ACI MATERIALS JOURNAL
Title No. 115-M88
Role of Nanosilica on the Early-Age Performance of
Natural Pozzolan-Based Blended Cement
by Gürkan Yıldırım, Burak Dündar, Burhan Alam, İsmail Özgür Yaman, and Mustafa Ş ahmaran
This investigation focused on the microstructural, workability,
mechanical, and hydration evolution of blended cements composed
of natural pozzolan with nanosilica (NS). In Turkey, the most
common supplementary cementitious materials are natural
pozzolans of volcanic origin. Volcanic pumice is a natural pozzolan
produced by the release of gases during the cooling and solidifica-
tion of lava. In this study, pumice powders with two different levels
of fineness were used to replace ordinary portland cement (OPC)
at 15%, 30%, and 45% by weight. Seven mixtures were proposed
with different levels of pumice fineness and OPC replacement rates,
as well as an additional control mixture without pumice powder.
Companion mixtures were also produced by adding 3% NS (by
total weight of cementitious materials) into the proposed mixtures
for a total of 14 different mixtures. Fresh properties measured by
flow test and mechanical performance validated by microstructural
analyses show that in the presence of NS, up to 30% pumice powder
can be replaced with OPC without risking workability and 2-day
strength measurements. In cases where the early-age strength is
necessary after the first 7 days, the same level of replacement can
be increased up to 45%. The successful outcomes of this study may
compensate for the drawbacks of OPC use in concrete mixtures and
popularize the use of natural pozzolans in locations where they are
more commonly available.
Keywords: hydration characteristics; mechanical properties; nanosilica;
pumice powder; workability.
INTRODUCTION
Portland cement is the most energy-intensive, costly,
and environmentally unfriendly ingredient of conventional
concrete. The energy required to produce one kilogram of
clinker is 850 kcal. To produce 1 tonne (2204.6 lb) of clinker,
1.7 tonnes (3747.9 lb) of rock is needed.1 Producing 1 tonne
of cement is responsible of the emission of 0.94 tonnes
(2072.4 lb) of CO2—0.55 tonnes (1212.5 lb) from calcina-
tion of raw clinker materials and 0.39 tonnes (859.8 lb) from
fuel emissions.2 The cement industry is responsible for 5 to
8% of the total anthropogenic CO2 in the atmosphere,3 and
the cost of cement represents more than 45% of the overall
cost of conventional concrete.1
To eliminate these drawbacks, researchers have been
investigating replacing portland cement with alternative
binders. In the last four decades, the search for alternative
binders has grown in popularity, with studies into the use
of fly ash, ground-granulated blast-furnace slag, silica fume,
rice husk ash, and others.4-8 Due to significant variations
in chemical compositions of common cement replacement
materials, their reaction products can be highly pozzolanic
or almost cementitious. Regardless of chemical composi-
tion, these materials, if carefully selected for specific appli-
ACI Materials Journal/November 2018
TECHNICAL PAPER
cations, are known to enhance the properties of concrete.9
However, despite their effectiveness, using high amounts of
replacement materials (especially those with highly pozzo-
lanic behavior such as fly ash) in concrete can significantly
reduce development of early-age strength.10
Recently, the use of nanomaterials in cement-based
systems such as paste, mortar, and concrete has become
popular. Nanosilica (NS) is of particular importance and has
recently been introduced as an advanced pozzolan to improve
the microstructure and stability of cementitious systems.11
Thanks to its high reactivity and fineness, NS is capable of
consuming portlandite formed as a result of cement hydra-
tion to produce additional calcium-silicate-hydrate (C-S-H)
gels.12 Moreover, even at very small rates of use, NS can
make cement hydration products denser by acting as a
nucleus, and it improves the interfacial transition zone. The
performance of mixtures with NS has been reported to be
better than those with silica fume.13,14 Given its relatively
high specific surface area and reactivity, NS was also used
in several studies to modify the early-age strength problem
of cement-based mixtures with high volumes of fly ash.15-17
Pumice is a natural material that forms when gases are
released from molten lava during solidification. In the
construction industry, it is most commonly used as an
aggregate for lightweight cement-based materials, given its
relatively low density, although it has potential to be used
in the production of blended cement after pulverization.18
Although there have already been numerous studies on
the use of pumice powder in cement-based materials,18-22
these are relatively limited compared to studies into other
replacement materials because the selection is limited by
local availability and/or easy importability of the material.
However, because Turkey has 40% of the world’s total
pumice reserve,22 use of pumice powder is more common
in the production of cement-based materials locally, making
it a reasonable alternative to portland cement. This study,
therefore, investigated the workability, mechanical, micro-
structural, and hydration characteristics of cement mortars
blended with pumice powder, with a special focus on modi-
fying the properties (especially early-age strength) through
the use of nanosilica.
ACI Materials Journal, V. 115, No. 6, November 2018.
MS No. M-2018-043.R1, doi: 10.14359/51706848, was received February 17,
2018, and reviewed under Institute publication policies. Copyright © 2018, American
Concrete Institute. All rights reserved, including the making of copies unless
permission is obtained from the copyright proprietors. Pertinent discussion including
author’s closure, if any, will be published ten months from this journal’s date if the
discussion is received within four months of the paper’s print publication.
969
 RESEARCH SIGNIFICANCE
To reduce the negative impacts of portland cement manu-
facture on environmental, economic, and societal levels, use
of alternative binders to replace portland cement in concrete-
like materials has been a common practice for years.
However, this practice is limited because these binders are
mostly less reactive than portland cement, which leads to
lower strength grades, especially at the early ages. More-
over, their availability is strictly dependent on the geological
and/or production-based location. Turkey is tremendously
rich in terms of naturally occurring pumice reserves. Thus,
utilization of pumice in concrete-making to reduce the nega-
tive impacts of portland cement manufacture is reasonable,
although research related to this subject is very limited. The
current study is important in that it investigates, for the first
Fig. 1—Particle size distributions of OPC, CP, and FP.
Fig. 2—SEM micrographs of: (a) ordinary portland cement; (b) coarse pumice; (c) fine pumice; and (d) nanosilica.
970
time in literature, according to authors’ best knowledge, the
properties of pumice-powder-blended cement mortars by
specifically concentrating on the modification of early-age
strength through the use of nanosilica.
Materials
Paste and mortar specimens were prepared depending
on the testing procedure. CEM I 42.5R ordinary portland
cement (OPC) (similar to ASTM Type I), pumice powder
(P) with two different finenesses, and nanosilica (NS) were
used as cementitious materials along with CEN standard
sand (for mortars), high-range water-reducing admixture
(HRWRA) and tap water. Acidic pumice, obtained from a
single source in eastern Turkey, had different particle sizes
with different grinding durations. Coarse pumice (CP) was
ground in a rotary mill for 250 minutes, and fine pumice
(FP) for 500 minutes. It should be noted that although they
are denoted as CP and FP, pumice used throughout the study
was in powdered form. Figure 1 shows the particle size
distributions of cementitious materials excluding NS (due to
flocculation problems that led to unreliable sizing results).
NS is a commercially available product that could be easily
acquired from the related markets. To more clearly compare
the sizes of different cementitious materials, scanning elec-
tron microscope (SEM) micrographs were used, as shown
in Fig. 2. CEN standard sand was naturally silica-based,
with silica content of at least 98% and a round shape. The
HRWRA contained an active ingredient of polycarboxylate
ether, with specific gravity of 1.1 and solid content of 40%.
Table 1 shows the chemical compositions of cementitious
materials obtained by X-ray fluorescence (XRF) analysis.
ACI Materials Journal/November 2018
Table 1—Chemical composition and physical Table 2—Average compressive strength results
properties of cementitious materials of 2- and 7-day-old mortar specimens after
Chemical composition, % OPC CP FP NS
preliminary testing
Loss on ignition 5.12 4.27 4.31 — 2-day 7-day

SiO2 18.6 62.0 62.3 99.2 NS utilization rate Results, MPa COV Results, MPa COV

Al2O3 4.55 15.6 15.7 0.38 0% (Control) 13.4 5.42 22.9 6.16

Fe2O3 3.05 4.91 4.94 0.04 1% 16.8 4.32 28.0 7.56

CaO 62.7 1.41 1.18 — 2% 17.1 5.51 28.2 2.76

MgO 1.58 0.19 0.18 0.21 3% 18.3 4.90 31.7 2.58

SO3 2.66 0.08 0.09 0.08 4% 18.1 0.90 28.7 1.43

Na2O 0.26 6.21 6.09 0.09 5% 16.8 5.07 29.2 8.90

K2O 0.53 4.81 4.63 — Notes: 1 MPa = 0.145 ksi; COV is coefficient of variation.

TiO2 — 0.30 0.30
Cl–
0.05 — —
Physical properties
Specific gravity 3.06 2.54 2.54
Blaine fineness, cm /g2
3250 5110 5787
BET, m /kg2
— — — 163.2
Preliminary testing
The optimum amount of NS to be used in mixtures was
determined with a series of preliminary tests including
uniaxial compressive strength measurements of mortar
mixtures with different NS utilization rates. As mentioned
previously, coarse and fine pumice made with different
grinding durations were used throughout the study. Different
rates of pumice replacement with OPC (by weight) were
15, 30, and 45%. For preliminary tests, however, only a
single type of pumice (CP) and an OPC replacement rate
of 25% were chosen. To determine optimum NS rate in
pumice-blended OPC mortar mixtures, NS was added by
1, 2, 3, 4, and 5% of total amount of cementitious mate-
rials (OPC + CP). A control mixture without NS was also
used for comparison in preliminary testing. Mixtures with
constant water-cementitious materials ratio (w/cm) and
similar proportions were prepared and tested in accordance
with the related ASTM standard. For each mortar mixture
design, 450 g (0.992 lb) of cementitious material (75% OPC
and 25% CP by weight), 1350 g (2.976 lb) of CEN stan-
dard sand, and 225 g (0.496 lb) of water were portioned for
specimen preparation. Adequate workability was acquired
using a constant amount of HRWRA of 7 g (0.015 lb) in
each mixture.
To avoid flocculation, NS was homogenously dispersed
in the mixing water separately using an ultrasonic mixer
before being added in the rest of the mixture ingredients.
The time for ultrasonication of NS with mixing water was
5 minutes, as suggested in literature.16 At the fourth minute
of ultrasonication, the rest of the dry ingredients (sand,
cement, and pumice) were mixed separately in a mortar
mixer for 1 minute at low speed. After 5 minutes, the ultra-
sonicated water-NS solution was added into the dry blend
and mixed at low speed for another minute. HRWRA was
added into the mixture after 1 minute of mixing at low speed.
The entire mixture was then mixed in the mortar mixture at
— high speed for two more minutes. After all mortar mixtures
— were prepared for preliminary testing, they were molded and
placed into 50 mm (2 in.) cubic molds in accordance with
ASTM C109. Molded mortar specimens were then placed
0.45
into the curing room at 23 ± 2°C (73.4 ± 3.6°F) and 95 ±
— 3% RH with their surfaces covered with wet fabric. After
24 hours, mortar specimens were removed from their molds,
placed into a lime-saturated water tank and kept there until
the completion of initial curing of 2 and 7 days, at which
time compressive strength tests were conducted on three
cubic specimens from each mixture. Average compressive
strength test results for specimens subjected to initial curing
are shown in Table 2. The table shows that addition of NS
into the control mixture led to increments in the average
compressive strength results regardless of the amount
chosen. However, the highest average compressive strength
results with respect to the control mixture were recorded
from specimens with 3% NS at both testing ages. Based on
these findings, the decision was made to continue the actual
testing with 3% NS.
FINAL TESTING PROGRAM
Mixture proportioning
Mixture proportions for the final testing program were
determined for three different pumice replacement ratios
with OPC (15, 30, and 45%) and pumice fineness (coarse
[CP] and fine [FP]). Control mixtures without pumice were
also produced. As mentioned, 3% NS was used in mixtures
by the total weight of cementitious materials (cement +
pumice powder), and two sets of mixtures (with and without
NS) were manufactured. Mixture proportions for the final
testing program are displayed in Table 3. The parameters of
the experimental program were pumice fineness, replace-
ment rate of pumice, presence of NS, and the individual
effects of these parameters on mixture properties. Ingredient
amounts (Table 3) were calculated according to standard
mixture proportioning and w/cm stated in the TS EN 196-1
standard. Preliminary testing determined that the optimum
amount of HRWRA necessary for adequate workability of
the mixtures was 7 g (0.015 lb). Depending on the testing
method (for example, heat of hydration), paste samples were
also produced without sand and HRWRA.
Mixtures were named to easily identify their ingredients.
Reference mixtures without pumice and NS are named

ACI Materials Journal/November 2018 971

Table 3—Mixture proportions for final testing program
OPC FP CP NS Water Sand HRWRA
Pumice, % Mixture ID grams (g)
Control 450.0 — — — 225 1350 7
0
Control-NS 436.5 — — 13.5 225 1350 7
15FP 382.5 67.5 — — 225 1350 7
15FP-NS 369.0 67.5 — 13.5 225 1350 7
15
15CP 382.5 — 67.5 — 225 1350 7
15CP-NS 369.0 — 67.5 13.5 225 1350 7
30FP 315.0 135.0 — — 225 1350 7
30FP-NS 301.5 135.0 — 13.5 225 1350 7
30
30CP 315.0 — 135.0 — 225 1350 7
30CP-NS 301.5 — 135.0 13.5 225 1350 7
45FP 247.5 202.5 — — 225 1350 7
45FP-NS 234.0 202.5 — 13.5 225 1350 7
45
45CP 247.5 — 202.5 — 225 1350 7
45CP-NS 234.0 — 202.5 13.5 225 1350 7

Note: 1 g = 0.0022 lb.

“Control”, and the control mixture with NS is named
“Control-NS”. For mixtures with different amounts of
pumice, names are based on pumice replacement rate and
type of pumice. For example, the mixture “15 FP” had 15%
fine pumice replaced with OPC, while mixture “45CP-NS”
had 45% of coarse pumice replaced with OPC and included
3% NS.
Sampling and testing methods
The experimental program consisted of a series of tests
carried out on mortar and paste specimens. Mortar speci-
mens were used to determine consistency, flexural strength,
and compressive strength, while paste specimens were
used to identify heat of hydration, X-ray diffraction (XRD)
analyses, and thermogravimetric analyses (TGA/DTA) of
different mixtures.
The same mixing and curing procedures detailed for the
preliminary testing program were followed for mortar and
paste mixtures. Consistency, flexural strength, and compres-
sive strength measurements were made on 40 x 40 x 160 mm
(1.6 x 1.6 x 6.3 in.) fresh and hardened prismatic mortar
specimens, while heat of hydration, XRD, and TGA/DTA
were analyzed on powder samples obtained from cubic paste
specimens measuring 50 mm (2 in.).
Consistency measurements of mortar mixtures in the fresh
state were made in accordance with ASTM C1437-13 using
the flow table method. In accordance with this method, a
flow mold was placed on the flow table and centered. Fresh
mortar was poured into the mold to a 25 mm (0.98 in.) thick-
ness and tamped 20 times. After that, the rest of the mold was
completely filled, and tamping was applied 20 more times.
Once surface leveling and overall cleaning of the mold were
complete, the mold was removed, and the flow table was
dropped 25 times in 15 seconds. As soon as the fresh mortar
finished spreading, two perpendicular spread diameters were
measured, averaged, and recorded as the final mini-slump
flow diameter.
To measure compressive strength results, two broken
pieces of specimens were tested under flexure (three-point
bending loading). Both flexural and compressive strength
tests were implemented at a loading rate of 1.5 kN/s (337.2 lb/s)
using universal testing equipment. Strength measurements
were recorded after the completion of 2, 7, 28, and 90 days.
The dimensions of the plate that crushed the broken mortar
specimen pieces were 40 x 40 mm (1.6 x 1.6 in., for compres-
sive loading of 1600 mm2 (2.56 in.2). The testing equip-
ment resulted in maximum loading level after final failure,
and compressive strength was automatically calculated by
the device itself, while flexural strength under three-point
bending was calculated manually using the related formula-
tion. For each testing age, six different specimens were used
for the strength calculations.
An isothermal calorimeter was used for measurements
related to the heat of hydration of different mixtures, oper-
ating at a temperature range of 5 to 90°C (41 to 194°F),
with eight calorimetric channels allowing eight simulta-
neous observations. The eight calorimetric channels were
combined to form a calorimeter tool (single heat – sink
block) embedded in a temperature-controlled air thermostat.
Each calorimetric channel is designed to have two sections:
one for the sample and one for the reference. The sample and
reference materials were held in 20 mL (0.68 oz) ampoules
during measurement. The w/cm by weight was 0.5 and was
constant for all mixtures. Pastes tested were prepared in
ampoules. NS was added to the mixing water and water-NS
solution was prepared in another container using an ultra-
sonic homogenizer. After the water and water-NS solution
were added to the ampoules with a syringe, the pastes were
mixed with a special needle. Immediately after mixing,
the test ampoules were placed in the test cell in the body
of the calorimeter. The calorimeter manual recommends

972 ACI Materials Journal/November 2018

Table 4—Flow values, average strength results, and total amounts of heat release of mixtures after
different initial curing periods
Total amount of heat
Flexural strength, MPa Compressive strength, MPa evolved, J
Flow
Mixture ID values, % 2-day 7-day 28-day 90-day 2-day 7-day 28-day 90-day 24 h 72 h
Control 150 5.6 5.6 9.6 10.3 30.0 44.7 58.2 64.1 917 1166
Control-NS 110 5.9 5.9 9.9 10.7 31.6 49.6 58.8 63.9 1185 1757
15FP 150 5.1 5.1 9.0 10.7 22.8 34.3 51.8 61.3 843 1087
15FP-NS 85 6.0 6.0 9.3 10.3 28.1 44.6 58.1 58.7 1128 1712
15CP 150 4.9 4.9 8.8 10.7 23.1 34.8 50.4 60.0 782 1000
15CP-NS 75 5.7 5.7 9.5 10.0 27.4 42.5 55.5 58.9 1023 1511
30FP 150 3.9 3.9 8.9 9.4 16.4 27.8 48.5 59.0 697 950
30FP-NS 100 5.0 5.0 9.5 11.4 20.6 36.1 49.9 57.6 882 1319
30CP 150 4.2 4.2 8.6 10.6 16.3 27.9 46.0 59.1 680 862
30CP-NS 90 4.9 4.9 9.4 10.8 20.3 36.9 48.4 53.2 894 1320
45FP 150 3.2 3.2 8.3 9.8 11.6 22.2 38.8 49.8 561 761
45FP-NS 80 3.9 3.9 8.2 11.1 13.9 28.5 47.0 52.3 792 1182
45CP 140 2.9 2.9 7.0 9.6 11.3 22.4 35.9 47.7 577 730
45CP-NS 75 3.9 3.9 9.1 10.4 13.6 26.4 45.3 50.5 845 1255

Note: 1 MPa = 0.145 ksi.

that the heat capacity of the test and reference samples
should be identical. To meet this requirement, any material
with a known heat capacity was calculated proportionally.
Quartz sand was used as reference material. Measurements
were recorded continuously for 72 hours in real time with
an eight-channel data logger connected to a computer.
Within each calorimetric channel, there were two heat flow
sensors—one under the sample and one under the reference.
The main route for heat exchange between the sample and its
surroundings was through the heat-flow sensor. The flow of
heat, caused by the temperature gradient across the sensor,
created a voltage signal proportional to the heat flow. The
eight twin calorimetric channels were held together in the
calorimeter block. The sample and reference calorimeters
for each channel were accessed from above for loading
through inlets marked A and B on the insulated thermostat
lid. The ampoule holding the sample was placed inside A,
and the reference ampoule inside B. The difference in heat
flow between the sample and the reference was monitored
(that is, side A minus side B); the exothermic process in side
A (the sample) resulted in positive heat-flow values.
The X-ray diffraction (XRD) method relies on the prin-
ciple of the diffraction of X-rays within a characteristic
order created by atomic patterns of a specific crystalline
phase of a material. This diffraction profile for each crys-
talline phase specifies a crystal that is like a fingerprint. The
XRD method does not destroy the sample and can analyze
even the smallest amounts. With the aim of observing the
quality and completeness of hydration and the quantities of
hydration products, hydrated cement paste samples were
ground into powder of approximately 20 mg (0.000044 lb)
in weight and finer than 150 μm (0.0059 in.) in particle size.
These samples, which represented all mixture proportions
(Table 3), were then analyzed. Each sample was prepared for
testing at 2, 7, and 28 days.
Thermogravimetric (TGA) and differential thermal analyses
(DTA) were conducted to acquire information from samples
under temperatures ranging from 25 to 1200°C (77 to
2192°F). The simultaneous system of TGA/DTA can be used
to determine the bound water and calcium hydroxide (CH)
content in specimens. Theoretically, the difference between
initial weight and the weight reading at 105°C (221°F) indi-
cates the initial existing bound water amount. At tempera-
tures between 400 and 500°C (752 and 932°F), CH decom-
poses into H2O and CaO. The weight difference among these
temperatures (exact values are read from the fluctuations on
the result files) indicates the resolving H2O amount sepa-
rated from CH.
RESULTS AND DISCUSSION
Mini-slump flow
Mini-slump-flow values obtained in flow table tests show
the consistencies of different mixtures (Table 4). The flow
value of the control mixture with no NS and pumice was
150%. Pumice incorporation into control mixtures without
NS, regardless of size and amount, did not negatively influ-
ence the flow values, with the exception of 45CP, which had
a slightly lower flow value of 140%.
Given the lower specific gravity of pumice compared to
OPC, mixtures with different amounts of pumice had higher
volumes because cement was replaced by weight. Consid-
ering the higher volumes of mixtures with pumice, it was
anticipated that the pre-determined amount of water would
not be adequate for achieving flow values similar to the
control mixture. However, this was not the case. As outlined
previously, to obtain similar mixture proportions and make
easier comparisons among different mixtures, HRWRA

ACI Materials Journal/November 2018 973

Fig. 3—Effect of: (a) pumice replacement on flexural strength; (b) NS addition on flexural strength; (c) pumice replacement on
compressive strength; and (d) NS addition on compressive strength of different mixtures. (Note: 1 MPa = 0.145 ksi.)
amount was kept constant throughout the study. Because
pumice is a porous material, right after the water is added,
some is directly absorbed by the individual pumice particles.
However, although the amount of water to be used for cement
hydration is reduced due to absorption, OPC amount is also
reduced as a result of pumice replacement. Therefore, for a
given pumice replacement rate, the total amount of water not
absorbed by pumice particles, and the reduced OPC led flow
rates of different mixtures to be almost identical at a constant
amount of HRWRA use because the water-reducing admix-
tures act on the surface of individual cement particles. These
findings show that replacing OPC with pumice up to very
high amounts does not have a negative effect on consistency
measurements, regardless of particle size.
Adding NS made a significant impact on reducing flow
values, irrespective of the use of pumice with different
particle sizes. Moreover, as seen in Table 4, the effectiveness
of NS in reducing the flow values of pumice-incorporated
mixtures was higher than in control mixtures. For example,
NS inclusion caused flow value of the control mixture to
drop by 27% (from 150 to 110%) while the flow value of
15FP dropped by 43% (from 150 to 85%). This trend held
true for CP and different pumice replacement rates. As
mentioned, when OPC is replaced with pumice, the amount
of water that will be instantaneously used for cement hydra-
tion is also reduced due to absorption by pumice particles.
Although the amount of non-absorbed water and reduced
OPC amounts compensate for each other with regard to
flow measurements, adding NS considerably reduced the
flow values of all mixtures due to the significantly higher
surface area of NS compared to the rest of the ingredients,
which increased the water demand substantially. However,
despite the reductions in flow measurements with NS, all the
mixtures had adequate flow results without any detrimental
effects on workability.
974
Flexural strength
Average results of flexural strength tests are tabulated
in Table 4. In Fig. 3, the same results are plotted based on
initial curing ages of 2, 7, 28, and 90 days. The coefficient of
variation in results was less than 10% for all specimens from
different mixtures. As expected and is very clear from Table 4
and Fig. 3, flexural strength results continuously increased
with time for all mixtures due to ongoing hydration reac-
tions, further improving the microstructural properties of
mortars. For mixtures without NS, pumice replacement with
OPC lowered the average flexural strength results of the
control mixture. This behavior, which can be more easily
seen in Fig. 3(a), was much more apparent at early curing
ages. For example, the 2-day average flexural strength value
of the control mixture dropped from 5.6 MPa (0.812 ksi) to
4.9, 4.2, and 2.9 MPa (0.711, 0.609, and 0.421 ksi) when
the rate of coarse pumice replacement with OPC was 15%,
30%, and 45%, respectively. Similar behavior with different
rates of reduction was also monitored when fine pumice
was replaced with OPC. Furthermore, reduction became
more pronounced at higher pumice replacement levels. This
was due to the considerable reductions in OPC as the main
binding material, which lowered the rate of hydration and
slowed the pozzolanic capability of pumice-incorporated
mixtures, especially at early curing ages. The average flex-
ural strength results of pumice-incorporated mixtures were
still lower than those of the control mixture after initial
curing periods of 7 and 28 days. However, when the initial
curing period was extended to 90 days, flexural strength
results of the pumice-incorporated mixtures either exceeded
(15FP, 15CP, and 30CP) or was very similar to the control
mixture (Fig. 3(a)). This was attributed to the slow progress
of the pozzolanic reactions of pumice, which contributes to
the strength development of mixtures, mostly at later ages.
Moreover, it is significant that the tendency of pumice to
decrease early-age and increase late-age flexural strength
ACI Materials Journal/November 2018
results compared to the control mixture was independent of
pumice particle size.
The effect of adding NS into the control and pumice-
incorporated mixtures is shown in Table 4 and Fig. 3(b).
They show that NS addition was effective in increasing
the average flexural strength results of mixtures with and
without pumice replacement, up to a certain extent, at the
end of almost all initial curing ages. It should be noted that
NS improved the values of pumice-blended mixtures more
than the control mixtures, which was observable in both
early- and late-age specimens depending on mixture type.
One explanation for the improvements could be that NS
stimulated hydration reactions and registered accelerated
pozzolanic capacity at both early and late ages. It has been
reported that pozzolanic reactions of silica fume start as early
as the first day of cement hydration.23 Given that the specific
surface area of nanosilica particles are at a fraction of silica
fume, enhanced pozzolanic capability can therefore be antic-
ipated before the first 24 hours of cement hydration.24 This
may be one reason for the improvements in flexural strength.
Another factor influencing flexural strength with NS incor-
poration may be physical. Using NS creates high numbers
of nucleation sites through a seeding effect, precipitating
cement hydration products thanks to extremely fine particle
size.16,17 Furthermore, replacing OPC with pumice makes
the microstructure of certain blended OPC mixtures even
finer than that of the control mixture without pumice, which
may provide additional nucleation sites and partly explain
the more pronounced improvements in the flexural strength
results of pumice-incorporated mixtures with NS. In addition
to the seeding effect, it is possible that NS may have acted as
reactive filler, reducing the rate of bleeding and increasing
the particle packing of solid ingredients by occupying space
between the OPC, pumice, and sand particles. This phys-
ical effect might also be a reason for the increased flexural
strength results recorded from NS-incorporated specimens.
Fig. 3(b) and Table 4 show that the average 2-day flex-
ural strength results of 15FP-NS and 15CP-NS were higher
than those of the control mixture. For 30FP-NS and 30CP-
NS, 2-day flexural strength results were almost the same as
the control mixture. For 45FP-NS and 45CP-NS mixtures,
2-day flexural strength results were smaller than those of the
control mixture. On the other hand, for almost all mixtures
with different sizes and replacement rates of pumice, late-age
(28- and 90-day) flexural strength results were either very
close to or higher than those of the control mixture. There-
fore, despite the variations in flexural strength results upon
replacing OPC with different amounts and sizes of pumice,
using NS can be advantageous to achieve results similar to
the control mixture at both early and late ages, as long as a
proper rate of pumice replacement is used.
Compressive strength
Average compressive strength results for specimens
subjected to 2, 7, 28, and 90 days of initial curing are
displayed in Table 4 and Fig. 3. The effect of HRWRA on
compressive strength results was eliminated by keeping the
HRWRA amount constant. For all predetermined testing
ages, individual compressive strength results of specimens
ACI Materials Journal/November 2018
belonging to each mixture were close to each other, with a
maximum COV value of 8% recorded for different mixtures.
The effect of pumice replacement with OPC on the
compressive strength results of mixtures without NS is
significant. Drastic drops in values with pumice incorpora-
tion were much more pronounced for early curing ages (2
and 7 days) and higher replacement rates (Fig. 3(c)). For
example, the 2-day average compressive strength result of
the control mixture decreased by 24%, 45%, and 61% when
FP was replaced with 15%, 30%, and 45% OPC, respec-
tively. Almost the same rates of decrement were noted when
CP was used instead of FP for the given replacement levels.
Decrements observed in the early-age compressive strength
results of mixtures with pumice were due to reduced OPC
amount and its negative effects on the rate of hydration and
pozzolanic behavior, as mentioned previously. Additionally,
the porous nature of pumice is likely to influence early-age
compressive strength results before pozzolanic reactions
start to become decisive on strength gain. However, despite
the lower average 2-day compressive strength results noted
from pumice-blended mixtures compared to the control
mixture, there were consistent increments in values with
prolonged age thanks to the continuous microstructural
development of mixtures as a result of pozzolanic reactions.
After 7 days of initial curing, the lowest average compres-
sive strength value was 22.2 MPa (3.22 ksi) (45FP). At 28
days, the lowest average compressive strength value was
35.9 MPa (5.21 ksi) (45CP). Although it was not possible to
obtain the value of the control mixture after 28 days (58.2 MPa
[8.44 ksi]), even the lowest average compressive strength
result obtained at a pumice replacement rate of 45% was
more than required (30 MPa [4.35 ksi]) for most conven-
tional construction practices.
When compared to the control mixture, pumice-incor-
porated mixtures showed clear differences in the rates of
increment in the average compressive strength results with
time. This behavior was independent of pumice fineness and
became clearer at higher pumice replacement levels. For
example, between the ages of 2 and 90 days, the average
compressive strength of the control mixture increased by
114% (from 30.0 to 64.1 MPa [from 4.35 to 9.30 ksi]), while
the increment levels for the same period for 15FP, 30FP and
45FP were 169% (from 22.8 to 61.3 MPa [3.31 to 8.89 ksi]),
260% (from 16.4 to 59.0 MPa [2.38 to 8.56 ksi]), and 329%
(from 11.6 to 49.8 MPa [1.68 to 7.22 ksi]), respectively. This
behavior is associated with the increased pozzolanic capacity
of pumice-incorporated mixtures, which require longer
curing periods to be more evident. Another explanation for
the behavior of mixtures containing pumice could be the
effect of internal curing. Pumice is a porous material with a
high number of micropores, even at the ground state.25 It is
therefore likely that some mixing water was absorbed by the
pumice particles during mixing of ingredients. The portion of
absorbed mixing water released to the cementitious systems
at late ages can promote the hydration and pozzolanic reac-
tions through the internal curing effect, leading to faster gains
in strength for pumice-incorporated mixtures. With further
curing, the rates of increment noted for the average compres-
sive strength results of mixtures containing pumice were
975
always higher than those noted for average flexural strength
results. The most probable reason for this trend is the fact that
flexural strength test results range in comparatively tighter
intervals and are governed by more complex material prop-
erties, such as tensile first cracking strength, ultimate tensile
strength, and tensile strain capacity.26
When NS was used in proportioning, general incre-
ments were observed in the average compressive strength
results of mixtures, similar to those seen in flexural strength
results. Adding NS did not make marked contributions to
the average compressive strength results of the control
mixture at the end of all curing ages. However, its effect on
pumice-blended mixtures was more pronounced. It should
be noted that the degree of effectiveness of NS addition in
increasing average compressive strength results of pumice-
blended mixtures depended on age and pumice replacement
rate with OPC. For example, the beneficial effects of NS
addition started to be visible after 2 days of initial curing
for replacement rates of 15% and 30%, while a similar
tendency was observed after 7 days of initial curing for a
replacement rate of 45%. After 2 days of curing, average
compressive strength results of 15FP-NS and 15CP-NS
were 28.1 and 27.4 MPa (4.08 and 3.97 ksi), respectively,
and after 7 days, the values were 44.6 and 42.5 MPa (6.47
and 6.16 ksi), respectively—very close to the compres-
sive strength results of the control mixture, which were
30.0 MPa (4.35 ksi) at 2 days and 44.7 MPa (6.48 ksi)
at 7 days. Average 2-day compressive strength results
of 30FP-NS and 30CP-NS were in the range of 20 MPa
(2.90 ksi), reaching an average of 36.5 MPa (5.29 ksi) after
7 days. On the other hand, 45FP-NS and 45CP-NS were not as
efficient as specimens with lower pumice replacement rates
in modifying microstructural properties to attain compres-
sive strength results similar to that of the control mixture at 2
and 7 days of curing (Table 4 and Fig. 3). However, even the
lowest average 28-day compressive strength recorded from
NS-incorporated mixtures with different pumice replace-
ment rates and fineness levels was 45.3 MPa (6.57 ksi)
(45CP-NS), which was more than enough for many common
construction applications and can be regarded as high-
strength. For explanations into the possible action mecha-
nisms of NS in improving compressive strength, please refer
to the earlier section on flexural strength.
Fig. 4—Rate of heat of hydration for mixtures with pumice
HYDRATION CHARACTERISTICS replacements levels of: (a) 15%; (b) 30%; and (c) 45%.
Heat of hydration
cantly more pronounced at higher replacement levels. Total
Figure 4 plots the isothermal calorimetry heat profiles,
amounts of heat release noted for pumice-blended mixtures
which show the heat of hydration per gram of paste mixtures
were also substantially lower than that of the control mixture
in the first 72 hours of hydration. The total amounts of heat
(Table 4). For example, after 24 hours of hydration, the total
evolved after 24 and 72 hours of hydration are summarized
amount of heat evolved for the control mixture decreased by
in Table 4 for all pastes. Depending on mixture proportions,
8% (from 917 J to 843 J), 24% (from 917 J to 697 J), and
there were clear differences in heat profiles and total amount
39% (from 917 J to 561 J) upon replacement of OPC with
of heat release due to pumice replacement rate and use of
FP by 15%, 30%, and 45%, respectively. Reflections of the
NS. There were clear reductions in the rate of heat evolu-
reduced hydration heats noted for pumice-blended mixtures
tion of the control mixtures when pumice was replaced
are also traceable from strength measurements. The lower
with OPC. Figure 4 indicates that, regardless of fineness,
amounts of heat evolvement were anticipated, given the
pumice incorporation led to smaller heat-of-hydration peaks
slow reaction rate of pumice and the OPC dilution effect on
than in the control mixture. This behavior became signifi-
pumice replacement.

976 ACI Materials Journal/November 2018

 Figure 4 and Table 4 clearly demonstrate that incorpo-
rating NS increased heat-of-hydration peaks and total heat
release, regardless of mixture type. Furthermore, NS caused
heat-of-hydration curves to shift to the left side, limiting
dormancy and reducing the time necessary for reaching
initial set, all of which pointing out to faster reactivity.
This finding, which was also realized in terms of strength
measurements (as previously discussed), was expected and
in line with other studies.27,28 Interestingly, the percental
differences in total heat release of the control and pumice-
based blended mixtures with NS were different. For example,
after 24 hours of curing, the total amount of heat release of
the control mixture increased by 29% (from 917 J to 1185 J)
with NS addition. After the same curing period, the rates
of increment with NS were 31%, 31%, and 46% for 15CP
(from 782 J to 1023 J), 30 CP (from 680 J to 894 J), and
45CP (from 577 J to 845 J) mixtures, respectively. Similar
rates were also noted for FP-blended mixtures and for
72 hours of curing. Despite the higher rates of increment in
total heat release results, however, similar rates of increment
were not noted from strength measurements (especially
compressive strength) of mixtures with and without NS,
especially at 45% pumice replacement level. This might be
related to the availability of portlandite (CH) in the mixtures
at early ages. As will be explained in the following sections,
when the replacement rate of OPC with pumice increases,
CH amount drops. Although adding NS into pumice-blended
mixtures may contribute to higher rates of heat release due
to the beneficial effects of NS in reducing the time needed
for pozzolanic reactions, gains in strength may not be as
complete due to the differences in strength levels of pozzo-
lanic and hydration-originated C-S-H gels. Portland cement
hydration is a process of dissolution-precipitation,29 and the
acceleration of this process can be monitored by the evolu-
tion of pH value and electrical conductivity, which reveal
the ionic concentration of the paste solution. Hou et al.28
showed that NS incorporation into cement paste results in
increments in pH values and electrical conductivity at early
ages, implying faster dissolution of cement particles. This
increment, again at early ages, was followed by sharper
decrements in electrical conductivity for specimens with
NS, which was attributed to the adsorption of ions by C-S-H
gels, indicating higher amounts of gel formation.30 Early-age
hydration can be nourished when uniform distribution of
small particles (for example, NS), which act as nucleation
sites, is achieved.27,31,32 It can therefore be stated that the
effectiveness of NS use in hydration acceleration is attained
with the help of high pozzolanic activity in very early ages,
which generates C-S-H gel and then acts as nucleation sites
to accelerate cement hydration.
In terms of its effect on the rate of heat of hydration,
pumice fineness was not of critical importance; the heat
profiles of mixtures with fine and coarse pumice were rela-
tively similar, irrespective of NS level (Fig. 4). A similar
trend was also observed for the total amount of heat release
after 24 and 72 hours, although FP replacement with OPC
resulted in slightly higher total heat release results. Given
the similarities of both heat profiles and the total amount of
ACI Materials Journal/November 2018
heat evolvement from using pumice with different fineness
levels, no detailed information was provided herein.
X-ray diffraction (XRD)
X-ray diffraction results alone are not sufficient for quan-
titative analysis of hydration products, due to factors such as
grain size and preferred orientation.33 However, it is possible
to identify main hydration products and observe the change
in relative levels of different phases. Consequently, XRD
results are commonly used to identify the hydration char-
acteristics of cementitious composites.34 Accordingly, to
complement the changes in microstructural properties, XRD
analyses were used to characterize hydration reactions. XRD
patterns of pastes at 2, 7, and 28 days are shown in Fig. 5.
This figure includes only the XRD patterns of speci-
mens with CP due to the similarities with FP. The 2θ values
obtained by the XRD analyses were evaluated and compared,
taking into consideration the values stated in literature,35-37
which state that 2θ values of approximately 9 and 23 degrees
coincide with the presence of ettringite; 18, 28, 34, 47, and
54 degrees coincide with the presence of portlandite (CH);
29 degrees coincides with the presence of calcium carbonate
(CaCO3) and 32, 33, 41, 42, and 51 degrees coincide with
the presence of C3S and C2S compounds of portland cement.
The XRD patterns in Fig. 5 show peaks of portlandite,
ettringite, and calcium carbonate, as well as anhydrous
phases. There were clear differences in the XRD peaks of
mixtures depending on the rate of CP replacement with
OPC, initial curing age, and NS addition. XRD results
revealed that portlandite peaks become less pronounced
with increased levels of CP replacement for a given initial
curing age, most probably due to reduced amounts of OPC
being hydrated. There was a general incremental trend in the
amount of portlandite with prolonged curing age, although
this does not appear to be the case for all CP replacement
levels. According to Fig. 5, for 15CP and 30CP mixtures,
CH peaks observed after 2 days become more and more
pronounced until the age of 28 days as a result of contin-
uous hydration reactions. However, for 45CP, densification
observed in the CH peaks did not last until 28 days, with
less pronounced CH peaks noted compared to 2- and 7-day
measurements. This behavior was attributed to the enhanced
pozzolanic capability of 45CP, which further reduced CH
amounts until the age of 28 days.
Adding NS reduced the intensity of CH peaks regard-
less of mixture type for all mixtures, thanks to the highly
pozzolanic nature of NS with its seeding effect.16 It should
be noted that the reduced intensity of CH peaks was observ-
able even at the age of 2 days, which suggests that pozzo-
lanic behavior can be effective even at the very early ages
of curing in the presence of NS.24 Although the CH peaks of
NS-incorporated specimens were less intensive compared to
those without NS at 2 days of initial curing, the reduction in
the intensity of the peaks dropped sharply after prolonged
curing ages and higher CP replacement levels, as seen in
Fig. 5. This may be due to the simultaneous effect of higher
amounts of CP and NS on consuming CH for further C-S-H
gel formation.
977

Fig. 5—X-ray diffraction patterns of paste samples after
different curing ages.
Thermogravimetric analyses (TGA/DTA)
Microstructural developments of mixtures were also backed
with thermogravimetric analyses (TGA/DTA) conducted on
pastes by focusing mainly on the total amounts of CH and
bound water at curing ages of 2, 7, and 28 days. The results
are provided in Fig. 6 for mixtures with FP and CP.
978
Fig. 6—Results of TGA/DTA analyses of paste samples after
different curing ages.
Similar to the findings reported for XRD analyses, the
percental CH amounts of mixtures decreased with increased
pumice replacement level because of reduced OPC amounts;
this trend was independent of pumice fineness. This is also
in line with the strength measurements and heat-of-hydra-
tion profiles of mixtures with different amounts of pumice,
as explained earlier. The TGA confirmed the abovemen-
tioned XRD findings in that there were clear increments in
CH amounts with further curing until the end of 28 days.
However, this was not the case for 45CP and 45FP. For these
mixtures, CH amounts increased until the end of 7 days,
followed by decrements after 28 days (Fig. 6), most prob-
ably due to pozzolanic reactions at later ages with higher
amounts of pumice further binding CH.
Marked reductions in CH amounts were noted with NS
incorporation, regardless of age, level of pumice replace-
ment, and pumice fineness. Figure 6 shows reductions with
varying rates in CH amounts of 2-day-old specimens when
NS was used. This also validates XRD findings and shows
that pozzolanic capacity in the presence of NS can be trig-
gered even at the very early stages of hydration.
ACI Materials Journal/November 2018
 Figure 6 also shows that the amounts of bound water
varied depending on mixture parameters (that is, initial
curing age, pumice replacement, and pumice fineness).
However, it can be generally stated that any parameter influ-
encing the further progress of C-S-H gel formation seems
to increase the total amounts of bound water obtained as
a result of TGA/DTA analyses. For example, there was a
general incremental trend in the amount of bound water with
further curing, reduced pumice replacement for a given age,
and use of NS. These results correspond with the study of
Prochoń and Piotrowski,38 who concluded that the degree of
hydration has an almost linear correlation with the amount
of bound water.
CONCLUSIONS
This study investigated the properties of natural pozzolan
(volcanic pumice) based blended cements with and without
nanosilica (NS) by taking a close look at workability,
mechanical, microstructural, and hydration characteris-
tics. Mixtures were blended with coarse (CP) and fine (FP)
volcanic pumice powders at OPC replacement levels of
15%, 30%, and 45% by weight. Mini-slump flow measure-
ments, flexural and compressive strength tests, isothermal
calorimeter, XRD, and TGA/DTA analyses were performed
to assess the performance of mixtures, and the following
conclusions were drawn:
• At a constant rate of HRWRA use, replacing OPC with
pumice powder up to 45% did not have any negative
impact on the mini-slump flow values of the control
mixtures. NS addition into both control and pumice-
based blended mixtures reduced flow values, irrespec-
tive of the amount and fineness of pumice, although the
mixtures still had adequate workability and flow values
were at levels that could easily be adjusted with slight
modifications in HRWRA amounts.
• After different initial curing ages, flexural and compres-
sive strength results of the control mixtures decreased
when OPC was replaced with pumice. This behavior
became more pronounced at higher levels of replace-
ment and was irrespective of pumice fineness. NS
addition into pumice-based blended mixtures enhanced
both flexural and compressive strength measurements.
Two- and 7-day strength measurements of NS-incor-
porated mixtures with OPC replacement of 15% were
either higher or similar to that of the control mixture.
Although the average 2- and 7-day strength measure-
ments of NS-incorporated mixtures with OPC replace-
ment of 30% were lower than that of the control mixture,
the lowest 2-day flexural and compressive strength
results were 4.9 MPa (0.71 ksi) and 20.6 MPa (2.99 ksi),
respectively, which are acceptable values for many
civil engineering applications with early-age strength
requirements. Adding NS into mixtures with OPC
replacements of 45% did not make substantial improve-
ments on 2-day strength measurements, although 7-day
compressive strength results of 28.5 MPa (4.13 ksi)
were achieved.
• Total amount of heat release decreased upon OPC
replacement with pumice, regardless of fineness. The
ACI Materials Journal/November 2018
rate of decrement became much more pronounced at
higher levels of replacement. With incorporation of NS,
total amounts of heat release increased, irrespective of
mixture type. After 24 hours, in which most of the heat
was released, total amounts of heat evolvement were
either less than or similar to that of the control mixture
with NS.
• Results of XRD and TGA/DTA analyses confirmed the
changes in compressive and flexural strength results and
hydration characteristics of mixtures were based on the
replacement levels of pumice with OPC and presence of
NS. Different pumice fineness levels were not as deci-
sive on mixtures properties, which was also confirmed
by similar results from different XRD and TGA/DTA
analyses.
AUTHOR BIOS
Gürkan Yıldırım is an Assistant Professor at the Department of Civil
Engineering in Kırıkkale University, Kırıkkale, Turkey. His research
interests include the development of composite materials for sustainable
infrastructures.
Burak Dündar is a Civil Engineer at The Scientific and Technological
Research Council of Turkey, Ankara, Turkey. His research interests include
the use of nanomaterials and supplementary cementitious materials in
cement-based composites.
Burhan Alam is an Instructor at the Department of Civil Engineering in
Middle East Technical University, Ankara, Turkey. His research interests
include the use and characterization of supplementary cementitious mate-
rials in cement-based materials.
İsmail Özgür Yaman is a Professor at the Department of Civil Engineering
in Middle East Technical University, Ankara, Turkey. His research interests
include nondestructive evaluation of concrete structures with emphasis on
ultrasonic testing and sustainability of construction materials.
Mustafa Şahmaran is a Professor at the Department of Civil Engineering
in Hacettepe University, Ankara, Turkey. His research interests include
advanced materials technology and composite materials development for
sustainable infrastructure.
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