Journal of Cleaner Production 226 (2019) 805e814

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Journal of Cleaner Production

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

A sludge and modified rice husk ash-based geopolymer: synthesis and

characterization analysis
Nana Wen a, b, Yading Zhao a, b, *, Zhenyun Yu a, b, Minghao Liu a, b
a
Key Lab of Structures Dynamic Behavior and Control of the Ministry of Education, Harbin Institute of Technology, Harbin, 150090, China
b
Key Lab of Smart Prevention and Mitigating of Industry and Information Technology, Harbin Institute of Technology, Harbin, 150090, China

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

Article history: There are many studies on the system of sludge and rice husk ash applied as the construction materials,
Received 31 August 2018 but in most cases, the sludge needs to be incinerated, which induced the environmental contamination.
Received in revised form This research investigated the viability of a novel geopolymer derived from non-calcined sludge and
14 March 2019
modified rice husk ash blend. The variable factors such as rice husk ash/sludge ratio, liquid alkaline
Accepted 3 April 2019
Available online 6 April 2019
activator/solid ratio and alkalinity on mechanical properties were studied, and the optimum mix ratio
was then determined. The results indicate that compressive strength first increases and then decreases
with the increase of the ratio of modified rice husk ash to dried sludge (RHA/DS). And at the RHA/DS ratio
Keywords:
Geopolymer
of 0.35 and liquid to solid ratio of 1.2, the geopolymer got the highest compressive strength. Mercury
Sludge intrusion porosimetry (MIP) and X-ray diffraction (XRD) demonstrate that the decrease of the number of
Rice husk ash macropores (larger than 200 nm) improve the internal microstructure and amorphous phase with some
Compressive strength crystalline as fillers. And the same results are confirmed by scanning electron microscope (SEM) analysis.
Heavy metal Toxicity characteristic leaching procedure (TCLP) shows the new geopolymers have good environmental
performance, with good sorption properties for heavy metals. However, relatively low mechanical
properties, uncertainty in raw materials’ chemical composition and in long-term performance as well as
durability, are a principal inhibition to use this material immediately.
© 2019 Elsevier Ltd. All rights reserved.

1. Introduction usage of sludge as construction and building materials. Most re-

The increasing demand of municipal wastewater has led to the
gradual increase of sludge generated annually (Suksiripattanapong
et al., 2015a). The massive final accumulation of sludge has a great
impact on the environment and its disposal has been urgent to be
solved (Wang et al., 2017). Sludge is a complex material which
contains microorganisms, organic matters, heavy metals, inorganic
minerals, pathogens, organic pollutants, etc. (Smith, 2009). The
main inorganic components in sludge are SiO2, Fe2O3 and Al2O3,
which makes sludge have the potential to be used as a source of
renewable energy. However, the risk of secondary pollution due to
heavy metals and high content of moisture are major drawbacks of
sludge utilization (Wang et al., 2017). Meanwhile, the presence of
organic matters in sludge and low pozzolanic activity inhibits the
* Corresponding author. Key Lab of Structures Dynamic Behavior and Control of
the Ministry of Education, Harbin Institute of Technology, Huanghe Road No.73,
Harbin, 150090, China.
E-mail address: zhaoyd@hit.edu.cn (Y. Zhao).
searches solve this problem by burning sludge into sludge ash
(Nimwinya et al., 2016; Waijarean et al., 2014b) which will lead to a
high cost of energy and new problems such as the emissions of
carbon dioxide, dioxin and furans when raw sewage sludge incin-
erated. With this respect, further investigation should be carried
out on sludge without sintering process like autoclave process
(Yang et al., 2013) or just burn at a low temperature to achieve basic
requirements such as deodorization and removing free water.
Rice husk is a high-yield agricultural waste with an annual
output of nearly 545 million metric tons all round the world (Feng
et al., 2004), but its comprehensive utilization rate is still very low.
If the recycling of rice husk cannot be reasonably developed, it will
inevitably cause environmental pollution (Li et al., 2011). Because of
that, lots of efforts have been made to incinerate rice husk directly
as a fuel to produce power or electricity, leading to the production
of large amounts of rice husk ash (RHA). However, only small
proportion of RHA is used as a supplementary material (Feng et al.,
2004; He et al., 2013). The main component of RHA is silica in
amorphous and partly in crystalline phases, some carbon as the

https://doi.org/10.1016/j.jclepro.2019.04.045
0959-6526/© 2019 Elsevier Ltd. All rights reserved.
806 N. Wen et al. / Journal of Cleaner Production 226 (2019) 805e814

major impurity and other trace elements like K and Ca (Chaudhary
and Jollands, 2004; He et al., 2013). High pozzolanic activity and
strong heavy metal sorption property of RHA make RHA can be
used as alternative cementitious binder and used to adjust the SiO2
content of the geopolymer (Daifullah et al., 2003; Khalid et al.,
1999; Krishnani et al., 2008). Moreover, it was found in the previ-
ous study that the RHA used in conjunction with flocculants like
aluminum chloride or other chemical conditioning agents has
better effect on dewaterability and solidification of sludge (Qi et al.,
2011). Thus, in this work, RHA modified by aluminum chloride was
applied as a sustainable precursor.
Geopolymer was first proposed by French scientist Joseph
Davidovits in 1985 (Davidovits and Sawyer, 1985). Because of low
CO2 emissions footprint, high-temperature resistance, high flexural
and compressive strength and low cost (Provis and Bernal, 2014;
Suksiripattanapong et al., 2015a), geopolymer is regarded as an
environmentally friendly building materials, which is excepted to
be used as an alternative to conventional Portland cement concrete
(Nie et al., 2016). Geopolymer is made by alumina silicate materials
and liquid alkaline activator in the planned proportions (Yan and
Sagoe-Crentsil, 2012). With the continuous researches, sources of
silica-alumina raw materials for geopolymers have greatly
expanded from kaolin (Jaya et al., 2016), volcanic pumice (Weiser
and Lane, 1991) to steel slag (Niklio c et al., 2016), fly ash, coal
gangue (Geng et al., 2017), waste glass (Tho-In et al., 2017), sludge
(Suksiripattanapong et al., 2015b), red mud (He et al., 2013), and
other industrial waste (Asavapisit and Macphee, 2007). Although
the amorphous silica in RHA is reactive and can be used as a
pozzolan, its use in geopolymer requires a secondary source of
aluminum for the Al content of RHA is close to zero (Poowancum
et al., 2015; Provis et al., 2015). The aluminum sources in sludge
can be used in geopolymerization process and can effectively
compensate for the shortcoming of RHA. It is also noteworthy that
geopolymer is an inorganic polymeric material with a zeolite-like
cage structure which has unique properties in the solidification of
heavy metals (Guo et al., 2013; Phair and Deventer, 2002;
Poowancum et al., 2015; Zhang et al., 2008).
There is, however, very limited research data on the preparation
of geopolymers with non-calcined sludge(S) and RHA. Systematic
studies on this topic should be performed. In this research, we
combined those two wastes to make S/RHA geopolymer. The
influential factors investigated (ratio of raw materials, liquid alka-
line activator(L) modulus, L content and curing time) and their
basic characteristic (compressive strength, mineral composition,
elemental composition, thermogravimetric analysis and micro-
scopic morphology) were systemically studied and leaching per-
formance of heavy metals was examined by toxicity characteristic
leaching procedure.
(300S).
The average grain size D50 of 300S, RHA and MRA was 13.84,
25.14 and 21.22 mm respectively. The particle size distribution and
chemical composition of 300S, RHA and MRA were shown in Fig. 1
and Table 1, which were obtained from laser particle (BT-2001) and
X-ray fluorescence (XRF) analysis.
2.2. Liquid alkaline activator(L) -Na2O ▪ nSiO2
Sodium silicate (Na2SiO3) solution consisted of 9% Na2O and 30%
SiO2 by weight. Sodium hydroxide (NaOH) pellets were mixed with
distilled water to obtained a concentration of 8, 10, 14, 18 M due to
preliminary studies (Suksiripattanapong et al.,2015a, 2015b;
Poowancum et al., 2015) which found NaOH with a concentration of
10 M could achieve better mechanics properties. After cooled down
at a room temperature, NaOH solution and sodium silicate
(Na2SiO3) were mixed to prepare the liquid alkaline activator (L)
with SiO2/Na2O molar ratio of 0.7, 0.8, 1 and 1.2 which was indi-
cated hereafter by LⅠ,LⅡ,LⅢ and LⅣ, respectively. The mixed solu-
tion was stored for 24 h before used.
2.3. Sample preparation
The RHA and dried sludge (DS) powder were mixed in mass
ratios of 0.25:1, 0.35:1, 0.5:1, 0.8:1 and 1:1 respectively. After dried
and sieved, the mixture was mixed with L at liquid-solid ratio (L/S)
of 1, 1.1 and 1.2. And then slurries were cast into 20  20  20 mm3
steel cube molds and sealed with a plastic film to prevent moisture
evaporation for 24 h. After that, geopolymer samples were
demolded and cured at the ambient room temperature until
reaching the testing age of 7 d.
2.4. Methods
2.4.1. Compressive strength
Compressive strength of geopolymer samples were measured
after 7 days of curing in accordance with SL237-020-1999 (China).
The compressive strength of each batch was tested at least six
samples and the mean values for the closest five were calculated to
assure the consistency of test result.
2.4.2. Toxicity characteristic leaching procedure (TCLP)
The leaching behaviors of heavy metals from geopolymer was
studied by TCLP which was an effective method to exam the

2. Materials and methods

2.1. Materials

Sludge was collected in this work from a major municipal

wastewater treatment plant in Heilongjiang, China, which had been
treated initially by biological leaching and framed filter press but
still smelly. RHA was taken from a power plant in Heilongjiang,
China. Like previous study, RHA was modified by 2 mol/L AlCl3,
which was denoted hereafter by MRA and then air-dried, homog-
enized, pulverized and sieved (0.8 mm sieve opening). After that,
MRA mixed with sludge. For the convenience of experimentation,
the mixture was dried at 300
C to achieve a better deal with the
deodorization and volume reduction of sludge, and also to reduce
the energy consumption and treatment cost during drying. The
control group was geopolymer sample with only S dried at 300
C Fig. 1. Particle size distribution of 300S, RHA and MRA.
 N. Wen et al. / Journal of Cleaner Production 226 (2019) 805e814
Table 1
Chemical composition of 300S, RHA and MRA.
Chemical composition (%) 300S RHA
SiO2 38.26 89.02
K2O 2.18 3.94
CaO 1.96 2.45
P2O5 11.9 1.43
Al2O3 12.1 0.77
SO3 5.0 0.62
Fe2O3 23.91 0.55
MgO 1.5 0.49
Etc. 3.19 0.73
mobility of heavy metals (Wang et al., 2016). Sample fragments
after compressive strength test were crushed and the particles less
than 9.5 mm were collected. An acetic acid solution (pH ¼ 2.88) was
added to the solid particles. A liquid-to-solid ratio of 20:1 by weight
was used. Metal concentrations were determined by inductively
coupled plasma atomic emission spectrometry (ICP-OES, PE Optima
8300) (Guo et al., 2013).
2.4.3. Mercury intrusion porosimetry(MIP)
Sample fragments were crushed after compressive strength test
and the circular particles of 1 cm3 of volume with similar size were
dried and collected. The pore size distributions of the geopolymer
were tested by a 9500-automatic mercury porosimeter (Micro-
metrics, USA). Mercury intrusion and extrusion curves were
measured by analyzing the testing data. Meanwhile, the wider
range of pore size can also be obtained (Li et al., 2018).
2.4.4. Thermogravimetric and differential thermal analysis (TG-
DTA)
Geopolymers with excellent mechanical properties were
selected for thermogravimetric (TG) and differential thermal
analysis (DTA) analysis by thermogravimetric analyzer TGA/DSC1/
1600HT from Mettler Toledo. Samples had been pre-dried for
10 h at 100
C, prior to thermogravimetric tests. In the TG-DTA
experiment, the samples were heated from room temperature to
1000
C at 10
C$min1.
2.4.5. Microstructural characterization
The mineral composition and crystal structure of each geo-
polymer powdered sample, which was ground by using crushed
fragments after compressive strength, were measured by X-ray
diffraction (XRD, X'Pert PRO) with Cu-Ka radiation (l ¼ 0.15419 nm)
and Fourier transform infrared spectroscopy (FTIR-650) with a
wave number range from 4000 cm1 to 250 cm1. The morphology
and element composition of hydration products were analyzed by
JEOL SX-4 scanning electron microscope (SEM) and energy
dispersive X-ray spectroscopy (EDS) after gold coating treatment.
3. Results and discussion
3.1. Effect of raw material mix ratio (MRA/DS) on compressive
strength
Fig. 2 shows the influence of RHA/DS ratios on the compressive
strength of geopolymers. As shown in the previous study, the 60-
day compressive strength of geopolymer prepared from sludge
incineration residue (calcined at 800
C) was 4e9 MPa, which also
revealed that the strength of non-calcined sludge was not devel-
oped at the early stages and was 0.76 MPa after 60 days of curing,
and the poor activity of unburned sludge results in very low me-
chanical properties (Waijarean et al., 2014a). Another reason for the
807
low strength in this work is the relatively high content of Cl in the
raw materials, which adversely affects the compressive strength
MRA (Deja, 2002; Lee and Deventer, 2002). The change in the RHA/DS
81.62
ratios is equivalent to the Si/Al ratios in the preparation of geo-
3.0 polymers, and results in different zeolite-like structure of the
0.74 geopolymers. Generally, the compressive strength of geopolymer
0.67 derived from waste are highly dependent on raw materials (Xu and
5.85
Deventer, 2003). As can be seen from Fig. 2, compressive strength
0.16
4.9 increases first and then decreases with the increasing RHA/DS ratio.
0.26 The geopolymer has optimal compressive strength when the RHA/
2.8 DS ratio was 0.35. Compared with the control group, the RHA/DS
geopolymers are superior to the pure sludge-based geopolymer at
low modulus, especially in LⅠ. And in LIV, S geopolymer performs
relatively better compressive strength development than most of S/
RHA geopolymers. When the Si/Al ratio is less than 0.35, on one
hand, Si content is positively related with MRA, which results in the
increase of the SieOeSi bond. It is noteworthy that the SieOeSi
bond is stronger than SieOeAl bond followed by AleOeAl bond
(Jong and Jr, 1980). On the other hand, MRA has a favorable micro-
filling effect allowing it to improve the degree of compaction,
thereby increasing the compressive strength of RHA/S geopolymers
(Rahier et al., 2003).
However, it is not the higher Si content, the better compressive
strength will be. When MRA exceeds a certain amount, the large
specific surface area of MRA will absorb too much water, resulting
in relatively less liquid in the geopolymerization reaction (disso-
lution-recombination-polymerization), and lead to an incomplete
hydration of raw materials. Meanwhile, higher concentration of
solution silicate will restain the reorganization of Si and Al,
generating the difficulty to establish the skeleton structure of
geopolymer (Duxson et al., 2005), which resulting in the decrease
of the compressive atrength. The results match with the conclusion
of a previous research (He et al., 2013). We can conclude that it is
the ratio of Si/Al involved in the geopolymerization reaction but not
the ratio of Si/Al in raw materials that contributes to the
compressive stress in the geopolymer (Provis et al., 2015).
3.2. Effect of liquid to solid ratio (L/S) on compressive strength
From Fig. 2, the effect of liquid to solid ratio (L/S) on compressive
strength is also analyzed. Water participates in two distinct dy-
namic processes in the geopolymerization reaction: on the one
hand, hydrolysis or dissolution of Si and Al can consume part of the
water; on the other hand, the polycondensation reaction can
regenerate water and finally seals in the pores of the geopolymer
(Shi et al., 2011). At high alkalinity like LⅠ, the compressive strength
is higher when the L/S ratio is larger, which can be explained by
three possible reasons: (a) in order to fully release the Si and Al in
the raw material reaction, it requires sufficient alkali to complete
the depolymerization reaction in the geopolymerization reaction;
(b) the reaction speed is fast at high alkalinity, and the increase of
the amount of L can promptly promote the formation of the gel
phase; (c) the geopolymer prepared at a higher L/S ratio has better
workability, which will encourage more uniform distribution of it
when casted and compacted on a vibrating table. However, at low
alkalinity, a higher L/S ratio will make the raw materials in the
preparation process easier to be segregated, which will lead to a
lower compressive strength.
3.3. Effect of types of liquid alkaline activator (L) on compressive
strength
Fig. 3 presents that the effect of different types of L on the
compressive strength of the geopolymer. The change in L results in
variable alkalinity. It is worth noting that the higher the alkalinity
808 N. Wen et al. / Journal of Cleaner Production 226 (2019) 805e814

Fig. 2. Effect of MRA/S ratios and L/S ratios on the compressive strength (a)LⅠ (b) LⅡ (c) LIII (d) LⅣ.

Fig. 3. Effect of types of liquid alkaline activator (L) on the compressive strength (a)L/S ¼ 1 (b) L/S ¼ 1.1 (c) L/S ¼ 1.2.
 N. Wen et al. / Journal of Cleaner Production 226 (2019) 805e814
is, the higher compressive strength it will be. The strong alkaline
environment is conducive to accelerate the dissolution of Si and Al
phases in raw materials. More Si and Al involved in the “reconsti-
tution-polycondensation” reaction will lead more gel phases to
form, resulting in a higher degree of geopolymerization reaction of
the raw materials and thus a higher compressive strength, which is
consistent with the conclusions of many studies (Duxson et al.,
2005; He et al., 2013). However, the alkalinity cannot be too high
(Hu et al., 2018). When it is too high, it is not easy to cast mold
during the preparation of geopolymer and the reaction exotherm is
too rapid, causing instability of the system structure. Conversely,
when the alkalinity is too low, the alkali cannot fully dissolve the Si
and Al phases in the raw materials and geopolymerization reaction
is not complete. As previous research, L is one of the most impor-
tant factors that affects the compressive strength of geopolymer
(Somna et al., 2011).
Large-volume utilization of sludge in a cost-efficient way is the
purpose of this study. In this work, the compressive strength of
geopolymer came to a maximum at 4.6 MPa, which is competitive
though not that much high. The method in this work provides a
new approach to deal with the sludge problems and thus there is no
criterion value of compressive strength for this novel material at
present.
3.4. Leaching tests results
TCLP were conducted on four kinds of geopolymers 0.35-Ⅰ (RHA/
S ratio of 0.35, LⅠ), 0.35-Ⅳ (RHA/S ratio of 0.35, LⅣ), 1-Ⅰ (RHA/S ratio
of 1, LⅠ) and S-Ⅰ (RHA/S ratio of 0, LⅠ) with a L/S ratio of 1.2. Leaching
indicators are measured in accordance with the standard GB
5085.3e2007. TCLP results are summarized in Table 2.
Many experimental studies (Xu et al., 2006; Zhang et al., 2008)
have shown that geopolymer mainly achieves the solidification of
heavy metals through both physical and chemical effects. The cage
structure of the geopolymer makes heavy metals enclosed in the
interior. Some heavy metals with radius close to Naþ combine in
the geopolymer backbone. A research (Zhang et al., 2008) sug-
gested that Cr3þ, Cd2þ and Pb2þin geopolymers can not only be
tightly locked into the 3D cross linked structures by dissolution of Si
and Al in alkaline solution, but also be associated with each other
and encapsulated in the binder structure. In this work, the presence
of RHA in geopolymer precursors increases the effective sorption
area and the sorption site, thus the removal rate of heavy metals
will be even higher. From Table 2, it can be easily found that the
concentrations of heavy metals leached from four geopolymers are
much smaller than the limited value, which can be donated to the
good heavy metal solidification of geopolymers.
From all analyzed above, as a kind of new building material, this
novel geopolymer can be applied in non-bearing structures in in-
dustrial and civil buildings. In addition, geopolymer have high
ability to solidification/stabilization of toxic chemicals and radio-
active wastes within their 3D network-structures. However,
because of relatively low compressive strength, uncertainty in raw
materials’ chemical composition and in long-term performance as
well as durability, S/RHA geopolymers cannot be used immediately
Table 2
Results of the leaching test of geopolymers (mg/L).
TCLP Ba Cr Cu Ni Pb
0.35-Ⅰ 0.017 0.027 0.014 0.028 0.008
0.35-Ⅳ 0.135 0.011 0.006 0.008 0.003
S-Ⅰ 0.001 0.023 0.006 0.007 0.009
1-Ⅰ 0.019 0.018 0.003 0.006 0.005
Limits 100 15 100 5 5
809
and further research on these topics should be carried out.
3.5. Mercury intrusion porosimetry (MIP) analysis
In the compressive strength test, the mechanical properties of
the geopolymer with RHA/DS ratio of 0.35, L/S ratio of 1.2, and LⅠ
(denoted as 0.35-Ⅰ) was the best. MIP were conducted on 0.35-Ⅰ
geopolymer. S-Ⅰ geopolymer was used as a control. Mercury
intrusion porosimetry curves by MIP are shown in Fig. 4 and pore
size distributions of different geopolymers are listed in Table 3.
Fig. 4a shows the cumulative mercury volume of the two geo-
polymers. Under the pressure, at the beginning the mercury
intrusion volume of the 0.35-I geopolymer is lower than that of the
SeI and then gradually increases. The final volume of 0.35-I is larger
than the SeI sample, suggesting a lager porosity. However, in
Fig. 4b, the number of big pores in 0.35-I is found to be less than
SeI, while the number of small pores is more than SeI and
consistent with the data in Table 3. The pore is classified into four
categories (Allen, 1977) according to the pore size: less than 20 nm
is a harmless pore, 20e50 nm is a less harmful pore, 50e200 nm is a
harmful pore, and larger than 200 nm is referred to as a multi-
poisonous pore. The reason for the difference between these two
geopolymers is the addition of MRA, which not only optimizes the
pore size distribution by reducing the average pore size and the
number of macropores, but also effectively improves the internal
microstructure of the geopolymer. Moreover, it inhibits the devel-
opment of micro cracks in voids to a certain extent, thereby
enhancing the performance of the geopolymer (Poowancum et al.,
2015).
As we all know, geopolymer with great mechanical properties
can relate to many factors, such as the fineness of raw materials,
mortars mixture design and so on. In this work, the most significant
influence factor is that sludge without being calcined at high
temperature contains a considerable amount of impurities, which
can influence to some extent the geopolymerization process and
directly affect the porous structure. RHA has high surface activity
while unburned sludge has low surface activity; the polymerization
and hardening in the surface occurs so fast that many active ma-
terials cannot keep participating in the geopolymerization reaction.
These two may be the reason of large pores and low compressive
strength. The possible methods to decrease the pores are as fol-
lows: (a) modify the sludge to improve its surface activity. Like the
usage of surfactant and a rational choice of sludge granularity; (b)
add other additives, such as fiber material, nano-SiO2, and nano-
Al2O3; (c) use ball milling under shear force to incur the dislocation
and transformation in the internal of crystals contained in the
sludge (Sun et al., 2018); (d) investigate a right curing system which
is well suited for S/RHA geopolymer (Mo et al., 2018).
3.6. FI-IR analysis
The FTIR spectra of different geopolymers are presented in Fig. 5.
In the geopolymers, there are different combinations of [SiO4]. Al
can either replace Si to form [AlO4] or as ions connecting two tet-
rahedrons. Therefore, the characteristic absorption bands of their
FTIR spectra mainly come from the stretching vibrations of
SieOeAl, SieOeSi, and AleOeAl. The four geopolymers have ab-
sorption peaks near 3400 cm1 and 1640 cm1 which represent the
stretching and bending vibrations of OeH bonds, indicating that
Zn during geopolymerization reaction, water was absorbed on the
0.07 surface or entrapped in the pores of the geopolymer (Swanepoel
0.28 and Strydom, 2002). Among them, the OeH peak of SeI is the
0.023 strongest, suggesting the most water contained, and the weakest
0.107 peak in 0.35-I reflecting the compactness of the 0.35-I geopolymer.
100
This is consistent with the result of compressive strength. Due to
810 N. Wen et al. / Journal of Cleaner Production 226 (2019) 805e814

Fig. 4. Mercury intrusion porosimetry curves of two of geopolymer (a) Cumulative Pore Volume (b) dV/dlogD Pore Volume.

Table 3
Pore size distribution of two geopolymers (%).

Porosity <20 nm 20e50 nm 50e200 nm >200 nm

S-Ⅰ 46.8 15 10 3 72
0.35-Ⅰ 52.1 23 23 9 45

the addition of MRA, the stretching vibration of CeH bonds

occurred at 2811 cm1 in 0.35-I, 0.35-Ⅳ and 1-I, which does not
appear in SeI geopolymer. The absorption band at about 1460 cm1
may relate to the stretching vibration of OeCeO (Andini et al.,
2008). The large absorption band at near 1020 cm1 corresponds
to the asymmetric stretching vibration peak of SieOeSi or
SieOeAl. However, the band at about 1020 cm1 of SeI geopolymer
is the lowest in intensity, suggesting a lower rate of geo-
polymerization reaction than S/MRA geopolymer (Tho-In et al.,
2017). Peaks at 777 cm1 is an intersubstitutable vibrational re-
gion of aromatic hydrocarbons, indicating the benzene series in
Fig. 6. XRD patterns of different geopolymers.
sludge still exist in the geopolymer. The band centered at about
570 cm1 represents the symmetrical stretching vibration of the
bicyclic structure. The RHA/DS ratio can significantly influence this 3.7. X-ray diffraction (XRD) analysis
absorbing band, resulting in the environmental change around the
[SiO4] tetrahedron. Moreover, absorption bands at around XRD analysis was applied to obtain mineral compositions of
455 cm1 can be found in all geopolymers, which corresponds to geopolymers. Fig. 6 shows the similarities in the mineral compo-
the bending vibration and stretching vibration of OeSieO and sition of four geopolymers. A weak, broad bump of non-crystalline
SieOeSi(Zawrah et al., 2016). phases between 23 and 30
2q is observed in all the geopolymers,

Fig. 5. FTIR spectra of different geopolymers.

 N. Wen et al. / Journal of Cleaner Production 226 (2019) 805e814
suggesting the present of amorphous phases like activated silica
and alumina (Geng et al., 2017). The existence of this bump can be
attributed to two aspects: one is that the RHA in raw materials is an
amorphous phase (Shen et al., 2011), and the other is that the
geopolymer itself is neoformed an amorphous phase (He et al.,
2012).
0.35-I, 0.35-Ⅳ and 1-I display almost the same crystal diffraction
peaks, however the hump of 1-I suggesting amorphous materials
are less prominent and the polymerization activity is lower, which
is the reason of lower compressive strength of 1-I, compared with
0.35-I and 0.35-Ⅳ. Some sharp peaks identified as crystalline
phases like quartz, halite, cristobalite and albite are found. How-
ever, weak peaks from cristobalite and albite are not included in
SeI, which is attributed to the absence of MRA in its raw materials.
In addition, the X-ray diffraction peak of gismondine (CaAl2Si2O8
 b, c and d, as S was the dominant precursor to make S-Ⅰ geopolymer,
▪4H2O) produced by the reaction of OH in a strong alkali envi-
ronment and the silica-alumina component of raw materials. This
mineral has a chain structure similar to organic polymers and can
form chemical bonds with [SiO4] and [AlO4] tetrahedra by dehy-
droxylation, which is the main source of strength increasement of
the geopolymer.
3.8. Thermogravimetric and differential thermal analysis (TG-DTA)
Fig. 7 presents the thermal behaviors of S-Ⅰ and 0.35-Ⅰ followed
by TG-DTA. As reported previously (Bell et al., 2009; Duxson et al.,
2006), the TG patterns of geopolymer can be divided into four
steps. The first step is attributed to the evaporation of water below
100
C. The second step is the loss of water produced by T-OH
(T ¼ Si or Al) polymerization as formula 3.1. The third step is
300e700
C and the fourth step is 700e950
C. The shrinkage of
the two latter steps is mainly due to the capillary condensation and
physical condensation resulting from the lower polymerization and
sintering of the viscous material.
≡T  OH＋HO  T≡/≡T  O  T≡＋H2O (3.1)
For geopolymer S-Ⅰ and 0.35-Ⅰ, the TG pattern of mass-loss is
similar. The mass loss can be attributed to the evaporation of water
physically or chemically and the decomposition of crystal phases
(Geng et al., 2017). However, weight loss of S-Ⅰwas about 22% and
18% for 0.35-Ⅰof the total weight, respectively, indicating a better
high-temperature resistance of 0.35-I.
As the DTA curve shows, SeI shows an obvious endothermic
peak near 90
C due to the free water evaporation, and the peak
area in SeI is relatively larger than that of 0.35-I implying that SeI
Fig. 7. TG-DTA diagram of the geopolymers (a)S-Ⅰ (b)0.35-Ⅰ
811
contains more free water which conforms to the analysis result of
FI-IR. The exothermic peak at 450
C represented the crystalline
phase transition and the combustion of organic matters in sludge.
The exothermic peak at 800
C represented the crystalline phase
transition. However, there was no significant mass loss at around
800
C for 0.35-I, probably due to the present of cristobalite and
albite in the RHA/S geopolymer, which is consistent with the results
in XRD. Since then, the TG curve has been slowly declining and kept
at this slow speed until 1000
C.
3.9. SEM analysis
Fig. 8 shows the micromorphological features of the two geo-
polymers, along with the EDS spectra of selected regions. In Fig. 8a,
it seems that S had dissociated and formed of a radial product. The
radial products were also identified from EDS analyses and
elementary composition (Si, Ca, O and a small amount of Al) of
which revealed as gismondine. However, a porous and inhomoge-
neous microstructure can be easily found. This phenomenon may
be caused by three reasons: one is air bubbles induced by opera-
tional errors during the sample preparation; the other is micro
cracks triggered by chemical shrinkage during the curing process;
and still other, the load of the compressive strength test may cause
the formation of cracks in the geopolymer matrix. Moreover, the
surface of S-Ⅰ was found smooth and accompanied with some
particulate mainly of heavy metals in the sludge.
Fig. 8e, f, g and h show the surface of 0.35- geopolymer. The
dense geopolymeric microstructure can be observed with a smaller
number of voids and smaller volume of pores. Compared with SeI,
it is denser, finer, and shape of it is batt-like forming an overall body
with gel-like properties, thus having a larger specific surface area
and exhibiting a better sorption property of heavy metals. Mean-
while, it is noteworthy that the geopolymer is a superficially porous
material, which can absorb molecules smaller than the pore size in
the pores. The large amount of micropores in the interior is the
reason of good sorption. As EDS analysis obtained from selected
region presented, the main elementary compositions are Na, Al, Si,
and O, which are the constituent element of the geopolymer (He
et al., 2013).
4. Conclusion
This paper investigates the utilization of sludge and rice husk
ash in construction materials by means of geopolymerization
812 N. Wen et al. / Journal of Cleaner Production 226 (2019) 805e814

Fig. 8. SEM image of the geopolymers of S-Ⅰ(a, b, c and d) and 0.35-Ⅰ(e, f, g and h).

reaction, resulting in a new type of S/RHA geopolymer. A variety of
parameters like RHA/DS ratio, L/S ratio and alkalinity of L were
examined to understand their effects on compressive strength. The
environmental performance of new geopolymer was conducted,
and the composition and microstructure of a superior geopolymer
were also characterized through MIP, XRD, IR, TG-DTA and SEM-
EDS. According to the above experimental results, following con-
clusions can be obtained.
I. The mechanical properties of S/RHA geopolymer depends on
many factors such as raw materials, liquid to solid ratio,
alkalinity, operation errors and uncertainties in geo-
polymerization. It is difficult to give a certain series of pa-
rameters on making geopolymer. The mechanical properties
of the geopolymer with a MRA/DS ratio of 0.35, a L/S ratio of
1.2, and LⅠ (denoted as 0.35-Ⅰ) is the best.
II. Compressive strength first increases and then decreases with
the increase of the RHA/DS ratios, and at about 0.35 reaches a
maximum.
 N. Wen et al. / Journal of Cleaner Production 226 (2019) 805e814
III. The addition of MRA can optimize the pore size distribution
and effectively improve the internal microstructure of the
geopolymer.
IV. Heavy metals in sludge have good leaching performance af-
ter consolidation by geopolymerization reaction, and toxicity
results are all within the limits.
V. MIP, XRD, IR, TG-DTA and SEM-EDS results shows that the
new geopolymer mainly consists of amorphous phase, with
some crystalline like quartz as fillers.
This work introduces a new way for sludge and rice husk
recycling, suggesting both of them can be used in construction and
building materials. However, many specific performances for
practical application are still unclear and the compressive strength
is not high enough, thus, further work is warranted to investigate
these topics.
Acknowledgements
The authors greatly appreciate the financial support of the
Heilongjiang Province Natural Science Foundation of China (Project
No. E2015004) and the Heilongjiang Province wall materials and
construction energy conservation plan project (Project Name:
Research on technology of using sewage sludge to fabricate non-
sintered wall materials) to this study.
Appendix A. Supplementary data
Supplementary data to this article can be found online at
https://doi.org/10.1016/j.jclepro.2019.04.045.
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