J. Am. Ceram. Soc.

, 96 [11] 3589–3595 (2013)

DOI: 10.1111/jace.12535
© 2013 The American Ceramic Society

Journal
Raman Spectroscopy of Anhydrous and Hydrated Calcium
Aluminates and Sulfoaluminates
David Torr
ens-Mart
ın,‡,† Lucia Fern
andez-Carrasco,‡ Sagrario Mart
ınez-Ram
ırez,§ Jordi Ib

an~ez,¶
Lluis Art
us, and Thomas Matscheik
¶

‡
Department of Architectural Technology I, Universitat Politecnica de Catalunya, Barcelona, Spain
§
Instituto de Estructura de la Materia, IEM-CSIC, Madrid, Spain
¶
Institut de Ciencies de la Terra Jaume Almera (CSIC), Barcelona, Spain
k
Holcim Technology Ltd, Innovation - Research and Development, Holderbank, Switzerland

Recent investigations have revealed the great potential of
Raman spectroscopy for the characterization of clinker miner-
als and commercial Portland cements. The usefulness of this
technique for the identification of anhydrous, hydrated, and
carbonated phases in cement-based materials has been demon-
strated. In the present work, the application of micro-Raman
spectroscopy for the characterization of the main clinker
phases of calcium aluminate cements and calcium sulfoalumi-
nate cement is explored. The main stable hydrated phases as
well as several important carbonated phases are investigated.
Raman measurements on the following phases are reported:
(i) pure, unhydrated phases: CA, C12A7, CA2, C2AS, cubic-
C3A, C4AF, and C4A3S;  (ii) hydrated phases: ettringite,
monosulfoaluminate, and hydrogarnet (C3AH6); (iii) carboa-
luminate phases: hemicarboaluminate and monocarboalumi-
nate. The present results, which are discussed in terms of the
internal vibrational modes of the aluminate, carbonate, and
sulfate molecular groups as well as stretching O–H vibrations,
show the ability of Raman spectroscopy to identify the main
hydrated and unhydrated phases in the aluminate and sulfoalu-
minate cements. The Raman spectra obtained in this work pro-
vide an extended database to the existing data published in the
literature.
I. Introduction
C ALCIUM aluminate cements (CACs) were originally devel-
oped as cement with improved sulfate resistance
compared with portland cement. Both CAC and portland
cements are based on calcium, silicon, aluminum, and iron
oxide.1 However, the composition of the two cements within
the CaO–SiO2–Al2O3 ternary system is quite distinct. CAC is
often used for the production of refractories. CACs with
low-grade alumina (40%–60% Al2O3) are generally produced
by melting bauxite and limestone. Their main reactive phase,
responsible for the strength properties of the material, is
anhydrous calcium aluminate (CA). Other minor mineralogi-
cal phases found in CACs are C2S (belite), C2AS (gehlenite),
and the ferrite solid solution.2 Refractory cements may
contain also C12A7, CA, and CA2.3
Calcium sulfoaluminate cement (CSA) is a binding mate-
rial used for rapid setting, early high strength development,
and shrinkage compensation. CSA requires essentially
H. Jennings—contributing editor
Manuscript No. 32739. Received February 19, 2013; approved July 2, 2013.
†
Author to whom correspondence should be addressed. e-mail: david.torrens@upc.edu
3589
gypsum, bauxite, and limestone as raw materials. By burning
of the raw materials at ~1300°C, a clinker based on the main
minerals C4A3S (yeelimite), C2S, and partially CS (anhydrite)
is formed. Depending on the used raw materials, phases such
as C4AF (brownmillerite), C3A, C12A7 (mayenite), and C2AS
can be found in minor amounts.4
C3AH6 (hydrogarnet, also known as katoite) and AH3
(gibbsite) are the main stable hydration products of CAC.5
In initial stages of the hydration reaction, the developed
hexagonal phases CAH10 and/or C2AH8 may decompose
onto C3AH6 and gibbsite depending on the service tempera-
ture of the concrete.
Ettringite is the main crystalline phase formed during the
hydration of CSA. Ettringite exhibits hexagonal structure built
up of columns of [Ca6Al2(OH)1224H2O]6+ oriented along the
z-axis; channels rise in the intercolumn space, filled with sul-
fate groups and crystallization water.6
The exposure to CO2 and/or the addition of limestone to
the cements (CAC, CSA as well as OPC) leads to the forma-
tion of carboaluminate type AFm phases (e.g., hemi- and/or
monocarboaluminate). In general, it may prove very difficult
to detect these phases by means of traditional analytical
methods, such as X-Ray Diffraction (XRD) or Infrared (IR)
absorption spectroscopy. Thus, the availability of additional
characterization tools to unambiguously identify these phases
would be highly desirable.
Several studies dealing with characterization of portland
and aluminate cements have been published so far. Dyer
et al.7 explored by means of FT-Raman (laser excitation of
1064 nm) the C3S, C2S, and C3A pure phases and attributed
the low signal-to-noise ratio of their spectra to high optical
fluorescence. Newman et al.8 used as excitation source a Nd:
YAG laser (1064 nm) to study cement-based systems and
concluded that the intensity of fluorescence decreases with
increasing degree of hydration; moreover, suggested the near-
infrared excitation as the adequate to study hydrated cement
phases.
Bonen et al.9 not only studied synthetic phases but also
commercial portland cement clinkers. In that work, it was
shown that the presence of impurities can modify the posi-
tion of the Raman bands arising from the silicate phases.
Such impurities may distort the crystalline structure of the
silicates and account for the observed differences between the
Raman spectra of synthetic and commercial clinkers. Raman
spectroscopy was also employed to study the structure of
C–S–H gel. Kirkpatrick et al.10 showed the similarity of the
structure of certain C–S–H to that of tobermorite. Garbev
et al.11 used a 532-nm laser excitation to investigate the
structural variations in C–S–H gel as a function of the Ca/Si
ratio. These authors found that changes in the Ca/Si ratio
3590 Journal of the American Ceramic Society—Torr

lead to systematic changes in the spectra, showing that rele-
vant structural information can be gained from the Raman
experiments.
Raman scattering has also been used to probe the hydra-
tion of portland cement phases. Ib
an ~ez et al.12 studied the
hydration and carbonation of C3S and C2S and confirmed
the fast and slow hydration reactions of C3S and C2S, respec-
tively. Black et al.13 investigated the hydration of C3A and
C4AF in the presence and absence of sulfate compounds.
These authors observed that the hydration of C3A is sizably
faster than that of C4AF. In both cases, however, the early
hydration stages gave rise to C4AH19. With regard to the
carbonation of these phases, the evolution of C3A to hemi-
and monocarboaluminate, with formation of aragonite, was
observed. In contrast, C4AF only gave rise to a hemicarbon-
ate phase together with calcite. The hydration in presence of
sulfate was observed to produce ettringite and different forms
of AFm. Frias et al.14 used Raman spectroscopy to investi-
gate the hydration of white cement pastes blended with
metakaolin.
Synthetic ettringite and monosulfoaluminate were studied
by Renaudin et al.15 The authors focused on the vibrational
modes of the sulfate group and the OH bonds. They
observed a shift in the symmetric stretching (m1) of the
sulfate group, from 990 cm1 in ettringite up to 982 cm1 in
the monosulfoaluminate. A shift in the stretching vibrations
of the OH bond were also observed, from 3638 cm1 in et-
tringite up to 3688 cm1 in the monosulfoaluminate. The
structural changes in the ettringite phase by partial substitu-
tion of Al3+ for Fe2+ was also investigated. More recently,
Mesbah et al.16 were able to identify Cl and CO32 substi-
tutions in AFm phases. In turn, Martinez-Ramirez et al.17
identified an AFt phase formed in the hydration of CSA.
This compound decomposes after carbonation and yields
rapidcreekite, a hydrated calcium sulfate–carbonate com-
pound.
McMillan et al.18 presented a Raman study about CA
glasses and crystals. They concluded that the Raman spec-
trum of CaAl2O4 glasses may be interpreted in terms of a
fully polymerized network of tetrahedral aluminate units,
which is depolymerised on addition of CaO as occurs in
binary silicate systems. Gastaldi et al.19 used Raman spec-
troscopy, in combination with XRD measurements, to inves-
tigate the hydration of CSA: the mineral phases responsible
for the observed Raman bands were identified and the hydra-
tion process was monitored.
In this work, Raman spectroscopy was used to study sev-
eral anhydrous, hydrated, and carbonated calcium aluminate
and sulfoaluminate phases. We discuss the results in terms of
the frequencies of the different vibrational modes of the
silicate, sulfate, and carbonate molecular groups and provide
an updated database of Raman-scattering data for aluminate
and sulfoaluminate cements. Particular emphasis is placed
with regard to the high-frequency regions, up to 4000 cm1,
corresponding to the stretching modes of OH bonds, which
are relevant for the study and identification of the hydrated
phases. This spectral range has been disregarded in many
previous works.
II. Materials and Methods
(1) Materials
Stoichiometric proportions of aluminum oxide, calcium oxide
and, when appropriate, anhydrous calcium sulfate were used
in the synthesis of CA, C12A7, CA2, cubic-C3A, C4AF,
C2AS, and C4A3S.  The powders were hand-grinded, pres-
sure-pelletized, and heated in a platinum crucible at tempera-
tures ranging from 1200°C to 1400°C.
Details about the preparation of the hydrated phases,
ettringite, monosulfoaluminate, hydrogarnet, hydroxy-AFm,
hemicarboaluminate, and monocarboaluminate can be found
in Ref. [20]
ens-Mart
ın et al. Vol. 96, No. 11
(2) Analytical Methods
X-Ray Diffraction was performed on flat samples by using a
Philips PW-1700 powder diffractometer (Ettlingen, Germany)
(Bragg–Brentano geometry) equipped with a sealed Cu X-ray
source, a secondary graphite monochromator to filter out the
CuKb radiation, and a scintillation detector. The measure-
ments were acquired with standard operating conditions of
40 kV and 50 mA. The angular range of the measurements
was 5°–60° (in 2h). The XRD patterns of the powders of
CA, C12A7, CA2, cubic-C3A, C4AF, C2AS, and C4A3S
showed that the samples did not contain any secondary com-
pound. In contrast, we found that some of the AFm sample
contained small proportion of hydrogarnet and some port-
landite in the case of C4AH13.
Micro-Raman measurements were performed at room tem-
perature with two different systems: (i) a Renishaw (Marne la
Valle, France) inVia micro-Raman system equipped with a Le-
ica microscope, a charge-coupled device (CCD) camera, and a
532-nm laser with an output power of 10 mW. Typical spectra
from 90 to 4000 cm1, with a resolution of 4 cm1, were
recorded with this system. Five 10-s scans were averaged to
improve the signal-to-noise ratio. (ii) a Jobin-Yvon T64000 tri-
ple spectrometer (Horiba, Barcelona, Spain) equipped with a
microscope, a CCD camera, and a 514.5-nm Ar laser. Typical
excitation powers were in the range 50–100 mW. The resolu-
tion of the measurements, acquired with the double subtrac-
tive configuration, was around 2 cm1. Long integration times
were considered (30 min).
The correct calibration of both instruments was verified by
comparing the frequency position of the Stokes and
anti-Stokes bands and/or by checking the position of the Si
first-order peak at 520.6 cm1. To check for the consis-
tency of the results, Raman spectra were collected on differ-
ent sample portions, which were found to yield similar
results in all samples investigated.
III. Results and Discussion
The Raman measurements on crystalline and amorphous
aluminates published in several of these studies9,11–19 have
been employed to investigate the samples of the present work.
(1) Raman Spectra of Anhydrous Powders
Figures 1–4 show the Raman spectra of the anhydrous
aluminate phases studied in this work. Table I displays the
wave numbers position of the main Raman peaks observed
in the different samples together with the band assignments.
Figure 1 shows the Raman spectrum of CA, dominated by
a strong, sharp signal at 522 cm1 and a weaker band at
Fig. 1. Raman spectrum of CA.
November 2013 Raman Spectroscopy Calcium Aluminates 3591

Table I. Calcium Aluminates Raman Absorption Bands

cm1

CA CA2 C3A C12A7

AlO45 m1 522 s/546 w 412 s/458 508 521

m3 793 661/689 s 757 772
vw, very weak; s, strong; m, medium; b, broad; w, weak; sh, shoulder; vs,
very strong.

AlO45 and Ca2+ ions show up in the spectrum. In particu-

lar, a more prominent peak is visible in the region close to
144 cm1.
In contrast, the Raman spectrum of CA2 (Fig. 2) exhibits
many different features that can be mainly ascribed to two
different groups of bands. The first group, located between
640 and 950 cm1 with two bands of comparable intensity at
661 and 689 cm1, can be attributed to m3 modes of the
Fig. 2. Raman spectrum of CA2. AlO45 tetrahedra. The second group of bands lies
below 500 cm1 with a strong, sharp peak at 412 cm1 and
a weaker feature at 458 cm1. These two bands probably
arise from m1 modes of the AlO45 tetrahedra and, together
with the peaks that are observed in the high–wave number
spectral region (up to 950 cm1), provide a fingerprint for
the presence of CA2 in the aluminate cements.
The Raman spectrum of our C12A7 sample is depicted in
Fig. 3. In this case, the spectrum is dominated by two Raman
bands, one at 521 cm1 and another one at 772 cm1. These
two features can be assigned to m1 and m3 modes of the
AlO45 groups, respectively. The absence of an additional
feature in the high-frequency shoulder of the m1 peak,
together with the lower frequency of the m3 peak and the pres-
ence of a relatively intense band at around 300 cm1 allows
one to discriminate between the presence of this phase and
that of CA. The band at 300 cm1 and the Raman features
that appear at lower wave numbers can be assigned to Ca–O
vibrations.
Figure 4 shows the Raman spectrum of cubic C3A, which
is dominated by two sharp bands at 508 and 757 cm1. The
C3A structure is based on isolated six-membered rings of
Fig. 3. Raman spectrum of C12A7. AlO45 tetrahedra.13 These rings are formed by two corner-
sharing oxygens per tetrahedron, giving rise to a structure
with two nonbridging oxygen per AlO45 group. These two
tetrahedra can be considered as AlO2 units. The strong
Raman band at 757 cm1 may be associated with a symmet-
ric stretching vibration of these AlO2 groups. The weaker
Raman bands and the strong absorption in this region may
be related to asymmetric aluminate stretching motions.
The Raman peak at 508 cm1 may be associated with m1
AlO45.15 These signals are characteristic of cubic C3A.13–16

Fig. 4. Raman spectrum of C3A.

546 cm1. This doublet, which can be assigned to symmetric

stretching (m1) of the Al–O bonds in the AlO45 tetrahedra,
allows one to unambiguously distinguish the presence of this
phase in aluminate cements. The broad band at 793 cm1
can be attributed to asymmetric stretching modes (m3) of the
AlO45 groups. In the low–wave number region of the spec-
trum, below 300 cm1, several external lattice modes of Fig. 5. Raman spectrum of C4AF.
3592 Journal of the American Ceramic Society—Torr

The sample also presents a weak band at 360 cm1 which
probably arises from Ca–O vibrations.
In contrast, the Raman spectrum of C4AF reveals the
poor crystallinity of the sample used in this study (Fig. 5).
Two broad bands show up in this spectrum: the first one
situated around 280 cm1, which can be ascribed to symmet-
ric (m2) and/or antisymmetric (m4) bending modes of the
O–Al–O (or O–Fe–O) bonds in the [(Fe,Al)O4]5 or [(Fe,Al)
O6]9 groups; the second band is located around 770 cm1
and can be assigned to [(Fe,Al)O4]5 or [(Fe,Al)O6]9
stretching vibrations.7,16,18
Figure 6 shows the Raman spectrum of C2AS. Several
groups of bands can be identified in this spectrum. Four
features are visible in the high-frequency spectral region of
the spectrum: a weak and relatively narrow band at
799 cm1 and a weak and broader feature at 853 cm1, both
of which can be attributed to m1 modes of the SiO44 groups.
Also, a peak of medium intensity at 916 cm1 and a sharper
band at around 980 cm1 are visible, both of which are
assigned to m3 modes of SiO44. On the other hand, two
Raman bands emerge at lower frequencies: a strong and
sharp peak at 631 cm1 and a weaker band around
658 cm1 arising from m3 vibrations from AlO45 tetrahedra.
This doublet above 630 cm1 provides a fingerprint for the
presence of C2AS and allows one to unambiguously identify
this phase from the Raman spectra. Additional weak bands
emerge in the spectrum at 411, 462, and 480 cm1. These
features can be assigned to m2 SiO44 modes, while the
Fig. 6. Raman spectrum of C2AS.
Fig. 7. 
Raman spectrum of C4A3S.
ens-Mart
ın et al. Vol. 96, No. 11
frequency position of the 531 cm1 peak is consistent with m1
modes from AlO45. In the low-frequency region, a sharp
band at 307 cm1 arising from internal modes of the alumi-
nate or sulfate ionic groups is particularly prominent.
In the case of C4A3S (Fig. 7), a very strong and sharp
band at 993 cm1 arising from m1 SO42 vibrations domi-
nates the Raman spectrum. Additional weaker bands at 1201
and 614 cm1, probably arising from m3 and m4 modes of
SO42,19 also appear in the spectrum. The spectrum reveals
that the wave number position of vibrational modes from the
AlO45 groups is lower in this sample: m3 and m1 modes are
found at 645 and 482 cm1, respectively. However, these
bands are fairly weak and broad, and as a consequence it is
fairly difficult to use these features for identification pur-
poses. The fact that the Raman spectrum of C4A3S only
exhibits a single sharp peak at 993 cm1 suggests that alter-
native analytical techniques should be used to unambigu-
ously identify the presence of C4A3S in the aluminate
cements.
(2) Raman Spectra of Hydrated Powders
The Raman spectra corresponding to synthetic hydrated CA
samples are displayed in Figs. 8–11 and Tables I–V.
Raman spectra of ettringite and monosulfoaluminate are
shown in Fig. 8. Both spectra exhibit a strong Raman signal
around 980 cm1 due to m1 SO42 vibrations as well as a
weak feature at 616 cm1 due to m4 SO42 vibrations.8 Both
Fig. 8. Raman spectra of ettringite and monosulfoalumante.
Fig. 9. Raman spectrum of hydroxy-AFm.
November 2013 Raman Spectroscopy Calcium Aluminates 3593

Table III. Ettringite and Monosulfoaluminate Raman

Absorption Bands
cm1

Ettringite Monosulfoaluminate

C3A3cSH32 C4ASH 12

Al(OH)6 534 525

SO42
m1 980 s 980 s
m3
m4 616 w 616 w
stretching O–H
3458 b
3557 sh
3619 b
3641 b
Fig. 10. Raman spectrum of C3AH6. 3692 s
vw, very weak; s, strong; m, medium; b, broad; w, weak; sh, shoulder; vs,
very strong.

Table IV. Katoite and Hydroxy-AFm Raman Absorption

Bands
cm1

Hydrogarnet AFm
C3AH6 C4AH13–19 Portlandite

Al(OH)6
m1 327 334w/357w
m3 521
stretching O–H
3620 3620
3651 s 3652 b
3673 vw
3694 vw
vw, very weak; s, strong; m, medium; b, broad; w, weak; sh, shoulder; vs,
Fig. 11. Raman spectra of hemicarboaluminate and monocarboa- very strong.
luminate.

Table V. Hemicarboaluminate and Monocarboaluminate

Table II. C4AF, C2AS, and C4A3S Raman Absorption Bands Raman Absorption Bands

cm1 cm1

C4AF C4A3S C2AS Hemicarboaluminate Monocarboaluminate

C4A
cH11 C4Ac0.5H12
SiO44
m1 799/853 Al(OH)6
m2 411/462/480 531 s 531
m3 916/980 CO32
AlO45 1068 s 1068 vw
m1 482 531 1086 w 1086
m3 645 631/658 stretching O–H
SO42 3542 b
m1 993 s 3592 sh
m3 1201 3615 sh
m4 614 3627
[(Fe,Al)O45] 280 b 3659 sh
[(Fe,Al)O69] 770 b 3670 s
3679 s
vw, very weak; s, strong; m, medium; b, broad; w, weak; sh, shoulder; vs, 3683 b
very strong.
vw, very weak; s, strong; m, medium; b, broad; w, weak; sh, shoulder; vs,
very strong.
spectra can be distinguished due to the different wave vector
position of the characteristic band arising from Al(OH)6
stretching vibrations. In the case of monosulfoaluminate, this and 3800 cm1, two broad bands emerge in the Raman spec-
band is fairly sharp and appears at 534 cm1, whereas in the trum of ettringite: a first, broad band around 3458 cm1,
case of ettringite it is much weaker and shows up at sizably and a second narrower band around 3641 cm1. In the case
higher wave numbers. In the high–wave number region of the monosulfoaluminate sample, a broad band about
corresponding to O–H stretching vibrations, between 3200 3619 cm1 with a shoulder centered at 3557 cm1 and a
3594 Journal of the American Ceramic Society—Torr

narrow, intense band at 3692 cm1 are visible in the Raman
spectrum. These Raman spectra reveal that the features
appearing in the high–wavenumber region of O–H stretching
vibrations may be highly informative to identify the presence
of hydrated aluminates in CAC and CSA.
In the case of the hydroxy-AFm (Fig. 9), several bands at
3620 (sharp), 3652 (broad), 3673 (very weak), and 3694 cm1
(very weak) are observed. It should be noted that, as
revealed by XRD, this sample contains sizable amounts of
hydrogarnet and portlandite [see also Ref. (20)]. Given that
the O–H stretching bands of hydrogarnet and portlandite,
respectively, emerge at 3651 and 3620 cm1, the observed
peaks at these wave number positions may be also assigned
to these two phases. However, in the case of the intense peak
at 3620 cm1 that dominates the Raman spectrum of
hydroxy-AFm, this peak can be unambiguously assigned to
the majority AFm phase. In the low–wave number spectral
region, bands arising from hydrogarnet at 327 (medium) and
521 cm1 (strong) are also observed (Fig. 10). These bands
are originated by stretching vibrations of the Al(OH)6
groups.7,17
At lower frequencies, hydroxy-AFm exhibit a somewhat
lower intensity as expected from the lower relative amount of
hydrogarnet, weak bands at 210, 250, 390, and 405 cm1 as
well as a somewhat sharper band at 358 cm1. The 250 and
358 cm1 bands can be attributed to portlandite, the rest of
weak, broad features provide additional signatures to identify
the presence of hydroxy-AFm.
Raman measurements on hCA and mCA samples yield
the spectra of Fig. 11. The main features that appear in the
low–wave number region for these two compounds arise
from stretching vibrations from octahedral Al(OH)6 and
stretching vibrations from the carbonate groups (CO32).
The band corresponding to Al(OH)6, centered around
531 cm1, is stronger in the case of mCA. The features
arising from the carbonate groups appear at similar wave
numbers for both compounds, but with different relative
intensities. The mCA sample exhibits a strong peak around
1068 cm1 and a weaker band at 1086 cm1.In contrast, the
spectrum from hCA exhibits a much weaker band at
1068 cm1, whereas the peak centered at 1086 cm1 domi-
nates the spectrum. The peak at 1068 cm1 is attributed to a
carbonate group directly bonded to the main layer (i.e.,
linked to Ca2+ cations), whereas the latter is believed to arise
from weakly bonded carbonate groups situated at the center
of the interlayer.9 The relative intensities of these two peaks
allow one to unambiguously discriminate the presence of
these two compounds in the aluminate cements. With regard
to the high–wave number peaks, the Raman spectrum of
mCA indicates that the degree of crystallinity of this phase is
much higher than that of hCA. Several bands at 3542
(broad), 3615 (shoulder), 3627, 3670 (strong), and 3679 cm1
(strong) emerge in the spectrum of mCA. In contrast, the
spectrum of hCA exhibits a broad band centered at
3683 cm1, with shoulders around 3659 and 3592 cm1.
The Raman bands tend to shift to higher wave numbers in
samples containing higher amounts of calcium oxide in the
formula unit (Tables I to V). In contrast, when the amount
of aluminum oxide in the formula unit increases, the wave
number of the bands tends to decrease. With regard to the
Raman bands associated with the sulfate groups, it is found
that these peaks display sizable intensity variations with
composition, whereas their wave number position remains
more or less unchanged. The combination of (i) the wave
number position of the aluminate bands, (ii) the intensity of
the sulfate bands, and (iii) the shape, number of bands, and
wave number position of the O–H stretching modes may be
highly informative to identify the presence of anhydrous and
hydrated aluminate phases in cement materials.
Tarte21 discussed on the factors influencing the vibrational
frequencies of cation-oxygen coordinated groups, namely the
value of the coordination number, ordinated groups, and
ens-Mart
ın et al. Vol. 96, No. 11
vibrational interactions with neighboring groups, in relation
to the characteristic vibrational modes of AlO4 tetrahedra
and AlO6 octahedra in a series of aluminate compounds. The
vibrational modes associated with the internal modes of the
[AlO45] complex ion have been identified in the Raman
spectra of different CAs.22–27
Spectra of CA, C12A7, and C3A show a similar profile, but
there is a difference in the relative intensity of m1 and m3 of
AlO45 absorption bands. When the Ca/Al ratio is low, the
m1/m3 relative intensity was found higher; as this ratio grows,
the relative intensity decreases: in the C3A spectrum, m3 is
higher than m1. However, in the case of CA2 spectrum, there
are many bands for m1 and also m3. According to Tarte,21 this
fact is due to the Al neighbors producing an environment
around each AlO4 rich in Al that provoke several signals.
In the hydrated aluminate phase spectra of ettringite and
monosulfoaluminate, we have two different structures. The
structure of ettringite is formed by columns of calcium oxide
and aluminum with hydroxyl anions where the sulfate is
located in the channels between these columns. Monosulfoa-
luminate structure is laminar, with layers formed for Ca and
Al and layers interspersed of sulfate. Raman spectra are simi-
lar in the sulfate bands, but they present the main differences
in the OH zone, indicating different structures, laminar, and
columns.
Respecting the carbonated phases, the mCA and hCA
have the same bands for the Al and the carbonate groups.
The difference in the spectra is due to the band intensity,
being lower for the hCA, due to the presence of hydroxyl
anions. The two phases have a laminar structure, but the
carbonate presence is higher in the mCA.
IV. Conclusions
We have carried out Raman-scattering measurements on
several anhydrous and hydrated CA cement phases. In the
case of the hydrated phases, particular attention has been
paid to the high–wave number spectral range corresponding
to stretching O–H vibrations. The Raman peaks observed for
the different phases have been assigned in terms of the inter-
nal vibrational modes of the aluminate, carbonate, and
sulfate molecular groups as well as stretching O–H vibra-
tions. Our data confirm the high sensitivity of Raman spec-
troscopy to identify the main hydrated and unhydrated
phases in the aluminate and sulfoaluminate cements. In the
particular case of mineral phases that are difficult to distin-
guish by means of XRD measurements, Raman spectroscopy
emerges as a highly effective tool for the identification
of these phases. The Raman data reported in the present
work allow one to extend the existing Raman database
published in the literature dealing with cements and related
compounds.
Acknowledgments
This study was funded by the MINECO (Ministerio de Econom
ıa y Competi-
tividad) through BIA0767-2008 project.
References
1
K. L. Scrivener, “Calcium Aluminate Cement”;pp. 64–93 in Advanced
Concrete Technology, Constituent Materials, Edited by J. Newman and B. S. Choo.
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