Construction and Building Materials 248 (2020) 118705

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Construction and Building Materials

journal homepage: www.elsevier.com/locate/conbuildmat

Development of a clinker-free white binder of one-part CaO-activated

GGBFS with TiO2 addition
Sungwon Sim, Dongho Jeon, Woo Sung Yum, Haemin Song, Do Hoon Kim, Jae Eun Oh ⇑
School of Urban and Environmental Engineering, Ulsan National Institute of Science and Technology (UNIST), UNIST-gil 50, Ulju-gun, Ulsan 44919, Republic of Korea

h i g h l i g h t s

A new clinker-free white GGBFS binder was proposed for substituting white cement.

All NaOH-activated GGBFS samples were not ‘‘white” nor ‘‘near white”.

All CaO-activated GGBFS samples were nearly white.

The CaO-activated sample with 16 wt% rutile was whiter than Portland white cement.

Rutile was more effective than anatase in improving whiteness in CaO activation.

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

Article history: In this study, a new clinker-free white binder that exhibits whiteness comparable to that of white
Received 21 October 2019 Portland cement was proposed by investigating the effects of an activator (i.e., CaO vs. NaOH) and added
Received in revised form 20 February 2020 TiO2 (i.e., anatase vs. rutile, dosage) on the surface colors of activated ground granulated blast furnace
Accepted 9 March 2020
slag (GGBFS). Overall, compared to the type or dosage of TiO2, the type of activator exhibited a more pro-
Available online 16 March 2020
nounced effect on the surface color although TiO2 was considerably beneficial for increasing whiteness.
As determined by ASTM E313, the results revealed that all NaOH-activated samples are neither ‘‘white”
Keywords:
nor ‘‘near white,” even with the highest dosage of the added TiO2, while all CaO-activated samples were
White binder
GGBFS
nearly white even without the added TiO2. In addition, NaOH and CaO produced different tints (i.e., green
TiO2 by NaOH and red by CaO activation, respectively) regardless of the presence of TiO2. In CaO activation,
Clinker-free white binder rutile was more effective than anatase in improving all color indices and whiteness; however, in NaOH
CaO activation activation, the addition of anatase was better for reducing tints of yellowness and greenness. The whitest
sample was obtained, which was whiter than white Portland cement on all days, by the addition of 16%
rutile in CaO activation; however, if strength was considered in addition to whiteness, the same system
with 4 wt% rutile would be the best candidate mixture.
Ó 2020 Elsevier Ltd. All rights reserved.

1. Introduction
White Portland cement (hereafter referred to as white cement)
is a special cement that has high mechanical properties compara-
ble to those of Portland cement (PC) with a high degree of white-
ness. Generally, white cement is used for decorating interior and
exterior components of architectural structures such as precast
curtain walls and ornamental concrete [1,2]. In the manufacturing
of white cement, a high degree of whiteness is obtained via the
reduction in the Fe2O3 content to less than 0.4–0.5 wt% in cement
clinkers [3,4]; thus, raw materials comprising very low quantities
of Fe2O3 (<0.5 wt%) are generally selected for production. In
⇑ Corresponding author.
E-mail address: ohjaeeun@unist.ac.kr (J.E. Oh).
addition, due to the lack of the Fe2O3 content in the raw materials,
a higher sintering temperature (1420–1450 °C) [5] for melting raw
materials is typically required for white cements than that for
melting PC (~1250 °C) [1]. Thus, market prices of white cements
are three to five times those of PC, and the energy consumption
and CO2 emission during the production are greater than those of
PC. Therefore, for environmental friendliness and cost savings,
white cement should be replaced with a new type of alternative
white binders with lower production costs, lower energy con-
sumptions, and lower CO2 emissions.
Over the past decades, extensive efforts have been made world-
wide to replace PC by the development of clinker-free (cementless)
structural binders for construction (e.g., geopolymer and alkali-
activated GGBFS) by using industrial by-products such as fly ash
or GGBFS [6,7]. The development of promising cementless binders

https://doi.org/10.1016/j.conbuildmat.2020.118705
0950-0618/Ó 2020 Elsevier Ltd. All rights reserved.
2 S. Sim et al. / Construction and Building Materials 248 (2020) 118705

would improve the recycling rate of industrial by-products and 2. Experimental program
reduce the current CO2 emissions from PC production. However,
very few studies have investigated potential cementless binders 2.1. Materials
that can substitute white cements (in fact, it was not possible to
find any previous work in this regard). White cement (Union White Cement Industrial Co., Korea) and
GGBFS is a ground powder of granulated blast furnace slag commercial GGBFS (Hannam Cement Co., Korea) were purchased.
(GBFS), which is an industrial by-product of iron manufacturing, Table 1 summarizes the chemical oxide compositions of GGBFS
and relatively has a high degree of whiteness compared to PC. By and white cement determined by X-ray florescence (XRF).
utilizing alkali activators (i.e., NaOH and water glass), GGBFS has All the chemicals used in this study (CaO, NaOH, CaCl2, and TiO2
been used as the precursor material for producing strong binders (anatase and rutile)) were analytical grade and purchased from
in many earlier studies [8,9]; however, practical problems for using Daejung Chemicals, Korea.
these activators is its high corrosive and hygroscopic properties [7] Fig. 1 shows the particle size distributions of white cement, raw
and it requires a great caution for its handling [10,11]. Compared to GGBFS, and TiO2 (anatase and rutile), which were examined by a
most PCs, GGBFS has a significantly lighter color and has been used laser diffraction particle size analyzer (HELOS (HI 199) and RODOS,
to replace white cement up to 30 percent when there is no visible Sympatec, Clausthal-Zellerfeld, Germany); the distributions of
color alteration [12]; thus, GGBFS was selected as a main precursor white cement and raw GGBFS were similar to those reported pre-
to develop a cementless white binder in this study. However, most viously [5]. The median sizes of white cement, raw GGBFS, anatase,
of the cementless GGBFS binders harden by alkali activation (e.g., and rutile were 7.37, 8.92, 0.70, and 0.91 mm, respectively. Notably,
activation with NaOH and/or Na silicate) and produce an unpleas- the TiO2 particles herein may be agglomerated to some extent;
ant hue and tint (mostly blue or green staining) on the surface after thus, the measured particle sizes are likely greater than those mea-
hardening [13–15]. Thus, it is imperative to find a way to solve the sured in an ideally well dispersed state. However, because each
blue or green coloration of the GGBFS to produce white cementless TiO2 was dry-mixed with other powder materials during sample
binders such as using other types of activators or adding some preparation prior to the addition of water (i.e., no dispersion pro-
chemical additives. cess during sample preparation), these aggregate sizes were likely
Recently, the use of calcium (Ca)-based activators (such as Ca to be the actual sizes required for the analysis of the study results.
(OH)2 and CaO) has been investigated as effective activators for Fig. 2 shows the XRD patterns of raw materials, which were
producing cementless GGBFS binders mainly due to their signifi- obtained using an X-ray diffractometer (D8 Advance; Bruker AXS,
cantly lower material costs and alkalinities than those of alkaline Germany) with an incident beam of Cu-Ka radiation (k = 1.5418
activators (such as NaOH and Na silicate) [6,10,16]. In the literature Å) at a 2h scanning range of 8°–60°. X’pert High-Score software
[17–19], however, the sole use of Ca-based activators has exhibited [30] was employed to identify the crystalline phases of raw mate-
slower and lower strength developments compared to those of PC. rials and TiO2 along with the Inorganic Crystal Structure Database
Thus, recently several supplementary additives were investigated (ICSD) [31] and the International Center for Diffraction Data (ICDD)
to enhance the strength of GGBFS binders activated with Ca- [32].
based activators [16,20–22]. To obtain an early high strength of The XRD pattern of white cement revealed the presence of
the CaO-activated GGBFS binder, CaCl2 was chosen as a supple- 3CaOSiO2 (C3S), 2CaOSiO2 (C2S), 3CaOAl2O3 (C3A), gypsum
mentary additive in this study. (CaSO42H2O), and calcite (CaCO3). The XRD patterns of raw GGBFS
Titanium oxide (TiO2) is an important white pigment, particu- revealed the presence of an amorphous phase and anhydrite
larly used for paints, coatings, plastics, and inks. Three TiO2 poly- (CaSO4). Notably, some portions of sulfate sources (e.g., gypsum
morphs exist: rutile, anatase, and brookite. As the synthesis of or anhydrite) are added to satisfy basicity index by increasing Ca
pure brookite is relatively more difficult than those of pure rutile content or grinding efficiency of coarse GBFS in the Republic of
and anatase, rutile and anatase are commercially available as Korea [20,33]. Anatase and rutile in this study exhibited XRD pat-
white pigments. In the construction sector, previous studies on terns nearly identical to their reference patterns in ICDD.
the addition of nano-TiO2 have focused only on mechanical prop-
erties [23–25] or highlighted the self-cleaning effect of TiO2 2.2. Methods
[26,27]. It was reported that the self-cleaning effect of TiO2 was
attributed from the photocatalytic and hydrophilic properties of Table 2 summarizes the mixture proportions of paste samples.
the TiO2 [26,27], and strength enhancing effect of it was resulted CaCl2 was used as an additive chemical in the mixtures of
from its pore refining and inert properties [23–25]. In addition to
its self-cleaning and inert filling effect, TiO2 possesses large
refractive index (refractive index: ~2.7 for rutile, ~2.5 for anatase). Table 1
Chemical compositions of white Portland cement and raw GGBFS.
A high light-scattering efficiency, which is essential to achieve
whiteness, is principally determined by a high refractive index White Portland cement GGBFS
(at least >2.0), in addition to an optimized particle size of a pig- Oxide Content (wt%) Oxide Content (wt%)
ment; thus, the use of rutile is preferred as a white pigment com-
CaO 74.83 CaO 45.04
pared to anatase [28,29]. SiO2 15.24 SiO2 33.55
In this study, two types of TiO2 (i.e., anatase vs. rutile) and SO3 4.08 Al2O3 12.86
activations (i.e., CaO vs. NaOH activation) were investigated to Al2O3 3.30 MgO 3.36
MgO 1.49 SO3 2.81
understand their effects on surface colors of hardened pastes pro-
Fe2O3 0.39 TiO2 0.61
duced by CaO activation of GGBFS. In addition, a mixture of a K2O 0.15 Fe2O3 0.51
cementless binder was proposed to produce white binders suit- SrO 0.10 K2O 0.45
able for the tile attachment of architectural buildings; thus, the Na2O 0.08 MnO 0.33
whiteness of the cured paste surface is more important than that TiO2 0.07 Na2O 0.29
La2O3 0.06 SrO 0.07
of the interior herein. To this end, compressive strength tests, X-
P2O5 0.04 BaO 0.05
ray diffraction (XRD), and chromatic evaluation measurements Others 0.17 Others 0.07
were conducted. Sum 100.00 Sum 100.00
 S. Sim et al. / Construction and Building Materials 248 (2020) 118705 3

100 1.2 100 1.2

Cumulative Distribution(%)

Density Distribution (g/cm3)

Cumulative Distribution(%)
Cumulative distribution Cumulative distribution

Density Distribution (g/cm3)

90 White 90 GGBFS
Density distribution Density distribution
Portland 1.0 1.0
80 80
cement
70 0.8 70 0.8
60 60
50 0.6 50 0.6
40 40
30 0.4 0.4
30
20 0.2 20 0.2
10 10
0 0.0 0 0.0
0.1 1 10 100 1000 0.1 1 10 100 1000
Particle size (µm) Particle size (µm)
(a) (b)
100 2.0

Density Distribution (g/cm3)

Cumulative Distribution(%)

90 1.8 TiO2
80 1.6 R: rutile
70 1.4 A: anatase
60 Cumulative distribution_R
1.2
50 Cumulative distribution_A 1.0
40 Density distribution_R 0.8
Density distribution_A
30 0.6
20 0.4
RA
10 0.2
0 0.0
0.1 1 10 100 1000
Particle size (µm)
(c)
Fig. 1. Particle size distributions of raw materials: (a) white Portland cement, (b) raw GGBFS, and (c) TiO2 (anatase and rutile) (;: median size value).

Measured patterns

Raw GGBFS

Measured patterns
White Portland cement
Reference patterns

Anatase used in this study

Anhydrite (CaSO4, 98-002-7474)

Rutile used in this study
Reference patterns
C3S (98-008-1100)
C3A (98-015-1369)

Calcite (CaCO3, 98-008-0869)

Anatase (TiO2, 01-084-1286)
Gypsum (CaSO4∙ 2H2O, 01-074-1433)

C2S (98-002-4640) Rutile (TiO2, 01-086-0148)

10 20 30 40 50 60 10 20 30 40 50 60
Position [°2Theta] (Copper (Cu)) Position [°2Theta] (Copper (Cu))

(a) (b)
Fig. 2. XRD patterns of (a) raw GGBFS and white Portland cement, and (b) TiO2 (anatase and rutile).

CaO-activated GGBFS as the addition of CaCl2 was reported to sig- der for tile attachment, there is no need to consider the corrosion
nificantly enhance strength in the same binder system [16]. The problem.
presence of CaCl2 in the binder likely induces corrosion problems In each row in Table 2, the sum of the wt% of GGBFS and the
if used in steel-reinforced concretes [5]; however, as stated earlier, activator (CaO or NaOH) (=weight of basic cementless binder)
as this study focused only on the development of cementless bin- was set to 100 wt% for all mixtures. Additives (CaCl2 and TiO2)
4 S. Sim et al. / Construction and Building Materials 248 (2020) 118705

Table 2
Mixture proportions of the prepared paste samples (relative wt%) (A: anatase, R: rutile).

Group Label Total Binder Water Water/Total

Binder (w/b)
White Portland Basic Cementless Binder CaCl2 TiO2 Sum
Cement
GGBFS Activator R A
CaO NaOH
W W 100.0 – – – – – – 100.0 35.0 0.35
Ca-A CaCc-0 – 95.0 5.0 – 2.0 – – 102.0 35.7 0.35
CaCc-A4 – 95.0 5.0 – 2.0 – 4.0 106.0 37.1 0.35
CaCc-A16 – 95.0 5.0 – 2.0 – 16.0 118.0 41.3 0.35
Ca-R CaCc-0 (=CaCc-0 in Ca-A) – 95.0 5.0 – 2.0 – – 102.0 35.7 0.35
CaCc-R4 – 95.0 5.0 – 2.0 4.0 – 106.0 37.1 0.35
CaCc-R16 – 95.0 5.0 – 2.0 16.0 – 118.0 41.3 0.35
Na-A Na-0 – 96.4 – 3.6 – – – 100.0 35.0 0.35
Na-A4 – 96.4 – 3.6 – – 4.0 104.0 36.4 0.35
Na-A16 – 96.4 – 3.6 – – 16.0 116.0 40.6 0.35
Na-R Na-0 (=Na0 in Na-A) – 96.4 – 3.6 – – – 100.0 35.0 0.35
Na-R4 – 96.4 – 3.6 – 4.0 – 104.0 36.4 0.35
Na-R16 – 96.4 – 3.6 – 16.0 – 116.0 40.6 0.35

and water were added in wt% relative to the weight of the basic
cementless binder. 0 or 2 wt% of CaCl2 was used, and 0, 4, or
16 wt% of TiO2 was used. Water was added into all mixtures, giving
a water to the total binder weight (w/b) ratio of 0.35. The weight of
NaOH was determined to generate the same moles of (OH) as that
produced by CaO in the mixture proportions. Ca-R, Ca-A, Na-R, and
Na-A were labeled as group names, which were varied according to
the type of activator and type of TiO2, and Group W was white
cement.
First, all binders (white cement and basic cementless binders),
activators (CaO or NaOH), and additives (CaCl2 and TiO2) were
completely dry-mixed for 5 min, followed by mixing with deion-
ized water for an additional 5 min. All of the mixed fresh pastes
were cast in 5 cm  5 cm  5 cm cubic molds for compressive
strength tests and whiteness index measurement. These pastes
were manually compacted to remove trapped air voids and
demolded after 24 h. All paste samples were cured in humidity
chambers at a constant temperature of 23 °C and a relative humid-
ity of 99% without controlling the air composition in the chambers
until each designed test was conducted.
Compressive strength tests were carried out on triplicate sam-
ples of each mixture by curing for 7 and 28 days. After strength
tests, fractured pieces of samples were collected and finely ground
for recording XRD patterns. Then, the powder samples were added
into isopropanol to stop further reaction by using a solvent-
exchange method for 2 weeks [34]. All samples were dried in a vac-
uum desiccator under ~60 cm Hg for 3 days [35].
Powder XRD patterns of the 7- and 28-day cured samples were
recorded to identify reaction products under the same instrumen-
tal conditions, which were used for raw GGBFS and white cement,
and the recorded XRD patterns were analyzed using the same soft-
ware and database.
The color impressions of the raw materials and hardened paste
samples were examined by a spectrophotometer (CR-20, Konica
Minolta, Tokyo, Japan), equipped with the CIE (Commission Inter-
nationale de l’Éclairage) standard illuminant D65 and CIE standard
colorimetric observer angle (i.e., 10°), after curing for 7 and 28 days.
The CIELAB system defined three color coordinates, L*, a*, and b*,
respectively, where L* indicates a degree of lightness (from black
when L* = 0 to white when L* = 100); a* indicates a degree of red-
ness (redder as a* is more positive) or greenness (greener as a* is
more negative); b* indicates a degree of yellowness (yellower as
b* is more positive) or blueness (bluer as b* is more negative). To
minimize the effect of water absorption or contamination of for-
eign matter on the sample whiteness, sample surfaces were
slightly scrubbed clean after drying. As stated earlier, this study
proposed a mixture of binder that produces a white binder suitable
for tile attachment in architectural buildings; thus, the whiteness

80
66.5
70
Compressive strength (MPa)

28 days
60
59.4 54.4
52.2 52.0 7 days
50 45.6 44.3

40 41.3 41.4
41.1
34.4 30.6
30 32.4 25.9
27.5 25.3 24.0
25.2
20 22.8 22.6 23.7
21.9
10

Fig. 3. Compressive strength testing results of the hardened paste samples.

 S. Sim et al. / Construction and Building Materials 248 (2020) 118705 5

of the surface is more important than that of the interior. On the
surface of each hardened sample, the same measurement was con-
ducted 10 times at different locations, and the average value was
determined for each color property (L*, a*, b*, WI, and T).
CIE whiteness index (WI) and tint index (T) values were auto-
matically calculated by the spectrophotometer using the following
formulae according to ASTM E313 [36], WI = Y + 800 (xn  x) + 1
700 (yn  y) and T = 900 (xn  x)  650 (yn  y), where xn and
yn are the chromaticity coordinates of the perfect reflecting dif-
fuser under CIE standard illuminant D65; x and y are the chro-
maticity coordinates; and Y is the luminance factor of samples.
Under the CIE standard illuminant D65 and the 10° observer, ASTM
E313 specifies xn and yn values of 0.3138 and 0.3310, respectively.
As the T value becomes positively higher, the surface shows more
greenness, while the value of T becomes negatively lower, the sur-
face displays more redness. The variables, x, y, and Y were mea-
sured by the spectrophotometer used in this study. Notably,
these equations are only restricted to use for near-white or white
samples, which should satisfy 40 < WI < 5Y  280 and
4 < T < +2 [36]; even when these two conditions are not satisfied
for measured samples, WI and T values still can be calculated, but
the WI and T values appear along with the mark ‘‘!.” The mark ‘‘!”
indicated that the measured values are either not credible to some
degree.

Fig. 4. XRD patterns of hardened samples of groups (a) Ca-A and Ca-R and (b) Na-A and Na-R at 7 and 28 days (}: hydrotalcite-like phase). In this study, there is a possibility
that the peaks identified as C-S-H may belong to C-A-S-H.
6 S. Sim et al. / Construction and Building Materials 248 (2020) 118705
In addition, the CIELAB system (i.e., L*, a*, and b*) was employed
to describe chromatic and lightness impressions of samples that
affect whiteness. To achieve a high degree of whiteness, L* should
have a high value (i.e., closer to 100), and a* and b* should be close
to zero; thus, a ‘‘perfect white” surface exhibits L* = 100, a* = 0, and
b* = 0 [37,38]. Unlike WI and T, there is no particular restriction on
the sample color conditions when the CIELAB system is applied;
thus, whiteness can be evaluated even for samples for which it is
difficult to apply WI and T.
3. Results and discussion
3.1. Compressive strength
Fig. 3 shows the results obtained for the compressive strength
of the hardened paste samples at 7 and 28 days. In the figure,
the error bars represented the standard deviations of the tested
results of the triplicate samples.
In the results, CaCc-0 achieved significantly higher strengths
than Na-0 at all days, which might be due to the strength enhanc-
ing effect of added CaCl2 [16,39,40]; previous studies reported that
the added CaCl2 considerably increased compressive strength of
cementitious binders by (1) acceleration of dissolution of amor-
phous phases of GGBFS and fly ash, (2) reduction in pore sizes
and volume, and (3) increase of C-S-H formation [16,39,40].
The effect of TiO2 addition on strength development depended
on dosage of TiO2. A few studies have reported strength improve-
ments of cement-based materials [25,41,42] and cementless bin-
ders [23,24] due to added TiO2; for instance, added TiO2
accelerated hydration of C3S by providing additional nucleation
sites for forming reaction products, or it induced pore-size refine-
ment during hardening in cementless binders. However, in this
study, 4 wt% of TiO2 did not make any obvious difference in
strength, while the strengths of all samples with 16 wt% TiO2 were
lower than those of the samples without TiO2 regardless of the
type of TiO2 and the type of activation. Considering that the
amount of the basic cementless binder (Table 2), which is the
source of strength, was reduced in proportion to the added wt%
of TiO2, the lower strength observed with the addition of 16 wt%
TiO2 was a clearly predictable result.
3.2. XRD analysis
Fig. 4 shows the XRD patterns of hardened samples in the Ca-A,
Ca-R, Na-A, and Na-R groups. Calcium silicate hydrates (C-S-H) (or
possibly, calcium aluminate silicate hydrate (C-A-S-H) [43,44])
were commonly synthesized in all groups regardless of the type
of activator, but the other phases were different. In CaO activation,
calcium hydroxide (Ca(OH)2), ettringite (Ca6Al2(SO4)3(OH)1226H2-
O), and hydrocalumite ((Ca2Al(OH)6(Cl1x(OH)x)∙3(H2O), x = 0–1,
Table 3
Measured CIELAB coordinates (L*, a*, b*), WI, and T of raw materials.
Raw material Measured values
L* a*
White Portland cement 94.0 (0.1) 0.33 (0.06)
GGBFS 91.7 (0.1) 0.67 (0.06)
CaO 98.4 (0.0) 0.17 (0.06)
NaOH 63.0 (1.1) 1.00 (0.50)
CaCl2 98.7 (0.2) 0.00 (0.00)
TiO2 (anatase) 98.1 (0.3) 0.40 (0.00)
TiO2 (rutile) 99.2 (0.7) 1.30 (0.00)
Note – L*: degree of lightness (L* = 0–100) (black when L* = 0, while white when L* = 100), a*: degree of redness (when positive) or greenness (when negative), b*: degree of
yellowness (when positive) or blueness (when negative), WI: whiteness index, T: tint index; ‘‘!” indicates that the values are out of range from the defined range of standard
ASTM E313. The values in () indicate standard deviations of measured values.
Al2O3-Fe2O3-mono (AFm) [45]) were formed; ettringite and hydro-
calumite were often observed in studies previously reported on the
CaO-activated slag with the addition of gypsum [21,22] and chlo-
ride salt [16,22], respectively. In NaOH activation, the U-phase
(NaCa4Al2(SO4)1.5(OH)129H2O, AFm) and hydrotalcite-like phases
[9,21] were detected. In this study, a new reaction product was
not formed due to the addition of TiO2 in both NaOH and CaO acti-
vation although the peak intensities were oddly affected by the
addition (e.g., the peak intensities of Ca(OH)2 in CaCc-A16) given
the well-known inertness of TiO2 [28].
3.3. CIELAB coordinates, whiteness index, and tint index
Table 3 summarizes the measured values of CIELAB coordinates
(L*, a*, and b*), WI, and T of raw materials.
Although these materials were nearly white to the human eye,
the a*, b*, and T values in Table 3 indicated that (1) raw GGBFS
exhibited a reddish tint, and (2) rutile exhibited a green hue to
some extent; however, (3) the white cement, CaO, CaCl2, and ana-
tase values exhibited inconsistent results between a* and T
because while their a* values suggested greenness (white cement,
CaO, and anatase) or colorless (CaCl2), their T values simultane-
ously indicated redness although greenness and redness cannot
be obtained together according to the CIELAB system and T values.
However, it is worth noting that the absolute T values for white
cement, CaO, CaCl2, and anatase were quite smaller compared with
those of GGBFS and rutile, and thus the extent of the measurement
error might be greater than the T values for white cement, CaO,
CaCl2, and anatase; therefore, white cement, CaO, CaCl2, and ana-
tase are likely nearly colorless rather than being green or red. Fur-
thermore, the direct comparison of the values between a* and T
had a limitation because these used different color spaces; never-
theless, these two systems are widely used for estimating color
impressions [46].
Fig. 5 shows the photographs of the hardened paste samples at
7 days. In these images, it was difficult to visually distinguish the
color difference among samples except that the samples of Na-0
clearly exhibited strong blue-green hues.
Fig. 6 plots the effect of the TiO2 addition on WI and T, and Fig. 7
plots the effect of the TiO2 addition on the CIELAB coordinate val-
ues, which provide additional quantitative information on the
color impressions of hardened samples; the corresponding values
for white cement were also provided in the figures for comparison.
In Fig. 6, all NaOH-activated samples (i.e., groups Na-A and Na-
R) exhibited ‘‘!” ahead of the measured values, while all white
cement and CaO-activated GGBFS samples exhibited WI and T val-
ues without ‘‘!”, which likely exhibit uncertainties to some extent
or are possibly even meaningless [47]. Particularly, the formulae of
WI and T in ASTM E313 were only designed to score whiteness or
yellowness of samples when the samples can be regarded commer-
WI T
b*
3.63 (0.06) 68.3 (0.2) 0.83 (0.06)
5.23 (0.15) 55.5 (0.5) 3.23 (0.06)
2.73 (0.06) 83.9 (0.2) 0.77 (0.06)
0.97 (0.55) !31.8 (4.0) !2.73 (0.85)
1.60 (0.10) 89.8 (0.4) 0.63 (0.06)
2.77 (0.21) 82.9 (1.3) 0.37 (0.12)
2.90 (0.20) 85.0 (1.3) 1.03 (0.12)
 S. Sim et al. / Construction and Building Materials 248 (2020) 118705 7

Fig. 5. Photographs of hardened paste samples at 7 days: (a) addition of anatase in CaO-activated GGBFS, (b) addition of rutile in CaO-activated GGBFS, (c) addition of anatase
in NaOH-activated GGBFS, and (d) addition of rutile in NaOH-activated GGBFS. In each figure, W is given for comparison.

cially ‘‘white” or ‘‘near white” [36,48]; thus, if a sample exhibits WI
and T values with ‘‘!,” the tested sample cannot be called commer-
cially ‘‘white.” Therefore, Fig. 6 confirmed that all NaOH-activated
GGBFS samples are quite far from ‘‘white” or ‘‘near white” even
when their WI values are measured to be relatively high (e.g.,
Na-R16), while all CaO-activated samples are generally observed
to be at least nearly white.
From Fig. 6(a), in the CaO-activated GGBFS system (i.e., samples
in groups Ca-A and Ca-R), with the increase in the wt% of TiO2, WI
also increased regardless of the type of TiO2; however, the whiten-
ing effect of rutile appeared to be greater than that of anatase at a
given wt% of TiO2 at all days; thus, the whitest sample is observed
by the addition of 16 wt% rutile (i.e., CaCc-R16), and this sample is
slightly whiter than white cement at all days.
8 S. Sim et al. / Construction and Building Materials 248 (2020) 118705

TiO2 addition: 0 wt% 4 wt% 16 wt% A: anatase, R: rutile

80
7 days WI of paste of white cement at 7d = 67 28 days
WI of paste of white cement at 28d = 63
70 67.3
63.6
62.2 !61.9 61.7
58.5 !61.6
54.5
60 52.0 55.9 !56.4 !58.8
51.6
51.6
Whiteness (WI)

49.3 49.3
50
!41.7 !42.1
!42.9 !39.6
40 !36.5 !36.5
!33.5 !33.5

30

20

10

0
CaCc-A16

CaCc-R16

Na-A16

Na-R16

CaCc-A16

CaCc-R16

Na-A16

Na-R16
CaCc-A4

CaCc-R4

Na-A4

Na-R4

CaCc-A4

CaCc-R4

Na-A4

Na-R4
CaCc-0

CaCc-0

Na-0

Na-0

CaCc-0

CaCc-0

Na-0

Na-0
Ca-A Ca-R Na-A Na-R Ca-A Ca-R Na-A Na-R
group group group group group group group group
(a)

TiO2 addition: 0 wt% 4 wt% 16 wt% A: anatase, R: rutile

8.0
7 days !6.92 !6.92 28 days
7.0 !5.92

Greener tint
6.0 !5.33

5.0 !4.78 !4.44

4.0 !3.63 !3.44 !3.43 !3.44

!3.03
Tint (T)

3.0 T of paste of white !2.30

2.0 cement at 7d = 0.27

T of paste of white
cement at 28d = 0.20
1.0
0.0
-1.0 Redder tint
-1.17
-2.0 -1.90
-2.07 -2.07 -2.07 -2.37
-3.0 -2.32 -2.83
-2.47 -2.83
-3.52 -2.90
-4.0
CaCc-A16

CaCc-R16

Na-A16

Na-R16

CaCc-A16

CaCc-R16

Na-A16

Na-R16
CaCc-A4

CaCc-R4

Na-A4

Na-R4

CaCc-A4

CaCc-R4

Na-A4

Na-R4
CaCc-0

CaCc-0

Na-0

Na-0

CaCc-0

CaCc-0

Na-0

Na-0

Ca-A Ca-R Na-A Na-R Ca-A Ca-R Na-A Na-R

group group group group group group group group

(b)
Fig. 6. Average measured values of (a) CIE whiteness (WI) and (b) tint (T) indices of each hardened paste sample at 7 and 28 days. Error bars are the standard deviations of the
values measured 10 times for each sample, and ‘‘!” indicates that the values are out of range from the defined range of standard ASTM E313.

From Fig. 6(b), all CaO-activated samples (groups Ca-A and Ca- the change of tint using only experimental data from this study.
B) exhibited relatively reddish tints, while the T values for the However, earlier studies using X-ray absorption near-edge struc-
NaOH-activated samples (groups Na-A and Na-R) roughly implied ture spectroscopy (XANES) in the construction sector
green; although these measured values were not reliable as they [13,14,49,50] have suggested that sulfur (S) in GGBFS is likely
were out of the standard range of T in ASTM E313. responsible for the blue-green coloration of cementitious materials
With the progress of curing, the T values for all groups in Fig. 6 when GGBFS is included in mixtures; the studies suggested that
(b) tended to change for all samples. Groups Ca-A and Ca-B tended the coloration was principally related to the change in oxidation
to become more reddish (except CaCc-R4), while Na-A and Na-R state of sulfur in GGBFS. In addition, in soda-lime-silica (SLS)
lost their greenish tints (in other words, Na-A and Na-R were glasses, it is known that color is generated by the presence of tran-
becoming reddish). Thus, this result possibly demonstrated that sition metal ions and their oxidation states; for instance, the con-
the tint of GGBFS systems activated by CaO and NaOH might centrations of Fe2+, Fe2+, and S2 in glass tend to determine the
become redder as curing days increased. It is difficult to explain color of glass from blue to green to olive, eventually, to amber
 S. Sim et al. / Construction and Building Materials 248 (2020) 118705 9

Na-A group (7d) Ca-A group (7d) Na-A group (28d) Ca-A group (28d)
Na-R group (7d) Ca-R group (7d) Na-R group (28d) Ca-R group (28d)
100 100
Note L* of W (7d) = 90.0 Note: L* of W (28d) = 87.46
L* (7d) L* (28d)

Whiter
Whiter
95 92.2
95 91.1
90.2
88.4
87.5 86.4
90 90
90.9
90.6
88.5 84.8 88.1 85.1
85 87.5 85 86.4 80.6
79.7
L*

80 80 83.6

L*
72.6 74.6
83.3
80.0
79.4 75
75
74.6
70 72.6 70

65 65

60 60
0 4 8 12 16 0 4 8 12 16
TiO2 (wt%) TiO2 (wt%)
(a)
Na-A group (7d) Ca-A group (7d) Na-A group (28d) Ca-A group (28d)
Na-R group (7d) Ca-R group (7d) Na-R group (28d) Ca-R group (28d)
 
a* (7d) Note: a* of W (7d) = -0.61 a* (28d) Note: a* of W (28d) = -0.50

Redder

Redder
0.54 1.01 0.90
 0.26 0.44  0.66

 0.43  0.66 0.53 0.37

0.26
-0.01
a*

 
a*
-1.78
-2.27
-2.18
Greener

 

Greener
-2.49
-2.65
-3.68
  -2.27
-2.38 -2.81

-3.68 -3.37 -3.43

 
0 4 8 12 16 0 4 8 12 16
TiO2 (wt%) TiO2 (wt%)
(b)
Na-A group (7d) Ca-A group (7d) Na-A group (28d) Ca-A group (28d)
Na-R group (7d) Ca-R group (7d) Na-R group (28d) Ca-R group (28d)
6 6
b* (7d) Note: b* of W (7d) = 1.93 b* (28d) Note: b* of W (28d) = 1.64

Yellower
Yellower

5 5 4.20
4.00 3.86 3.96
3.53
4 3.30 4 3.50
4.00 3.88 3.96
3 2.64 3 2.51
3.44 3.21
1.39 2.98
2 1.46
b*

2
b*

2.60 0.76 2.51

2.61
1 1 1.34
1.39
0 0
0.25
-1 -1
Bluer

Bluer

-2 -2
0 4 8 12 16 0 4 8 12 16
TiO2 (wt%) TiO2 (wt%)
(c)
Fig. 7. Measured values for the CIELAB coordinates (L*, a*, and b*) of hardened paste samples at 7 and 28 days: (a) L*, (b) a*, and (c) b*. Note – L*: degree of lightness (L* = 0–
100) (black when L* = 0, while white when L* = 100), a*: degree of redness (when positive) or greenness (when negative), b*: degree of yellowness (when positive) or blueness
(when negative).

[51,52]. Therefore, similarly, the change in the oxidation state of
iron and sulfur in GGBFS is possibly related to the change of tint
with increasing curing time.
From Fig. 7, CaO activation led to significantly different tenden-
cies with respect to the L*, a*, and b* values compared to NaOH
activation as follows: (1) at a given wt% of TiO2, CaO activation
always exhibited higher lightness and a greater degree of yellow-
ness than those observed for NaOH activation; in particular, even
CaO activation without TiO2 led to considerably high values of L*,
similar to that of white cement, at all days (e.g., L* of W = 90.0,
and L* of CaCc-0 = 87.5 at 7 days); (2) regardless of the wt% of
the added TiO2, CaO activation produced a reddish tint, while
NaOH activation generated a greenish tint. Thus, the type of activa-
tor likely exhibits a greater effect on L*, a*, and b* than the type and
wt% of TiO2 in this study.
In Fig. 7(a), regardless of the type of activator and the type of
TiO2, the L* value gradually increased with the increase in the addi-
tion amount of TiO2. However, compared to anatase, rutile was
slightly more effective in increasing L* at a given wt% of TiO2. In
addition, a similar tendency was observed for NaOH activation.
In Fig. 7(b), the overall tendency of the a* values in CaO and
NaOH activations were totally consistent with the T values
although the T values in NaOH activation were not relatively reli-
able. In CaO activation, with the increase in the addition amount
of rutile, a* tended to decrease on the positive axis, while the addi-
tion of anatase rather led to the increase of a* although a few
10 S. Sim et al. / Construction and Building Materials 248 (2020) 118705

80.0 80.0
Groups Ca-A and Ca-R Groups Ca-A and Ca-R

Whiter
Whiter
70.0 70.0

60.0 60.0

50.0 50.0
WI

WI
40.0 40.0

30.0 30.0
Anatase addition : R² = 0.970 Anatase addition : R² = 0.061
20.0 Rutile addition : R² = 0.975 20.0 Rutile addition : R² = 0.444

10.0 10.0
Whiter Greener Redder
0.0 0.0
82.0 84.0 86.0 88.0 90.0 92.0 94.0 -0.5 0.0 0.5 1.0 1.5
L* a*
(a) (b)

80.0
Groups Ca-A and Ca-R
Whiter

70.0

60.0

50.0
WI

40.0
Anatase addition : R² = 0.822
30.0
Rutile addition : R² = 0.813
20.0

10.0
Yellower
0.0
0.0 1.0 2.0 3.0 4.0 5.0
b*
(c)
Fig. 8. Relationships of whiteness (WI) with CIELAB coordinates: (a) L*, (b) a*, and (c) b* in Ca-A and Ca-R groups; all plots included all samples of Ca-A and Ca-R regardless of
days of curing.

exceptions were observed (e.g., at 4 wt% anatase); this trend is
more clearly observed when the a* values at 16 wt% are compared
with those at 0 wt%. However, in NaOH activation, addition of ana-
tase was more effective for removing the greenish tint.
On the other hand, in the case of b* in Fig. 7(c), regardless of the
type of TiO2, all b* values were positive for all samples. In CaO acti-
vation, the b* value tended to decrease with increasing the amount
of TiO2, but rutile led to the slightly more reduction of b* for the
paste samples than anatase. However, in NaOH activation, the b*
values with the addition of anatase were roughly lower than those
with rutile; in addition, for both types of TiO2, when 4 wt% TiO2
was added, the b* value tended to increase, but when the addition
amount was increased to 16 wt%, the b* value tended to decrease
and became smaller than that of 0 wt%.
Thus far, all results indicated that rutile is more effective than
anatase for improving all color indices (WI, T, L*, a*, and b*) to
increase the whiteness in the CaO activation of GGBFS. In this
study, the higher refractive index of rutile was surely one of the
causes for the better improvement than anatase [28]. In addition,
rutile in this study exhibited greenness unlike anatase (Table 3).
Thus, given that, basically, the CaO-activated GGBFS sample with-
out any TiO2 (i.e., CaCc-0) exhibited a reddish tint, the use of rutile
is likely to be effective for reducing the reddish tint. However, in
NaOH activation, the use of anatase was better for reducing chro-
matic properties (i.e., a* and b*) although all NaOH-activated sam-
ples cannot be called white or near white.
Fig. 8 shows the relationships of the whiteness (WI) with the
CIELAB coordinates (L*, a*, and b*) for the Ca-A and Ca-R samples.
As the WI values in NaOH activation exceeded the defined range of
standard ASTM E313, no plots were made for Na-A and Na-R.
Generally, as stated earlier, to obtain a higher grade of white-
ness, L* should be a higher value (near 100), and a* and b* should
be near zero (e.g., a ‘‘perfect white” surface has L* = 100, a* = 0, and
b* = 0) [37,38].
In CaO activation in Fig. 8, WI was closely related to L* and b*
regardless of the type of TiO2 and days of curing. Whiteness was
linearly improved by increasing L* and decreasing b* to zero, but
WI was more accurately related to L* than b*. However, Fig. 8
revealed that a* is considerably less related to WI, and the degree
of relationship between a* and WI noticeably varied depending on
the type of TiO2; with the addition of rutile, WI roughly increased
as a* approached zero; however, with the addition of anatase, it
was difficult to obtain any noticeable relationship between WI
and a* (R2 = 0.061 in Fig. 8(b)). Thus, Fig. 8 supports the earlier con-
clusion that the addition of rutile is approximately better for
removing reddish tints in the CaO-activated GGBFS system.
4. Conclusions
In this study, the effects of the type of added TiO2 (i.e., anatase
vs. rutile) and the type of activation (i.e., CaO vs. NaOH activation)
on the surface colors of hardened pastes produced using GGBFS
were investigated. In addition, a mixture proportion of binder that
produces a white binder suitable for tile attachment in architec-
tural buildings was proposed. The whitest sample was observed
 S. Sim et al. / Construction and Building Materials 248 (2020) 118705
with the addition of 16 wt% rutile for CaO activation (i.e., CaCc-
R16), which was slightly whiter than white cement at all days. In
this study, when only whiteness was considered, the CaO-
activated GGBFS system with 16 wt% rutile (i.e., CaCc-R16) was
suggested to be the best candidate for a new cement-free white
binder; however, if strength was also considered, the same system
with 4 wt% rutile (i.e., CaCc-R4) would be the best. More detailed
conclusions were given as follows:
(1) Regardless of the type of TiO2 for both activations, 4 wt% of
added TiO2 made no significant changes in strength, while
all samples with 16 wt% TiO2 exhibited lower strengths than
those without TiO2.
(2) According to ASTM E313, all NaOH-activated GGBFS samples
were not ‘‘white” nor ‘‘near white,” while all CaO-activated
samples were generally seen to be at least more than nearly
white.
(3) The use of TiO2 was not capable of generating a complete
transition of tint type (e.g., from green to red, or vice versa)
in samples. All CaO-activated samples exhibited slightly red-
dish tints, while all NaOH-activated samples exhibited
greenish tints.
(4) In CaO activation, rutile was more effective than anatase for
improving all color indices, while in NaOH activation, ana-
tase was better than rutile for reducing tints of yellowness
and greenness.
(5) In CaO activation, WI was linearly improved by increasing L*
and decreasing b*; however, WI was more accurately related
to L* than b*.
CRediT authorship contribution statement
Sungwon Sim: Conceptualization, Investigation, Methodology,
Data curation, Writing - original draft. Dongho Jeon: Investigation,
Validation, Writing - review & editing. Woo Sung Yum: Investiga-
tion, Formal analysis, Writing - review & editing. Haemin Song:
Formal analysis, Writing - review & editing. Do Hoon Kim: Data
curation, Writing - review & editing. Jae Eun Oh: Conceptualiza-
tion, Methodology, Writing - review & editing, Funding acquisition.
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.
Acknowledgments
This study was supported by the National Research Foundation
of Korea (NRF) grant (2016R1D1A1B03932908) funded by the
Korea government (MSIT), as well as by a grant (18TBIP-
C144132-01) from the Technology Business Innovation Program
(TBIP) funded by the Ministry of Land, Infrastructure and Transport
of Korea.
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