JOURNAL OF RAMAN SPECTROSCOPY

J. Raman Spectrosc. 2006; 37: 555–561

Published online 8 December 2005 in Wiley InterScience (www.interscience.wiley.com). DOI: 10.1002/jrs.1428

Micro-Raman spectroscopy in white portland cement

hydration: long-term study at room temperature
Sagrario Martinez-Ramirez,1∗ Moisés Frı́as1 and Concepción Domingo2
1
Instituto de Ciencias de la Construcción ‘Eduardo Torroja’ (CSIC), C/Serrano Galvache 4, 28033, Madrid, Spain
2
Instituto de Estructura de la Materia (CSIC), C/Serrano 121, 28006, Madrid, Spain

Received 3 May 2005; Accepted 12 September 2005

The long-term hydration of white portland cement has been followed through micro-Raman spectroscopy,
choosing for excitation the most adequate laser wavelength as deduced from a critical analysis of the
previously reported Raman data. The bands of the corresponding spectra were attributed to the various
anhydrous and hydrated phases, with full hydration of the anhydrous phases taking place after 180 days.
Sulphoaluminates were seen to form in two different local environments, at 3 and 180 days respectively.
Carbonates, as a secondary reaction product, were found in three different local environments. Copyright
 2005 John Wiley & Sons, Ltd.

KEYWORDS: white cement; micro-Raman; hydration; sulphoaluminates

INTRODUCTION in both, white and gray cement, and identified substantial

Spectroscopic techniques have proved to be appropriate
tools for studying cement hydration; however, fluorescence
effect in anhydrous cement can give anomalous results. With
the micro-Raman technique, spectra can be obtained for
surface samples just a few microns thick and with minimal
interference from the surrounding water. On such a scale,
the interference from fluorescence, so often a problem when
working with bulk cement slurry is also minimized. Spectra
can be obtained rapidly and extensive sample preparation is
not needed.
Raman spectroscopy has been used extensively to study
cement, clinker, or even hydration process; however, it is
not easy to compare results since different type of samples,
date collection, etc. have been employed. These results are
summarized in Table 1.
Bensted1 pioneered the collection of Raman spectra for
the individual minerals in cement components as well as in
the hydration products, including ettringite.
Gosh and Handoo10 published a brief review of the use of
IR and Raman spectroscopy for cement and concrete studies.
Conjeaud and Boyer2 successfully applied a Raman
microprobe to the study of individual calcium silicate crystals
Ł Correspondence to: Sagrario Martinez-Ramirez, Instituto de
Ciencias de la Construcción ‘Eduardo Torroja’ (CSIC) C/Serrano
Galvache 4, 28033 Madrid, Spain. E-mail: sagrario@ietcc.csic.es
Contract/grant sponsor: The Spanish Ministry of Science and
Technology.
Contract/grant sponsor: ERDF.
Contract/grant sponsor: European Community.
differences between them. They conducted a study of the
hydrated phases with both synthetic and industrial cement,
although it was not clear whether the white or gray product
was analyzed.
Dyer and Hendra3 in turn, collected Raman spectra for
pure cement minerals such as C3 A, C3 S and C2 S. They
reported that the spectra obtained showed weak vibration
bands against high background signals and concluded that
the high fluorescence of the samples may have contributed
to the poor results.
Bonen et al.4 studied synthetic samples of clinker compo-
nents (C3 S; ˇ-C2 S; cubic and orthorhombic C3 A and C4 AF),
as well as commercial clinkers obtained from the same plant
with the same chemical composition but a different thermal
history. The former were produced under standard oxidizing
conditions, and the latter under reducing conditions. They
reported that band wavenumbers may have shifted owing
to the inclusion of impurities in the silicate phases, which in
some cases may be associated with a change in the crystalline
structure of such phases.11
Monitoring the alite hydration process with Raman
spectroscopy, Tarrida et al.5 were able to observe the
formation of the C–S–H gel and CH, as C3 S hydration
proceeded; they used these observations to derive the
hydration kinetics. In 2002, these authors12 studied in situ
hydration of Portland cement with Raman spectroscopy.
The maximum hydration time studied was 29 days.
Kirkpatrick et al.6 assigned bands to a synthesized
C–S–H gel, as well as to two minerals, tobermorite and

Copyright  2005 John Wiley & Sons, Ltd.

 556

Table 1. Observed Raman bands for C3 S; C2 S, clinker and C–S–H (in cm
1 ) in the 1100–400 cm
1 range

Synthetic Clinker
Author/year/exciting
laser source C2 S C3 S C3 A C4 AF C2 S C3 S C3 A C4 AF CSH

Bensted1 /1973/632.8 nm He–Ne ˛0 -C2 S

892 – – – – – – – –
864
Conjeaud and 860 885 860 885

Copyright  2005 John Wiley & Sons, Ltd.

Boyer2 /1980/514.5 nm Ar 848 845 848 845
832 832
813 813 – –
S. Martinez-Ramirez, M. Frı́as and C. Domingo

761 750 750

508
Dyer and Hendra3 /1993/1064 nm 1376 1393 1050
Nd:YAG 1105 1007
1023 626
574
Bonen, et al.4 /1994/1064 nm ˇ-C2 S Triclinic Monoclinic ˇ-C2 S 1464–1439
Nd:YAG 1460–1450 1340 1361 1390
1116
1125–1112 1016 1040–1003
1030–980 925 938 – – – – –
798 799
714 722
663–669
679–671 593
541
5 C
Tarrida et al. /1995/514.5 nm Ar Triclinic 662
880 524
840
– 809 – – – – – –
542
518
Kirkpatrick et al.6 /1997/488 nm 950–1000
ArC – – – – – – – – 664–669
450

J. Raman Spectrosc. 2006; 37: 555–561

 Table 1. (Continued)

Synthetic Clinker
Author/year/exciting
laser source C2 S C3 S C3 A C4 AF C2 S C3 S C3 A C4 AF CSH

Remy et al.7 /1997/514.5 nm ArC
-C2 S ˇ-C2 S 977 ˛-C2 S

924 896 966
885 858 900

Copyright  2005 John Wiley & Sons, Ltd.

838 845 850–855
813 556 530–517 – – – – – – – –
410 538 400–380
400 520
424
Deng et al.8 /2002/632.8 nm 976
He–Ne 857 835 850
754 737
680
620
– – – – 554 544
536
516 517 506
422 450
Black and Breen9 /2004/632.8 nm 1010–1021
He–Ne 980–960
858
– – – – – – – – 650–680
630–600
540–435
This work/2005/514.5 nm ArC 1121 1133
1010
972 731 700–600
851
851 836
539
420

C2 S D 2CaOÐSiO2 ; C3 S D 3CaOÐSiO2 ; C3 A D 3CaOÐAl2 O3 ; C4 AF D 4CaOÐAl2 O3 ÐFe2 O3 ; C–S–H D CaOÐSiO2 ÐnH2 O.

J. Raman Spectrosc. 2006; 37: 555–561

Micro-Raman spectroscopy in white portland cement hydration
557
558 S. Martinez-Ramirez, M. Frı́as and C. Domingo

jennite, structurally very similar to the gel, on the basis of This would justify the differences in the values obtained for
their earlier work with nuclear magnetic resonance. synthetic samples, clinkers and cement.
Remy et al.7 used Raman spectroscopy to study the In addition to the dearth of experimental studies on white
polymorphism and high temperatures involved in dicalcium cement, it can be clearly seen that there is a need to explore
silicate transformation. Not all the Raman active bands for this line of research more thoroughly. For this reason, the
ˇ-C2 S were detected in this study. present paper aims to conduct the first detailed study of the
Deng et al.8 studied the hydration of an oilfield cement evolution of commercial white cement for long hydration
with Raman spectroscopy and environmental scanning times (360 days), using micro-Raman technique with visible
electron microscopy (ESEM), comparing the results with laser excitation.
patterns for clinker and ettringite anhydrous phases.
Black and Breen9 used Raman spectroscopy to character- EXPERIMENTAL
ize fresh and aged nanocrystalline C–S–H phases. System-
atic changes in the spectra mirrored the phases occurring in The chemical and mineralogical composition of the white
the C–S–H structure, including phase changes. They found cement used in the study, given in Table 2, was the European
different carbonate species (calcite, aragonite and vaterite) in standard UNE 80-304-86-14 - compliant. The samples were
the aged samples. stored in a closed container at 20 ° C with some water in the
Table 1 lists the results of different authors of Raman bottom in order to get an environment with 100% RH. After
spectroscopic studies of the synthetic anhydrous phases 3, 28, 90, 180 and 360 days of curing, the samples were dried
(C3 S, C2 S, C3 A, C4 AF) present in clinker and the C–S–H in a desiccator at 105 ° C for 24 h and then ground to particle
gel obtained when cement is hydrated. The discrepancies sizes of less than 75 microns. The samples were prepared
that can be seen in the table in connection with the with a water/cement ratio 0.5.
Micro-Raman measurements were taken with an RM
band wavenumbers reported are due both to differences
1000 Renishaw Raman Microscope System equipped with
in the excitation sources used and the great diversity of
a laser at 514 nm, a Leica microscope and an electrically
the samples analyzed – synthetic, clinker, white cement,
refrigerated CCD camera. The spectra shown here were
gray cement, etc. Moreover, in many cases insufficient
obtained with 20ð magnification objective lenses. The laser
information was provided about experimental conditions,
output was 50 mW. Time acquisition was 5 min. The software
in terms of both the samples used and the conditions under
employed for data acquisition and analysis was WIRE for
which the spectra were recorded. It should be noted that
Windows and Galactic Industries GRAMS/32TM. Ten scans
synthetic anhydrous silicate phases are pure, whereas the
were recorded to improve the signal-to-noise ratio. Spectra
phases formed in cement manufacture are solid solutions,
at three different points were taken for each sample to
a fact that may occasion modifications in the respective
minimize problems arising because of the possible lack of
Raman vibration bands. Newman et al.13 recently noted that
sample uniformity. The Raman spectra presented are the
the spectral bands observed with near-infrared excitation
representative measurements of the three points.
(Nd:YAG laser operating at 1064 nm) are due entirely to
structured fluorescence effects and these bands conceal the
Table 2. Chemical composition of
true Raman bands. These authors further noted that the
white cement
1064-nm line is appropriate for studying hydrated – but
not anhydrous – cement. Table 1 shows that the vibrational Oxides Percentage (%wt)
wavenumbers of the different cement phases and the C–S–H
gel are reproducible with the 514.5-, 632.8-, and 488-nm lines, SiO2 23.65
but not with the 1064-nm line. Consequently, any of the 3 Fe2 O3 0.22
visible wavelengths seems to be appropriate for studying Al2 O3 3.34
cements. CaO 67.09
MgO 0.79
In the complex chemical composition of cement, alite and
K2 O 0.84
belite are the majority phases. For this reason and for the
Na2 O 0.9
sake of simplification, cement composition is often likened
SO3 1.82
to that of its silicate phases and more specifically to the
L.O.Ia 1.12
majority alite phase. Alite, however, is a C3 S-base solid
Specific surface 1.04 m2 /g
solution and belite a C2 S-base solid solution. Clinker alites
C2 S D 14.70%
typically contain11 3–4% of oxide impurities (MgOÐNa2 O).
C3 S D 70.54%
Belites, in turn, usually contain 4–6% of oxide impurities,
C3 A D 8.48%
chiefly11 , Al2 O3 and Fe2 O3 . The presence of these impurities
C4 AF D 0.67%
prompts a change in the crystalline structure of the silicate
phases that may cause modifications in the Raman spectra. a
Loss on ignition at 1000 ° C.

Copyright  2005 John Wiley & Sons, Ltd. J. Raman Spectrosc. 2006; 37: 555–561

RESULTS
The vibration band characteristics of C3 S and ˇ-C2 S silicate
phases can be seen on the Raman spectrum for the initial
white cement in Fig. 1. According to the literature,2,5,7,8 the
band in the 800–900 cm
1 region is due to the Si–O group
stretching vibrations. The sharpest peak – at 836 cm
1 – is
assigned to C3 S, whereas the band at 851 cm
1 is due to the
Si–O group vibrations in the two silicate phases, C3 S and
C2 S. The band at 887 cm
1 has been identified by a number
of authors2,5 to be a satellite. The midwavenumber region
ranges from 518 to 542 cm
1 ; this group of vibrational modes
has been assigned to O–Si–O bending modes. The band
at 539 cm
1 is attributed to Si–O out-of-plane 4 bending.
According to Tarrida et al.12 the bands below 400 cm
1 are
probably due to Ca–O vibrations.
Note the lack of any band in the 750 cm
1 region, which is
where the aluminate (C3 A) phase vibrations would appear.
The band appearing at 1010 cm
1 is due to Si–O–Si
3 symmetrical bending in the ˇ-C2 S units. The 1.82% SO3
content in the sample is probably to be found in the form of
gypsum, a compound exhibiting a SO4 2
1 vibration band
at 1010 cm
1 . Consequently, this band may be due to the
vibrations of both the sulphate groups in the gypsum and
the silicate groups in the ˇ-C2 S. Finally, the band appearing at
1121 cm
1 is due to the vibrations of the ˇ-C2 S units, although
it is not assigned as such in the literature.4 The weak band
at 1082 cm
1 is due to symmetrical C–O stretching in the
carbonate groups present in calcium carbonate, existing in
the sample.
When white cement is hydrated, changes appear in
the vibration bands (Fig. 2). After 3 days of hydration,
changes clearly take place in the region between 800 and
836
851
white cement
Raman Intensity
887
1010
1082
354
539
1121
420
619
972
914
200 400 600 800 1000
-1
wavenumber (cm )
Figure 1. Micro-Raman spectrum of anhydrous white cement.
Copyright  2005 John Wiley & Sons, Ltd.
Micro-Raman spectroscopy in white portland cement hydration 559
initial
Raman Intensity
3 days
28 days
90 days
180 days
360 days
200 300 400 500 600 700 800 900 1000 1100 1200
wavenumber (cm-1)
Figure 2. Micro-Raman spectra evolution of white cement.
Curing time: 0, 3, 28, 90, 180 and 360 days.
900 cm
1 – the band at 836 cm
1 decreases, while the band at
851 cm
1 remains unaltered.
The C3 S phase is known to hydrate relatively rapidly and
the C2 S phase more slowly.15 The band associated to the latter
one disappears entirely after 180 days, a clear indication that
the silicate phases are wholly hydrated by that time. The
intensity of the band at 539 cm
1 , associated with C2 S phase,
declines substantially after 28 days and disappears altogether
after 180 days of hydration.
An increase in the intensity of a band and a new band are
observed in white cement hydration. The first, at 357 cm
1 ,
is due to vibrations involving Ca–O polyhedra, such as the
A1g mode of portlandite6 formed during the hydration of the
silicate phases in white cement. The second band to appear,
a wide band at 600–700 cm
1 , is due to the main Si–O–Si
bending vibrations in the C–S–H gel. The latter is the chief
compound formed during cement hydration. The width of
this band is very likely a reflection on the largely amorphous
nature of the C–S–H gel.
The aluminate (C3 A) also reacts with gypsum during
cement hydration to form ettringite, which ultimately
develops into a calcium monosulphoaluminate. Despite the
results of chemical and mineralogical analyses of the sample
indicating that it has a C3 A content of 8.48% (Table 1), there
are no bands in the 750 cm
1 region in the spectrum for the
initial cement that would denote the presence of aluminate
phases. It might be thought that the detection threshold
for aluminate phases in this type of cements is higher than
8.5%. The stretching symmetric of SO4 groups in different
environments present in both the initial gypsum and the
possible ettringite or monosulphoaluminate formed can be
seen on the enlargement of the 900–1000 cm
1 zone shown
in Fig. 3.
Although Tarrida et al.12 sustain that the band appearing
1200 1400 in the 900–1000 cm
1 region is due to C–S–H gel vibrations,
the authors of the present study believe that it is due to the
sulphates present in the sulphoaluminate phases. A band is
observed in the initial sample at 972 cm
1 , due to of the SO4 4

J. Raman Spectrosc. 2006; 37: 555–561
560 S. Martinez-Ramirez, M. Frı́as and C. Domingo
972
1010
984
Raman Intensity
990
954
3 days
920 940 960 980 1000
-1
wavenumber (cm )
Figure 3. Micro-Raman spectra of sulphate vibrations of white
cement.
group 3 vibrations;8 after 3 days of hydration, a shoulder
appears at 990 cm
1 , assigned to the ettringite formed in the
sample as a product of the reaction between the aluminate
and the gypsum. The band at 1010 cm
1 , initially assigned
to ˇ-C2 S, is likewise observed to disappear at this age; the
disappearance of a band at the same wavenumber after only
3 days of hydration clearly indicates that it was due solely
to the gypsum. Since after 3 days of hydration the vibration
band at 1010 cm
1 disappears and the intensity of the band
at 972 cm
1 increases, it is possible to consider that this band
is due to sulphate vibrations.
A wide band is observed after 180 days of hydration,
with three peaks at 954 cm
1 , 984 cm
1 and 1020 cm
1 . Since
the vibration bands corresponding to the anhydrous silicate
phases disappear at this age, these three bands are assigned
to sulphate groups with different local environments. There
is no literature on the vibration wavenumbers of the
sulphoaluminate phases present in the samples, other than
ettringite,8,16,17 which leads to the belief that the bands
at 954 cm
1 would be due to compounds in which the
sulphate groups bond to groups more voluminous than
water (carbonated ettringite). The band at 1020 cm
1 , in
turn, would be assigned to sulphate groups bonding to
groups less voluminous than water, such as in the case of
monosulphoaluminates.
The bands due to symmetrical C–O stretching vibrations
of the carbonate group can be seen in the 1030–1100 cm
1
region on the spectrum in Fig. 4. These carbonate groups
are generated primarily by carbonation of the portlandite
present in hydrated cements, which may take place at any
of the various stages in the process, including hydration,
drying, grinding and so on.
This wide band very likely encompasses the vibra-
tions of the different forms in which calcium carbonate
crystallizes (calcite, aragonite and vaterite). According to
Copyright  2005 John Wiley & Sons, Ltd.
1077
initial initial
1082
3 days 3 days
180 days 28 days
90 days
90 days
180 days
360 days
Raman Intensity
28 days
360 days
1020
180 days
initial
3 days
180 days
1020 1040 1020 1040 1060 1080 1100 1120
-1
wavenumber (cm )
Figure 4. Micro-Raman spectra in carbonates region.
Martinez-Ramirez et al.18 the calcite, aragonite and vaterite
mix generates a wide band that would combine the three
chief vibration bands corresponding to carbonate groups in
different environments, at 1076, 1085 and 1090 cm
1 .
Deng et al.8 suggest that the carbonate ion may replace
the sulphate ion in the ettringite structure to form ettringite
carbonate or thaumasite. The carbonate and sulphate bands
in thaumasite appear at 1072 and 990 cm
1 , respectively, and
overlap – also respectively – with the carbonate and ettrin-
gite bands. The band at 658 cm
1 , attributed to the vibra-
tions of silicate groups in an octahedral environment,16,17
would clearly identify the presence of thaumasite, but as
this band overlaps with the C–S–H gel band, the pres-
ence of this compound cannot be confirmed. Ettringite
and thaumasite can clearly be identified by micro-Raman
spectroscopy;17 in Raman spectra of ettringite no signifi-
cant peaks were observed in the region below 950 cm
1 ,
allowing thaumasite and ettringite to be readily distin-
guished on the basis of the thaumasite octahedral Si peak at
658 cm
1 .
Deconvolution of the peaks in the interval 1120–
1030 cm
1 in the initial and the 360-day spectra (Figs 5(a)
and (b)) shows that the two peaks in the initial sample (1053
and 1082 cm
1 ) subsequently develop into three (1063, 1078
and 1090 cm
1 ), an indication that the carbonates are found
in different environments. The deconvolutions presented
here are based on the best fit obtained in each case with the
minimum number of bands. A decrease in the width of the
band is observed, indicating that some organization of the
carbonates groups is produced.
CONCLUSIONS
Micro-Raman spectroscopy has proved to be a useful
technique for the study of anhydrous and hydrated white
cement, inasmuch fluorescence of the sample is eliminated,
as well as it is able to identify the crystalline and amorphous
J. Raman Spectrosc. 2006; 37: 555–561

(a) initial white cement
1082
Raman Intensity
1053
1020 1040 1060 1080
-1
wavenumber (cm )
Figure 5. Deconvolution of the peaks in the interval 1120–1030 cm
1 for (a) the initial cement and (b) after 360 days of hydration.
components present in cement samples at different hydration
ages. Additionally, the spectra can be obtained rapidly and
extensive sample preparation is not needed. The micro-
Raman technique depicts the difference in hydration speed
in the two silicate phases (C3 S and C2 S).
In the present study, in which white cement hydration
was analyzed for the first time over a full 360-day period, the
anhydrous phases were found to be consumed after 180 days.
The vibration band at 836 cm
1 , characteristic of C3 S, shrank
rapidly in the first few days of hydration, whereas the band
at 851 cm
1 , associated with C2 S, declined gradually during
the first 90 days, disappearing altogether after 180 days.
The Raman spectra for the samples after 180 days of
hydration are similar to the spectra for the 360-day samples,
providing evidence that the main changes take place in the
first 3 months of hydration, when the anhydrous phases are
present.
Micro-Raman spectroscopy is a useful technique to
study white cement hydration as well as thaumasite and
ettringite identification. In this paper, Raman spectra reveal
the presence of sulphate and carbonate groups in different
environments in the hydrated white cement.
Acknowledgements
The Spanish Ministry of Science and Technology and the ERDF
cofunded the Ramón y Cajal contract granted to SMR. The authors
also thank the European Community for the Contract (Marie Curie)
given to one of the authors.
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J. Raman Spectrosc. 2006; 37: 555–561