Cement and Concrete Composites 71 (2016) 53e62

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Cement and Concrete Composites

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

The inuence of mechanical activation by vibro-milling on the earlyage hydration and strength development of cement
Konstantin Sobolev a, *, Zhibin Lin b, Yizheng Cao c, Hongfang Sun c, Ismael Flores-Vivian d,
Todd Rushing e, Toney Cummins e, William Jason Weiss f
a

Civil and Environmental Engineering, University of Wisconsin e Milwaukee, Milwaukee, WI 53211, USA
Civil and Environmental Engineering, North Dakota State University, Fargo, ND 58102, USA
School of Civil Engineering, Purdue University at Lafayette, West Lafayette, IN 47907, USA
d
s de los Garza, 66455 Nuevo Leo
noma de Nuevo Leo
n, Av. Universidad s/n, Cd. Universitaria, San Nicola
n, Mexico
Universidad Auto
e
U.S. Army Engineer Research and Development Center, Vicksburg, MS 39180, USA
f
Civil & Construction Engineering, Oregon State University, 1491 SW Campus Way, Corvallis, OR 97331, USA
b
c

a r t i c l e i n f o

a b s t r a c t

Article history:
Received 3 August 2015
Received in revised form
21 April 2016
Accepted 26 April 2016
Available online 27 April 2016

This paper presents results from an experimental investigation that evaluated the mechanical activation
of portland cement using vibro-milling. In this investigation, the duration of the vibro-milling was
systematically varied and its inuence was evaluated using mortar samples. In addition, the amount of
activated cement used in the mortar samples was varied and evaluated. X-ray diffraction (XRD) and
scanning electron microscopy (SEM) were used to evaluate differences in hydration products and the
structure of activated cement and mortars. The activated cements were tested to determine the inuence
of activation on the rate of hydration and compressive strength development. The test results suggested
that the use of mechanical activation can improve early-age structure formations and compressive
strength. A 32% and 25% increase in 1-day strength were observed for the systems with Type I and Class
H cements, respectively. This increase in 28-day strength was 16% and 58% for Type I and Class H cement,
respectively. It was observed that longer milling times did not necessarily improve performance, and
15 min appeared to be sufcient vibro-milling time to provide valuable benets.
2016 Published by Elsevier Ltd.

Keywords:
Mechanically activated cement
Vibro-mill
Calorimetry
Compressive strength
Degree of hydration

1. Introduction
World-wide production of portland cement has increased by
approximately 50% during the past decade [1,2] due to growing
demand for infrastructure development and renewal. This trend is
a signicant factor that inuences the technological development
of manufacturing facilities in the cement industry. In addition to
market pressure for cement, there has been increasing attention to
the environmental impacts associated with the manufacturing of
cement with specic focus on the amount of energy and natural
resources consumed and the volume of pollutants, like CO2, NOx,
and SOx, emitted in the production process. As a result, there can be
substantial benets in producing cements with high early strength,
improved tensile/exural strength, and improved performance,
since advanced characteristics enable the carbon footprint of the

* Corresponding author.
E-mail address: sobolev@uwm.edu (K. Sobolev).
http://dx.doi.org/10.1016/j.cemconcomp.2016.04.010
0958-9465/ 2016 Published by Elsevier Ltd.

overall structure to be reduced. It is well known that use of supplementary cementitious materials, such as y ash (FA) and ground
granulated blast furnace slag (GGBFS) can result in signicant
performance, environmental and economic benets [2e10]. For
example, enhancement of mechanical properties and chloride ion
penetration was reported when GGBFS was used in binary and
ternary blended cement compositions [11,12]. While the use of
supplementary cementitious materials has become an important
development in modern concrete technology, it gives rise to
considerable technical challenges in fresh concrete, due to the
potential for delayed setting time and low rates of strength
development [13,14]. Fine grinding and mechanical activation
[8e10,15,16] have been suggested as effective methods to improve
the reactivity of the blended cement constituents [17e19]. The
surface area of solid materials is increasing during ne grinding,
which inuences the surface reactivity. Fine grinding not only
generates a larger surface area, but also results in the formation of
defects, surface changes that can increase the reactivity of the
material, and chemical activation [15,20,21]. The enhanced

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K. Sobolev et al. / Cement and Concrete Composites 71 (2016) 53e62

reactivity due to mechanical activation has the potential to improve

setting and early-age strength development of blended cementbased materials [8e10,17e19,22e24]. For these reasons, mechanical activation of cement has been the topic of several investigations
[15,17e26].
This paper explores the emerging concept of mechanical activation of cement [27]. Unlike dry grinding that has been used for
conventional cement, the proposed concept explores activation in
an aqueous medium. The activation in an aqueous medium may
result in mechanical activation as well as chemical activation due to
accelerated hydration and chemical transformations. Although the
overall effects of such activation and the addition of nano-scale
materials such as nanosilica, nano-clay, or SiO2-rich reactive powders [2,4e7], are not completely understood, the proposed concept
is promising.
Sobolev et al. [27] proposed that mechano-chemical activation
and nanocatalyst use in cement could intentionally tailor cement
material properties (e.g., the higher densication of binder due to
the help of ultrane particles), thereby improving its performance.
This concept is based on the introduction of super-ne, submicroor nano-sized binders into conventional cement systems. In order
to improve the pozzolanic potential and the reaction ability of
mineral additives, super-ne grinding of these materials was proposed to signicantly increase the surface area [25e27]. In another
study, nano-cement was produced by ultrasound treatment or
high-speed mixing and used in quantities up to 20% as an additive.
It was demonstrated that such activated cement materials speed
the reaction and help to increase the rate of strength development
at early ages.
The aim in this paper is to discuss results of a study that
investigated the effects of mechanical activation on the properties
of portland cement based mortars. Mechanical properties and
microstructural characteristics of activated cements were evaluated and compared with the properties of reference binders. This
work provides insight into the inuence of the activated cement on
the hydration kinetics, microstructure development, and mechanical properties of cement based materials.

Graded quartz sand (ASTM C778) and tap water were used to
produce mortar specimens.
2.2. Mechanical activation of cement
Mechanical activation was performed using vibro-milling
(vibro-energy grinding mill). The Type I OPC blended with water,
nanosilica, chemical admixtures (with a total weight of 6 kg) was
milled for 5, 15, 30, and 60 min using 32 kg of stainless grinding
media (mini-cylpebs of 10 mm in diameter and 20 mm in length).
The composition of the activated cement is described in Table 2.
To produce activated cement slurry, Type-I OPC was pre-mixed
with water and admixtures as reported in Table 2. The resulting
slurry was placed into the vibro-mill within 2 min (as counted from
the initial contact of cement and water) and milled for specic
durations. To control the transformations of AC during the milling,
small quantities (40 ml) of activated cement slurry were obtained
from the chamber at specied time intervals during the activation,
starting at 5 min and ending at 60 min. To compensate for the
material loss (about 1%) the collected slurry specimen was replaced
by the same volume of fresh (non-activated) slurry of the same
composition. Due to very small volume of fresh material injected, it
was assumed that the contribution of sample replacement on the
quality of AC can be neglected. To ensure the uniform distribution
of all components in the slurry and the overall quality of activated
cement, the obtained sample was placed into a beaker on a scale to
verify the target density of 1.53 kg/l and so to provide a measurement of the concentration. Due to the application of nanosilica, all
slurries were stable meeting the target water to solid ratio of 1.23.
The collected samples were further analyzed by x-ray powder
diffraction (XRD) and scanning electron microscopy (SEM). To
extend the shelf life of the activated cement, the suspension was
frozen and maintained at
10 5  C until the mortar was batched.
The activated cement obtained using this procedure was tested in a
standard mortar as practical replacement for OPC as described in
the following sections.
2.3. Mechanical activation and microstructure investigation

2. Materials and experimental matrix

2.1. Materials
A Type-I ordinary portland cement (OPC, ASTM C150) and a
Class H cement (HPC, API 10A) were used in this investigation. The
Bogue compositions and Blaine neness of the OPC and HPC are
reported in Table 1. When compared to OPC, Class H cement has
considerably higher content of C3S (63.8%) and, in spite of lower
specic surface area, provided slightly higher early-age and 28-day
strength. Typical X-ray diffraction for the OPC is plotted in Fig. 1.
A colloidal dispersion of nanosilica (NS, Cembinder-8; EKA
Chemicals) was used as a viscosity modier. This nano-silica had
approximately 50% of the particles by mass in a size range from 1 to
100 nm. Commercially available polycarboxylate superplasticizer
(SP) (PCE/SP, 31% concentration, Handy Chemicals) was used.

Table 1
Bogue composition of Type I and Class H cement.
Composition and properties

C3S (%)
C2S (%)
C3A (%)
C4AF (%)
C4AFC2F (%)
Blaine neness, m2/kg

54.5
17.9
7.9
8.2
e
380

63.8
13.0
e
e
12.6
316

To better understand how the mechanical activation inuenced

the chemical composition of the slurry, the collected samples of
activated cement slurry were studied using XRD with a Siemens
D500 Diffractometer and SEM using a Topcon SM300 scanning
electron microscope. The hydration of the activated cement slurry
was stopped by immersing the activated cement specimen into
isopropyl alcohol for 24 h followed by drying in an oven at 60  C for
24 h.
Fig. 1 presents the XRD patterns of the OPC and activated
cement after 15 and 60 min of activation. It can be observed that the
activated cement is composed of the same compounds (C2S, C3S,
C3A, and C4AF) as the reference OPC, with some differences
observed for C3S.
The highest peak (32e33 ) corresponds to the overlap of peaks
for C2S and C3S, which has a reduced intensity for the activated
cement when compared with the base OPC. A similar observation is
also evident at 42 and 52 . This can be explained by the preferential hydration of the C3S. The activated cement also contains
small quantities of portlandite, (18 ) for the 15 and 60 min vibromilling. While it is evident that the activated cement has signicant volumes of unhydrated phases, a small portion of the material
has reacted due to activation process.
SEM reveals that some of the activated cement is represented by
smaller rectangular particles in the size range of 1.5e28 mm
(Fig. 2(a)); however, after prolonged milling (more than 30 min), AC
forms the agglomerates which can reduce its performance

K. Sobolev et al. / Cement and Concrete Composites 71 (2016) 53e62

55

Fig. 1. XRD patterns of reference ordinary portland cement (OPC) and activated cement (AC) after 15 min and 60 min of vibro-milling.

Table 2
Composition of activated cement.
Type

AC

Composition, % by mass
OPC

Water

SP (as dry component)

Nanosilica

Tributyl phosphate

43.1

53.9

1.9

0.9

0.2

remaining six mixtures were prepared using the Class H cement. In

each series, a reference mortar was prepared (e.g., the Type I and
Class H sample, respectively). The additional samples denote mixtures that contain the activated cement. The rst number denotes
the amount of activated cement used, and the second number denotes the duration of time that the activated cement was in the

Fig. 2. SEM micrographs of activated cement (AC) after vibro-milling for (a) 15 min and (b) 60 min (2000  magnication).

(Fig. 2(b)). The formation of agglomerates can be explained by

accelerated depletion of gypsum and the formation of ettringite
and AFt phases which are observed with XRD at 9 and 23 .

2.4. Experimental test matrix

Table 3 shows the testing matrix and sample identication used
in this investigation. A series of nine mixtures were evaluated. The
rst three mixtures were made with Type I OPC while the

vibro-mill. For example, sample I20-15 denotes the mortar made

with Type I cement using 20% of activated slurry that was processed
for 15 min in the vibro-mill. In Table 3, I-C denotes the Type I
cement, H-C denotes the class H cement, S refers to sand, W refers
to tap water, and SP refers to superplasticizer. It should be noted
that the amount of SP refers to the total SP used, which is the sum of
SP in the activated cement and the SP added to the mortar.
The water-to-cementitious material ratio (w/c) of standard
mortars was 0.25, and the sand-to-cementitious material ratio (S/C)

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K. Sobolev et al. / Cement and Concrete Composites 71 (2016) 53e62

Table 3
Experimental matrix of the mortar mixtures with (a) Type I and (b) Class H cements.
(a)
Mix id

I target
I10-15
I20-15

AC slurry

Composition, g


Activation time (min)

Temperature at mixing ( C)

AC

I-C

NS

TP

SP

Total SP

e
15
15

e
28
28

e
596
1194

2600
2340
2080

3900
3900
3900

650
325
e

5.4
e
e

1.2
e
e

23.4
14.0
2.3

23.4
25.3
25.0

(b)
Mix id

H target
H10-5
H10-15
H10-30
H10-60
H20-15

AC slurry

Composition, g

Activation time (min)

Temperature at mixing ( C)

AC

H-C

NS

TP

SP

Total SP

e
5
15
30
60
15

e
28
e
28
24
26

e
596
596
596
596
1194

2600
2340
2340
2340
2340
2080

3900
3900
3900
3900
3900
3900

650
325
325
325
325
e

5.4
e
e
e
e
e

1.2
e
e
e
e
e

5.2
e
11.7
e
3.5
2.3

5.2
11.3
23.0
11.3
14.8
25.0

was 1.5. The activated cement mortars were compared with identical (composition wise) mixtures based on OPC; therefore, the
reference OPC mortars were prepared with the same quantities of
chemical admixtures and nanosilica used in the mortars with 10%
of activated cement (denoted as I target, Table 3a). It should be
noted that the same activated cement based on the Type I OPC was
used in the mortars based on Type I OPC and Class H cements. The
activated cement slurry was added to the mortars replacing 10% or
20% of cement by mass. When the same mixture proportions were
used to compare the activated cement mortars with reference Class
H cement mortars (denoted as H target, Table 3b), the Class H
cement mixtures H10-15 and H20-15 had a greater workability.
Therefore, lower dosage of SP was used in the remaining Class H
cement mortars (including reference) as reported in Table 3b.
Table 3 provides the detailed mixture proportions of the mortars.
Due to addition of nanosilica and ultrane milling of AC all tested
mixtures had excellent workability and low segregation.

diameter tube container that was 52-mm tall (Fig. 3). Two 2.4mm diameter steel rods were inserted into the predrilled holes of
the nonconductive plastic lid to serve as electrodes with a spacing
of 20 mm between the rods as demonstrated in Fig. 3. After mixing,
the mortar was placed in the molds, external vibration was applied
to consolidate the mortar, and the lid was sealed using a nonconductive tape. For each mixture, two impedance specimens
were prepared.
The specimens for compressive testing were cast in plastic cylinder molds with inner diameters of 5.1 cm and heights of 10.2 cm.
External vibration was used to consolidate the mortar, and the
cylinders were sealed until the age of testing, either 1, 7, or 28 days.
Two specimens were tested at each age and the average strength
reported.

2.5. Mixing procedures, mortar preparation, and proportions

The hydration kinetic was investigated using isothermal calorimetry, while the physical properties were examined using electrical impedance and compressive strength testing. A description of
each of these testing procedures is described below.

Mixing was performed in accordance with ASTM C305 with a

few minor exceptions. First, all of the components with the
exception of the activated cement slurry were placed in the mixing
bowl, and the conventional mixing procedure (ASTM C305) was
used. After the completion of the mixing procedure, the activated
cement slurry was placed into the mixing bowl; the mortar samples
were prepared following the ASTM standard C305 with an extra
3 min of mixing at the end of the nal mixing step. The revolution
speed of the extra mixing is the same as the nal step of mixing in
C305, which is 285 10 rpm/min.
Unless noted otherwise, all of the experiments described in this
paper were performed at room temperature (23 2  C). The
experimental procedures are described in the following sections.

3. Experimental testing procedures

2.6. Specimen preparation

After mixing, the samples were poured into molds to cast the
specimens that were used for testing. The isothermal specimens
were prepared immediately and taken to the calorimeter while the
remaining specimens were being cast. The isothermal calorimetry
specimens consisted of placing approximately 15 g of the mixed
mortar in a glass vial that was maintained at a temperature of
23 0.1  C. The mortar in the vial was rodded, and then the vial was
sealed, weighed, and placed in the isothermal calorimeter.
The electrical impedance apparatus consisted of a 34-mm

Fig. 3. Electrical impedance spectroscopy mold used for resistivity measurement

(Note: the non-conductive tape that was used to seal the top of the chamber is not
shown).

K. Sobolev et al. / Cement and Concrete Composites 71 (2016) 53e62

57

3.1. Calorimetry

3.4. Compressive strength

The rate of heat and cumulative heat generation was assessed

using a TAM Air isothermal calorimeter with a stable baseline.
Immediately after mixing, approximately 15 g of the mortar was
transferred to a glass vial (22-mm diameter and 55-mm height),
sealed, and placed into a chamber (maintained at 23 0.1  C) to
conduct 60-h testing. Before the data collection was started, the
isothermal specimen was held for 45 min to reach equilibration and
perform steady heat measurement. It should be noted that the
isothermal calorimeter does not capture the hydration reaction that
may have occurred in the activated cement during processing or
during the rst 60 min after water was added to the cement in the
mixer.

Compressive strength was measured by breaking specimens

after 1, 7, and 28 days of curing using a Forney FX700 compression
machine following the procedure outlined in ASTM C-39. The
specimens were maintained in the molds and kept sealed until age
of testing. At the age of testing, the appropriate specimens were
removed from the molds, and the two ends of the specimen were
cut using a diamond tipped saw to insure that the two ends were
parallel. The ends were then ground smooth. Two Teon sheets
with thickness of 0.002 in. (0.05 mm) were placed between the
specimen and the platens to reduce the friction. Two specimens
were tested for each age and the average strength of the two tests
was recorded.

3.2. SEM (scanning electron microscopy)

4. Results and discussion

BSE (Backscattering electron) investigation performed with a

SEM device was used to observe the microstructure of AC mortars
at the age of 28 days. BSE observation requires specimens to have a
at surface with minor roughness. After mixing, the mortar was
transferred to a plastic cylinder mold (22-mm diameter, 55-mm
height), sealed, and cured at 23  C. At the desired curing age, the
specimens were cut into 5-mm-thick slices and immersed in
methanol to stop the hydration process. After oven-drying for at
least 24 h, the pieces were epoxy saturated under a low vacuum
and held at 70  C for 8 h. Then the specimens were cut with a lowspeed saw to expose a fresh surface. The fresh surface was then
polished using 15-, 9-, 3-, 1-, and 0.25-mm diamond paste on top of
Texmet paper for 4 min each. Before loading the specimens into the
SEM chamber, the specimens were gold coated to form a conductive surface. SEM was conducted on a FEI Quanta 3D with a eld
emission gun working at 20 kV.

The following sections discuss the results of the isothermal

calorimetry, electrical impedance, and compressive strength
testing.

3.3. Electrical impedance spectroscopy

A Solartron SI 1260 Impedance/Gain-phase Analyzer was used
for the electrical impedance measurements. The electrical impedance of the cast specimens was measured continuously to obtain
the resistance as a function of aging time. The measurements were
taken over a range of frequencies from 106 to 1 Hz in the direction
of decreasing frequency. The measuring voltage was 500 mV. The
electrical impedance measurement container [28] is displayed in
Fig. 3.
A total of 18 specimens were tested. The measurements were
performed by measuring each of the 18 specimens in turn. After
each cycle of 18 measurements, the measurements were restarted
from the rst specimen. Each measurement requires approximately
70 s per specimen. This implies that each specimen was measured
approximately every 20 min. The cyclical measurements continued
for 200 h or a little more than 8 days. The imaginary and real
impedance of each specimen was recorded.
The electrical impedance for each specimen was plotted using a
Nyquist plot [29] (the absolute value of imaginary impedance
versus real impedance). The resistance is determined at the point
that corresponds to the minimum imaginary impedance. The
average of the two specimens is used as the average resistance for
these mixtures. The resistivity (r can be calculated using Equation
1

R
K

r ;

(1)

where R is the measured electrical resistance (ohms) and K the

geometry factor (22.15 m
1) [28].

4.1. Isothermal calorimetry

Calorimetry was performed since the hydration of cement is an
exothermic reaction and the rate of heat evolution (dQ) and cumulative heat evolution (Q) reect the rate of hydration and degree
of hydration, respectively. The degree of hydration (DOH) was
estimated by the ratio Q/Q, where Q represents the cumulative
heat given off in a particular time and Q represents the theoretical
amount of heat that is generated when the cement is fully hydrated.
Q can be calculated by multiplying the theoretical value of each
hydration component (C3S, C2S, C3A, and C4AF) by the proportion of
respective component [30].
The inuence of AC processing time is illustrated using the cumulative heat and DOH of Class H series as reported in Fig. 4. In this
study, after preliminary testing (mixtures H10-15 and H20-15), the
superplasticizer (SP) dosages were adjusted for the mixtures H,
H10-5, H10-30, H10-60 (Table 3b) to reduce the ow to the levels
observed with OPC based mortars and minimize the potential
segregation. To analyze the hydration process, the dosage of SP has
to be considered along with the content of AC, since both can inuence the rate of hydration. To evaluate the effect of SP on the rate
of hydration, plain Class H mortar specimens were prepared with
varied SP level, including 0.2%, 0.4%, 0.6%, and 0.9% by weight of
cement, consistent with the dosage used in the Class H series
(Table 3b). The measured calorimetry results of those specimens
are reported in Fig. 4(a). The age at which each specimen gave off a
cumulative heat of 50 J/g was plotted vs. SP content, Fig. 4(b). It can
be observed that the age to reach 50 J/g of cement almost increases
linearly with the dosage increment of SP. This indicates that SP acts
as a retarder in the early hydration and can inuence the hydration
dramatically. The plots of the rate of heat evolution and cumulative
heat evolution in Fig. 4(a) and (b) demonstrate the inuence of AC is
a combined effect of both grinding and SP. In order to assess the
inuence of the SP, the results of the Class H specimens were
shifted using a value of t* to account for the retardation caused by
SP as demonstrated in Fig. 4(c). The values of t* are taken as the
difference between the age of the specimens to be studied to reach
50 J/g and the age of H-SP-0.2% mixture to reach 50 J/g. This means
that the H-SP-0.2% specimen is considered as a reference and all
other specimens are corrected accordingly. The curves in Fig. 4(c)
are corrected to demonstrate that this approach appears to be a
reasonable method to account for the inuence of the SP.
This correction of the SP dosage was also applied to the Class H
series specimens where both plasticizer and grinding were varied

K. Sobolev et al. / Cement and Concrete Composites 71 (2016) 53e62

200

H, SP% = 0.4%
H, SP% = 0.6%
H, SP% = 0.9%

150
30
100

20
H, SP% = 0.2%
H10-5, SP% = 0.4% 10
H10-15, SP% = 0.9%
H10-30, SP% = 0.4%
H10-60, SP% = 0.6%
0
48
60

50

0
0

12

24

36

t (h)
(a)
40
35
30
25
20
15
10

Cumulative heat evolution

(J/g of cement)

Age to reach 50 J/g of cement (h)

40

DOH (%)

Cumulative heat evolution

(J/g of cement)

58

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

SP content (%)
(b)
200

4.2. Assessment of microstructure

150

100

H,
H,
H,
H,

50

0
0

12

24

36

SP%
SP%
SP%
SP%

=
=
=
=

48

0.2%
0.4%
0.6%
0.9%
60

t-t* (h)

(c)
Cumulative heat evolution
(J/g of cement)

as a way to ascertain the inuence of the mechanical grinding. The

cumulative heat curve of the H, H10-5, H10-15, H10-30, and H10-60
mortars were corrected using corresponding t* as demonstrated in
Fig. 4(d) for the same SP level. When this correction was applied to
the H, H10-5, H10-15, H10-30, and H10-60 mortars, it helped to
eliminate the inuence of SP thereby enabling the inuence of
grinding to be more clearly seen. According to Fig. 4(d), the hydration was accelerated as the grinding time increased from 5 min
to 15 min. However, further increases in grinding time to 30 min
and 60 min had a little effect, or even a negative effect, on the
hydration due to the competition between the acceleration caused
by the additional grinding and deceleration caused as a result of the
partial hydration (Fig. 1) and agglomeration (Fig. 2) that takes place
during the additional grinding process. In this regard, the activation
time of 15 min for AC composition is selected as optimal.
The inuence of AC content was studied with Class H cement
(Fig. 5) as well. The aforementioned method [as summarized by
Fig. 4(c)] was used to re-plot the data demonstrating that an increase of AC content from 10% to 20% reduces the age to release the
same cumulative heat, indicating the acceleration of hydration due
to the AC addition within the initial 60 h.
A similar trend was observed in mortars with Type I cement
(Fig. 6) demonstrating a faster rate of reaction of the system with
20% activated cement as compared to the system with 10%. It
should also be noted that unlike the class H series that had a similar
overall heat release after 60 h, the heat evolved was higher with the
system that contained 20% AC. When compared with plain Type I
mortar, the addition of AC accelerates the early hydration of the
initial 15 h for I10-15 and 22 h for I20-15 [Fig. 6]. After that, the
plain Type I mortar catches up and exceeds the value of I10-15 and
slightly exceeds the value for I20-15.

200

150

100
H
H10-5
H10-15
H10-30
H10-60

50

0
-24

-12

12

24

36

48

The BSE images of H, H10-15, and H20-15 mortars after 28 days

of curing are reported in Fig. 7. The porosity (as determined from a
pixel pitch of 0.3 mm) was assessed using reported BSE images
(single measurement for each reported image). Plain H mortar had
a structure with porosity of 13.7%. The addition of 10% AC (H10-15)
reduced porosity down to 9.8% through lling out the voids with
smaller ground unhydrated particles or extra CeSeH formed due to
the improved hydration. Increase of AC content to 20% reduced the
porosity further to 7.7% and formed a very dense structure. Thus,
the introduction of AC to Class H cement decreases the porosity and
improves the packing of initial particulate blend, indicating a potential enhancement of compressive strength.
For the Type I cement series, the BSE images are summarized in
Fig. 8. Much higher porosity values were obtained in this series. The
I10-15 and I20-15 mortars with 10% and 20% of AC addition had
slight reduction of porosity from 30.7% (I) to 27.22% and 28.2%,
respectively. Therefore, no signicant difference of porosity was
observed in I10-15 and I20-15 mortars.
4.3. Electrical impedance spectroscopy (EIS)

60

t-t* (h)

(d)
Fig. 4. The inuence of SP content and grinding time on the hydration of Class H
cement. (a) Cumulative heat evolution vs. age. Class H mortars were prepared with
varied SP levels (0.2%, 0.4%, 0.6%, and 0.9%) as standards. (b) The age of the mixtures
listed in (a) to reach 50 J/g of cement vs. SP content. (c) The adjusted cumulative heat

The EIS technique has been used to investigate the microstructural evolution during cement hydration [32e37]. The electrical
properties of hydrating cement based materials are inuenced by
the volume of uid lled pores, the pore solution chemistry, and
the tortuosity of the pores. As the system hydrates, the pore volume

curves to account for the SP dosage. (d) The correction extension to Class H series
mixtures with variation of grinding time; the inuence of SP is considered to have
been eliminated.

200

H, SP% = 0.2%
H10-15, SP% = 0.9%
H20-15, SP% = 0.9%

150

59

40

30
100

20

50

DOH (%)

Cumulative heat evolution

(J/g of cement)

K. Sobolev et al. / Cement and Concrete Composites 71 (2016) 53e62

10
H, SP% = 0.9%

0
0

12

24

36

48

60

t (h)

Cumulative heat evolution

(J/g of cement)

(a)
200

150

100

50

0
-24

H
H10-15
H20-15
-12

12

24

36

48

60

t-t* (h)

(b)

200

40

150

30

100

20

50

I, SP% = 0.9%
I10-15, SP% = 0.9%
I20-15, SP% = 0.9%

0
0

12

24

36

48

DOH (%)

Cumulative heat evolution

(J/g of cement)

Fig. 5. The inuence of AC slurry content on Class H series. (a) Cumulative heat evolution and (b) the normalized data to eliminate the inuence of SP.

10

60

Age (h)
Fig. 6. Inuence of AC content on Type I cement.

decreases due to the formation of solid hydration products leading

to an increase in the electrical resistivity. The pore solution in
cement paste can be inuenced by ionic species like K, Na, OH[31], which dramatically inuence the pore solution conductivity.
Before the conventional cementitious system can be compared
with the system containing AC materials, an understanding of the
inuence of the grinding activation on the pore solution chemistry
is needed. The resistivity of nanosilica (CB), superplasticizer (SP),
and tributyl phosphate (TP) were measured (along with tap water)
as listed in Table 4.
According to the test results, the nanosilica solution (CB) is
highly conductive. As a result, the pore solutions in the AC mortar

Fig. 7. SEM images of three Class H cement mixtures with AC at the age of 28 days.

60

K. Sobolev et al. / Cement and Concrete Composites 71 (2016) 53e62

Table 4
Electrical resistivity of the three admixtures and the tap water.
Parameters

Nanosilica (CB)

SP

TP

Tap water

Resistivity (ohm*m)

3.0

4.7

6.3E05

20.5

would have a higher conductivity than the mortar without AC even

if the same pore space exists.
The electrical conductivity of a conventional mixture containing
nanosilica (CB) and TP (the same amount as 10% and 20% replacement of AC) was measured to provide a comparison to the resistivity of the conventional paste without the added inuence of
grinding. The results are reported in Fig. 9(a) and Fig. 10. It should
be noted that the only difference between the two mixtures I with
CB and TP and the reference I is the extra nanosilica and TP used in
the mixture. From the results, it is observed that the resistivity is
decreased for both I cement and H cement mortars due to the high
conductivity of the nanosilica solution as well as any ionic species
that may have come from the TP.
Fig. 9(b) demonstrates the results of the resistivity development
for the Type I OPC with different AC replacements (10% and 20%). It
can be noticed that the resistivity is higher for the two mixtures
containing AC at the early age (between 8 and 16 h). This is likely
attributable to the more rapid rate of reaction and is consistent with
the calorimetry results from Fig. 6, which proves that the two AC
mortars have higher DOH than the plain system. After 16 h, however, the two mixtures with AC begin to have lower resistivities
than the reference (Fig. 9(b)). This is due to the high conductivity of
the admixtures in the pore solution of the AC based mixtures.
The inuence of the different grinding times was investigated
on the H cement mortars. Fig. 10 reports the results of the resistivity
development of the four mixtures with specimen age. It is stated
above that, with CB and TP, the resistivity is lower than that of the
mixture H. However, with addition of AC, the overall sample resistivity increases, which is probably due to the fact that grinding
results in a denser packing system as shown in Fig. 10. It is noteworthy that the 5 min grinding had the highest resistivity, which
implies the densest packing. Consequently, a longer grinding time
might not be favored for a high packing density.
4.4. Mechanical properties

Fig. 8. SEM images of three Type I cement mixtures with AC at the age of 28 days.

Fig. 11(a) reports the compressive strength results for the Type I
cement mortars with different amounts of AC levels. The strengths
at the ages of 1, 7, and 28 days tend to increase with increasing AC
replacement levels. Comparing the unconned compressive
strengths of I20-15 with the plain mortar I reveals an increase in
compressive strength of 32%, 20%, and 16% at the three ages of 1, 7,
and 28 days, respectively. This may be attributed to the reduction in
porosity and seed effect that is obtained by grinding the AC. Small
cement particles ll in the gaps between normal size particles and
hence make the material denser. Second, the increased hydration
rates due to seed effect at the early age, as revealed by calorimetry,
may explain why the increase in 1-day strength is highest at early
ages with the AC.
Fig. 11(b) demonstrates the results of the compressive strengths
of the class H cement mortar with different amounts of AC. It
should be remembered that both the SP and grinding inuence the
rate of cement hydration. The strength at 1 day is 6% lower for the
mixture with 10% AC while it is 25% higher for the mixture with 20%
AC. This may be attributed to the higher amounts of SP that slow
the hydration reaction. At one day, the DOH is reduced by 36% and
10%, respectively, according to Fig. 4(a). However, when the 7- and
28-day compressive strengths are compared, it can be noted that

Resistivity (ohm*m)

80

60

40
I
I10-5
I20-15
I with CB and TP (10%)
I with CB and TP (20%)

20

0
0

40

80

120

160

200

Age (h)

(a)

Compressive strength (MPa)

K. Sobolev et al. / Cement and Concrete Composites 71 (2016) 53e62

120

1-day Strength (MPa)

7-day Strength (MPa)
28-day Strength (MPa)

100
80
60
40
20
0

I10-15

(a)

20

10

0
4

12

16

20

Age (h)

(b)

Fig. 9. The resistivity development of hydrating mortars with different AC replacements for (a) the rst 200 h; (b) the rst 20 h.

120

Compressive strength (MPa)

30

I20-15

Mixtures

I
I10-15
I20-15

120

1-day Strength (MPa)

7-day Strength (MPa)
28-day Strength (MPa)

100
80
60
40
20
0

H10-15

H20-15

Mixtures

100

(b)

80
60
H
H10-5
H10-30
H10-60
H with CB and TP

40
20
0
0

40

80

120

160

200

Age (h)
Fig. 10. Resistivity development of the H cement mixtures with AC versus age for
mixtures with different grinding time.

the compressive strength improved with increasing AC replacement. The 7- and 28-day compressive strength of H20-15 increased
by 45% and 57% vs. reference H mortar. This observation is
consistent with the reduction in porosity observed with the SEMBSE, Fig. 7. Therefore, the use of AC in Class H cement systems
decreases the porosity and improves the compressive strength.
Fig. 11(c) demonstrates the strength results of H cement pastes
with 10% replacement by AC with different grinding times. The 1day strength had a decreasing trend, which is probably due to the

Compressive strength (MPa)

Resistivity (ohm*m)

40

Resistivity (ohm*m)

61

120

1-day Strength (MPa)

7-day Strength (MPa)
28-day Strength (MPa)

100
80
60
40
20
0

H10-5

H10-15

H10-30

H10-60

Mixtures
(c)
Fig. 11. Compressive strength of the mortars at ages of 1, 7, and 28 days made with (a)
Type I cement with 10 and 20% of AC (b) Class H cement with 10 and 20% AC (c) Class H
cement with 10% activated cement produced at different grinding times.

62

K. Sobolev et al. / Cement and Concrete Composites 71 (2016) 53e62

different SP loadings for each mixture. For example, the reference H

has the highest 1-day strength, since it has the lowest SP loading,
(0.2 wt % of cement). The 7 and 28-day strengths are not affected
much by SP and have an interesting trend. The 7 and 28-day
compressive strength are greatest for mixtures containing AC
cement that had been milled for 15 min. The strength test results
appear to agree with the resistivity development, i.e. longer
grinding time seems to reduce the early-age resistivity suggesting a
less favorable packing and higher porosity. This is probably because
during the longer grinding time in the presence of water, the
cement slurries (especially, aluminate phases) are hydrated and
agglomerated (Fig. 2(b)). Compared with AC slurry milled for
15 min, the highly hydrated cement materials might not be favorable for further incorporation into the system, which makes the
system less uniform. At the same time, the longer grinding time
makes the cement particles ner and hence a packing density is
achieved. With this counterbalance, the optimum AC grinding time
is 15 min.
5. Conclusions
This paper described a series of experiments that were performed to evaluate the inuence of mechanically activated cements
on the rate of hydration, structure of the hydrated products, and
mechanical properties of mortars based on two types of cements.
The X-ray diffraction (XRD) and scanning electron microscopy
(SEM) prove that the activated cement consists of nely ground
unhydrated cement and hydrated products that are stabilized in a
slurry containing cement hydrates, water and chemical admixtures.
It was found by calorimetry and EIS tests that the use of activated
cement can increase the rate of hydration, and hence increase the
development of early-age compressive strength.
From the strength results based on Type I cement mortars it was
found that with AC replacement the 1-day compressive strength is
increased most (32%). On the other hand, the improved packing
density from the ground small particles produces a denser material,
which increases the overall strength development. The increase in
28-day strengths at 20% AC replacement are up to 16% and 58% for
Type I and Class H cement mortars, respectively.
Acknowledgments
The authors acknowledge the nancial support of the U.S. Army
Engineer Research and Development Center under Cooperative
Research Agreement number W81EWF93519497-144PRJ35BM.
Permission to publish was granted by Director, Geotechnical and
Structures Laboratory. The activation grinding, X-ray Diffraction,
and SEM were carried out in the facility of Advanced and NanoCement Laboratory (ANCL) at University of Wisconsin-Milwaukee.
The remainder of the testing was conducted in Pankow Concrete
Laboratory at Purdue University.
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