Bitumen

Construction and Building Materials 192 (2018) 593–609
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Construction and Building Materials

journal homepage: www.elsevier.com/locate/conbuildmat
Understanding the bitumen ageing phenomenon: A review

R. Tauste, F. Moreno-Navarro, M. Sol-Sánchez, M.C. Rubio-Gámez ⇑
Construction Engineering Laboratory of the University of Granada (LabIC.UGR), C/ Severo Ochoa s/n, 18071 Granada, Spain
h i g h l i g h t s
Most common techniques employed in bitumen ageing analysis were discussed.

Short-term ageing, long-term ageing and UV ageing methods tests were studied.
A deep analysis of the antioxidant additives commonly studied is provided.
a r t i c l e i n f o a b s t r a c t
Article history: The ageing phenomenon in asphalt mixtures is one of the most important factors affecting its service life.
Received 11 December 2017 The current paper provides an overview of a number of studies related to the ageing process in bitumen,
Received in revised form 11 October 2018 to determine the main component affecting this phenomenon. Moreover, a review is presented of the in-
Accepted 20 October 2018
laboratory tests used to simulate the different ageing processes (short-term ageing, long-term ageing, UV
ageing) that occur in the field, along with a description of the techniques currently employed to analyse,
from different perspectives, what happens to the binder after ageing. Finally, a summary is presented of
Keywords:
the various types of anti-ageing additives (antioxidants, UV blockers, UV absorbers) that are currently
Ageing
Asphalt
most commonly studied, along with their effects. This document reveals the importance of assessing
Bitumen the influence of UV radiation in any ageing study that is related to field data, and the need for a standard
Oxidation to simulate bitumen ageing. In addition, it highlights the importance of considering the influence of other
Antioxidant components of the mixture on the ageing of the bitumen and the need to conjointly consider different
Rejuvenator types of techniques in order to fully understand the phenomenon.
Ó 2018 Published by Elsevier Ltd.
1. Introduction [3]. In the more recently proposed bitumen models, the asphalte-
nes remain dispersed in the form of nano-agregates (formed by
Bitumen is a hydrocarbon product produced by removing the the addition of several asphaltene molecules) as an ‘island’, or
lighter fractions (such as liquid petroleum gas, petrol and diesel) group of islands, within the maltene phase [1]. The maltenes in
from crude oil during the refining process [1]. This material is turn can be divided into saturates, aromatics, and resins (Fig. 1).
mainly used in the construction industry for its waterproofing Resins are dispersing agents or peptisers for the asphaltenes. Thus
characteristics and thermoplastic behaviour. Although it is combining saturates, aromatics and asphaltenes produces the con-
employed in roofing applications as well as for sealing and insulat- ditions for asphaltic flow. The glass transition temperature of the
ing purposes, the main use of this material is in the construction of maltenes and the effective asphaltenes content (amount of dis-
roads and other paved areas (accounting for approximately 85% of persed asphaltenes and resins) are the two most significant prop-
its total consumption) [2]. With respect to studying this material, erties linking the structure of the bitumen with its behaviour and
bitumen has been traditionally understood as a colloidal system rheology (ductility at a given temperature/frequency) [5]. The ratio
composed of micelles of high polarity and molecular weight, of resins to asphaltenes determines, in terms of the traditional col-
known as asphaltenes (these are the solid particles responsible loid model and to simplify, in a certain way the solution (‘sol’, with
for aggregate adhesion), which remain in an oily environment of almost pure maltene-like behaviour and rapid relaxation modes)
lower molecular weight known as maltenes (that grant fluidity) or gelatinous (‘gel’, with high asphaltenes content leading to very
slow relaxation modes) character of the bitumen [6–9]. The
microstructural model offers a different perspective from the
⇑ Corresponding author. colloidal model when it comes to the structure of the bitumen,
E-mail addresses: [email protected] (R. Tauste), [email protected] (F. Moreno- describing it as a complex solution of uniformly distributed
Navarro), [email protected] (M. Sol-Sánchez), [email protected] (M.C. Rubio-Gámez).
https://doi.org/10.1016/j.conbuildmat.2018.10.169
0950-0618/Ó 2018 Published by Elsevier Ltd.
594 R. Tauste et al. / Construction and Building Materials 192 (2018) 593–609
Fig. 1. Separation of bitumen into its various fractions, highlighting the SARA fractions [4].
hydrocarbon molecules of widely varying molecular weight and simulating and analysing in laboratory the ageing of binder or
polarity, these characteristics being key to understand the changes bituminous mix to identify general differences in terms of what
produced in the binder from another point of view [10]. The chem- occurs in the material in situ. However, these studies are often
ical analysis of the binder is often conducted according to the type focused on a specific material or technique, which creates the chal-
of molecules rather than studying each chemical component, since lenge of identifying all the available possibilities for studying the
there are thousands of such components within the bitumen. ageing phenomenon in terms of both the short and long-term per-
Therefore, a more effective form of analysis could be to examine formance of bitumen, and ultimately, its contribution to the dura-
the evolution of different typologies grouped into molecular types bility and quality of pavements.
or fractions with a narrower range of properties that are based on Therefore, the current paper provides a technical overview of the
their chemical functionality [11,12]. The proportion in which dif- various studies related to the ageing process in bitumen. This covers
ferent types of molecules are present in the bitumen will deter- an analysis of the typologies and factors involved in binder ageing
mine their behaviour. and the study of how the other components of the mixture or the
Possibly one of the most important factors affecting this mate- use of polymer-modified binders could affect the ageing dynamics.
rial is the ageing phenomenon, since it is largely related to some of Moreover, a review is also included of the tests used to simulate
the most common pathologies that affect bituminous mixtures, what occurs in the field, along with the techniques currently
which is its principal use. Bitumen has been known to be prone employed to analyse what happens to the binder after ageing.
to chemical ageing from the very beginning of its use in road con- Finally, a review is presented of the anti-ageing additives that are
struction [13]. The ageing process of a binder consists mainly of the most commonly studied, along with their effects. In doing so, this
loss of its most volatile components (whose content is already low review provides a general perspective of a phenomenon that exerts
in paving grade asphalts since these are commonly used in other a considerable impact on the service life of pavements, and serves
refined products) along with an oxidation process and polymer as a starting point for future works that could provide a more in-
reactions that lead to changes in its composition and physico- depth analysis of the ways in which ageing can be simulated, along
chemical properties. These outcomes lead to an increase in the vis- with novel ways of preventing or reversing the phenomenon.
cosity and stiffness of bitumen [14], which causes hardening of the
material and a loss of agglomerating power [9,15]. Due to chemical 2. Typologies of ageing and factors involved
changes in the colloidal structure of bitumen, bituminous mixture
is also affected and various pathologies may appear in asphalt The ageing process that affects bituminous mixtures is highly
pavements. Some of these include the detachment of particles dependent on the chemical composition of the bitumen, which,
caused by a loss of agglomerating power, an increased likelihood in turn, depends on its crude oil nature (paraffinic or naphthenic).
of fracture behaviour of the pavement due to the decreased resis- Bitumen consists of a considerable variety of numerous compo-
tance to fatigue (more marked at higher temperatures of service) nents, the nature of which can vary from one binder to another,
[16], or an increase in the probability of thermal cracking associ- making it difficult to isolate and identify shared characteristics
ated with the greater stiffness of the binder (which makes it more [1]. Furthermore, other inherent parameters of the mixture (void
brittle). content, layer thickness, type of aggregates, etc.) as well as the
Due to the importance of the consequences of ageing, there are climatic conditions (temperature, solar radiation, etc.) have an
a vast number of studies that have explored, through different per- important influence on the ageing process. In the following
spectives, the range of variables or factors underlying this phe- sections, the different mechanisms that play a role in the ageing
nomenon along with the way it could be prevented or reversed phenomenon, along with the factors that condition them, are pre-
by the use of certain additives. There are also several ways of sented and discussed.
R. Tauste et al. / Construction and Building Materials 192 (2018) 593–609 595
2.1. Ageing mechanisms low void content following several years of service [20]. The effects
of oxidation in the bitumen structure can be summarized as dehy-
In the application of bitumen as binder for the manufacturing of drogenation, oxidation of alkyl sulfurs into sulfoxides, oxidation of
asphalt mixtures, two main stages of ageing of the bitumen can be benzyl carbons into ketones and oxidation of the latter with the
considered. First, ‘‘short term ageing” occurs at high temperatures subsequent dicarboxylic anhydrides and formation of carboxylic
during the process of mixing, storage, spreading and compaction. acids (the other main carbonyl compounds) [12,28]. Oxygen
Second, ‘‘long-term ageing” refers to the process that occurs removes hydrogen atoms from carbon atoms, thereby causing a
throughout the service life of the mixture due to the action of oxy- rise in the proportion of asphaltenes as well as a reduction in the
gen and UV radiation. In spite of the fact that some previous amount of resins and the most aromatic compounds. These pro-
authors such as Vallerga et al. [17] and Traxler [18] have proposed cesses also lead to a rise in the polarity, acidity, and condensation
up to 15 different factors that may have some kind of influence on of molecules.
the ageing phenomenon, the mechanisms currently universally The oxidation and volatilization processes (the irreversible
accepted (regardless of the stage of ageing) include oxidation, mechanisms), are slow at room temperature but their effects are
evaporation of the components with the lowest molecular weight, accelerated when the bitumen is exposed to high temperatures
and physical (steric) hardening [15,19,20]. [14], such as during the manufacturing, transportation, and laying
The latter is a reversible process that changes the rheological of the mixture (short term ageing) and continue in the case of oxi-
properties of the bitumen without altering its chemical composi- dation during the service life of the pavement. Temperature signif-
tion [21]. This process is associated with the formation of ordered icantly influences the kinetics of ageing, with its effects being
structures by waxes in the maltenes phase [22] that is influenced related to the binder. In general terms, the rate of oxidation is dou-
by the linear alkanes present in the asphaltenes fraction [12]. bled with each 10 °C rise in temperature above 100 °C [1]. This
The phenomenon — often slow to develop at room temperature, relationship is also observed when simulating the ageing process
but proceeding more rapidly as the temperature drops — is related in laboratory. Lu et al. [20] observed that between four and eight
to the inner reorganization of the binder molecules. Its effects are times more hours are required to obtain the same ageing state if
moderate and consist of a hardening effect, which is reversible the test temperature used during the PAV test simulation is
with heat application [1]. However, this has an impact on the final reduced from 100 °C to 75 °C.
characteristics of the binder [23]. Consequently, oxidation is considered to be the main ageing
The evaporation of volatile components (saturates and aromat- mechanism affecting binder [15,20] since its effects, in contrast
ics) is also regarded as an ageing mechanism. This phenomenon to steric hardening, are irreversible, affecting the chemical and
depends mainly on temperature (most of the evaporation takes physical features [6,23] of the bitumen. In addition, its contribution
place upon mixing and laying and an additional 10–12 °C above is more significant than evaporation, as previously described.
the mixing temperature could double the emissions of volatiles From a chemical point of view, asphalt ageing is a process of in
[24]) and the exposure conditions (such as the diffusion rate and service ‘‘auto” oxidation (the binder reacts with oxygen generating
the length or thickness of the diffusion path [1]). In any case, the new compounds that continue reacting with the oxygen, thus
contribution of the evaporation of volatile compounds to ageing developing the ageing process). With this process, the active func-
is limited when compared with the oxidation process [25,26]. This tionalities of asphalt molecules are decomposed through the
could be due to the current control in the refining conditions of the oxidative dehydrogenation of polycyclic perhydroaromatics inter-
bitumen, which ensures a limited presence of these compounds in mediate hydroperoxides (Fig. 2, a). The hydroperoxides are suffi-
the bitumen. This restriction is a consequence of their use in other ciently unstable to form free radicals (Fig. 2, c). These, on the one
more valuable fractions of the refining process and is also put in hand, contribute to the initiation and increase in the rate of the
place to limit the potential toxic fume emissions when heating reactions involving benzylic carbon that contribute to form car-
the bitumen. bonyl functions such as ketones (Fig. 3) and, on the other hand,
The third ageing mechanism is bitumen oxidation. Thurston react with thio-ethers (aliphatic sulphides and thiophenic or aro-
et al. [3] verified how the components of the bitumen, particularly matic sulphides) to form sulfoxide (Fig. 2, b) [12,29].
asphaltenes and resins, absorb oxygen and in subsequent research Regarding the different fractions that form part of the bitumen
they concluded that ageing is not only caused by physical harden- (saturates, aromatics, resins and asphaltenes), ageing could be
ing but is also a consequence of oxidative processes. Oxidative age- summarized as a process in which saturates vary, aromatics are
ing is, therefore, an irreversible diffusion-driven phenomenon consumed, and an increase of resins and asphaltenes occurs [30].
controlled mainly by thermal reactions between atmospheric oxy- In other words, the components move from more nonpolar frac-
gen and bitumen components, which alter its chemical features. tions to the more polar fractions as oxygen-containing functional
This ageing process is also affected by photo-oxidation reactions groups are formed in the asphalt [12]. The relation among the
that occur in the upper part of the binder, exposed in surface layers asphaltenes and resins is important because if the former are the
of the road that can catalyze the oxidative reactions (UV penetra- components that grow the most, the resins would be in deficit,
tion is limited to a few micrometres when oxygen penetration goes thus facilitating greater asphaltene condensation and accelerating
beyond millimetres, and thus field aging is seen to occur in the top ageing kinetics [15,31]. When the aromatic/resin fraction is not
inch below the surface [12]). Bitumen is a good light absorber and, present in sufficient quantities to peptize the asphaltene micelles,
despite the low penetration, photo-oxidation can affect the ageing or their solvating capacity is insufficient, they can further bond
process, particularly for certain kinds of polymer-modified binders together. This can lead to an irregular, open packed structure of
[27]. The oxidation process is diffusion driven since it is influenced linked micelles in which the internal voids are filled with an inter-
by access of the oxygen to the bitumen present in the mixture. micellar fluid of mixed constitution. These bitumens are more
Thus, factors such as the void content of the mixture, the depth close to a ‘gel’ structure, in terms of the classic colloid model, that
of the different layers of the road, and the bitumen content or give way to a more rigid behaviour (the asphaltenes tend to stack
the presence of cracking in the mixture could all affect the amount in planes, forming large molecular clusters with polar pi-bonding,
of binder exposed and, therefore, the amount of bitumen that is little free volume, and few degrees of molecular motion to facilitate
potentially aged. These facts could account for the differences that flow for relieving stresses [32]). From another perspective, the loss
are sometimes found between the results of ageing simulations in of the maltene phase disturbs colloidal stability and can cause floc-
laboratory and the lower degree of ageing found in mixtures with a culation of the large non-soluble asphaltene, which are typically
Fig. 2. Example of oxidation reaction sequence for polycyclic perhydroaromatics in asphalt. (a) Formation of hydrogen peroxide or perhydroaromatic hidroperoxide. (b)
Sulfoxide formation. (c) Hidroperoxide decomposition into free radicals [12].
Fig. 3. Example of ketone and sulfoxide formation through oxidation of asphalt benzylic carbon [12].
suspended in the maltene solution and stabilized by resins. Floccu- have two adjacent benzylic carbon moieties. The oxidation of these
lation can cause the binder to become stiffer and more brittle while molecules firstly results in the formation of dicarboxylic anhydride
the increased amount of asphaltene in oxidized asphalt compared after which ketones are formed by condensation. Carboxylic acids
with the virgin binder could further increase the propensity for the are produced in small amounts. On the other hand, sulfoxides are
asphaltene to undergo micellisation [33]. the result of the oxidation of organic sulphides [12]. This con-
From another point of view, as previously mentioned, as bitu- tributes towards increasing polar-polar interactions, leading to an
men ages through the oxidation process, the potentially active increment in viscosity [28]. The ketones and carboxylic acids pro-
molecular points (such as benzyl hydrogen and aliphatic sulphide) duced are of high polarity, having strong associations (through Van
turn into polar groups (carbonyls and sulfoxides respectively) der Waals forces) with other active polar sites in the binder, result-
when they react with oxygen. The resulting carbonyl compounds ing in an increase in apparent molecular weight that reduces the
formed include ketones, dicarboxylic anhydrides and carboxylic mobility of molecules to flow. In this way, bitumen undergoes
acids [6]. Ketones are formed from specific aromatic molecules that hardening and embrittlement through an increase in stiffness
[34]. This mechanism is favoured at ambient pavement tempera- In this regard, Wu et al. [35] concluded that viscosity and stiff-
tures and is the predominant cause of age-induced embrittlement ness of the binder increase primarily after exposure to ultraviolet
[32]. radiation, which clearly highlights the strong link between this
Further, and similar to the ageing mechanism of other poly- kind of ageing and film thickness. This is in accord with the find-
mers, most of the bitumen molecules reach their excited state ings of other studies such as that of Martinez et al. [44]. The higher
and become more easily oxidised in the presence of oxygen due rates were found for thickness below 150 mm. Furthermore, they
to the action of UV radiation [7]. This type of ageing is linked to established a relationship between the intensity of the radiation
that produced during the service life of the pavement (long-term and the increase of the carbonyl group. There also exists a propor-
ageing) [35] and several studies have demonstrated that its effects tional relationship with the increase of viscosity (especially from
are different from those found in the thermo-oxidative conven- 20 mw/cm2) but to a lesser extent than the one previously
tional laboratory tests used to emulate this phenomenon for both described.
binder and the mixture as a whole [27,36,37]. The effects of solar In relation to the influence of the temperature, Zeng et al. [45]
radiation were ignored for a long time since it only affects the found that the effect of UV radiation is clear at temperatures above
upper layers of the pavement due to the high absorption coefficient 50 °C, finding combined effects of the two factors on the oxidation
of asphalt binder and the low penetration of the radiation. Never- of the bitumen at 70 °C, particularly when it contains polymers
theless, asphalt binder ageing due to the ultraviolet radiation must (SBS in this case). Finally, Afanasieva et al. [46] pointed out that
be considered jointly with thermal oxidation, particularly in sur- UVB radiation has the strongest negative impact since they
face layers placed in geographical regions where there is high solar observed that the greatest damage was located in the area in which
radiation intensity and high relative air humidity [38]. this type of radiation was presented (280–315 nm). Despite the
test conditions, it also should be noted that even for the same
2.2. Factors involved in the ageing process typology of binder there are likely to be behavioural differences
depending on their origin, given that there would be variations
Once the main ageing mechanisms of the binders have been in their composition. Those bitumens that contain more asphalte-
described, this section will detail the different factors that condi- nes and are of a less aromatic nature will be those that show the
tion these mechanisms. It is clear that bitumen is the component greatest resistance to ageing by UV radiation [28].
of the mixture that is most significantly affected by the ageing pro- In addition to these general considerations, it is interesting to
cess. Nevertheless, when it comes to studying the ageing of a bitu- pay attention to the influence of using bitumen modified with dif-
minous mixture it is not only important to consider the type of ferent types of polymers or the nature of the aggregates in the mix-
binder used. In addition to this latter factor, studies such as that ture on the ageing kinetics of the binders due to their effect on
of Orencio-Marron et al. [9] or Petersen [12] indicate the impor- binder chemistry.
tance of analysing other factors such as the compaction of the mix-
ture and its influence on the void percentage when assessing the 2.2.1. Polymer modified bitumens
ageing of a mixture. Void percentage is a factor to be considered The addition of polymers can influence the ageing of bitumen,
in the ageing phenomenon since it determines the rate at which making it more difficult to study this phenomenon, particularly
this process occurs by controlling the degree to which oxygen when it comes to analysing their long-term performance since, in
can access the bitumen. Thus, a low void content will lead to a addition to oxidation, polymer degradation can also influence the
lower rate of ageing (and vice versa) during the service life of the ageing process. This gives way to insoluble cross-linking products
material [12,20]. Moreover, it has long been demonstrated resulting from bitumen and the degradation of the polymers, as
[39,40] that the bitumen content of the mixture also influences well as to those coming from other radical reactions [47]. Li et al.
its ageing through the thickness of the film of binder on the aggre- [48] in their study noted that the ageing of polymers covers four
gate. The higher the content and, therefore, the greater the thick- stages: initiation, growth, transfer, and termination of free radicals.
ness, the more marked the reduction in ageing. During ageing, free radicals are formed from the rupture of links in
In terms of the bitumen, the rate and amount of oxidation the chains of polymers by exposure to heat or light. These radicals,
depends on the chemical composition of the material, which in when in contact with oxygen, form peroxide radicals that react
turn controls the average radius of the diffusing molecules and with the polymer giving way to new radicals, which then repeat
the viscosity of the medium, affecting the rate of oxygen diffu- the process.
sion. For this reason, even minimal changes between binder of Polymers employed in bitumen modification could be classified
similar characteristics but different sources can have an impact into elastomers and plastomers. Among the former, the elastomer
on the ageing kinetics, since the nature of the crude of origin most widely used is probably SBS (Styrene-Butadiene-Styrene).
(paraffinic or naphthenic) conditions not only its generic compo- However, in terms of ageing, this modification has low resistance
sition but also the structure of the fractions [41]. Furthermore, to heat, oxidation and ultraviolet (UV) because of the presence of
the environmental conditions (temperature, difference in air double bonds and a-H in PB blocks [49]. This fact leads to the
composition, weather, rainwater, length of solar radiation path apparition of undesired chemical reactions (e.g. formation of per-
in different zones, length of exposure to weathering) and inter- oxy radicals and hydroperoxides). Nevertheless, several studies
molecular interactions or polarity have an indirect impact on this [20,23,50] have found that polymer degradation could somehow
phenomenon [34,38,42]. Since oxidation proceeds from the sur- reduce the stiffening of bitumen caused by long-term ageing.
face down through the pavement as a function of time, when Miró et al. [14] found that SBS and Crumb Rubber (which also have
cores are analysed it is important to consider the extent to which elastomers as part of their composition) modified binders offered a
the oxidation has gone down through the pavement, since age more stable response against the effects of ageing at medium-high
hardening of the bitumen would be more severe in the upper part temperatures, with SBS being particularly less affected. As temper-
of the pavement and decrease with depth [12,43]. Beyond the ature decreases, the impact of ageing on the neat binder becomes
chemical composition of the bitumen, and the factors previously less marked, whilst Crum Rubber becomes more susceptible to
mentioned that constitute the main aspects affecting this process, ageing. Nonetheless, it should be noted that conclusions regarding
other factors such as exposure to UV radiation of the upper layers the ageing of Crumb Rubber modified binders are not generalizable
of the course could also influence in some way the dynamics of to other elastomer-modified binders. Crumb Rubber is manufac-
ageing. tured using elastomer as a raw material, but it also includes filler
and other additives such as anti-oxidants. For this reason, the aging stone (basic nature), which, as previously mentioned, are
of Crumb Rubber modified binders is difficult to estimate given aggregates with a greater absorption capacity, its ability to attract
that current aging tests (such as RTFOT or PAV) induce major struc- polar fractions lies on its surface, and so as ageing progresses their
tural changes in the product along with the fact that the rheologi- absorption will be smaller. Conversely, in aggregates of an acidic
cal measurements made when testing these binders are not nature such as granites, since they have lower absorptive capacity,
reliable due to the coarse particle size. Various studies [51,52] have the surface will take longer to be covered and they will therefore
analysed the process by which the ageing of polymer-modified lose their ability to catalyse ageing. For this reason, the impact of
bitumen is conditioned by both the ageing of bitumen and polymer aggregates should be noted in the later stage of the process when
degradation, showing that this additive helps to avoid the forma- a lower proportion of the ageing process occurs [58,59].
tion of sulphoxide groups and reduces the increase in carbonyl In relation to the filler, Wu & Airey [60] state in their study that
groups following ageing. An explanation of this phenomenon could binders recovered from limestone mastics contain more oxidation
be related to the fact that the initial polymeric free radicals react products than those recovered from gritstone. This implies that
with certain asphalt components, producing a link between them basic minerals could catalyse the oxidation of bitumen. Neverthe-
and providing the asphalt fraction trapped in the polymeric net- less, Lesueur et al. [13] found no evidence to support this possibil-
work with a certain level of protection against oxidation [29]. ity; in their study they found no anti-ageing effects from using
Dehouche et al. [47] compared the ageing effects of SBS with a either limestone or granitic filler. They propose that this discrep-
binder modified with plastomers using EVA (Ethyl Vinyl Acetate). ancy could be related to the kind of test used (use of Thin Film
Prior to the ageing process, they observed a much finer dispersion Oven Test, TFOT; Rolling Thin Film Oven Test, RTFOT; Rotating
of EVA particles than SBS in the bitumen. However, after thermo- Cylinder Ageing Test, RCAT in mastics). All of these tests of ageing
oxidative ageing, the hardening of the samples was more pro- depend significantly on film thickness, which is heavily influenced
nounced for base and EVA modified bitumen than that modified by the increase of viscosity due to the addition of filler. Further-
with SBS. Whilst in SBS-modified binders ageing causes both poly- more, the filler creates a geometrical barrier to oxygen diffusion
mer degradation and bitumen oxidation, the addition of EVA seems and the employment of porous filler could increase the absorption
to induce the oxidative hardening of the materials. of bitumen.
For all of these reasons, Lesueur et al. [13] have suggested lim-
2.2.2. Influence of the aggregates iting the amount of filler tested (10% in volume or 20% in weight)
Apart from the influence of void content on the ageing of bitu- and to use tests that avoid the effects of film thickness (preferably
minous mixture, aggregates (which are part of this) may play an PAV for short-term with a test time of 5 h, and 20 h for the long-
important role in this phenomenon. The effect of minerals on bitu- term). Following this process, they found an anti-ageing improve-
men ageing has received only limited attention and it has even ment in both Portland cement and hydraulic lime, but to a lesser
been suggested that they have no effect except in the case of using extent than hydrated lime, possibly due to the lower surface area
hydrated lime as an additive (this limits the increase in viscosity of the former two.
experienced and reduces the asphaltene content following the age-
ing process [13]). However, some authors such as Lu and Isacsson
[6] have included the exudation and migration of oil from bitumen 3. Simulation of ageing in laboratory
to aggregate as a further factor in the ageing process. Moreover,
Wu et al. [53] described a variety of effects of the type of aggregate 3.1. Simulation of ageing in bituminous binders
on the ageing of bitumens and the way in which this occurs at dif-
ferent stages. Several laboratory methods have been used to emulate the age-
Without taking into account the absorption of oils, aggregates ing phenomenon of the binders during the different phases of their
can influence ageing through three mechanisms that can accelerate production process as well as during the service life of the materi-
or retard the process. First, minerals present on the surface of the als. These often involve increasing the temperature, reducing the
aggregate can catalyse the oxidation of bitumen [54]. Second, the thickness of the film of bitumen, increasing the pressure of oxygen
surface of the aggregate can absorb some of the polar functional or a combination of all of these as a way to generate severe ageing
groups of bitumen creating a viscous layer around them and delay- conditions. Airey [36] in 2003 conducted a thorough review of the
ing the increase in viscosity of the bitumen due to ageing [55]. methods used in binders and bituminous mixtures. Similarly,
Finally, the surface of the aggregate can absorb some of the bitu- Andersson & Bonaquist [61] carried out a review of novel test
men fractions creating an internal imbalance that accelerates the methods such as the Modified German Rotating Flask (MGRF) used
ageing process [56]. to assess short-term ageing.
The type of aggregate is therefore an important factor to take Nowadays the most widely used tests are the thin film oven test
into account. Anderson et al. [57] confirmed that aggregates with (TFOT), rolling thin film oven test (RTFOT), pressure ageing vessel
a lower capacity to absorb polar fractions (such as quartzite and (PAV) and ultraviolet testing (UV). The first two, TFOT and RTFOT,
granite) are those that accelerate bitumen oxidation to a greater are used to simulate ageing during storage, mixing, transport and
extent as opposed to others with a larger absorption capacity, such placing (short-term ageing) and show similar results [6] whilst
as limestone. Nevertheless, in their study Wu et al. [53] point out the other two are used to examine ageing during the service life
that when it comes to studying the bitumen extracted after simu- of the material (long-term ageing).
lating the ageing of the mixture, certain factors should be taken In relation to short-term ageing, the TFOT test (EN 12607-2
into account. First, due to the fact that limestone absorbs a greater [62]) consists of ageing 3.2-mm thick bitumen films in an oven
proportion of polar fractions, it protects these from oxidation and for 5 h at 163 °C. This test was introduced in the US paving grade
evaporation, thereby decreasing the rate of ageing. However, they specifications in 1955. Following a similar principle, the TFOT
also note that some of those components might not be recoverable was later surpassed by the RTFOT developed in the early 1960s.
using the extraction techniques commonly employed and, as a The main reason behind this change was that the bitumen in TFOT
result, these could not account for obtaining a lower value of age- is not agitated or rotated during the test, giving rise to concerns
ing and a recovered bitumen of lower stiffness. about whether the ageing could be limited to the surface of the
Concerning the issue of how the effect of the aggregates are dis- bitumen sample. In this case, the binder is aged in 1.25-mm thick
tributed in time, it should be considered that in the case of lime- rotating films in glass bottles at 163 °C for 75 min. RTFOT is now
the preferred standard method in both the US and Europe (AASHTO modified bitumen with SBS [20]. This test is the one that utilises
T 240 [63]; EN 12607-1 [64]) for simulating the ageing that takes the lowest temperature, and is closest to the temperature condi-
place in the asphalt mixing plant [13]. This method, however, tions that are expected during the service life of the material.
has the inconvenience of requiring a difficult process for cleaning There are different ways in which UV ageing has been simulated,
the glass bottles that also entails a loss of material. In addition, since there is no standardized procedure, which makes comparison
Besamusca et al. [65] pointed out that whilst these protocols can between results more difficult. Though most of the studies agree on
be considered satisfactory for paving grade binders, work is still using a 500 W lamp [45,67,69,70,71] for certain short-term ageing
needed to develop testing solutions for highly viscous binders such simulations there are differences in terms of the intensities
as hard grade and polymer-modified binder as well as warm mix employed, the thickness of the film of bitumen, and the condition-
binders. The problem with the latter is that there are several differ- ing of the samples. Zeng et al. [45], for example, placed the lamp at
ent techniques for their production. When the binder is pre- 500 mm from a film of bitumen of 2 mm thickness at a temperature
blended, it can be tested as supplied. However, in other techniques, of 80 °C, whilst other authors [38,70,71] tested a film of 3 mm at
modifiers are added at the asphalt mixer or a foaming process is 60 °C during a period that ranges from 6 to 9 days. There are also
used and so the binder cannot be tested except when recovered variations in the intensity of radiation employed, which can range
from the mix, which introduces a further variable since the recov- between 450 and 1200 lW/cm2. Wu et al. [35] used a
ery method could have an impact on its properties. In this case, the temperature-controlled stove and a UV lamp (UROT) varying the
authors suggest evaluating the asphalt mixture produced by mod- intensities used as well as the thickness of the film tested (50,
ification/foaming of the binder in the mixer. 100, 150 and 200 mm) (Fig. 5). Similarly, different temperatures
In the case of polymer-modified bitumens, research has shown (45, 65, and 80 °C) were tested and compared with bitumen under
that because of the rather lower ageing temperature of 163 °C and the same conditions but without UV radiation, and in both cases
the high viscosity of these materials, the binder could become too with previously aged specimens using RTFOT. Whatever the
viscous to flow and to spread into uniform thin film [66]. As a solu- method employed, it is clear that the influence of UV radiation on
tion, Anderson & Bonaquist [61] concluded that the Modified Ger- the ageing of the upper layers of the pavement wearing courses
man Rotating Flask test (MGRF) could be an acceptable alternative cannot be neglected. Durrieu et al. [27] demonstrated that this kind
to RTFOT for both neat and modified asphalt binders. Airey [36] of ageing occurs rapidly and after 10 h of exposure to UV radiation it
analysed some adaptations to the RTFOT in order to solve the oper- is possible to reach oxidation levels similar to those found after an
ative difficulties of these binders. These solutions often consist of RTFOT + PAV simulation or after one year of service.
the inclusion of a cylindrical piece of steel inside the bottles to The European standard also includes other test methods such as
secure the film thickness and avoid escape of the material the Rotating Flask Test (RFT, EN 12607-3 [72]) for short-term age-
(Fig. 4). Another possible solution would be to increase the RTOFT ing, and the Rotating Cylinder Ageing Test (RCAT, EN 15323 [73])
test temperature. Yan et al. [66] proposed an increase to 178 °C to for both long and short-term simulation [74], but their use is far
allow fluidification of the bitumen. They compared a modified ver- less extensive than those described previously. Lu et al. [20] found
sion of the MRTFOT (using different temperatures, in order to con- similar results using RTFOT and RCAT at 163 °C for 4 h while Besa-
firm whether 178 °C is sufficient) with the standard test until they musca et al. [75] found a good correlation of this last test with the
both achieved the same effect, assuming that at this temperature ageing that occurred during road asphalt production. In addition,
the effect of the metal bar is no longer necessary. Lu et al. [20] observed comparable results using RCAT at 90° and
Further, as mentioned previously, the Pressure Ageing Vessel 4 h and the previously defined PAV for two alternatives
Test (PAV) and the UV ageing techniques simulate what occurs (100 °C-20 h and 75 °C-120 h). However, they detected some
during the service life of bitumen (long-term ageing) [67]. The differences in long-term ageing when using polymer-modified
Pressure Ageing Vessel Test (EN 14769 [68]), consists of condition- binders. This fact supports the idea that different types of binder
ing binders in 3.2-mm thick films for 20 h at a temperature of will need different approaches, particularly those of a higher
100 °C under an air pressure of 2.07 MPa. When it comes to the viscosity, as in the case of polymer-modified bitumens [65].
study of polymer modified binders, the high dependence of this Nevertheless, it should be noted that not all of these techniques
material on temperature led to the proposal that PAV at 75 °C is always simulate perfectly what happens in reality. For example, Lu
the optimal test for simulating long-term ageing in polymer- et al. [20], in their work, found a higher content of sulphoxides and
a lower content of carbonyl groups than those obtained in
Fig. 4. Ageing bottles with steel rod for MRTFOT (right) and without steel rod for
conventional RTFOT (left). Fig. 5. Ultraviolet ageing oven [45].
laboratory. This indicates the existence of mechanisms that have setting them in 0.5 MPa pressure, 85 °C temperature and 24 h
not been fully simulated by the ageing tests. Similarly, Airey [36] duration. This conditioning phase is followed by a cooling period
demonstrated a greater loss of volatility and less oxidative ageing of 24 h before releasing the air pressure and opening the vessel.
after TFOT or RTFOT with respect to what occurred in the field. Fur- The stiffness modulus (EN 12707-26 Annex C [82]) after condition-
thermore, and in relation to long-term ageing, Besamusca et al. ing is divided by the value obtained before conditioning (retained
[75] and Erksine et al. [76] suggest that PAV and RCAT are deficient, stiffness modulus). This, along with the saturation of the specimen
as they fail to age bitumen to a degree that reflects 8–10 years of after the test (retained saturation), constitutes the parameters used
service. In relation to this, Petersen [12] proposed that the most as an indication of the sensitivity of the compacted mixture to
important determinant of oxidative ageing of the pavement during combined ageing/moisture effects [83]. The effects of ageing can
its service life is the maximum, not the average, temperature expe- therefore be measured by the increase in stiffness modulus [84]
rienced. Therefore, the use of accelerated ageing tests that or by using the conditioning as a way to consider the effect of
employed temperatures significantly higher than those experi- different aggregates or filler on the bitumen recovered from the
enced by the pavement could be a possible reason for observed dif- mixture [85].
ferences in the results. In addition, other possible causes of Moreover, it is worth noting the methods proposed in the
divergence in the results could be the lack of study concerning studies of Orencio-Marron [9] and Wu et al. [53], which follow
the effect of UV radiation on surface courses and the influence of, the procedure developed within the Strategic Highway Research
among other factors, the nature of the aggregates and the void con- Program and collected in the standard AASHTO R 30 ‘‘Standard
tent of the mixtures. practice for conditioning of hot mix asphalt mixture” [86]. The first
takes into account the effect of the manufacture and construction
3.2. Simulation of ageing in bituminous mixtures of the pavement using mixtures without compaction. The second
evaluates ageing during the period of service. In the latter, speci-
Studies evaluating the ageing of bituminous mixtures as a mens manufactured in the laboratory are placed into a forced air
whole are less common and are often limited to extended periods stove at 85 °C for 5 days. These procedures do not take into account
of warming of the bituminous material before its compaction, or the effect of environmental agents, layer thickness of the mix, or its
involve the use of adaptations of the methods used to evaluate bin- position in the pavement. However, the results seem to correspond
ders [36]. However, a new standard [77] developed for CEN TC227, with the effect of ageing over a period of between 7 and 10 years of
which allows for the assessment of the effect of oxidative ageing of service. These results are in accordance with those obtained by Qin
asphalt mixtures, was submitted to the members of CEN (Comité et al. [87] with the extraction of binder from core samples at
Européen de Normalisation) for approval. This standard aims to 75 mm depth that has been in place for 8 years in McLean, Virginia.
provide methods for laboratory ageing of both loose bituminous Nevertheless, this same study concluded that field ageing at the
mixtures and compacted specimens, produced either in the labora- pavement surface is far more severe than standard laboratory age-
tory or in cores extracted from the field. ing and cannot be simulated by RTFO-PAV ageing, which also
With respect to the procedures used for loose asphalt, the mix- occurs in other studies such as that carried out by Lerfald [43] in
ture is placed into a pan and conditioned within a heating cabinet Norwegian Pavements when analysing the upper part of cores
with forced air ventilation for a specific duration at an elevated
from different regions. This is likely to be related to the absence
temperature to accelerate ageing by oxidation. Additionally, pres-
of the UV radiation effect at this depth [88], as also pointed out
sure can be applied for further acceleration of conditioning. The
by Liu et al. [74] and Lin et al. [89] who found that ageing is at
procedure for long-term ageing has an extended phase of condi-
its highest in the upper part of the pavement, as shown by an
tioning in comparison with the short-term ageing procedure. For
increased level of viscosity. In relation to this, Lopes et al. [90]
testing compacted specimens or cores from the field, two methods
found better correlation with the ageing on site when simulating
have been proposed. The first of these is similar to the procedure
weather and UV conditions in laboratory for surface layers. This
used for testing loose mixtures. In the second procedure however,
confirms the importance of taking into account the penetration
the specimens are placed within a triaxial cell (comparable to tri-
of the oxidation when analysing pavement cores; otherwise, the
axial cells used for permeability tests on soils) and subjected to a
measured chemical and physical properties of the asphalt from
forced flow of gaseous oxidant agent (ozone enriched compressed
the whole core would only be an average of the levels of oxidation
air) for a specific duration at a specific temperature. In addition, it
throughout the depth of the core [12]. Moreover, Besamusca et al.
has also been proposed to use the aged material to assess the effect
[91] found in their work that the extraction process to recover the
of ageing on binder characteristics, taking into account the poten-
tial effects of mineral aggregates on ageing [78]. binder from the asphalt mixture (Fig. 6) should be considered with
In addition to this standard, there is already an existing test care since they found that even a small quantity of solvent has a
standard for hot mix asphalt ageing, known as the Saturation Age- substantial influence on the chemical test results (they have
ing Tensile Stiffness (SATS) test (EN 12697-45 [79]). The SATS test proposed the Gel Chromatography technique as a simple way to
is the first test procedure to combine both ageing and moisture identify possible solvent pollution).
damage by conditioning pre-saturated asphalt mixture specimens
at an elevated temperature and pressure in the presence of 4. Laboratory tests for the evaluation of ageing
moisture [80], assessing the durability of adhesion with particular
aggregate/filler combinations. In the conditioning phase, five Ageing influences both the chemistry and rheology of bitumen,
pre-saturated specimens (100 mm in diameter and 60 mm in and so there are various ways of assessing this phenomenon
thickness) are subjected to moisture saturation by using a vacuum beyond the classic tests of penetration (EN 1426 [92]), softening
system. They are then transferred into a pressurized vessel par- point (EN 1427 [93]) and evaluation of viscosity (commonly tested
tially filled with water, where they are subjected to a conditioning through the Brookfield or rotational viscosity test – EN 13302 [94]).
procedure by storage at 85 °C temperature and 2.1 MPa pressure The ageing process often leads to an increase in both viscosity and
for 65 h. Most of the specimens are conditioned above the water softening point, thereby reducing the binder penetration [6,95] so
line, but some are conditioned below [78]. Grenfell et al. [81] it is possible to establish an ageing index related to these or any
introduced a modification of parameters in order to extend the other physical properties both before and after ageing. The ageing
procedure to a wide range of typically used asphalt mixtures, index is defined as the ratio of a given binder property after a given
proportion and molecular weight of the different fractions, and

can help to model the behaviour of the aged binder. In this section,
some of the most widespread techniques used to assess the effects
of ageing on the binders from different approaches will be pre-
sented and discussed. A summary of these techniques and the
parameters analysed can be found in Table 1.
4.1. Rheological evaluation
The study of rheology is one of the methods most commonly

used in the characterization of the binders and its use is present
in most of the studies on bitumen ageing. This allows for character-
izing bitumen at a certain temperature according to both the con-
stitution (chemical composition) and structure (physical layout) of
the molecules in the material. Changes in any of these aspects will
be detectable by this technique [1]. The rheological analysis is
commonly carried out using a Dynamic Shear Rheometer (DSR)
and is usually focused on the evolution of Complex modulus (G*)
and the phase angle (d) under different temperatures (temperature
sweep) [31,70] or frequencies (frequency sweep) [87,97]. In
addition, it is also common to evaluate other parameters such as
Fig. 6. Rotary evaporator commonly used for bitumen extraction. ‘‘G*/sind” or ‘‘G*sind” proposed in SUPERPAVE to evaluate the resis-
tance to plastic deformations and fatigue respectively [28,98].
Finally, the use of ratios between any of these variables at a fixed
level of ageing to that before ageing. Lin et al. [89] assert that the temperature and frequency [6,99] before and after certain ageing
variation in viscosity is the most representative measure with processes is another tool that has been widely employed.
respect to the results obtained in the field. The results show that with ageing, the complex modulus
Chemical changes can be analysed from different perspectives increases and the phase angle decreases [100]. These findings indi-
by using a range of evaluation techniques. Therefore, it is possible cate that ageing renders the mechanical properties of the bitumen
to analyse the formation of sulfoxides and carbonyl compounds; more solid-like. The magnitude of the changes is dependent on
the transformation of generic fractions; the increase in the amount bitumen type and evaluation conditions [6]. Commonly, at low fre-
of molecules of greater size; or the molecular association through quencies (or at medium-high temperatures), an increased complex
the analysis of their weight or the microstructure of the binder modulus is observed for the aged bitumen in comparison with the
[6,19,50,90]. These techniques allow for studying the ageing phe- original bitumen. In contrast, at high frequencies (or at low tem-
nomenon from different points of view but the use of only one test peratures), ageing has little influence on complex modulus [31].
could lead to incomplete assumptions since each technique has its
own limitations and the results could vary from one binder to
another, depending on their nature or ageing conditions. For this 4.2. Atomic force microscopy (AFM)
reason, in order to fully understand the ageing behaviour of a
specific binder, various techniques should be combined and com- Bitumen chemistry at the molecular level may result in a vari-
pleted with some of the classic tests (which will provide a starting ety of intermolecular associations (structuring), which are closely
point) along with a complete rheological study. related to the physical properties of the binder [101]. This micro-
The relationship between the chemical analysis and physical scopy tool allows for studying the topography and phasing contrast
characteristics has been widely demonstrated as shown in studies of a sample surface, and is particularly useful for multi-phase
such as the one of Weigel & Stephen [96], which found that the materials such as bitumen. In addition, AFM is also relatively easy
physical, rheological, and ageing behaviour of bitumen could be to operate since the tests are carried out under ambient conditions
derived from the chemistry of the bitumen through correlation [102]. Several studies [8,50,52,103] have employed this technique
with the SARA analysis. This can be conducted by studying the to analyse the micro scale mechanical properties of the asphalt
Table 1
Most common techniques employed in bitumen ageing analysis.
Technique Typology of Parameters analysed References

analysis
Atomic force microscopy (AFM) Microscopy Microstructure and micro mechanical properties of bitumen [8,50,52,101–104,107]
Fourier transform infrared spectroscopy (FTIR) Chemical Amount of carbonyls groups and sulfoxides [6,8,20,29,66,70,87,95]
Amount of butadiene groups [8,29,45,52,95]
Thin-Layer Chromatography with Flame Ionization Chemical Saturates, aromatics, resins and asphaltenes content [6,15,30,31,47,111]
Detection (TLC_FID)
High pressure gel permeation chromatography (HP-GPC) Chemical Chemical groups number and average molecular weight [6,50,93,116,130]
Softening Point Test Mechanical Softening temperature increment or ageing index [8,13,30,31,95,97,99]
Penetration Test Mechanical Penetration Increment or ageing Ratio [30,31,95,97]
Brookfield or rotational viscosity determination Mechanical Viscosity ageing index at different temperatures [8,30,70,95,99]
Dynamic shear rheology (DSR): Frequency sweep test Rheological Complex modulus (G*). Phase angle (d) [6,23,31,66,70,97,100]
Dynamic shear rheology (DSR): Temperature sweep test Rheological Complex modulus (G*). Phase angle (d) [6,23,31,70,87,97,100]
Dynamic shear rheology (DSR) test: G*/sind determination Rheological Plastic Deformation resistance [23,30,95,98,99]
Dynamic shear rheology (DSR) test: G*Sind determination Rheological Fatigue resistance [30,95,98,99]
phases, evaluating how different ageing techniques affect the inner process or lead to phase separation. In terms of the action of UV
morphology of the binder. ageing, this leads to a new phase separation, which is conditional
Bitumen microstructures mainly consist of two phases, in upon the sensitivity of the different molecules to this type of
which some elliptical bee-phase structure randomly distributes radiation.
in a matrix phase. Aguiar-Moya et al. [104] found that regardless When analysing the results of this technique, Das et al. [106]
of the type of asphalt binder, the percentage of bee phase (Fig. 7) pointed out that since PAV residue undergoes heating and cooling
on the surface was modified, and surface roughness decreased with several times during sample collection and preparation, and
the degree of ageing [95]. Wu et al. [97] also found bee-structures because of this thermal history, the aged surface layer melts down
for SBS modified binder after ageing, which had not appeared pre- in the asphalt and results in a homogeneous matrix. Thus, the sur-
viously. This is in accordance with the results found in the study of face changes entirely and AFM scanning may show completely dif-
Cannone-Falchetto et al. [102] where a proportional increase in the ferent surface information, which could be far removed from that
bee-structures could be observed in long-term aged materials. The found in real field ageing.
type and the shapes of the surface structures found were different
for unmodified and polymer modified bitumen. Whilst a more reg- 4.3. Fourier transform infrared spectroscopy (FTIR)
ular shape is presented for unmodified bitumen, a needle-like
topography was found in the modified bitumen, although in both The infrared spectroscopy technique allows for the identifica-
cases there was a significant increase in the length of the shapes. tion of the functional groups of a substance. This technique has
Whether there exists consensus about how the bee-structure is been widely used in the analysis of aged bitumen
modified after ageing [52,101,102,105], identifying the phe- [6,19,20,35,70,95,108] as it allows for the evaluation of the amount
nomenon behind the appearance of these bee-shaped microstruc- of carbonyl compounds (ketones, dicarboxylic anhydrides and car-
tures has always been an issue of concern [106]. Whereas in the boxylic acids) and sulfoxides present in the bitumen (Fig. 8). FTIR is
beginning the phenomenon was mainly associated with asphalte- more sensitive to identifying the differences in ageing kinetics
nes, technological development has allowed for reaching the con- between asphalts of varying sources when compared with evaluat-
clusion that bee-shaped microstructures are mainly wax-induced. ing the evolution of the weight of the different generic fractions
In this regard, Pauli et al. [101] hypothesised that the interaction [12]. After the preparation of the samples in solvent, the number
between crystallising paraffin waxes and the remaining asphalt of these groups can be measured through the peaks found in the
fractions was mainly responsible for the structuring, which made areas of infrared, which are around 1030 cm1 for the sulfoxides
them refer to this specific behaviour as ‘wax-induced phase sepa- and 1705 cm1 for the carbonyls [20]. Because of the oxidation
ration’. This study also revealed that the measured wax fractions reaction, the increase in these two functional groups indicates
did not fully correlate with the observed percentage of bees. In the degree of ageing of the binder since this is connected to the
contrast, in their study Aguiar-Moya et al. [104] concluded that increase in viscosity values [109]. Furthermore, this parameter
these ‘‘bee-structures” were not related to the asphaltenes, recrys- could be of interest for establishing relations with the results
tallized paraffinic waxes, thermal oxidation or polymer modifica- obtained in the field [89]. The dynamics of the formation of these
tion of bitumen but are instead linked to the aromatic fraction of groups are closely linked to the temperature and several studies
bitumen. Thus, their size, shape, and topography are influenced [20,50] have found that the increase in the components of the car-
by thermal oxidation through the combination of aromatics with bonyl groups that occurs with ageing correlates with the increased
the remaining SARA fractions of bitumen. Regardless of the type stiffness found in these types of bitumen. Similarly, in bitumens
of asphalt binder, the percentage of bee phase on the surface was modified with SBS, it has been possible to use this technique to
modified, and surface roughness decreased with the degree of age- compare how this polymer appears to inhibit the formation of sul-
ing [107]. foxides following ageing. In the case of polymer-modified bitu-
On the other hand, Zhang et al. [8] demonstrated how the TFOT mens such as the SBS, ageing could also be studied by analysing
(short-term ageing) reduces the contrast between the matrix and the band of butadiene double bond, which is located around
the scattered elements within, leading to a single-phase behaviour. 985 cm-1. In this way it is possible to monitor the deterioration
Moreover, they confirmed that changes in morphology following of the SBS due to UV ageing through the modification of the buta-
long-term ageing (PAV) vary substantially depending on the bitu- diene copolymer by diminution of the double bond [27,35].
men used, which could either accelerate the previously described
Fig. 7. Tomographic image of bee structures in bitumen [8]. Fig. 8. Example of FTIR spectrum for different bitumens [70].
Various procedures can be employed to assess the peak. Dony obtained is generally poorer than that resulting from the use of
et al. [105] assert that the fixed limit method is practical when a chromatography, where the effect of the solvent is combined with
multitude of spectra must be interpreted. However, this can gener- selective absorption [1]. These methods usually begin by precipi-
ate misleading results, since negative areas can be taken into tating the asphaltene by using n-heptane after which chromato-
account in the calculation. For this reason, they propose the use graphic separation is conducted to separate the remaining
of the valley to valley and the deconvolution methods [110]. components (saturates, aromatics, and resin). The system mainly
consists of an auto-sampler, a photodiode array detector (PDA), a
4.4. Thin-layer chromatography with flame ionization detection column-box, and a pump. The detector is connected to the system
(TLC_FID) to provide information regarding the concentration and molecular
weight of the sample [74].
This technique permits the evaluation of the development of Normally, in GPC, larger molecules will travel faster through the
the four generic fractions that constitute the bitumen: saturates, column and appear at shorter retention times. Consequently, a sig-
aromatics, resins, and asphaltenes, and is the most commonly nal at shorter retention times may be the result of an increase in
employed method for conducting the SARA analysis. As ageing pro- molecular weight [115] but could also indicate the formation of
ceeds, an increase in the content of asphaltenes and resins is associations between molecules [116]. Components that are less
observed while saturates tend to remain the same due to their soluble in a specific solvent will have a higher tendency to agglom-
inert nature in comparison with oxygen (Fig. 9) [6]. Fractions erate. With this technique, it is possible to obtain the number and
essentially depend on the molecular polarity such that any changes average molecular weights of the different groups.
in the latter involve transformations between fractions of the type: Through molecular weight analysis it is possible to observe an
aromatic-> resins-> asphaltene for both unmodified and polymer increase in the larger molecules and subsequently a decrease in
modified binders [15,31,47,111]. This technique is considered as the smaller molecules, which confirms that the migration of com-
representative as the standard ASTM D 4124 [112] liquid chro- ponents exists in the ageing process with aromatics generating
matography but it is faster and consumes less material. resin fractions, which in turn generate asphaltenes [117]. This
In the study conducted by Del-Pozo et al. [30], a review is pre- can also be found in the study of Sun et al. [50], which, at the same
sented of some chemical indexes associated with this technique. time, confirmed the degradation of SBS polymer (18% after short-
The first of these is the IC (colloidal stability index), which allows term ageing and 41% after long-term ageing) into small molecules
for determining the durability of the bitumen according to its ini- to restrain the ageing reaction during the entire process.
tial chemical composition [113]. This index adopts the traditional
model of a colloidal structure and establishes the relationship
between flocculants and dispersants: 5. Anti-ageing additives
Asphaltenes þ Saturates
IC ¼ There have been numerous additives tested, seeking to mini-
Aromatics þ Resins mize the ageing effect in bituminous binders. A summary of all
Further, another index could be established by considering these additives, their effects, and some studies where they were
polar molecules (asphaltenes and resins) in front of the non- tested, is presented in this section and summarized in Table 2.
polar molecules (aromatics and saturates) following the model of The additives most commonly used in bitumen are antioxidants,
interpretation proposed in SUPERPAVE. Finally, the last index con- which act in two different ways, either as radical scavengers
siders the loss of aromatics. In general, a decrease in aromatics can (primary antioxidants) or by inhibiting the formation of peroxides
be observed in both short and long term ageing, whilst the asphal- (secondary antioxidants) which serve to prevent the initiation of
tene content increases in the short term (the resins also experience the oxidation process, the first of which is the most effective
a slight increase) [89]. After PAV, Del-Pozo et al. [30] found that [28,118]. According to Dessouky et al. [23], there are four com-
resins increase significantly, although these changes can vary pounds that inhibit the oxidation of hydrocarbons in the bitumen:
according to the type of binder studied. 1) phenols that break the chain reaction with peroxide radicals; 2)
inhibitors of ageing by reaction with alkyl radicals; 3) agents that
4.5. Gel permeation chromatography (GPC) split peroxides without the formation of free radicals and, 4) agents
that consume the di-oxygen molecules at a faster rate, avoiding
Solvent extraction is an interesting and relatively fast way to oxidation. Among the different compounds included in these addi-
study the binder components [114], but the separation that is tives, those most commonly found include amines, hindered phe-
nols, phosphites and organic zinc compounds. Some examples of
these additives are Vitamin E, DLTDP (dilauryl thiodipropionate)
[42] and Zinc dialkyldithiophosphate (ZZDP) [29], phenothiazine,
dialkyl phosphorodithioate, or zinc dibutyldithiocarbamate
[12,15]. It should be noted that these additives are commonly used
to delay the ageing process in polymers at an industrial scale,
whilst only a few studies have explored their use in bitumen at lab-
oratory scale with satisfactory results. Nonetheless, it is important
to consider that their effect could be reduced in service, since the
mobility of these compounds in the viscous medium at service
temperatures might be smaller [49].
Radical scavengers react with peroxy radicals, preventing fur-
ther propagation of the free radical chain. Li et al. [48] observed
that antioxidants that work as free radical scavengers supply
hydrogen atoms to terminate active free radicals, generating a
stable one, which improves resistance to ageing. An example of
this kind of additive could be found in the study of Cortés et al.
Fig. 9. Effect of ageing on bitumen TLC-FID chromatogram [6]. [28] who evaluated the antioxidant BHT (butylated hydroxy-
toluene) whose action is based on the collection of the previously such as SasobitTM, RedisetTM WMX, Cecabase RTTM 945, and Evotherm
mentioned free radicals (free-radical scavenger). Banerjee et al. 3GTM were shown to have in addition an anti-ageing effect.
[119] studied further examples of radical inhibitors of a phenolic Peroxide inhibitors react with hydroperoxide molecules that are
nature such as antioxidant in conventional bitumens. Among generated in the oxidation process (which is why they are also
these, some additives commonly employed in warm-mix asphalt known as peroxide or hidroperoxide decomposers) preventing
Table 2
Antioxidant additives commonly studied.
Additive Common Use Effect Typical Dosage References

Vitamin E Antioxidant Free- radical scavenger 1% by weight of binder (Apeagyei, 2011 [42]; Dessouky et al., 2015 [111])
(Primary antioxidant)
Furfural (C4H3O-CHO) Antioxidant Free- radical scavenger 2% by weight of binder (Apeagyei, 2011 [42], Fini et al. 2016 [33]; Kassem
(Primary antioxidant) et al. 2017 [122])
Butylated hydroxytoluene Antioxidant Free- radical scavenger 5% by weight of binder (Cortés et al., 2010 [28])
(BHT) (Primary antioxidant)
Hindered phenol (IrganoxÒ Antioxidant/ Free- radical scavenger 3% by weight of binder (Dessouky et al., 2015 [120])
1076) Polymer stabilizer (Primary antioxidant)
Sterically hindered phenolic Polymer stabilizer/ Free- radical scavenger 0.6–2% by weight of binder (Apeagyei, 2011 [42]; Zhao et al., 2015 [71];
stabilizer. IrganoxÒ 1010 Antioxidant (Primary antioxidant) Kassem et al., 2017 [122])
Dilauryl thiodipropionate Antioxidant Peroxide inhibitor 1.5% by weight of binder (Apeagyei, 2011 [42], Kassem et al., 2017 [122])
(DLTDP (Secondary antioxidant)
Modified amine surfactant Antioxidant Peroxide inhibitor 1% by weight of binder (Kassem et al., 2017 [122])
(Redicote AP) (Secondary antioxidant)
phenyl-b-naphthylamine Antioxidant Peroxide inhibitor 2% by weight of binder Zaidullin et al., 2013 [15]
(Neozon D) (Secondary antioxidant)
Zinc dibutyl Antioxidant in gear Peroxide inhibitor 1% by weight of binder (Ouyang et al. 2006 [29]; Cong et al. 2012 [38])
dithiocarbamate (ZDBC) oil formulations (Secondary antioxidant)
Fine crystal line long chain Organic WMA Peroxide inhibitor 2.5% by weight of binder (Banerjee et al., 2012 [119])
aliphatic hidrocarbon additive (Secondary antioxidant)
(SasobitTM)
Fatty amine surfactants and Synthetic WMA Peroxide inhibitor 1.5% by weight of binder (Banerjee et al., 2012 [119])
olyethylenes (RedisetTM additive (Secondary antioxidant)
WMX)
Fatty acids C18 unsaturated Synthetic WMA Peroxide inhibitor 0.5% by weight of binder (Banerjee et al., 2012 [119])
(Cecabase RTTM 945) additive (Secondary antioxidant)
Fatty amine derivative Synthetic WMA Peroxide inhibitor 0.5% by weight of binderr (Banerjee et al., 2012 [119])
(Evotherm 3GTM) additive (Secondary antioxidant)
Dilauryl thiodipropionate Antioxidant Prymary + Secondary 2% DLTDP + 1.5% furfural by (Apeagyei, 2011 [42], Kassem et al., 2017 [122])
(DLTDP) + Furfural antioxidant weight of binder
(C4H3O-CHO)
Zinc dialkyldithiophosphate Antioxidant/ butyl Free radical scavenger 1% by weight of binder (Ouyang et al. 2006 [29]; Cong et al. 2012 [38] ;
(ZDDP) rubber stabilizer + peroxide inhibitor Cong et al. 2013 [69])
Crumb rubber Bitumen modifier Radiation shield/ 10–20% by weight of binder (Ali et al. 2013 [99]; Raad et al. 2001 [121]
Peroxide inhibitor Ghavibazoo et al. 2015 [122])
Solution Styrene-Butadiene Co-polymer PMB with improved 3% by weight of binder (Dessouky and Diaz, 2015 [123]; Kassem et al.,
Rubber (SSBR) Solprene- enhanced with anti- ageing behaviour 2017 [124])
1205 oxidant agents
Solution Ethylene-Butylene/ Co-polymer PMB with improved 3% by weight of binder (Dessouky and Diaz, 2015 [123]; Kassem et al.,
Styrene (SEBS) Calprene- enhanced with anti- ageing behaviour 2017 [124])
H6120 oxidant agents
Diatomite/Diatomite Filler/Antioxidant Absorb volatile fraction/ 4% by weight of binder (Cong et al., 2016 [95], Baldi-Sevilla et al., 2016
Hydrophobic Oxigen shield [128])
Hydrated lime Filler/Antioxidant Oxidation inhibitor Up to 10 wt% based on the (Lesueur et al. 2016 [13]; Apeagyei, 2011 [42],
mastic [13,42], 2% by weight of Kassem et al. 2017 [124] Plancher et al. 1976 [125])
binder [124]
Nanosilica Filler/Antioxidant Oxidation inhibitor 4–6% by weight of binder (Yao et al. 2013 [126]; Fini et al. 2015 [127]; Baldi-
Sevilla et al. 2016 [128])
Sepiolite Ultraviolet Radiation/Oxigen shield 5% by weight of binder (Cortés et al., 2010 [28])
antioxidant
Organ-Montmorillonite Ultraviolet Radiation/Oxigen shield 3–4% by weight of binder (Yu et al. 2009 [67]; Liu et al. 2013 [130])
(OMMT) antioxidant
Layered Double Hydroxides Ultraviolet Radiation shield 3% by weight of binder (Zhao et al. 2015 [71]; Wu et al. 2012 [97], Xu et al.
(LDHS) antioxidant 2015 [132]; Zhang et al. 2016 [98])
Organophilic LHDs (OLHDs) Ultraviolet Radiation shield 3% by weight of binder (Xu et al., 2015 [132])
antioxidant
Triethoxyvinylsilane LDHs Ultraviolet Radiation shield 2% weight of binder (Zhang et al., 2016 [98])
(TEVS-LDHs) antioxidant
Carbon black (CB) Ultraviolet Radiation shield/ 0.5–1% by weight binder (Cortés et al. 2010 [28]; Cong et al. 2012 [38];
antioxidant Peroxide inhibitor/ Free Apeagyei, 2011 [42]; Kassem et al. 2017 [124];
radical scavenger Zhang et al. 2009 [129])
Octabenzone (UV531) Ultraviolet Ultraviolet absorber 0.5–0.6% by weight of binder (Cong et al. 2013 [69]; Feng et al. 2016 [70])
antioxidant
Bumetrizole (UV326) Ultraviolet Ultraviolet absorber 0.5–0.6% by weight of binder (Cong et al. 2013 [69]; Feng et al. 2016 [70])
antioxidant
Hindered amine light Ultraviolet Ultraviolet absorber 0.6% by weight of binder (Feng et al., 2016 [70])
stabilizer (HALS) antioxidant
(Tinuvin 770Ò)
the formation of the peroxy radicals [28,29,118]. Among the addi- among others, seek to act as a screen that blocks ultraviolet radia-
tives that break the chain through inhibiting the reaction of perox- tion from accessing oxygen, thereby improving resistance to ageing
ide radicals (secondary antioxidants) it is common to find hindered [118,131].
amine stabilizers and hindered phenolics along with sulphur com- In relation to this issue, some studies [97,132] have specified
pounds [120]. The two main typologies of antioxidant can also be the Layered Double Hydroxides (LDHs) as a material resistant to
combined, resulting in a thermo-oxidative stability much greater ultraviolet light that could be interesting to employ as an additive.
than the sum of the individual antioxidants. In relation to this, This has a layered structure that protects from radiation through
Apeagyei [42] found through rheological evaluation that the com- some of the metals present in its structure, which absorb the radi-
bination of DLTDP (secondary) and furfural acid (primary) resulted ation and act as a shield. This additive increases the penetration
in a lower rate of ageing than the use of these antioxidants sepa- and ductility of bitumen and decreases the softening point. The
rately. In addition, these reduce the stiffness of bitumen at low study of bitumen rheology with and without the addition of 5%
temperatures and increase it at high temperatures. of LHDs by weight of bitumen shows a greater resistance to ageing
On the other hand, several studies [99,121,122] have proposed when this additive is incorporated. This kind of additive can lead,
the use of crumb rubber in certain conditions for its anti-oxidant however, to compatibility issues with bitumen since it possesses
effect demonstrated through physical and rheological tests. Crumb hydrophilic layers of an inorganic nature [132]. Consequently, it
rubber has been shown to affect the kinetics of ageing in two ways. has been proposed to synthesise this compound in a manner that
First, CRM retards asphalt oxidization through the release of is more organophilic (OLHDs) to produce an additive that behaves
antioxidants. Second, CRM continued to interact with asphalt dur- even better than the original in relation to thermal susceptibility
ing its ageing through the absorption of aromatics [122]. The use of and variation in rheological parameters after ageing. A similar
copolymer additives such as Solution Styrene-Butadiene Rubber or result can be obtained by the addition of TEVS-LDHs (Tri-
Solution Ethylene-Butylene/Styrene (SEBS) has also shown to be ethoxyvinylsilane surface organic modified layered double hydrox-
highly effective in reducing ageing, in addition to improving the ides) which has been shown to decrease the tendency of bitumen
intermediate temperature stiffness and producing to greater stiff- to deteriorate, with the result that LDHs, with a surface modified
ness at high temperatures (increasing the rutting resistance) when by TEVS, were far superior to unmodified materials in terms of
compared with the base control binders [123,124]. enhancing resistance to UV ageing [98]. This could be due to the
The addition of Hydrated lime [13,125] as a contribution filler to fact that the organic modification of the TEVS surface improves
the mixture is common practice at industrial scale, not only for its the dispersion and stability of LDHs in bitumen.
antioxidant effect, but also because of the other benefits that it Further, in order to enhance the ageing resistance of bitumen,
provides in terms of the final properties of the asphalt mixture. ultraviolet absorbers (UVA) have been used as a modifier to inhibit
The main reason why a strong base material of this type affects the ageing process of bitumen by converting the destructive UV
ageing is linked to the concentration of polar molecules from the energy into harmless heat energy. Feng et al. [70] proposed the
bitumen on its surface, which prevents them from further reacting use of additives such as octabenzone, bumetrizole and tinuvin
[9]. Cong et al. [95] suggested using diatomites as binder modifier, 770 evaluated through FTIR analysis and viscosity and module
whether in their natural state or after a treatment that renders complex index, the latter additive being the one that presents
them hydrophobic. In both cases, better ratios of ageing were the optimal performance in terms of improving UV ageing. Never-
found in relation to penetration, point of softening, and dynamic theless, in all of these cases the reactions of chain scission, poly-
viscosity with respect to that of the bitumen base. This additive, condensation and oxidation of the bitumen are slowed down by
on the one hand, absorbs the volatile fraction and, on the other the UVAs. The introduction of these additives does not generate
hand, acts as a shield that prevents the entry of oxygen. Other stud- new chemical structures in the bitumen since no chemical reaction
ies [126,127,128] have explored the antioxidant properties of occurs between the bitumen and UVAs. The UVAs also have little
nanosilica, finding an improved rutting resistance and a reduction influence on the branched aliphatic structure of the bitumen,
in overall susceptibility to oxidation. This latter effect could be although they increase its aromatic structure. The joint use of
linked to the large surface area and pore size as well as the pres- photo and thermal-antioxidants has also been studied [69,71]. In
ence of hydroxyl groups on the nanosilica surface. The interaction relation to this, Cong et al. [38] reported that antioxidants or UV
of these groups with both polar aromatics and asphaltene mole- absorbers used separately cannot improve both thermal stability
cules contribute towards a delay in the oxidation process. and photo stability, and in some cases even the opposite effect
Most of the studies focus on analysing the effects of a specific was found for thermal-oxidative ageing or UV ageing. This could
additive on a given type of bitumen, whereas it would be desirable be influenced by the typology of the thermal antioxidant; peroxide
to consider a range of different binders. Kassem et al. [124], for decomposers generally result in being more effective against a
example, found that the use of a primary phenolic additive varied combination of photo and thermal oxidation than dark oxidation
according to different binders. It is important to identify the pre- [12]. Nevertheless, the joint use of antioxidants and UVAs (ZZDP
cise effect that an additive will have on the aged binder and if, and UV351 in this case) could improve both ageing resistance for
for instance, this effect changes according to whether a polymer base or polymer modified binder [69]. Feng et al. [70] attributes
modified or unmodified bitumen was used. to UVA some benefits for thermal oxidation stability, proposing
With respect to additives used against ageing caused by ultravi- that free radicals caused by the heat from bitumen molecules
olet radiation, some recommendations include carbon black (CB) or may be captured by the UVAs.
inorganic additives of the montmorillonite type, such as sepiolite Finally, studies such as those of Karlsson & Isacsson [133] or
or organ-montmorillonite (OMMT) [28,67,129]. Carbon black is a Contreras et al. [134] have examined the diffusion of rejuvenating
very versatile additive since it acts as a primary antioxidant, additives in bitumen to determine optimal temperature and con-
hydroperoxide decomposer and photo-oxidative stabilizer. Its tact times using Fourier transform infrared spectroscopy with
effectiveness has been attributed to the many surface groups such attenuated total reflectance (FTIR-ATR). This technique adds to
as the quinones, phenols, carboxyphenols and lactones present on the already discussed FTIR, and uses a horizontal ATR accessory
its structure [42]. On the other hand, Liu et al. [130] noticed that with Zinc Selenide (SeZn) crystal [133] or a diamond prism of sev-
the addition of montmorillonite notably improved the short term eral rebounds [134]. In any case, bitumen is placed on the glass
ageing performance of bitumen, although such an effect was not with a gauge of between 500 and 200 lm. A rejuvenating film of
evident in terms of long-term performance. These nano materials, the same thickness is then placed over the binder with a new
gauge, maintaining a constant temperature throughout the process tives. Thus it is possible to study the formation of sulfoxides
of diffusion. For each temperature, a diffusion constant is calcu- and carbonyl compounds (FTIR analysis), to observe the
lated through a concentration graph (the absorbance of different changes in the bitumen micro-structure (Atomic force micro-
peaks of the IR spectrum obtained as a function of the time in sec- scopy), to assess the evolution of the different fractions of the
onds) assuming a one-dimensional system that follows the Fick’s bitumen (TLC_FID) or to analyse the amount of molecules of a
law. The optimal diffusion results are obtained when the rejuvena- certain size as well as their connections through their weight
tor and bitumen were at the test temperature from the beginning (evaluation HP-GPC). These are techniques that should be used
of the process. in conjunction with rheological analyses to provide a global
perspective of what is really happening when the binder ages.
- The anti-ageing additives most commonly used in bitumen are
6. Conclusions antioxidants, which act in two different ways, either by inhibit-
ing the formation of peroxides or by absorbing free radicals. In
The ageing process of asphalt pavements can significantly affect relation to the additives specific to UV ageing, the Layered Dou-
their durability and service life. Therefore, the analysis of how this ble Hydroxides (LDHs) and their modifications have been
phenomenon affects bitumen has been the subject of a number of widely studied to prevent ultraviolet radiation from accessing
research articles over the years. This paper offers a sound basis on oxygen (thus enhancing the resistance of the binder to ageing).
which to develop further studies since it presents a review of the In addition, the ultraviolet absorbers (UVA) have also been
causes and factors involved as well as the influence of the compo- proved as effective modifiers for inhibiting the ageing process
nents of the mixture and the use of polymer-modified bitumens. In of bitumen via converting the destructive UV energy into harm-
addition, it describes the different techniques that are currently less heat energy. The joint use of antioxidants and UVAs could
employed to simulate and analyse the dynamics of bitumen ageing improve the ageing resistance of both common and polymer
and the additives most commonly used to prevent or reverse their modified binder but generally, a preliminary study is needed.
effects. Based on the review presented here, the following conclu- In any case, the study of any of these additives should not be
sions can be drawn: limited to a specific binder but rather binders of different origin
and their interactions with polymer-modified binders should be
- The main cause of binder ageing is the oxidation that leads to considered.
irreversible chemical changes in the binder, which, in turn, have - In accord with the previous conclusions, although the main
an impact on its mechanical response and resistance. However, mechanism underlying the ageing phenomenon has been
the study of ageing should include UV simulation since, even widely studied from different points of view and there are sev-
though its penetration only affects the upper layer of the course, eral techniques for its analysis, there are still certain aspects
several studies have demonstrated that its effects are different that could be improved. For instance, the correlation between
from those found in the conventional thermo-oxidative tests, results from the field and those of the laboratory can still be
with viscosity and stiffness values that increase to a greater enhanced. A consideration of the level of penetration of the oxi-
extent after exposure to ultraviolet radiation. For this reason, dation, the comparative study of different typologies of mixture
its effect on surface layers should not be neglected, particularly with different components, or studying the influence of the UV
in zones of high solar radiation and humidity. effect on the upper layers of the pavement through a more stan-
- It is important to take into account the differences in ageing dard method could reduce the differences between laboratory
behaviour between binders that share similar characteristics results and real behaviour. With regard to anti-ageing additives,
but are of different origin, as well as the influence of the other in order to improve their applicability it could be interesting to
components of the mixture on binder ageing such as the void further explore their effects in a wider range of binders, study
content or the binder content. The nature of the aggregates or the joint use of antioxidants and UV anti-ageing additives, as
the filler employed can also influence the chemical reactions well as examine on site the diffusion and effects of these addi-
of the binder through the ageing process. The analysis of the tives throughout the course of the ageing process.
ageing of a polymer-modified binder requires special attention
since it involves the degradation of the polymer within the
Conflict of interest
remaining bitumen, and the resulting chemical reactions affect
the ageing dynamics in different ways depending on the type of
None.
polymer.
- The RTFOT for short-term ageing and the PAV test for long-term
ageing are the tests most widely used to simulate binder ageing, References
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Construction and Building Materials 192 (2018) 593–609

Contents lists available at ScienceDirect

Construction and Building Materials

Understanding the bitumen ageing phenomenon: A review

Most common techniques employed in bitumen ageing analysis were discussed.

proportion and molecular weight of the different fractions, and

4.1. Rheological evaluation

The study of rheology is one of the methods most commonly

Technique Typology of Parameters analysed References

Additive Common Use Effect Typical Dosage References

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