu et al. assessed the feasibility of using biobinder from shear rheometer, a Fourier-transform infrared spectrometer,
swine manure as an alternative to petroleum-based bitumen. and a temperature-modulated differential scanning calorimeter
Biobinder reduced the glass transition temperature and thus showed that modification with bio-oil increased resistance to
enhanced the low-temperature behavior. The addition of rutting and fatigue by enhancing low-temperature perform-
biobinder made the bitumen much softer and increased its ance. This was attributed to the plasticizing influence of bio-oil.
elasticity and temperature susceptibility.108 Increasing the concentration of bio-oil in the bitumen
Uz and Gokalp used waste vegetable cooking oil (sunflower decreased the glass transition temperature. The addition of a
oil) as an economical bio-oil to recover aged bitumen after mixture of rapeseed oil and polymer simultaneously had the
both short-term aging and long-term aging. The addition of best results in rheological and high-temperature properties;
bio-oil to bitumen was in the range of 2−10 wt %. They using either bio-oil or a polymer individually showed a smaller
concluded that 3 and 6 wt % were the doses of bio-oil needed improvement in resistance to fatigue.114
for efficient recovery from short-term and long-term aging, Adesina and Dahunsi mixed waste cooking oil (WCO) with
respectively.109 high-density polyethylene (HDPE) as an additive to bitumen.
Zhou et al. investigated whether sulfur had an effect on the Individually, WCO influenced the physical properties of
performance of biomodified rubberized bitumen. The bio-oils bitumen by decreasing the softening point and increasing the
used were produced from corn stover, castor oil, miscanthus, penetration; HDPE demonstrated a vice versa effect, resulting
wood pellets, or waste vegetable oil. The presence of sulfur in in a higher softening point and lower penetration. Used
bitumen diminished its elasticity in the first days. However, the together, WCO acted as a modifier, while HDPE acted as a
elasticity increased to some extent in the following days of the stabilizer of WCO; the high values obtained for the penetration
aging period. The difference observed in curing time was due index showed a reduction of the temperature susceptibility of
to sulfur crystallization and its interaction with bitumen. the binder and higher flexibility that are more appropriate for
Bitumen with bio-oil from vegetable oil was the case most cold climates. HDPE would fix the rutting problems of bio-oil-
influenced by sulfur in curing rate, elasticity, and percent modified bitumen. By increasing the specific gravity of
recovery. This was attributed to the presence of the many bitumen, the softening point and penetration showed higher
unsaturated compounds in vegetable oil that could react with and lower values, respectively. A higher specific gravity
sulfur.110 improves the stabilizing behavior of modified bitumen.115
Wang et al. investigated the antifatigue, antimoisture, Pahlavan and Fini investigated the effect of phenolic
anticracking, and antirutting performance of a rejuvenator compounds in the bio-oils from castor, miscanthus, wood
from cotton. They concluded that the anticracking perform- pellet, corn stover, and waste vegetable oil on sulfur
ance was restored to the original value. It also reduced the crystallization in bitumen. Sulfur crystallization would initiate
damage rate relative to conventional bitumen and had a premature cracks because of mechanical and thermal loads,
positive effect on the high-temperature performance without leading to reductions in bitumen’s durability and work-
any side effects.111 ability.116 The results of their study showed that the thermo-
Lv et al. used each of five bio-oils (soybean oil, straw oil, mechanical characteristics of high-sulfur bitumen can be
vegetable oil, castor oil, or waste biological oil) for preparation controlled if the sulfur crystallization is hindered by
of bioasphalt. They concluded from various analyses introducing phenolic compounds to bitumen.
performed that bio-oil would reduce the high-temperature Yadykova and Ilyin used clean woody biomass along with
performance. The bio-oil from soybean showed the highest two types of silica nanoparticles (hydrophilic and hydro-
rutting index and the least sensitivity to the bio-oil dosage. phobic) to improve the adhesion and cohesion properties of
Vegetable oil showed the least sensitivity to temperature. At bitumen. Their analyses of rheological and morphological
low temperatures, the addition of bio-oils improved the properties were at normal and high temperatures. The optimal
performance; soybean oil had the largest value of the stiffness amount of bio-oil used was 5 wt %, which increased the
modulus. Straw oil showed an ascending trend followed by a adhesive strength of bitumen to the silica surface. Increasing
descending trend for the stiffness modulus. Waste oil was the the bio-oil amount to 15% increased the yield stress and
optimum bio-oil based on the creep rate and the stiffness enhancement in stiffness and elasticity.117
modulus. Soybean oil was the optimum bio-oil for the rutting Lin et al. used liquid bio-oil from bamboo charcoal as an
index and strain recovery. The main variation of bio-oil for additive to bitumen. They found that it had a positive influence
bitumen was physical modification.112 on softening behavior, brittleness, rutting, and resistance to
Karnati et al. produced an economical, sustainable biobinder fatigue cracking in bitumen relative to base bitumen. Increasing
from swine manure via a hydrothermal liquefaction process, in the bio-oil dosage from 6 to 12 wt % improved the workability
order to replace silane coupling agents for surface modification and compaction of the bitumen.118
of silica nanoparticles. The biobinder outperformed unmodi- Lyu et al. used waste tire rubber and waste bio-oils from
fied bitumen in low-temperature mechanical properties, rutting soybean as a hybrid system to create biomodified rubberized
resistance, and susceptibility to fatigue cracking. It provided bitumen. Biomodification reduced the glass transition temper-
better dispersion in the bituminous matrix and strengthened ature by a dilution effect and enhanced the low-temperature
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behavior of bitumen. Bio-oil mitigated the phase separation, as decreases the flow number. Both the increased ITS values and
it has a different resistance to deformation. More elasticity at a the decreased flow number indicate higher brittleness.136 The
high temperature and a more viscous behavior at a low amount of aging varies between different bitumen mixtures.
temperature were observed for biomodified rubberized bitu- The types of materials, the bitumen, and the aggregates used
men.119 are very important factors in the aging rate of bitumen. In fact,
Nizamuddin et al. produced bio-oil from waste plastic films the types of molecules and the chemical composition of the
for use as a rejuvenator in bitumen. The bio-oil was 5−8 wt % bitumen highlight the bitumen’s character.137
of the total mass of bitumen. The main constituent of the bio- Bitumen is composed of organic molecules that react to the
oil was fatty acids. The results showed that bio-oil-modified oxygen in the air, which is called an oxidation reaction. The
bitumen was significantly softer than neat bitumen. The bio-oil passage of unauthorized loads, the high heat of the environ-
had a positive effect on the rheological and thermo-chemical ment, and the oxidation of bitumen cause the aging
properties of bitumen and could restore the properties of aged phenomenon to intensify during the service life of asphalt.
bitumen. A decrease in complex modulus and an increase in Transporting, spreading, and condensing bitumen at a high
phase angle and crossover frequency were indicative of higher temperature causes its initial aging, which causes the
softening point and higher viscosity along with lower stiffness evaporation of its compounds and oxidizes it. Aging is not
and lower elasticity. The addition of bio-oil enhanced the necessarily a negative phenomenon; a small amount of aging
resistance to fatigue.120 will optimize the characteristics of the mixture.138 Other causes
of aging include changes in the bitumen structure over time,
4. CHEMICAL AGING polymerization caused by sunlight irradiation (especially
Most of the oxidation phenomenon takes place during the ultraviolet irradiation), and condensation polymerization.
service life of the pavement. During oxidation, the asphaltenes Aging affects the chemical composition of bitumen. Bitumen
and resins fractions of bitumen absorb oxygen in an irreversible is a colloidal mixture that consists of large molecules called
process that alters the bitumen’s characteristics. The oxidation asphaltenes in the discrete phase and saturates, aromatics, and
of bitumen reduces its elasticity and increases its hardness; resins in the continuous (liquid) phase of bitumen.139 The
these changes are called bitumen chemical aging.41 The reason resins-to-asphaltenes ratio in bitumen is a determinative factor
for increased asphalt hardening is that the intermolecular in bitumen characteristics.140 If the ratio of a mixture falls off
bonds of asphalt become stronger because of the creation of toward the pure maltene, the mixture shows a solution
functional groups after oxidation.121 According to stud- behavior; if most of the mixture is asphaltenes, the mixture is in
ies,122−124 carbonyl compounds and sulfoxides increase during gelatinous form.141
the aging process. Alkyl sulfurs can be oxidized into sulfoxides; The methods of simulating aging in the laboratory include
benzylic carbons will oxidize into ketones and subsequently the aging of bitumen alone and the aging of a mixture of
change to carboxylic acids and carbonyls.125 Aromatics are bitumen and materials. There are three methods for applying
reduced and the amounts of resins and asphaltenes increase. aging on bitumen in a laboratory environment: continuous
Another study showed that the level of saturates remains heating methods; using oxygen or air blowing; and using
constant, but aromatics and resins would decrease in amount infrared and ultraviolet waves. A rolling thin-film oven
by oxidizing and being changed to asphaltenes.126−129 There is (RTFO), a pressure aging vessel (PAV), and ultraviolet
another kind of chemical aging: photo-oxidation, which is (UV) irradiation are three methods used for artificial aging of
connected to ultraviolet (UV) irradiation. Because of exposure bitumen.37,142
of the asphalt surface to sunlight, polymerization of bitumen 4.2. Solutions. Mills-Beale et al. showed that the
molecules takes place, and the number of asphaltenes application of bio-oil from swine manure resulted in decreasing
molecules in the binder increases, making it stiffer.18 carbonyl and sulfoxide indexes at higher temperatures, which
4.1. Problems. The changes from chemical aging increase helped to reduce the stiffness of the bitumen.93 Hosseinnezhad
the molecular weight and softening point while decreasing the et al. produced four types of bio-oils (from corn stover, wood
penetration, ductility, and dispersity.130 Hou et al. studied the pallet, swine manure, or miscanthus) through a hydrothermal
relationship between the rheological behavior of asphalt and liquefaction process and pyrolysis for application in bituminous
the asphalt’s absorbance. Changes in asphalt’s absorbance mixtures. Bio-oils produced from woody biomass contain ether
during the aging process show that the composition and and alcohol components in their structure. Bio-oils from swine
properties of asphalt have been changed. The asphaltenes manure and miscanthus are much more polar than other bio-
fraction showed a higher absorption coefficient than the oils because of the presence of asphaltenes with aromatic rings.
maltene.131 A temperature increase could have a positive As a result, modifying bitumen with miscanthus increases the
impact on the kinetics and aging process.132,133 The aging susceptibility to oxidation. Bio-oil from swine manure contains
process of asphalt is commonly a first-order kinetics equation the heaviest fractions among all the bio-oils investigated in this
that has large activation energy.130 Using antioxidants in study. The maximum stress build-up was observed for corn
bitumen could prevent its oxidation process134 and increase stover followed by wood pallet, swine manure, and
resistance to the formation of carbonyl and sulfoxides; in this miscanthus.143
case, the molecular weight of asphalt remains constant.122 Qiu Guarin et al. reported that rapeseed oil has a higher content
et al. added a nonionic dispersant to bitumen to decelerate the of resins and lower values of aromatics than fish oil. However,
aging process and the physical hardening of asphalt. Inhibition both of them have hydrophilic behavior and prefer to cover the
of asphaltenes aggregation causes a reduction in asphalt aggregate surface instead of the binder surface due to their
hardening.135 polarity. Generally, bitumen with fish oil showed a slightly
One of the tests that could be used for recognition and better performance compared with rapeseed oil.95
determination of the aging process is the Indirect Tensile Park et al. tested bio-oils from different biomass sources
Strength (ITS) test. Aging increases the ITS values and such as pine bark, fir, walnut shells, coconut husk, birch, or
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peanut shells. They showed that bio-oils containing phenolic restore the properties of aged bitumen. Hybrid bio-oils helped
compounds from biomasses such as birch or pine bark are to balance the heteromolecules and decrease the size of
effective as antiaging biomodifiers.18 Pahlavan et al. used bio- asphaltenes aggregates in the bitumen.150
oils that were rich in phenolic compounds to increase the Kabir et al. modified the rubber surface with bio-oils to
durability of bitumen. All of the bio-oils contained phenolic improve the interaction between bitumen and rubber. The five
compounds and decreased the chemical aging of the bitumen. bio-oils tested were from wood pellet, waste vegetable oil, corn
The amount and structure of phenolic constituents in a bio-oil stover, miscanthus, or castor oil. The results showed that there
had a direct effect on the bio-oil’s efficacy.144 In another study, were both physical and chemical interactions between bitumen
Fini et al. studied the effect of the chemical composition of and modified rubber because of the existence of polar aromatic
various recycling agents on the aging property of bitumen. It rings and phenolic resins in bio-oils. Wood-based bio-oils
was found that all of the agents used could decrease the size of caused more adhesion of rubber on the bitumen and prevented
asphaltene agglomerates.145 Hosseinnezhad et al. concluded its easy separation. However, waste vegetable oil did not show
that bitumen samples modified with oils from wood pellet, suitable interaction with bitumen despite good adhesion on the
miscanthus, corn stover, or animal waste showed lower values rubber surface.151 In another study, they used these five bio-
of an aging index. This was attributed to chemical structure of oils as modifiers of rubber and carbon black in bitumen to
the bio-oil and the presence of carbonaceous particles. Another investigate the resistance to ultraviolet aging. The results
factor that affected the improvement of the antiaging property showed that wood-based bio-oils again had better performance
of bio-oils was their lower polarizability. The researchers also in restoring the properties of aged bitumen because of the
investigated the effect of ultraviolet exposure on bitumen presence of furfural in their structure. This type of rejuvenator
properties.146 The results confirmed that ultraviolet light can needed a minimum dosage of 57% to affect the properties of
be adsorbed by carbonaceous particles and retard the aging aged bitumen.152
progress in a bitumen modified by the bio-oils. Li et al. compared the effect of different compositions
Yang et al. studied bitumen modified by bio-oil in the range present in bio-oils on their performance. According to their
of 2−10 wt % to determine its chemical composition and its results, they concluded that rejuvenators containing a high
effect on the aging behavior of bitumen. Bio-oil from wood amount of aromatics and alkanes and a lower amount of
waste contains a high amount of oxygen. FTIR results of the ketones showed higher efficacy at restoring the properties of
bio-oil found compounds such as aromatics, alcohols, ketones, aged bitumen.153 Uz and Gokalp used waste vegetable cooking
ethers, esters, alkanes, nitrogenous compounds, carboxylic oil (sunflower oil) as an economical bio-oil to recover aged
acids, aldehydes, acyls, amides, and water. Compatibility with bitumen after both short-term and long-term aging. The
bitumen decreased by increasing the bio-oil concentration.147 addition of bio-oil to bitumen was in the range of 2−10 wt %.
Hung et al. modified bitumen with hexadecanamide and They concluded that 3 and 6 wt % dosages of bio-oil were
hecadecanoic acid as two surfactants derived from animal and needed for efficient recovery from short-term and long-term
plant bio-oils. Amide molecules could crystallize at the silica aging, respectively.109
surface, and they prefer to self-assemble rather than adsorb to Wang et al. developed a rejuvenator consisting of both SBS
asphaltenes and waxes; thus, they would not mix well with as a polymer and cotton oil as a bio-oil. They performed
bitumen and would finally separate out. They interact with dynamic shear rheometer, bending beam rheometer, and
each other through H-bonding instead of interacting with rotational viscosity tests to assess the temperature susceptibility
bitumen. However, acid molecules had good mixing capability at low, high, and service temperatures. They showed that bio-
and had no effect on the interface of bitumen and air. The oil rejuvenators could significantly recover the properties of
mixture of amide and acid covered each solubility problem aged bitumen at both low and high temperatures. The
without any interaction between them. Other components in rejuvenator changed the asphaltenes content of aged bitumen
bio-oils would help the solubility behavior of the mixture and and changed the structure of the binder toward gel structure, as
could act as antistripping agents along with amide it created agglomerations between polar and nonpolar
molecules.148 constituents.154
Tabatabaee and Kurth evaluated the influence of vegetable Shariati et al. worked on a hybrid bio-oil from swine manure
oil on the stability of bitumen. They showed that the addition for desorption of bitumen from the surface of siliceous stones.
of bio-oil could limit the increase in the Colloidal Instability During aging, interfacial interactions between stones and
Index after the aging process. They introduced this bio-oil as bitumen increase, and self-aggregation of bitumen molecules
an appropriate rejuvenator for aged bitumen. The bio-oil also takes place. The hybrid bio-oil could neutralize the polar
had a positive effect on the glass transition temperature, and interaction between silica and bitumen through hydrogen
physical hardening did not diminish the bio-oil’s impact.149 bonds, and the hybrid bio-oil would replace the bitumen on
Oldham et al. found that the approximate addition of 16.6% the surface of silica and help to desorb the aged bitumen.155
bio-oil from swine manure could restore the m-value of Huang et al. derived a viscous liquid bio-oil from epoxidized
reclaimed asphalt pavement. The lengths of bee-like structures vegetable oil and added it to bitumen as a rejuvenator, in order
increased after bitumen aging. The introduction of the to investigate its effect on rheological and chemical parameters.
biorejuvenator caused a reduction of bee size. After the The biorejuvenator showed a bad effect on resistance to
addition of about 21% bio-oil, the bee size could be restored to rutting. The biorejuvenator could decrease the sulfoxide index
the original case. The bee length has an important role in of aged bitumen, but it did not restore the functional groups to
various bitumen parameters. As a result, the type of bio-oil has their original intensity. It reduced the values of average
a significant role in the bee structure and consequently affects molecular weight, polydispersity, and large molecular size in
the rheological and mechanical parameters (e.g., viscosity, aged bitumen.156
stiffness, and relaxation constant).99 Pahlavan et al. tried using Pahlavan and Fini showed that the presence of phenolic
a hybrid rejuvenator containing swine manure and algae to compounds in bio-oils from castor, miscanthus, wood pellet,
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corn stover, or waste vegetable oil could hinder sulfur adhesion between bitumen and aggregate is weakened by the
crystallization and control the thermal and mechanical presence of emulsifying agents such as salt and clay
behavior of bitumen. Wood-pellet oil contains a high amount compounds in the pavement and also by the adhesion of
of phenolic compounds. These compounds have phenoxyl water droplets to aggregate.162
radicals and interact with polysulfide radicals through electron 5.2. Problems. Water flows freely inside a bituminous
delocalization and hydrogen donation.116 mixture when the surface layer of bitumen contains a certain
Park et al. investigated the production of bio-oils from each amount of moisture. Also, water in the surface layer causes
of six biomasses (pine bark, walnut shells, fir, birch, peanut pressure because of the load of a vehicle on the surface. This
shells, or coconut husks) obtained from agricultural residue, part of the water gradually penetrates the interface between the
softwood, hardwood, or wood bark using pyrolysis. The bio- bitumen and the aggregate; the bitumen structure breaks and
oils are rich in phenolic compounds and could be used as causes the bitumen film to gradually separate from the surface
modifiers for bitumen to decelerate its aging process. The of the aggregate, ultimately leading to the deterioration of
efficacy of each bio-oil as an antiaging agent was dependent on adhesion between the bitumen and the aggregate. Adhesive
its phenolic compounds and how they could interact with free failure results in clean aggregate surfaces, grooving, and
radicals. Pine bark and walnut shells contained the highest sanding.163−168 A comprehensive explanation of the theories
content of phenolic compounds, while birch and peanut shells of adhesion phenomena between bitumen and aggregate can
had the lowest content. All six bio-oils could hinder the be found in the literature.169 The main cause of this
formation of the carbonyl group in the aging process; however, phenomenon is a decrease in the temperature of mixing and
fir was the best at delaying the formation of the sulfoxide compaction. A decrease in temperature causes the water in the
group.18 aggregate not to evaporate well, and the remaining moisture
Zheng et al. used three bio-oils (waste wood oil (WWO), prevents the material from being coated with bitumen.
WCO, and straw liquefied residue oil (SLRO)) for Moisture reduces the durability of pavement via pothole
disaggregation of nanoclusters of asphaltenes. They found formation, stripping, and raveling of the bitumen surface.
that WWO and WCO could disaggregate the nanoaggregates These phenomena result in driving accidents. The stiffness of
by increasing the activation energy. However, neither of those bitumen decreases after exposure to water. However, low water
bio-oils could restore the dispersion behavior of aged content caused a reverse effect and slightly increased the
asphaltenes to the original case. SLRO showed a negative stiffness. Mixtures possessing high air voids have a negative
effect on asphaltenes dispersion and was unable to disturb the effect on durability. Also, the relation between moisture
nanoclusters.157 exposure and durability was found to be reversible.170 The
presence of wax in a bio-oil can increase the rate of hydrate
5. MOISTURE SUSCEPTIBILITY formation, and the volume of hydrate particles is greater
The adhesion between aggregates and bitumen are impacted compared with those of wax-free oil models. As a result, the
by factors such as interlocking mechanism, physisorption and increased porosity of hydrate leads to water escaping from the
chemisorption.158 Moisture damage in asphalt pavements is hydrate shell and the water’s penetration into the surface. This
often a chemistry-driven and time-dependent phenomenon phenomenon is repeated when wax is present in bitumen. The
which is associated with polarizable and high acid content of presence of long chains of alkanes in wax prevents the
bitumen.159 Another reason for water damage to asphalt interaction of hydrate molecules through hydrogen bonding. It
pavements is that the bituminous mixtures have too much void increases the hydrate porosity, so water molecules can
space. The air-void ratio is between 8% and 12%, and water is penetrate into bitumen and affect its properties, causing
likely to attack the surface layer of the pavements.160 Guarin et promotion of moisture susceptibility.171
al. concluded that rapeseed oil and fish oil as biobinders 5.3. Solutions. To fix this problem, additives such as
changed the hydrophobic behavior of the binder to partially polymers, sulfur, rubber, antistripping agents, nanoparticles,
hydrophilic and increased the polarity of binder because of an and antioxidants have been applied to improve the adhesion
increase in the resins fraction. properties of binder and reduce the moisture susceptibility. If
5.1. Mechanisms. Despite the fact that several factors the surface of an aggregate is coated by such materials, the
cause a bituminous mixture to become bare at the same time, dominant electrical charge would be changed and the surface
all researchers have concluded that the main factor is water. energy of the aggregate would be reduced. Surfactants do the
Great efforts have been made to prevent water diffusion into opposite mechanism, as they would reduce the surface energy
pavement. However, the presence and penetration of water is of the binder and change the physicochemical properties of
unavoidable; there are different sources of water, each of which bitumen and aggregate.162,172−179 The Pneumatic Adhesion
enters the pavement structure in various ways. Stripping could Tensile Testing Instrument (PATTI) test and the pull-off test
happen through different mechanisms such as pore pressure, are standard tests for measuring tensile strength, and the peel
detachment, displacement, osmosis, hydraulic scouring, test is used to determine the fracture energy.180
emulsification, and spontaneously.161 Excessive pore pressure Hosseinnzhad et al. used biomodifiers in bitumen and tested
in undrained conditions causes the breaking of the bituminous the dewetting and moisture damage of the bitumen. Wood
layer around the aggregates and causes water to penetrate pellets, miscanthus, corn stover, and animal waste were the
between the bitumen and the aggregates. In the detachment main bio-oils applied in this study. Contact-angle measure-
mechanism, a thin layer of water covers the aggregate and ments showed that the bio-oils from animal source had higher
separates the bitumen from the aggregate. Because of the lack adsorption on a siliceous surface due to their amine-rich and
of complete coverage of the aggregate by bitumen, the polar functional groups.10 Dus et al. concluded that water films
adhesion of bitumen to stone materials is weakened by water in bitumen are formed during the aging period and depend on
and the bitumen is separated from the surface of the aggregate the bitumen and its characteristics. They claimed that aging
in displacement phenomena. In emulsification, the internal and moisture damage are related and should be considered
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simultaneously.181 The same conclusion was reported in content from 12 to 0.27 mg KOH/g. The acidity of bio-oil
another study.182 Water influences the kinetics of oxygen is a significant parameter for bitumen durability and moisture
reactions. Hence, both oxygen and moisture should be damage.188
considered as parameters affecting the chemical composition A hybrid bio-oil from swine manure (20% by weight) and
and stability of bitumen.183 algae (80% by weight) was produced and studied by Shariati et
Fini et al. showed that the composition of a rejuvenator al.155 They reported that the resistance to moisture damage
could affect its adsorption behavior to the surface of siliceous increased by introducing this hybrid bio-oil to bitumen.
minerals resulting in increasing the bitumen’s resistance to Generally, the main goal of using bio-oils in asphalt for
moisture damage. For instance, the presence of amide and reduction of moisture susceptibility is that they can improve
amine groups in a modifier could minimize its desorption from the binding between bitumen and aggregate and prevent water
siliceous stones in the asphalt mixture.184 Mousavi et al. penetration into the asphalt matrix.
studied four types of biomodifiers (swine manure, waste
vegetable oil, algae oil, and a mixture of swine manure and 6. TEST ANALYSES PERFORMED IN THE LITERATURE
algae) to test their effect on bitumen’s susceptibility to Table 1 shows the tests and analyses performed in studies as
moisture. They showed that there are two important measures solutions to overcome physical aging, chemical aging, and
that affect moisture susceptibility: polarizability, and the moisture susceptibility, in order to understand the role of
moisture-induced shear-thinning index (MISTI) value. The various bio-oils as additives and rejuvenators of bituminous
MISTI is an indictor used to evaluate susceptibility of a mixtures and bitumen.
bitumen-aggregate interface to moisture damage.185 Lower 6.1. Bio-Oil Properties and Effects. Table 2 shows a
values of polarizability and MISTI values closer to 1.0 indicate summary of the effects of different bio-oils on the stiffness,
lower moisture susceptibility. Among these four bio-oils, waste viscosity, chemical aging, and moisture damage of bitumen in
vegetable oil showed the highest susceptibility to moisture bituminous mixtures. Also, the table shows the physical
because of the existence of long-chain alkanes and fatty acids. characteristics of the bio-oils used in the literature.
The mixture of swine manure and algae oil showed the best The effect of various bio-oil additions to bitumen on its
values for polarizability and MISTI and hence the lowest stiffness and physical hardening have been investigated via
moisture susceptibility. Algae oil and swine manure individu- different analyses and parameters. The influence of each bio-oil
ally came after that.186 on the decrease or increase of a specific parameter of stiffness is
Among the four types of bio-oils from corn stover, wood mentioned in Table 2. Since there are different parameters for
pellet, swine manure, and miscanthus that were produced various bio-oils, a decisive conclusion could not be made as to
through a hydrothermal liquefaction process and pyrolysis by which bio-oil has the highest impact on bitumen stiffness.
Hosseinnezhad et al., wood pellet showed the lowest surface However, modified bitumen with waste cooking oil, swine
tension, which indicates a better wettability behavior.143 A manure, seaweed, wood, waste vegetable cooking oil, and
mixture of hexadecanamide and hecadecanoic acid from animal miscanthus showed better effects. Viscosity as a rheological
and plant bio-oils as two surfactants added to bitumen by property is another important characteristic of bitumen that is
Hung et al. had a great influence on the wettability and affected by bio-oil modification. The changes in viscosity of
morphology of the interface between bitumen and glass.148 bitumen after the addition of different bio-oils are considered
Fernandes et al. showed that the moisture sensitivity of the in this table based on the data in the literature. As shown, in
modified mixture was reduced after the addition of waste most cases, bio-oil would decrease the viscosity of the bitumen
motor oil, SBS, and waste rubber to bitumen.96 Rajib et al. mixture. The data shown for viscosity are in the range of 120−
applied rejuvenators to study the susceptibility of asphalt to 140 °C. The third characteristic that is investigated in this
moisture damage. Some of the modifiers had a negative effect paper is chemical aging. It is usually analyzed in the literature
on hindering moisture damage because of their chemical through either SARA analysis or carbonyl and sulfoxide
nature. The restoration capacity and polarizability of indexes. A comparison of the effects of different bio-oils on
rejuvenators influenced the amount of resistance to moisture the chemical aging behavior of pristine bitumen and the
damage. Rejuvenators with lower polarizability showed better variations of carbonyl and sulfoxide indexes are also shown in
results.187 Table 2. Swine manure and vegetable oil are two bio-oils that
Kabir et al. used bitumen modified with bio-oils derived when added to bitumen caused lower values of the carbonyl
from wood pellet, waste vegetable oil, corn stover, miscanthus, and sulfoxide indexes in modified bitumen after aging. For
or castor oil. They showed that all of the bio-oils except some bio-oils, the change in the wt % of aromatics, resins, and
miscanthus demonstrated low levels of moisture susceptibility. asphaltenes is representative of the bio-oil’s efficacy at resisting
This means that the chemical composition of a bio-oil has an chemical aging. Table 2 compares the SARA fractions of
important role in its efficacy as a bitumen modifier.151 In bitumen before and after the addition of rapeseed, fish, or
another work with similar materials to their previous study, vegetable oils. As shown, the weight percents of resins and
Wang et al. demonstrated that bitumen biomodified with asphaltenes fractions have diminished, which indicates the
cotton showed higher moisture resistance.111 Oldham et al. positive effect of these bio-oils on the chemical aging of
reduced the acidic content of waste cooking oil using the bitumen and restoring its characteristics.
esterification process and used it for bitumen rejuvenation. The effectiveness of adding bio-oils to bitumen to increase
They tested the effect of acidic compounds on the moisture the resistance to moisture damage can be measured by a
susceptibility of bitumen. The results showed that acidic reduction of surface tension, a reduction of contact angle, or a
compounds could be substituted by water molecules, which is value of the moisture-induced shear-thinning index (MISTI)
bad for bitumen. As a result, detraction of acidic compounds in closer to 1.0. MISTI is an indicator used to evaluate the
waste cooking oil leads to enhancement of the resistance to susceptibility of a bitumen-aggregate interface to moisture
moisture damage. Esterification could decrease the acid damage.189 As shown in Table 2, various bio-oils have been
4800 https://doi.org/10.1021/acs.energyfuels.2c03824
Energy Fuels 2023, 37, 4791−4815
 Table 1. Tests Performed to Investigate the Impact of Bio-Oils on Bitumen’S Properties
Ref. Bio-oil source Tests and models performed
91 Switchgrass Rotational viscometer (RV), Arrhenius-type and power law models, viscosity temperature susceptibility (VTS), shear susceptibility values (SS), activation energy Ea
92 Oakwood RV, Arrhenius-type and power law models, VTS, SS, activation energy Ea
93 Swine manure Fourier transform infrared spectroscopy (FTIR), RV, dynamic shear rheometer (DSR), rolling thin-film oven (RTFO), pressure aging vessel (PAV), bending beam rheometer
Energy & Fuels

(BBR)
94 Waste wood Dynamic modulus, indirect tensile (IDT) strength, asphalt pavement analyzer (APA), four-point beam fatigue
143 Corn stover, wood pallet, swine Thermogravimetric analysis, attenuated total reflectance Fourier-transform infrared spectroscopy (ATR-FTIR), thin-layer chromatography with flame ionization detection (TLC-
manure, miscanthus FID), gel permeation chromatography (GPC), gas chromatography−mass spectroscopy (GC−MS), H NMR and C NMR, DSR, surface tension (drop shape analyzer),
95 Rapeseed, fish RV, DSR, RTFO, PAV, BBR, SARA analysis, differential scanning calorimetry (DSC), atomic force microscopy (AFM), surface free energy (sessile drop), universal sorption device
(USD)
147 Waste wood Element composition and GC-MS characterization, RTFO, PAV, automated flocculation titrimetry (AFT)
148 Animal- and plant-derived AFM, ATR-FTIR, and contact-angle measurement
96 Waste motor oil FTIR, DSR, wheel-tracking test, fatigue cracking resistance
149 Vegetable RTFO, PAV, SARA (saturates, aromatics, resins, asphaltenes) fractionation, TLC-FID, AFM, DSC, BBR
97 Municipal solid waste Gas chromatograph (GC), FTIR spectroscopy, accelerated aging, RV
98 Waste cooking oil FTIR, RV, rutting resistance and fatigue cracking resistance (complex module and phase angle), DSR
99 Swine manure RTFO, PAV, carbon-hydrogen-nitrogen-sulfur (CHNS) analyzer, ATR-FTIR, RV, thermoelectric bending beam rheometer (TE-BBR), direct tension system (DT), AFM
101 Pine tree DSR, dynamic viscosity
28 Palm kernel RTFO, RV, activation energy (Ea), thermogravimetric analysis (TGA), DSC, FTIR
103 Seaweed FTIR, TGA, GPC, AFM, scanning electron microscopy (SEM), fluorescence microscopy (FM), DSR
104 Waste cooking oil FTIR, RV, DSR, BBR
105 Vegetable RTFO, PAV, DSR, BBR, frequency sweep, penetration and softening point, viscosity

4801
106 Wood FTIR, attenuated total reflectance (ATR), TLC-FID, RV, DSR
151 Wood pellet, waste vegetable oil, TLC-FID, multiple stress creep recovery (MSCR), segregation test, bitumen bond strength (BBS), ATR-FTIR, quantum mechanical calculations
corn stover, miscanthus, castor oil
pubs.acs.org/EF

107 Swine manure, miscanthus pellet, BBR, finite element model

corn stover, wood pellet
108 Swine manure FTIR, DSC, TGA, DSR
109 Waste vegetable cooking oil Penetration, softening point, viscosity, DSR, rutting factor, fatigue factor, BBR, RTFO, PAV
(sunflower)
110 Corn stover, castor oil, miscanthus, DSR, ATR-FTIR, MSCR
wood pellets, waste vegetable oil
3, Cotton RTFO, PAV, BBR, temperature sweep, RV, frequency sweep, SARA fractioning, linear amplitude sweep (LAS), MSCR, DSR, FM, FTIR
111
188 Waste cooking oil GC-MS, FTIR, RTFO, PAV, DSR, Glover-Rowe (G-R) parameter analysis, moisture-induced shear-thinning index (MISTI)
112 Soybean, straw, vegetable oil, castor Temperature sweep (TS), MSCR, BBR, FTIR, SEM
oil, waste oil
155 Swine manure, waste cooking oil RTFO, PAV, nonperiodic density functional theory (DFT), DSR, MISTI
113 Swine manure RTFO, PAV, dynamic light scattering (DLS), field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), FTIR, DSR, DT, inverse gas
chromatography-surface energy analyzer (iGC-SEA)
114 Rapeseed DSR, RTFO, VTS, FTIR-ATR, modulated differential scanning calorimetry (MDSC)
115 Waste cooking oil Penetration, softening point, specific gravity, penetration index
156 Vegetable RFTO, PAV, MSCR, LAS, DSR, FTIR, GPC
116 Castor oil, miscanthus, wood pellet, GC-MS, Anton Paar modular compact rheometer, DFT
corn stover, waste vegetable oil
18 Pine bark, walnut shells, fir birch, Differential thermogravimetry (DTG), TG-FTIR, GC-MS, RTFO, DFT
Review

peanut shells, coconut husks

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https://doi.org/10.1021/acs.energyfuels.2c03824
Energy & Fuels pubs.acs.org/EF Review

used for this purpose, and almost all of them except cotton
could reduce the moisture damage in bitumen. In Table 2, if
there is not a parameter in the literature measuring the change
in physical hardening, chemical aging, or moisture damage, the
cells are filled with N/A (not available). If the effect of a bio-oil
on these parameters is only mentioned qualitatively in the
literature, then its effect is expressed as “decrease” or “increase”
in Table 2, without a variation percentage.

7. CHALLENGES, GAPS, AND PERSPECTIVES

These are four gaps in the current literature regarding bio-oils:
7.1. The Lack of Standard Methods for Performance
Characteristics and Reporting of Each Bio-Oil’s Effects
in Bitumen. There are different methods to characterize the
performance of bitumen modified by bio-oils. Some research
studies have used basic performance indexes such as
penetration, ductility, and softening point for performance
characteristics of bio-oil-modified bitumen, while others have
evaluated the effect of bio-oils on the chemo-rheological
SARA analysis, FTIR, GPC, TGA, DSC, environmental scanning electron microscopy (ESEM), AFM, DSR

properties of bitumen modified by bio-oils thorough more

advanced techniques. For example, Girimath and Singh193 used
Tests and models performed

waste wood biomass to produce bio-oil and introduced

different dosages of bio-oil to bitumen. The results showed
that the penetration value of the base bitumen increased with
an increase in bio-oil content. However, an increase in bio-oil
content decreased the softening point and viscosity of the
bitumen. Pahlavan, Rajib, Deng, Lammers, and Fini194 studied
a bio-oil produced through a balanced feedstock of swine
manure and algae as a bitumen modifier. The crossover
modulus and crossover frequency results showed that the bio-
oils were able to increase the crossover modulus and crossover
frequency values, indicating improved performance of the
bitumen. The effect of groundnut shell bio-oil on the
performance of bitumen was examined by Singh, Yenare, and
RTFO, PAV, TG, FTIR, frequency sweep, MSCR, LAS

Showkat.195 They reported that the Delta T Critical (ΔTc) of

RTFO, PAV, DSR, frequency sweep, MSCR, FTIR

all dosages of bio-oil modification sustained the m-controlled

nature of the base bitumen, and 10% bio-oil improved the
relaxation characteristics of the bitumen. Also, the results
indicated an enhancement in the recovery potential of bitumen
modified by groundnut shell bio-oil. G-R parameters were used
by Haghshenas, Nsengiyumva, Kim, Santosh, and Amelian196
to evaluate the effect of soybean oil on the performance of
bitumen. The modified bitumen showed better midtemper-
ature cracking resistance than the control bitumen. Although
researchers have attempted to examine the effect of bio-oils on
DSC, sessile drop

the performance characteristics of bitumen using different

methods, there is a need to develop a standard method for
performance characterization of these materials.
7.2. The Lack of Long-Term Field Performance Data
to Conduct Comprehensive Life-Cycle Assessments and
Life-Cycle Analyses. Recently, several research projects were
developed and implemented to understand the field perform-
ance of asphalt pavements containing bio-oils. Xie, Tran,
Julian, Taylor, and Blackburn197 used a bio-oil produced
Bio-oil source

through fast pyrolysis of pine trees and a bio-oil derived from

fatty acid in asphalt pavements with 25% recycled asphalt
Waste plastic film
Bamboo charcoal
Table 1. continued

pavement (RAP) and 5% recycled asphalt shingles (RAS). The

Clean wood

two-year field performance data showed that all pavement

Soybean

sections including the ones with bio-oils had a good ride

quality. However, the bio-oils did negatively affect the rutting
performance of the pavement sections, and the pavement
sections with these oils were more prone to crack. More
Ref.
117
118
119
120

recently, the National Center for Asphalt Technology (NCAT)

4802 https://doi.org/10.1021/acs.energyfuels.2c03824
Energy Fuels 2023, 37, 4791−4815
 Table 2. Studies of Bio-Oils, Giving Each Bio-Oil’s Source, Composition, and Effects on Bitumen’s Properties
Chemical Moisture dam- Density Viscosity
Ref. Bio-oil source Composition Stiffness Viscosity aging age (kg·m3) pH (@ Temp.)
91 Switchgrass p-Hydroxylphenyl, guaiacyl, syringyl N/A Decrease N/A N/A N/A N/A N/A
92 Oakwood N/A N/A Decrease N/A N/A N/A N/A N/A
Energy & Fuels

93 Swine manure N/A BBR creep Decrease Carbonyl N/A 1010 N/A N/A
stiffness: index: 33.3%
4.76% de- decrease
crease
Sulfoxide
index: 31.6%
decrease
94 Waste wood N/A Indirect tensile N/A N/A N/A 1200 2.50 0.10 Pa·s
strength: (135 °C)
16.7% de-
crease
143 Corn stover Conessine, 10-methyl-8-tetradecan-1-ol acetate, propanoic acid, 2-(3acetoxy-4,4,14-trimethylandrost-8-en- N/A N/A wt % asphal- Surface tension: 2.87 N/A 1250
17-yl), 4H-1-benzopyran-4-one,2-(3,4-dimethoxyphenyl)-3,7-dimethoxy, 2H-1-benzopyran-3-carboxylic tenes: 167% 31 dyn/cm
acid, 2-ethoxy-2,4-diphenyl-, ethyl ester, cholestan-3-one, cyclic1,2 ethanediyl aetal, cyclohexane, 1,4- increase
dimethyl-2-octadecyl wt % resins:
65% increase
wt % aro-
matics: 95%
decrease
138 Wood pellet Ingol 12-acetate, (7a-isopropenyl-4,5-dimethyloctahydroinden-4-yl)methanol, methenolone, E-10, 13, 13- N/A N/A wt % asphal- Surface tension: 2.80 N/A 1230
trimethyl-11-tetradecen-1-ol acetate, cyclohexane, 1,4-dimethyl-2-octadecyl-, 7-(2-hydroxy-1-methyl- tenes: 111% 28 dyn/cm
ethyl)-1, 4adimethyldecahydronaphthalen-2-ol, acetic acid, spiro[4.5]decan-7-one, 1,8-dimethyl-8,9- increase

4803
epoxy-4-isopropyl wt % resins:
90% increase
wt % aro-
matics: 98%
pubs.acs.org/EF

decrease
Swine manure N/A N/A N/A wt % asphal- Surface tension: 5.97 N/A 960
tenes: 67% 38 dyn/cm
increase
wt % resins:
77.5% in-
crease
wt % aro-
matics: 81%
decrease
Miscanthus 10-(Methoxycarbonyl)-N-acetylcochinol, 4-H-benzopyran-4-one, 2-(2,6-dimethoxyphenyl)-5,6-dime- N/A N/A wt % asphal- Surface tension: 2.95 N/A 1050
thoxy-, N-carboxylethylcolchiceine, propanoic acid, 2-(3acetoxy-4,4,14-trimethylandrost-8-en-17-yl), tenes: 200% 35 dyn/cm
2H-1-benzopyran-3-carboxylic acid, 2-ethoxy-2,4-diphenyl-,ethyl ester, acetic acid, 10-methyl-8- increase
tetradecan-1-ol acetate wt % resins:
52.5% in-
crease
wt % aro-
matics: 81%
decrease
95 Rapeseed N/A Indirect tensile N/A wt % asphal- Contact angle: N/A N/A 15.60
strength: tenes: 1% 24% decrease mm2/s
31.4% de- increase (60 °C)
crease
Review

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 Table 2. continued
Chemical Moisture dam- Density Viscosity
Ref. Bio-oil source Composition Stiffness Viscosity aging age (kg·m3) pH (@ Temp.)
wt % resins:
36% increase
Energy & Fuels

wt % aro-
matics: 12%
decrease
Fish Ethyl ester Dynamic N/A wt % asphal- Contact angle: N/A N/A 10.50
shear: tenes: 10% 28% decrease mm2/s
16.27% de- increase (60 °C)
crease
wt % resins:
21% increase
wt % aro-
matics: 10%
decrease
147 Waste wood Furfural, 3-methyl-1, 2-cyclopentandione, phenol, 2-methoxyphenol, cresol, 2-methoxy-4-methylphenol, 2- N/A N/A Carbonyl N/A N/A N/A N/A
methoxy-4-vinylphenol, eugenol, 2,6 dimethoxyphenol, isoeugenol, levoglucosan, 4-allyl-2,6 dimethox- index: 10%
yphenol, 3,5 dimethoxy-4-hydrobenzaldehyde increase
Sulfoxide
index: 40%
increase
148 Animal- and hexadecanamide and hecadecanoic acid N/A N/A Decrease Contact angle: N/A N/A N/A
plant-de- 37.5% decrease
rived for amide-
based, 16%

4804
decrease for
acid-based
96 Waste motor N/A Dynamic stiff- N/A N/A Decrease N/A N/A N/A
oil ness modu-
pubs.acs.org/EF

lus: 12% de-

crease
149 Vegetable N/A Stiffness index: N/A wt % asphal- N/A N/A N/A N/A
without tenes: 20%
change decrease
wt % resins:
7% decrease
wt % aro-
matics: 25%
increase
97 Municipal Heterocyclic, benzene (including phenolic)-based and long-chain aliphatic acids, ketone, ester N/A Decrease: N/A N/A 972 N/A N/A
solid waste 44%
98 Waste cook- N/A Fatigue factor: Increase: N/A N/A N/A N/A N/A
ing oil 28.6% de- 135%
crease
99 Swine manure Hexadecanamide, hexadecanoic acid, tetradecanal o-methyloxime, 2-tridecanone o-methyloxime, n-butyl Stiffness: Decrease: Average length N/A
octadecanamide, octadecanoic acid, cholest-7-ene, cholest-3-ene, cholest-4-ene, and vitamin-E 33.5% de- 81% of bee struc-
crease ture: 30%
decrease
101 Pine tree N/A Penetration: Decrease: N/A N/A N/A N/A 0.025, 0.04
360% in- 53% Pa·s
crease (40 °C)
28 Palm kernel amide (−NH), carbamate (−CN), and urethane carbonyl groups N/A Decrease or Decrease N/A 1114 10−11 1313.3 cP
Review

Increase (25 °C)

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 Table 2. continued
Chemical Moisture dam- Density Viscosity
Ref. Bio-oil source Composition Stiffness Viscosity aging age (kg·m3) pH (@ Temp.)
(based on
bio-oil
Energy & Fuels

dosage)
103 Seaweed N/A Softening N/A Decrease N/A
point: 42 °C
increase
104 Waste cook- saturated hydrocarbons, unsaturated hydrocarbons, sulfinyl compounds, amides, and esters Bending creep Decrease: N/A N/A 950 6.1 0.1463 Pa·s
ing oil stiffness: 64% (25 °C)
1033.3% de-
crease
105 Vegetable N/A Penetration: Decrease: Decrease/In- N/A 1100 N/A 0.405 Pa·s
18.2% in- 15% crease (60 °C)
crease (based on
bio-oil dos-
age)
106 Wood Ester Penetration: Decrease: N/A N/A N/A N/A 712 mm2/s
198.05% in- 62.5% (60 °C)
crease
151 Wood pellet Similar to 40 N/A N/A Decrease Decrease 1230 2.80 N/A
Waste vegeta- N/A 1250 2.87 N/A
ble
Corn stover Similar to 40 1050 2.95 N/A
Miscanthus Similar to 40 950 6.10 0.1463 Pa·s
(25 °C)

4805
Castor N/A 1100 N/A 0.405 Pa·s
(60 °C)
107 Swine manure N/A Recovery ratio: N/A N/A N/A N/A N/A N/A
116.1% in-
pubs.acs.org/EF

crease
Miscanthus N/A Recovery ratio: N/A N/A N/A
pellet 103.2% in-
crease
Corn stover N/A Recovery ratio: N/A N/A N/A
25.8% in-
crease
Wood pellet N/A Recovery ratio: N/A N/A N/A
29.0% in-
crease
108 Swine manure N/A Phase angle: N/A N/A N/A N/A N/A N/A
3.4% de-
crease
109 Waste vegeta- Linoleic acid, oleic acid, palmitic acid, stearic acid, palmiotetic acid, elcosatrienoic acid, linoleic acid Penetration: N/A Decrease N/A N/A N/A N/A
ble cooking 233.3% in-
oil (sun- crease
flower)
110 Corn stover N/A Complex mod- N/A Decrease N/A 1250 N/A N/A
ulus: 122.2%
decrease
Castor oil N/A Complex mod- 881
ulus: 25.0%
decrease
Review

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 Table 2. continued
Chemical Moisture dam- Density Viscosity
Ref. Bio-oil source Composition Stiffness Viscosity aging age (kg·m3) pH (@ Temp.)
Miscanthus N/A Complex mod- 1050
ulus: 130.0%
Energy & Fuels

decrease
Wood pellets N/A Complex mod- 1230
ulus: 87.5%
decrease
Waste vegeta- N/A Complex mod- 898
ble ulus: 60.0%
decrease
3, Cotton Epoxy N/A N/A Decrease MISTI: 6% de- 1030 N/A N/A
111 crease
188 Waste cook- Similar to 52 N/A N/A Decrease MISTI: 14% de- N/A N/A N/A
ing oil crease
112 Soybean N/A Stiffness mod- N/A N/A N/A 980 N/A 130.4 Pa·s
ulus: 29.6% (60 °C)
decrease
Straw N/A Stiffness mod- 980 N/A 121.3 Pa·s
ulus: 36.0% (60 °C)
decrease
Vegetable N/A Stiffness mod- 940 N/A 85.4 Pa·s
ulus: 54.3% (60 °C)
decrease
Castor oil N/A Stiffness mod- 990 N/A 129.5 Pa·s
ulus: 87.5% (60 °C)

4806
decrease
110 Waste oil N/A Stiffness mod- 920 N/A 88.6 Pa·s
ulus: 62.9% (60 °C)
decrease
pubs.acs.org/EF

155 Swine manure Similar to 48 and 49 N/A N/A Decrease N/A N/A N/A N/A
Waste cook- Similar to 52 N/A N/A Decrease MISTI: 15% de-
ing oil crease
113 Swine manure Similar to 48 and 49 Rutting resist- N/A Carbonyl N/A N/A N/A N/A
ance: 14.0% index: 33.3%
increase decrease
Sulfoxide
index: 83.3%
decrease
114 Rapeseed Fatty acid methyl ester Rutting pa- Decrease: N/A N/A N/A N/A N/A
rameter: 70%
17.9% de-
crease
115 Waste cook- N/A Penetration: N/A N/A N/A N/A N/A N/A
ing oil 22.22% in-
crease
156 Vegetable N/A N/A N/A Carbonyl N/A 1100 N/A 0.405 Pa·s
index: 84% (60 °C)
decrease
Sulfoxide
index: 54%
decrease
Review

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 Table 2. continued
Chemical Moisture dam- Density Viscosity
Ref. Bio-oil source Composition Stiffness Viscosity aging age (kg·m3) pH (@ Temp.)
116 Castor oil N/A Complex mod- N/A Decrease N/A N/A N/A N/A
ulus: 90%
Energy & Fuels

decrease
Miscanthus Similar to 40 Complex mod- 1050 2.95 N/A
ulus: 80%
decrease
Wood pellet Similar to 40 Complex mod- 1230 2.80 N/A
ulus: 90.5%
decrease
Corn stover Similar to 40 Complex mod- 1250 2.87 N/A
ulus: 82%
decrease
Waste vegeta- N/A Complex mod- N/A N/A N/A
ble ulus: 85%
decrease
18 Pine bark Catechol, 4-alkylcatechol, aromatics N/A N/A Carbonyl N/A N/A N/A N/A
index: 20%
increase
Sulfoxide
index: 21%
increase
Walnut shells Phenol, alcohol, ester, ketone, aldehyde Carbonyl
index: 73%
increase

4807
Sulfoxide
index: 29%
increase
Fir Alcohol, phenol (palkylphenol and o-guaiacol), ether, carboxylic acids Carbonyl
pubs.acs.org/EF

index: 127%
increase
Sulfoxide
index: with-
out change
Birch Ester, carboxylic acids, aldehydes Carbonyl
index: 67%
increase
Sulfoxide
index: 93%
increase
Peanut shells Ketone, alcohol, aldehyde, phenol Carbonyl
index: 87%
decrease
Sulfoxide
index: 14%
decrease
Carbonyl
index: 47%
increase
17 Coconut Alcohol, ketone, ether, phenol Sulfoxide
husks index: 36%
increase
Review

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 Table 2. continued
Chemical Moisture dam- Density Viscosity
Ref. Bio-oil source Composition Stiffness Viscosity aging age (kg·m3) pH (@ Temp.)
117 Clean wood N/A Decrease: N/A N/A N/A N/A N/A
91%
Energy & Fuels

118 Bamboo char- Ethanone, 1-(2-furanyl)-, furan-2-carbonyl chloride, tetrahydro-, 2-cyclopenten-1-one, 2,3-dimethyl-, 2- Complex mod- N/A N/A N/A N/A N/A 43.13 cP
coal ethyl-3-methylcyclopent-2-en-1-one, phenol, phenol, 2-methoxy-, phenol, 2-methyl-, phenol, 3-methyl-, ulus: 65.6% (60 °C)
creosol, phenol, 4-ethyl-, phenol, 4-ethyl-2-methoxy-, phenol, 3,4-dimethyl-, phenol, 2,6-dimethoxy-, 17- decrease
pentatriacontene, 3,5-dimethoxy-4-hydroxytoluene, dasycarpidan-1-methanol, acetate (ester), hexade-
canoic acid, methyl ester, 10-octadecenoic acid, methyl ester, butanoic acid
119 Soybean Saturated fatty acid, ether, alkane Complex mod- N/A Decrease N/A N/A N/A N/A
ulus: 85%
decrease
120 Waste plastic Alkyl aliphatic and aromatics, phenol, alcohol, amino acid Complex mod- N/A N/A N/A N/A N/A N/A
film ulus: 67%
decrease
190 Waste cook- N/A Rutting factor: Decrease: N/A N/A 1130 6.7 0.4 Pa·s
ing oil 90% de- 55% (135 °C)
crease
191 Clean wood N/A N/A Increase: N/A N/A 1125 N/A N/A
130%
192 Tall N/A N/A N/A wt % asphal- Decrease N/A N/A 0.034 Pa·s
tenes: 96% (60 °C)
decrease
wt % resins:
89% increase
wt % aro-

4808
matics: 8%
decrease
pubs.acs.org/EF
Review

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Energy & Fuels pubs.acs.org/EF Review

used a bio-oil in an asphalt containing 20% RAP and 5% RAS. because of their limited application and the lack of accurate
The field performance data indicated that the bio-oil did not technoeconomic analysis on industrial bio-oils. Bio-oil
deteriorate the ride quality and rutting performances of production needs energy for three steps: dewatering the wet
pavement sections although it accelerated the failure related biomass to dry biomass, heating dried biomass to the pyrolysis
to cracking. In another study, field performance data collected temperature, and decomposing the biomass during the reaction
by Bastola, Khedmati, and Haghshenas198 showed that the use of pyrolysis.206 The costs associated with the energy needed to
of a bio-oil in the second layer of a pavement structure might produce bio-oils result in an increase in the cost of bio-oil
have indirectly resulted in more cracks (fatigue and thermal) production. As a result, some bio-oils may not be able to
and ruts in the surface layer after two years. These studies compete with fossil fuel products.207 In addition, there are
provide some information on the performance of pavement other costs that need to be taken into account for biomass
sections built using bio-oils; however, more demo projects and collection, handling, and storage. More importantly, a bio-oil
longer-term field mentoring data are needed to conduct cannot be added directly to bitumen due to safety concerns if
comprehensive life-cycle assessments and life-cycle analyses. the bio-oil has large amounts of water (30%−40%) and volatile
7.3. High Variation among Bio-Oils Made from the compounds.208 This concern can be addressed by improving
Same Feedstock through Different Processing Meth- the bio-oil production procedures; for example, the water can
ods, Leading to Variations in Performance. The be removed at a reduced temperature of about 95 °C.
composition of a bio-oil is a complex function of several However, the moisture sensitivity of asphalt must be carefully
factors: feedstock, pyrolysis technique, char-removal system, evaluated before using the produced bio-oils, since the
condensation system, and storage conditions. The performance performance of asphalt can significantly be influenced by
of a bitumen modified by a bio-oil is dependent on the source moisture. In addition, the main hurdles that limit the
and preparation method of the bio-oil. Wang, Jing, Zhang, application of seed bio-oils are the relatively low bio-oil yields
Cao, and Lyu199 made bio-oil from swine manure through a from plant seed and a production/collection process that is
fast-pyrolysis process at 550 °C under a reaction time of 1 s. time-consuming and labor intensive.209 Some researchers
They reported that the swine manure bio-oil improved the recommended using chemical solvents such as n-hexane to
workability of the bitumen; however, the bio-oil negatively increase oil yields. However, using chemical solvents can
affected the high-, low-, and midtemperature performance of significantly increase the cost of bio-oil production.210
bitumen. In contrast, Fini, Kalberer, and Shahbazi200 used a Therefore, research studies should be directed to produce a
thermochemical liquefaction process to produce bio-oil from bio-oil that is safe, cost-effective, and can be simply introduced
swine manure at 305 °C under 10.3 MPa pressure for a 80 min to bitumen at the larger scale.
residence time. The results showed that the bio-oil improved
bitumen’s low-temperature properties and its workability. 8. CONCLUSIONS
Similar findings were reported by Mills-Beale, You, Fini,
Zada, Lee, and Yap.93 Portugal, Lucena, Lucena, Costa, and de The significant emphasis on sustainability and carbon
Lima201 investigated the effect of fresh and waste maize oils on sequestration combined with the increasing price of bitumen
the performance of bitumen. It was found that the use of waste used as a binder in asphalt roads has promoted the use of
maize oil resulted in a higher reduction in the viscosity of the environmentally friendly materials such as bio-oils. Currently,
bitumen, while fresh maize oil had lower stability at different there is no comprehensive review of bio-oils made from
temperatures. Samara, Offenbacker, Mehta, Ali, Elshaer, and different feedstocks and the bio-oils’ effects on asphalt
Decarlo202 studied the effect of organic and petroleum properties. This review paper studied the effects of various
products on the performance of bitumen modified by these bio-oils on bitumen properties and showed that bio-oils can
oils. They reported that corn- and vegetable-oil-modified decelerate the rate of aging in neat bitumen and restore aged
bitumen were less susceptible to aging compared to tall oil, and bitumen. Bitumen modified by bio-oils can make asphalt more
aromatic extract oil. However, a research study performed by resistant to chemical aging, physical aging, and moisture
Fini, Hosseinnezhad, Oldham, Chailleux, and Gaudefroy203 damage. Bio-oils’ molecular species such as phenolic
showed that bio-oil derived from corn stover is more compounds work as free-radical scavengers to delay oxidation
susceptible to aging compared to swine manure bio-oil. The (also referred to as chemical aging). Bio-oils work to improve
effect of corn oil and soybean oil as bitumen modifiers was the solubility of wax within the total mixture and prevent wax
evaluated by Ji, Yao, Suo, You, Li, Xu, and Sun.204 It was crystallization (also referred to as physical aging). Bio-oil
reported that the viscosity and stiffness of bitumen were molecules such as N-methyl-2-pyrrolidone, harmane, and 1-
decreased, which in turn improved the resistance to fatigue and butyl-piperidine with high affinity toward aggregates increase
the low-temperature cracking resistance of bitumen. Con- bitumen’s binding to stone aggregates and reduce water
versely, the results presented by Haghshenas, Rea, Reinke, intrusion into the bitumen−aggregate interface, improving the
Yousefi, Haghshenas, and Ayar205 showed that bitumen resistance of asphalt to moisture damage. This review has
modified with corn oil did not pass the bending beam identified the following critical research gaps: (1) the lack of
rheometer (BBR) relaxation criterion (m-value ≥ 0.300) at low standard methods for evaluating and reporting the perform-
temperatures after the extended aging process. These contra- ance characteristics of each bio-oil in bitumen; (2) the lack of
dictory observations show that the source and preparation long-term field-performance data on bio-oils to support
method of bio-oils significantly affects the performance of comprehensive life-cycle assessments and life-cycle analyses;
bitumen modified by the bio-oils. (3) high variation among bio-oils made from the same
7.4. The Lack of Accurate Technoeconomic Analysis feedstock through different processing methods, leading to
on Industrial Bio-Oils to Facilitate Entry of Bio-Oils into variation in performance characteristics; (4) the lack of
the Asphalt Market. The larger scale production and use of accurate technoeconomic analysis on industrial bio-oils to
bio-oils in asphalt pavement construction can be challenging facilitate the entry of bio-oils into the asphalt market.
4809 https://doi.org/10.1021/acs.energyfuels.2c03824
Energy Fuels 2023, 37, 4791−4815
Energy & Fuels pubs.acs.org/EF Review

■ ASSOCIATED CONTENT
Data Availability Statement
(6) Hosseinnezhad, S.; Zadshir, M.; Yu, X.; Yin, H.; Sharma, B. K.;
Fini, E. Differential Effects of Ultraviolet Radiation and Oxidative
Aging on Bio-Modified Binders. Fuel 2019, 251, 45−56.
All data, models, and code generated or used during the study (7) Habal, A.; Singh, D. Influence of recycled asphalt pavement on
appear in the submitted article. interfacial energy and bond strength of asphalt binder for different
types of aggregates. Transp. Res. Rec. 2018, 2672 (28), 154−166.
■ AUTHOR INFORMATION
Corresponding Author
(8) Fallah, F.; Khabaz, F.; Kim, Y.-R.; Kommidi, S. R.; Haghshenas,
H. F. Molecular dynamics modeling and simulation of bituminous
binder chemical aging due to variation of oxidation level and saturate-
Elham H. Fini − School of Sustainable Engineering and the aromatic-resin-asphaltene fraction. Fuel. 2019, 237, 71−80.
Built Environment, Arizona State University, Tempe, Arizona (9) Haghshenas, H. F.; Rea, R.; Reinke, G.; Zaumanis, M.; Fini, E.
85287-3005, United States; orcid.org/0000-0002-3658- Relationship between colloidal index and chemo-rheological proper-
0006; Email: efini@asu.edu ties of asphalt binders modified by various recycling agents. Constr.
Build. Mater. 2022, 318, 126161.
Authors (10) Hosseinnezhad, S.; Shakiba, S.; Mousavi, M.; Louie, S. M.;
Karnati, S. R.; Fini, E. H. Multiscale evaluation of moisture
Abolhasan Ameri − Department of Chemical Engineering,
susceptibility of biomodified bitumen. ACS Appl. Bio Mater. 2019, 2
Shiraz Branch, Islamic Azad University, Shiraz 74731- (12), 5779−5789.
71987, Iran (11) Raman, N. A. A.; Hainin, M. R.; Hassan, N. A.; Ani, F. N. A
Hamzeh F. Haghshenas − Turner-Fairbank Highway review on the application of bio-oil as an additive for asphalt. J.
Research Center, Federal Highway Administration (FHWA), Technol. 2015, 72 (5), 105−110.
McLean, Virginia 22101, United States; orcid.org/0000- (12) Fini, E. H.; Oldham, D.; Abu-Lebdeh, T. Synthesis and
0002-4234-4536 Characterization of Bio-Modified Rubber (BMR) asphalt: A
sustainable waste management solution for scrap tire and swine
Complete contact information is available at: manure. J. Environ. Eng. 2013, 139 (12), 1454−1461.
https://pubs.acs.org/10.1021/acs.energyfuels.2c03824 (13) Kousis, I.; Fabiani, C.; Ercolanoni, L.; Pisello, A. L. Using bio-
oils for improving environmental performance of an advanced
Notes resinous binder for pavement applications with heat and noise island
The authors declare no competing financial interest. mitigation potential. Sustain. Ener. Technol. Assess. 2020, 39, 100706.
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A review. Renewable Sustain. Ener. Rev. 2012, 16 (7), 4406−4414.
Dr. Ameri is an Assistant Professor of Chemical Engineering at Shiraz (15) Baloch, H. A.; Nizamuddin, S.; Siddiqui, M. T. H.; Riaz, S.;
Branch of Islamic Azad University. His research focuses on biofuels, Jatoi, A. S.; Dumbre, D. K.; Mubarak, N. M.; Srinivasan, M. P.;
renewable energy, nanotechnology, and enhanced oil recovery. He Griffin, G. J. Recent advances in production and upgrading of bio-oil
received his PhD in Chemical Engineering from Shiraz University. from biomass: A critical overview. J. Environ. Chem. Eng. 2018, 6 (4),
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laboratories at SES group & Associates LLC, FHWA Turner-Fairbank Fini, E. H. Turning Two Waste Streams into One Solution for
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(18) Park, K.-B.; Kim, J.-S.; Pahlavan, F.; Fini, E. H. Biomass Waste
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to Produce Phenolic Compounds as Antiaging Additives for Asphalt.
ment of Science, a Fulbright Scholar of Aalborg University of ACS Sustain. Chem. Eng. 2022, 10 (12), 3892−3908.
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modelling of biobased and nature-inspired materials for use in the biomass in hot-compressed water and its comparisons with other
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