Introduction
714
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
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
Introduction of fresh
concrete mix
Mould dimensions:
- height: 20 cm
- width: 15 cm
- Thickness : 3 cm
20 cm
3 cm
Impregnation
resin
Varnish
Concrete
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Figure 2. Cross-section of the AV sample observed by SEM: a layer of varnish was deposited on the surface of the concrete.
Alite
Alite
White parts:
Ferrite
Belite
Alite
Alite
Belite
Alite
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.
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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.
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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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Results
Reference Raman spectra
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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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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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
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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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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
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
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
Concrete samples
Polished
AR
AR
AS
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
AR
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
Acknowledgements
724
AS
X
X
X
X
X
X
AV
X
X
X
X
X
X
X
X
X
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