This is a postprint version of the following published document:

Agzenai , Y., Pozuelo, J., Sanz, J., Pérez, I. y Baselga, J.

(2015): Advanced Self-Healing Asphalt Composites in the
Pavement Performance Field: Mechanisms at the Nano
Level and New Repairing Methodologies. Recent Patents
on Nanotechnology, 9 (1), pp. 43-50.

© Bentham Science Publishers, 2015

 Advanced Self-Healing Asphalt Composites in the Pavement
Performance Field: Mechanisms at the Nano Level and New
Repairing Methodologies
Yahya Agzenai1, Javier Pozuelo1, Javier Sanz2, Ignacio Pérez3 and Juan Baselga1*

Abstract: In an effort to give a global view of this field of research, in this mini-review we highlight the most
recent publications and patents focusing on modified asphalt pavements that contain certain reinforcing
nanoparticles which impart desirable thermal, electrical and mechanical properties. In response to the
increasing cost of asphalt binder and road maintenance, there is a need to look for alternative technologies and
new asphalt composites, able to self-repair, for preserving and renewing the existing pavements. First, we will
focus on the self-healing property of asphalt, the evidences that support that healing takes place immediately
after the contact between the faces of a crack, and how the amount of healing can be measured in both the
laboratory and the field. Next we review the hypothetical mechanisms of healing to understand the material
behaviour and establish models to quantify the damage-healing process. Thereafter, we outline different
technologies, nanotechnologies and methodologies used for self-healing paying particular attention to
embedded micro-capsules, new nano-materials like carbon nanotubes and nano-fibres, ionomers, and
microwave and induction heating processes.

Keywords: Asphalt pavements, induction heating, micro-capsules, microwave absorption, road engineering,
self-healing, carbon nanotubes, graphite, silicon dioxide, titanium dioxide.

1. INTRODUCTION content promotes healing through polar-polar bonds. Addi-

tionally, the wax content is also an important healing agent
Asphalt is a viscoelastic material produced through the
due to the van-der-Waals interactions between long chain
refining of petroleum and widely used on paving roads and
aliphatic hydrocarbon molecules.
streets (more than 94% of pavements around the world are
based on asphalt binder). It adheres to aggregate particles Healing, defined as the partial recovery of mechanical
binding them in asphalt concrete. Ideally, asphalt must pre- properties (i.e. strength and stiffness) during the rest period,
serve its initial properties despite the daily traffic loads and can be understood as a diffusion process between the crack
the climate changes (especially temperature and moisture) faces which erases the discontinuity of the material [2, 4, 5].
for a prolonged period. However, after an in-service period To quantify this process many factors should be considered
of a few years, the flexibility and relaxation capacity of as- such as type of the mixture, rest period and temperature. For
phalt concrete decreases, the binder becomes brittle causing instance, a soft asphalt binder shows a higher healing capaci-
aggregate segregation, and an extensive damage appears on ty than a hard asphalt binder; also, high asphalt content fa-
its surface. This ageing process begins at the hot mixing ini- vours healing [6, 7] as well as long rest periods before load-
tial stage and continues throughout its service life due to ing [8], especially when the material is subjected to high
heat, oxygen, and ultraviolet radiation (UV) exposure. That temperatures [9].
is the reason why asphalt concrete wearing courses should be In view of the self-healing property of asphalt and his
regularly maintained and repaired [1]. temperature dependency it is reasonable to develop new
It is well-known that asphalt has a self-healing capacity thermal-based technologies and composite materials to repair
for repairing ageing damage which restores its functionality pavement. Various schemes have been proposed and suc-
at least to some extent [2, 3]. Its complex chemical composi- cessfully applied at both, laboratory and filed scales. Here,
tion contributes to healing, i.e. the aromatic components we will focus on microwave heating, induction heating, ion-
promote healing because of the π -stacking of the aromatic omers and micro-encapsulation.
rings, or its amphoteric character associated to the heteroatom The overall objective of this mini-review is to examine
an updated current state of knowledge on fatigue-healing in
*Address correspondence to this author at the Department of Materials asphalt pavement. We will try to identify the principal mech-
Science & Engineering (IAAB), Universidad Carlos III de Madrid, Av. anisms of self-healing in asphalt which are necessary to be
Universidad 30, 28911 Leganés, Madrid, Spain; Tel: +34 91 624 94 67; considered in self-healing pavement design. Then we will
Fax: +34 91 624 94 30; E-mail: jbaselga@[Link]

1
Department of Materials Science & Engineering (IAAB), Universidad Carlos III de Madrid, Av. Uni-
versidad 30, 28911 Leganés, Madrid, Spain; 2Department of Electrical Engineering, Universidad
Carlos III de Madrid, Av. Universidad 30, 28911 Leganés, Madrid, Spain; 3Technical Department,
PROAS S.A., Ctra. Daganzo, M-100, Km 5,5. 28806 Alcalá de Henares, Madrid, Spain
1
summarize the investigations made during the last two
where R is the net macroscopic healing,  !! (!) is the intrinsic
decades to repair old pavements, macro-cracks and potholes.
healing function of the material, ∅(!, !) is the wetting distri-
bution function, and τ is the time variable.
2. SELF-HEALING The wetting distribution function, ∅ !, ! , defines wet-
Healing is a well-known phenomenon which occurs in ting at the contact of the two cracked surfaces in a domain X
materials and biological systems. It can be defined as the over time t. For analytical purposes, the wetting function can
ability of a material to repair damages automatically and be simplified by considering that wetting occurs at a constant
autonomously. To enhance this property sometimes an ex- rate and this rate is dictated by the mechanical, and the vis-
ternal trigger is necessary; in this work we focus on the non- coelastic properties of the asphalt material. For example,
autonomous self-healing process [10]. asphalt with higher surface free energy will have stronger
intermolecular forces of attraction between the two cracked
Although the healing capacity of different materials has surfaces and will therefore wet at a faster rate. Based on the
been addressed in the literature, only a few papers report on
quasi-static analysis of cohesive fracture of linear viscoelas-
asphalt self-healing. Suresh classified the healing mecha-
tic media, Schapery developed an equation that relates the
nism, or fatigue crack growth delay, into five categories [11]:
work of cohesion and the material properties (Poisson coef-
(i) Plasticity-induced: during crack propagation the material
ficient and creep compliance parameters) with the wetting of
is plastically deformed at the crack tip; once the load is re-
the crack surfaces. Thus, the rate of wetting of a crack sur-
moved, residual stresses in the matrix induce micro-closures face is given by [14]:
and reduce the theoretical opening of the crack front; (ii)
Oxide-induced: deposit of debris oxide on freshly broken !!
surfaces especially in humid conditions; the thickness of this !∅(!, !) 1 !!! !
(2)  
= !! = ! − !!
oxide layer may be large enough to prevent total closure !" !! !! 4(1 − ! ! )!!! !
changing the propagation kinetics of the crack; (iii) Rough-
ness-induced: the irregularities and the micro movements of where, !! is the work of cohesion; ν is the Poisson coeffi-
the fracture surfaces prevent the total closure in absence of cient; !! , !! , and m are the creep compliance parameters
load; (iv) Viscous fluid-induced: a viscous fluid penetrates obtained from the generalized Andrade creep function
within a growing fatigue crack affecting its propagation rate; ! ! = !! + !! ! ! ; and !! is a material constant that can be
and finally, (v) Transformation-induced: phase transfor- calculated from m. The meaning of  !! , β, and !! is illustrat-
mations at the tip of the fatigue crack can delay the crack ed in Fig. (1).
growth rate.

2.1. Hypothetical Mechanisms

Crack healing occurs immediately after removing the Tensile stress in this zone
external load; at this time two phenomena take place: first
the viscoelastic recovery in the bulk material, and second the
Crack closing speed
healing in the cracked zone. The difference between both Crack Surface
processes is that while the former is due to molecular rear-
rangement within the material, the latter is a consequence of
wetting and inter-diffusion between the faces of the crack to
reach the properties of the virgin material. Based on the pio-
neering work of Wool and O´Connor in polymer healing, the
β
healing process is made of the following three stages: Healing process zone
i. Wetting of the two faces of a nano-crack.
ii. Interfacial cohesion between the crack faces. Fig (1). Crack propagation and fracture process/healing zone in
iii. Diffusion and randomization of molecules from one face mode I loading (adapted from Little et al. [2]).
to the other to reach the properties of the virgin material.
The next steps of the healing asphalt process (i.e. the
By using the reputed model proposed by de Gennes to
strength gain caused by interfacial cohesion and diffusion of
explain the movement of a polymer molecule in a worm like
molecules between crack faces) are described by the intrinsic
fashion inside a cross linked polymeric gel [12], Wool and
O´Connor suggested a new approach to describe the healing healing function  !! ! . Little et al. [15]. proposed a modi-
by combining an intrinsic healing function of the material fied form of the Avrami equation, equation (3), which is
with a wetting distribution function using the following con- commonly used to describe processes such as kinetics of
volution integral [13]: phase transformations in solids and chemical reaction rates.
!
!! ! = !! + !(1 − ! !!" ) (3)  
!!!
!∅(!, !)
!= !! (! − !) !"   (1) Where, p, q, and r, are material-related parameters that de-
!!!! !" fine the time-dependent strength gain at the interface. This
equation introduces a constant, !! , which represents the in-

2
stantaneous strength gain across wetted crack surfaces as a
result of their interfacial work of cohesion, and a second
term, which is a time-dependent strength gain caused by in-
ter-diffusion of the molecules between crack faces.
Among other attempts, Darabi et al. [16] suggested a
continuum damage mechanics framework to model asphalt
healing, in line with Palvadi et al. [17] who proposed another
model to quantify healing in asphalt composites. Hou et al.,
[18] based on a phase field model, simulated the self-healing
mechanism of asphalt from mechanical and thermodynamic
arguments; they realized that the reduction of surface free
energy originates the gradual disappearance of the initial
cracks as temperature increases. Considering self-healing as
a diffusive process, molecular dynamic simulations can also
be employed to investigate the internal mechanism. A re- Fig. (2). Typical RDEC plot with three behavior steps. (Adapted
markable review was published recently by Greenfield re- from Carpenter et al. [24]).
garding bituminous materials [19].
(iii) Ultrasonic waves. Films of asphalt binder held be-
2.2. Methods to Quantify Asphalt Concrete Self-Healing tween two protuberances (glass or steel) simulating two ag-
As the healing process in pavements is usually related to gregates in the asphalt mix, are submitted to cyclic loadings
micro cracking and fatigue damage, the most common way in both tension and compression; the rate of healing in the
to quantify it involves the use of diverse fatigue tests carried asphalt film is quantified by ultrasonic wave transmission.
out with different rest periods allowing asphalt to heal. Dif- When the signal amplitude decreases it reflects film damage
ferent approaches have been successfully used to quantify while if it increases healing process may take place [25].
the magnitude of healing in different asphalt binders, mas- More advanced techniques using neural networks for ultra-
tics, or mixtures. sonic detection can evaluate more quickly and effectively the
damage state of asphalt mixture [26].
(i) Although there is a lack on a widely accepted test to
measure the fatigue performance of asphalt binders, the use (iv) Dynamic mechanical analysis (DMA) is another
of Dynamic Shear Rheometer (DSR) for evaluating damage technique used to measure the fatigue characteristics of as-
behaviour under continuous oscillatory shear stress (fatigue phalt mixtures (only asphalt binder with fine aggregates).
tests) and damage recovery after load removal (healing tests) The DMA is an efficient tool to perform dynamic analysis of
has been reported by different authors like Lu et al. [20], Qiu asphalt mixtures under controlled-strain: tension, compres-
et al. [21] and Santagata et al. [22] Different parameters like sion and torsion. There are two methods to evaluate the fa-
Relative Dissipated Energy ratio (DER), Crack Propagation tigue life of the asphalt mixtures using this technique: (a) the
Amplitude (RCPA) and Relative Healing Index (RHI) have loss of the normalized dynamic modulus, and (b) the rate of
been described to quantify the fatigue behaviour of the as- change of dissipated energy which is the amount of energy
phalt binders. dissipated in each load cycle due to the damage of the spec-
imen. A deep theoretical background of this technique and
(ii) Shen et al. [23] use the Four-Point Bending Beam Test the methodology used to perform measurements are reported
and the Ratio of Dissipated Energy Change (RDEC) ap- in the work of Kim et al. [27].
proach to evaluate the fatigue behaviours of different asphalt
mixes. During a cyclic fatigue test, the stress-strain hystere- 3. NOVEL TECHNOLOGIES IN NON-AUTONOMOUS
sis loops do not overlap. The area inside this loop indicates SELF-HEALING
the amount of dissipated energy in the form of mechanical
work, heat generation, or damage. RDEC is defined as the Pavement repair and rehabilitation is handled in many
ratio of dissipated energy change between two consecutive ways, ranging from sealing or filling cracks, to resurfacing,
loading cycles and is given by: which is both uneconomical and technically unsound. The
challenges are to increase the lifetime of the asphalt pave-
!"!!! − !"!
!"#$ = ments, to make the pavements apt for an immediate and local
!"! repair of the generated damage without stop traffic circula-
Fig. (2) illustrates the three stages in which the damage tion and to recycle the old pavements.
curve represented by RDEC vs. loading cycles can be divid- As it has been already mentioned, the healing rate of as-
ed. After an initial loading period (step I) the damage curve phalt increases with temperature; for this reason, the addition
develops a plateau. During this plateau step (step II) there is of conductive additives that may improve its thermal and
a relatively constant percentage of input energy being turned electrical conductivity and the use of adequate devices to
into damage. This step extends all over the main service life locally heat the pavement have been proposed to heal the
until a dramatic increase in RDEC appears which gives a cracks and repair the pavement. Based on the temperature
sign of true fatigue failure (step III). effect two main techniques are used:

3
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4
Table 1. Benefits and drawbacks of asphalt self-healing techniques.

Technique   Benefits Drawbacks

Microwave Fast, selective and uniform heating. High costs.

More reproducibility and better yields. Difficulty to control deepness of penetration which depends mainly on the frequency
Fits environmental issues. and dielectric properties of the material.

Easy to move from one location to other. Need more knowledge and studies for each system and each geometry.

Multi-time recovery. Has to be shielded to avoid interference with other equipment.

Could affect the body organs especially at high frequency.
Explosion possibility for example in presence of volatile reactants.
Depends on the electrical conductivity of the material.

Induction heating Can heat materials with low thermal No data about in situ progress.
conductivity. High manufacture costs.
Transferable readily. The recovery ratio is limited.
Fast, selective and uniform heating. Heating mechanism is much more complicated than conventional techniques.
Fits environmental issues. Depends of the electrical conductivity of the material.
Multi-time recovery.

Encapsulation High recovery ratio. Only work in the top-layer.

Good compatibility Helpful only once.
Additional fixing agent cannot be outfit once the original agent has been drained.

Ionomers Multi-time recovery. Blend.

Stable at high temperature. Limited to cracks in first stage.
Good compatibility

Rejuvenator materials consist of lubricating and extender another procedure employing anthracite coal. It is an excel-
oils, which contain a high proportion of maltene constituents. lent lossy microwave absorbing material due to its high car-
Su et al. reported the synthesis of novel microcapsules in bon content that may be added to the asphaltic mixture in the
which the rejuvenator core had been encapsulated by a hard range 10-30 wt%. Other reason for the use of anthracite is its
shell, which was fabricated by in-situ polymerization of hydrophobicity, which makes it chemically stable and
methanol–melamine–formaldehyde (MMF) pre-polymer. weather resistant. These asphaltic concrete compounds facili-
The mechanism of this method was a two-step coacervation tate the penetration of heat, which in turn debond ice from
with the aid of styrene maleic anhydride as a nonionic dis- the concrete and create strong bonds throughout the repaired
persant. The compact shell structure obtained with this pavement [44-46].
method made the microcapsules able to resist the melting
temperature of asphalt [40, 41]. Further and importantly, for keeping uniform temperature
of the asphalt materials exposed to microwave radiation,
Several proposals to prepare advanced asphalt compo- Hutcheson et al., [47] used another reinforcing candidate,
sites susceptible to microwave heating in an efficient manner ferrite powder, a ferromagnetic material, with Curie tempera-
are reported in the literature. Jeppson, was the first to use ture between 100 and 125 ºC and high volume resistivity.
microwave energy for heating and reconditioning of an as- Compared to metals, ferrite powders are preferred as they do
phalt pavement. In his US patent No. 4,319,856 he describes not oxidize during heating although they appreciably en-
a large variability in the ability of asphalt to be heated by hance the heating of asphalt only up to the Curie tempera-
microwave energy and he attributes most of the heating to ture. Thereafter, further radiation will not be effective and
silicate rocks absorbing the microwave energy in varying heating will be relatively insignificant due to the high vol-
degrees [42]. To solve this, he used a sheet of microwave ume resistivity. This approach was very useful reducing sig-
reflective material such as a metal foil to be applied below nificantly the required time to melt asphalt with only 2 to 5
the road surfaces to concentrate the microwave energy in the wt.%. The advantage of ferrites as good lossy microwave
top layer of asphalt material. This was achieved reflecting materials was confirmed by Bowen et al. in their US patent
the microwave energy from the metal foil layer [ 43]. No. 5092,706; they provide a new methodology for repairing
Following the same concept, Long et al., proposed in a a void such as a pothole in asphalt pavement, mixing ferrites
series of patents the use of a three-layer sheet on top of the in the tack used for the tack layer and then applying micro-
concrete: a reflective layer, a heat insulator layer and a wave energy to heat the tack which forms a strong interface
graphite containing epoxy top layer. Although this technique bond between the asphalt patch and the inner surface of the
reaches his objective it remains very expensive. To reduce pothole [ 48].
the variability in microwave heating, Long et al. considered

5
 Regarding induction heating, García et al. attempted to es [56]. Sun et al. employed carbon nanotubes to improve
make conductive asphalt mastic by addition of steel wool the compatibility of SBS rubber and asphalt. When the SBS
fibres, and used induction heating to heat the mastic enhanc- absorbs the carbon nanotubes, the SBS becomes more evenly
ing its self-healing properties [31]. The results suggested the distributed in the asphalt matrix resulting in a more stable
existence of a limiting volume fraction of fibres at which all composite with better performance [57]. The effects of SBS
the fibres were surrounded by asphalt binder; above this val- on the properties of modified asphalt mixtures have also
ue temperature don’t increase anymore appearing clusters in been studied in the presence of nano-SiO2. The results of
the medium susceptible to oxidation and loss of properties. workability tests (Marshall Stability, indirect tensile strength,
Furthermore, this value was coincident with the quantity tensile strength ratio and indirect tensile stiffness modulus)
needed to reach the maximum conductivity of the mastic, indicated that the mixtures with 5% SBS and 2% nano-SiO2
below this optimum volume fraction the mastic behaves as a had the most improved mechanical behaviour [58].
non-conductive material, although the heating effect still
Hao et al., mixed nano calcium carbonate into asphalt.
exist as a result of local conductivity [49]. To find the opti-
Data showed that the mixing of 6% of these inorganic nano-
mum fibre content Garcia et al. used the percolation theory,
particles improved both the high temperature performance
i.e. the volume of conductive additives was progressively
and water stability of asphalt concrete [59]. Nanoclay parti-
increased and each mixture was analysed separately until the
cles also modify and improve the rheological characteristics
resistivity dropped suddenly to a second plateau [50]. It was and the rutting resistance of bitumens and asphalt compo-
proved that the use of induction heating didn’t damaged the
sites. However, fatigue performance decreases at low tem-
mastic and the number of times that a pavement could be
peratures [60, 61].
healed was dependent on the maximum temperature reached.
Furthermore, sand–bitumen ratio was a key factor in the de- Tanzadeh et al. carried out wheel-tracking test on ordi-
sign of conductive asphalt mixtures and it couldn’t be con- nary and nano-TiO2 modified hot mix asphalt samples. The
sidered separately from the amount of conductive particles. results of their study showed that the use of nano-TiO2 in
To increase the sand-bitumen ratio, they added graphite [50]. asphalt binder samples improves rutting resistance in asphalt
pavement under dynamic loading in comparison with the
The use of other forms of carbon and their effects on as-
ordinary mixtures [62]. Shafabakhsh et al., also investigated
phalt properties has also been explored by other groups. Wen
the effect of nano-TiO2 in asphalt mixtures. They found that
et al. pursued to increase the softening point of asphalt by
replacing 5% of bitumen by nano-TiO2 the creep behaviour
addition of carbon black. They achieved a notable increase of asphalt mixture even at high temperature was improved.
from 40.1 to 80.9 ºC upon addition of 7 vol.% of carbon
Nano-TiO2 prevents tensile cracks from being easily gener-
black in combination with sand. At the same time the addi-
ated by horizontal tensile stresses [63].
tion of carbon black decreased the electrical resistivity of the
asphalt, especially when the carbon black volume fraction Qiu et al., conducted self-healing tests to study the effect
exceeded the percolation threshold [51]. of nanoparticles (full vulcanized rubber nanopowders) into
asphalt binder. Preliminary results indicated that the shear
A comparative study of three additives: carbon fibres,
modulus recovery (1.5 hours) occurred faster than strength
graphite and carbon black were reported by Wu et al. Their
recovery (6 hours). It could be concluded that these nanopar-
results showed that conductive carbon fibres were much
ticles improved the self-healing capacity of asphalt binder
more effective than conductive fillers (graphite or carbon
and, thus, the service life. However, it is important to take
black) to increase the conductivity of the asphalt mixtures,
the different test temperatures into account before drawing
but it was very difficult to prepare well dispersed mixtures general conclusions since vulcanized rubber is insoluble in
because fibres form cluster aggregates in the mixture. In ad-
asphalt [64].
dition, a remarkable enhancement of conductivity was de-
tected using a combination of two or more fillers [52] that Only a few studies have been conducted using ionomers;
could be explained in terms of two kinds of contacts: short in most cases they were employed in polymeric systems
range contacts within the clusters and long range contacts whether to control morphology, modify physical properties
due to the bridging effect of fibres [52-54]. and/or to enhance self-healing behaviour. For instance, Var-
ley and Zwaag reported a comparative work between Surlyn
The decrease of the characteristic length of conductive
8940 ionomer and a non-ionic polymer with similar back-
fillers for asphalts down to the nanoscale is a challenging
bone: linear low-density polyethylene LLDPE. Results show
issue. The main envisaged benefit is concerned with the skin
that the healing rate under ballistic impact depends mainly
depth when using high frequency radiation for heating. In the
on the presence of ionic clusters [65]. Regarding application
microwave range, skin depth may be as small as tens of na- on paving materials, an European patent EP0548412 A1 pub-
nometers so the majority of the filler may be inactive against
lished by Luc and al. report the use of ionomers in a bitumi-
radiation if its size is in the micron range or higher.
nous material; the resulting systems were able to resist to
A limited number of works have been reported to date flow at high temperature (up to 210 ºC) [66]. US Pat. No.
with nanofillers. Pang et al. reported bitumen modified with 4839404 describes new bituminous materials with more ad-
inorganic nanomaterials prepared from carbon nanotubes, herence to aggregates, based on α, β ethylenically unsaturat-
nano-ceria and coal tar, which had good high and low tem- ed carboxylic acid ionomer and any kind of bitumen. Alt-
perature performance and anti-aging properties [55]. Goldin hough the patent provides the manufacture method, no char-
et al. also used carbon nanotubes dispersed in bitumen along acterization of the mechanical, rheological or thermal prop-
with technical carbon and organoclay to produce an organic- erties of the resulting products is given [67]. Shi Ying stud-
based asphalt concrete apt to be utilized to make road surfac- ied asphalt/copolymers of ethylene and methacrylic acid

6
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