Durability of bitumen

Bitumen is affected by presence of oxygen, UV

radiation, and temperature changes.
It ages and hardens during its production,
mixing, storage, and in service.
For asphalt pavements to achieve its design life,
bitumen should not harden excessively.
Thus, durability of asphalt pavement depends on
durability of bitumen.
Bitumen ageing / hardening
4 principal mechanisms:

Oxidation
Loss of volatiles
Physical hardening
Exudative hardening
 Oxidation

Bitumen slowly oxidizes when in contact with air.

Degree of oxidation depends on temperature,
time duration, and thickness of bitumen film.
Oxidation rate doubles for each 100C increase in
temperature above 1000C.
Hardening due to oxidation is the main cause of
ageing of bitumen.
 Loss of volatiles

Evaporation of volatile components depends

mainly upon temperature and the conditions of
exposure.
Penetration grade bitumens are relatively
involatile and therefore the amount of hardening
resulting from loss of volatiles is usually fairly
small.
 Physical hardening

This occurs when bitumen is at ambient

temperature and is usually attributed to
reorientation of bitumen molecules and the slow
crytallisation of waxes.
Physical hardening is reversible in the sense
that upon reheating the original viscosity of the
bitumen is obtained.
 Exudative hardening

This results from the movement of an oily

component which exudes from the bitumen into
the mineral aggregate.
It is a function of both the exudation tendency of
the bitumen and the porosity of the aggregate.
 Hardening of bitumen during
storage

When bitumen is stored in bulk at high temperature very

little hardening occurs, because the surface of the
bitumen exposed to oxygen is very small in relation to
the large volume.
If the bitumen is being circulated and is falling from the
pipe entry at the top of the tank to the surface of the
bitumen, significant hardening may occur because
surface area to volume ratio of the bitumen is very high.
 Hardening of bitumen during
mixing with aggregate
During mixing with aggregates and filler, bitumen film coating
is 5 15 microns thick.
So, when bitumen is mixed with hot aggregates and spread
into thin films in the pugmill, conditions are very favourable for
oxidation and loss of volatiles.
As a rule of thumb, during mixing bitumen hardens by approx
one grade, e.g. 100 pen to 70 pen, 70 pen to 50 pen etc.
The degree and amount of hardening depends on various
factors such as, temperature, duration of mixing, bitumen
content (relates to bitumen film thickness) etc.
To avoid excessive hardening, these need to be controlled.
 Hardening of bitumen during mixing
with aggregate
Fig. 8.1 shows that reducing the thickness of the bitumen film
significantly increases the ageing index of the bitumen.
The type of mixer also affects amount of hardening during mixing.
Less hardening in drum mixer as compared to conventional batch
mixer.
 Hardening of bitumen in a mix during
hot storage, transport and laying

Some hardening take place during hot storage, whether in silo or in

vehicle.
Amount of hardening depend on duration of exposure to oxygen,
thickness of bitumen film, and temperature of mix.
When a hot mix is discharged into a storage silo, air enters with the
mix and some is trapped in the voids of the material.
During storage some of the oxygen in this trapped air will react with
bitumen.
Oxidation of the bitumen will cease if no additional air enters the
storage silo / vehicle.
Hardening of bitumen in a mix during
hot storage, transport and laying
Mixing temperature should not be increased just
to compensate for long transport haul or low
ambient temperatures.
The reduction in viscosity achieved by
increasing the mixing temperature will be lost
because of additional oxidation of the bitumen.
In addition it may adversely affect long-term
performance of the material.
Hardening of bitumen on the road
Most of bitumen
hardening occurs during
mixing and to a lesser
extent during hot storage
/ transport.
Under adverse
conditions hardening of
bitumen can also occur
on the road.
Fig. 8.2 shows the
ageing index of bitumen
after mixing, storage,
transport, application
and in service.
Hardening of bitumen on the road
The main factor which
influences bitumen
hardening on the road is
the void content of the
mix.
Table 8.1 shows bitumens
recovered from 3 asphalt
concrete mixes after 15
years service.
The bitumen recovered
from the mix with the
lowest void content had
hardened very little.
However, where void
content is high,
substantial hardening had
occurred.
Hardening of bitumen on the road
Similarly, Fig. 8.3 shows the in-situ bitumen properties of 5
years old asphalt concrete with voids ranging from 3% - 12%.
At void content < 5% very little hardening in service occurred.
But, void content > 9% penetration fell from 70 to <25.
Hardening of bitumen on the road

Fig. 8.4 shows

effect of void
content on
hardening (by
change in
penetration) of
high PI bitumen
from an extensive
study in the UK by
Shell Bitumen UK.
Hardening of bitumen on the road

Fig. 8.5 shows

effect of void
content on
hardening (by
change in S.P.) of
high PI bitumen
from an extensive
study in the UK by
Shell Bitumen UK.
Hardening of bitumen on the road

Fig. 8.6 shows data on HRA

wearing course produced
using 50 pen bitumen in the
UK.
It shows that after 8 years in
service, little additional
compaction of the asphalt had
occurred and the void content
remained at about 5%.
In this well compacted
material no significant bitumen
hardening had occurred.
Hardening of bitumen on the road

Bitumen at the surface of the road hardens

much faster than the bitumen in the bulk of the
asphalt mix, because of 3 reasons:
A constant supply of fresh oxygen,
Higher temperatures at road surface,
Photo-oxidation of bitumen by UV radiation
Hardening of bitumen on the road

Photo-oxidation causes a skin 4 5 microns thick to

form rapidly on the surface of the bitumen film.
This is induced by natural UV radiation which is
absorbed in the upper 10 microns of a bitumen film.
The skin formation can retard oxygen absorption and
loss of volatiles.
However, oxidized skin material is highly soluble in
rainwater and is easily abraded away, thus exposing
fresh bitumen.
Hardening of bitumen on the road

The speed of surface

oxidation is illustrated in
Fig. 8.7 in which
penetration, S.P., and PI
of bitumen recovered
from the surface and
bulk of an asphalt
concrete mix over a
number of years are
plotted.
After 7 yrs the
penetration at the
surface is 25, whereas
for the bitumen in the
bulk of the mix is 45.
 Ageing tests

Ageing simulation in the lab includes:

TFOT bitumen (3.2 mm thick layer) stored in
horizontally rotating plates at 1630C for 5 hrs.
RTFOT 35g bitumen in cylindrical glass containers
fixed in a vertical rotating shelf, with pre-heated air jet
blown into the glass jar periodically. Test temperature
1630C for 75 minutes.
PAV residue from RTFOT or TFOT samples (50g)
placed in special plates subjected to 1000C temperature
and 2.1 MPa (305 psi) pressure for 20 hrs.
 Adhesion in bitumen

One of the main functions of bitumen is to act as an adhesive

to bind the aggregates in the asphalt pavement.
Adhesion of bitumen to most aggregates is not a problem if
water is not present.
Since aggregate is wetted more easily by water than by
bitumen, the presence of water results in difficulties, either in
the initial coating of the aggregate or maintaining an adequate
bond between the bitumen and the aggregate.
Failure of the bond already formed is known as stripping.
 Adhesion in bitumen
This failure is brought about by the displacement of the
bitumen from the aggregate surface by water.
The nature of aggregates exerts considerable influence on
bitumen adhesion due to differences in their affinity for
bitumen.
A majority of aggregates are classified as hydrophilic (water
loving) or oleophobic (oil hating).
Aggregate types with high silicon oxide content, e.g. quartz
and granite, i.e. acidic aggregates, are more difficult to coat
with bitumen than basic aggregates such as basalt or
diabase.
 Adhesion in absence of water
Bitumen adheres well to most aggregates if they
are clean, dry, and not too dusty.
To get a good adhesive bond, the bitumen must
wet the aggregate.
This process is largely controlled by the viscosity
of bitumen.
The higher the viscosity, the longer it takes the
bitumen to wet the aggregate.
 Adhesion in absence of water
For practical purposes, the wetting should
occur almost instantaneously, thus, too high a
viscosity could result in inadequate coating.
If the aggregate is dusty, bitumen viscosity may
increase, possibly resulting in inadequate
coating of the aggregate.
It is unusual for the bond between bitumen and
aggregate to fail once good adhesion is
established, except by the action of water.
 Adhesion in the presence of water

Adhesion problems in presence of water arise in

2 ways: 1st due to aggregate being wet before
mixing, 2nd due to effect of rain on the material
after it has been laid.
Aggregate is normally dried by heating before
mixing with bitumen.
 Adhesion failures caused by
presence of water
Stripping is usually associated with mixes which are
permeable to water.
There is little risk of stripping in low void content dense
asphalt or macadam.
The risk of stripping occurring is a function of the affinity
between aggregate and bitumen, and its consequent
ability to resist the displacing effect of water.
This does not mean that bad weather inevitably brings
problems with certain aggregate, it merely implies a
greater risk.
 Adhesion failures caused by
presence of water
The nature of mineral aggregate, especially the filler, is
the dominant factor influencing adhesion.
Difference in bitumen are largely due to differences in
rheological properties.
Maintenance of bitumen adhesion is governed by the
minimum viscosity of bitumen in service.
This can be illustrated by comparing the Marshall
properties of asphalt before and after soaking in water
for 4 days at 600C.
 Adhesion failures caused by
presence of water
These tests showed that differences between different
bitumens were primarily due to differences in void
content of the specimens tested.
The variation in void content was the result of the
specimens being compacted at the same temperature
and not at the equi-viscous temperature.
Differences between bitumens can be eliminated when
specimens are compacted at equi-viscous temperatures.
 Adhesion failures
caused by presence of
water

Fig. 9.1 shows the

retained Marshall
stability plotted
against the amount of
water absorbed
during 4 days soaking
at 600C.
It clearly shows the
importance of
absorbed water and
the dominance of
aggregate and filler
type.
 Adhesion failures caused by
presence of water
The volume of water absorbed depends on the void content of
the mix.
For a particular void content, the water absorbed is
significantly lower if the filler is limestone, and even lower if
hydrated lime is present.
For retained stabilities less than 30%, the amount of water
absorbed was greater than the void content of the mixes,
suggesting that considerable swelling must have taken place.
This suggest that some failures which appear to be due to
loss of adhesion between the aggregate and the bitumen,
may in fact, be due to the breakdown of the structure of the
mix.
 Fundamental properties of the
bitumen/aggregate/water system
Displacement of one liquid by another on a solid surface
arises from the physio-chemical forces acting on the system.
The surfaces of most aggregates are electrically charged; for
e.g. silica, which is a common constituent of igneous rocks,
possesses a weak negative surface charge resulting from the
presence at the surface, of oxygen atoms which are not fully
saturated electrically.
The chemical bond between bitumen and aggregate is
primarily due to relatively weak dispersion forces, whereas
water, which is very polar, is strongly attracted to the charged
aggregate surface by orientation forces.
 Fundamental properties of the
bitumen/aggregate/water system
Aggregate surfaces are therefore, to a greater or lesser
degree hydrophilic or oleophobic.
Acidic aggregate is more hydrophilic than basic
aggregate.
If the surface of aggregate is wet, it is almost impossible
to disperse the water with bitumen and for the bitumen to
adhere to the aggregate.
However, it is possible for water to penetrate a film of
bitumen and detach the bitumen from the aggregate.
 The factors affecting
bitumen/aggregate adhesion
The factors which influence bitumen/aggregate adhesion are
numerous and complex.
Table 9.1 identifies some of these, of which approx 80% are
considered to be controllable during production and construction.
 Disbonding / Stripping mechanism

Generally 2 modes of failure in a bitumen/aggregate

system: adhesive and cohesive.
If the aggregate is clean and dry and the mix is
effectively impermeable, then the mode of failure will be
cohesive.
However, if water is present, the failure mode will almost
certainly be a loss of adhesion caused by stripping of
bitumen from aggregate.
Several mechanisms of disbonding can be identified.
 Displacement

This theory arises from consideration of the

thermodynamic equilibrium of the 3 phase
bitumen/aggregate/water system.
If water is introduced at the
bitumen/aggregate interface, then
consideration of surface energies involved
shows that the bitumen will retract along the
surface of the aggregate.
 Fig. 9.3 shows an aggregate Displacement
embedded in bitumen film
with point A representing
the equilibrium contact
position when the system is
dry.
When in contact with water
the equilibrium point shifts
and the new interface
moves or retracts over the
surface to point B.
This new equilibrium
position has a contact angle
which will depend on the
type and viscosity of the
bitumen used.
 Detachment
This occurs when bitumen and aggregate are separated by a
thin film of water or dust, although no obvious break in the
surface of the bitumen film is apparent.
Although the bitumen film completely encapsulates the
aggregate particle, no adhesive bond exists and the bitumen
can easily be peeled from the aggregate surface.
This process is reversible; if the water is removed the bitumen
may re-adhere to the aggregate.
A second mechanism of disbonding must be occurring to
allow the ingress of water between the bitumen and the
aggregate.
 Film rupture
This occurs where the bitumen fully coats the aggregate,
but at sharp edges or asperites, where the bitumen film
is thinnest, water can penetrate through the film to reach
the aggregate surface.
This movement of water to the aggregate surface may
occur with the water in vapour or liquid form.
Once such a process has started it is possible for the
water to spread between the bitumen and the aggregate
to produce a detached film of bitumen.
 Film rupture

The speed with which the water can penetrate

and detach the bitumen film will depend on the
viscosity of bitumen, nature of aggregate
surface, thickness of bitumen film, and presence
of filler and other components.
Once significant detachment of the bitumen film
from the aggregate has occurred, stresses
imposed by traffic will easily rupture the film and
the bitumen will retract, exposing water-covered
aggregate.
 Blistering and pitting
If the temperature of the
bitumen in the pavement
increases, the viscosity of
the bitumen will be reduced.
If this is associated with a
recent rainfall, the bitumen
may creep up the edges of
water droplets to form a
blister (fig. 9.4).
If the temperature is
increased, the blister will
expand, leaving a pit in
which may allow access of
water to the aggregate
surface.
 Hydraulic scouring
This occurs in the wearing course and is caused by the
action of vehicle tyres on a saturated pavement surface.
Water can be forced into surface voids in front of the
vehicle tyre.
On passing, the action of the tyre sucks up this water,
thereby inducing a compression-tension cycle in these
surface voids, which may result in debonding of bitumen
from the aggregate.
Suspended dust and silt in the water can act as an
abrasive and accelerate debonding.
 Pore pressure
This debonding mechanism is most important in open or poorly
compacted mixes.
In these types of mixes, water can be trapped as the material is
compacted by traffic.
Once the material becomes effectively impermeable, subsequent
trafficking induces a pore water pressure.
This creates channels around the bitumen/aggregate interface
leading to loss of bond.
Higher temperatures acting on the entrapped water result in
expansive stresses accelerating water migration and debonding.
Low temperature may lead to formation of ice which is equally
destructive.
 Chemical disbonding
Diffusion of water through the bitumen films can
lead to double layers of water at the aggregate
surface.
The presence of water causes the aggregate
surface to adopt a negative surface charge
against a slightly negative charged bitumen.
This results in two negatively charged surfaces
in contact and a net repulsion results.
As more water is attracted to the aggregate
surface debonding of bitumen film will result.
 Adhesion testing
Adhesion tests fall into six categories, with
several examples in each category, but
individual tests of each category differ in detail
rather than in principle:
Static immersion tests
Dynamic immersion tests
Chemical immersion tests
Immersion mechanical tests
Immersion trafficking tests
Coating tests
 Static immersion tests
Aggregate coated with bitumen is immersed in water and the
degree of stripping estimated by a visual inspection after a
period under water.
One e.g. of this type of tests is the total water immersion test.
This test involves coating 14 mm single size aggregates with
a known quantity of bitumen.
The coated aggregate is then immersed in distilled water at
250C for 48 hrs.
The percentage of bitumen stripped off the aggregate is
estimated visually.
Drawback of method: reproducibility of test is poor.
 Dynamic immersion tests
This is very similar with the static immersion
tests but the sample is agitated mechanically by
shaking or kneading.
The degree of stripping is estimated visually
together with a subjective judgment whether the
mix remains cohesive or separates into
individual particles of aggregates.
Reproducibility of this type of tests is also very
poor.
 Chemical immersion tests
In this type of tests aggregate coated in bitumen
is boiled in solutions containing various
concentrations of sodium carbonate.
The strength of the solution of sodium carbonate
in which stripping is first observed is used as a
measure of adhesivity.
However, the artificial conditions of the tests
make it of doubtful value in predicting road
performance.
 Immersion mechanical tests
These involve measurement of a change in a mechanical
property of a compacted bituminous mix after immersion in
water.
The ratio of the property after immersion divided by the initial
property is an indirect measure of stripping.
A number of mechanical properties can be measured
including shear strength, flexural strength and compressive
strength.
Probably the most popular is the retained Marshall stability,
i.e. ratio of Marshall stability after immersion and before
immersion, quoted as percentage.
 Immersion trafficking tests
Almost all tests described earlier seem to assume that traffic
passing over the pavement does not influence stripping,
whereas traffic can play an important role in stripping.
A test which simulates the effect of traffic is the immersion-
wheel tracking test.
It consists of 3 solid-tyred wheels which traverse 3 specimens
in a reciprocating motion of 25 cycles/min in a water bath of
400C.
Each wheel is loaded to give total weight approx 20 kg.
The criterion adopted to measure stripping is the time
necessary to produce failure.
Immersion-wheel tracking test
 Improving bitumen/aggregate
adhesion

Hydrated lime has been used as anti-stripping

additive in bituminous mixes, usually as part of
the mineral filler of between 1% to 3%.

Acknowledgement: Main reference is the Shell Bitumen Handbook