Construction and Building Materials 58 (2014) 182–192

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Construction and Building Materials

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Effect of SO3 and MgO on Portland cement clinker: Formation of clinker

phases and alite polymorphism
Xuerun Li, Wenlong Xu, Shaopeng Wang, Mingliang Tang, Xiaodong Shen ⇑
State Key Laboratory of Materials-Oriented Chemical Engineering, College of Materials Science and Engineering, Nanjing Tech University, Nanjing 210009, China

h i g h l i g h t s

 SO3 hindered the formation of C3S by increasing the formation temperature by 100 °C.
 SO3 could promote the formation of C2S rims, indicating the dissolution of C2S.
 MgO enhanced the formation of C3S in both the blank and SO3-bearing clinkers.
 MgO favored the formation of M3 type alite, whereas SO3 could stabilize M1 alite.
 Seven characteristic windows in XRD were confirmed to identify the M1 and M3 types of alite.

a r t i c l e i n f o a b s t r a c t

Article history: The effects of SO3 and MgO on the formation of cement clinker and the polymorphism of alite were
Received 26 November 2013 thoroughly investigated. Quantitative analysis of the mineral composition was performed using the
Received in revised form 9 February 2014 Rietveld method based on powder X-ray diffraction patterns. Clinkerization of the raw meal was
Accepted 11 February 2014
observed by ex-situ experiments. The C3S and C2S contents were linearly related to the SO3/MgO ratio.
Adding SO3 hindered the formation of C3S, the formation temperature of which increased by approxi-
mately 100 °C. MgO enhanced the formation of C3S by both accelerating the clinkerization reactions
Keywords:
and lowering the formation temperature of C3S. The C4AF content increased when MgO was added.
MgO
SO3
Microscopically, MgO led to the formation of small C3S crystals, whereas SO3 enlarged the size of C3S
Cement clinker crystals and promoted the formation of C2S rims. M3 alite was the primary component of the MgO-doped
Microscopy clinkers, whereas the M1 type was stabilized by SO3; these results were confirmed using seven charac-
Alite polymorph teristic windows of high-angle-resolution XRD patterns.
C2S rims Ó 2014 Elsevier Ltd. All rights reserved.

1. Introduction
MgO and SO3 are the most common minor components of
cement clinkers [1–3]. As such, the effect of these components
on cement clinkers was previously investigated using design of
experiments (DoE) [4]. It was observed that MgO and SO3 could
stabilize different types of alite, and the traits of the polymorphs
were identified using X-ray diffraction (XRD) [1,5–8]. XRD data
collected at higher resolution (full width at half maximum
(FWHM) 6 0.072°) without Ka2 can be used as precise characteriza-
tion of the polymorphs of C3S [8].
MgO reduced the solubility of SO3 in belite [9] and therefore
compensated for the negative effects of SO3. Because MgO seems
to favor exsolution of the sulfate from belite, the inhibition of the
conversion of C2S to alite was more readily overcome [10]. The
liquid temperatures could be lowered by 50 °C with MgO [1,11].
It was determined that excess MgO in the clinker might generate
periclase when the MgO content exceeds 2% [1,12].
The presence of SO3 in the clinkers reduced the amount of C3A1
and the C3S/C2S ratio [13]. The sulfate concentration in belite was
determined to be between four and five times that in alite [14].
Therefore, the reaction of CaO with belite is inhibited, consequently
suppressing C3S formation [15]. This effect increased the amount of
belite and decreased the amount of alite in the clinkers [10,15–17].
SO3 existed in both clinker phases and alkali sulfates; anhydrite
hardly formed in works clinkers [14]. Strunge [15,18–20] also
observed that sulfur is combined preferentially in the matrix (clinker
phases) and sulfate phases.

⇑ Corresponding author. Tel.: +86 25 83587234; fax: +86 25 83221690. 1

Nomenclature: C = CaO, S = SiO2, A = Al2O3, F = Fe2O3, $ = SO3, nomenclature is not
E-mail addresses: xdshen@njtech.edu.cn (X. Shen), xuerunli@163.com (X. Li). used if the compounds are presented in their full representation.

http://dx.doi.org/10.1016/j.conbuildmat.2014.02.029
0950-0618/Ó 2014 Elsevier Ltd. All rights reserved.
 X. Li et al. / Construction and Building Materials 58 (2014) 182–192
The crystal size of the alite was heterogeneous, ranging from
small to enormous in the clinkers with increasing sulfur content
[13]. Campbell [21] deduced the linear relationship between alite
crystal size and SO3 concentration in clinkers (for SO3 ranging from
0.09% to 1.10%). For instance, the alite crystal size increased from
0.050 mm to 0.150 mm as the SO3 content increased from 0% to
2.60% [15].
Prolonged heating of the clinkers to 1550 °C may also generate
large alite crystals and promote the recrystallization of dendritic
C2S in the interstitial phases by dissolving rounded C2S particles
during super cooling [22]. Some of the recrystallized C2S reacted
further to form C3S on the edges of the formed alite. C3S crystal
growth occurred continuously, creating new layers on the surface
of alite crystals after reheating for hours. The formation of these
layers was hindered when C2S crystallized to form dendritic struc-
tures, breaking down to irregular surfaces [23].
With respect to the formation of the clinker phases, previous
reports have established the various steps of the process [1]. How-
ever, the difficulties lie in accurately investigating clinkerization
during industrial production processes. The minerals formed dur-
ing the sintering process have been observed to depend primarily
on the degree of calcinations the heterogeneity of the raw meal
and the circulation of the volatile components [1]. Recently, due
the development of XRD techniques and quantitative analysis
methods, both in-situ and ex-situ experiments are sufficient for
investigating the development of the mineral composition of clink-
ers during the sintering process [24–26].
Although comprehensive studies detailing the clinkerization
process have been published recently, the use of less-powerful
techniques (with respect to both hardware and software) has re-
stricted these studies, and imprecise quantitative investigations
have been documented.
More-detailed research describing the effects of MgO and SO3
on cement clinker formation is presented in this paper. Herein,
the formation of clinker phases during the sintering process is
clearly described. The formation of clinkers was investigated using
ex-situ XRD quantitative analysis, and the polymorphism of alite
was also monitored using high-angular-resolution XRD.
2. Experimental
2.1. Sample preparation
Cement clinker was synthesized using analytical-grade CaCO3, SiO2, Al2O3,
Fe2O3 MgO and CaSO4
2H2O
MgO was added directly to the samples, whereas the
CaO added to the samples was derived from gypsum. The prepared raw meals were
homogenized in a ball mill bottle with agate balls for 12 h. Subsequently, the meal
Fig. 1. Large clinker pieces (from the clinker produced to test materials properties) placed on Pt slices for laboratory production; samples shown in (a) contain 1.5% SO3,
whereas those in (b) contain 4.0% SO3.
183
Table 1
The burdening of the raw meals and the potential mineral compositions (%).
C3S C2S C3A C4AF SiO2 Al2O3 Fe2O3 CaCO3
57.53 24.143 9.539 9.41 23.40 5.57 3.10 67.93
was pressed into discs for sintering. The potential mineral composition of the
clinker and the composition of the raw materials are listed in Table 1 (the blank
clinker). Appropriate amounts of MgO (0%, 2%, 4% and 6%) and SO3 (0%, 0.5%,
1.5%, 3% and 4%) were added to the blank clinkers.
Cubic discs of raw meal (60  60 mm) were sintered in a resistance furnace; the
temperature was calibrated using Ferro PTCR-MTH testing rings (Ferro Electronic
material systems, ±5 °C), as shown in Fig. 1. Large clinker pieces were produced
for materials property testing; this process will be discussed separately in another
paper. The samples were placed in platinum crucibles, heated up at a rate of 10 °C/
min, calcined at 1000 °C for 30 min and sintered (1500 °C) for 60 min. For the sam-
ples with independent doses of SO3, the holding time was prolonged to yield a low-
er f-CaO content due to the hindrance caused by SO3 during the formation of C3S
(up to 80 min). The sintered clinkers were cooled with forced air. Higher SO3 con-
tents with plentiful liquid could blend the pieces down by side. The volatile liquid
caused a layer of components to remain attached to the Pt pieces (Fig. 1(b)).
Ex-situ experiments were carried out using small raw meal blocks (approxi-
mately 1 cm in diameter and crushed from the 60  60 mm pieces). The raw meal
blocks were heated at 10 °C/min and removed from the furnace as soon as the de-
sired temperatures (900 °C or 1000 °C–1550 °C in intervals of 50 °C) were reached.
The sintered samples were immediately cooled in forced air. The samples were
carefully powdered for XRD data collection; this process was carried out rapidly
to prevent the hydration of the active lime.
2.2. Characterization
2.2.1. X-ray diffraction (XRD)
All samples were finely ground in preparation for the powder diffraction mea-
surements. For quantitative analysis, XRD data were collected on a Rigaku Miniflex
using Cu Ka radiation (k = 0.15406 nm) operated in the reflection geometry (h/2h) at
room temperature, and an automatic six-sample changer was used. Data were col-
lected from 10° to 70° (2h) in step sizes of 0.01° at 5°/min. The X-ray tube was oper-
ated at 40 kV and 15 mA. Quantitative analysis was performed using the Rietveld
method with GSAS [27] EXGUI [28]. The profile was fitted using the Pseudo-Voigt
function. The background was fitted graphically using the Shifted Chebyschev poly-
nomial with 10 out of 20 manually selected points. The following parameters were
fitted: phase fractions, lattice parameters and profiles (GU, GV, and GW). The crystal
structures and the corresponding references used in the refinements are listed in
Table 2.
The Rietveld fittings of the samples are displayed in Figs. 2 and 3. More details
for quantitative data and fittings can be obtained in Supplementary material, page
S2–S7. The statistical plots for the residue of the refinements are also provided (in-
set plot (a)). Better fittings could be achieved when the sintering temperature ex-
ceeded 1300 °C. Inset plot (b) shows the details of the fittings. As demonstrated,
the refinements of these samples yielded acceptable results. For samples sintered
at a lower temperature, the residues of the fitting showed fluctuations, as demon-
strated in inset plot (a). However, all of the obtained quantitative results were
determined to be reasonable.
184 X. Li et al. / Construction and Building Materials 58 (2014) 182–192

Table 2
Bibliographic information and ICSD collection codes for all of the related crystalline phases.

Phases Refs. Mineral Namea ICSD No. Phases Refs. Mineral Name ICSD No.
b
C3S [29] N/A 64759 C2S [30] Larnite 79553
C3A [31] N/A 1841 C4AF [32] Brownmillerite 2841
f-CaO [33] Lime 52783 MgO [34] Periclase 31051
CaCO3 [35] Calcite 73446 SiO2 [36] Quartz 174
C2F [37] Srebrodolskite 15059 Fe2O3 [38] Hematite 154190
C4A3$ [39] N/A 9560 C$ [40] Anhydrite 1956
Al2O3 [41] Corundum 31545
a
Mineral name associated with the description of the ICSD card.
b
The C2S formed above 1300°C occurred in the alpha form; consequently, cooling the sample promoted the formation of the beta form of C2S. Therefore, larnite was used
during the refinement.

Fig. 2. Rietveld refinements for the samples (M0S00 sintered at 1200 °C) during the sintering process. Inset plot (a) is the box chart for Rwp, whereas (b) is a more detailed
view of the refinement.

Fig. 3. Rietveld refinements for the samples (M0S00 sintered at 1550 °C) during the sintering process. Inset plot (a) is the box chart for Rwp and (b) provides a more detailed
view of the refinement.
 X. Li et al. / Construction and Building Materials 58 (2014) 182–192 185

For the characteristic windows of the alite polymorphs, XRD data were obtained
using a Rigaku Smartlab with Cu Ka radiation (k = 0.15,406 nm), but without the
Ka2 (k = 0.15, 444 nm) line of Cu radiation. Data were collected from 10° to 70°
(2h) in step sizes of 0.02° at 5°/min, with the X-ray tube operated at 45 kV and
200 mA. The angular resolution was 0.055° based on the full width at half maxi-
mum (FWHM) value of standard Si(311) (FWHM311) at 56.12°.
2.2.2. Microscopy
Microscopic images were captured using a Leica Microsystems GmbH micro-
scope (Wetzlar, Germany) equipped with a Leica DFC 480 camera. The samples
were embedded in epoxy resin before polishing. The polished samples were washed
in alcohol with an ultrasonic cleaner. The polished surface was etched in an alcohol-
HNO3 solution for 10 s [23].

Fig. 4. Formation of the clinker during the sintering process. (a) M0S00, (b) M0S15, (c) M2S00, (d) M4S00, (e) M4S15 and (f) M4S40.
186 X. Li et al. / Construction and Building Materials 58 (2014) 182–192

3. Results and discussion
3.1. Sintering of the clinker
Fig. 4 shows the variations in the mineral composition during
the heating process. Adding SO3 hindered clinker formation
(Fig. 4(a, b, e and f)), leading to increase in C2S content and de-
creases in C3S content. The formation of C3S was delayed by SO3
(approximately 100 °C higher). Consequently, C3S started to form
at higher temperatures, up to 1400 °C, 1350 °C and 1400 °C for
M0S15, M4S15 and M4S40, respectively. The C3S content in the fi-
nal clinkers, especially for samples with excess SO3 or indepen-
dently dosed SO3, decreased dramatically to 50% and 33% for
samples M4S40 and M0S15, respectively (see Fig. 4(c)). Another
transition phase called ye’elimite (C4A3$) formed at approximately
1050–1350 °C when SO3 was present, and peaked at approximately
1250 °C, in agreement with previous reports [25,42]. For C2F, mar-
ginal differences occurred with various dopants. However, there

Fig. 5. Contour plots of the clinker composition vs. SO3 and MgO doses: (a) C3S, (b) C2S, (c) C3A, (d) C4AF, (e) f-MgO and (f) C$.
 X. Li et al. / Construction and Building Materials 58 (2014) 182–192 187

was little C5S2$ (which should be formed during the sintering pro-
cess [43,44]) in the SO3-dosed samples during the sintering process
in this study.
In contrast, MgO enhanced alite formation, generating more
alite in the clinker (Fig. 4(a) and (b)) and further compensating
for the negative effects of SO3 [4]. An approximately 10% increase
in C3S content was achieved by adding MgO (Fig. 4(a, c and d)).
For SO3-containing samples, an impressive 30% increase in C3S con-
tent was achieved (Fig. 4(b) and (e)). The initial formation temper-
ature of C3S was reduced by approximately 50 °C after adding MgO.
However, the C3A content decreased and C4AF content increased
when MgO was added (Fig. 4(a, c and d)). Periclase formed at the
very beginning of the clinkerization process in samples dosed with
MgO (Fig. 4(c, d, e and f)), appearing at approximately 750 °C in the
industrially produced clinker [1]. However, the periclase only ap-
peared in the final clinker when the dose was above 4%
((Fig. 4(c) and (d)).
Because MgO appears to favor exsolution of the sulfate from
belite, the inhibition of the conversion of C2S to alite is more read-
ily overcome [9,10]. Independently added SO3 inhibited C3S forma-
tion, generating a clinker with tremendous amounts of f-CaO and
C2S [4].
3.2. Mineral composition
MgO and SO3 were observed to affect the mineral composition
of the clinker formed. The contour plots of the phase compositions
versus the MgO and SO3 doses presented in Fig. 5 reveal the de-
tailed variations in the phase compositions. Larger SO3 doses were
detrimental to C3S formation (Fig. 5(a)). For independent doses of
SO3, the C3S content decreased dramatically with the increase in
SO3 dose (Table 3) by 54.81% and 44.04% C3S for M0S05 (0.5% dos-
age of SO3) and M0S15 (1.5% dosage of SO3), respectively.
Furthermore, the C2S, C3A and anhydrite contents were primar-
ily controlled by the added SO3 (Fig. 5(b, c and f)). Previous publi-
cations have also supported the idea that an increased SO3 content
in clinker increases the amount of measured C3A [45], as illustrated
in Fig. 5(c).
MgO also favored the formation of C4AF (Table 3, Fig. 4(a), (c)
and (e)). In both the blank and independently dosed SO3 clinkers,
the C4AF content was only approximately 5.5% (Table 3). When
MgO was added, the amount of C4AF climbed up to approximately
10%. Adding SO3 to the MgO-bearing clinkers decreased the C4AF
content, resulting in a minimum value in the 3.0% SO3-dosed
samples.
MgO and SO3 governed the periclase and anhydrite contents,
respectively. Periclase became abundant when the MgO concentra-
tion exceeded 4%; this concentration was much higher than the
incorporation limit of the clinker phases [1,12]. Anhydrite ap-
peared when the amount of SO3 exceeded 1.5%, coinciding with
published results indicating that anhydrite was detected when
clinker contained more than 1.5% SO3 [13]. The actual SO3 content
in the clinker was 2.42–3.04% when the dose exceeded 3.0% (see
Table 3).
The mineral compositions of the clinker were subsequently fit-
ted to the SO3/MgO ratio or the SO3 and MgO doses (see Fig. 6).
These fittings could simplify the correlation between the additives
and the mineral composition. All of the fitted equations are listed
in Table 4. The C3S and C2S contents were dependent on the SO3/
MgO ratio. However, the C3A and C4AF contents were somewhat
less dependent on the SO3/MgO ratio. The poorly fitted equations
for these two phases are also listed in Table 5. The periclase and
anhydrite contents were linearly related to the dosages of MgO
and the SO3, respectively (see Fig. 5(e) and (f) and Fig. 6(c) and (d)).
The theoretical amounts of MgO incorporated into the clinker
minerals were 1.39% and 1.78% (Table 5), whereas the experimen-
tal value of MgO gained by linear fitting amounted to 1.50% (see
Table 4, the intercept of the f-MgO fitting equation indicates the
amount of incorporated MgO). The incorporated MgO content con-
firmed that the amount of MgO incorporated into alite in this study
was the highest. The theoretical amount of MgO incorporated
(1.78%) was closer to the observed value. This result is in agree-
ment with the finding that periclase crystals occur in clinkers only
if the MgO content exceeds 2% [1,12].
3.3. Alite polymorphs
An exhaustive investigation of the polymorphism of alite was
performed using XRD techniques, the results of which are illus-
trated in Figs. 7 and 8. The characteristic windows for alite were se-
lected based on the criterion that reflections did not occur with
other minerals. In addition to the characteristic windows (five win-
dows) proposed by Maki [1,5] (W4 and W7 in Fig. 8) and Courtial
[6] (W1, W2 and W5 in Fig. 8) confirmed by Wang [8], four more
windows were used to identify the M1 and M3 types of alite; thus,
there were nine characteristic windows in the XRD patterns (see
Fig. 8). The characteristic windows of W1 and W2 could be ob-
served only for M1 obtained after doping with both MgO and
SO3; this peak was less intense in the blank sample and samples
with independently dosed SO3, which implies that these two
windows were not suitable for the general identification of alite

Table 3
Mineral compositions of the resultant clinkers calculated using the Rietveld method (%).

Labels MgO dosage SO3 dosage C3S C2S C3A C4AF f-CaO f-MgO C$ Rwpa SO3b
M0S00 0.0 0.0 62.21 20.96 11.21 5.46 0.17 0.00 0.00 12.31 0
M0S05 0.0 0.5 54.81 27.96 11.86 5.07 0.31 0.00 0.00 14.46 0.20
M0S15 0.0 1.5 44.04 38.91 10.04 5.86 0.75 0.00 0.00 15.44 0.62
M2S00 2.0 0.0 66.39 17.77 2.83 12.12 0.10 0.78 0.00 10.89 0
M2S15 2.0 1.5 62.32 27.97 1.99 8.21 0.24 0.00 0.00 11.49 0.71
M2S30 2.0 3.0 47.63 32.92 9.63 7.32 0.50 0.47 1.50 11.12 3.04
M2S40 2.0 4.0 40.48 41.28 9.33 6.00 0.63 0.00 2.27 11.82 3.54
M4S00 4.0 0.0 63.25 18.83 5.03 9.10 0.20 3.64 0.00 11.98 0
M4S15 4.0 1.5 61.82 23.29 4.51 7.35 0.23 2.80 0.00 17.04 0.62
M4S30 4.0 3.0 48.75 34.64 5.00 6.97 0.56 2.91 1.17 12.11 3.03
M4S40 4.0 4.0 43.99 36.13 5.81 7.78 0.60 3.26 2.45 15.68 3.62
M6S00 6.0 0.0 64.27 16.17 5.71 9.58 0.18 4.09 0.00 11.22 0
M6S15 6.0 1.5 61.16 20.67 4.55 8.61 0.30 4.58 0.15 11.11 1.38
M6S30 6.0 3.0 52.78 26.25 8.51 5.78 0.62 4.97 1.08 11.43 3.42
M6S40 6.0 4.0 41.85 35.55 8.66 7.01 0.65 4.06 2.22 12.14 3.61
a
Rwp is the weighted residue of the Rietveld refinement.
b
SO3 content measured by chemical methods.
188 X. Li et al. / Construction and Building Materials 58 (2014) 182–192

Fig. 6. The fitted plot of the mineral content, the SO3/MgO and the MgO and SO3 doses; (a) and (b) are the silicate and interstitial phases fitted to SO3/MgO, respectively; (c) is
the f-MgO content fitted to the MgO dosages and (d) is the C$ content fitted to the SO3 dosage.

Table 4
Fitted equations of the mineral composition and the fitting parameters.

Phases Equitation Adj. R2

a
C3S Y = 12.49X + 62.70 0.6071
C2S Y = 11.99X + 19.84 0.7615
C3A Y = 2.51X + 4.33 0.3150
C4AF Y = 1.80X + 9.16 0.3585
f-MgO Y = 1.03 MgOb–1.50 0.9086
C$ Y = 0.89 SO3b–1.34 0.9686
a
X=SO3/MgO.
b
MgO and SO3 were the dosed amounts.

Table 5
Incorporation of MgO in the clinker phases (%) [7,12,46].

C3S C2S C3A C4AF Total MgO

MgO percent Ave. mineral 54.38 27.95 6.98 7.48 N/A Fig. 7. XRD patterns of clinkers. W1–W8 are the characteristic windows for the
composition alite polymorphs.
Percenta 1.3/2.0 b
0.6 2.0 4.5 N/A
Ave. in clinkerc 0.74/1.13 0.15 0.13 0.37 1.39/1.78
polymorphs. Without these two windows, the remaining seven
a
Incorporated MgO content in clinker phase reported in the literature. (W3–W9) were still sufficient to differentiate between the M1
b
1.3% was the average MgO content incorporated into alite, whereas 2.0% was
and M3 types of alite.
the highest MgO content incorporated into alite.
c
Incorporated MgO content in the sample clinker based on the average mineral The blank sample without MgO and SO3, as well as samples
composition of all of the samples obtained. with independently dosed SO3, were identified as M1 alite (the
characteristic peaks of the blank and the M1 alite were similar,
 X. Li et al. / Construction and Building Materials 58 (2014) 182–192 189

Fig. 8. Characteristic XRD patterns of alite in clinkers.

Fig. 9. Microscopic view of M0S00 clinker. Inter. refers to the interstitial phases (C3A and C4AF), and the typical C2S and C3S phases are labeled.

with only a shift in the patterns (see Fig. 8)). Samples with inde-
pendently dosed MgO were identified as typical M3 alite; adding
SO3 to the MgO-bearing samples stabilized the M1 alite. Within
the range of SO3 doses used in this study (the lower limit of added
SO3 was 1.5% in the raw meal and the lower limit of SO3 in the
resultant clinker was 0.71%), the alite was uniformly of the M1
type. There was only a weak relationship between the SO3/MgO
ratio and the polymorphism of the alite; however, it has been
reported that the relationship is valid in works clinkers [1,3].
Alite polymorphs were accurately distinguished among the
seven characteristic windows using an XRD device equipped for
high angular resolution utilizing monochromatic Ka1 radiation
(k = 0.15406 nm). MgO stabilized the M3 alite, whereas SO3
promoted the formation of M1 alite, as indicated by the
190 X. Li et al. / Construction and Building Materials 58 (2014) 182–192

Fig. 10. Microscopic view of M4S30 (a, b and c) and M4S40 (d, e and f). Inter. refers to the interstitial phases (C3A and C4AF); black arrows indicate the C2S rims; and the
typical C2S and C3S phases are labeled.

Fig. 11. Microscopic view of M6S00 (a, b and c) and M6S40 (d, e and f). Inter. refers to the interstitial phases (C3A and C4AF); black arrows indicate the C2S rims; and the
typical C2S and C3S phases are labeled.
 X. Li et al. / Construction and Building Materials 58 (2014) 182–192
documented characteristics of the differently modified alite phases
[1,3,6,8]. However, the discussion here is based only on the XRD
data gathered for the alite in the clinker. The complexity of the
clinker, because it is a mixture of several minerals, might lead to
misidentification of the subtle traits of alite. More authoritative
results should be gathered using other techniques with synthetic
alite. These results are beyond the scope of this paper and thus will
be discussed in a later publication. A detailed characteristic win-
dows for other samples were presented in the Supplementary
materials, page S8–S13.
3.4. Microscopic observation of clinker
The MgO and SO3 doses affected the size of the alite in the clin-
ker. Alite occurred as small crystals in the blank clinker, whereas
belite occurred as round, lamellar crystals (Fig. 9). With the in-
crease in SO3 content, the alite crystals grew dramatically (as large
as 60 lm; see Figs. 10 and 11) [15,21] to reach almost 4 times the
size of the ordinary clinker (15–25 lm) [1]. When the SO3 doses
exceeded 3%, tiny C2S crystals (mostly secondary belite) appeared
attached to the edges of alite in the interstitial phase [47]. Smaller
alite crystals formed as the MgO increased (Fig. 9(a), Fig. 10(a) and
Fig. 11(a)); this phenomenon has also been reported for M3 [3].
The minor components of the interstitial phase were identified as
small belite crystals and called ‘C2S rims’ [22,47,48].
Belite dissolved in the interstitial phase, accompanied by the
growth of alite [22]. Sintering the clinker for 20 h at 1550 °C dis-
solved almost all of the belite in the clinker. The increase in the
alite crystal size as a function of the SO3 dosage was mainly caused
by the dissolution of belite and the growth of the alite phase. In
addition, the formation of C2S rims occurred because the SO3 that
was abundant in the belite structure [14] had evaporated, resulting
in the dissolution of belite during the sintering process, especially
when the clinker was treated for a prolonged time at high temper-
ature. The C2S rims in the clinker indicated C3S growth by the
incorporation of small C2S crystals. In the slowly cooled clinkers,
the number of small C2S crystals on the alite surface and the con-
tent of C3A in the interstitial melt predominantly depended on the
rate of cooling [23].
C2S rim formation was primarily caused by the peritectic reac-
tions between the liquids and minerals. The C2S rims surrounding
C3S (L + C2S ? C3S) appeared when the Al2O3/Fe2O3 was lower than
the ratio for the invariant point of 2.2 [48,49]. The C4AF content
was lower in the final clinker when the SO3 content was increased
(see Table 3 and Fig. 5), indicating that the rims were not formed
during the typical reaction (L + C2S ? C3S + C4AF). The appearance
of C2S rims in samples with high SO3 doses (over 3.0%) was not sur-
prising because the Al2O3/Fe2O3 ratio was 1.8. However, C2S rims
formed only when SO3 appeared in the clinker. Indeed, there were
no C2S rims in the SO3-free clinkers. This effect was caused by the
MgO in the clinker system [48], which altered the properties of the
liquids. The microscopic picture for clinkers doped with 2% of MgO
can be obtained in Supplementary materials, pages S14.
4. Conclusions
Adding SO3 hindered the formation of C3S by increasing the
formation temperature by approximately 100 °C. C4A3$ formed at
1050–1350 °C, and the maximum amount of the phase was
obtained at 1250 °C. The SO3 dose was the dominant factor affect-
ing the final C3S content. C$ appeared in the final clinker when the
SO3 dosage exceeded 1.34%.
MgO enhanced the formation of C3S in both the blank and SO3-
bearing clinkers. MgO promoted the formation of C3S, especially
when SO3 was present in the clinker. The C4AF content increased
191
when MgO was added. The MgO content incorporated into the clin-
ker phases was equal to 1.5%. The C3S content was linearly related
to the SO3/MgO ratio.
MgO caused small C3S crystals to form, whereas SO3 caused C3S
crystals to grow. SO3 could also promote the formation of C2S rims,
indicating that C2S had dissolved and C3S crystals had grown.
MgO favored the formation of M3 type alite, whereas SO3 could
stabilize M1 alite. The polymorph of alite observed in the blank
clinker was M1 alite. Overall, seven characteristic windows were
used to identify the M1 and M3 types of alite using XRD patterns
with high angular resolution.
Acknowledgements
The first author is grateful to Ms. Xiaoqing Xu, who graduated
from Nanjing Tech University, and offer thanks to the National
Basic Research Program of China (2009CB623100) and Priority
Academic Program Development of Jiangsu Higher Education
Institutions (PAPD) for their financial support. The support of the
Program for Changjiang Scholars and Innovative Research Team
in University (PCSIRT, No. IRT1146) is also appreciated.
Appendix A. Supplementary material
Supplementary data associated with this article can be found, in
the online version, at http://dx.doi.org/10.1016/j.conbuildmat.
2014.02.029.
References
[1] Taylor HFW. Cement Chemistry. Thomas Telford; 1997.
[2] Maki I, Fukuda K, Yoshida H, Kumaki J. Effect of MgO and SO3 on the Impurity
Concentration in Alite in Portland Cement Clinker. J Am Ceram Soc
1992;75(11):3163–5.
[3] Maki I, Goto K. Factors influencing the phase constitution of alite in portland
cement clinker. Cem Concr Res 1982;12(3):301–8.
[4] Li X, Huang H, Xu J, Ma S, Shen X. Statistical research on phase formation and
modification of alite polymorphs in cement clinker with SO3 and MgO. Constr
Build Mater 2012;37:548–55.
[5] Maki I, Kato K. Phase identification of alite in portland cement clinker. Cem
Concr Res 1982;12(1):93–100.
[6] Courtial M, de Noirfontaine MN, Dunstetter F, Gasecki G, Signes-Frehel M.
Polymorphism of tricalcium silicate in Portland cement: a fast visual
identification of structure and superstructure. Powder Diffr 2003;18(1):7–15.
[7] Thompson RA, Killoh DC, Forrester JA. Crystal chemistry and reactivity of the
magnesium oxide-stabilized alites. J Am Ceram Soc 1975;58(1–2):54–7.
[8] Wang S, Li X, He J, Pan Z, Shen X. Precise characterization of polymorphs of
tricalcium silicate using X-ray diffraction. J Chin Ceram Soc
2014;42(2):178–82.
[9] Gartner E, Tang F. Formation and properties of high sulfur Portland cement
clinkers. Il Cemento 1987:84.
[10] Gutt W, Smith MA. Studies of the role of calcium sulfate in the manufacture of
Portland cement clinker. Trans British Ceram Soc 1968;67(10):487–510.
[11] Swayze MA. A report on studies of: 1. The ternary system of CaO–C5A3–C2F, 2.
The quaternary system CaO–C5A3–C2F–C2S, 3. The quaternary system as
modified by 5% magnesia, Part 1. Am J Sci 1946;244(2):65–94.
[12] Dreizler I, Knoefel D. Effect of magnesium oxide on the properties of cement.
Zement-Kalk-Gips, Ed. B 1982;35(10):537–50.
[13] Horkoss S, Lteif R, Rizk T. Influence of the clinker SO3 on the cement
characteristics. Cem Concr Res 2011;41(8):913–9.
[14] Taylor HFW. Distribution of sulfate between phases in Portland cement
clinkers. Cem Concr Res 1999;29(8):1173–9.
[15] Strunge J, Knoefel D, Dreizler I. Effect of alkalies and sulfur on the properties of
cement Part I. Effect of the sulfur trioxide content on cement properties.
Zement-Kalk-Gips Ed. B 1985;38(3):150–8.
[16] Horkoss S. OPC clinker with high SO3. World Cement 2004(June):71–4.
[17] Older I, Zhang H. Investigation on high SO3 Portland cement clinkers. World
Cem Res Develop 1996:73–7.
[18] Strunge J, Knoefel D, Dreizler I. Effect of alkalies and sulfur on the properties of
cement Part II: effect of alkalies and sulfate on the properties of cement, taking
into account the silica ratio. Zement-Kalk-Gips Ed. B 1985;38(8):441–50.
[19] Strunge J, Knoefel D, Dreizler I. Effect of alkalies and sulfur on the properties of
cement Part III: effect of alkalies and sulfate on the properties of cement taking
into account the alumina ratio and the lime standard. Zement-Kalk-Gips Ed. B
1986;39(7):380–6.
[20] Strunge J, Knoefel D, Dreizler I. Influence of alkalis and sulfur on the properties
of cement Part IV: comprehensive survey. ZKG Int Ed. B 1990;43(4):199–208.
192 X. Li et al. / Construction and Building Materials 58 (2014) 182–192
[21] D. Campbell, Microscopical examination and interpretation of portland
cement and clinker, 2nd ed., Portland Cement Association Skokie, Illinois,
USA, 1999.
[22] Masaki K, Maki I. Effect of prolonged heating at elevated temperatures on the
phase composition and textures of portland cement clinker. Cem Concr Res
2002;32(6):931–4.
[23] Ono Y. Ono’s method: fundamental microscopy of portland cement
clinker. Chichibu Onoda Cement Corporation; 1995.
[24] Snellings R, De Schepper M, De Buysser K, Van Driessche I, De Belie N.
Clinkering reactions during firing of recyclable concrete. J Am Ceram Soc
2012;95(5):1741–9.
[25] De la Torre AG, Cuberos AJM, Alvarez-Pinazo G, Cuesta A, Aranda MAG. In situ
powder diffraction study of belite sulfoaluminate clinkering. J Synchrotron
Radiat 2011;18:506–14.
[26] De la Torre AG, Aranda MAG. Accuracy in Rietveld quantitative phase analysis
of Portland cements. J Appl Crystallogr 2003;36:1169–76.
[27] Larson AC, Dreele RBV. General Structure Analysis System (GSAS). Los Alamos
National Laboratory Report LAUR 1994:86–748.
[28] Toby B. EXPGUI, a graphical user interface for GSAS. J Appl Crystallogr
2001;34:21–210.
[29] Nishi F, Takéuchi Y. Tricalcium silicate Ca3O [SiO4]: the monoclinic
superstructure. Z Kristallogr 1985;172(3–4):297–314.
[30] Tsurumi T, Hirano Y, Kato H, Kamiya T, Daimon M. Crystal structure and
hydration of belite. Ceram Trans 1994;40:19–25 (CEMENT TECHNOLOGY).
[31] Mondal P, Jeffery J. The crystal structure of tricalcium aluminate, Ca3Al2O6.
Acta Crystallographica Section B: Structural Crystallography and Crystal
Chemistry 1975;31(3):689–97.
[32] Colville A, Geller S. Crystal structures of Ca2Fe1.43Al0.57O5 and Ca2Fe1.28Al0.72O5.
Acta Crystallographica Section B: Structural Crystallography and Crystal
Chemistry 1972;28(11):3196–200.
[33] Smith DK, Leider H. Low-temperature thermal expansion of LiH, MgO and CaO.
J Appl Crystallogr 1968;1(4):246–9.
[34] Schiebold E. The crystal structure of periclase. Z Kristallogr, Kristallgeom,
Kristallphys, Kristallchem 1921;56:430.
[35] Maslen E, Streltsov V, Streltsova N. X-ray study of the electron density in
calcite, CaCO3. Acta Crystallographica Section B: Structural Science
1993;49(4):636–41.
[36] Le Page Y, Donnay G. Refinement of the crystal structure of low-quartz. Acta
Crystallographica Section B: Structural Crystallography and Crystal Chemistry
1976;32(8):2456–9.
[37] Berggren J. Refinement of the Crystal Structure of Di-calcium Ferrite Ca2Fe2O5.
Acta Chem Scand 1971;25:3616–24.
[38] Baron V, Gutzmer J, Rundlöf H, Tellgren R. Neutron powder diffraction study of
Mn-bearing hematite, a-Fe2 xMnxO3, in the range. Solid State Sci
2005;7(6):753–9.
[39] Saalfeld H, Depmeier W. Silicon-Free Compounds with Sodalite Structure.
Kristall und Technik 1972;7(1–3):229–33.
[40] Morikawa H, Minato I, Tomita T, Iwai S. Anhydrite. Refinement. Acta
Crystallographica, Section B: Structural Crystallography and Crystal
Chemistry 1975;B31(8):2164–5.
[41] Cox DE, Moodenbaugh AR, Sleight AW, Chen HY. Structural refinement of
neutron and x-ray data by the Rietveld method: application to aluminum
oxide and bismuth vanadate (BiVO4). NBS Spec Publ (U S) 1980;567:189–201.
[42] Puertas F, Varela MTB, Molina SG. Kinetics of the thermal decomposition of
C4A3$ in air. Cem Concr Res 1995;25(3):572–80.
[43] Pliego-Cuervo YB, Glasser FP. The role of sulphates in cement clinkering:
subsolidus phase relations in the system CaO–Al2O3–SiO2–SO3. Cem Concr Res
1979;9(1):51–5.
[44] Pliego-Cuervo YB, Glasser FP. Role of sulphates in cement clinkering: the
calcium silicosulphate phase. Cem Concr Res 1978;8(4):455–9.
[45] Tagnit-Hamou A, Sarkar SL. The influence of varying sulphur content on the
microstructure of commercial clinkers and the properties of cement. World
cement 1990;21(9):389–93.
[46] Ludwig U, Wolter A. The Formation and Stability of Tricalcium Silicate and
Alites. Zement-Kalk-Gips 1979;32:455–9.
[47] Crumbie A, Walenta G, Füllmann T. Where is the iron? Clinker microanalysis
with XRD Rietveld, optical microscopy/point counting, Bogue and SEM-EDS
techniques. Cem Concr Res 2006;36(8):1542–7.
[48] Uda S, Asakura E, Nagashima M. Influence of SO3 on the Phase Relationship in
the System CaO–SiO2–Al2O3–Fe2O3. J Am Ceram Soc 1998;81(3):725–9.
[49] Hewlett PC, Lea FM. Lea’s chemistry of cement and concrete. fourth
ed. Elsevier; 2004.