Arabian Journal of Chemistry (2016) 9, S138S143

King Saud University

Arabian Journal of Chemistry

www.ksu.edu.sa
www.sciencedirect.com

ORIGINAL ARTICLE

Characteristics of Portland blast-furnace slag

cement containing cement kiln dust and active silica
a,*
A. Abdel Rahman , S.A. Abo-El-Enein b, M. Aboul-Fetouh a, Kh. Shehata a

a
Faculty of Science, Al-Azhar University, Cairo, Egypt
b
Faculty of Science, Ain Shams University, Cairo, Egypt

Received 17 May 2010; accepted 27 February 2011

Available online 3 March 2011

KEYWORDS Abstract This investigation dealt with the effect of active silica, silica fume (SF) or rice husk ash
Slag cement; (RHA), on the mechanical and physico-chemical characteristics of the hardened blended cement
Cement kiln dust; pastes made of Portland blast-furnace slag cement (PSC) containing cement kiln dust (CKD) cured
Silica fume; under normal conditions. Two blends made of PSC and CKD, improved by SF and two blends
Rice husk ash; made of PSC and CKD improved by RHA were investigated. Hardened blended cement pastes
Active silica were prepared from each cement blend by using water/cement ratio (W/C) of 0.30 by weight and
hydrated for various curing ages of 1, 3, 7, 28 and 90 days at the normal curing conditions under
tap water at room temperature. Each cement paste was tested for its physico-chemical and mechan-
ical characteristics; these characteristics include: compressive strength and kinetics of hydration.
The phase composition of the formed hydration products was identied using X-ray diffraction
(XRD) and differential thermal analysis (DTA). It was found that the partial substitution of
PSC by 10% and 15% of CKD is associated with an increase in the rate of hydration and a sub-
sequent improvement of compressive strength of hardened PSCCKD pastes. In addition, the
replacement of PSC, in PSCCKD blends, by 5% active silica was accompanied by further
improvement of the physico-mechanical characteristics of the hardened PSCCKD pastes.
2011 Production and hosting by Elsevier B.V. on behalf of King Saud University. This is an open access
article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/3.0/).

1. Introduction slag. It is generally recognized that the rate of hardening of

slag cement is somewhat slower than that of ordinary Portland
Portland blast-furnace slag cement is a mixture of ordinary cement during the rst 28 days but thereafter increases so that
Portland cement and not more than 65 wt.% of granulated at 12 months the strengths become close to or even exceed
those of Portland cement. The slag cement is more sulfate
* Corresponding author. Tel.: +20 80914442860. resistant than Portland cement. Granulated blast-furnace
E-mail address: adel1697@yahoo.com (A. Abdel Rahman).
slag by itself is hydraulically very weak. Due to its glassy struc-
Peer review under responsibility of King Saud University.
ture, a highly alkaline medium is required in order to disinte-
grate the silicatealuminates network of the slag glass; the
liberated free lime during the hydration of Portland cement
clinker is normally used to provide this alkalinity (Wanga
Production and hosting by Elsevier et al., 2010).

http://dx.doi.org/10.1016/j.arabjc.2011.02.029
1878-5352 2011 Production and hosting by Elsevier B.V. on behalf of King Saud University.
This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/3.0/).
Characteristics of Portland blast-furnace slag cement containing cement kiln dust and active silica S139

The idea of adding slags and pozzolana such as y ash, rice 2. Experimental
husk ash or silica fume to Portland cement concrete is widely
practised because it helps to reduce cost and conserve energy Portland blast-furnace slag cement (PSC) was obtained by
resources and environment. Burning of rice husk ash at low mixing of 65% ordinary Portland cement (OPC) with 35%
temperature (450600 C) yields a silica ash consisting of 85 granulated blast-furnace slag (GBFS). Very ne powder of ce-
94% amorphous silica with high surface area (Ganesan ment kiln dust (CKD) was supplied from Turah Cement Com-
et al., 2008; Chindaprasirt and Rukzon, 2008). Silica fume con- pany, Egypt, and condensed silica fume (SF) was provided by
sists of 8596% amorphous active silica with a specic surface Ferro-silicon alloys Company, Kom-Ombo, Aswan, Egypt.
area of 2025 m2/g. Rice husk ash (RHA) was obtained from burning of rice husk
Nataraja and Nalanda (2008) investigated a variety of slag, in an electric furnace at 600 C for 2 h. The chemical oxide
y ash, and cement dust in the performance of industrial by- composition of these starting materials is given in Table 1.
products in controlled low-strength materials. The object of The ingredients of the different mixes were mixed for one
study was to determine the effect on cement quality when hour using a ball mill using three balls to attain complete
low levels of by-product additives are incorporated into Port- homogeneity. The samples were kept in airtight containers un-
land cement. Blended/multi-blended cements based on indus- til the time of paste preparation. The mix composition of the
trial pozzolanic materials like y ash, calcined clay, micro different mixes is given in Table 2.
silica, granulated slag, etc., are the best examples of cementi- The different blended cement pastes were prepared from
tious materials. This class of cements shows improved long- each cement blend by using the initial water/cement (W/C) ra-
term strength and durability (Nochaiya et al., 2010). Mecha- tio of 0.30, and then molded into cubic steel molds having the
nisms and kinetics of slag hydration in hydrated slag cements internal dimensions 2 2 2 cm. Immediately after molding,
were discussed by Daimon (Daimon et al., 1980) and others the molds containing specimens were cured in a humidity
(Lee et al., 2009). Slag grains develop membranes that control chamber at 100% relative humidity at a constant temperature
diffusion and densify the paste matrix that exhibits low perme- 23 2 C for the rst 24 h. The cubic specimens were de-
ability; Ca(OH)2 is gradually consumed by slag grains and Mg molded and then cured under tap water until the desired time
content forms hydrotalcite. of testing, such as 3, 7, 28 and 90 days were reached.
The effect of CKD substitution instead of ordinary Portland At each hydration time, all pastes were tested for their com-
cement OPC, blast furnace slag cement BFSC, and sulfate resis- pressive strength, bulk density, total porosity, phase composi-
tance cement SRC on the mechanical properties of some concrete tion of the formed hydration products and hydration kinetics
mixes containing them, and also, the determination the optimum in order to study the effect of partial substitution of slag ce-
quantity of CKD which could be recycled in the manufacture of ment by CKD and/or SF or RHA on the physico-mechanical
these types of cements were studied (Shoaib et al., 2000). characteristics of Portland blast-furnace slag cement pastes.
The utilization of CKD and some other industrial solid
wastes in the eld of cement industry and other building prod- 3. Results and discussion
ucts was also reported (Abo-El-Enein, 1997, 2005).
Yajun and Cahydi (2003) studied the effects of 020% silica 3.1. Compressive strength
fume on microstructure and compressive strength of blended
cement pastes; the strength of Portland cement paste was im- The results of compressive strength kg/cm2 of the various
proved in the presence of silica fume (SF) as a result of inter- blended cement pastes are given in Table 3 at all ages of
action with lime and water to produce additional amounts of hydration.
calcium silicate hydrates. In addition, the physico-mechanical
characteristics of autoclaved blended cement pastes were im-
proved by addition of silica fume as reported in an earlier pub-
lication (EL-Shimy et al., 2004). The hydraulic reactivity of Table 2 Mix composition of the various blended cements.
rice husk ash was affected by thermal treatment leading to a Mix No.
type of active silica available for different application (EL- M control M-a M-b M-c M-d M-e M-f
Hosiny et al., 1996).
The object of this work is to study the effect of partial sub- PCS% 100 90 85 85 80 85 80
CKD% 0 10 15 10 15 10 15
stitution of PSC by CKD and active silica SF or RHA on the
SF% 0 0 0 5 5 0 0
physico-chemical and mechanical characteristics of the hard- RHA% 0 0 0 0 0 5 5
ened slag cement pastes.

Table 1 Chemical oxide composition of starting materials.

Materials Oxide (%)
SiO2 Al2O3 Fe2O3 CaO MgO SO3 Na2O K2O L.O.I* Cl Free CaO
PSC 21.81 6.18 3.25 60.24 2.14 2.43 0.53 0.11 2.39 0.007 2.70
CKD 8.17 1.90 1.12 44.32 1.61 4.02 2.43 11.13 15.63 6.71 15.9
SF 96.10 0.52 0.70 0.21 0.48 0.10 0.31 0.49 1.14 0.00 0.43
RHA 95.6 0.3 0.3 0.4 0.3 0.2 1.3 1.6 1.0
*
L.O.I = Loss of Ignition.
S140 A. Abdel Rahman et al.

Table 3 Compressive strength, kg/cm2 of the hardened cement pastes made of PSC, PSCCKD and PSCCKDSF or RHA blends
after curing up to 90 days.
Days Mix No.
M control M-a M-b M-c M-d M-e M-f
1 221.85 291.25 227.30 316.20 300.70 318.75 305.90
3 349.25 379.30 377.90 426.15 387.5 402.90 371.65
7 453.10 484.40 465.75 555.90 489.00 524.30 479.75
28 613.00 690.15 652.85 731.85 637.5 703.00 676.50
90 717.50 799.35 757.00 823.65 777.15 797.35 755.75

The results of Table 3 indicated that the compressive silica, in PSCCKD blends (M-a and M-b) leads to an improve-
strength increases with the increase of curing age for the hard- ment in the strength values at the early ages of hydration as com-
ened PSCCKD blended cement pastes. Therefore, larger pared with those of PSCCKD blends.
amounts of cement hydrates and more cementing (strength-
producing) materials are formed with increasing age of 3.2. Kinetics of hydration
hydration; these hydrates act as binding centers between the
unhydrated parts of cement grains. At the same time, the ini- 3.2.1. Chemically combined water content (Wn, %)
tial formation of hydration products and their deposition with- The results of chemically combined water content (Wn, %) of
in the pore system (originally water lled spaces) of the the various blended cement pastes investigated are given in
hardened paste lead to a continuous decrease in the total Table 4 at all curing ages.
porosity of the hardened paste with increasing age of hydra- The results of Table 4 show that the chemically combined
tion. In addition, the increased values of compressive strength water content increases with increasing age of hydration for
with the presence of CKD is mainly due to the enhanced acti- all of the blended cement pastes investigated. When Portland
vation of the granulated slag fraction of slag cement with the blast-furnace slag cement (PSC) is mixed with water, the Port-
alkalis present in CKD leading to the formation of excessive land cement fraction is the rst to hydrate to give the initial
amounts of hydration products; these hydrates act as binding hydration products, mainly as calcium silicate hydrates and free
centers between the unhydrated parts of cement grains leading calcium hydroxide. Then, the free calcium hydroxide liberated
to relatively higher strength values. This positive effect is actu- as a result of hydration of Portland cement clinker acts as an
ally valid for the hardened PSCCKD pastes having CKD activator for granulated slag leading to the formation of hydra-
contents up to 10% Mix (M-a). However, for the PSCCKD tion products similar to those of Portland cement; therefore,
blends containing higher contents of CKD a negative effect Ca(OH)2 causes a sort of breaking of the silica framework of
on the mechanical properties and durability is obtained at later granulated slag leading to a continuous hydration of slag grains.
hydration ages; this is due to the higher contents of alkalis, sul- From the results of Table 4 the chemically combined water con-
fates and chlorides of the blends having relatively higher CKD tent (Wn, %) increased with the presence of CKD at all ages of
contents. Therefore, the optimum partial substitution of PSC hydration with optimum 10% CKD content; these results con-
by CKD is mainly restricted to 10%. rm the variation of compressive strength values.
The results of compressive strength of blended cement pastes Evidently, the blended cement paste made of Mix (M-c)
made of PSCCKDSF blends of Mixes (M-c and M-d) are gi- gives the highest Wn-values as compared with the pastes made
ven in Table 3. The results indicated that the compressive of Mixes (M control) and (M-d). Therefore, silica fume, due to
strength increases with the increase of curing age. Evidently, its very high surface area and very small grain size, interacts
the substitution of 5% PSC by SF in Portland slag cement con- rapidly with the free calcium hydroxide, liberated from clinker
taining 10% and 15% CKD, Mixes (M-c and M-d), however, hydration, leading to the formation of excessive amounts of
leads to an improvement in strength values as compared with calcium silicate hydrates (CSH). Also the results show that
those of PSC at all ages of hydration. The role of silica fume the variations of Wn values with increasing age of hydration
in the improvement of the strength results is mainly due to the are almost parallel to the changes in the compressive strength
interaction of the reactive silica fume with the free lime and alka- values shown in Table 3.
lis released from OPC clinker and CKD hydration. This leads to
the formation of additional amounts of calcium silicate hydrates
Table 4 Chemically combined water content of the hardened
which results in an increase in the total content of binding cen-
cement pastes at different ages of hydration.
ters in the specimens leading to an increase in the strength values
of the hardened PSCCKDSF pastes. Again, the hardened Days Chemically combined water content (Wn, %)
paste made of PSCCKD blend containing 10% CKD and Mix No.
5% SF, Mix (M-c), possesses the highest strength values. This
M control M-a M-b M-c M-d M-e M-f
indicates that the optimum composition of PSCCKDSF
blend is represented by Mix (M-c). 1 9.89 10.13 10.06 10.12 10.03 9.98 10.00
3 12.51 13.84 13.75 14.13 13.95 13.79 13.81
The results of compressive strength of the PSCCKDRHA
7 14.16 15.61 15.25 15.90 15.75 15.66 15.40
blended cement pastes, made of Mixes (M-e and M-f), indicate
28 16.31 17.20 16.90 16.77 16.53 16.53 16.42
that the compressive strength increases with the increase of cur- 90 17.85 18.98 18.70 18.60 17.96 18.29 17.88
ing age. Obviously, substitution of 5% PSC by SF, as an active
Characteristics of Portland blast-furnace slag cement containing cement kiln dust and active silica S141

Table 5 Free lime content of the hardened blended cement Table 6 Bulk density and total porosity of blended cement
pastes at different ages of hydration. pastes made of Mixes (M control, M-a and M-b) at different
Days Free lime content (CaO, %) hydration ages.

Mix. No. Days Mix. No.

M control M-a M-b M-c M-d M-e M-f Bulk density, g/cm3 Total porosity, %

1 6.17 6.60 6.23 6.65 6.55 6.61 6.45 M control M-a M-b M control M-a M-b
3 7.70 7.80 7.72 7.95 7.85 7.85 7.77 1 2.165 2.173 2.170 27.64 26.95 25.73
7 8.05 8.11 8.02 8.62 8.54 8.50 8.33 3 2.169 2.182 2.177 25.87 24.45 23.28
28 7.54 7.91 7.60 8.12 8.08 8.02 7.90 7 2.185 2.195 2.186 22.91 21.36 20.14
90 7.37 7.88 7.51 7.98 7.65 7.88 7.50 28 2.190 2.202 2.186 21.61 20.47 19.80
90 2.200 2.210 2.223 19.62 19.45 19.25

3.2.4. Phase composition of the formed hydrates

The results in Table 4 indicate that blended cement pastes The phase composition of the formed hydration products was
made of slag cement admixed with both of CKD (10% and studied by means of X-ray diffraction (XRD) and differential
15%) and RHA (5%) give higher Wn-values as compared with thermal analysis (DTA).
those made of slag cement containing CKD alone. The addi- X-ray diffractograms of the hardened blended cement
tional formation of (CSH) during the interaction between pastes shown in Fig. 1 for (PSC control), and Fig. 2 for Mix
RHA, as an active silica, with free lime released accounts for (M-a) contain of PSC + 10% CKD indicated that the main
higher strength values of the hardened PSCCKDRHA phases identied are calcium silicate hydrates (CSH), calcium
paste. hydroxide (CH) and gehlenite-like calcium aluminosilicate hy-
drate (C2ASH8) as well as calcium carbonate (CC ).
3.2.2. Free lime content (CaO, %) The diffractograms of (Fig. 2) obtained for the PSCCKD
The results of free lime contents (CaO, %) of the hardened paste made of Mix (M-a) indicated the formation of the same
blended cement pastes made of all mixes are given in Table 5 hydration products shown in Fig. 1 for the hardened PSC
as a function of curing age. paste (M control) with only one main basic difference, namely,
From the results of the Table 5 the free lime content in- the increased intensity of the peaks characterizing calcium
creases with increasing age of hydration during the early ages hydroxide in the hardened PSCCKD paste of Mix (M-a).
and up to 7 days for all of the hardened PSCCKD blended This indicates the larger amounts of free calcium hydroxide
cement pastes; this was followed by a gradual decrease in the liberated from CKD in addition to the Portland cement frac-
free lime content up to 90 days of hydration. In fact, the free tion of slag cement (PSC).
lime content is released as a result of hydration of Portland ce- Figs. 3 and 4 show the X-ray diffractograms of the formed
ment clinker fraction of slag cement; while the activated hydra- hydration products obtained for PSCCKDSF and PSC
tion of granulated slag leads to a consumption of free lime. CKDRHA pastes of Mixes (M-c) and (M-e), respectively.
Therefore, the values of free lime contents reported in Table The main phases identied are calcium silicate hydrates
5 represent a net effect between the amounts of free lime liber- (CSH), calcium hydroxide (CH), calcium carbonate (CC )
ated by clinker hydration and the free lime consumed as a re- and gehlenite-like calcium aluminosilicate hydrate (C2ASH8).
sult of activation of slag hydration. The results of Figs. 3 and 4 are similar to those of the paste
The results of free lime contents given in Table 5 indicate made of Mix (M-a), shown in Fig. 2, with an exception of
that the free lime content also increases with increasing age
of hydration during the early ages up to 7 days for the hard-
ened PSCCKDSF and PSCCKDRHA blended cement
pastes; this was followed by a gradual decrease in the free lime
content up to 90 days of hydration. Again, this indicates that a
net increase in the free lime content of these pastes is obtained
at the early hydration ages (up to 7 days) which was followed
by a net decrease in the free lime content at the later ages of
hydration for the hardened PSCCKDSF and PSCCKD
RHA pastes.

3.2.3. Bulk density and total porosity

The results of bulk density and total porosity for hardened
PSCCKD pastes are given in Table 6.
The bulk density increases and total porosity decreases with
curing time up to 90 days for all blended cement pastes. Evi-
dently, the addition of CKD to PSC gives high bulk density
and low total porosity at all ages of hydration. As the hydra-
tion proceeds the hydration products ll parts of the total pore
volumes; therefore, the bulk density increases and the total Figure 1 XRD pattern of hardened cement pastes of Mix (M
porosity decreases. control) curing after 3, 28 and 90 days.
S142 A. Abdel Rahman et al.

Figure 4 XRD patterns of hardened cement pastes of Mix (M-e)

Figure 2 XRD pattern of the hardened cement pastes of Mix curing after 3, 28 and 90 days of hydration.
(M-a) curing after 3, 28 and 90 days of hydration.

Figure 5 The DTA thermogram of the hardened cement paste

Figure 3 XRD patterns of the hardened cement pastes for Mix
Mix (M control) cured up to 90 days.
(M-c) curing after 3, 28 and 90 days of hydration.

the amount of free calcium hydroxide which is almost con-

sumed as a result of its interaction with the active SF or
RHA leading to the formation of excessive amounts of calcium
silicate hydrates.
The results of DTA thermograms obtained for the hard-
ened PSC paste of Mix (M control) are shown in Fig. 5. There
appeared four endothermic peaks in the thermograms; these
are located at 120, 450, 525 and 680 C. The endotherms lo-
cated at 120 and 450 C are mainly due to the decomposition
of calcium silicate hydrates (CSH) and gehlenite hydrate
(C2ASH8), respectively; whereas the endotherms appeared at
525 and 680 C are attributed to the decomposition of calcium
hydroxide (CH) and the small amounts of calcium carbonate
(CC ), respectively. Evidently, the peaks characterizing the
(CSH and C2ASH8) phases become more distinguishable after
28 and 90 days of hydration.
The results of DTA thermograms obtained for the hard-
ened PSCCKDRHA paste of Mix (M-e) are shown in Figure 6 The DTA thermogram of the hardened cement pastes
Fig. 6. This shows the presence of the six endotherms. These of Mix (M-e) cured up to 90 days.
Characteristics of Portland blast-furnace slag cement containing cement kiln dust and active silica S143

endotherms are located at 100, 150, 180, 470, 530 and 670 C. Abo-El-Enein, S.A., 2005. Utilization of industrial solid wastes in the
The rst three endotherms located at 100, 150 and 180 C are eld of building materials technology. Proc. 1st. Ain Shams Univ.
mainly due to the removal of adsorbed water and the decom- Inter. Confr. Environ. Eng., Cairo. pp. 11251141.
position of the three types of calcium silicate hydrates, namely: Chindaprasirt, P., Rukzon, S., 2008. Strength, porosity and corrosion
resistance of ternary blend Portland cement, rice husk ash and y
high-lime calcium silicate hydrate (CSH-II), low-lime calcium
ash mortar. J. Construct. Build. Mater. 22, 16011606.
silicate hydrate (CSH-I) and tobermorite-like calcium silicate
Daimon, M. 1980. Mechanism and kinetics of slag cement hydration.
hydrate (CSH-T), respectively. The two endotherms located Proc. 7th. Int. Chem. Cem., Paris. , I 2/1I 2/8.
at 470 and 530 C are mainly attributed to the decomposition EL-Hosiny, F.I., Abo-El-Enein, S.A., El-Didamony, H., Khalil,
of gehlenite-like calcium silicate hydrate (C2ASH8) and cal- Kh.A., 1996. Effect of thermal treatment of rice husk ash on the
cium hydroxide (CH), respectively. The weak endotherm lo- surface properties of hydrated lime-rice husk ash binders. J. Therm.
cated at 670 C is mainly attributed to the decomposition of Anal. 46, 105116.
calcium carbonate (CC ). EL-Shimy, E., EL-Shafai, M.M., Abo-El-Enein, S.A., 2004.
Characterization of autoclaved blended cement pastes containing
silica fume. Industria Italiana del Cemento (iiC), LXXIV 795,
4. Conclusions 166173.
Ganesan, K., Rajagopal, K., Thangavel, K., 2008. Rice husk ash
The main conclusion derived from this study is summarized as blended cement: assessment of optimal level of replacement for
follows: strength and permeability properties of concrete. J. Construct.
Build. Mater. 22, 16751683.
Lee, Tzen-Chin, Wang, Wei-Jer, Shih, Ping-Yu, Lin, Kae-Long, 2009.
1. Addition of cement kiln dust (CKD) to Portland blast-fur-
Enhancement in early strengths of slag-cement mortars by adjust-
nace slag cement (PSC) leads to an improvement of the ing basicity of the slag prepared from y-ash of MSWI. J. Cem.
physico-chemical and mechanical properties of the hard- Concr. Res. 39, 651658.
ened (PSCCKD) pastes with an optimum constitution of Nataraja, M.C., Nalanda, Y., 2008. Performance of industrial by-
PSC (90%)CKD (10%) blend. products in controlled low-strength materials (CLSM). Waste
2. The partial replacements of (PSC) by active silica (SF or Manag. 28, 11681181.
RHA) lead to an improvement of the physico-mechanical Nochaiya, Thanongsak, Wongkeo, Watcharapong, Chaipanich,
characteristics of the hardened PSCCKD pastes made Arnon, 2010. Utilization of y ash with silica fume and
with the optimum constitution (PSC, 90% and CKD, properties of Portland cementy ashsilica fume concrete. Fuel
89, 768774.
10%).
Shoaib, M.M., Balaha, M.M., Abdel-Rahman, A.G., 2000. Inuence
3. The results of hydration kinetics and phase composition of
of cement kiln dust substitution on the mechanical properties of
the formed hydrates could be related to the results of com- concrete. J. Cem. Concr. Res. 30, 371377.
pressive strength of the various hardened cement pastes. Wanga, Xiao-Yong, Leea, Han-Seung, Parkb, Ki-Bong,
Kimc, Jae-Jun, Goldend, Jay S., 2010. A multi-phase kinetic model
References to simulate hydration of slag-cement blends. J. Cem. Concr.
Compos. 32, 468477.
Abo-El-Enein, S.A., 1997. Utilization of cement kiln dust in cement Yajun, Ji, Cahydi, J.H., 2003. Effect of densied silica fume on
industry and building products. First International Symposium on microstructure and compressive strength of blended cement pastes.
the Cement Industry, Assiut, Egypt, pp. 810. Cem. Concr. Res. 33, 15431548.