Received: 20 October 2019 Revised: 17 January 2020 Accepted: 13 April 2020

DOI: 10.1002/sia.6797

RESEARCH ARTICLE

Carbonation study and determination of cement to sand ratio

in hardened cement mortar by X-ray photoelectron
spectroscopy

Siddharth Singh1 | Mickey Mecon Dalbehera2 | Anujay Rawat3 | Pratibha Sharma4

1
Acoustics Instrumentation and Mechanical
Systems Group, CSIR-Central Building The determination of cement and sand content in an aged cement mortar is a chal-
Research Institute Roorkee, Roorkee, India
lenging problem for civil engineers. Techniques like x-ray diffraction (XRD), ther-
2
Structural Engineering Group, CSIR-Central
Building Research Institute Roorkee, Roorkee, mogravimetric analysis (TGA) and electrochemical impedance spectroscopy (EIS) are
India well established, which can give some insight of the hydrated products. The present
3
Organic Building Materials Group, CSIR-
study is an attempt to use x-ray photoelectron spectroscopy (XPS) technique for
Central Building Research Institute Roorkee,
Roorkee, India the evaluation of ordinary Portland cement (OPC), sand (aggregate) composition and
4
Environmental Science and Technology carbonation study in hardened cement mortar. Carbonation analysis and cement to
Group, CSIR- Central Building Research
Institute Roorkee, Roorkee, India
sand ratio for all mortar compositions has been determined and studied in detail in
the present work. The C 1s spectra of cement mortar with ratios 1:1, 1:3 and 1:6
Correspondence
Siddharth Singh, Acoustics Instrumentation
shows carbonate formation on the surface with 21, 40 and 32 atomic percent,
and Mechanical Systems Group, CSIR- Central respectively. An increase in SiO2 content corresponding to sand is observed for all
Building Research Institute Roorkee, Roorkee
247667, India.
three mortar mix. The formation of silica gel due to carbonation has not been
Email: singhsiddharth86@gmail.com observed in the mortar samples. The cement to sand ratio for all three mortar mixes
is found to be in 20–30 percent error limit due to the heterogeneous nature of the
mortar system.

KEYWORDS

carbonation, cement mortar, C-S-H, x-ray photoelectron spectroscopy

1 | I N T RO D UC TI O N these data do not necessarily provide enough information to quantify

Civil engineers usually face a challenging task of ensuring quality at
the construction site. Lack of adequate cement content at the con-
struction site in the concrete/mortar can lead to irreversible damage
to the building. The need to determine the cement content in hard-
ened cement mortar is mainly due to two reasons namely, the quality
of construction is not up to the specification. Secondly, an older con-
struction is being repaired or expanded and it is desired to match the
repairing materials with existing construction materials. The frequent
chances of problem in building structures is usually cement to sand
composition, water cement (w/c) ratio and aggregates. The cement to
sand ratio is an important parameter in cement mortar mix because it
influences most of the properties of hardened cement mortar, espe-
cially compressive strength and durability.1 Though a rough estimation
of the raw materials can be done in hardened cement mortar, but
the cement content with accuracy.
There is a difficulty in assessing the quantity of cement in hard-
ened cement concrete or mortar because of the fact that mortar itself
is a very heterogeneous product. The chemical compounds viz., cal-
cium silicates present in cement provides strength and durability after
hydration. However, in the reported literature, the constituents of
cement and concrete are reported as oxides. The way in which these
products mix is very intricate, and detailed study has been mentioned
elsewhere.2 Modern Portland cements (PCs), by definition, all tend to
have these compounds in appropriate amount irrespective of their
manufacturing facilities.
The aggregates used in mortar and concrete are built from lime, sil-
ica, alumina and iron oxide. Aggregates can be separated from hydrated
Portland cement by their solubility in acids. Aggregates tend to fall into
two categories, those containing mainly silica and the other containing

Surf Interface Anal. 2020;1–8. wileyonlinelibrary.com/journal/sia © 2020 John Wiley & Sons, Ltd. 1
2 SINGH ET AL.

calcium and magnesia. These aggregates can be directly made available TABLE 1 Physical properties of ordinary Portland cement tested
from mines or produced from construction and demolition waste.3 as per IS: 403

As far as cement-sand mortar characterisation is concerned, x-ray Test IS: 8112-1989

diffraction (XRD) is one of the most widely used techniques for deter- Parameter value recommendation
mination of the crystalline/amorphous phase and semiquantitative Standard consistency (% of 30
analysis of the constituent compounds. The determination of primary water by wt. of cement)
hydration products (i.e., C-S-H) of cement remains a challenging task Setting time (min)
because of mostly C-S-H is present in the amorphous phase, which Initial 65 30 (min)
produces overlapping humps in diffraction patterns. Singh and Sub- Final 290 600 (max)
ramaniam4 have reported the quantification of amorphous phases in Compressive strength (MPa)
the hydrated cement products. However, it is not possible to quantify 3 days 27.5 23 (min)
the amorphous aluminosilicate and silicates gel through XRD.
7 days 39.2 33 (min)
According to Scrivener and co-workers5 have stated that hydration
28 days 46.8 43 (min)
products, namely, AFm phases (calcium monocarboaluminate and cal-
Fineness
cium monosulfoaluminate), cannot be detected in XRD of hydrated
By air permeability(m2/kg) 355 225 (min)
cement because of their poor crystallinity. Similarly, thermogravimetric
Soundness (mm) 1.4 10 (max)
(TG) method is also used for investigating the qualitative and quantita-
tive analysis of hydrated cement products described elsewhere.6 Sev-
eral researchers have reported that the analysis of hydration products, 2.1.2 | Fine aggregate
i.e., calcium hydroxide Ca(OH)2, C-S-H, ettringite, and calcium carbon-
ate through the TG method in which water loss from C-S-H occurs at The fine aggregate (sand, SiO2 rich composition) used for the experi-
150
C to 400
C, creating a discrepancy with the existing components mental investigation was locally available river sand. The colour
4,7–11
like moisture and ettringite. Few researchers have analysed the appearance of the fine aggregate was dark grey. The aggregates were
properties of hardened cement paste and effect of carbonation by x- initially dried in natural sunlight and then sieved through 5-mm sieve
ray photoelectron spectroscopy (XPS) technique.12,13 Their main focus size to remove the coarser material such as pebble. In present study,
of the study was based on carbonation and Ca/Si ratio determination the sieve analysis of fine aggregate was carried in a mechanical shaker,
after decalcification of C-S-H component. The literature have not as per IS: 2386 and IS: 383, and details are presented in Table 3. The
shown any study or analysis regarding determination of cement-sand further details are mentioned elsewhere.17,18 Table 4 shows the
ratio in an aged mortar composition. chemical composition of sand (fine aggregate) used in the preparation
In the present study, the estimation of cement-sand ratio in hard- of mortar mixes. The presence of silica was found as a major compo-
ened cement mortar, and its quantification have been studied in detail nent with 63 weight percent.
by XPS technique. Specific gravity, water absorption and moisture content tests
have been carried out as per the procedure laid in IS: 2386.17 Cement
mortar was prepared using cement and sand with water cement (w/c)
2 | EXPERIMENTAL ratio of 0.5. Three mixes were prepared with varying cement to sand
ratio, i.e.,, 1:1, 1:3 and 1:6. The specimens were water cured for
2.1 | Materials 28 days under ambient conditions. After water curing of the mortar
specimens, all the samples were kept in an open air atmosphere for
2.1.1 | Cement 180 days under ambient relative humidity (RH) condition of 60–70%.
Preliminary carbonation test for all the specimens were tested by phe-
The cement is one of the constituents, which imparts binding strength nolphthalein indicator.
to the concrete or mortar mix. Therefore, it is required that the
cement to be used for the experimental work should meet the require- TABLE 2 Chemical analysis of ordinary Portland cement (OPC)
used in cement mortar specimen preparation tested as per IS: 4032
ments as per the relevant codes. The cement used in the present
investigation was ordinary Portland cement(OPC)-43 grade. The phys- Constituent Weight %
ical and chemical properties of the cement were tested as per IS: 4031 Silica 20.80
and IS: 403214,15 standards, respectively. The physical and chemical Aluminium oxide 4.40
properties of cement are mentioned in detail in Tables 1 and 2, respec- Iron oxide 3.8
tively, conforming to the provisions of Indian standard IS: 8112.16
Calcium oxide 60.10
The OPC contains five main constituents. (1) Tricalcium silicate
Magnesium oxide 3.30
(Ca3SiO5 or C3S), (2) dicalcium silicate (Ca2SiO4 or C2S), (3) tricalcium
Sulphuric anhydride 3.00
aluminate (Ca3Al2O6 or C3A), (4) tetracalcium aluminoferrite
Insoluble residue 4.6
(Ca4Al2Fe2O10 or C4AF) and (5) sulphate phase (CaSO4·2H2O).
SINGH ET AL. 3

TABLE 3 Physical properties of fine aggregate ΔE2instrument = ΔE2analyser + ΔE2X-ray ð1Þ

S. Physical Tested IS: 383-1970
No. properties values recommendations where ΔEanalyser is given by
1. Specific gravity 2.64 2.60–2.70

W α2
2. Fineness 2.34 2.00–3.50 ΔE = Ep + ð2Þ
2R 2
modulus
3. Water 1.65 -
absorption (%) where Ep is the pass energy of the analyser, W is the slit width, α is
4. Moisture 0.38 - the acceptance angle of the analyser, which is ±20
, and R is the
content (%) radius of the concentric hemispherical analyser with value 279.2 mm.
5. Grading Zone II - The slit width of the PHI Versa probe 5000 analyser is 4 × 12 mm
6. Appearance Dark grey and X-ray line width of Al Kα is about 0.2 to 0.3 eV.
Putting the above values in Equation 1 and then in Equation 2,
we can get the resolution of XPS instrument as 0.4 to 0.6 eV
TABLE 4 Chemical composition of sand
depending upon the pass energy used to collect the photoelectrons.
Constituent Weight % In addition to chemical-state analysis, the XPS can be used to
Silica 62.77 determine the atomic concentration of the various constituent ele-
Aluminium oxide 12.20 ments, which can be described by the equation:
Iron oxide 9.09
Ii X
Calcium oxide 10.90 ai = = I=ASF: ð3Þ
ASF i
Magnesium oxide 1.82
Potassium oxide 3.22
for all i. Ii is the intensity/area under the curve for the ith element.
ASF is the atomic sensitivity factor of the individual element.
2.2 | Instrumentation The chemical composition of cement and sand was done by x-ray
fluorescence (XRF) Bruker S4 Pioneer instrument.
The surface characterisation of the prepared mortar mixes was carried
out by XPS technique. The XPS is a very powerful technique which is
used to analyse the surface features of a given compound (mortar) 3 | RESULTS AND DISCUSSION
composition. The chemical state of individual elements in the mortar
mixtures was analysed by XPS (PHI Versa Probe 5000 II [ULVAC- 3.1 | Phenolphthalein test of mortar samples
PHI]). Mononchromatised anode of Al Kα (hν = 1486.6 eV) was used as
a source for x-ray generation and subsequently photoelectron ejection Figure 1 shows the phenolphthalein test for carbonation detection of
from sample surface. Survey and core level XPS spectra of the respec- all the mortar samples. The effect of carbonation on the surface of the
tive mortar compositions were recorded under ultra-high vacuum mortar samples were initially tested by phenolphthalein indicator. The
(UHV 10−10 Torr) condition. For survey spectrum, the pass energy of cement mortar is exposed to ambient air atmosphere, which has CO2
the analyser was set at 187.5 eV, whereas for the core level, the spec- and moisture as its constituents. The CO2 in presence of moisture
tra were collected at a lower pass energy of 11.750 eV in order to (OH−) in the mortar results in the formation of carbonic acid (H2CO3)
achieve better resolution. Prior to the data collection, the z-alignment as an intermediate product, which shifts the pH level of mortar sam-
of each data accusation point was done with 200-μm x-ray beam diam- ples towards acidic range. Among the hydrated products, Ca(OH)2
eter. The data recording was done at a step size of 0.1 eV with x-ray readily reacts with CO2 resulting in the formation of CaCO3.20 There-
probe beam of 100 μm diameter. The electron neutraliser and Ar ion fore, any carbonate formation on the surface of the sample will show
gun were used during the experiment for charge loss compensation no change in colour under phenolphthalein test, whereas the non-
occurred during XPS process and also for surface cleaning (if required). carbonated part of the sample will eventually turn into pink appear-
The C 1s reference binding energy (BE) peak at 284.5 eV was ance. As evident from Figure 1, the inner part of the mortar samples
used for peak shift correction.19 In the curve fitting procedure, both does not show any carbonation effect. The carbonation effect of C-S-
Gauss and Lorentz type of functions were used to obtain a better fit, H product, which is supported by formation of silica gel in the speci-
and the background treatment was done by Shirley function to the mens, has been studied in the next subsections.21,22 As evident from
original data. MULTIPAK software has been used for deconvolution the XRF analysis of the sand, the presence of CaO and its interaction
and analysing the data. with atmospheric CO2 leads to the formation of calcium carbonate.
One of the most important parts in XPS analysis is its electron The formation of CaCO3 from Ca(OH)2 may be considered as non-
energy analyser, and therefore, its energy resolution is of paramount substantial because of the reason that the mortar samples have been
importance, which can be described by the equation: exposed to ambient air conditions for only 180 days, which is
4 SINGH ET AL.

F I G U R E 1 Phenolphthalein
test for carbonation detection of
the mortar samples

considerably not adequate enough time period for carbonation from
Ca(OH)2.
The main drawback of the phenolphthalein test is that it can only
predict the carbonation effect in a given mortar sample. It cannot
determine the extent of carbonation in the sample. Here, we
introduce XPS as a tool to determine not only the carbonate estima-
tion but also the cement to sand ratio determination in a given mortar
sample. XPS technique provides a detailed information regarding sur-
face elements in the mortar samples up to a depth of 75 Å.19 The core
level analysis of the elements in the surface or near surface region

F I G U R E 2 X-ray
photoelectron spectroscopy (XPS)
core level spectra of A, Ca 2p; B,
C 1s; C, Si 2p and D, O 1s in 1:1
of cement to sand mortar
composition
SINGH ET AL.
gives semi-quantitative and chemical-state information of the individ-
ual elements.
3.2 | XPS analysis of mortar samples
Figure 2 represents the core level spectra of Ca 2p, C 1s, Si 2p and O
1s for 1:1 mortar composition. All the spectra are deconvoluted for
individual composition analysis. The major component of cement,
i.e., C3S/C2S after combining with water forms a complex product as
calcium silicate hydrate (C-S-H).
The evidence of carbonate formation is shown in C 1s spectrum
in Figure 2B. The adventitious carbon (C–C) bond is situated at
284.5 eV, whereas the carbonate peak is situated at 289.5 eV.19 The
carbonate formation in the sample may be attributed to the reaction
of Ca(OH)2 and CO2 at the sample surface or the initial presence of
CaO in the aggregate, which upon reaction with CO2 leads to forma-
tion of carbonates. Small amount of potassium is also visible in the C
1s spectrum confirming the presence of potassium oxide.
Upon the confirmation of carbonate species from the C 1s spec-
trum, the XPS plot of Ca 2p is shown in Figure 2A is analysed. It is evi-
dent that Ca in C-S-H and Ca in CaCO3 phases are present in the
composition. But the peak separation of these two compounds is very
close to each other on BE scale, and peaks are overlapping in the
range of 346.5–347.5 eV. Therefore, it is very difficult to analyse and
estimate the concentration of C-S-H and CaCO3 from the Ca 2p
F I G U R E 5 Stacked X-ray
photoelectron spectroscopy (XPS)
plots of Ca 2p, Si 2p and O 1s
spectra for 1:1, 1:3 and 1:6
mortar samples
5
spectrum. Upon aging of the various mortar compositions, the Ca 2p
spectra shows no shift in its peak BE for various mortar mixes. This
has been confirmed in Figure 5, where Ca 2p BE peaks of all three
mortar compositions are at the nearly same BE level.
Figure 2C shows the deconvoluted Si 2p spectrum. The silicon
present in C-S-H and sand (fine aggregate) α-SiO2 is shown very
explicitly in the spectrum. The major peak of Si corresponds to C-S-
H situated at around 102.5 eV (Mollah et al.12), and Si
corresponding to sand (α-SiO2) is at 103.6 eV.20 Figure 2D shows
the deconvoluted O 1s spectrum. The deconvoluted peaks
corresponding to CaCO3, C-S-H and sand are the majority peaks in
the O 1s spectrum. Similarly, Figures 3 and 4 show the core level
plot for 1:3 and 1:6 mortar compositions. In these two composi-
tions, the surface carbonation has occurred and is evident from the
C 1s spectrum in Figures 3B and 4B, respectively, at 289.5-eV BE
level. The presence of K2O is also evident in both C 1s spectra. The
K 2p core level BE range lies in the vicinity of the C 1s spectrum
with K 2p3/2 peak corresponding to K2O situated around 293 eV.20
The Si 2p spectrum in Figures 3C and 4C shows peak at 103.0 and
102.8 eV corresponding to sand (α-SiO2) and C-S-H peak at 102.1
and 101.6 eV, respectively.Whereas SiO2 peak in O 1s spectrum of
1:3 and 1:6 mortar sample is located at 532.3 and 532.0 eV, respec-
tively, and C-S-H, CO32− peaks at 531 and 530.7 eV,
12,13
respectively.
Figure 5 shows the stacked Ca 2p, Si 2p and O 1s spectra. As
mentioned earlier, the Ca 2p in all the mortar compositions remain
6 SINGH ET AL.

F I G U R E 3 X-ray
photoelectron spectroscopy (XPS)
core level spectra of A, Ca 2p, B,
C 1s, C, Si 2p and D, O 1s in 1:3
of cement to sand mortar
composition

F I G U R E 4 X-ray
photoelectron spectroscopy (XPS)
core level spectra of A, Ca 2p; B,
C 1s; C, Si 2p and D, O 1s in 1:6
of cement to sand mortar
composition
SINGH ET AL. 7

TABLE 5 Peak binding energy values for carbonate, sand and C-S-H from Ca 2p, C 1s, Si 2p and O 1s in all three mortar mixes

Peak positions (eV)

Mortar composition CO32− (C 1s) CO32− (O 1s) CO32− (Ca 2p) C-S-H (O 1s) C-S-H (Si 2p) SiO2 (O 1s) SiO2 (Si 2p)
1:1 289.3 530.5 346.5–347.3 530.5–531.4 102.5 532.4 103.6
1:3 289.2 531.0 346.5–347.3 531 102.1 532.3 103
1:6 289.5 530.7 346.5–347.3 530.7 101.6 532.0 102.8

hydroxides react with carbon dioxide leading to formation of carbon-

F I G U R E 6 Atomic concentration plot of carbonate, SiO2 and C-S-
H in different mortar mixtures
unaffected even upon the aging of the samples. But there is a notice-
able peak shift in the Si 2p and O 1s spectra towards the higher BE
range. This may be attributed to the increase in the quantity of sand
in the mortar mixture as compared with cement. The O 1s peaks of
the mortar mixes are broad and asymmetric in nature attributing to
the presence of hydroxides, carbonates and metal oxides peaks as
confirmed in the respective deconvoluted spectrum. In the present
study, formation of hydroxides has not been shown because these
ates. Similar broad and slight asymmetric spectrum is also observed
for Si 2p spectrum for all the three mortar mixes due to the presence
of multiple compounds as shown in Figures 2, 3 and 4, respectively.
Table 5 shows the BE peak values of carbonate, SiO2 and C-S-H prod-
uct from C 1s, O 1s, Ca 2p and Si 2p peaks.
Figure 6 shows the atomic concentration of calcium carbonate, C-
S-H and SiO2 corresponding to sand from the Si 2p, O 1s and C 1s
spectra. The nature of carbonate plot from C 1s spectrum has an ini-
tially increasing trend up to 1:3 mortar mix and decreasing thereafter.
This may be attributed to porous nature of the mortar samples (1:3
and 1:6 mortar mix), which has higher sand content as compared with
1:1 mortar sample. Porous nature of the samples allows more penetra-
tion of CO2 in the sample thereby increasing the carbonation effect.
However, the 1:6 mortar composition shows slightly less carbonation
as compared with 1:3 mortar sample. This may be attributed to the
heterogeneous nature of the sample, which has varying properties
from one data collection point to another in XPS analysis. For sand
(SiO2), the plot has almost linear increasing trend in both Si 2p and O
1s spectra. The C-S-H plot has a decreasing trend with the increasein
sand content as observed in Si 2p and O 1s spectra. The silica gel that
has a structure of SiO4 tetrahedron and linked by Si–O–Si bonds rep-
resents a greater extent of polymerisation. The formation of the silica
gel as a result of carbonation of C-S-H products upon aging has not
been observed in the present study. The formation of silicate products
in the C-S-H occurs at the BE level 102.2 eV in Si 2p spectrum
(Mollah et al.12). The standard silica gel has a peak BE level around
104 eV. The obtained spectrum for Si 2p shows no hump or signature
of silica gel. Therefore, Si in C-S-H is not converted to silica gel and
remained in the silicate form.19 The atomic concentration of SiO2, C-
S-H and CaCO3 from various spectra is listed in Table 6.
The estimation of cement to sand ratio in a given mortar compo-
sition can be calculated as
h i
At:conc:of C-S-H + CO2− 2−
3 ðO 1s spectrumÞ – ðAt:conc:of CO3 ðC 1s spectrumÞ
:
At:conc:of SiO2 ðO 1s spectrumÞ

TABLE 6 The atomic concentration of carbonate, C-S-H and sand composition in 1:1, 1:3 and 1:6 mortar mixes

Mortar composition Atomic concentration %

CO32− (C 1s) C-S-H+ CO32− (O 1s) C-S-H (Si 2p) SiO2 (O 1s) SiO2 (Si 2p)
1:1 21 65 80 30 20
1:3 40 64 50 40 50
1:6 32 42 28 50 72
8 SINGH ET AL.
For all the three mortar compositions, the actual cement to
sand ratio shows 20–30% of error margin from the XPS calcula-
tion. XPS technique is very efficient in surface analysis of the mor-
tar composition but has some limitations with heterogeneous
samples, which have varying properties in its composition. Also, in
the present study, the volume of samples prepared is in bulk,
which can increase the error margin. Therefore, to reduce the error
margin in XPS analysis, a large number of data points or area must
be scanned to get better results.
4 | CO NC LUSIO N
The mortar mixes of various cement and sand composition are
analysed and presented in the current study. The main focus is on
the engineering aspect of the hydrated cement product formation
and mortar composition, i.e., cement and sand ratio determination.
The Si 2p, C 1s, O 1s and Ca 2p spectra of the different mortar
compositions were analysed. The carbonation effect is evident in
all three mortar compositions as confirmed by phenolphthalein test
and XPS analysis. The Si 2p peak in sand (SiO2) is situated around
103 eV, which is slightly higher than Si 2p peak corresponding to
C-S-H hydration product (102 eV). Similarly, the O 1s peak
corresponding to sand is also at higher BE level as compared with
O 1s peak corresponding to C-S-H. The formation of silica gel has
not been found in the present study. The C-S-H and sand (SiO2)
content were determined from and O 1s and C 1s spectra and is
found to be in accordance with cement and sand ratio in respec-
tive mortar mixes within 20–30 percent of error limit. This high
percentage of error limit is attributed to heterogeneous nature of
the mortar mixes and a limited number of data points or area
scanned.
The present study has a practical application in ensuring the
quality of the infrastructure sector. By applying the XPS analysis,
an approximate estimation of various cement mortar mixes can be
determined, which could be of significant use to the field engi-
neers. The future scope of work can be extended to reinforced
cement concrete taking into account the effect of various types of
cement into consideration. The role of coarse aggregates, various
types of super plasticizers and pozzolanic binders such as flyash
and GGBS in the mortar mix may be further investigated.
ACKNOWLEDGEMEN T
The authors are grateful to the Director of CSIR-CBRI, Roorkee, for
providing the motivation and support towards this research work.
ORCID
Siddharth Singh https://orcid.org/0000-0002-8123-0697
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How to cite this article: Singh S, Dalbehera MM, Rawat A,
Sharma P. Carbonation study and determination of cement to
sand ratio in hardened cement mortar by X-ray photoelectron
spectroscopy. Surf Interface Anal. 2020;1–8. https://doi.org/
10.1002/sia.6797