Cement and Concrete Research xxx (xxxx) xxx–xxx

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Cement and Concrete Research

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The use of rice husk ash as reactive filler in ultra-high performance concrete
⁎
Sung-Hoon Kanga,b,c, Sung-Gul Honga, Juhyuk Moonc,d,
a
Department of Architecture & Architectural Engineering, Seoul National University, 1 Gwanak-ro, Gwanak-gu, Seoul 08826, Republic of Korea
b
Department of Civil and Environmental Engineering, National University of Singapore, 1 Engineering Drive 2, Singapore 117576, Singapore
c
Institute of Construction and Environmental Engineering, 1 Gwanak-ro, Gwanak-gu, Seoul 08826, Republic of Korea
d
Department of Civil and Environmental Engineering, Seoul National University, 1 Gwanak-ro, Gwanak-gu, Seoul 08826, Republic of Korea

A R T I C LE I N FO A B S T R A C T

Keywords: In this study, rice husk ash (RHA)-based reactive filler was used in ultra-high performance concrete (UHPC) to
Agricultural byproduct improve mechanical properties without heat-treatment. This strategy replaces inert quartz filler with the reactive
Rice husk ash RHA filler, to increase the amorphous silica content while maintaining the physical role of the micron-sized
Ultra-high performance concrete quartz filler. Due to the high porosity of RHA, internal curing is effective, which promotes the hydration reaction
Amorphous silica
over a long period of time. Experimental results show an outstanding strength around 200 MPa after 91 days,
Reactive filler
Pozzolanic reaction
under ambient conditions (20 °C and 60% relative humidity). This was possible due to the promotion of poz-
zolanic reaction by additional water and amorphous silica provided by the porous (i.e., internal curing effect)
and reactive filler, respectively; hence, the volume of capillary pores was reduced. The result reported herein will
further promote the utilization of agricultural byproduct for the development of reactive RHA-based construc-
tion materials.

1. Introduction The chemical composition of RHA varies depending on the com-

Rice is one of the most important agricultural products, especially in
Asia [1–3]. Its production has increased over the past decade, and
global paddy production in 2017 was estimated to be 760 million tons
[4]. Moreover, with the prospect of the global population continuing to
increase until 2050, this figure is expected to rise [5,6]. Rice husk is a
byproduct of the rice milling process, accounting for about 20–23% of
the paddy weight [1–3,7,8], meaning that > 150 million tons of the
byproduct are produced annually. However, about 83% of this amount
is simply discarded as waste [5], polluting water and soil [1,9–11].
Therefore, research and development for solving these problems have
been performed in various industrial fields. In the green technology
field, rice husks are considered as a source of biomass [2,12] which is
used as a fuel to produce electricity or steam in a power plant
[2,11,13–15]. After the husk is burned, about 20% of the original
weight of the fuel remains as rice husk ash (RHA) [13,15]. The ash is
often disposed of in rivers or landfill and can contaminate the en-
vironment [11,12,16–19]. The use of rice husk as a fuel causes another
environmental issue related to the treatment of waste RHA; if the ash is
not treated properly, use of the rice husks cannot be considered com-
pletely “eco-friendly” [20]. Therefore, appropriate treatment and
proper utilization of RHA are attracting increasing attentions in in-
dustrial fields [14,21].
bustion conditions (particularly the maximum temperature) [2,22,23].
When it is burned at high temperatures above 700 °C, only crystalline
silica remains [24], which can be used in the ceramic and steel in-
dustries [2]. However, when crystalline silica is exposed to air, it can be
hazardous to human health by causing the disease silicosis; hence, it has
been proposed that RHA should be burned at low temperatures
[1,24,25]. Burning rice husks below 700 °C produces amorphous silica,
which is used as a supplementary cementitious material (SCM) in
construction materials and as a filler in rubber or paint [2,21]. The use
of RHA in construction materials is an active research field [7,26,27].
RHA is a highly reactive pozzolanic material, and it has been success-
fully used to replace some of the cement [21,22,28–33] or silica fume
(SF) [7,27,34,35] in concrete, without noticeable degradation in
strength and durability. Another promising application of RHA is the
production of sodium silicate solutions, key materials for producing
geopolymers [36–38].
RHA produced via controlled combustion is a porous material
containing a high concentration (85–95 wt%) of amorphous silica
[16,28,34,35,39]. The optimal combustion temperature for obtaining
the highest content of amorphous silica is 500–700 °C [10,28,40,41],
and the content can even be as high as that in SF (> 90 wt%). The
commercial construction material with the largest amount of SF per
unit volume is ultra-high performance concrete (UHPC) [27,42]. Hence,

⁎
Corresponding author at: Institute of Construction and Environmental Engineering, 1 Gwanak-ro, Gwanak-gu, Seoul 08826, Republic of Korea.
E-mail address: juhyukmoon@snu.ac.kr (J. Moon).

https://doi.org/10.1016/j.cemconres.2018.09.004
Received 13 March 2018; Received in revised form 1 August 2018; Accepted 21 September 2018
0008-8846/ © 2018 Elsevier Ltd. All rights reserved.

Please cite this article as: Kang, S.-H., Cement and Concrete Research, https://doi.org/10.1016/j.cemconres.2018.09.004
S.-H. Kang et al.
Fig. 1. Optimized combustion program to obtain amorphous silica from rice husk (a), color (or purity) differences of RHA depending on cooling process (b), and
obtained WRHA, GRHA, and BRHA (c).
studies are being conducted to replace some of the SF with RHA in
UHPC [27,34,35].
However, the morphology (i.e., particle shape and size) of SF and
RHA are completely different. SF has perfectly spherical ultra-fine
particles that act as both a Pozzolan and nano-sized filler in low water-
to-cement ratio (w/c) concrete such as UHPC [35,43–46]. In particular,
unreacted SF particles can fill nano-sized pores and improve the mi-
crostructure of the concrete [47,48]. Although RHA is pulverized after
combustion, its average particle size is generally 5–20 μm, which is
50–100 times the size of the nanoscale SF particles [7,27,35,39]. As a
result of these physical differences, the use of RHA to replace SF can
change the microstructural characteristics of UHPC [27]. One of the
most important principles in the development of UHPC is to optimize
the particle packing of granular mixtures, where a similar size dis-
tribution between adjacent classes of granular materials is critical
[43,49]. SF is an essential material for producing UHPC with out-
standing mechanical performance and durability [27], because it can
fill void between cement particles and participate as pozzolanic mate-
rial; however, incorporation of micro-sized filler is also essential to
achieve the desired properties. Quartz powder (QP) with an average
particle size of 5–25 μm is generally considered an ideal physical filler
2
Cement and Concrete Research xxx (xxxx) xxx–xxx
material [43,49]; RHA has a similar size distribution.
Based on the reviewed composition principle and physical proper-
ties of raw materials of UHPC, it is more reasonable to use RHA as a
substitute for QP, rather than SF. QP is composed of nearly 100%
crystalline silica and is an inert material in UHPC, unless it is exposed to
temperatures above 150 °C [43,50,51]. Hence, in commercial UHPCs
which generally not experience a temperature over 90 °C regardless of
heat treatment, the QP simply acts as a micro-sized filler [43,52–55].
However, due to the amorphous silica content, RHA can act as a re-
active powder like SF even at ambient temperature [50,56]. Thus, the
use of RHA as filler in UHPC can further promote the pozzolanic re-
action without relying on heat treatment. This reaction plays a crucial
role in determining the outstanding mechanical performance (com-
pressive strength > 150 MPa) and durability of UHPC [43,57–59].
The feasibility of using RHA as a SCM of low w/c concrete and
UHPC have been well understood after the studies by Zhang et al. [7]
and Tuan et al. [27], especially its role compared to SF. However, the
use of RHA instead of QP filler in UHPC has not been sufficiently in-
vestigated. Thus, the main objective of this work is to study the effect of
RHA filler on the material properties of UHPC, in particular, the re-
placement ratio of QP filler and the RHA combustion conditions. In
S.-H. Kang et al. Cement and Concrete Research xxx (xxxx) xxx–xxx

addition to its use as an alternative to the filler, the use of the ash as a
substitute for SF was also considered. This was in order to directly
compare two different approaches that utilize RHA to replace QP and
SF, such as: 1) similarity in physical characteristics (particle size and
shape) with QP despite difference in chemical composition, and 2) si-
milarity in chemical composition (high purity amorphous silica con-
tent) with SF despite difference in physical characteristics.
Although amorphous silica can be obtained by controlled combus-
tion of RHA at 500–700 °C, it is not always possible to obtain high
purity materials [39]. Due to the temperature difference between the
inside and outside of the bunch of rice husk, two types of ash, white
RHA (WRHA) and black RHA (BRHA), are generated. WRHA is a high-
purity siliceous material, treated under an appropriate temperature
(500–700 °C), while the purity of BRHA is very low due to high carbon
content [60]. Therefore, the uncontrolled RHA is divided into two
types: BRHA containing high carbon contents (< 500 °C), and the RHA
composed of crystalline silica (> 700 °C) [40,61]. It has been reported
that crystalline silica in the RHA does not adversely affect the me-
chanical properties of concrete [15,40]. However, the effect of BRHA
on the performance of concrete is not well understood. Therefore, this
study investigated the effects of WRHA and BRHA on the mechanical
properties, pozzolanic reaction, and pore structure, particularly when
these are used as filler in UHPC.
2. Materials and methods
2.1. Materials
Ordinary Portland cement (OPC)-type I (Hanil Cement, Korea), SF
(Grade 940U, Elkem, Norway), QP, silica sand, and WRHA or BRHA
(Suncheon, Korea) were used to manufacture UHPC samples. BRHA was
obtained by uncontrolled combustion at about 400 °C in a plant. WRHA
and grey RHA (GRHA) were produced by burning in a programmable
temperature furnace at 650 °C for 2 h (heating and cooling rates of 2 °C/
min), as shown in Fig. 1a. The combustion program was optimized
during preliminary tests to obtain a pure white RHA. It was also ob-
served that slow cooling is a key factor in ensuring high purity, in-
dicated by the white color (see Fig. 1b). After burning, all RHAs were
ground in a ball mill. The obtained colors of the WRHA, GRHA, and
BRHA were almost perfectly white, gray, and black, respectively as
shown in Fig. 1c. Previous studies proposed that additional acid treat-
ments are necessary after the burning process to obtain pure white RHA
[39,62,63], especially for using the RHA as a SCM in white concrete
[64]. In the current study, however, WRHA was obtained without any
additional treatments, probably due to the carbon that affects the color
[39,61–63] being completely removed by the slow heating and cooling
processes (2 °C/min compared to 5–20 °C/min in previous studies
[13,16,35,39]).
The chemical compositions of the raw materials determined by
X–ray fluorescence (XRF) analysis (XRF-1700, Shimadzu, Japan) are
shown in Table 1. Additionally, quantitative XRD analysis was per-
formed for the phase composition of cement, as presented in Table 2. It
was confirmed that SF, QP, and WRHA were mostly (> 90 wt%)
composed of silicon dioxide (SiO2), unlike GRHA and BRHA. Compared
with WRHA, the SiO2 content in GRHA was 3.7 wt% lower, while the
loss on ignition (LOI) was 4.26 wt% higher, without notable differences
in the other components. This indicates that the impurities removed
during ignition resulted in the low SiO2 content and dark color of the
controlled RHA. In addition, the results of the analysis of the phase
composition by X–ray diffraction (LabX XRD–6000, Shimadzu, Japan)
are shown in Fig. 2. It was observed that QP contained crystalline
quartz, while SF and WRHA were composed of amorphous silica. Two
analysis results yielded concentrations of 97 wt% amorphous silica in
SF, 98 wt% crystalline quartz in QP, and 92 wt% amorphous silica in
WRHA. The BRHA was also composed of amorphous phases, where the
SiO2 content was only 24 wt% and the remainder was thought to be
impurities indicated by the LOI (Table 1). To obtain more information
about the composition of the LOI material, elemental analysis (Flash EA
1112, Thermo Electron Corporation, USA) was performed, which con-
firmed that BRHA contained up to 46 wt% carbon. Therefore, it can be
concluded that unburned organic materials accounted for the majority
of the LOI. Previous studies have reported 54 wt% and 3.5 wt% of
carbon contents in RHA, when burned at 400 °C for 4 h [63] and 500 °C
for 2 h [62], respectively. This indicates that the carbon content de-
creases sharply between 400 °C and 500 °C.
Fig. 3 shows the particle size distributions of the materials used for
manufacturing UHPC. The particle size distribution of SF was measured
by image-processing of scanning electron microscopy (SEM; JSM-7800F
Prime, JEOL, Japan) based images, while other materials were analyzed
using the laser diffraction method (Mastersizer 3000, Malvern Instru-
ments, UK) [43,48]. The results showed that the particle sizes of the
prepared RHAs were about 100 times larger than that of SF, while the
values were in between those of cement and QP. SEM images (Fig. 4)
show the particle morphology, where the OPC and QP particles were
irregular, while the SF particles were perfectly spherical. However,
WRHA had a porous structure (Fig. 4d–f) and BRHA showed protruding
structures on its outer surface (Fig. 4g–i). The shape of the ground RHA
particles was also irregular [21].
As presented in Fig. 5, the result of absorbency test confirmed that
WRHA has much better (almost twice) moisture absorption capacity
than BRHA. The method used is as follows: 0.3 g of RHA (oven-dry mass
at 110 °C ± 5 °C) was placed in a chamber set as 20 °C and 100% re-
lative humidity, and its weight change as a function of time was mea-
sured by an electronic scale (precision of ± 0.1 mg). The absorbency in
the test result (Fig. 5) indicates the weight of moisture absorbed by 1 g
of the dry ash [42,65]. As shown in the result, the absorption behavior
of all RHAs used tended to show equilibrium after 12 h. At 30 h, the
ground WRHA absorbed 15.0% of moisture by its dry weight, while the
ground BRHA absorbed 7.4%. In addition, unground WRHA and BRHA
absorbed 18.3% and 9.6% at 30 h, respectively. The difference in ab-
sorption capacity between WRHA and BRHA was probably caused by
differences in their microstructures. Nonetheless, all the RHAs used
possess a sufficient absorption capacity to be used for internal curing of
concrete, as their absorbencies exceeded the minimum absorption (5%)
for a commercial internal curing agent such as light weight aggregate
[66]. Another interesting result is that the absorption capacity (between

Table 1
Chemical composition of raw materials (wt%).
Materialsa SiO2 Al2O3 TiO2 Fe2O3 MgO CaO SO3 Na2O K2O MnO P2O5 LOIb Total

Cement 20.80 4.82 0.29 3.33 3.30 61.74 1.86 – 0.90 0.09 – 2.50 99.63
Silica fume 96.90 0.29 0.01 0.15 0.18 1.54 – 0.16 0.64 0.03 0.05 0.02 99.97
Quartz powder 97.70 0.49 0.08 0.05 0.21 1.37 – 0.02 0.02 0.01 – 0.02 99.99
WRHA 92.00 0.31 – 0.38 0.47 0.97 – 0.20 3.87 0.28 0.75 0.76 99.99
GRHA 88.30 0.25 – 0.37 0.40 0.91 – 0.16 3.63 0.27 0.69 5.02 100
BRHA 23.81 0.09 – 0.12 0.13 0.26 – 0.07 1.02 0.07 0.20 74.33 100

a
WRHA, GRHA and BRHA are the controlled white and grey RHAs, and the uncontrolled black RHA, respectively.
b
Loss of ignition.

3
S.-H. Kang et al.
Table 2
Phase composition of cement used by quantitative XRD (wt%).
3CaO∙SiO2 2CaO∙SiO2 (Alpha) 2CaO∙SiO2 (Beta) 2CaO∙SiO2 (Gamma)
70.52 0.44 14.46 – 0.89
Fig. 2. XRD patterns of raw materials (A: alite, Al: aluminate, B: belite, F: ferrite, G: gypsum, Q: quartz).
Fig. 3. Particle size distributions of raw materials measured by image analysis
method for SF and laser diffraction method for OPC, QP, silica sand, WRHA,
and BRHA.
12 and 30 h) is 20% lower in ground RHA than unground RHA. This can
be an evidence of the decrease in absorption capacity due to partial
collapse of the porous microstructure of RHA, as suggested in some
previous studies [67,68].
2.2. Preparation of UHPC samples
Table 3 shows the selected mix proportions used to prepare UHPC
samples. The sample names were derived from the RHA ratio and the
original material replaced by RHA. For instance, the samples QP(W-
50%) and QP(W-100%) indicate that 50% and 100% of QP were re-
placed by WRHA, respectively. As mentioned in the introduction, 50%
of the SF was also replaced by WRHA and BRHA in the samples SF(W-
50%) and SF(B-50%), respectively. It is noted that the superplasticizer
(SPPL) contents of the sample QP(W-100%) had to be adjusted for
suitable workability.
To manufacture the UHPC samples, OPC, SF, QP, silica sand, and
RHA were homogenously blended for 10 min using a 5 L Hobart mixer
Cement and Concrete Research xxx (xxxx) xxx–xxx
3CaO∙Al2O3 3CaO∙Al2O3 (Ortho) 4CaO∙Al2O3∙Fe2O3 CaCO3 CaSO4·2H2O Anhydrite
0.56 9.57 1.56 1 1
at a low speed, and then water and SPPL (polycarboxylate-ether type)
were added to the dry mixture, as specified in the previous studies
[69–71]. Once the mixture became liquid, it was mixed at a high speed
for 2 min to ensure a homogeneous mixture. After the mixing, the flow
test was performed using ASTM conical cone without shock, as stated in
the standards [72,73]. The test results are shown in Table 3. Two
samples of Ref and QP(W-50%) satisfied the consistence class Cv
(230–270 mm), while the others belonged to the class Ct (< 230 mm)
[73]. When RHAs were used instead of SF or QP in UHPC, the work-
ability tended to decrease; especially, it was significant when BRHA was
added in the concrete. Immediately after the flow test, the fresh UHPC
was placed in the prepared molds and then cured under ambient con-
ditions (20 °C and 60% relative humidity) after 1 day of sealed curing at
20 °C. As silica sand is inert, it was excluded from the hydration reac-
tion tests, such as the hydration heat test, XRD, and thermogravimetric
(TG) analysis [43].
2.3. Experimental methods
2.3.1. Isothermal calorimetry
To investigate the effect of RHA addition on the hydration reaction
of UHPC at early ages, isothermal calorimetry was performed using a
TAM Air system (TA Instruments, USA). During the first 72 h, the hy-
dration heat of 15 g of paste samples was measured under isothermal
conditions at 20 °C. The obtained heat flow and cumulative heat were
normalized by the weight (gram) of the cement in each paste sample
[74,75].
2.3.2. Compressive strength
The compressive strengths of the samples were measured at 7, 28,
and 91 days. According to ASTM C109 [76], cubic specimens
(50 mm × 50 mm × 50 mm) were loaded using a universal testing
machine on each test day, and the average of three results was used to
determine the strength.
2.3.3. X–ray diffraction and thermogravimetric analyses
The paste samples cured for 28 days were ground into powders and
their hydration reactions were stopped by the method using
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S.-H. Kang et al. Cement and Concrete Research xxx (xxxx) xxx–xxx

Fig. 4. Microscope images of raw materials: OPC (a), SF (b), QP (c), WRHA with various resolutions (d, e, f), and BRHA with various areas (g, h, i).

HighScore Plus) and the database such as inorganic crystal structure

database [80] and crystallography open database [81].
TG analysis was performed to quantitatively determine the por-
tlandite contents in the hydrated samples. The prepared powder
(20 ± 3 mg per sample) was placed in an aluminum holder, and in-
serted in the analyzer (Q500 TGA, TA Instruments, USA). Once the
sample weight and temperature, displayed on the instrument, were
equilibrated, the heating started with a rate of 10 °C/min (from 40 °C to
1000 °C) in a nitrogen atmosphere (100 mL/min of flow rate). To
identify the weight loss of portlandite between 400 and 500 °C, the first
derivative of the TG curve (DTG) was used. Then, the portlandite
contents were estimated using the tangential method [74,82] and re-
scaled based on the dry sample weight at 500 °C [74,77].

2.3.4. Pore structure analysis

The pore size distribution and porosity of the UHPC samples were
Fig. 5. Moisture absorption characteristics of RHAs before and after pulver-
measured by mercury intrusion porosimetry (MIP). The samples hy-
ization. Each point on the graph was determined by average of three mea-
surements.
drated for 28 days were cut into small cubic pieces (5 mm in size) using
a precision cutter, and the pieces were immerged in isopropanol to stop
the hydration [43,83]. The dried samples were tested at a surface
isopropanol and diethyl-ether [77]. The powders were placed in a tension of 485 erg/cm2, mercury contact angle of 130°, and maximum
holder of XRD analyzer (LabX XRD–6000, Shimadzu, Japan), and the pressure of 400 MPa.
scanning was performed using Cu-Kα radiation at 40 kV and 40 mA,
following previous studies [78,79]. The scanning range, step size and
3. Results
time per step were 5–80° (2θ), 0.02° (2θ) and 2.4 s, respectively. Al-
though the scanning was performed up to 80° (2θ), the range of 5–50°
3.1. Hydration reaction at early ages
was analyzed. This is because important peaks were satisfactorily de-
tected in this range, and meaningful data could not be obtained due to
The heat flow and cumulative heat of the paste samples are shown
the overlap of peaks at high angle of > 50° (2θ). The collected XRD
in Fig. 6a and b, respectively. When 50% of the SF or QP were replaced
patterns were identified using a software (PANanalytical X'pert
by WRHA without changing w/c or the SPPL-to-cement ratio (SPPL/c),

5
S.-H. Kang et al. Cement and Concrete Research xxx (xxxx) xxx–xxx

Table 3
Mix proportion of UHPC samples (kg/m3).
Sample OPC Silica sand SF QP WRHA BRHA Watera Superplasticizerb Flow diameterc [mm]

Ref 800 880 200 200 – – 200 9.6 255

SF(W-50%) 800 880 100 200 100 – 200 9.6 225
QP(W-50%) 800 880 200 100 100 – 200 9.6 230
QP(W-100%) 800 880 200 – 200 – 200 14.4 200
SF(B-50%) 800 880 100 200 – 100 200 9.6 160
QP(B-50%) 800 880 200 100 – 100 200 9.6 180

a
Water in superplasticizer is included.
b
Solid contents of polycarboxylate-ether type superplasticizer.
c
Flow table test using ASTM conical mold [72] without shock, as specified in NF P18-470 [73].

the hydration reaction was greatly accelerated, comparing SF(W-50%)
or QP(W-50%) with the corresponding reference sample (Ref). Thus,
the beginning of the acceleration period occurred earlier. This could be
attributed to a reduction in the effective w/c due to water absorption by
porous materials such as RHA. A lower effective w/c value of cement
pastes (0.2–0.3) result in faster formation of the main hydration peak
[75]. Indeed, the addition of absorbent materials to UHPC resulted in
the earlier start of the main hydration reaction [84,85].
Between the two samples of SF(W-50%) and QP(W-50%), the ef-
fective w/c should be the same. Nevertheless, the main hydration peak
of SF(W-50%) was formed earlier than that of QP(W-50%), owing to
early beginning of the acceleration period. This can be explained by the
filler effect. Similar with limestone powder, QP also accelerates cement
hydration by providing additional sites for nucleation and growth of
hydration products, which shortens the duration of induction period
[86–90]. In this study, SF(W-50%) contained these powders twice as
much as QP(W-50%), as shown in Table 3. One more notable result in
Fig. 6a is the shoulder peaks formed in the post-acceleration period of
the three samples, Ref, SF(W-50%) and QP(W-50%). In the case of ce-
ment paste, generally two small peaks are formed in the descending
branch of the main hydration peak, due to the formation of etrringite
and ettringite-monosulfate conversion [91,92]. However, in the case of
UHPC, heat evolution curve can be significantly different with this,
owing to various factors such as low w/c conditions, contribution of
SCMs such as SF and RHA, the filler effect, and the retarded hydration
by SPPL.
In the case of QP(W-100%), which contained the largest amount of
WRHA and SPPL, the initial hydration was delayed, compared with Ref.
The amount of SPPL in this sample was 50% higher than for the other
samples. The polycarboxylate-ether SPPL effectively improves the
workability of self-compacting concrete such as UHPC [93], and also
retards hydration by steric hindrance between cement particles
[94,95]. Thus, the delay might be caused by the increase in SPPL/c
along with the decrease in QP contents, despite the previously
mentioned factors related to hydration acceleration. This delay is also a
cause for the result of lower cumulative heat of QP(W-100%) than that
of Ref for the first 72 h (Fig. 6b). Nevertheless, it is hard to conclude
that the incorporation of WRHA decreases cement hydration at early
ages. This is because cumulative heat was higher for the first 36 h, when
WRHA was incorporated without changing SPPL/c, as in the case of SF
(W-50%) or QP(W-50%). However, the heats of the two samples were
slightly lower than that of Ref at 72 h. Various factors such as the filler
effect [82] and decrease in effective w/c [75,84] could contribute to the
change in early age-hydration reaction. Meanwhile, the use of BRHA
significantly disrupted the hydration reaction of UHPC at early ages; in
addition to delaying the start of the acceleration period, it reduced the
cumulative hydration heat for the first 3 days. This was likely due to
negative effects from the unburned organic materials. This retardation
phenomenon was particularly pronounced when a portion of SF, rather
than QP, was replaced by BRHA.
3.2. Compressive strength development
Fig. 7a and b show the compressive strengths of the samples and
their 91 days–strength ratios relative to Ref, respectively. Except for the
samples containing BRHA, all samples satisfied the minimum cube
strength for UHPC (145 MPa) during the test period [73]. However, the
required time for the minimum strength was different among the
samples. First of all, two samples of SF(B-50%) and QP(B-50%) did not
reach the minimum strength for 91 days; thus, strictly speaking, these
cannot be classified as UHPC. The sample Ref also did not satisfy the
strength for 28 days, while all the samples containing WRHA showed
higher strength than 145 MPa on the 28 days. Among them, the
28 days-strength of QP(B-100%) was particularly high as 160 MPa,
compared to other two samples of 147 MPa. Based on this, it is observed
that the use of WRHA instead of SF or QP in UHPC shortens the period
to achieve the ultra-high strength under ambient curing conditions.
The obtained results also confirm that the use of WRHA as a

Fig. 6. Heat flow (a) and cumulative heat (b) of UHPC samples at early ages.

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S.-H. Kang et al.
Fig. 7. Compressive strength development of UHPC samples (a), and relative strength with respect to 91 days-strength of Ref sample (b).
substitute for QP rather than SF is more effective for improving the
strength of UHPC, especially in long-term ages. Compared to the Ref,
the compressive strengths of the three samples containing WRHA were
higher between 7 and 91 days. As for the 91 days-strength, SF(W-50%)
was higher than Ref but only by 1.7%. However, when WHRA was used
to replace QP, the strength increased significantly, by 7.7–18.5%, de-
pending on the replacement ratio. This is mainly attributed to re-
markable increases in the long-term strength between 28 and 91 days.
3.3. Mineralogical characteristics
The results of XRD analysis of hydrated pastes are presented in
Fig. 8. In all samples, unreacted cement clinkers (i.e., alite, belite,
aluminate, and ferrite) and ettringite were detected without notable
differences in their peak intensities among the samples. The result that
monosulfate was not detected is in good agreement with previous stu-
dies on UHPC [43,57,82]. This also suggests that the shoulder peaks
shown in Fig. 6a were the result of etrringite formation rather than
ettringite-monosulfate conversion. Moreover, based on the XRD pat-
terns of the raw materials (Fig. 2), the quartz peak shown in Fig. 8
Fig. 8. XRD patterns of UHPC samples at 28 days (A: alite, Al: aluminate, B: belite, E: ettringite, F: ferrite, G: gypsum, P: portlandite, Q: quartz).
7
Cement and Concrete Research xxx (xxxx) xxx–xxx
should be from QP only; thus, the peak intensity of the paste sample
should be proportional to the QP content. Indeed, when half of QP in
the paste was replaced with the RHA filler, the intensity was weakened
by half, as shown in the patterns of QP(W-50%) and QP(B-50%). When
all of the QP were replaced with WRHA, the quartz peak was not de-
tected in QP(W-100%). The peak heights of portlandite (2θ = near 18°)
for the two samples containing BRHA were significantly higher than the
other samples (that showed similar peak heights). In the following
section, the different portlandite contents among the samples will be
discussed using TG results.
3.4. Portlandite content
The TG and DTG curves of the samples are presented in Fig. 9. Two
noteworthy differences were found among the samples. First, the
weight loss of the sample containing BRHA (black dashed line) was
significantly higher than that of the other samples, due to the very high
LOI of BRHA (Table 1). During the thermal analyses, unburned organic
materials in SF(B-50%) were removed over the temperature range of
250–1000 °C, resulting in additional weight loss. In addition, the
S.-H. Kang et al. Cement and Concrete Research xxx (xxxx) xxx–xxx

Fig. 9. TG and DTG curves of UHPC at 28 days.

Fig. 10. Portlandite contents in UHPC at 28 days.
additional weight loss at 250–400 °C means that the heat was not
homogeneously transferred to all parts of the stacked rice husks during
the uncontrolled combustion at 400 °C when manufacturing the BRHA.
Another notable difference was the peak area of the DTG curves at
400–460 °C, which is related to the portlandite content [74,82]; the
quantitative values derived from this area are shown in Fig. 10. It has
been reported that the RHA produced by controlled combustion can
promote portlandite consumption and the resulting pozzolanic reaction
in low w/c concrete [7,27,34]. For this reason, the portlandite contents
of the samples containing WRHA were lower than that of Ref. In ad-
dition, the current study reveals that this promotion is more effective
when WRHA is used as a filler in UHPC, rather than a part of SF. This
consumption was slightly more effective when 50% of the QP was re-
placed by WRHA rather than 100%. On the other hand, when SF was
replaced with BRHA, the pozzolanic reaction was greatly decelerated.
This could be due to the low silica content and high carbon content of
BRHA, compared to WRHA. In addition to this, a change in physical

Fig. 11. Pore size distribution of UHPC at 28 days: Log differential intrusions (a) and cumulative pore volume (b).

8
S.-H. Kang et al.
Table 4
Total porosity and pore size distribution of UHPC samples.
Sample Total porosity [%] Pore size distribution [%]
Gel pores Medium capillaries (10–50 nm)
(< 10 nm)
Ref 9.66 1.94 4.25
SF(W-50%) 10.30 2.02 5.02
QP(W-50%) 8.17 2.17 2.96
QP(W-100%) 9.90 2.06 3.85
SF(B-50%) 11.06 2.37 2.60
QP(B-50%) 16.42 2.02 2.39
characteristics by significant loss in workability, as shown in Table 3,
can affect the reaction.
3.5. Pore structure
Fig. 11 and Table 4 show the pore size distribution and total por-
osity of the samples. The classification of pore sizes was determined
according to previous studies [96–98], which are generally accepted in
the field of concrete technology. The use of WRHA as filler was effective
in refining the pores of UHPC. Although there were no notable differ-
ences in the critical pore diameter (around 20 nm) among Ref, QP(W-
50%) and QP(W-100%), the peak height was lower in the two samples
containing WRHA compared to Ref. In particular, the pore structure in
the range of 10–50 nm, which corresponds to the capillary pores of low
w/c concrete [71,97,98], became finer. This means that the micro-
structure of UHPC was densified at 28 days by the use of RHA filler.
Both the reduction of effective w/c which makes cement paste more
compact [85], and promotion of the pozzolanic reaction (Fig. 10) which
fills up capillary pores by forming additional C-S-H gels, contributes
this result [99–101]. However, substitution of SF with RHA was not
effective in improving the pore structure of low w/c concrete (e.g., SF
(W-50%) in Fig. 11a), which has also been reported in previous studies
[7,27]. This indicates that the small capillary pores (10–50 nm) that can
be filled by SF particles [47,48], were not adequately filled by RHA
particles as they were physically different to the SF particles. Mean-
while, the pore structure of UHPC was significantly degraded with the
incorporation of BRHA. In particular, the increase in the volume of
pores larger than 50 nm was remarkable, possibly due to the decom-
position of the organic materials into gas, or the undesirable irregular
shape of BRHA particles negatively affecting the granular packing.
4. Discussion
It is an unusual case that the compressive strength of UHPC exceeds
200 MPa without heat treatment [102]. The Ref sample in this study
showed a lower strength than this (164 MPa at 91 days), and the
strategy of replacing half the SF with WRHA did not result in any sig-
nificant change in the strength. Although this method effectively pro-
moted the pozzolanic reaction, it negatively affected the capillary pore
structure. Moreover, when BRHA was used as a filler, the unburned
carbon therein had a negative effect on the hydration reaction and pore
structure, resulting in a significant strength loss. However, when WRHA
was used to replace half or all of the inert QP filler, the strength at
91 days increased by 7.7% and 18.5%, respectively. In the latter case,
the strength reached almost 200 MPa at 91 days. Moreover, since it has
been reported that the addition of steel fiber (2–2.5 vol%) can further
increase the compressive strength of UHPC by up to 10–25 MPa
[49,102], ultra-high performance fiber-reinforced concrete containing a
reactive filler is expected to have a strength of > 200 MPa after 91 days,
without requiring heat treatment.
The outstanding mechanical performance and durability of UHPC is
attributed to a compact mix composition due to the low w/c and
9
Cement and Concrete Research xxx (xxxx) xxx–xxx
Large capillaries (50 nm–10 μm) Air voids (> 10 μm)
2.47 1.00
2.51 0.75
1.70 1.33
3.06 0.94
4.66 1.43
9.11 2.90
optimized granular packing, as well as the intensified pozzolanic re-
action due to the presence of SF containing amorphous silica with a
high specific surface area [43,49,57]. This reaction proceeds slowly
over a long period, unless accelerated by heat treatment [57]. Despite
the controlled combustion, amorphous silica contents in RHA are gen-
erally lower than that of SF [7,34]. Therefore, as in this study, when SF
(SiO2 = 97 wt%) is replaced by WRHA (SiO2 = 92 wt%), the amount of
amorphous silica in UHPC should decrease slightly; nevertheless, the
pozzolanic reaction was promoted. While the particle size of RHA was
much larger than that of SF, its specific surface area was higher due to
its porous structure [7,22,27,34,35]. As the specific surface area of
amorphous silica source increased, the pozzolanic reaction is ac-
celerated [61]. However, the porosity was increased when SF was re-
placed with RHA, especially in the size range of capillary pore [7,27].
This suggests that RHA is hard to fully replace physical role of the
unreacted SF particles (i.e., nano-sized filler), although it has similarity
in chemical composition with SF. It has been reported that only 10% of
SF in UHPC participate in the pozzolanic reaction under ambient curing
conditions [56], which means that almost all of the SF act simply as an
inert filler. Thus, a more effective use of RHA in UHPC as a chemically
reactive filler, would be to provide additional amorphous silica by re-
placing micron-sized filler (QP), rather than by replacing nano-sized
filler (mostly unreacted SF) [103].
By replacing QP with WRHA, the amount of reactive Pozzolan in
UHPC is increased without changing the amount of both nano-sized
(i.e., SF) and micro-sized (i.e., QP or RHA) fillers. Furthermore, unlike
QP, porous WRHA can provide both water and amorphous silica, two
key ingredients for the pozzolanic reaction. The release of the absorbed
water by RHA in UHPC has been demonstrated in the study by Van
et al. [34]. In the current study, this method indeed promoted the
pozzolanic reaction (Fig. 10), decreased capillary pore volume
(Fig. 11), and in turn increased compressive strength (Fig. 7). An im-
portant role of the RHA in the strength development is internal curing
effect that can promote long-term hydration reactions [14,34]. Porous
materials such as RHA initially absorb a portion of the mixing water,
where the absorbed water can promote hydration over a long period
[27,104,105]. Therefore, from the beginning of the process, the effec-
tive w/c of the samples containing RHA should be lower than that of
Ref, which contributes to increasing the strength of UHPC [34,102]. In
addition, pores in the RHA itself allow water to be stored (Fig. 5) and
release to the surrounding over long-term ages (> 28 days) [27]; thus,
hydration promotion by internal curing could be possible even after
28 days. As shown in Fig. 7, the compressive strength of the samples
containing WRHA was higher than that of Ref. In particular the strength
development was particularly remarkable between 28 and 91 days
when used as filler.
In UHPC, the pozzolanic reaction plays a crucial role for the long-
term strength development [43,57]. However, the strength of QP(W-
100%) was higher than that of QP(W-50%), even though it showed less
significant improvement in the pozzolanic reaction (Fig. 10) and pore
refinement (Fig. 11). This is an interesting result, but not new. Pre-
viously, as a result of replacing all SF with RHA, the compressive
S.-H. Kang et al.
strength of UHPC was increased, without improvement in portlandite
consumption and pore refinement [27]; unfavorable effects by SF have
been mentioned as a possible reason. However, this is not sufficient to
explain the result of the current study, because SF contents are identical
in both cases of QP(W-100%) and QP(W-50%). Instead, the contents of
WRHA are different. When UHPC contains a porous material such as
WRHA, the effective w/c is reduced due to the absorption of mixing
water. This causes workability loss; thus, SPPL/c of QP(W-100%) is
higher than that of QP(W-50%) to compensate the loss [93]. Although
decreasing the effective w/c and increasing SPPL/c can adversely affect
the hydration reaction, they can improve the microstructure and me-
chanical performance of UHPC [34,49,106]. This is because the mix
composition is more compact from the beginning. Therefore, the
strength of QP(W-100%) can be higher than that of QP(W-50%), despite
a low degree of pozzolanic reaction. In addition, the volume of capillary
pores in QP(W-100%) can be higher than QP(W-50%), due to nano-
sized pores (3–100 nm) within WRHA, as reported in recent studies
[35,41,107].
5. Conclusion
This study was aimed at utilizing RHA as a reactive filler of ambient-
cured UHPC to improve its mechanical property. Based on the results
obtained, following conclusions can be drawn.
- A porous and pure white RHA (amorphous silica content: 92 wt%)
was manufactured by the process optimized in this study: combus-
tion at 650 °C for 2 h with heating and cooling rates of 2 °C/min. The
obtained unground WRHA showed 18.3% of moisture absorbency at
30 h, while it reduced to 15.0% after grinding process. Regardless of
the pulverization, their absorption capacities was enough to be used
as an internal curing agent.
- It was confirmed by the isothermal calorimetry that replacement of
half of SF or QP by WRHA without changing w/c or SPPL/c, sig-
nificantly accelerates initial hydration reaction of UHPC; the former
was more prominent than the later, possibly due to the filler effect.
However, when all of QP was replaced with WRHA while increasing
SPPL/c, the hydration reaction at early stage (< 72 h) was de-
celerated, because of the influence of SPPL.
- The use of WRHA was effective to improve the compressive strength
of UHPC, especially at long-term ages. All the UHPC samples con-
taining WRHA satisfied the minimum cube strength for UHPC
(145 MPa) at 28 days, while the classical UHPC sample without
WRHA did not achieve the strength at this time. The strength im-
provement was especially remarkable when the ash was used as
substitute of QP, rather than SF. By replacing half or all of QP with
WRHA, the strength increased by 7.7% or 18.5% at 91 days, re-
spectively, whereas it increased by 1.7% when SF was replaced with
WRHA.
- Microstructural investigation by XRD, TG analysis and MIP con-
firmed promotion of the pozzolanic reaction and densification of
microstructure in the range of capillary pore, when WRHA was used
as a substitute for QP of UHPC. Although the use of the ash instead
of SF was also effective to promote the reaction, it showed limita-
tions in reducing the capillary pores.
Considering the environmental problems related to disposal of RHA,
utilization of this agricultural byproduct is an important matter.
Studying the use of RHA as a raw material for concrete is also im-
portant, as it can be utilized as sustainable and multi-functional pro-
ducts. Consequently, the enhancement of mechanical performance
presented in this study can contribute to provide a clear motive for the
development of reactive filler products for UHPC and other high
strength concretes.
10
Cement and Concrete Research xxx (xxxx) xxx–xxx
Acknowledgment
This research was supported by Basic Science Research Program
through the National Research Foundation of Korea (NRF) funded by
the Ministry of Education (2017R1A6A3A03007381). The Institute of
Engineering Research in Seoul National University provided research
facilities for this work.
References
[1] W.-K. Cheah, C.-H. Ooi, F.-Y. Yeoh, Rice husk and rice husk ash reutilization into
nanoporous materials for adsorptive biomedical applications: a review,
Mesoporous Biomater. 3 (2016) 27–38.
[2] J. Prasara-A, S.H. Gheewala, Sustainable utilization of rice husk ash from power
plants: a review, J. Clean. Prod. 167 (2017) 1020–1028.
[3] S. Prasertsan, B. Sajjakulnukit, Biomass and biogas energy in Thailand: potential,
opportunity and barriers, Renew. Energy 31 (2006) 599–610.
[4] Food and Agriculture Organization of the United Nations, FAO Rice Market
Monitor, FAO, 2017, p. 35.
[5] E. Menya, P.W. Olupot, H. Storz, M. Lubwama, Y. Kiros, Production and perfor-
mance of activated carbon from rice husks for removal of natural organic matter
from water: a review, Chem. Eng. Res. Des. 129 (2018) 271–296.
[6] J.S. Wallace, Increasing agricultural water use efficiency to meet future food
production, Agric. Ecosyst. Environ. 82 (2000) 105–119.
[7] M.H. Zhang, R. Lastra, V.M. Malhotra, Rice-husk ash paste and concrete: some
aspects of hydration and the microstructure of the interfacial zone between the
aggregate and paste, Cem. Concr. Res. 26 (1996) 963–977.
[8] R. Siddique, K. Singh, Kunal, M. Singh, V. Corinaldesi, A. Rajor, Properties of
bacterial rice husk ash concrete, Constr. Build. Mater. 121 (2016) 112–119.
[9] C. Sookkumnerd, N. Ito, K. Kito, Financial viabilities of husk-fueled steam engines
as an energy-saving technology in Thai rice mills, Appl. Energy 82 (2005) 64–80.
[10] N.S. Msinjili, W. Schmidt, A. Rogge, H.-C. Kühne, Performance of rice husk ash
blended cementitious systems with added superplasticizers, Cem. Concr. Compos.
83 (2017) 202–208.
[11] J. Alex, J. Dhanalakshmi, B. Ambedkar, Experimental investigation on rice husk
ash as cement replacement on concrete production, Constr. Build. Mater. 127
(2016) 353–362.
[12] D. Liu, W. Zhang, H. Lin, Y. Li, H. Lu, Y. Wang, A green technology for the pre-
paration of high capacitance rice husk-based activated carbon, J. Clean. Prod. 112
(2016) 1190–1198.
[13] R.-S. Bie, X.-F. Song, Q.-Q. Liu, X.-Y. Ji, P. Chen, Studies on effects of burning
conditions and rice husk ash (RHA) blending amount on the mechanical behavior
of cement, Cem. Concr. Compos. 55 (2015) 162–168.
[14] K. Kunchariyakun, S. Asavapisit, K. Sombatsompop, Properties of autoclaved
aerated concrete incorporating rice husk ash as partial replacement for fine ag-
gregate, Cem. Concr. Compos. 55 (2015) 11–16.
[15] G. Rodríguez de Sensale, Strength development of concrete with rice-husk ash,
Cem. Concr. Compos. 28 (2006) 158–160.
[16] W. Xu, Y.T. Lo, D. Ouyang, S.A. Memon, F. Xing, W. Wang, X. Yuan, Effect of rice
husk ash fineness on porosity and hydration reaction of blended cement paste,
Constr. Build. Mater. 89 (2015) 90–101.
[17] Y. Chen, Y. Zhu, Z. Wang, Y. Li, L. Wang, L. Ding, X. Gao, Y. Ma, Y. Guo,
Application studies of activated carbon derived from rice husks produced by
chemical-thermal process—a review, Adv. Colloid Interf. Sci. 163 (2011) 39–52.
[18] G. Sua-iam, N. Makul, Utilization of high volumes of unprocessed lignite-coal fly
ash and rice husk ash in self-consolidating concrete, J. Clean. Prod. 78 (2014)
184–194.
[19] L.C. da Rosa, C.G. Santor, A. Lovato, C.S. da Rosa, S. Güths, Use of rice husk and
sunflower stalk as a substitute for glass wool in thermal insulation of solar col-
lector, J. Clean. Prod. 104 (2015) 90–97.
[20] Y. Liu, Y. Guo, W. Gao, Z. Wang, Y. Ma, Z. Wang, Simultaneous preparation of
silica and activated carbon from rice husk ash, J. Clean. Prod. 32 (2012) 204–209.
[21] Z.-H. He, L.-Y. Li, S.-G. Du, Creep analysis of concrete containing rice husk ash,
Cem. Concr. Compos. 80 (2017) 190–199.
[22] G.R. de Sensale, A.B. Ribeiro, A. Gonçalves, Effects of RHA on autogenous
shrinkage of Portland cement pastes, Cem. Concr. Compos. 30 (2008) 892–897.
[23] J. James, M. Subba Rao, Reactivity of rice husk ash, Cem. Concr. Res. 16 (1986)
296–302.
[24] V.M. Malhotra, P.K. Mehta, Pozzolanic and Cementitious Materials, Taylor &
Francis, Amsterdam, The Netherlands, 1996.
[25] A.M. Yusof, N.A. Nizam, N.A.A. Rashid, Hydrothermal conversion of rice husk ash
to faujasite-types and NaA-type of zeolites, J. Porous. Mater. 17 (2010) 39–47.
[26] M. Alkaysi, S. El-Tawil, Z. Liu, W. Hansen, Effects of silica powder and cement type
on durability of ultra high performance concrete (UHPC), Cem. Concr. Compos. 66
(2016) 47–56.
[27] N. Van Tuan, G. Ye, K. van Breugel, O. Copuroglu, Hydration and microstructure
of ultra high performance concrete incorporating rice husk ash, Cem. Concr. Res.
41 (2011) 1104–1111.
[28] D.G. Nair, A. Fraaij, A.A.K. Klaassen, A.P.M. Kentgens, A structural investigation
relating to the pozzolanic activity of rice husk ashes, Cem. Concr. Res. 38 (2008)
861–869.
[29] V.G. Papadakis, S. Tsimas, Supplementary cementing materials in concrete: part I:
efficiency and design, Cem. Concr. Res. 32 (2002) 1525–1532.
S.-H. Kang et al.
[30] V. Saraswathy, H.-W. Song, Corrosion performance of rice husk ash blended
concrete, Constr. Build. Mater. 21 (2007) 1779–1784.
[31] M.F.M. Zain, M.N. Islam, F. Mahmud, M. Jamil, Production of rice husk ash for use
in concrete as a supplementary cementitious material, Constr. Build. Mater. 25
(2011) 798–805.
[32] R. Zerbino, G. Giaccio, G.C. Isaia, Concrete incorporating rice-husk ash without
processing, Constr. Build. Mater. 25 (2011) 371–378.
[33] G. Giaccio, G.R. de Sensale, R. Zerbino, Failure mechanism of normal and high-
strength concrete with rice-husk ash, Cem. Concr. Res. 29 (2007) 566–574.
[34] V.-T.-A. Van, C. Rößler, D.-D. Bui, H.-M. Ludwig, Rice husk ash as both pozzolanic
admixture and internal curing agent in ultra-high performance concrete, Cem.
Concr. Compos. 53 (2014) 270–278.
[35] H. Huang, X. Gao, H. Wang, H. Ye, Influence of rice husk ash on strength and
permeability of ultra-high performance concrete, Constr. Build. Mater. 149 (2017)
621–628.
[36] J.M. Mejía, R. Mejía de Gutiérrez, C. Montes, Rice husk ash and spent diatomac-
eous earth as a source of silica to fabricate a geopolymeric binary binder, J. Clean.
Prod. 118 (2016) 133–139.
[37] R.H. Geraldo, L.F.R. Fernandes, G. Camarini, Water treatment sludge and rice husk
ash to sustainable geopolymer production, J. Clean. Prod. 149 (2017) 146–155.
[38] E. Kamseu, L.M. Beleuk à Moungam, M. Cannio, N. Billong, D. Chaysuwan,
U.C. Melo, C. Leonelli, Substitution of sodium silicate with rice husk ash-NaOH
solution in metakaolin based geopolymer cement concerning reduction in global
warming, J. Clean. Prod. 142 (2017) 3050–3060.
[39] A. Salas, S. Delvasto, R.M. de Gutierrez, D. Lange, Comparison of two processes for
treating rice husk ash for use in high performance concrete, Cem. Concr. Res. 39
(2009) 773–778.
[40] J.H.S. Rêgo, A.A. Nepomuceno, E.P. Figueiredo, N.P. Hasparyk, Microstructure of
cement pastes with residual rice husk ash of low amorphous silica content, Constr.
Build. Mater. 80 (2015) 56–68.
[41] W. Xu, T. Lo, W. Wang, D. Ouyang, P. Wang, F. Xing, Pozzolanic reactivity of silica
fume and ground rice husk ash as reactive silica in a cementitious system: a
comparative study, Materials 9 (2016) 146.
[42] S.-H. Kang, S.-G. Hong, J. Moon, Absorption kinetics of superabsorbent polymers
(SAP) in various cement-based solutions, Cem. Concr. Res. 97 (2017) 73–83.
[43] S.-H. Kang, J.-H. Lee, S.-G. Hong, J. Moon, Microstructural investigation of heat-
treated ultra-high performance concrete for optimum production, Materials 10
(2017) 1106.
[44] T. Oertel, U. Helbig, F. Hutter, H. Kletti, G. Sextl, Influence of amorphous silica on
the hydration in ultra-high performance concrete, Cem. Concr. Res. 58 (2014)
121–130.
[45] T. Oertel, F. Hutter, U. Helbig, G. Sextl, Amorphous silica in ultra-high perfor-
mance concrete: first hour of hydration, Cem. Concr. Res. 58 (2014) 131–142.
[46] G. Long, X. Wang, Y. Xie, Very-high-performance concrete with ultrafine powders,
Cem. Concr. Res. 32 (2002) 601–605.
[47] Y.-H. Kwon, S.-H. Kang, S.-G. Hong, J. Moon, Acceleration of intended pozzolanic
reaction under initial thermal treatment for developing cementless fly ash based
mortar, Materials 10 (2017) 225.
[48] Y.-H. Kwon, S.-H. Kang, S.-G. Hong, J. Moon, Intensified pozzolanic reaction on
kaolinite clay-based mortar, Appl. Sci. 7 (2017) 522.
[49] P. Richard, M. Cheyrezy, Composition of reactive powder concretes, Cem. Concr.
Res. 25 (1995) 1501–1511.
[50] I. Schachinger, H. Hilbig, T. Stengel, Effect of curing temperature at an early age
on the long-term strength development of UHPC, Proceedings of the 2nd
International Symposium on Ultra High Performance Concrete, Kassel University,
Kassel, Gemany, 2008, pp. 205–212.
[51] H. Zanni, M. Cheyrezy, V. Maret, S. Philippot, P. Nieto, Investigation of hydration
and pozzolanic reaction in reactive powder concrete (RPC) using 29Si NMR, Cem.
Concr. Res. 26 (1996) 93–100.
[52] National Precast Concrete Association (NPCA), Ultra High Performance Concrete
(UHPC): Guide to Manufacturing Architectural Precast UHPC Elements, Carmel,
USA, (2013).
[53] Association Française de Génie Civil (AFGC), Ultra High Performance Fibre-re-
inforced Concrete-recommendations (Revised Edition), Paris, France, (2013).
[54] Japan Society of Civil Engineers (JSCE), Recommendations for Design and
Construction of Ultra High-strength Fiber-reinforced Concrete Structures-draft (in
Japanese), Tokyo, Japan, (2004).
[55] Korea Concrete Institute (KCI), Design Recommendations for K-UHPC (in Korean),
Seoul, Korea, (2012).
[56] C. Pfeifer, B. Moeser, C. Weber, J. Stark, Investigations of the pozzolanic reaction
of silica fume in Ultra-high performance concrete (UHPC), The International
RILEM Conference on Material Science-MATSCI, Aachen, Germany, 2010, pp.
287–298.
[57] A. Korpa, T. Kowald, R. Trettin, Phase development in normal and ultra high
performance cementitious systems by quantitative X-ray analysis and thermo-
analytical methods, Cem. Concr. Res. 39 (2009) 69–76.
[58] Z. Wu, C. Shi, K.H. Khayat, S. Wan, Effects of different nanomaterials on hardening
and performance of ultra-high strength concrete (UHSC), Cem. Concr. Compos. 70
(2016) 24–34.
[59] C. Selleng, B. Meng, P. Fontana, Phase composition and strength of thermally
treated UHPC, Proceedings of the 4th International Symposium on Ultra-High
Performance Concrete and High Performance Materials, Kassel University, Kassel,
Gemany, 2016, pp. 7–8.
[60] Z.A.M. Ishak, A.A. Bakar, U.S. Ishiaku, A.S. Hashim, B. Azahari, An investigation
of the potential of rice husk ash as a filler for epoxidized natural rubber—II.
Fatigue behaviour, Eur. Polym. J. 33 (1997) 73–79.
11
Cement and Concrete Research xxx (xxxx) xxx–xxx
[61] H. Kizhakkumodom Venkatanarayanan, P.R. Rangaraju, Effect of grinding of low-
carbon rice husk ash on the microstructure and performance properties of blended
cement concrete, Cem. Concr. Compos. 55 (2015) 348–363.
[62] S. Chandrasekhar, P.N. Pramada, L. Praveen, Effect of organic acid treatment on
the properties of rice husk silica, J. Mater. Sci. 40 (2005) 6535–6544.
[63] M. Patel, A. Karera, P. Prasanna, Effect of thermal and chemical treatments on
carbon and silica contents in rice husk, J. Mater. Sci. 22 (1987) 2457–2464.
[64] R.M. Ferraro, A. Nanni, R.K. Vempati, F. Matta, Carbon neutral off-white rice husk
ash as a partial white cement replacement, J. Mater. Civ. Eng. 22 (2010)
1078–1083.
[65] S.-H. Kang, S.-G. Hong, J. Moon, Importance of monovalent ions on water reten-
tion capacity of superabsorbent polymer in cement based solutions, Cem. Concr.
Compos. 88 (2018) 64–72.
[66] ASTM C1761/C1761M-17, Standard Specification for Lightweight Aggregate for
Internal Curing of Concrete, ASTM International, West Conshohocken, PA, 2017,
p. 8.
[67] K. van Breugel, G. Ye, N. Van Tuan, Ultra high performance concrete made with
rice husk ash for reduced autogenous shrinkage, Proceedings of the 4th
International FIB Congress, Mumbai, India, 10–14 February 2014; Authors ver-
sion, Universities Press, 2014.
[68] G. Ye, N. Van Tuan, H. Huang, Rice Husk Ash as smart material to mitigate au-
togenous shrinkage in high (ultra-high) performance concrete, Third International
Conference on Sustainable Construction Materials and Technologies, Kyoto,
Japan, 2013.
[69] S.-H. Kang, S.-G. Hong, J. Moon, Importance of drying to control internal curing
effects on field casting ultra-high performance concrete, Cem. Concr. Res. 108
(2018) 20–30.
[70] S.-H. Kang, S.-G. Hong, J. Moon, Shrinkage characteristics of heat-treated ultra-
high performance concrete and its mitigation using superabsorbent polymer based
internal curing method, Cem. Concr. Compos. 89 (2018) 130–138.
[71] S.-H. Kang, S.-G. Hong, J. Moon, The effect of superabsorbent polymer on various
scale of pore structure in ultra-high performance concrete, Constr. Build. Mater.
172 (2018) 29–40.
[72] ASTM C230/C230M-14, Standard Specification for Flow Table for Use in Tests of
Hydraulic Cement, ASTM International, West Conshohocken, PA, 2014, p. 6.
[73] NF P18-470, Ultra-high Performance Fibre-reinforced Concrete - Specifications,
Performance, Production and Conformity, Association Française de Normalisation
(AFNOR), Saint-Denis, France, 2016.
[74] K. Scrivener, R. Snellings, B. Lothenbach, A Practical Guide to Microstructural
Analysis of Cementitious Materials, CRC Press, 2016.
[75] J. Justs, M. Wyrzykowski, F. Winnefeld, D. Bajare, P. Lura, Influence of super-
absorbent polymers on hydration of cement pastes with low water-to-binder ratio,
J. Therm. Anal. Calorim. 115 (2014) 425–432.
[76] ASTM C109/C109M-16a, Standard Test Method for Compressive Strength of
Hydraulic Cement Mortars (Using 2-in. or [50-mm] Cube Specimens), ASTM
International, West Conshohocken, PA, 2016, p. 10.
[77] A. Schöler, B. Lothenbach, F. Winnefeld, M. Zajac, Hydration of quaternary
Portland cement blends containing blast-furnace slag, siliceous fly ash and lime-
stone powder, Cem. Concr. Compos. 55 (2015) 374–382.
[78] Y. Jeong, C. Hargis, S. Chun, J. Moon, Effect of calcium carbonate fineness on
calcium sulfoaluminate-belite cement, Materials 10 (2017) 900.
[79] Y. Jeong, C.W. Hargis, S.-C. Chun, J. Moon, The effect of water and gypsum
content on strätlingite formation in calcium sulfoaluminate-belite cement pastes,
Constr. Build. Mater. 166 (2018) 712–722.
[80] A. Belsky, M. Hellenbrandt, V.L. Karen, P. Luksch, New developments in the
Inorganic Crystal Structure Database (ICSD): accessibility in support of materials
research and design, Acta Crystallogr. Sect. B: Struct. Sci. 58 (2002) 364–369.
[81] S. Gražulis, A. Daškevič, A. Merkys, D. Chateigner, L. Lutterotti, M. Quirós,
N.R. Serebryanaya, P. Moeck, R.T. Downs, A. Le Bail, Crystallography Open
Database (COD): an open-access collection of crystal structures and platform for
world-wide collaboration, Nucleic Acids Res. 40 (2012) D420–D427.
[82] W. Huang, H. Kazemi-Kamyab, W. Sun, K. Scrivener, Effect of cement substitution
by limestone on the hydration and microstructural development of ultra-high
performance concrete (UHPC), Cem. Concr. Compos. 77 (2017) 86–101.
[83] Z. Wu, C. Shi, K.H. Khayat, Influence of silica fume content on microstructure
development and bond to steel fiber in ultra-high strength cement-based materials
(UHSC), Cem. Concr. Compos. 71 (2016) 97–109.
[84] J. Justs, M. Wyrzykowski, D. Bajare, P. Lura, Internal curing by superabsorbent
polymers in ultra-high performance concrete, Cem. Concr. Res. 76 (2015) 82–90.
[85] D. Snoeck, D. Schaubroeck, P. Dubruel, N. De Belie, Effect of high amounts of
superabsorbent polymers and additional water on the workability, microstructure
and strength of mortars with a water-to-cement ratio of 0.50, Constr. Build. Mater.
72 (2014) 148–157.
[86] G. Ye, X. Liu, G. De Schutter, A.M. Poppe, L. Taerwe, Influence of limestone
powder used as filler in SCC on hydration and microstructure of cement pastes,
Cem. Concr. Compos. 29 (2007) 94–102.
[87] G. Ye, X. Liu, A.M. Poppe, G. De Schutter, K. van Breugel, Numerical simulation of
the hydration process and the development of microstructure of self-compacting
cement paste containing limestone as filler, Mater. Struct. 40 (2007) 865–875.
[88] B. Lothenbach, G. Le Saout, E. Gallucci, K. Scrivener, Influence of limestone on the
hydration of Portland cements, Cem. Concr. Res. 38 (2008) 848–860.
[89] T. Oey, A. Kumar, J.W. Bullard, N. Neithalath, G. Sant, G. Scherer, The filler effect:
the influence of filler content and surface area on cementitious reaction rates, J.
Am. Ceram. Soc. 96 (2013) 1978–1990.
[90] A. Kumar, T. Oey, G. Falzone, J. Huang, M. Bauchy, M. Balonis, N. Neithalath,
J. Bullard, G. Sant, The filler effect: the influence of filler content and type on the
S.-H. Kang et al.
hydration rate of tricalcium silicate, J. Am. Ceram. Soc. 100 (2017) 3316–3328.
[91] P. Hewlett, Lea's Chemistry of Cement and Concrete, 4th ed., Butterworth-
Heinemann, Oxford, UK, 2010.
[92] P.K. Mehta, P.J. Monteiro, Concrete-Microstructure, Properties and Materials,
McGeaw-Hill, New York, USA, 2006.
[93] O.H. Wallevik, J.E. Wallevik, Rheology as a tool in concrete science: the use of
rheographs and workability boxes, Cem. Concr. Res. 41 (2011) 1279–1288.
[94] M. Lesti, S. Ng, J. Plank, Ca2+−mediated interaction between microsilica and
polycarboxylate comb polymers in a model cement pore solution, J. Am. Ceram.
Soc. 93 (2010) 3493–3498.
[95] F.-R. Kong, L.-S. Pan, C.-M. Wang, D.-L. Zhang, N. Xu, Effects of polycarboxylate
superplasticizers with different molecular structure on the hydration behavior of
cement paste, Constr. Build. Mater. 105 (2016) 545–553.
[96] S. Mindess, J.F. Young, D. Darwin, Concrete, 2nd edition, Prentice Hall, 2003.
[97] K.K. Aligizaki, Pore Structure of Cement-based Materials: Testing, Interpretation
and Requirements, Taylor & Francis, Abingdon, Oxfordshire, UK, 2006.
[98] P.K. Mehta, Concrete: Structure, Properties and Materials, Prentice-Hall,
Englewood Cliffs, NJ, USA, 1986.
[99] D. Heinz, H.-M. Ludwig, Heat treatment and the risk of DEF delayed ettringite
formation in UHPC, Proceedings of the 1st International Symposium on Ultra-High
Performance Concrete Kassel University, Kassel, Germany, 2004, pp. 717–730.
[100] M. Cheyrezy, V. Maret, L. Frouin, Microstructural analysis of RPC (reactive
12
Cement and Concrete Research xxx (xxxx) xxx–xxx
powder concrete), Cem. Concr. Res. 25 (1995) 1491–1500.
[101] A. Gonzalez-Corominas, M. Etxeberria, C.S. Poon, Influence of steam curing on the
pore structures and mechanical properties of fly-ash high performance concrete
prepared with recycled aggregates, Cem. Concr. Compos. 71 (2016) 77–84.
[102] K. Wille, A.E. Naaman, G.J. Parra-Montesinos, Ultra-high performance concrete
with compressive strength exceeding 150 MPa (22 ksi): a simpler way, ACI Mater.
J. 108 (2011) 46–54.
[103] E. Fehling, M. Schmidt, J. Walraven, T. Leutbecher, S. Fröhlich, Ultra-High
Performance Concrete UHPC: Fundamentals, Design, Examples, John Wiley &
Sons, 2014.
[104] M. Wyrzykowski, P. Lura, F. Pesavento, D. Gawin, Modeling of internal curing in
maturing mortar, Cem. Concr. Res. 41 (2011) 1349–1356.
[105] M. Wyrzykowski, S. Ghourchian, S. Sinthupinyo, N. Chitvoranund, T. Chintana,
P. Lura, Internal curing of high performance mortars with bottom ash, Cem. Concr.
Compos. 71 (2016) 1–9.
[106] A. Arora, M. Aguayo, H. Hansen, C. Castro, E. Federspiel, B. Mobasher,
N. Neithalath, Microstructural packing- and rheology-based binder selection and
characterization for ultra-high performance concrete (UHPC), Cem. Concr. Res.
103 (2018) 179–190.
[107] H.T. Le, H.-M. Ludwig, Effect of rice husk ash and other mineral admixtures on
properties of self-compacting high performance concrete, Mater. Des. 89 (2016)
156–166.