Construction and Building Materials 250 (2020) 118844

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Construction and Building Materials

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Influence of sulfur trioxide in clinker on the hydration heat and physical

properties of Portland cement
Makio Yamashita a,⇑, Takumi Harada a, Etsuo Sakai b, Koichi Tsuchiya c,d
a
Mitsubishi Materials Corporation, Cement Company, Cement Research Institute, 2270, Yokoze, Yokoze-machi, Chichibu-gun, Saitama 368-8504, Japan
b
Tokyo Institute of Technology, School of Materials and Chemical Technology, 2-12-1 Ookayama Meguro-ku, Tokyo, Japan
c
National Institute for Materials Science, Research Center for Structural Materials, 1-2-1 Sengen, Tsukuba, Ibaraki 305-0047, Japan
d
University of Tsukuba, Graduate School of Pure and Applied Sciences, 1-1 Tennoudai, Tsukuba, Ibaraki 305-5877, Japan

h i g h l i g h t s

The effects of clinker SO3 on cement hydration and hardening were studied.

The alite and aluminate hydration was affected with increase SO3 in clinker.

Decreasing shrinkage with increase clinker SO3 was smaller compare to gypsum.

Cement properties with high SO3 clinker can be adjusted by the gypsum added.

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

Article history: The cement industry has achieved stable usage of waste gypsum board in clinker production. However,
Received 22 August 2019 few studies have focused on the heat of hydration and physical properties of cements with high-SO3 clin-
Received in revised form 30 January 2020 ker with different C3A and gypsum contents. Clinker with different amounts of SO3 and coexisting C3A
Accepted 20 March 2020
was prepared in an electric furnace. Cement samples were then prepared by adding gypsum.
Increasing the clinker SO3 content accelerated the alite reaction and caused aluminate hydrate reaction
to occur later. Compressive strength at 3 days increased with SO3 content whereas that after 28 days
Keywords:
decreased. The drying shrinkage strain of mortar decreased with increasing SO3 content of the clinker
Cement clinker
SO3
and gypsum at each C3A content. The decrease of drying shrinkage attributed to SO3 in the clinker was
Gypsum smaller than that caused by gypsum SO3. As the clinker SO3 content increases, cement physical properties
C3A can be maintained by adjusting the gypsum content.
Heat flow Ó 2020 Elsevier Ltd. All rights reserved.
Drying shrinkage

1. Introduction
The use of waste and by-products in cement production plays a
valuable role in preserving regional environments. The amount of
waste and by-products used by the Japanese cement industry in
2017 was 28 million tons, which was equivalent to about 10% of
the total industrial waste generated that year [1]. Recycling waste
that is difficult to use in other industries contributes substantially
to environmental protection as well as carbon dioxide emission
reduction. Recent efforts in environmental protection have
increased the recycling rates of many types of waste [2]. However,
the amount of cement produced in Japan will soon decrease
because of a decline in construction investment [3]. To maintain
the amount of waste recycled in the cement production process,
⇑ Corresponding author.
E-mail address: mkyamast@mmc.co.jp (M. Yamashita).
the waste usage per ton of clinker or cement needs to be increased
further.
Waste gypsum board is difficult to dispose of at normal landfill
sites [4–6]. Recently, the cement industry has achieved stable
usage of waste gypsum board as a raw material in cement produc-
tion which increases the sulfur trioxide (SO3) content of clinker [7].
Cement contains SO3 originating from the clinker and gypsum con-
tent during the clinker grinding process. During the past few dec-
ades, ordinary Portland cement has usually had a clinker SO3
content of below 1%. However, the thermal valorization of indus-
trial waste, tires, and solvents as well as the use of high-sulfur fuel
in cement kilns has been attracting attention recently [8,9]. These
processes increase the sulfate levels in Portland cement clinker,
affecting the chemical, mineralogical, physical, and mechanical
characteristics of both the clinker and cement. Furthermore, SO3
in clinker influences low-temperature burning [10,11], so its inclu-
sion in clinker is expected to increase in the future.

https://doi.org/10.1016/j.conbuildmat.2020.118844
0950-0618/Ó 2020 Elsevier Ltd. All rights reserved.
2 M. Yamashita et al. / Construction and Building Materials 250 (2020) 118844

SO3 is a common minor component of cement clinker. As such,
the effect of SO3 on the mineral composition of clinker and cement
properties has been investigated in many studies [12,13]. Previous
researchers reported that the influence of SO3 in clinker on cement
properties depends on the coexisting alkali (Na2Oeq) content in the
clinker [14–16]. The influence of SO3 in clinker on the properties of
cement might depend on the C3A content of the cement because
SO3 can react with C3A in the pore solution in cement in an early
stage of aging. However, few studies have focused on the heat of
hydration and drying shrinkage of Portland cement with high-
SO3 clinker with different C3A contents and added gypsum.
The objective of this paper is to evaluate the heat flow and
physical properties, including setting time, compressive strength,
and level of drying shrinkage, of cements produced with high-
SO3 clinker prepared in laboratory with different C3A and gypsum
levels. The following cement nomenclature is adopted hereafter to
simplify the description of the cement phase: C = CaO, S = SiO2,
A = Al2O3 and F = Fe2O3.
2. Experimental
minimal amount of reagents (10%) was used to adjust the moduli
and minor elements of the clinker sample. The SO3 content of the
clinker was adjusted from 1.2% to 2.4% using calcium sulfate.
Regarding clinker mineral composition, C3A ranged from 10% to
14% with complementary decreasing C2S content from 15% to
11%. The total alkali content was fixed (0.59%–0.63% Na2O eq) in
the clinker samples to avoid their influence on the cement
properties.
The prepared fine raw meals were homogenized in a rocking
mixer for 30 min. Subsequently, water (18%) was added and the
resulting mixture was pressed into a cube (2  2  2 cm) for sin-
tering. The cube of starting materials was calcined at 1000 °C for
60 min and then burned at 1450 °C for 90 min in an electric fur-
nace, before being quenched in air. JIS R 5204: 2019 ‘‘Chemical
analysis method of cement by X-ray fluorescence” and Japan
Cement Association Standard (JCAS) I-01: 1997 ‘‘Determination
method for free calcium oxide” were followed to determine the
chemical composition and amount of free lime (f.CaO) in the clin-
ker. Tables 1 and 2 summarize the chemical composition and
Bogue’s mineral composition of the clinker samples.

2.1. Production of clinker samples 2.2. Cement production

Each clinker sample was prepared such that the level of moduli
and Bogue’s mineral composition were the same as those of ordi-
nary Portland cement clinker based on JIS R 5210: 2015 ‘‘Portland
cement.” Raw materials from an operating cement plant and com-
mercially available reagents (e.g., calcium carbonate, silicon oxide,
aluminum oxide, iron oxide, calcium sulfate, and alkali carbonate)
were used as starting materials to adjust the clinker moduli along
with the sulfur oxide and alkali oxide contents of the clinker. A
Cement samples were produced in the laboratory using the
clinker samples and gypsum dihydrate. The obtained clinker was
crushed using a jaw crusher, passed through a 3.5-mm sieve, and
then roughly ground with a ball mill under constant conditions.
Gypsum was added to adjust the SO3 content of the cement sam-
ples. Fig. 1 shows the experimental design matrix for the SO3 and
C3A contents in the clinker samples and added gypsum. Each mix-
ture was ground with a ball mill (diameter of 50 cm, length of

Table 1
Chemical compositions of laboratory clinker samples (%).

C3A%-SO3% ig.loss SiO2 Al2O3 Fe2O3 CaO MgO SO3

10–1.2 0.23 21.45 5.85 3.12 65.99 1.20 1.12
10–1.8 0.21 21.25 5.91 3.06 65.40 1.20 1.86
10–2.4 0.27 21.13 5.35 3.03 64.99 1.19 2.39
12–1.2 0.27 20.78 6.48 3.00 65.93 1.19 1.27
12–1.8 0.26 20.64 6.54 3.03 65.49 1.20 1.83
12–2.4 0.31 20.59 6.38 2.95 65.11 1.17 2.46
14–1.2 0.30 20.16 7.19 3.01 65.81 1.19 1.28
14–1.8 0.29 20.02 7.14 2.98 65.38 1.18 1.91
14–2.4 0.31 19.88 7.19 3.02 64.94 1.19 2.49
Na2O K2O TiO2 MnO P2O5 SrO total Na2Oeq f.CaO
0.29 0.45 0.27 0.11 0.11 0.05 100.25 0.59 0.63
0.30 0.47 0.27 0.10 0.11 0.05 100.19 0.61 0.58
0.30 0.49 0.27 0.10 0.11 0.05 100.19 0.62 0.64
0.29 0.46 0.27 0.10 0.11 0.05 100.21 0.59 0.59
0.31 0.49 0.27 0.11 0.10 0.05 100.32 0.63 0.57
0.31 0.49 0.27 0.11 0.10 0.05 100.32 0.63 0.65
0.30 0.47 0.27 0.11 0.10 0.05 100.24 0.60 0.59
0.31 0.50 0.28 0.11 0.10 0.05 100.26 0.63 0.72
0.30 0.49 0.27 0.11 0.10 0.05 100.34 0.62 0.72

Table 2
Moduli and mineral compositions of laboratory clinker samples (%).

C3A%-SO3% HM (–) SM (–) IM (–) AI (–) C3S C2S C3A C4AF

10–1.2 2.17 2.39 1.87 3.67 58.6 14.9 10.2 9.5
10–1.8 2.16 2.37 1.93 3.60 55.3 15.2 10.5 9.3
10–2.4 2.17 2.38 1.93 3.61 53.5 15.1 10.4 9.2
12–1.2 2.18 2.19 2.16 3.21 59.0 12.4 12.1 9.1
12–1.8 2.17 2.16 2.16 3.16 56.2 12.8 12.2 9.2
12–2.4 2.18 2.21 2.16 3.23 54.4 12.7 11.9 9.0
14–1.2 2.17 1.98 2.39 2.80 58.4 11.0 14.0 9.2
14–1.8 2.17 1.98 2.39 2.81 56.3 10.8 13.9 9.1
14–2.4 2.16 1.95 2.38 2.76 53.5 11.3 14.0 9.2
 M. Yamashita et al. / Construction and Building Materials 250 (2020) 118844
15
C3A
14 14
13
Clinker C3A (%)
12 12
11
10
10
1.2
9 SO3
8 0.0
0.5 1.0 1.5
Clinker SO3 (%)
Fig. 1. Ranges of SO3 and C3A contents of clinker samples and added gypsum.
46 cm, 60 rpm, ball with a weight of 30 kg and diameter of 25 mm)
to a Blaine specific surface area (Blaine fineness) of 3350 ± 50 cm2/
g. Diethylene glycol was used as a grinding agent at a ratio of 0.03%
of the clinker. No gypsum hemihydrate was detected in each fin-
ished cement.
2.3. Mineral analysis of clinker
Clinker samples were crushed, passed through a 5-mm sieve,
and then ground to reach a certain fineness using a crusher and
disk mill. The Blaine fineness of each clinker sample was deter-
mined in accordance with JIS R 5201 ‘‘Physical testing methods
for cement,” and was adjusted between 3500 and 4000 cm2/g
because the fineness of the clinker affects the quantitative mineral
composition determined by X-ray diffraction (XRD) using the Riet-
veld method [17].
Crystalline phases in the clinker samples were analyzed by XRD
using a Bruker D8 ADVANCE diffractometer with Bragg–Brentano
geometry equipped with a Cu target (k = 1.5406 Å) operating at
40 kV and 40 mA. A range of diffraction angle, 2h, between 10°
and 65° was analyzed with a step of 0.01°. After acquisition, XRD
patterns were processed using Bruker DIFFRAC plus EVA software,
which allowed the identification of crystalline phases (PDF-
4 + 2015 database from the International Center for Diffraction
Data). Phase quantification was performed via Rietveld refinement
[18] using the fundamental parameter approach [19] and Bruker
TOPAS version 3 software (QXRD). The Rietveld analysis of mineral
compositions included alite, belite, aluminate (cubic, orthorhom-
bic), ferrite, and lime. Anhydrite (0.5%) was detected in high-SO3
(2.5%) clinker, which is consistent with the findings of a previous
study [7].
2.4. Physical testing of cement
The cement characteristics were evaluated using the following
techniques.
2.4.1. Heat flow
Isothermal conduction calorimetry was performed at 20 °C
using a heat flow monitor (CHC-OM6, Tokyo Riko Co.) in accor-
dance with ASTM C 1702–17 ‘‘Standard Test Method for Measure-
ment of Heat of Hydration of Hydraulic Cementitious Materials
Using Isothermal Conduction Calorimetry” (Method B: external
mixing). The specified masses of cement (20 g) and distilled water
(10 g) were weighed in two separate cylindrical polyethylene vial
of diameter 31.3 mm and height 52.5 mm. A fixed water-to-
3
2.0
1.5
Gypsum SO3 (%)
1.0
0.5
1.8 2.4
SO3 gyp.=1.2% C3A=12%
2.0 2.5 3.0 0.5 1.0 1.5 2.0 2.5 3.0
Clinker SO3 (%)
cement ratio (w/c) of 0.5 was used for all the mixtures to ensure
proper mixing. At the time of mixing, the distilled water was added
to the cement and manually mixed for 30 s with a toothpick. The
vial was sealed and then placed in the calorimeter cell. Data log-
ging was initiated 1 min before placing the vial in the calorimeter.
This method of external mixing has the advantage of taking less
than 1 min and minimal thermal effects because of accurate mix-
ing and handling. Using this approach, it appears that external
mixing corrections, as outlined in ASTM C 1702, can be avoided
for both difficulty to mixing and lost heat of hydration data at early
stages. The variation of the measurement was represented by the
coefficient of variation (CV = standard deviation/mean), which is
2% on main peak height and 1% on cumulative heat of hydration,
respectively. The hydration heat flow was monitored for 168 h
(7 d) and then integrated to determine the heat of hydration.
2.4.2. Setting time and compressive strength
The cement setting time and compressive strength were evalu-
ated according to JIS R 5201: 1997 ‘‘Physical testing method for
cement.” This test covers the determination of the compressive
strength of hydraulic cement mortars using prismatic specimens
(40  40  160 mm).
2.4.3. Drying shrinkage
Drying shrinkage of cement samples was determined by AS
2350 Method 13 ‘‘Determination of drying shrinkage of cement
mortars” using samples stored under drying conditions of
60 ± 5% RH and 20 °C. Mortar prismatic specimens of
40  40  160 mm were cast for each cement sample for shrinkage
testing. Length and mass changes were determined according to JIS
A 1129-3: 2010 ‘‘Methods of measurement for length change of
mortar and concrete Part 3: Method with dial gauge.” The prisms
were demolded and then immediately placed in a dry room at con-
stant temperature and RH to measure drying shrinkage.
3. Results and discussion
3.1. Mineral composition
Conventional clinker minerals (e.g., alite, belite, aluminate, and
ferrite) were identified in all clinker samples by XRD. A small
amount of anhydrite (CaSO4; 0.5%) was identified in the XRD pro-
file of the high-SO3 (2.5%) clinker sample. The presence of anhy-
drite in the high-SO3 clinker is attributed to a thermodynamic
effect [7]. Fig. 2 shows the main mineral compositions of the clin-
ker samples with different SO3 and C3A contents determined by
4 M. Yamashita et al. / Construction and Building Materials 250 (2020) 118844
Fig. 2. Mineral composition of clinker samples determined by Rietveld calculation. (a) Alite, (b) belite, (c) aluminate, and (d) ferrite.
XRD and the Rietveld method. As the SO3 content of the clinker
samples increased, belite content increased and alite and alumi-
nate contents decreased compared with those of the base clinker,
which has been reported in several studies on clinker produced
in an electric furnace [20] and cement kiln [8]. The effect of SO3
in clinker on the mineral composition was not influenced by the
C3A amount of the clinker. The calculated slopes of regression lines
were in good agreement with those reported in previous studies
[7,8].
3.2. Isothermal calorimetry
3.2.1. Initial hydration rate
In general, the hydration heat flow of Portland cement is char-
acterized by a few main maxima: (1) an initial peak occurring in
the first hour of hydration, (2) a second maximum between 6
and 12 h, and (3) a third maximum as a shoulder or more definite
peak about 12–24 h after the second maximum [21]. Regarding the
effects of SO3 and C3A on cement hydration, many studies have
focused on pure phases, especially alite and C3A and usually with
gypsum addition, to accumulate basic knowledge of the main
hydration reactions. However, few studies have investigated the
direct influence of clinker SO3 content on Portland cement
hydration.
The hydration heat flow of the cement with a constant gypsum
SO3 content of 1.2% is presented in Fig. 3. The initial peak during
the first 2 h (P1) is ascribed to the effects of the heat of wetting
of the cement, corresponding to a combination of the heat of disso-
lution of silicate, interstitial, and other minor phases and calcium
hydroxide formation from f.CaO. With increasing amount of C3A
in the clinker, the intensity of the heat flow peak during the first
2 h tended to increase. All the cements prepared from clinker sam-
ples with high SO3 contents, which also contained some alkali sul-
fate, showed a slightly higher heat flow during the first 2 h than
was the case for cements produced from low-SO3 clinker samples.
In this period, the intensity of this peak was mainly influenced by
the amount of C3A regardless of the sulfate dissolution in the clin-
ker. No effect of clinker SO3 content on C3A dissolution rate was
observed at this stage. The clinker with high SO3 content suggested
higher dissolution of alite in the first 2 h than that of the reference
clinker.
3.2.2. Influence of clinker SO3 and C3A contents on the alite reaction
The main heat evolution peak (P2: hereafter called the ‘‘silicate
reaction peak”) in the time range from approximately 5 to 10 h was
mainly attributed to the heat released from the silicate reaction,
which involves the dissolution of the alite phase and precipitation
of portlandite and C-S-H phases [22,23]. It is well known that the
heat evolution profiles of model systems composed of alite, C3A,
and gypsum are strongly influenced by the gypsum content
[24,25]. In the case of properly sulfated cement, the reaction rate
of alite is strongly accelerated during the nucleation and growth
period compared with the case of an undersulfated cement. The
increased alite reaction rate at the early stage in the presence of
more calcium sulfate is consistent with the observation of the
accelerating effect of sulfate on the reactions of C3S, alite, and
belite reported in the literature [26–28].
 M. Yamashita et al. / Construction and Building Materials 250 (2020) 118844 5

amounts of SO3 and C3A in the clinker. Here, the influence of

the SO3 content of clinkers with different C3A contents on the
exothermic peaks attributable to the aluminate reaction was
investigated.
Two shoulder peaks were found after the alite peak, as P3
and P4, here after called ‘‘sulfate depletion peak.” These sulfate
depletion peaks originate from the heat released from the disso-
lution of C3A and precipitation of ettringite and monosulfate,
even though the silicate contributes markedly to the heat flow.
These shoulder peaks were especially clear for the high-SO3
clinker samples. Scrivener and Pratt [32] suggested that the heat
flow peak at 8–10 h (P3) could be attributed to ettringite forma-
tion occurring after the depletion of gypsum. The subsequent
shoulder broad peak at 20 h (P4) was ascribed to the formation
of the monosulfate phase from C3A and ettringite. This broad
peak shifted to the right with increasing SO3 content of the clin-
ker regardless of the amount of C3A in the cement. These results
show that SO3 in the clinker induced this sulfate depletion peak
as well as gypsum.
Clinker samples with both high SO3 and high C3A contents
displayed a fifth heat flow peak at 30 h (P5), which was attrib-
uted to the aluminate reaction [24]. Previous studies on systems
of alite, aluminate, and gypsum could not fully explain this peak,
but it is related to the formation of the monosulfate phase after
the space is filled [24].

3.2.4. Influence of SO3 origin on cement hydration heat

The hydration heat flow curves of the cement samples with
different clinker SO3 and gypsum to give a constant C3A of
12% are presented in Fig. 4. It is well known that the heat

15
60 (a) SO3 gyp.=0.3
Fig. 3. Rate of heat liberation of cement samples with the same gypsum SO3
Heat flow (J/g h)

content (1.2%).
SO3 cli.
10 1.2%
40
1.8%
In this study, the height of the silicate reaction peak (P2) was 2.4%
almost unaffected by the clinker SO3 content even though the 20 5
amount of alite determined by QXRD in high-SO3 clinker was lower
than that of the base clinker (a maximum of about 7%). From the
heat flow profile in the time period of 3–10 h, the silicate reaction 0 0
peak shifted slightly to the left with increasing clinker SO3 content, 0.0 0.5 1.0 0 12 24 36 48 60
Time (h)
indicating accelerated alite hydration, like the case for gypsum.
These profiles indicated that dissolved SO3 in the clinker might 15
60
accelerate the hydration of alite in a similar manner to gypsum (b) SO3 gyp.=0.8
Heat flow (J/g h)

and/or induced formation of the M1 polymorph phase in the clin-

10
ker [29,30], which is an early strength type of alite. 40
Some studies revealed that the hydration reaction of alite slows
down when hydration occurs in aluminum-rich solutions [25]. In 5
20
this study, both the position and height of the silicate reaction peak
were not affected by the amount of C3A present in the clinker sam-
ple. This result shows that the alite reaction is not strongly influ- 0 0
enced by the variation of the alite/C3A ratio in properly sulfated 0.0 0.5 1.0 0 12 24 36 48 60
Time (h)
cement [24].
15
60 (c) SO3 gyp.=1.2
3.2.3. Influence of clinker SO3 and C3A contents on sulfate depletion
Heat flow (J/g h)

Portland cement mixed with water initially displays strong 10

exothermic behavior caused by the rapid dissolution and initial 40
hydration of mainly the aluminate phase. If sufficient sulfate is
available in the solution, the hydration rate rapidly decreases as 20 5
aluminate reacts with calcium and sulfate to form ettringite and/
or monosulfate. Isothermal calorimetry of cement is often complex
with several heat flow maxima depending on the dissolution kinet- 0 0
0.0 0.5 1.0 0 12 24 36 48 60
ics of sulfate and/or the amounts of aluminate and sulfate [31]. As Time (h)
expected, the cement investigated in this study also showed this
complex behavior, which was probably partly caused by the high Fig. 4. Rate of heat liberation of cement samples with the same C3A content (12%).
6 M. Yamashita et al. / Construction and Building Materials 250 (2020) 118844
evolution profile of alite is strongly influenced by gypsum content
[33,34]. In general, depending on the gypsum content, the system
behaves in an undersulfated or properly sulfated manner. Cement
with a gypsum content to give 0.3% SO3 is undersulfated because
the silicate reaction peak is weaker than that of properly sulfated
systems. The delay and broadening with decreasing clinker SO3
content is probably related to the presence of aluminum in solu-
tion because of the early aluminate reaction [34,35]. However,
the alite peak intensity enhanced considerably with increasing
clinker SO3 content. This shows that even though the gypsum con-
tent was low, clinker SO3 plays the same role as gypsum SO3 to
obtain a properly sulfated system. That is, the influence of the ori-
gin (clinker or gypsum) of SO3 in cement on its heat evolution pro-
file was small. The alite reaction remained almost unchanged when
the SO3 in cement was constant.
3.2.5. Cumulative heat of hydration
Fig. 5 (a) and (b) show the cumulative heat of hydration of
cement samples with constant amount of gypsum content and
constant C3A content, respectively, after 7 d. The heat of hydration
at 7 d increased with C3A constant and decreased with increasing
clinker SO3 content. C3A in cement continually hydrated after early
rapid hydration. At the early stage, SO3 in the clinker enhanced the
alite reaction but then this reaction slowed down over 7 d. The dif-
ference of SO3 source (clinker or gypsum) did not have an obvious
effect on the cumulative hydration heat of the cement samples.
A multiple linear regression was calculated to evaluate hydra-
tion heat based on C3A and SO3 in the clinker. The regression equa-
tion (Eq. (1) below) was statistically significant, with an R2 value of
0.9969. Predicted hydration heat increased by 13 J/g for each per-
cent of C3A and decreased by 10 J/g for each percent of SO3 in the
clinker sample.
½Hydration heat at 7 days ðJ=gÞ ¼ þ13C3 A  11SO3 þ 237
In Eq. (1), C3A is the C3A content of the clinker and SO3 is SO3
content of the clinker.
Fig. 5. Cumulative heat of hydration of cement samples.
Table 3
Hydration rate and heat of hardening of clinker phases used this study.
- Alite Belite
Hydration rate (%)*1 70 20
Heat of hardening(J/g)*2 502 260
*1: After 7 d, Asaka [37], *2: Kurdowski [36].
The relationship between the hydration heat with different C3A
and SO3 contents of the clinker samples and the mineral composi-
tion was investigated. Heat of hydration was then calculated from
reported heat [36] data and hydration rate [37] for comparison
with the measured heat. The values for heat of hardening and
hydration rate at 7 d used in the calculation are listed in Table 3.
Fig. 6 shows the relationship between the calculated heat of hydra-
tion and measured values. There was a linear relationship between
calculated and measured values, although was a difference of 50–
70 J/g at the same amount of added gypsum. This result shows that
the variation of hydration heat with clinker SO3 and C3A content
mainly depended on the actual mineral composition. Conversely,
some studies showed that the hydraulic activity of prepared C2S
doped with SO3 was higher than that of the reference non-
activated b-C2S [38–40]. Further investigation of the reaction ratio
and enthalpy of individual clinker minerals are needed to clarify
the hydration heat behavior of cements produced with high-SO3
clinker.
3.3. Setting time and compressive strength
Fig. 7 illustrates the setting time of cements produced using
clinker samples containing different amounts of SO3 and C3A and
gypsum with 1.2% and 0.8% SO3. The cement setting time was
accelerated by about 10 and 2 min when the amount of SO3 and
C3A in the clinker, respectively, was increased by 1%. The slight
acceleration of setting time by a higher SO3 content in the clinker
can be accounted for by the heat flow profile at the initial stage of
hydration, which showed accelerating alite hydration. Meanwhile,
the accelerating effect of C3A in clinker and retarding effect of gyp-
sum in cement are well known [41]. These slight differences in set-
ting time are not problematic in practice.
Fig. 8 and Fig. 9 present the relationship between the clinker
ð1Þ
SO3 content and compressive strength of cement samples with
different C3A and gypsum contents. The compressive strength after
3 d increased with clinker SO3 content when the gypsum content
Aluminate Ferrite Lime Gypsum
80 40 100 100
1093 420 1168 142
 M. Yamashita et al. / Construction and Building Materials 250 (2020) 118844 7

420 420
(a) SO3 gyp.=1.2% (b) C3A=12%
400 400

Measured heat (J/g)

Measured heat (J/g)

y = 1.0297x + 24.06
380 380

360 360

SO3 cli.=1.2% SO3 gyp.=0.3%

340 340 SO3 gyp.=0.8%
SO3 cli.=1.8%
7d SO3 cli.=2.4% 7d SO3 gyp.=1.2%
320 320
300 320 340 360 380 300 320 340 360 380
Calculated heat (J/g) Calculated heat (J/g)
Fig. 6. Relationship between calculated and actual hydration heat for cements with different contents of (a) clinker SO3 and (b) gypsum SO3.

Fig. 7. Setting time of cements.

38 52 65
Compressive strength (N/mm 2)
Compressive strength (N/mm 2)

Compressive strength (N/mm 2)

(a) 3d SO3 gyp.=1.2% (b) 7d SO3 gyp.=1.2% (c) 28d SO3 gyp.=1.2%
36 50 63

34 48 61

32 46 59

C3A=10% C3A=10% C3A=10%

30 44 57
C3A=12% C3A=12% C3A=12%
C3A=14% C3A=14% C3A=14%
28 42 55
0.5 1.0 1.5 2.0 2.5 3.0 0.5 1.0 1.5 2.0 2.5 3.0 0.5 1.0 1.5 2.0 2.5 3.0
Clinker-SO3 (%) Clinker-SO3 (%) Clinker-SO3 (%)

Fig. 8. Compressive strength of cement samples with constant gypsum SO3 content of 1.2% after (a) 3, (b) 7, and (c) 28 days.

was kept constant (1.2% of SO3) and it decreased after 28 d. These after 28 d of cement produced using high-SO3 clinker can be main-
results coincide with those of previous studies [16,20]. The tained by adjusting the C3A content in the clinker and/or amount of
decrease in strength at 28 d increased with the C3A content of gypsum content.
the clinker. The influence of SO3 in the added gypsum on the com- The initial increase of compressive strength of cement samples
pressive strength of the cement samples was similar to that of SO3 produced using high-SO3 clinker did not appear to be influenced by
in the clinker. These results reveal that the compressive strength the variation of the mineral composition of the clinker measured
8 M. Yamashita et al. / Construction and Building Materials 250 (2020) 118844

38 52 65
(c) 28d
Compressive strength (N/mm 2)

Compressive strength (N/mm 2)

Compressive strength (N/mm 2)

(a) 3d C3A=12% (b) 7d C3A=12% C3A=12%
36 50 63

34 48 61

32 46 59

SO3 gyp.=0.3% SO3 gyp.=0.3% SO3 gyp.=0.3%

30 44 57
SO3 gyp.=0.8% SO3 gyp.=0.8% SO3 gyp.=0.8%
SO3 gyp.=1.2% SO3 gyp.=1.2% SO3 gyp.=1.2%
28 42 55
1.0 1.5 2.0 2.5 3.0 1.0 1.5 2.0 2.5 3.0 1.0 1.5 2.0 2.5 3.0
Clinker-SO3 (%) Clinker-SO3 (%) Clinker-SO3 (%)

Fig. 9. Compressive strength of cement samples with a constant C3A content of 12% after (a) 3, (b) 7, and (c) 28 days.

by QXRD (see Fig. 2); for example, decreasing alite content. How- with 10–14% of C3A and 0.3–1.2% of SO3 in gypsum. When the
ever, SO3 in clinker accelerates silicate hydration, as found in the amount of gypsum in the cement is constant (gypsum
heat flow profiles, because it shows mostly similar behavior to that SO3 = 1.2%), drying shrinkage decreased with increasing SO3 con-
of SO3 in gypsum. This result suggests that SO3 in clinker corre- tent of the clinker. The influence of gypsum and C3A in the clinker
sponds to not only alkali sulfate and anhydrite, but also part of on drying shrinkage displayed a similar trend to that in previous
the SO3 in silicate might dissolve and affect silicate hydration, as studies [42]. A multiple linear regression was calculated to com-
is the case for SO3 in gypsum. Therefore, adjusting the C3A content pare the amount of drying shrinkage strain at 28 days based on
of the clinker and/or amount of gypsum content to the cement can the clinker SO3, gypsum SO3, and C3A. The calculated regression
suppress the variation of compressive strength of samples pro- equation (Eq. (2)) was statistically significant, with an R2 value of
duced using high-SO3 clinker. 0.921169. Predicted relative drying shrinkage decreased by 0.138
for each percent of SO3 in the clinker and 0.195 for each percent
of SO3 in gypsum and increased 0.061 for each percent of C3A in
3.4. Drying shrinkage
the cement sample. The influence of SO3 in the clinker on the
decrease of drying shrinkage was about 55% of that of SO3 in
The drying shrinkage of mortar and concrete may increase with
gypsum.
the aluminate content of the cement, whereas it may decrease at
higher gypsum content [42]. The addition of anhydrite to mortar ½Relative drying shrinkage at 28 d
and concrete also lowers shrinkage compared with the case with-
¼ 0:1383SO3 cli  0:2551SO3 gyp þ 0:0606C3 A þ 0:8667 ð2Þ
out anhydrite [43]. However, there are few studies directly inves-
tigating the effects of SO3 in clinker on drying shrinkage and where SO3cli is SO3 in the clinker (%), SO3gyp is SO3 in gypsum (%),
comparing the effects of SO3 in gypsum and C3A in cement on dry- and C3A is C3A in the cement sample (%).
ing shrinkage. Fig. 11 shows the relationship between the relative weight loss
The relative drying shrinkage and weight loss of cement sample and relative drying shrinkage of the reference cement, which con-
to that of the reference cement produced using clinker with 1.2% tained clinker with 1.2% SO3 and 10% C3A and gypsum with 1.2%
SO3, and 10% C3A and gypsum with 1.2% of SO3 were determined. SO3. Under the drying conditions used, drying shrinkage of mortar
Fig. 10 presents the relationship between clinker SO3 content and increased with the loss of water, which corresponded to weight
relative drying shrinkage strains at 28 d of cement mortar samples loss. With increasing C3A content of the clinker, drying shrinkage

1.4 1.4
28d 28d
Relative drying shrinkage (-)

Relative drying shrinkage (-)

C3A
1.3 1.3
14% Gyp-SO3
1.2 1.2
0.3%
1.1 12% 1.1
0.8%
1.0 10% 1.0

0.9 0.9 1.2%

SO3 gyp = 1.2% C3A = 12%
0.8 0.8
1.0 1.5 2.0 2.5 3.0 1.0 1.5 2.0 2.5 3.0
Clinker-SO3 (%) Clinker-SO3 (%)

Fig. 10. Relative drying shrinkage strain of cement mortar bars.

 M. Yamashita et al. / Construction and Building Materials 250 (2020) 118844 9

1.4 1.4
C3A=10% SO3 gyp = 1.2% SO3 gyp.=0.3%

Relative drying shrinkage (-)

Relative drying shrinkage (-)

1.3 C3A=12% 1.3 SO3 gyp.=0.8%
C3A=14% SO3 gyp.=1.2%
1.2 1.2

1.1 1.1

1.0 1.0

0.9 0.9
28d 28d C3A = 12%
0.8 0.8
0.7 0.8 0.9 1.0 1.1 1.2 0.7 0.8 0.9 1.0 1.1 1.2
Relative weight loss (-) Relative weight loss (-)
Fig. 11. Relationship between relative weight loss and relative drying shrinkage of cement samples.

increased even though the weight loss slightly decreased at the
same clinker SO3 and gypsum contents, as shown in Fig. 11(a). This
result shows the increase in drying shrinkage with C3A content was
caused by chemical shrinkage associated with C3A hydration. The
measured shrinkage of mortar under the drying conditions deter-
mined by AS 2350 Method 13 includes a combination of drying
and autogenous and/or chemical shrinkage [44].
Fig. 11 (b) displays the relationship between the weight loss
and drying shrinkage for cements with different clinker SO3 con-
tents and amounts of added gypsum at constant C3A content. The
amount of drying shrinkage increased linearly with the weight loss
of the mortar bar. The influence of SO3 on this relationship was
similar for SO3 originating from the clinker and added gypsum.
The drying shrinkage decrease attributed to SO3 in the cement
was probably caused by ettringite or monosulfate formation,
which facilitated not only decreased water loss but also consumed
the C3A in the mortar during the early stage of hydration. The dif-
ferent effects of SO3 in clinker and gypsum on the drying shrinkage
might be explained by the dissolution of SO3 over time and the for-
mation of expansive ettringite. Such shrinkage is strongly associ-
ated with the surface tension effect generated from the water
loss of mortar from a critical pore size; for example in the size
range of 3–30 mm [45]. One reason that the cement with high
SO3 clinker has large drying shrinkage is because it may contain
pores of the critical size in the early stage of hydration as a result
of the short setting time and high early-age mechanical properties.
It has been reported that alkali sulfates increase drying shrinkage
[46] because the alkali ions in alkali sulfates tend to accelerate
the hydration rate of aluminate [47,48]. Therefore a slight increase
of the alkali sulfate content in clinker with a high SO3 content [12]
might have an adverse effect on drying shrinkage.
4. Conclusion
Portland cement clinker samples with increased amounts of SO3
(1.1%  2.5%) and different C3A contents (10%  14%) were pro-
duced in an electric furnace and then the influence of clinker SO3
content on cement heat flow and physical properties was investi-
gated. The mineral composition of the high-SO3 clinker was similar
to that found in previous studies. As the clinker SO3 content
increased, the alite reaction was accelerated and three exothermic
peaks attributed to the aluminate hydrate reaction were retarded
and became apparent in the heat flow profile. The variation of
hydration heat with clinker SO3 and C3A contents mainly depended
on the actual mineral composition. The compressive strength of
cement produced using clinker with a high SO3 content increased
at 3 days and then decreased over time regardless of C3A content.
The drying shrinkage strain of mortar decreased with increasing
clinker SO3 content as well as the amount of gypsum content at
each C3A content. The decrease in drying shrinkage caused by the
increase of clinker SO3 content was half of that induced by SO3 in
the added gypsum. Our results illustrate that the physical proper-
ties, include drying shrinkage, of cement produced using high-SO3
clinker can be maintained by adjusting the amount of gypsum
added.
CRediT authorship contribution statement
Makio Yamashita: Conceptualization, Methodology, Formal
analysis. Takumi Harada: Investigation, Resources. Etsuo Sakai:
Supervision. Koichi Tsuchiya: Writing - review & editing.
Declaration of Competing Interest
The authors declare that they have no known competing finan-
cial interests or personal relationships that could have appeared
to influence the work reported in this paper.
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