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Fourier Transform Infrared Spectroscopy (FTIR)
Fourier Transform Infrared Spectroscopy (FTIR)
Abstract
The FT-IR results shown in this work were obtained using a Nicolet iS10
spectrometer (Thermo Fisher Scientific Inc.). It was equipped with a deuterated
triglycine sulfate (DTGS) detector and controlled by OMNIC software.
In Transmission mode (Tr), our sampled pellets were manufactured by mixing
250 mg of potassium bromide (KBr) with 3 mg of material (clinker or cement
powder, or powder directly sampled into the bulk of hardened samples). 16 scans
were recorded over the range 4,000-400 cm-1 with a spectral resolution of 4 cm -1.
The background spectrum was collected using a pure KBr pellet and the spectra
of samples were corrected with a linear baseline.
In Attenuated Total Reflexion (ATR) mode, our hardened samples were directly
analyzed over a thickness of a few µm and a sampling area of about 1 mm². The
crystal used was made of diamond. 16 scans were routinely recorded over the
range 4000-650 cm-1 with a spectral resolution of 4 cm -1. The background
spectrum was collected at ambient atmosphere before analyzing each sample.
The spectra of hardened samples were corrected with a linear baseline.
The diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS)
allowed measuring a range between 400 and 4000 cm -1. The incident beam was
reflected off the ground sample towards an overhead mirror upon which the
diffusely scattered rays were collected and measured in the detector.
2.2 Advantages and limits compared to other methods
Clinker and anhydrous cement phases were already studied in 70’ in order to
characterize the IR bands of alite, belite and calcium aluminate. Bensted &
Varma [2], and Ghosh & Chatterjee [3,4] published in 1974 certain of the first
main papers about the FT-IR analyses applied in the cement industry. Ghosh &
Handoo [5] wrote one of the first review papers in 1980. These first papers were
mainly devoted to the analyses using transmission mode (only [4] used ATR
mode).
Table 1 and Figure 1 show our own analyses done in Transmission mode
concerning the specific peaks of synthetic clinker phases. Indeed, pure Ca 3SiO5
and Ca2SiO4 phases were prepared by successive heating (at 1600°C) of a
mixture of finely divided calcium carbonate (from Sigma-Aldrich, Germany) and
silica (Aerosil 200 from Degussa, France) with appropriate stochiometric
proportions. All the spectra are conformed to those found in literature [2-5]. A
double peak at 995-900 and 938-883 cm -1, assigned to Si-O asymmetric
stretching vibrations, characterizes mainly C2S and C3S phases, respectively.
The detection of ferrite phase is difficult due to the absence of resolved and fixed
peaks but aluminates phase (C3A) is easier to detect due to a large set of thin
peaks assigned to Al-O bond.
Table 1: FT-IR bands of the
synthetic clinker phases
Wave-number (cm-1) with intensity of the band
Clinker (s: strong; m: medium; l: low)
phases
Si-O Al-O Si-O Al-O Si-O
C4AF –
Poorly resolved bands
Ca4Al2Fe2O10
Synthetic C3S
Synthetic C2S
Synthetic C3A
617 m,
Afwillite (crystalline micro- 3352 l, 985 m, 911 860 m,
520 s, 450 s
structure; Ca/Si ratio=1.5) 1660 l 963 s s 781 m
490 s
C-S-H (colloidal gel like 3356 l, 1000 s, 950 814 667 l,
456 s
structure; Ca/Si ratio=1.5) 1640 l 950 s s m 496 s
Portlandite – 3642
Ca(OH)2 s
Ca(OH)2
C-S-H C-S-H
(Ca/Si=0.9) (1.5)
C-S-H
(Ca/Si=1.5) C-S-H
(0.9)
Figure 3 shows the IR bands of our synthetic C-S-H samples in the 1300-700
cm-1 range. The spectrum of C-S-H 1.5 (calcium/silicon ratio of 1.5), which is
usually found in young hardened cement paste, is then compared to the one of
aged C-S-H (calcium/silicon ratio of 0.9). A shift of the bands to higher wave
numbers is then highlighted after ageing, due to the polymerization of silica
during the de-calcification process.
3431
Ettringite m,
3637 1115s, 857 53
Ca6Al2(SO4)3(OH)1 1680-
s 617 m l 7m
2 / 26H2O 1640
m
3363m
Monocarbo-
,
aluminate 367 3624 354 1363 s, 954 66 53
3005m
Ca4Al2(CO3)(OH)12 6m m 3m 873 m m 9l 5s
, 1650
/ 5H2O
l
Hemicarbo- 3642 3367-
aluminate 367 m, 354 3007m 1364 954 67 53
Ca4Al2(CO3)0.5 6m 3624 4m , 1645 s m 1l 7s
(OH)13 / 5.5H2O m l
Monosulfo- 367 354 3423 s, 1380 1150 57 525
aluminate
1650 9
Ca4Al2(SO4)(OH)12 2m 9m l m s
m m
/ 6H2O
C4AH13 ; 3400m 1383,
367 354 105 66 52
Ca4Al2(OH)14 / , 1641 880
3m 1m 0 l 7l 2s
6H2O l L,l
C3AH6
366 810 537
(Hydrogarnet) ;
0s l s
Ca3Al2(OH)12
C2ASH8
3442m 1050
(stratlingite) ; 366 951 524
, 1652 s,
Ca2Al2SiO2(OH)10 / 9l s s
l 452 s
2.25H2O
Ettringite
C4AH13
Monocarboaluminate
Hemicarboaluminate
References