materials

Article
The Application of Electrical Parameters to Reflect the
Hydration Process of Cement Paste with Rice
Husk Ash
Hui Wang 1, *, Lingxuan Hu 2 , Peng Cao 3 , Baoxin Luo 1 , Jing Tang 1 , Feiting Shi 4, *, Jinyan Yu 1 ,
Hongjie Li 1 and Kaikai Jin 1
1 School of Civil and Environmental Engineering, Ningbo University, Ningbo 315000, China
2 School of Civil Engineering, Harbin Institute of Technology, Harbin 150090, China
3 College of Architecture and Civil Engineering, Beijing University of Technology, Beijing 100124, China
4 Civil Engineering Department, Yancheng Institute of Technology, Yancheng 224051, China
* Correspondence: wanghui4@nbu.edu.cn (H.W.); shifeiting@ycit.cn (F.S.)




Received: 1 July 2019; Accepted: 27 August 2019; Published: 2 September 2019


Abstract: This paper aims to study the electrical parameters (electrical resistivity and alternating
current (AC) impedance spectroscopy) of cement paste with rice husk ash (RHA). The water to
cement (Mass ratio of water to cement (w/c)) ratios of the paste in this study varied from 0.4 to
0.5. The mass ratio of rice husk ash in each w/c ratio of specimens ranged from 0% to 15% by t
mass of cement. Scanning electron microscopy (SEM) and X-ray diffraction (XRD) were used to
determine the microstructures of specimens. Moreover, the slump flow and plastic viscosity of fresh
paste were determined. The results indicated that with the increasing dosage of RHA, the fluidity
decreased, while the plastic viscosity increased. Meanwhile, a high w/c ratio led to a low plastic
viscosity and high slump flow. The electrical resistivity of RHA cement paste gradually ascended
with the increasing curing period. The conduction of specimens intricately changed by mixing RHA,
a reasonable equivalent circuit was selected to describe the conduction mechanism by AC impedance
spectroscopy. Additionally, the results of XRD and SEM showed that RHA could effectively promote
the hydration process as well as decrease the size and number of cracks in hardened cement paste.

Keywords: electrical resistivity; AC impedance spectroscopy; cement paste; rice husk ash;
equivalent circuit

1. Introduction
Rice husk ash (RHA) is produced from agricultural waste (rice husk) [1–4]. The main component
of RHA contains a large amount of amorphous silica. Therefore, like silica fume, RHA is a kind of
active mineral admixture [5]. Zhuang et al. pointed out that RHA is effective to decrease the porosity
and Ca(OH)2 in cement paste [6]. Moreover, as described in some literatures, RHA possesses a very
high pozzolanic reactivity comparable with that of silica fume (SF) [7–9]. RHA has been proven by
scholars to replace silica fume for achieving high strength/performance concrete [10,11].
Van et al. reported that the addition of RHA can reduce free water in high strength/performance
concrete, thus improving its mechanical properties [12]. Additionally, RHA is able to decrease the
pore size and numbers in concrete, thus enhancing the compressive strength and impermeability [13].
Moreover, RHA was considered as an internal curing agent to decrease autogenous shrinkage [14].
However, RHA may decrease the fluidity of fresh concrete. The influences of RHA on the rheological
properties of fresh concrete and the rheological mechanism were unknown.
The hydration of cement material is a complicated physical and chemical process [15]. This process
controls the microstructure and macro performance of cement matrix [16]. Many literatures on studying

Materials 2019, 12, 2815; doi:10.3390/ma12172815 www.mdpi.com/journal/materials

Materials 2019, 12, 2815 2 of 14

hydration mechanism have been published [17]. Generally, some researchers analyzed the hydration
and hardening mechanisms by means of scanning electron microscopy (SEM), X-ray diffraction
(XRD), and Fourier transform infrared spectroscopy (FT-IR) [18,19]. It is known that continuous
monitoring of hydration process information may not be obtained from the above methods. In addition,
the preparation environment when drying samples for microscopy observations and analysis to
characterize hydration process will also affect the test results. Aiming at these problems, some scholars
have begun to focus on nondestructive testing methods, electrical testing methods, microwave energy
methods, and ultrasound detection methods. These methods are the most commonly used testing
methods [20–22]. Compared with the methods mentioned above, nondestructive testing (NDT) is
undoubtedly a better way to analyze the complex hydration process of cement materials.
Recently, electrical properties of cement-based materials were determined to reflect the service
performance of concrete, e.g., the hydration process etc. Wang et al. pointed out that cement mortar with
carbon nanofibers was able to sense freeze-thaw damage of materials, environmental temperatures,
applied stress, strain etc. by sensing the evolution of the specimen’s electrical resistivity [23].
The self-sensing cement composite with conductive fibers is called intrinsic self-sensing concrete [24].
Moreover, Han et al. found that the electrochemical impedance spectroscopy (EIS) and equivalent
circuits are able to analyze the conductive mechanisms of cement-based composite with conductive
fillers [25]. However, few researchers focus on the conductive performance of plain RHA cement paste
with different rheological properties and curing ages. Obviously, little attention was paid to electrical
properties of cement-based materials that reflected the hydration process of RHA cement matrix [26].
This paper studies the influence of rice husk ash content and curing ages on the rheological
properties (slump flow and plastic viscosity) and electrical parameters (electrical resistance and
alternating current (AC) impedance spectroscopy) of cement paste. Mass ratio of RHA varied from 0%
to 15% by the total mass of bind materials. In this research, water-cement (w/c) ratios were 0.4, 0.45,
and 0.5. SEM technology has greatly helped to elucidate the microstructures, and the XRD method
was applied to determine the composition of specimens with RHA.

2. Experiment

2.1. Raw Materials

The 42.5 ordinary Portland cement (P.O 42.5) provided by Yancheng Conch Cement Co., Ltd.
(Yancheng, China) was used as the binder material in this research. The fluidity of fresh paste was
adjusted by a polycarboxylate-based, high-range water-reducing agent. The RHA was fabricated by
burning origin rice husk in an airtight high temperature furnace. The furnace filled with rice husk
was first heated at a rate of 10 ◦ C to 500 ◦ C for 2 h, and then the calcined residue was ground in a
vibrating mill for 15 min. The particle size distribution and chemical compound were the same as in
Reference [27]. The particle passing percentage and chemical composition of cement and RHA are
shown in Tables 1 and 2. In Table 2, “R2 O” means “Na2 O + K2 O”. The particle passing percentage of
cementitious materials was provided by Yancheng Conch Cement Co., Ltd. The method for testing the
particle passing percentage of cementitious materials was obtained according to the testing method for
the particle size of cement. Additionally, the chemical composition of cement and RHA were chosen in
a previous study [27].

Table 1. Particle passing percentage of the cementitious materials.

Particle Size/um
0.3 0.6 1 4 8 16 32 64
Types
Cement (P.O 42.5) 0 0.33 2.66 15.01 28.77 46.64 72.73 93.59
RHA 0 0.58 6.84 18.32 32.14 51.62 78.45 96.32
Materials 2019, 12, 2815 3 of 14

Table 2. Chemical composition of the cementitious materials.

Chemical Composition/%
Types
SiO2 Al2 O3 Fe2 O3 MgO CaO SO3 R2 O MnO H2 O
Cement (P.O 42.5) 20.86 5.47 3.94 1.73 62.23 2.66 0.48 0 0
RHA 91.56 0.19 0.17 0.65 1.07 0.47 3.92 0.74 0.23

2.2. Mixing Proportion

Table 3 shows the mixing proportions of all groups of the paste. In this experiment, the w/c ratios
were 0.4, 0.45, and 0.5. In each group of specimens, the dosage of RHA varied from 0% to 15%.

Table 3. Mixing proportion of fresh cement paste.

Samples Cement Water RHA Water Reducing Agent

RHA-1 100 40 0 0.6
RHA-2 95 40 5 0.6
RHA-3 90 40 10 0.6
RHA-4 85 40 15 0.6
RHA-5 100 45 0 0.6
RHA-6 95 45 5 0.6
RHA-7 90 45 10 0.6
RHA-8 85 45 15 0.6
RHA-9 100 50 0 0.6
RHA-10 95 50 5 0.6
RHA-11 90 50 10 0.6
RHA-12 85 50 15 0.6

2.3. Specimens Preparation and Measurement

Cement and water were mixed uniformly in the NJ-160A cement paste mixer and stirred at a speed
of 140 rpm for 2 min. Next, the mixture was mixed again at a speed of around 285 rpm for another
2 min. After that, the slump flow of the prepared fresh paste was measured by using a steel cone with a
bottom diameter of 60 mm, a top diameter of 36 mm and a height of 60 mm. Additionally, an NXS-11B
rotating viscometer manufactured by Chengdu Leadership Instruments Co., Ltd. (Chengdu, China)
was used to determine the plastic viscosity of the paste. To measure the electrical resistance, specimens
with a size of 20 mm × 30 mm × 35 mm were fabricated and then the electrical resistances were tested
by a TH2810D LCR digital electric bridge (Changzhou Tonghui Co., Ltd., Changzhou, China) with
a frequency ranging from 100 Hz to 10 kHz. The tests were conducted at an AC voltage of 1 V and
frequency of 10 kHz with the embedded two-pole layout method, as shown in Figure 1a. The electrodes
were made of corrosion resistant AISI 316L stainless steel mesh with a size of 2.0 cm × 3.5 cm and a
thickness of 0.8 mm. The AC electrical resistance along the longitudinal axis direction of the cube
was determined. Three specimens were measured for each group. The electrochemical impedance
spectroscopy was tested by an electrochemical workstation (Shanghai Chen Hua Instrument Co., LTD,
Shanghai, China) as shown in Figure 1b. The microstructure and crystal types of hydration products
were determined by JSM-6360LV scanning electron microscope (Japan electron optics laboratory, Tokyo,
Japan) and D8 ADVANCE X-ray diffractometer (Bruker Corp., Tokyo, Japan) respectively. Before the
experiments, the samples were dried in a vacuum drying oven (Shanghai Yi Heng Instrument Co.,
LTD DZF-6020, Shanghai, China) at 60 ◦ C. When SEM observations were carried out all samples were
metallized with gold.
Materials 2019, 12, x FOR PEER REVIEW 4 of 14

C
Materials 2019, 12, 2815 4 of 14

(a)

(b)

Figure 1. Electrical parameters measurement: (a) Electrical resistance measurement; (b) Alternating
current (AC) impedance spectroscopy.
spectroscopy.

3. Results
3. Results and
and Discussion
Discussion

3.1. Rheological Performance of Cement Paste

3.1. Rheological Performance of Cement Paste
Figure 2 shows the variation of slump flow and plastic viscosity with the increasing dosage of
Figure 2 shows the variation of slump flow and plastic viscosity with the increasing dosage of
RHA. The shear rate for plastic viscosity determination was 8 rpm. As shown in Figure 2, more RHA
RHA. The shear rate for plastic viscosity determination was 8 rpm. As shown in Figure 2, more RHA
resulted in a lower slump flow and higher plastic viscosity. Moreover, higher w/c ratios presented
resulted in a lower slump flow and higher plastic viscosity. Moreover, higher w/c ratios presented
higher slump flow and lower plastic viscosity. The increasing content of RHA decreased the slump
higher slump flow and lower plastic viscosity. The increasing content of RHA decreased the slump
flow and increased plastic viscosity because the incorporation of RHA could adsorb some free water in
flow and increased plastic viscosity because the incorporation of RHA could adsorb some free water
fresh paste that had resulted in decreasing the fluidity and increasing the viscosity of fresh paste [12].
in fresh paste that had resulted in decreasing the fluidity and increasing the viscosity of fresh paste
However, higher w/c ratios led to higher fluidity and lower viscosity, this was attributed to the fact
[12]. However, higher w/c ratios led to higher fluidity and lower viscosity, this was attributed to the
that cement paste with higher w/c ratios contains more free water, therefore the flowing property was
fact that cement paste with higher w/c ratios contains more free water, therefore the flowing property
improved, and the viscosity was decreased by higher w/c ratios [28].
was improved, and the viscosity was decreased by higher w/c ratios [28].
Materials 2019, 12, 2815 5 of 14
Materials 2019, 12, x FOR PEER REVIEW 5 of 14

120
250 w/c-0.35
w/c-0.35
100 w/c-0.40
w/c-0.40
w/c-0.45 w/c-0.45
200
80
Slump flow /mm

60

h /Pa
150

40
100
20

50 0
0 5 10 15
0 5 10 15
RHA content /%
RHA content /%
(a) (b)

Figure 2.
Figure 2. Slump
Slump flow
flow and
andviscosity
viscosityofoffresh
freshpaste
pastewith
withdifferent dosage
different of of
dosage Rice husk
Rice ashash
husk (RHA): (a)
(RHA):
Slump flow; (b) Viscosity.
(a) Slump flow; (b) Viscosity.

3.2.
3.2. Electrical
Electrical Resistivity
Resistivity
Figures
Figures 3–53–5show
showthe theelectrical
electricalresistivity
resistivity ofofspecimens
specimens with with RHA
RHA content
content ranging
ranging fromfrom 0% 0%to to
15%.
15%. As As shown
shown in in Figures
Figures 3–5, 3–5, the
the resistivity
resistivity ofofall
allspecimens
specimensincreased
increased with
withthe theincreasing
increasingcuringcuring
time
timebecause
becausethe theincreasing
increasinghydration
hydrationof ofthe
thecement
cementpaste pastemight
mightdecrease
decreasethethefree
freeconductive
conductiveions ionsinin
the
the cement
cement paste
pastethus
thusresulting
resultingin indecreasing
decreasingthe theconductivity
conductivity[28–31].
[28–31]. Therefore,
Therefore, the the resistivity
resistivity of of
specimens
specimens increased
increased withwith increasing
increasing curing
curing ages.
ages. At the the curing
curing ages
ages from
from 33 hh to to 24
24h, h,the
theelectrical
electrical
resistivity
resistivity of of the
the cement
cement paste
paste with
with RHA
RHA from
from 0% 0% to to 10%
10% linearly
linearly increased
increased withwith the the curing
curing ages.
ages.
However, for the specimens with 15% RHA content, the electrical resistivity
However, for the specimens with 15% RHA content, the electrical resistivity of all specimens rarely of all specimens rarely
changed
changed with with the curing ages. ages. Moreover,
Moreover,the theelectrical
electricalresistivity
resistivityofof specimens
specimens withwith w/cw/c ratios
ratios of
of 0.4
0.4
andand 0.45
0.45 decreased
decreased slightly
slightly with
with RHARHA content.
content. ThisThis might
might bebe attributed
attributed toto thethefact
factthat
thatRHARHAisisa
apozzolanic
pozzolanicmaterial,
material,hence,
hence,the theportlandite
portlanditefirst
first formed
formed and and then
then reacted with RHA, and and thus
thus the
the
setting
setting time
time and hardening
hardening were were delayed
delayedwithwiththe theincrease
increaseininRHA RHA content
content [21].
[21]. However,
However, when whenthe
the curing
curing ages ages ranged
ranged from from
336336h toh 672
to 672 h, the
h, the electrical
electrical resistivity
resistivity of specimens
of specimens withwith w/cw/c ratios
ratios of
of 0.4
0.4
andand 0.45
0.45 increased
increased slightly
slightly withRHA
with RHAcontent,
content,because
becauseRHA RHAisiseffective
effective to
to diminish conductive
conductive free free
ions
ionsby byaccelerating
acceleratinghydration
hydration and anddecreasing
decreasingthe thefluidity
fluidityof offresh
freshpaste.
paste.Above
Aboveall, all,thetheconductive
conductive
performance
performance of of specimens
specimens with with RHA
RHA isis aacomplex
complexprocess.
process. The
The addition
addition of of RHA
RHA was was effective
effective to to
decrease
decreasethe thefluidity
fluidityof ofthe
thefresh
freshpaste
pasteand
andreduce
reducethe thefree
freewater
waterin inthe
thecement
cementpaste,
paste,thusthusdecreasing
decreasing
the
theconductive
conductiveions ionsof ofpore
poresolution
solutionandandincreasing
increasingthe theresistivity
resistivityof ofspecimens.
specimens.The The retarding
retardingaction
action
of
ofRHA
RHAin incement
cementpastepastemight
mightdecrease
decreasethetheresistivity
resistivityof ofspecimens
specimens[21].[21]. In
In this
this study,
study,w/c w/cratios
ratioshadhad
little
littleinfluence
influenceon onthe
theresistivity
resistivityof ofspecimens.
specimens. ThisThis might
mightbe beattributed
attributedto tosome
somecomplicated
complicatedreasons reasons
that
thatwill
willbebestudied
studiedin inthe
thefuture.
future.
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1000
1000
1000

•cm
•cm
0

•cm
0

ρ/Ω
5%
0
ρ/Ω
5%
ρ/Ω 10%
5%
10%
15%
10%
15%
15%
100
100
100

10 t/h 100 1000

10 t/h 100 1000
10 t/h 100 1000
Figure 3. Electrical resistivity of specimens with w/c ratio of 0.40.
Figure 3. Electrical resistivity of specimens with w/c ratio of 0.40.
Figure 3. Electrical resistivity of specimens with w/c ratio of 0.40.

1000
1000
1000
•cm
•cm
•cm

0
ρ/Ω

05%
ρ/Ω

0
ρ/Ω

5%
10%
100 5%
10%
15%
100 10%
100 15%
15%

10 t/h 100 1000

10 t/h 100 1000
10 t/h 100 1000
Figure 4. Electrical resistivity of specimens with the w/c ratio of 0.45.
Electricalresistivity
Figure4.4.Electrical
Figure resistivityof
ofspecimens
specimenswith
withthe
thew/c
w/cratio
ratioof
of0.45.
0.45.
Figure 4. Electrical resistivity of specimens with the w/c ratio of 0.45.

1000
1000
1000
•cm
•cm
•cm

0
ρ/Ω

05%
ρ/Ω

0
ρ/Ω

5%
10%
100 5%
10%
15%
100 10%
100 15%
15%

10 t/h 100 1000

10 t/h 100 1000
10 t/h 100 1000
Electrical resistivity
Figure 5. Electrical resistivity of
of specimens
specimens with the w/c ratio of 0.50.
Figure 5. Electrical resistivity of specimens with the w/c ratio of 0.50.
Figure 5. Electrical resistivity of specimens with the w/c ratio of 0.50.
3.3. Electrochemical Impedance Spectroscopy (EIS)
3.3. Electrochemical Impedance Spectroscopy (EIS)
3.3. Electrochemical Impedance Spectroscopy (EIS)
3.3. Electrochemical Impedance Spectroscopy
The electrical resistances of the cement (EIS)
paste with different w/c ratios are shown in Figures 6–8.
The electrical resistances of the cement paste with different w/c ratios are shown in Figures 6–8.
The
EIS and electrical resistances of the cement paste with differentthew/c ratios areofshown in Figures 6–8.
Thecorresponding
EIS and electrical
corresponding
equivalent
resistances
equivalent
circuits
of the cementwere used
circuits paste
to analyze
werewith
useddifferent
to analyze
mechanism
w/c ratios conductive
are shown
the mechanism in properties.
of Figures 6–8.
conductive
EIS
The and corresponding
and real equivalent circuits were used to analyze the spectroscopy
mechanism ofrepresent
conductive
EIS imaginary
and corresponding
properties. The imaginary
components
equivalent of the electrochemical
and real circuits were of
components used impedance
the toelectrochemical
analyze the mechanism
impedance ofspectroscopy
the
conductive
properties.
electrical The imaginary and real components of the electrochemical impedance spectroscopy
properties.reactance
represent The
the
and resistance,
imaginary
electrical and real
reactance
respectively [25].
and components
It can
of the
resistance, respectively
be seen that the imaginary
electrochemical
[25]. It can beimpedance
seen that the
and real
spectroscopy
imaginary
represent the electrical reactance and resistance, respectively [25]. It can be seen that the imaginary
represent
and the electricalofreactance
real components all groups and resistance,
increase respectively
linearly with real[25]. It can be seen
components that the imaginary
as frequency decreases
and real components of all groups increase linearly with real components as frequency decreases
and real components of all groups increase linearly with real components as frequency decreases
Materials 2019, 12, 2815 7 of 14

Materials 2019, 12, x FOR PEER REVIEW 7 of 14

components of all groups increase linearly with real components as frequency decreases from left to
right. Theto
from left Chi-squared is less than or
right. The Chi-squared is equal to 2.053
less than × 10−3
or equal to .2.053
This ×verifies thatverifies
10−3. This the selected equivalent
that the selected
circuits
equivalentare circuits
reasonable are for describing
reasonable for the conductive
describing pathways in
the conductive Figures in
pathways 6–8. When6–8.
Figures theWhen
waterthe to
cement ratio (Mass ratio of water to cement) was 0.40, the growth rate
water to cement ratio (Mass ratio of water to cement) was 0.40, the growth rate of imaginary of imaginary components with
real components
components with wasrealaccelerated
components by was
the increased
acceleratedcuring ages.
by the However,
increased when
curing the However,
ages. water cement when ratios
the
were
water0.45 and 0.50,
cement ratiosthe growth
were 0.45 rates of thethe
and 0.50, imaginary and real
growth rates components
of the imaginarywere random.
and real The internal
components were
causes
random. willThe
be studied
internalincauses
the future.
will be Meanwhile,
studied inastheshown in Figures
future. Meanwhile,6–8, the
as increase
shown inofFigures
the curing
6–8,ages
the
was effective
increase to increase
of the curing agesthe real
wascomponents,
effective towhich meant
increase thethat
realthe electrical resistances
components, which meant of specimens
that the
increased as well. The
electrical resistances ofincorporation
specimens increasedof RHAascan decrease
well. the real components
The incorporation of RHA can at the initial the
decrease curing
real
ages (3–24 h) but increase the real components at the long-term curing
components at the initial curing ages (3–24 h) but increase the real components at the long-termages (1–28 d). This behavior
was
curingdescribed
ages (1–28andd).analyzed in Part 3.2.
This behavior was described and analyzed in Part 3.2.
Figure 9 shows the corresponding
Figure 9 shows the corresponding equivalent circuits
equivalent of specimens
circuits with RHA.
of specimens with The
RHA. circular section
The circular
can be represented by the parallel of resistance and capacitance elements. The
section can be represented by the parallel of resistance and capacitance elements. The initial resistance initial resistance (Rs )
corresponds
(Rs) corresponds to thetocontact resistance
the contact between
resistance specimen
between and electrodes.
specimen Then, the
and electrodes. Then,following series
the following
connected electrical components represented shunt-wound
series connected electrical components represented shunt-wound resistance resistance (R 1 ) and electrical capacitance
(R1) and electrical
(C 1 ) of the pore
capacitance (C1solution.
) of the poreA conductive
solution. A pathway was pathway
conductive formed bywas the formed
pore solution
by theinpore
the cement
solutionmatrix.
in the
The addition of RHA can decrease the fluidity and enhance the hydration
cement matrix. The addition of RHA can decrease the fluidity and enhance the hydration thus thus blocking the conductive
channels
blocking in thespecimens.
conductiveMoreover,
channels due to the electrical
in specimens. capacitances
Moreover, due to of thespecimens, the specimens
electrical capacitances of
present
specimens,strong
thezero drift phenomena
specimens present strongin thezero
electrical performance.
drift phenomena in the electrical performance.

2500 2500

2000 2000

1500 1500
-Zi(Ω)
-Zi(Ω)

1000 3h 1000
1d 3h
14d 1d
500 28d 500 14d
28d
0 0

0 100 200 300 400 500 0 100 200 300 400 500
Zr(Ω) Zr(Ω)
(a) (b)

2000 2000

1500 1500
-Zi(Ω)

-Zi(Ω)

1000 1000 3h
1d
3h 14d
500 500
1d 28d
14d
0 28d
0

500 1000 1500 500 1000 1500 2000 2500

Zr(Ω) Zr(Ω)
(c)
(d)

Figure6.6. Electrochemical
Figure Electrochemical impedance
impedance spectroscopy
spectroscopy (EIS)
(EIS) curves
curves of
of specimens
specimens with
with w/c
w/c ratio
ratio of
of 0.40:
0.40:
(a)RHA-1; (b)RHA-2; (c)RHA-3; (d)RHA-4.
(a) RHA-1; (b) RHA-2; (c) RHA-3; (d) RHA-4.
Materials 2019, 12, 2815
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Materials 2019, 12, x FOR PEER REVIEW 8 of 14
2500 2500
2500 2500
2000 2000
2000 2000
1500 1500

Ω) Ω)
1500
Ω) Ω)

1500

-Zi(-Zi(
-Zi(-Zi(

1000 1000 3h
1000 1d
3h
1000 3h
14d
1d
500 1d
3h 500
28d
14d
14d
1d 500
500 28d
28d
14d 0
0 28d
0 0
0 200 400 600
0 200 400 600 Zr(Ω)
Zr(Ω) 0 200 400 600
0 200 400 600 Zr(Ω)
Zr(Ω)
(a) (b)
(a) (b)

2500 2500
2500 2500
2000 2000
2000 2000
1500 1500
Ω) Ω)
Ω) Ω)

1500 1500
-Zi(-Zi(
-Zi(-Zi(

1000 1000
3h
1000 3h 1000
1d
3h
500 1d
3h 500 14d
1d
500 14d
1d 500 28d
14d
28d
14d
0 0 28d
28d
0 0
600 800 Zr(Ω) 1000 1200 600
800 1000 1200 1400 1600 1800
Zr(Ω)
600 800 Zr(Ω) 1000 1200 600 800 1000 1200 1400 1600 1800
Zr(Ω)
(c) (d)
(c) (d)
Figure 7. EIS curves of specimens with w/c ratio of 0.45: (a) RHA-5; (b) RHA-6; (c) RHA-7; (d) RHA-
Figure 7.
8.
Figure 7. EIS
EIS curves
curves of
of specimens
specimenswith
withw/c
w/cratio
ratioofof0.45:
0.45:(a)
(a)RHA-5;
RHA-5;(b)
(b)RHA-6;
RHA-6;(c)(c)RHA-7;
RHA-7;(d)(d) RHA-
RHA-8.
8.
2500 3000
2500 3000
2500
2000
2500
2000 2000
1500 2000
Ω) Ω)

1500 3h 1500
Ω) Ω)

-Zi(-Zi(
-Zi(-Zi(

1000 1d
3h 1500
1000 3h
1000 14d
1d
1d
3h
28d
14d 1000
500 500 14d
1d
28d 28d
500 500 14d
0 28d
0
0 0
0 200 Zr(Ω) 400 600
0 200 Zr(Ω) 400 600
0 200 Zr(Ω) 400 600
0 200 Zr(Ω) 400 600
(b)
(a)
(b)
(a)
Figure 8. Cont.
Materials 2019, 12, 2815 9 of 14
Materials 2019, 12, x FOR PEER REVIEW 9 of 14
Materials 2019, 12, x FOR PEER REVIEW 9 of 14

2000 2500
2000 2500

2000
1500 2000
1500
1500 3h
1500 3h

Ω)
Ω)

1000 1d

Ω)
Ω)

1000 3h 1d

-Zi(
-Zi(

3h

-Zi(
-Zi(

1d 1000 14d
1d 1000 14d
28d
500 14d 28d
500 14d
28d 500
28d 500

0 0
0 0
500 1000 1500 500 1000 1500 2000 2500
500 1000 1500 500 1000 1500 2000 2500
Zr(Ω) Zr(Ω)
Zr(Ω) Zr(Ω)

(c) (d)
(c) (d)

Figure 8. EIS curves of specimens with w/c ratio of 0.50: (a) RHA-10; (b) RHA-11; (c) RHA-12; (d)
Figure 8.
Figure 8. EIS
EIScurves
curvesofofspecimens
specimenswith
withw/c
w/cratio
ratioofof
0.50: (a) (a)
0.50: RHA-10; (b) (b)
RHA-10; RHA-11; (c) RHA-12;
RHA-11; (d)
(c) RHA-12;
RHA-12.
RHA-12.
(d) RHA-12.

Figure9.9.Corresponding
Figure Correspondingequivalent
equivalentcircuits
circuitsofofspecimens
specimenswith
withRHA.
RHA.
Figure 9. Corresponding equivalent circuits of specimens with RHA.
3.4. Microscopic Analysis
3.4.Microscopic
3.4. MicroscopicAnalysis
Analysis
Figure 10 shows the XRD patterns of specimens after a 28-day standard curing. From Figure 10 it can
Figure10
Figure 10 showsthe the XRDpatterns
patternsof ofspecimens
specimensafterafteraa28-day
28-daystandard
standardcuring.
curing.From
FromFigure
Figure10 10
be seen that theshows
diffraction XRD
peaks of 3CaO·SiO 2 (C3 S), 2CaO·SiO2 (C2 S), and SiO2 are significantly strong,
it can be
it can be seen
seen thatthat the diffraction
the crystallinity peaks
diffraction peaks of 3CaO·SiO
of 3CaO·SiO 2 (C3S), 2CaO·SiO2 (C2S), and SiO2 are significantly
2 (C3S), 2CaO·SiO2 (C2S), and SiO2 are significantly
which indicates good [32,33]. Results indicated that all specimens were mainly constituted
strong,
strong, which indicates
which indicates good crystallinity
good crystallinity [32,33]. Resultsindicated
[32,33]. Results indicatedthatthatall
allspecimens
specimenswereweremainly
mainly
of unhydrated cement particles such as 3CaO·SiO 2 (C 3 S), 2CaO·SiO2 (C 2 S), SiO2 , and hydration
constituted of
constituted of unhydrated
unhydrated cement
cement particles suchsuch as 3CaO·SiO
3CaO·SiO2 2 (C (C3S),
3S), 2CaO·SiO2 (C2S), SiO2, and
products like calcium hydroxide (CH)particles
and hydrated as calcium silicate 2CaO·SiO
(C-S-H). Figure210 (Cshows
2S), SiO2, and
that the
hydration
hydration products
products like
like calcium
calcium hydroxide
hydroxide (CH)
(CH) and
and hydrated
hydrated calcium
calcium silicate(C-S-H).
silicate (C-S-H).Figure
Figure10 10
height of diffraction peaks of SiO2 increased with the increase of RHA, whereas the height of diffraction
showsthat
shows that theheight
heightofofdiffraction
diffractionpeaks
peaksof ofSiO
SiO2 2increased
increasedwith withthe
theincrease
increaseof ofRHA,
RHA,whereas
whereasthe the
peaks of CHthe and C3 S decreased with the increase of RHA. These results can be attributed to the high
height of
heightcontent diffraction
of diffraction peaks of CH and C 3S decreased with the increase of RHA. These results can be
RHA leadingpeaks of fraction
to a low CH and of C3SiO
S decreased with the
in the cement increase
paste. of RHA.
Moreover, the These results
increasing can be
dosage of
attributedto
attributed tothe
thehigh
highRHARHAcontent leading2to
contentleading toaalow
lowfraction
fractionof ofSiO
SiO2 2ininthe
thecement
cementpaste.
paste.Moreover,
Moreover,
RHA might have accelerated the hydration process of the cement paste, which led to the decrease of
theincreasing
the increasingdosagedosageof ofRHA
RHAmight
mighthave
haveaccelerated
acceleratedthe thehydration
hydrationprocess
processof ofthe
thecement
cementpaste,
paste,
CH and C3 S [17–19].
which led to the decrease of CH and
which led to the decrease of CH and C3S [17–19].C 3S [17–19].
 Materials 2019, 12, 2815 10 of 14
Materials 2019, 12, x FOR PEER REVIEW 10 of 14

○ C3S 17-0445
□ C2S 33-0302
▽
▽ SiO2 46-1045
★ ★
★ CH 72-0156
▽ □
★○◆
◆ ▽ ○○
★
★▽
◆ C-S-H
★
RHA-4
▽
★
★
▽ ○ □
★ ◆◆ ★
▽ ○○ ★▽ ★
★ ▽ ★
RHA-3
○ □
▽ ★◆◆ ★ ★
▽ ○○ ▽
★
★ ▽ ★ RHA-2
○
▽ ★ ◆□ ★
★▽
◆ ▽ ○ ○ ★
RHA-1
10 20 30 40 50 60 70 80
2Theta (° )
(a)

○ C3S 17-0445
□ C2S 33-0302
★
▽
▽ SiO2 46-1045
★ ★ CH 72-0156
▽ ★○ □
◆ ▽ ○○
★
★
▽ ◆ C-S-H
★
RH A -8

▽ ★
★
○
▽ ★ ◆□ ★
▽ ○○ ★▽ ★
RHA -7
▽
★ ★
▽ ○
★ ◆□ ★
▽ ○○ ★▽ ★
RH A -6
★ ▽ ○
★
▽ ★ ◆□
▽ ★
★▽
○ ○
★ RHA -5
10 20 30 40 50 60 70 80
2Theta ( ° )

(b)

○ C3S 17-0445
□ C2S 33-0302
▽ ▽ SiO2 46-1045
★ ○ ★ ★ CH 72-0156
▽ ★
□
◆ ★ ★▽
◆ C-S-H
▽ ○○
◆ ★
▽ RHA-12
★ ○
□★
▽ ★◆ ★
▽ ○○ ★▽
◆★
★ RHA-11
▽ ★
○
▽ ★ ◆□
▽ ○○ ★ ★▽
◆★
★ RHA-10
★
▽
○
▽ ★ ◆□
★
▽ ○
○ ★▽ ◆★
RHA-9
10 20 30 40 50 60 70 80
2Theta (° )
(c)

Figure
Figure 10.10.
XRDXRD spectra
spectra of specimens
of specimens with
with RHA:
RHA: (a)(a)
w/cw/c ratio
ratio of 0.40;
of 0.40; (b)(b)
w/cw/c ratio
ratio of 0.45;
of 0.45; (c) (c)
w/cw/c ratio
ratio
of of 0.50.
0.50.
Materials 2019, 12, 2815 11 of 14
Materials 2019, 12, x FOR PEER REVIEW 11 of 14

Figure 11
Figure 11 shows
shows the
the scanning
scanning electron
electron microscope
microscope (SEM)
(SEM) photos
photos ofof specimens.
specimens. TheThe curing
curing ages
ages
of all specimens were 28 days. As shown in Figure 11, Ca(OH) crystals can be observed
of all specimens were 28 days. As shown in Figure 11, Ca(OH)22 crystals can be observed obviously obviously
when
when RHARHA isisnot
notadded
addedtotothe
thepaste.
paste. Many
Many flocky
flocky hydration
hydration products
products existexist in specimens
in specimens whenwhen
they
they contain RHA. Moreover, cracks in specimens decreased with the
contain RHA. Moreover, cracks in specimens decreased with the increasing dosage of increasing dosage of RHA.
RHA.
Additionally,
Additionally, the
the decreasing w/c ratios
decreasing w/c led to
ratios led to reduce
reduce the
the numbers
numbers andand size
size of
of crack
crack in
in specimens.
specimens.
Results indicate
Results indicate that
that RHA
RHA waswas effective
effective to
to improve
improve thethe compactness
compactness and and decrease
decrease the
the cracks
cracks in
in
specimens. Previous research pointed out that the amorphous silica in RHA reacted with calcium
specimens. Previous research pointed out that the amorphous silica in RHA reacted with calcium
hydroxide forming
hydroxide forming C-S-H.
C-S-H. Moreover,
Moreover, as as described
described in in Sensale’s
Sensale’s research,
research, the
the particle
particle size
size of RHA was
of RHA was
less than 45 µm, as being the nucleation point due to hydration products [34]. Therefore, RHA was
less than 45 µm, as being the nucleation point due to hydration products [34]. Therefore, RHA was
able to improve the compactness of the cement paste.
able to improve the compactness of the cement paste.

(a) (b)

(c) (d)

(e) (f)

Figure 11. Cont.

Materials 2019, 12, 2815 12 of 14
Materials 2019, 12, x FOR PEER REVIEW 12 of 14

(g) (h)

(i) (j)

(k) (l)
Figure 11.
Figure 11. SEM
SEM micrographs
micrographs of of specimens
specimenswith
withRHA:
RHA:(a)(a)RHA-1
RHA-1(10000);
(10000);(b)
(b)RHA-2
RHA-2(10000);
(10000);(c)
(c)RHA-3
RHA-
3 (10000);
(10000); (d)(d) RHA-4
RHA-4 (10000);
(10000); (e) RHA-5
(e) RHA-5 (10000);
(10000); (f) RHA-6
(f) RHA-6 (10000);
(10000); (g) RHA-7(10000);
(g) RHA-7(10000); (h) RHA-8(h) (10000);
RHA-8
(10000);
(i) RHA-9 (i)(10000);
RHA-9 (j)
(10000);
RHA-10(j) (10000);
RHA-10(k) (10000);
RHA-11(k) (10000);
RHA-11(l) (10000);
RHA-12 (l) (10000).
RHA-12 (10000).

4.
4. Conclusions
Conclusions
Based
Based on
on this
this study,
study,the
thefollowing
followingconclusions
conclusionscan
canbe
bedrawn.
drawn.
(1) The slump
(1) slump flow
flowof offresh
freshcement
cementpaste pastewas
was reduced,
reduced, and
and thethe plastic
plastic viscosity
viscosity waswas increased
increased by
by the
the increasing
increasing addition
addition of RHA
of RHA andand lower
lower w/c w/c ratios.
ratios.
(2) The
(2) The resistivity
resistivity of
of all specimens increased
all specimens increased with
with the
the increasing
increasing curing
curing ages.
ages. The
The addition
addition ofof RHA
RHA
had a complex influence on the conduction of specimens, due to its influence
had a complex influence on the conduction of specimens, due to its influence on the number of on the number of
electrical
electrical free
free ions
ions and
andthe
theretarding
retardingaction
actioninincement
cementpaste.
paste.The
Theequivalent
equivalentcircuits consisted
circuits consistedof
three resistor elements and three capacitance elements. Resistors or capacitances
of three resistor elements and three capacitance elements. Resistors or capacitances were in were in series
connection respectively. A parallel circuit was more reasonable between each capacitance and
resistor.
(3) RHA was effective to improve the compactness of the cement paste. Moreover, the hydration
Materials 2019, 12, 2815 13 of 14

series connection respectively. A parallel circuit was more reasonable between each capacitance
and resistor.
(3) RHA was effective to improve the compactness of the cement paste. Moreover, the hydration
products (CH) were decreased by the increasing addition of RHA.

Author Contributions: Investigation, Writing—Original Draft Preparation, Visualization, Software, Resources,

Project Administration and Funding Acquisition, H.W.; Investigation, Data Curation and Formal Analysis, L.H.,
P.C. and B.L.; Writing—Review and Editing, F.S.; Supervision and Methodology, J.Y., H.L. and K.J.
Funding: This study was sponsored by the K.C. Wong Magna Fund in Ningbo University, National Natural
Science Foundation of China [No.51808300], Science and Technology Projects of the Ministry of Housing and
Urban Rural Development of China [No. 2018-K9-024; No. 2018-K9-054], Natural Science Foundation of Ningbo
[No. 2018A610357], and School Research Fund of Ningbo University [No. XYL19010].
Conflicts of Interest: The authors declare no conflict of interest.

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