Research Article

Received: 29 June 2009

Revised: 4 March 2010

Accepted: 27 March 2010

Published online in Wiley Online Library: 22 June 2010

(wileyonlinelibrary.com) DOI 10.1002/sia.3548

Analyses of the surfaces of concrete by Raman

and FT-IR spectroscopies: comparative study of
hardened samples after demoulding and after
organic post-treatment
M. Cholleta and M. Horgniesb
Concrete surfaces were studied by two spectroscopic techniques, FT-IR (in ATR mode) and Raman, to establish a nondestructive
method to analyze the distribution of hydrated and organic phases. The surface composition of ordinary clinker, polished
concrete, concrete after demoulding, and coated concrete as used in building construction was studied. The clinkers mineral
phases and the polished concrete were first analyzed by Raman spectroscopy to determine a spectrum database of the specific
phases located on the surface of the concrete. Then, both spectroscopic techniques were used to analyze, directly, the surface
of hardened concrete after demoulding. No impact of roughness or porosity was highlighted using Raman spectroscopy; many
cementitious, or hydrated phases (alite, belite, tricalcium aluminate, ferrite, portlandite and ettringite) were clearly identified.
FT-IR in ATR mode only identified some hydrated phases: portlandite and CaOSiO2 H2 O (CSH), but organic residues from
the demoulding oil were characterized by this technique. Furthermore, the convenience of using these techniques together
was tested by analyzing the composition of concrete surfaces coated by different organic post-treatments. FT-IR spectroscopy
was useful to identify the main organic groups at the concrete surface, whereas Raman spectroscopy was especially able to
characterize the mineral/hydrated phases under a thick post-treatment layer (constituted of polyester varnish). Due to their
own specificities, these complementary techniques should be used together to easily identify all the mineral phases and organic
c 2010 John Wiley & Sons, Ltd.
residues/coatings on concrete surfaces. Copyright

Keywords: concrete surface; clinker; mineral phases; organic coating; Raman -spectroscopy; FT-IR spectroscopy

Introduction

714

A surface of concrete is the seat of numerous chemical reactions:

during the moulding time (hydration, influence of the demoulding
oil) and after demoulding (exchanges with the environment,
impacts of post-treated coatings). Moreover, industrial treatments
influence the materials properties and especially, durability of
aesthetics. All these effects must be evaluated. Contrary to clinker
mineral phases, whose tricalcium silicate (alite), dicalcium silicate
(belite), tricalcium aluminate and tetracalcium aluminoferrite
(ferrite) are already well studied by spectroscopic methods, the
analysis of the surfaces of concrete was not commonly performed
using spectroscopic techniques. This is mainly due to the surfaces
specific characteristics: roughness, porosity and heterogeneity
due to the use of sand and aggregates in the mix-design. For
example, the surface must be polished for SEM observations
and X-rays microanalyses, but this preparation can induce a
loss of information about the surface. This paper is devoted to
characterization methods that can be easily used on the hardened
surface of concrete.
Raman spectroscopy is certainly a powerful candidate tool
to characterize various areas of a surface. Measurements were
indeed local, and the analyzed concrete does not need to be
prepared. In building material studies, Raman spectroscopy has
been commonly used for over thirty years but some older pioneer studies exist.[1,2] High-quality Raman spectra on building
materials were difficult to obtain, because of the interference
with fluorescence of the studied material, until the develop-

Surf. Interface Anal. 2011, 43, 714725

ment of Raman -spectrometer.[2 6] This technique is a powerful and accurate probe of the constituents of heterogeneous
material. Raman -spectroscopy offers various noteworthy studies on clinker constituents characterization,[7,8] as well as on
cement hydration and carbonation.[9,10] Moreover, Raman spectroscopy investigations allow in situ investigation of the hydration
reaction/carbonation.[11 13] Other studies were performed on
hardened samples, as mortars[14 17] and old historical samples,[18]
thanks to the nondestructive approach of Raman spectroscopy.
On the contrary, Fourier Transform Infrared (FT-IR) spectroscopy
had been well acknowledged in building material science for
several decades.[19] Almost all previous infrared studies were
carried out using transmission mode on powder samples (mixed
in KBr and pressed in pellets). This FT-IR spectroscopy mode was
mainly used to study the hydration kinetics of pure C2 S, pure C3 S

Correspondence to: M. Horgnies, Lafarge Research Center, 95 Rue du

Montmurier -BP15- 38291 Saint Quentin Fallavier, France.
E-mail: matthieu.horgnies@lafarge.com

The standard cement chemistry nomenclature was used throughout this article:
C CaO, S SiO2 , A Al2 O3 , F Fe2 O3 and H H2 O.
a Universite Claude Bernard Lyon1 - Laboratoire de Sciences de la Terre - UMR
CNRS 5570, 2 rue Raphael Dubois 69622 Villeurbanne, France
b Lafarge Research Center, 95 Rue du Montmurier -BP15- 38291 Saint Quentin
Fallavier, France

c 2010 John Wiley & Sons, Ltd.

Copyright

Analyses of the surfaces of concrete by Raman and FT-IR spectroscopies

and cement powder.[20 24] Other studies described the attribution
of various FT-IR vibration peaks to specific mineral phases
(portlandite, ettringite, silicates) according to the experimental
conditions.[25 29] Infrared spectroscopy (in transmission mode)
was also used to characterize the carbonation kinetics because
vibration modes from CO3 2 units were easily detected. Different
studies investigated the carbonation depth by analyzing powder
from a concrete wall,[30] the influence of carbonation at the
interface between the aggregates and old hardened concrete,[31]
the study of concretes composition after several years of
ageing.[32] However, almost no publication by our knowledge
had directly considered the first micrometers of the concretes
surface using the ATR (Attenuated Total Reflection) mode. This
lack of application was one of the root purposes of this study: to
prove that the surface of a concrete sample can be easily analyzed
with this method in spite of the intense infrared peaks induced
by the residual water amount. Finally, FT-IR spectroscopy is also
interesting to characterize various organic species (such as methyl
CH3 , methylene CH2 , alcohol CO, carbonyls C O, amine CN
vibration modes, etc.). This characterization method (by ATR)
had been commonly used to study coatings and polymers.[33,34]
However, this technique had some limitations due to sample
roughness as a good contact between the sample surface and the
crystal is required.
In this study, Raman -spectroscopy was used to characterize
the surface of concrete just after demoulding, after a siloxane
post-treatment and after coating with a polyesterpolyurethane
varnish. As in most previous studies, a database of the main mineral
phases of the concrete was first established from many reference
samples such as clinker and polished concrete surfaces. This stage
was necessary for an accurate identification of the phases. A
shift of the Raman signal could be induced by the variability
of the chemical composition or by the samples environment
(isolated grain, grains in cement) or also by incorrect spectrometer

Introduction of fresh
concrete mix

Mould dimensions:
- height: 20 cm
- width: 15 cm
- Thickness : 3 cm
20 cm

Spread of demoulding oil

(15 g/m)

3 cm

Figure 1. Schematic drawing of the introduction of the fresh concrete into

the mould.

calibration. This database was then used on various surfaces of

concrete to identify the phase distribution after demoulding and
to evaluate post-treatments efficiency. FT-IR spectroscopy was
also used to complement the Raman spectroscopy results and
to confirm the studys methodology. All the FT-IR spectra were
performed in the ATR mode to prove the advantages and the
limits of the method to characterize concrete surfaces just after
demoulding or after an organic post-treatment.

Impregnation
resin

Varnish

Concrete

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715

Figure 2. Cross-section of the AV sample observed by SEM: a layer of varnish was deposited on the surface of the concrete.

M. Chollet and M. Horgnies

Alite
Alite

White parts:
Ferrite

Belite

Alite

Alite

Belite

Alite

Grey parts:
Tricalcium
aluminate

Zoom on the interstitial phase

Grey parts:
Tricalcium
aluminate

Alite

Alite

White parts:
Ferrite

Belite

Figure 3. Pictures of a polished sample of clinker recorded by SEM: different phases are noticed on the pictures.

Materials and Method Materials

Hardened samples of concrete

716

A specific concrete mix-design was prepared using ordinary

cement. This was made up of 20% of Ordinary Portland Cement
(CEM I 52.5 PMES from Lafarge, La Malle, France), mixed with
10% of limestone filler, 40% of sand (04 mm) and 30% of gravel
(510 mm). The concrete was prepared mixing the cement using
a water to cement ratio (W/C) of 0.4. The concrete samples
were prepared by pouring the fresh mixture into a rectangular
mould made of steel. No steps of agitation or densification
were used. Figure 1 describes the preparation of the concrete
samples. The vegetal oil (Chryso Dem ECO2 from Chryso SAS,
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Sermaises-du-Loiret, France) was spread on the surface of the

mould (15 g/m2 ) about 15 min before pouring the concrete mix.
All the concrete samples were removed from their moulds after
20 h and stored for 28 days under ambient conditions (25 C;
50% humidity) to complete the hydration. No aggregates were
directly observed at the surface of the samples. The referenthardened samples of concrete were named AR. They exhibited
a porosity of 15% (determined by mercury intrusion porosimetry)
and a roughness of 10 m (+/0.5 m). This roughness was
measured by profilometry in order to calculate the arithmetic
mean of the profile deviations from the mean line (Ra). Five
specimens of hardened concrete were prepared, depending on
the characterization method they were intended for: (i) A first

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Surf. Interface Anal. 2011, 43, 714725

Analyses of the surfaces of concrete by Raman and FT-IR spectroscopies

Figure 4. Raman spectra of the surface of the AR concrete after demoulding: (a) on a grain of belite, peaks of calcite are also observed; (b) on a grain of
ferrite, peaks of alite are also detected; (c) on a grain of tricalcium aluminate, peaks of ferrite, alite and calcite are also observed.

one was analyzed by SEM and Raman after being polished;

(ii) Two samples were analyzed after demoulding (without any
other preparation) by Raman; and (iii) Two other samples were
studied after demoulding by FT-IR.
Organic post-treatments

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Organic post-treatments provide protection against chemical and

biological environmental damages. Two distinct post-treatments
were applied on all the surface of the concrete samples, 28 days
after demoulding. The first formula was a siloxane oil (Silres BS 290
from Wacker Chemie AG, Munchen,
Germany), mainly comprising

iso-octyl trimethoxysilane (with a density of 1.05 g/cm3 ). After

being diluted with an aliphatic solvent, at a 1 : 15 weight ratio,

siloxane oil was applied by brushing on the surface of concrete. This

post-treated sample was named AS. This siloxane post-treatment
reacted with atmospheric moisture or pore water to generate
an active siloxane ingredient and liberate alcohol. The siloxane
impregnated the post-treated concrete surface without forming
any varnished hardened layer. The second formula was a varnish
(Comethane 231 from SEPV, Arpajon, France). Its formula was
based on a polyesterpolyurethane film-forming resin, but it also
contained xylene and naphta aromatic solvents. This varnished
post-treatment was brushed on the surface of the concrete
and this post-treated sample was named AV. The thickness
of the varnish layer was measured by observing a cross-section
with SEM. Figure 2 shows one picture of the cross-section. The

M. Chollet and M. Horgnies

Figure 5. FT-IR spectra (recorded in the ATR mode) of: (a) surface of a reference concrete after demoulding; (b) demoulding oil.

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Analyses of the surfaces of concrete by Raman and FT-IR spectroscopies

software. The ATR mode was used to study a sampling area
of approximately 1 mm.[2] The crystal used was made of diamond
and 256 scans were routinely recorded with a spectral resolution
of 2 cm1 . Analyses were systematically done between 650 and
4000 cm1 . The background was collected at ambient atmosphere
before analyzing each sample of concrete. Infrared spectra were
automatically corrected with a linear baseline (OMNIC software).
FT-IR (in the ATR mode) made observations of the sample over
a thickness around a few m. No specific preparation of the
samples was used before FT-IR analyses: the surfaces of concrete
were studied after demoulding or after deposition of the posttreatment.

Results
Reference Raman spectra

Figure 6. Raman spectra of the surface of AS concrete after demoulding

and deposition of a siloxane post-treatment: in the wavelength region of
silicate internal modes.

mean thickness of the varnish layer was estimated about 10 m

(+/1 m).

Clinker

Analytical methods
SEM
Samples of clinker were characterized by using a high resolution
field-effect gun digital scanning electron microscope (SEM FEG
Quanta 400 from FEI Company, Hillsboro, OR, USA) using an
accelerating voltage of 15 keV and a current intensity of 1
nA). Pictures of clinker were obtained after being polished and
metalized.
Raman -spectroscopy
Raman spectra were acquired using a LabRam HR800 spectrometer
(Jobin Yvon Horiba, Villeneuve dAscq, France) at the Laboratoire
de Sciences de la Terre, Lyon, France. An Ar+ Spectra Physics
laser was used as excitation source with a 514.3 nm wavelength.
The incident beam was focused on a 5 5 m spot through
an Olympus Mplan ASO objective with 50 magnification. The
spectra were recorded in backscattering geometry by a CCD
detector. The Raman shift was calibrated before measurements
according to the silicon peak at 520 cm1 . This led to a 4 cm1
spectral resolution and an analyzed sample thickness from 500
to 50 m, according to phase transparencies. Raman spectra were
acquired in 3 or 5 accumulations of 5 or 30 s each in two spectral
windows: 1702000 cm1 , and 26004500 cm1 , permitting to
characterize the lattice and internal modes as well as the symmetric
stretching vibration of the hydroxyls.
Fourier Transform Infrared Spectroscopy (FT-IR)

Spectra acquired on this sample allow a highly accurate characterization of the alite and belite, the major constituents of clinker.
The analyzed clinker consists of the same Ordinary Portland clinker
used for the mix-design of the concrete (CEM I 52.5 PMES from
Lafarge, La Malle, France). Figure 3 presents the spectra of the
main phases of the clinker-polished surface. Belite and alite were
identified by SEM observations from their typical grain shape, prior
to Raman spectroscopy analysis. The most intense peaks of alite
and belite are at 840 cm1 and 838 cm1 respectively. They are
related to the symmetrical stretching mode of the SiO bond in
the [SiO4 ]4 unit. The alite spectrum presents also bands at 548
and 880 cm1 . The belite presents peaks at 371, 416, 512, 533, 552,
840, 853, 889, 945, 973 and 1000 cm1 . All these wavelengths correspond to those reported in literature.[2,12,38,39] The broad band
at 730 cm1 , which is often observable on alite and belite Raman
spectra could be attributed to the ferrite interstitial phase.[35,40,41]
No evidence of tricalcium aluminate was found by Raman spectroscopy on the clinker, despite it could be highlighted by
SEM observations.
Polished section of AR concrete
More phases are observable on this sample. Raman spectrum of
portlandite and ettringite were obtained in addition to the ones
of alite, belite and ferrite. Portlandite is characterized in the AR
concrete at low frequency by a single peak at 354 cm1 which
corresponds to the most intense peak of portlandite reported in
literature. It is related to the bending mode vibration frequency.[39]
The OH stretching vibration wavelength is present at 3616 cm1
which also conforms to literature. Ettringite Ca6 Al2 (SO4 )3 .32H2 O
Raman spectrum presents a peak at 989 cm1 , related to the
symmetrical stretching mode vibration frequency of the [SO4 ]2
unit.[40] Raman bands characteristic of the ferrite are at 260, 313,

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719

The FT-IR spectrometer of the Research Center of Lafarge,

St Quentin Fallavier, France (Nicolet iS10 from Thermo Fisher
Scientific Inc., Waltham, MA, USA) was equipped with a deuterated
triglycine sulfate (DTGS) detector and controlled by OMNIC
Surf. Interface Anal. 2011, 43, 714725

Available Raman data on clinker and cement mineral phases vary

of a few cm1 in peak positions.[8,10,35,37] This can be explained by
variations in the chemical composition and by the environment
of the studied material: isolated grains, cement powder, hardened
concrete, etc. This explains why a Raman database should be
established from samples whose main phases are easily identified.
In this section, spectra were acquired directly on the surface of
clinker and on a polished section of AR concrete to establish
reference Raman data.

M. Chollet and M. Horgnies

Figure 7. FT-IR spectra (recorded in the ATR mode) of: (a) surface of concrete after a siloxane post-treatment (AS); (b) reference siloxane post-treatment.

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Surf. Interface Anal. 2011, 43, 714725

Analyses of the surfaces of concrete by Raman and FT-IR spectroscopies

Figure 8. Raman spectra of the surface of the AV concrete after demoulding and coating with a polyester varnish: (a) in the wavelength region of silicate
internal modes; (b) in the wavelength region of the OH stretching modes.

728, 912 and at 1464 cm1 (broad band). The most intense band
at 728 cm1 corresponds to the symmetrical stretching mode
vibration wavelength of the [(Fe,Al)O4 ]5 unit. These wavelengths
are close to those reported in literature by Fukuda et al.:[35] 265,
320 and 750 cm1 and those of Deng et al.:[39] 256, 308 and
737 cm1 . The peaks bases are broadened on the spectrum of the
ferrite indicating an amorphous occurrence. This phenomenon
had already been discussed.[2,35] Fukuda et al.[35] suggested that
the ferrite becomes amorphous by heating under a laser beam;
this could also induce a shift of the 750 cm1 band to 730 cm1 .
This shift could be also related to the Al/Fe ratio of the ferrite
phase, as suggested by Conjeaud and Boyer.[2] Finally, bands of
impregnation resin that was required for sample polishing, are
also identified (113, 392, 640, 671, 917, 935, 1112, 1185, 1456 and
1610 cm1 ). These bands are present on most the spectra acquired
on the samples observed by SEM. Moreover, these bands can not
be associated with any reference mineral phases in available
literature.
The concretes surface after demoulding

Surf. Interface Anal. 2011, 43, 714725

The surface of a concrete after siloxane post-treatment

Calcium carbonate and portlandite are detected by Raman
spectroscopy on the paste as well as alite, belite and ferrite on
the grains of the AS concrete sample (after using a siloxane-based
post-treatment). Characteristic peaks of silica are also detected at

c 2010 John Wiley & Sons, Ltd.

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721

The AR concretes surface, observed under the optical microscopy

of the Raman spectrometer, presents many grains in a homogeneous paste. Grain sizes are mostly between 10 and 20 m.
These grains are identified by Raman -spectroscopy as alite and
belite (Fig. 4a). Other smaller grains are recognized as amorphous
ferrite (Fig. 4b) or present two bands at 500 and 749 cm1 not yet
observed. These wavelengths are attributed to the bending and
asymmetric stretching mode of the [AlO4 ]5 unit, respectively; this
is typical of an aluminous silicate such as tricalcium aluminate.[36,37]
Raman spectra acquired in the paste always displays the calcium
carbonate bands only, mainly the calcite ones, which is the most
thermodynamically stable among the polymorphs in atmospheric
conditions.[6,9] The spectrum displays strong and sharp bands at
156, 283, 713 and 1083 cm1 , typical of a very well crystallized
calcite. However, some spectra reveal the occurrence of vaterite

and aragonite polymorphs. Moreover, no hydrated phases such as

portlandite were observed by Raman -spectroscopy. This phase
could be carbonated by ambient atmosphere after demoulding,
at least in the first tens m, which were the maximum penetration
depth of the laser beam.
Figure 5 compares the FT-IR spectrum of a referent AR concrete
with the one of the demoulding oil. Firstly, the main compound
detected at this surface is calcium carbonate. This observation is
in good agreement with the Raman spectroscopy analysis. Several
strong bands highlight the presence of this mineral: at 1413 cm1
assigned to the CO stretching vibration; at 712 and 873 cm1
corresponding to the CO bending vibrations.[22,30,31] Moreover,
two minor bands at 1800 and 2510 cm1 are also attributed to
this mineral. A part of calcium carbonate detected may also result
from the limestone filler used in the mix-design of concrete.
Contrary to Raman spectroscopy, hydrates are detectable by FTIR spectroscopy. Portlandite is barely detected at 3640 cm1
due to the OH stretching vibration: the attribution of this
peak is well referenced in literature.[22,23,25] Secondly, the major
bands at 974 cm1 is characteristic of CSH ([SiO4 ]4 stretching
vibration).[24] Concerning the other parts of the spectrum, the
band at 1111 cm1 may be attributed to the [SO4 ]2 stretching
vibration.[28] The sharp peak around 3409 cm1 is assigned
to the stretching vibrations of the OH band from residual
water.[32] At least, some weak organic bands between 2850
and 2925 cm1 , attributed to methyl and methylene groups,
are detected. By comparing Fig. 5(a) and (b), we hypothesize
that these organic compounds are the residues of the vegetal
demoulding oil.

M. Chollet and M. Horgnies

Figure 9. FT-IR spectra (recorded in ATR mode) of: (a) surface of concrete after deposition of a polyester varnish; (b) reference polyesterpolyurethane
varnish deposited on an aluminum sheet.

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Analyses of the surfaces of concrete by Raman and FT-IR spectroscopies

204, 464, 695 and 1158 cm1 (Fig. 6). The most intense band at
464 cm1 is typical of the SiO vibration of [SiO4 ]4 in the quartz
structure. Bands at 401 and 806 cm1 could also be attributed
to silica but are shifted of 10 cm1 higher than usual, suggested
slight changes within structure. This is probably due to interaction
with siloxane, but more analyses have to be carried out to prove
this assumption. No signal of the organic compound, indicating a
siloxane oil post-treatment, was highlighted at the AS surface. This
specific post-treatment is liquid. It is not supposed to induce any
varnished hardened layer but it probably penetrates deep into the
surface of concrete.
Figure 7(a) and (b) presents the FT-IR spectra of AS post-treated
concrete and pure siloxane oil. The main peaks of the AS sample
are attributed to calcium carbonate that could be induced by
the carbonation process (the sample was stored 28 days before
applying the post-treatment) and/or the presence of limestone
filler. No portlandite is detected at the surface, contrary to the
FT-IR spectrum of AR sample. Figure 7(a) presents two weak bands
that can be assigned to the residues of siloxane oil at 778 and
1270 cm1 . The attribution of these siloxane bands is confirmed
by the analyses of the pure siloxane oil (Fig. 7(b)) where these
both bands are observed. Moreover, the intense broad band is
detected between 1000 and 1200 cm1 on the AS sample could
overlap the band of the SiOSi units (detected between 1000
and 1100 cm1 on the referent siloxane oil, Fig. 7(b)). The infrared
bands detected on the AS sample show that a part of the siloxane
post-treatment had impregnated the surface of the concrete.
The concrete surface after coating with a polyester
polyurethane varnish
Figure 8 shows the typical Raman spectra acquired on the surface
of the AV concrete. Strongest peak at 1083 cm1 and other peaks
at 283 and 713 cm1 are attributed to calcite. The peaks at 354
and 3616 cm1 reveal the presence of portlandite. As for the AR
concrete surface, the presence of calcite in this sample could be
attributed to the limestone used in the mix-design of concrete
or to carbonation during the 28-day storage before the varnish
application. Mineral phases are in consequence detectable by
Raman spectroscopy below a coating. Other peaks at 618, 998,
1028, 1193, 1447 and 1600, 2920 and 3053 cm1 cannot be easily
attributed to minerals according to the available data in literature.
These peaks are probably related to the vibration frequencies of
several organic bonds of the varnish post-treatment. The peak

at ca. 2920 cm1 can be assigned to the asymmetric stretching

vibration mode of the CH bond in the methylene, whereas the
peak at 3053 cm1 can be attributed to the stretching vibration
mode of the CH bond in an aromatic group.
The study of the AV concrete sample by FT-IR underlines
the presence of organic molecules as Raman spectroscopy
investigations. In Fig. 9(a), no specific mineral phase is detected
but the presence of a polyester-polyurethane resin is well
established. Indeed, the strong bands at 10001072, 15501570
and 16401725 cm1 indicate the presence of CO bonds, CN
bonds and urea units (NHC O), respectively. Several bands, at
1519 and 3300 cm1 are linked to the NH bond.[34] Moreover, a
set of significant bands at 699, 760 and 3026 cm1 is attributed
to phenyl ring vibration modes of the aromatic solvent (xylene)
used in the coating. Finally, strong bands at 1453, 2850 and
2919 cm1 are assigned to the vibration modes of the methyl units.
Almost all these peaks are detected at the surface of the same
varnish coated on an aluminium substrate (Fig. 9(b)). However, the
presence of unreacted N C O units (specific peak of isocyanates
at 2270 cm1 ) is not clearly highlighted on the coated AV concrete.

Conclusion
Results from Raman -spectroscopy (summarized in table 1) and
FT-IR in the ATR mode (summarized in Table 2) have proved that
study the concrete surface without any prior sample preparation
could be easily achievable. Raman -spectroscopy combined with
SEM observations first identified the clinkers mineral phases.
Almost all Raman peaks, attributed to belite, alite and ferrite,
conformed to literature spectra. The analysis of the polished
concrete surface allows obtaining the Raman spectra of hydrated
phases (portlandite, ettringite) that also conformed to literature.
The broadening of some ferrite peaks could be related to
amorphization under the laser beam. Most of the areas located
at the surface of concrete after demoulding were composed
of calcium carbonate, caused by carbonation of hydrates such
as portlandite and presence of limestone filler in the mix.
However, the calcite signal was present in every spectrum thus
showing that the hydrated phases may have undergone significant
carbonation during the several weeks after demoulding. This
significant carbonation appeared to occur on at least the first m
of thickness. Consequently, portlandite was rarely observed and
no signal corresponding to CSH was detected at the surface

Table 1. Raman bands observed for concrete phases and post-treatments. Their occurrence in the concrete samples and clinker are also reported

Phase

Surf. Interface Anal. 2011, 43, 714725

Clinker

371, 416, 512, 533, 552, 840, 853, 889, 945, 973, 1000
548, 838, 880
260, 313, 728, 912, 1464
500, 749
354, 3616
989
156, 283, 713, 1083
204, 401, 464, 695, 806, 1158
630, 701, 796, 856, 996, 1094, 1115, 1184, 1238
618, 998, 1028, 1193, 1447, 1600, 2920, 3053

X
X
X

c 2010 John Wiley & Sons, Ltd.

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X
X
X

X
X
X
X

X
X
X

AV

X
X
X
X

X
X

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Belite
Alite
Ferrite
Tricalcium aluminate
Portlandite
Ettringite
Calcite
Silicates
Siloxane post-treatment
Polyesterpolyurethane varnish post-treatment

Raman shift (cm1 )

Concrete samples
Polished
AR
AR
AS

M. Chollet and M. Horgnies

Table 2. Assignment of all infrared bands recorded on AR, AS and AV concrete samples. Their occurrence in the concrete samples are also reported
Concrete samples
Assignment

FTIR band (cm1 )

AR

OH (in portlandite Ca(OH)2 )

SiO4 (in CSH)
SO (in [SO4 ]2 units)
CO (in CaCO3 )
OH (in H2 O)
C O (in CO2 )
SiOCH3 (in siloxane units)
SiOSi (in siloxane units)
CH2 /CH3
CH2 /CH3
CH CH
CH (in aromatic units)
CH
NH
CN
C O (in urea units)
CO (in ester units)

3640
974
1111
712, 872, 1410, 1800, 2510
1650, 32003400
20002200
778, 1270
10001200
2850, 2925
1453
3026
699, 760, 3060
1383
1520, 3300
1570
16401725
10101220

X
X
X
X
X

by Raman spectroscopy. Belite and alite (and minor phases such

as ferrite and tricalcium aluminate) were also identified by Raman
-spectroscopy. Their residual presence could be caused by the
interaction with the demoulding oil.[42] The FT-IR analyses of
concrete showed intense peaks attributed to calcite while some
other peaks were assigned to portlandite and CSH. The signal
of these hydrated phases were found thanks to the important
area analyzed by the IR beam (1 mm2 ) compared to the local
analyses done using the Raman -spectroscopy (some m2 ).
Finally, the detection of certain organic bands was attributed to
organic residues of the demoulding oil. After post-treatment with
siloxane oil, siloxane organic residues that have impregnated the
surface were only detected by FT-IR. Raman -spectroscopy is
a less sensitive tool for the detection of these organic residues.
Moreover, the FT-IR in ATR mode identified several strong bands
of the polyesterpolyurethane resin that coated the concrete.
FT-IR analyses could not detect any mineral phases, but Raman
-spectroscopy was able to measure the signal of some minerals
under this organic coating. As a conclusion, these both techniques
allow rapid and complementary analysis to characterize concrete,
with or without an organic coating. Raman -spectroscopy was
interesting to study the mineral phase distribution even if a
thin organic coating (few m of thickness) covers the concretes
surface. FT-IR spectroscopy in the ATR mode was a less proficient
tool for determine the mineral phases but this technique was
useful to identify the organic residues (from demoulding oils)
and protective coatings that cover the hardened concrete. The
intrinsic roughness and porosity of the concrete did not affect the
interpretation of spectroscopic results.

Acknowledgements

724

The authors would like to thank C. Bouillon and M. Dykman for

their help during the SEM and FT-IR analyses, G. Montagnac for
his assistance during Raman spectroscopy analysis, and finally, I.
Daniel and F. Thoue for their advice.
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