Analytica Chimica Acta 444 (2001) 241250

Direct and continuous methodological approach to study the

ageing of fossil organic material by infrared microspectrometry
imaging: application to polymer modied bitumen
Jrme Lamontagne
a,b,
, Franoise Durrieu
b,1
, Jean-Pascal Planche
c,2
,
Virginie Mouillet
d,3
, Jacky Kister
a
a
CNRS UMR 6171, GOAE, Case 561, Universit dAix-Marseille III, 13397 Marseille Cedex 20, France
b
Laboratoire Central des Ponts et Chausses, 58 Boulevard Lefebvre, 75732 Paris Cedex 15, France
c
Centre de Recherche ELF-Solaize, B.P. 22, Chemin du canal, 69360 Solaize, France
d
Laboratoire Rgional des Ponts et Chausses, CETE Mditerrane, B.P. 37000, 13791 Aix en Provence Cedex 3, France
Received 29 March 2001; received in revised form 26 June 2001; accepted 26 June 2001
Abstract
Anewsimulation method was developed for studying the ageing of polymer modied bitumens (PmBs). An ageing cell spe-
cially was designed and tted to a Fourier transforminfrared (FTIR) microscope to continually and directly study the oxidation
of PmBby FTIRmicroscopy imaging. The method was applied to a styrenebutadienestyrene (SBS) modied bitumen. This
PmB features a two-phase structure with polymer-rich areas along with polymer poor regions. Changes in the chemical prop-
erties were observed during ageing. This structural and functional evolution was monitored in both phases simultaneously to
determine the kinetics of appearance and disappearance of chemical species. The method also allows the study of ageing by ki-
netic mapping. Moreover, this methodology allows the analysis of PmBsamples without destroying their internal equilibrium.
This paper presents some of the possibilities of this new ageing cell. 2001 Elsevier Science B.V. All rights reserved.
Keywords: FTIR microscopy; Polymer modied bitumens; Ageing simulation; Microstructure; Process analysis
1. Introduction
Any fossil organic material evolves with time, due
to ageing. This is particularly the case for paving bitu-

Corresponding author. Tel.: +33-4-91-28-83-16;

fax: +33-4-91-28-82-34.
E-mail addresses: m9804529@educ-012.u-3mrs.fr (J. Lamon-
tagne), durrieu@lcpc.fr (F. Durrieu), jean-pascal.planche@cres.elf-
antar.fr (J.-P. Planche), virginie.mouillet@equipement.gouv.fr
(V. Mouillet).
1
Tel.: +33-1-40-43-51-64; fax: +33-1-40-43-65-14.
2
Tel.: +33-4-78-02-64-78; fax: +33-4-78-02-60-90.
3
Tel.: +33-4-42-24-78-27; fax: +33-4-42-24-78-18.
minous binders which are submitted to two main age-
ing steps: rstly, the mixing process with aggregates
at high temperature and the laying process on the road
where their mechanical properties and chemical struc-
tures evolve rather quickly, and secondly, the service
life in the pavement where their evolution is slower
but steady. Due to the increase of trafc, more and
more polymer modiers are used to improve bitumen
performance. For a polymer to be effective in road ap-
plications, it has to be compatible with the bitumen
and to improve the binder contribution to the pavement
resistance to the main distresses at pavement service
temperatures, such as rutting, cracking from fatigue
0003-2670/01/$ see front matter 2001 Elsevier Science B.V. All rights reserved.
PII: S0003- 2670( 01) 01235- 1
242 J. Lamontagne et al. / Analytica Chimica Acta 444 (2001) 241250
or low temperature, moisture damage, without making
the polymer modied bitumen (PmB) too viscous at
mixing temperatures. In other words, it must improve
the overall performance of the pavement [13], and
moreover, this improvement has to be durable with
time.
To analyse the durability of the asphalt mixture, it
is necessary to study the evolution of the bituminous
binder used. Furthermore, ageing is one of the impor-
tant issues being discussed to set up performance re-
lated test methods and then specications in Europe.
Ageing is already a very complex process in unmod-
ied bitumens, and the degree of complexity increases
after polymer modication [4]. Therefore, the possi-
bility to understand and to predict how any changes in
composition or process can affect PmB evolution dur-
ing ageing is of prime importance. The main cause for
ageing is oxidation. It has to be controlled or at least
taken into account to prevent premature failures of the
pavement which would cause industrial and econom-
ical damages.
Depending on a number of parameters, PmBs gener-
ally display polymer nodules dispersed in a continuous
bitumen phase, or a bitumen phase dispersed within
a continuous polymer phase, or even two interlocked
continuous phases. Those parameters are mainly the
bitumen composition, polymer nature and content and
the manufacturing method [57]. Most paving PmBs
involve lowpolymer content. Their microstructure fea-
tures polymer nodules swollen by bitumen fractions,
dispersed in a continuous bitumen phase [8].
Global analytical techniques such as spectroscopy
developed for neat bitumens are not sufcient enough
in the case of heterogeneous systems at a microscopic
scale [912]. Microscopy techniques are indispens-
able [13]. Current microscopy techniques can show
PmB microstructure [1416], but cannot inform on
the structural and chemical changes occurring with
a polymer modication. Among other microspec-
troscopy techniques, IR microscopy was chosen
[1719] because it allows at the same time the visual-
isation of PmB microstructure and the chemical char-
acterisation of the different observed micro-phases
separately [20].
So, the knowledge of the PmBs ageing chemical
mechanisms is essential to judge of their durability.
Binder ageing is usually assessed through conven-
tional standardised ageing tests such rolling thin lm
oven test (RTFOT) and pressure ageing vessel (PAV).
Those are supposed to simulate mixing for the RTFOT
(75 min, 163

C, air ow of 4 l/min) and eld ageing

for the PAV (20 h, 100

C, air pressure of 2.1 MPa).

However, those ageing simulations give only punc-
tual indications. One aim of this study was to develop
by Fourier transform infrared (FTIR) microscopy a
direct continuous and rapid test method for studying
slow evolution phenomena like oxidation in each of
the PmB micro-phases. To achieve this goal, an ageing
cell was developed in our laboratory, to be specially
adapted and designed for the FTIR microscope. So, it
became possible to continuously study the oxidation
of PmB by FTIR microscopy imaging. The present
paper deals with the presentation and the characteri-
sation of this ageing cell in order to demonstrate the
applicability of the method.
2. Experimental
2.1. Materials
Two PmBs were manufactured at 180

C temper-
ature, under moderate shear stirring, by adding 3%
of linear styrenebutadienestyrene (SBS) to a bitu-
men, belonging to the 70/100 penetration grade in the
French specication according the norm EN 12591.
This bitumen can be considered as aromatic accord-
ing to its characteristics, evaluated by FTIR and UV
synchronous uorescence [21]. In a second step, the
PmB was articially aged through the PAV test [22].
2.2. Fourier transform infrared
(FTIR) microscopy
The micro-FTIR analysis was performed on a Nico-
let Protg 460 spectrometer coupled with a Nicolet
Nic-Plan IR microscope which was tted with a MCT
detector cooled with liquid nitrogen. The microscope
is equipped with an CDD camera allowing to visu-
alise the sample on the PCs screen and to record
photos. The standard analytical conditions were X 15
IR objective, 40 m diameter spot, 64 scans, spectral
resolution of 8 cm
1
. Spectra were rationed to the
background collected on a clean area of the NaCl win-
dow in the same analytical conditions. Assignments
of the main IR bands were determined by reference
J. Lamontagne et al. / Analytica Chimica Acta 444 (2001) 241250 243
to previous works [20]. Due to their high absorbance,
PmBs can be analysed only in the transmission mode.
The samples are prepared by leaving a hot droplet of
PmB owing on a NaCl window (13 mm diameter,
1 mm thickness), in order to obtain a lm thickness of
about 20 m. Such a preparation permits to visualise
the sample heterogeneity and to quantify it by FTIR
analysis.
3. Procedure
3.1. Focal point analysis
In FTIR spectroscopy, the IR beam size is relatively
wide and cannot accurately separate micro-phases
individually. FTIR can only analyse the mean of
micro-phases. On the other hand, by adjusting the IR
beam size (until 10 m 10 m), FTIR microscopy
allows to analyse point by point and separately the
micro-phases (see Fig. 1). In the case of PmBs, FTIR
microscopy allows to simultaneously visualise and
Fig. 1. Interest of the FTIR microscopy with regard to FTIR spectroscopy: () spectra of bitumen micro-phase; () spectra of polymer
micro-phase.
Fig. 2. Chemical mapping of the PmB: video image (a), spectra
collected on two different areas (b), chemical mapping (c).
244 J. Lamontagne et al. / Analytica Chimica Acta 444 (2001) 241250
Fig. 3. Visualisation by video image and by IR mapping structural and chemical structure evolution of the PmB after PAV.
characterise chemically the copolymer dispersion in
the bitumen, by identifying the chemical species of
bitumens that interact with the polymer to swell it [23].
So, this chemical analysis of the two micro-phases is
realised in situ, without modifying the internal equilib-
rium, in a punctual way and using FTIR spectroscopy
characterisation techniques.
3.2. Analysis by mapping
The IR spectra of molecular compounds feature ab-
sorption bands that can be associated with specic
Fig. 4. Principle scheme of the ageing cell.
functional groups. One can plot the variation of such
absorption band intensities versus wave number on
few points of interest of the sample under study. By
using a motorised xy sample stage (Spectra-Tech ad-
vantage motorised-mapping stage (AMS)) and appro-
priate software techniques, it is possible to produce
functional group maps on a large area of the sam-
ple (Fig. 2) [24]. In this way, the micro-morphology
of PmB can be characterised by recording IR map-
ping of the two micro-phases distribution (polymer
and bitumen). Moreover, the motorised stage under
the IR microscope allows to collect a large number of
J. Lamontagne et al. / Analytica Chimica Acta 444 (2001) 241250 245
spectra in a very short period of time, using a video im-
age as guide (Fig. 2a). Once these spectra are collected
(Fig. 2b), they can be correlated with their spatial lo-
cation on the sample. FTIR micro-imaging can, thus,
be used to complete other usual imaging techniques
and to correlate the microstructure (visible image) with
the chemical composition (spectroscopic characterisa-
tion). IR mapping parameters are optimised to select
a beam size allowing a good compromise between the
spatial resolution and signal/noise ratio of the spectra
(about 40 m 40 m).As already described, physi-
cal blends of PmBs usually feature heterogeneous mi-
crostructures including nodules. IR microscopy allows
to conrm the polymer nature of these nodules ac-
cording to the polymer characteristic absorption band
such as 965 cm
1
for the butadiene, in the case of bi-
tumen modied with SBS copolymer. The chemical
mapping (Fig. 2c) of SBS bitumen blend is based on
an index dened as the ratio of the copolymer absorp-
tion band at 965 cm
1
to the bitumen absorption band
at 1376 cm
1
[5].
3.3. Analysis of the conventional simulated ageing
So far, changes in PmB microstructure during age-
ing has been studied discontinuously by characterising
the sample by FTIR microscopy before and after con-
ventional ageing in laboratory such as PAV test. Fig. 3
shows chemical changes in the PmB before and after
ageing. This method points out the evolution of the
polymer network (reduction of the interval between
the indexes [5]) generated by the ageing.
However, it is not possible to follow in continuous
the ageing phenomenon. This approach was developed
by FTIR spectroscopy for neat paving grade bitumens
[2527]. The purpose of this work was to adapt this
approach for FTIR microscopy in order to study PmB
ageing.
4. The heating ageing cell: design and
development
In order to study the PmBs structural evolution
during ageing, an ageing simulation method directly
observable and analysable by IR microscopy was de-
veloped. An ageing cell was purposely designed with
a number of requirements: horizontal mode, regulated
heating and adaptability to the motorised stage of the
microscope.
4.1. Scheme
The design and the development of the ageing cell
had to face a key problem that was the limited space
between the motorised stage and the objective of the
microscope. Consequently, the total thickness of the
heating cell had to be limited to 1.8 cm. This cell is
displayed in Fig. 4.
It consists of a metallic body heated by two heating
cartridges. These two cartridges are connected to a
regulator (WATLOW 988) connected to a temperature
probe tted in the centre of the cell. A heated gas
ow is ushed through the cell. The gas heating block
is connected to a second regulator WATLOW 988.
Moreover, the system is equipped with a by-pass to
select the gas. Analysis can be performed either under
oxidant gas (air) or under neutral gas (argon), allowing
the thermal effect to be dissociated from the oxidative
effect during simulated ageing. Synthetic air (80% N
2
,
20% O
2
) under 1 bar pressure was usually used.
A NaCl window (13 mm 1 mm) supporting the
sample is tted at the bottom of the cell. A removable
upper NaCl window (30 mm2 mm) is xed by some
screws during analysis conditions. The cell is locked
on a Teon stand itself tted in the motorised stage of
the microscope. The use of a Teon stand reduces the
heat diffusion to the motorised stage, not to inuence
the moving precision.
4.2. Validity of the cell
4.2.1. Temperature calibration
The calibration of the cell was realised using
standard compounds of Ker bench for which the
melting points (Y) are well known. We recorded their
actual melting temperature (X) in the cell.
The testing are repeated three times for each com-
pound in order to validate the results. The tempera-
ture calibration curve is tted with the equation Y =
0.955X +1.368.
4.2.2. Choice of the ageing temperature
A convenient oxidation test time is 2 h, because it
is sufciently short without preventing from studying
early initiation stages. It is also close to the duration
246 J. Lamontagne et al. / Analytica Chimica Acta 444 (2001) 241250
Fig. 5. Evolution of the PmBs microstructure as a function of the temperature and the lighting of the sample. Picture dimensions as in Fig. 2.
of some of the industrial simulation test of ageing.
The objective was, therefore, to determine the max-
imal temperature making possible the study of the
microstructure evolution of the PmB during 2 h of
ageing. Tests were, thus, performed at different tem-
peratures (16380

C). The rst observation in visible

mode show the microstructural evolution of the PmB
during the ageing at different temperatures in Fig. 5.
Fig. 6. Repeatability of rate of temperature increase. Temperature initially regulated at 25

C.
The rst test of oxidation of the PmBwas performed
with the light continually on, allowing to observe the
sample in visible mode at a temperature of 163

C, as
specied in the conditions of the RTFOT normalised
test. After 10 min, copolymer-rich areas are no longer
observable, as if the copolymer network had dis-
appeared. A second test was performed at 163

C,
but switching the light on, only during video image
J. Lamontagne et al. / Analytica Chimica Acta 444 (2001) 241250 247
acquisition. On this second test, the copolymer net-
work is observable during 50 min. So, a continuous
lighting of the sample during the oxidation test at high
temperature articially speeds up the degradation of
the polymeric network by adding photo-oxidation to
thermal ageing. This side effect undesirable as part
of this study, was photo-oxidation because no tem-
perature was associated to it as measured with the
sounding line tted in cell centre. Consequently, to
minimise this effect, the light allowing visualisation of
the sample was switched on only during video image
recording. Other tests were performed then lowering
the temperature from 160 to 130

C, by steps of 10

C.
In agreement with Petersen et al. [28] observations
on the chemical oxidation kinetics of bitumen, the
evolution of the PmBs microstructure lasted for 2 h
at 130

C. The study was then conducted at 130

C
during the rest of the study.
4.2.3. Repeatability of the rate of temperature
increase
A good repeatability of the rate of temperature in-
crease is necessary because of the high reactivity of
some chemical species during the rst minutes of
heating (appearance or disappearance of some func-
tions [27], such as the carbonyls).We designed the
Fig. 7. Kinetic of microstructural evolution of the PmB during
oxidation (130

C, air). Areas analysed in continuous by IR: () for

the bitumen matrix and () for the copolymer-rich area. Picture
dimensions as in Fig. 2.
cell with two regulators each tted out with a mi-
croprocessor allowing to program the temperature in-
crease. Tests were performed with different rates of
temperature increase to reach 130

C. The regulator
was programmed to obtain a temperature increase of
11

C/min to 25135

C (instruction temperature cor-

responding to an actual temperature of 130

C). This
time of 10 min is enough for the PmB sample to ho-
mogeneously reach 130

C. The repeatability of the

method is satisfactory (Fig. 6).
5. Results and discussion
From the sample already analysed (Fig. 3) the po-
tential of this new ageing simulation cell is presented.
Fig. 9. Kinetic evolution of the polymer network of the PmB by
IR mapping.
248 J. Lamontagne et al. / Analytica Chimica Acta 444 (2001) 241250
Fig. 8. Kinetic evolution of different species of the PmB: butadiene (a), carbonyl (b), aliphatic (c), aromatic (d); () for the bitumen
matrix and () for the copolymer-rich area.
5.1. Kinetic evolution by punctual analysis
At rst, the evolution of this PmB microstructure
was studied for 2 h. Spectra and video images were
recorded every 15 min while the sample was oxidised
by the air. This kinetic evolution of this PmB mi-
crostructure (Fig. 7) was observed in the visible mode,
showing the copolymer nodule sizes to be stable for
1530 min, after which they appeared to swell.
The FTIR microscopy equipped with the ageing cell
allows one to study continuously the indexes in two
focal points (Fig. 7).
These structural indexes [21] are calculated from
spectra band areas measured from valley to valley [9].
These spectrometric indexes were set previously and
allow to describe the state of the copolymer, oxy-
genated functions, aliphatic and aromatic structures.
5.1.1. Copolymer sensitivity
The butadiene index is relative to the absorption
band at 965 cm
1
. The FTIR microscopy analysis
conrms the degradation of the polymer network ob-
served by visible microscopy (Fig. 8a). A fall of bu-
tadiene rate occurs after 1530 min. The drop of this
index indicates with no doubt that the polybutadiene
part of the copolymer undergoes signicant degrada-
tion during ageing. The bitumen is not the only con-
stituent of the binder that chemically evolves. It was
also observed by optical microscopy (Fig. 7) that the
polymeric network cohesion disappears after 60 min
IR microscopy conrms this result. FTIR microscopy
with this ageing cell is a new methodology which can
show that the copolymer is damaged by the oxida-
tion of the unsaturated polybutadiene part resulting in
chain scission, as already described in [29].
5.1.2. Formation of carbonyl compounds
The carbonyl index (corresponding to the C==O
functions) is relative to the absorption band at
1720 cm
1
[30,31]. The bitumen fraction trapped
in the polymeric network produces less carbonyl
functions than the bitumen matrix (Fig. 8b) during
J. Lamontagne et al. / Analytica Chimica Acta 444 (2001) 241250 249
60 min, until such test time the copolymer network
has not disappeared. The copolymer seems to protect
the bitumen fraction trapped in this network against
oxidation.
5.1.3. Sensitivity of aliphatic structures
At the beginning, the aliphatic index is higher in the
copolymer enriched area than in the bitumen matrix
(Fig. 8c). This is in agreement with [20]. The gap
between the aliphatic index of the bitumen matrix and
that of polymer enriched areas lowers after 60 min.
The copolymer seems to protect the trapped aliphatic
in its network as long as this networks stays. This is
similar to the carbonyl formation.
5.1.4. Sensitivity of aromatic structures
At the beginning, the aromatic index is more im-
portant in the bitumen matrix than in the copoly-
mer enriched areas (Fig. 8d) as described in [20].
During ageing, this index increase slightly in the bi-
tumen matrix. In the copolymer-rich areas, the in-
dex increases rapidly after 45 min. Transformation of
naphthenic compounds into aromatic compounds is
assumed to occur but cannot be conrmed at this
point.
This new methodology of ageing simulation allows
at the same time to visualise in continuous the evo-
lution of the microstructure of a PmB by optic mi-
croscopy, to identify the chemicals structures respon-
sible of this evolution by IR analysis and to study their
evolution during ageing.
By optical microscopy, we observed that the
copolymer nodules submitted to thermal oxidation
had an induction period. Then they swell until they
disappear in the bitumen matrix. From a structural
point of view, we showed that the copolymer seems to
protect the bitumen fractions trapped in its network.
This protection results in the limitation of the forma-
tion of carbonyl functions and aromatic structures and
limitation of the destruction of aliphatic structures.
Moreover, we have demonstrated that the failure of
the polymeric network observable in visible mode
corresponds to the decrease of the butadiene index,
that could be attributed to the scission of butadiene
chains. Ageing is a combined effect of the bitumen
oxidation and the copolymer degradation. The bitu-
men ages differently whether it is trapped or not by the
copolymer.
5.2. Kinetic evolution by infrared mapping
We tried to follow during the ageing the evolution
of the polymeric network of a PmB by IR mapping
(Fig. 9). This was possible with the horizontal cell
designed and realised to be adapted to the IR micro-
scope. Hence, several testing were performed in or-
der to optimise the technical parameters, beam size
(40 m 40 m), analysis step (20 m), number of
scans (16), resolution (8 cm
1
), size of the area anal-
ysed (130 m100 m). Consequently, the ratio time
of mapping acquisition/time of kinetic was improved.
Mapping and video images were recorded at regu-
lar period of time (30 min) during air oxidation of
the sample.The variation of the characteristic index of
the polybutadiene repartition is 1.08 (maximum: 1.22,
minimum: 0.16) at the origin and decreases down to
0.17 (0.320.15) after 2 h of oxidation. So there is a
degradation of the copolymer when exposed to heat
in the presence of air. This new study allowed to visu-
alise in visible mode the degradation of the polymeric
network and to conrm it by IR mapping. This study
by continuous IR mapping will be particularly of in-
terest in the case of more complex microstructures.
6. Conclusion
The present work reports a new methodology for
simulating the PmBs ageing which occurs during both
mixing and laying processes in road construction and
during further eld service conditions. A specially de-
signed ageing cell was adapted to the FTIR micro-
scope; it made possible the visualisation of the PmBs
microstructural evaluations during continuous ageing
inside the microscope. So very useful information was
provided for the understanding of the oxidation phe-
nomena through which undergoes ageing. Moreover,
this work saved time in studies on PmBs in compar-
ison with the usual FTIR analysis which addresses
only specied ageing times such as in the conditions
of the RTFOT or the PAV tests. Our study pointed out
to what extent PmBs are affected by oxidation: oxi-
dation level, oxidation rate and chemical functions in-
volved. Such an accurate and continuous analysis of
the formation or disappearance of chemical functions
would be helpful not only for neat bitumen or polymer
modied bitumen, but also for other kinds of fossil
250 J. Lamontagne et al. / Analytica Chimica Acta 444 (2001) 241250
organic matter, e.g. heavy petroleum products, indus-
trial oils, etc. This methodology may be extended to
study other parameters such as environmental temper-
ature and gas nature. It has been already suggested to
be apply it in the eld of formulations for food and
cosmetic industries which stress the effect of ageing
in quality standards.
Acknowledgements
The authors thank the Laboratoire Central des Ponts
et Chausses and Elf-Antar France for their nancial
support.
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