Construction and Building Materials 208 (2019) 394–401

Contents lists available at ScienceDirect

Construction and Building Materials

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

Influence of rice husk ash on the waterproof properties of ultrafine fly

ash based geopolymer
Huajun Zhu a,c,⇑, Guangwei Liang a,b,c, Jun Xu a,c, Qisheng Wu a,c, Munan Zhai a,c
a
School of Materials Science and Engineering, Yancheng Institute of Technology, Yancheng, Jiangsu 224051, PR China
b
Key Laboratory for Advanced Technology in Environmental Protection of Jiangsu Province, Yancheng Institute of Technology, Yancheng, Jiangsu 224051, PR China
c
School of Materials Science and Engineering, Jiangsu University, Zhenjiang, Jiangsu 212013, PR China

h i g h l i g h t s

The ultrafine fly ash based geopolymer with RHA was prepared.

The improvement in waterproof property of ultrafine fly ash based geopolymer was realized efficiently.

Mechanism of RHA for improving waterproof properties of geopolymer was clarified.

The RHA can be perfectly used as a supplementary cementitious material in concrete industry.

a r t i c l e i n f o a b s t r a c t

Article history: This work studies the influence of rice husk ash (RHA) on the waterproof and microstructural properties
Received 16 October 2018 of ultrafine fly ash (UUFA) based geopolymer. Fly ash based geopolymer (FG) pastes containing different
Received in revised form 29 January 2019 amounts of RHA were prepared and characterized. Combining with the softening coefficient, surface
Accepted 4 March 2019
properties of samples, TG and FT-IR etc. tests, the mechanism was uncovered. The results indicate that
not only would the specific honeycomb-hole effect and active SiO2 brought by RHA synergistically lead
to the densification of structure, but also decline the existence of calcium hydroxide and promote the for-
Keywords:
mation of gel, which make a significant contribution to the improvement of waterproof property.
Rice husk ash
Ultrafine fly ash
Ó 2019 Published by Elsevier Ltd.
Geopolymer
Waterproof

1. Introduction
Geopolymer is a kind of inorganic cementitious material with
amorphous three-dimensional network structure formed by min-
eral polycondensation from silicon-aluminum raw material [1–3].
As a new green cementitious material, geopolymers have excellent
properties such as high strength, corrosion resistance and good
sealing effect, which make them widely used in the fields of build-
ing materials, solid sealed nuclear waste and aerospace materials
[4–6]. For this reason, the study of geopolymers has attracted the
attention of many related scholars.
Fly ash is a typical reusable resource, which is a byproduct from
the coal combustion [7]. Due to the special action of fly ash as a
precursor arising from its ‘ball-bearings’ structure, it is excellently
used in the production of building materials and development of
⇑ Corresponding author at: School of Materials Science and Engineering,
Yancheng Institute of Technology, Yancheng, Jiangsu 224051, PR China.
E-mail address: hjzhu2008@ycit.edu.cn (H. Zhu).
sustainable materials [8,9]. Shaikh et al. [10] studied the effect of
ultrafine fly ash contents on the compressive strength and durabil-
ity properties of concretes. The roles of ultrafine fly ash in the for-
mation of C–S–H were to accelerate the pozzolanic activity and
promote more gels formation. Previous researches show that the
ultrafine fly ash makes a significant contribution to the optimiza-
tion of the rheology of geopolymer owing to its‘ball-bearings’
and dispersing agent effects. The utilization of ultrafine fly ash
improves the workability of geopolymer and broadens its applica-
ble field greatly [11]. Ren et al. [12] used the fly ash as modifier to
modify the crystallization behavior of blast furnace slag. The com-
position of precipitate did not change with the variation in the fly
ash content, while did change the content of precipitate. Moreover,
the crystallization temperature of minerals was affected markedly
as the addition of fly ash. The relationship between mechanical
properties of concrete and active fly ash was studied [13]. It indi-
cated that the addition of fly ash has a significant improvement
in concrete strength, besides, Aquis Na2SiO3 activator is the most
suitable activator for fly ash in view of enhancing properties.

https://doi.org/10.1016/j.conbuildmat.2019.03.035
0950-0618/Ó 2019 Published by Elsevier Ltd.
 H. Zhu et al. / Construction and Building Materials 208 (2019) 394–401 395

Rice husk ash (RHA) is a kind of high silicon pozzolanic ash 100
material with specific potential value. RHA was mainly composed UFFA
of amorphous SiO2, and because of the role of SiO2 gel particle, a RHA
large number of nanoscale porosities was formed by non- 80
compact agglomeration [14–16]. This is also the fundamental rea-

Cumulative volume (%)

son why rice husk ash has huge specific surface area and ultra-high
pozzolanic activity. Ahsan and Hossain [17] used RHA as a cemen- 60
titious material in concrete industry. Results showed the finer
RHA-modified concrete had better concrete properties than the
coarse RHA-modified concrete, and the optimum replacement is 40
10%. A superhydrophobic coating material was prepared from rice
husk ash [18]. This coating did not affect the surface hardness or
the compressive strength significantly, but the coating resulted in
20
a higher hydrophobicity due to the increase of surface roughness
and reduction of surface porosity. Thomas [19] presented an over-
view of a novel green concrete, which was partially comprised of
0
rice husk ash as a supplementary cementitious material. It is 0.1 1 10 100 1000
potential of RHA for improving self-compactness, shrinkage and
Particle size ( μm)
permeability, and resistance to chloride, carbonation of concrete.
Prior researches showed that ultrafine fly ash and RHA could be Fig. 1. Particle size distribution of UFFA and RHA.
partially used as replacement of cementitious materials, while only
very limited data could be available about the application of ultra-
fine fly ash and RHA for preparing waterproof material. Hence, this Table 2
Mix compositions and proportions of the geopolymer pastes.
research is aimed at the development of waterproof material. In this
study, the influence of RHA contents on the waterproof properties Sample name Fly ash content (%) Rice husk ash content (%) l/b
of ultrafine fly ash based geopolymer was systematically investi- F10R0 100 0 0.5
gated. The water resistance was also evaluated by relevant tests. F9R1 90 10 0.5
This research has a great significance in promoting the further F8R2 80 20 0.5
F7R3 70 30 0.5
application of RHA and development of fly ash based geopolymer.
F6R4 60 40 0.5
F5R5 50 50 0.5
2. Materials and methods

2.1. Experimental materials

Ultrafine fly ash (UFFA) was a by-product collected from the exhaust smoke of
coal combustion supplied by Sika Ltd. (Suzhou, China). Rice husk obtained from
Debo Bioenergy Technology Co., Ltd. (Hefei, China), used as partial replacement of
ultrafine fly ash. Rice husk ash (RHA) was pretreated in an electrically heated muffle
furnace with a condition of room temperature to 800 °C and heating rate of 3 °C/
min in air for 0.5 h. The oxide compositions and the particle size distribution of
the UFFA and RHA are listed in Table 1 and Fig. 1 respectively. The alkaline activator
was prepared by blending sodium silicate solution (Na2O = 8.16 wt%, SiO2 = 26.01 -
wt%) with sodium hydroxide pellets (96 wt% purity) and distilled water to reach a
modulus of 1.5 (molar ratio of SiO2 to Na2O) and a concentration of 37 wt%. Then
equilibrate this activator to room temperature prior to using.
2.2. Composition design and synthesis of specimens
In total, six mixes were developed. One was the control mix (F10R0), and the
other five mixes (F9R1, F8R2, F7R3, F6R4 and F5R5) were prepared by partial
replacement of UFFA with RHA in proportions of 10%, 20%, 30%, 40% and 50%. The
sodium silicate activator was used at constant liquid to binder mass ratio of 0.5
to prepare paste. The mixture proportions are described in Table 2. The specimens
cast in 20  20  20 mm cubical molds was used to measure the effects of RHA con-
tents on the mechanical and waterproof properties of FG. The specimens were cured
sealedly at room temperature for 24 h, and then de-molded to steam-cured at 50 °C
until 7 and 28 days arrived.
2.3.2. Water absorption test
The water absorption of each specimen was determined to analyze the water-
proof property of FG. The water absorption (Wa) is a parameter related to the water-
proof property [20], reflecting the capability of the anti-entering of the interior of
samples to water and it can be calculated by Eq. (1):
Mi  M
Wa ¼  100% ð1Þ
M
where Mi is the quality of specimen after i hour procedure of saturating water (i = 2,
12, 18 and 24), M is the quality of specimen after drying to constant mass in an oven
at 100 °C.
2.3.3. Calculation of the softening coefficient value
Softening coefficient (K) is a significant index for evaluating waterproof of
materials, which represents the property especially mechanical property main-
tained after saturating water. The ratio of the compressive strength after water sat-
uration to that after drying was defined as the softening coefficient [20]. It is
generally considered that the material whose K > 0.85 is strong waterproof mate-
rial. Softening coefficient (K) can be calculated by Eq. (2):
Cw
K¼ ð2Þ
Cd
where Cw is the compressive strength value of specimen after saturating water 24 h,
Cd is the compressive strength value of specimen after drying 24 h.

2.3.4. Microhardness of specimen surface

2.3. Experimental methods
2.3.1. Mechanical performance test
A WHY-200 Auto Test Compression Machine capable of a maximum force value
of 200 kN, was applied to determine the compressive strength of FG at the ages of 7
and 28 days. The density test was carried out by using DX-300C Automatic Density
Measuring Instrument.
Interfacial compactness between aggregates has great effects on hygroscopicity
of specimen. Microhardness (Hv) was measured to evaluate the compactness of
specimen surface [21]. This test was carried out at 0.5 kgf loads and 10 s maintain-
ing loading time by using a HV-10 Vickers Hardness Tester. The microhardness was
calculated by Eqs. (3) and (4):

Table 1
Compositions of rice husk ash and ultrafine fly ash by X-ray fluorescence analysis. LOI is loss on ignition at 1000 °C, wt%.

SiO2 Al2O3 CaO MgO Fe2O3 K2O TiO2 Na2O LOI

Rice husk ash 93.1 0.3 1.5 0.6 0.2 2.3 0.03 0.06 0.8
Ultrafine fly ash 54.6 14.6 12.5 4.5 4.6 2.7 0.8 2.6 1.0
396 H. Zhu et al. / Construction and Building Materials 208 (2019) 394–401

2
d contents up to 50%. The lower density of RHA itself could bring
F¼ ð3Þ
2sin68 the reduction of density in the geopolymer system.

P
Hv ¼ ð4Þ
F
where F is the area of indentation, d is the impression diameter and P is the load
value.
2.3.5.. Contact angle test
In order to study the relationship between RHA contents and hydrophobicity of
specimen surface, the contact angle was introduced in this research [22]. The con-
tact angle of specimen surface was measured by using the contact angle goniometer
(JC2000C1), a DH HV1351UM system with a maximum error was 0.1°. The liquid
droplet was deposited under gravity by a syringe pointed vertically down onto
the surface of specimen. The angle could be captured by a high-resolution camera
and analyzed by analysis software.
2.4. Characterization methods of specimen
The phase structure were characterized by X-ray diffraction (XRD) using a
diffractometer (RIGAKU, model D/max) with CuKa radiation in the range of
2h = 5°–80° at 2.4°/min scanning rate. The morphologies of geopolymer specimens
with different RHA contents were determined by a field emission scanning electron
microscope (JEOL, model JSM-7001F) at the testing conditions of 10 kV accelerating
voltage and 10 mm working distance. Thermogravimetric analysis (TGA) measures
weight changes in the specimen as a function of temperature in the nitrogen atmo-
sphere, indicating the mass loss in correspondence with the phase decomposition.
The FT-IR analysis of the samples at age of 28 d was performed using Fourier trans-
form infrared spectrometer (American Nicolet STD-11202624D).
3. Results and discussion
3.1. Effect of RHA contents on the mechanical performance of fly ash
based geopolymer
Table 3 lists the compressive strength of F10R0, F9R1, F8R2,
F7R3, F6R4 and F5R5 geopolymer samples at the ages of 7 and
28 days respectively. For the reference F10R0 paste, the compres-
sive strength at 7 d is 61.9 MPa and it increases to 69.5 MPa at
28 d. The compressive strength of F9R1 shows a slightly decreasing
compared with the reference F10R0 paste at the same age. How-
ever, it shows a sharply decreasing in compressive strengths at
all ages when the addition dosage of RHA up to 30%. This indicates
that the RHA contributes less to the compressive strength develop-
ment of FR paste in comparison to the fly ash. It is probable related
to the limited availability of Al resource due to the partial replace-
ment of UFFA by RHA, resulting to this phenomenon. However, the
waterproof property gains an improvement due to the filling effect
from RHA particles, which would be discussed in the next few
sections.
According to Fig. 2, the density of F10R0 specimen was 2.018 g/
cm3 and 2.065 g/cm3 at ages of 7 and 28 days respectively, which
showing a development of mechanical performance as curing time
goes on. The density decreased constantly with the increase of RHA
3.2. Effect of RHA contents on the waterproof property of fly ash based
geopolymer
3.2.1. Water absorption
The effects of RHA dosages on water absorption of geopolymer
at 7 d and 28 d curing ages are shown in Fig. 3. It exhibits relative
lower water absorption when the content of RHA is below 30%,
especially at the age of 7 d. The lowest water absorption of sample
F8R2 was just 2% and 0.4% at 7 d and 28 d curing ages respectively.
Considering the honeycomb-hole microstructure and hollow state
of RHA [23,24], the lower water absorption would be the results
from interpenetrating action and filling effect between UUFA and
RHA. The existence of unfilled honeycomb-hole in pastes produced
by the excessive RHA addition contributes to the increasing of
water absorption. This is consistent with the development of com-
pressive strength in previous work.
3.2.2. Softening coefficient value
To characterize the effect of RHA contents on fly ash based
geopolymer, softening coefficient was determined to evaluate the
waterproof properties. Fig. 4 shows the softening coefficient of
the fly ash based geopolymer pastes at all different ages. For the
reference F10R0 paste, the softening coefficient at 7 d is 0.65 and
it increases to 0.74 at the age of 28 d. The softening coefficient
shows a markedly increase with the addition of RHA under 20%,
however, it appears to decrease when the dosage beyond 20%.
The softening coefficient value reaches to the maximum (0.85
and 0.81 at the ages of 7d and 28d, respectively) with 20% RHA
adding, which increase by 30.7% and 9.5% compared with F10R0
paste at corresponding ages. It could be the persuasive evidence
illustrating RHA contributes more to the waterproof property
development than the fly ash. This may be due to that the func-
tions of highly ‘‘superpozzolan” activity from RHA together with
the effect of water absorption improved by honeycomb-hole
microstructure.
3.3. Effect of RHA contents on the surface hydrophobic properties of fly
ash based geopolymer
3.3.1. Microhardness value
The microhardness (Hv) values of sample surface are described
in Fig. 5. It shows that the development rules in Hv of specimen
2.1
7days
28 days
2.0
Density value (g/cm3)

contents, the density value reached to the minimum (1.682 g/cm3

and 1.807 g/cm3 in correspondence with 7 d and 28 d) when RHA
1.9

Table 3
Compressive strength of the geopolymer specimens after 7 and 28 days curing.
1.8
Mixtures RHA contents Compressive strength
(MPa)
7d 28 d 1.7
F10R0 0% 61.9 69.5
F9R1 10% 58.9 67.5
F8R2 20% 50.7 63.4 F10R0 F9R1 F8R2 F7R3 F6R4 F5R5
F7R3 30% 42.9 47.6
Samples
F6R4 40% 39.7 41.6
F5R5 50% 32.7 38.7
Fig. 2. Density of F10R0, F9R1, F8R2, F7R3, F6R4 and F5R5 sample.
 H. Zhu et al. / Construction and Building Materials 208 (2019) 394–401 397

(a) 724.22 MPa respectively at the ages of 7d and 28d. It is probably

9 no exaggeration to think that the active SiO2 in RHA reacts with
2h the hydrates of UUFA such as Ca(OH)2 resulting in the decrease
8
12 h of Ca(OH)2 spatial distribution in paste is the fundamental cause
7 18 h for the increase of Hv.
24 h
water absorption (%)

6
3.3.2. Contact angle
5 Static water contact angle images of F10R0, F9R1, F8R2 and
F5R5 specimens at the ages of 7 d and 28 d are exhibited in
4
Fig. 6. Referring to the contact angle values of all geopolymer spec-
3 imens listed in Table 4. It could be apparently observed that the
addition of RHA makes great contributions to the improvement
2 of contact angle. For the reference sample, the contact angles on
the surface were 41° and 45° respectively. While in F8R2 system,
1 the contact angles gain 36.07% and 30.48% improvement at the
F10R0 F9R1 F8R2 F7R3 F6R4 F5R5 respective curing ages. It is likely to be considered that the
improvement behavior is the result synergistically determined by
Samples the denser structure, brought by the active SiO2 and honeycomb-
(b)
hole effect, and the lower water absorption. However, the over-
2.0 much RHA contents contribute to the water absorption rise up
2h rather than the formation of dense structure.
1.8 12 h
18 h
1.6 24 h 3.4. Thermogravimetric analysis (TGA)
water absorption (%)

1.4

1.2 Fig. 7 displays the mass loss fractions of the geopolymer pastes
at four different temperature periods. The main mass loss of all
1.0 samples is centered within 250 °C, which is due to the dehydration
0.8 of free water at around 100 °C and the evaporation of physical and
chemical bound water in gel between 100 and 200 °C. Further-
0.6
more, it is worthwhile to note that there are no significant mass
0.4 loss occurring at both 400–600 °C and 600–800 °C temperature
ranges, indicating the presence of C-(A)-S-H and N-A-S-H amor-
0.2
phous gels. The mass loss between 400 and 600 °C is probably
F10R0 F9R1 F8R2 F7R3 F6R4 F5R5 determined by the existence of calcium hydroxide. The reaction
between calcium hydroxide and active SiO2 originated from the
Samples
extra RHA contents, declining the mounts of calcium hydroxide,
Fig. 3. Water absorption of F10R0, F9R1, F8R2, F7R3, F6R4 and F5R5 sample: (a) 7 and then decreasing the mass loss under the corresponding time
and (b) 28 days. ranges. For the mass loss behavior in the range of 600–800 °C, it
exhibits a poor change depending on the decomposition of calcite
(CaCO3). This means that the extra calcium source released from
0.85 7 days RHA dissolution promotes the formation of gel phase rather than
calcite together with the SiO2-rich weakens the reaction of calcium
Softening coefficient value

28 days
hydroxide with carbon dioxide.
0.80

800
0.75 7 days
700 28 days
Microhardness value (MPa)

0.70 600

500
0.65
400

F10R0 F9R1 F8R2 F7R3 F6R4 F5R5 300

Samples
200
Fig. 4. Softening coefficients of F10R0, F9R1, F8R2, F7R3, F6R4 and F5R5 sample.
100

surface with the addition of RHA. The Hv value increase with the 0
addition of RHA, and it begins to decrease when its content is F10R0 F9R1 F8R2 F7R3 F6R4 F5R5
beyond 20% especially a sharp reduction of Hv in comparison with Samples
reference sample can be observed in F6R4 and F5R5. The maximum
values of Hv occur in F8R2 system were 637.65 MPa and Fig. 5. Microhardness of F10R0, F9R1, F8R2, F7R3, F6R4 and F5R5 sample.
398 H. Zhu et al. / Construction and Building Materials 208 (2019) 394–401
Fig. 6. Contact angles of F10R0, F9R1, F8R2 and F5R5 sample: (a) 7 and (b) 28 days.
Table 4
Contact angle of the geopolymer specimens after 7 and 28 days curing.
F10R0 F9R1
7 days 41.16 45.66
28 days 45.41 51.70
3.5. Fourier transform infrared spectroscopy (FT-IR) analysis
The FTIR spectra for all the pastes at age of 28 d are presented in
Fig. 8. It apparently illustrates that a band associated with the
vibrations of OH and H-OH at approximately 1640 and
3420 cm1, which was assigned to the existence of crystal or
absorbed water produced during the reaction procedures. The
strongest vibration of T-O-Si bonds at 982–1003 cm1 (where
T = tetrahedral Si or Al) could be attributed to the formation of
gel phases. According to the previous studies [25,26], it is probable
to present the C-(A)-S-H and N-A-S-H gel that is centered at around
980 and 1000 cm1 wavenumbers, respectively. The lower Ca/Si
resulted from the increases of RHA dosage promoting the develop-
ment of C-(A)-S-H gel phases in correspondence with the relatively
higher wavenumber observed in Fig. 6. However, the wavenumber
bands weaken or even disappear in samples F6R4 and F5R5 with
the more addition of RHA, which indicates that the excessive
RHA content makes a negative role in the procedure of reaction
and is unfavorable to the formation of gel phases. This result is
consistent with the change regulation of softening coefficient. That
is to say, the addition of RHA dosage should not beyond 20%.
3.6. Morphology and mineralogical composition
3.6.1. XRD
Fig. 9 shows the mineralogical changes of hardened pastes con-
taining different dosages of RHA at the age of 28 d. According to
Fig. 9, calcium silicate and quartz are the main crystallized prod-
ucts along with almost no cristobalite in F10R0 paste. The peak
intensity of calcium silicate phase enhanced with the increasing
of RHA content, which is assigned to the introduction of silicon
source, came from RHA, promoting the more formation of C-S-H
gel and a long period time of hydration reaction. It also indicated
that the more reaction production especially calcium silicate
formed with the addition of RHA, implying the reduction CH due
to the silicification of calcium sources, consistent with the result
of TGA test. Just because of the introduction of abundant silicon
source, the diffraction patterns of cristobalite enhance obviously
F8R2 F7R3 F6R4 F5R5
56.01 40.52 37.43 24.36
59.25 46.27 37.83 23.10
due to the unreacted RHA remains existent. In addition, the
decrease of UFFA content in the system results in the peak inten-
sity of quartz weakened.
3.6.2. SEM
The geopolymer samples with different RHA contents after
28 days curing at 50 °C were chosen for SEM testing. As shown in
Fig. 10, images in Fig. 9(a)–(f) illustrate the effects of RHA on the
microstructure of geopolymer. The F10R0 sample will appear a
large amount of voids and a small amount of microcracks, which
were probably caused by the crystallization of the gel phase and
function of microstress from hydration. The microcracks began to
reduce and even disappear along with the refinement of voids
and reduction in quantity of aperture could be observed in samples
F9R1 and F8R2, attributed to the filling effect of RHA. The role of
rice husk ash as an active filler can also be found from related stud-
ies, which is in good agreement with the results in this experiment
[27]. While it appears large unfilled voids or more microcracks in
comparison with sample F10R0 when the content of RHA up to
30%. These phenomena persuasively testify that the proper addi-
tion of RHA is beneficial to the formation of a denser and homoge-
neous microstructure in geopolymer, consistent with the contact
angle and microhardness results presented in this work.
4. Conclusion
In this study, the effect of RHA on the waterproof and
microstructural properties of fly ash based geopolymer was inves-
tigated. It was obvious that the increasing of RHA contents from 0
to 20% achieved a significant improvement on the waterproof
property of geopolymer. The optimum level in this study for the
blend of rice husk ash used was 20%. At this level, there was an
obvious improvement in the waterproof property, which includes
microhardness, contact angle and softening coefficient, etc param-
eters gained enhancements. The RHA particles with active SiO2 and
honeycomb-hole structure provide the extra kinetic sources for the
later reaction and result in honeycomb-hole effect. Moreover, a
more compact structure of geopolymer was formed by the filling
 H. Zhu et al. / Construction and Building Materials 208 (2019) 394–401 399

(a)
13.0 0.8

< 250 °C 0.6

12.5 400-600°C
Weight loss <250 ºC (%) 600-800°C

Weight loss 400-600 ºC (%)

0.7

Weight loss 600-800 ºC (%)

12.0
0.5
0.6
11.5

11.0 0.4
0.5

10.5

0.3 0.4
F10R0 F9R1 F8R2 F7R3 F6R4 F5R5
Samples
(b)
13.0 0.8
< 250 °C
0.7
400-600°C
12.5 600-800°C 0.7
Weight loss <250 ºC (%)

Weight loss 400-600 ºC (%)

Weight loss 600-800 ºC (%)
0.6

12.0
0.6
0.5

11.5
0.5
0.4

11.0

0.3 0.4

10.5

0.2 0.3
F10R0 F9R1 F8R2 F7R3 F6R4 F5R5
Samples

Fig. 7. Mass loss fractions at different temperature regions of F10R0, F9R1, F8R2, F7R3, F6R4 and F5R5 sample: (a) 7 and (b) 28 days.

(6)
♠ − Quartz
1638.52 (5) 3448.78 ♣
♣ − Cristobalite
987.37

1638.52 (1) 3448.78 ♦ − Calcium Silicate

(2)
1642.94
♣
987.37

(3) 3415.61
1649.16
3437.65
F5R5 ♦
(4) ♠
1644.52 F6R4 ♠
♣ ♦
3413.57 F7R3 ♠ ♦
1645.01
F8R2
♠
991.72

3435.11
♦
(1) F10R0 F9R1
♣ ♠
(2) F9R1 ♦
982.08

F10R0
(3) F8R2 ♠ ♦
(4) F7R3
(5) F6R4
996.38

(6) F5R5 10 20 30 40 50 60 70 80
2 Theta°
1002.92

700 1400 2100 2800 3500 Fig. 9. XRD patterns of F10R0, F9R1, F8R2, F7R3, F6R4 and F5R5 sample.
-1
Wave number (cm )

Fig. 8. FTIR spectra of F10R0, F9R1, F8R2, F7R3, F6R4 and F5R5 paste. effect of SiO2 particles, contributing to the development of
geopolymer waterproof property significantly. The calcium
brought by RHA promotes the formation of gel phase and the abun-
400 H. Zhu et al. / Construction and Building Materials 208 (2019) 394–401
Fig. 10. SEM images of (a) F10R0, (b) F9R1, (c) F8R2, (d) F7R3, (e) F6R4 and (f) F5R5 sample.
dant SiO2 component in RHA weakens the reaction of calcium
hydroxide with carbon dioxide, which are the rooted cause for
the enhancement of waterproof property.
Conflict of interest
None.
Acknowledgements
Acknowledged financial supports include the National Natural
Science Foundation of China (51502259,51572234), Postgraduate
Practical Innovation Project of Jiangsu Province (SJCX18_0885),
the ‘‘Six Top Talents” program of Jiangsu Province (2016-XCL-
070), the Science and technology project from Ministry of Housing
and Urban-Rural Development of the People’s Republic of China
(2015-K4-007) and Joint Open Fund of Jiangsu Collaborative Inno-
vation Center for Ecological Building Material and Environmental
Protection Equipments and Key Laboratory for Advanced Technol-
ogy in Environmental Protection of Jiangsu Province and Supported
by Open Project of Key Laboratory for Ecological Environment
Materials of Jiangsu Province (JH201827).
References
[1] C. Shi, A. Fernández-Jiménez, A. Palomo, New cements for the 21st century: the
pursuit of an alternative to Portland cement, Cem. Concr. Res. 41 (2011) 750–
763.
[2] C. Ma, A.Z. Awang, W. Omar, Structure and material performance of
geopolymer concrete: a review, Constr. Build. Mater. 186 (2018) 90–102.
[3] C. Bai, P. Colombo, Processing, properties and applications of highly porous
geopolymer: a review, Ceram. Int. 44 (2018) 16103–16118.
[4] A.A. Siyal, M.R. Shamsuddin, M.I. Khan, N.E. Rabat, M.Z. Zulfiqar, Z. Man, J.
Siame, K.A. Azizli, A review on geopolymers as emerging materials for the
absorption of heavy metals and dyes, J. Environ. Manage. 224 (2018) 327–339.
[5] P. Zhang, Y. Zhang, K. Wang, J. Zhang, A review on properties of fresh and
hardened geopolymer mortar, Compos. Part. B 152 (2018) 79–95.
[6] L.H.J. Martin, F. Winnefeld, E. Tschopp, C.J. Müller, B. Lothenbach, Influence of
fly ash on the hydration of calcium sulfoaluminate cement, Cem. Concr. Res. 95
(2017) 152–163.
[7] L. Mo, L. Lv, M. Deng, J. Qian, Influence of fly ash and metakaolin on the
microstructure and compressive strength of magnesium potassium phosphate
cement paste, Cem. Concr. Res. 111 (2018) 116–129.
[8] N. Toniolo, A.R. Boccaccini, Fly ash-based geopolymers containing added
silicate waste. A review, Ceram. Int. 43 (2017) 14545–14551.
[9] Z. Zhang, J.L. Provis, J. Zou, A. Reid, H. Wang, Toward an indexing approach to
evaluate fly ashes for geopolymer manufacture, Cem. Concr. Res. 85 (2016)
163–173.
[10] F. Shaikh, S. Supit, Compressive strength and durability properties of high
volume fly ash (HVFA) concretes containing ultrafine fly ash (UFFA), Constr.
Build. Mater. 82 (2015) 192–205.
[11] T. Yang, H. Zhu, Z. Zhang, X. Gao, C. Zhang, Q. Wu, Effect of fly ash microsphere
on the rheology and microstructure of alkali-activated fly ash/slag pastes, Cem.
Concr. Res. 109 (2018) 198–207.
[12] Q. Ren, Y. Zhang, Y. Long, Z. Zou, J. Pei, Crystallisation behaviour of blast
furnace slag modified by adding fly ash, Ceram. Int. 44 (2018) 11628–11634.
 H. Zhu et al. / Construction and Building Materials 208 (2019) 394–401
[13] Y. Hefni, Y.A.E. Zaher, M.A. Wahab, Influence of activation of fly ash on the
mechanical properties of concrete, Constr. Build. Mater. 172 (2018) 728–734.
[14] D. Ouyang, K. Chen, Study on the Microstructure of rice husk ash, J. Mater. Sci.
Energy 85 (2003) 647–650.
[15] M. Vigneshwari, K. Arunachalam, A. Angayarkanni, Replacement of silica fume
with thermally treated rice husk ash in Reactive Powder Concrete, J. Clean.
Prod. 188 (2018) 264–277.
[16] W. Khan, K. Shehzada, T. Bibi, S.U. Islam, S.W. Khan, Performance evaluation of
Khyber Pakhtunkhwa rice husk ash (RHA) in improving mechanical behavior
of cement, Constr. Build. Mater. 176 (2018) 89–102.
[17] M.B. Ahsan, Z. Hossain, Supplemental use of rice husk ash (RHA) as a
cementitious material in concrete industry, Constr. Build. Mater. 178 (2018)
1–9.
[18] H. Husni, M.R. Nazari, H.M. Yee, R. Rohim, A. Yusuff, M.A. Ariff, N.N.R. Ahmad,
C.P. Leo, M.U.M. Junaidi, Surperhydrophobic rice husk ash coating on concrete,
Constr. Build. Mater. 144 (2017) 385–391.
[19] B.S. Thomas, Green concrete partially comprised of rice husk ash as a
supplementary cementitious materials – a comprehensive review, Renew.
Sustain. Energy Rev. 82 (2018) 3911–3923.
[20] Q. Wu, H. Ma, Q. Chen, B. Gu, S. Li, H. Zhu, Effect of silane modified styrene-
acrylic emulsion on the waterproof properties of flue gas desulfurization
gypsum, Constr. Build. Mater. 197 (2019) 506–512.
401
[21] J. Gao, C. Qian, B. Wang, K. Morino, Experimental study on properties of
polymer-modified cement mortars with silica fume, Cem. Concr. Res. 32
(2002) 41–45.
[22] P. Duan, C. Yan, W. Luo, A novel waterproof, fast setting and high early
strength repair material derived from metakaolin geopolymer, Constr. Build.
Mater. 124 (2016) 69–73.
[23] D. Ouyang, K. Chen, Microstructure and chemical activity of rice husk ash
burden at low temperature, J. Chin. Ceram. Soc. 31 (2003) 1121–1124.
[24] A. Mehta, R. Siddique, Sustainable geopolymer concrete using ground
granulated blast furnace slag and rice husk ash: strength and permeability
properties, J. Clean. Prod. 205 (2018) 49–57.
[25] T.A. Aiken, J. Kwasny, W. Sha, M.N. Soutsos, Effect of slag content and activator
dosage on the resistance of fly ash geopolymer binders to sulfuric acid attack,
Cem. Concr. Res. 111 (2018) 23–40.
[26] I. García-Lodeiro, A. Fernández-Jiménez, M.T. Blanco, A. Palomo, FTIR study of
the sol-gel synthesis of cementitious gels: C-S-H and N-A-S-H, J. Sol-Gel. Sci.
Technol. 45 (2008) 63–72.
[27] S. Kang, S. Hong, J. Moon, The use of rice husk ash as reactive filler in ultra-high
performance concrete, Cem. Concr. Res. 115 (2019) 389–400.