Materials Letters 65 (2011) 1179–1183

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Materials Letters
j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / m a t l e t

Effects of calcination parameters on the silica phase of original and leached rice
husk ash
Jianfeng Shen, Xinzhi Liu, Shuguang Zhu ⁎, Houlei Zhang, Junjie Tan
School of Power Engineering, Nanjing University of Science and Technology, Nanjing 210094, China

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

Article history: This paper presents a contribution to the study of the effects of calcination parameters, including temperature
Received 25 October 2010 and time, on the silica phase of original and leached rice husk ash. X-ray diffraction (XRD) analysis reveals the
Accepted 16 January 2011 presence of totally crystalline silica in the original rice husk ash prepared at 800 °C. Fortunately, no indication
Available online 25 January 2011
of the presence in crystalline phase is found in the leached rice husk ash due to leaching. However, specific
surface area analysis indicates that the high calcination temperature or the long calcination time renders the
Keywords:
Rice husk
amorphous silica in the leached rice husk ash less activity. Therefore, the leaching procedure, the low
Leaching calcination temperature and the short calcination time are proposed in order to prepare more active
Amorphous materials amorphous silica from the rice husk.
Phase transformation © 2011 Elsevier B.V. All rights reserved.
Ceramics

1. Introduction Based on the research results, an appropriate process is proposed to

The annual production of rice leaves behind about 40 million tons
of husk as waste products in China. When the rice husk (RH) is
calcined at moderate temperature, the ash contains about 92–97%
silica which exists in amorphous form and exhibits high activity [1–3].
Therefore, during the last few decades, the rice husk ash (RHA) has
been used as an important raw material for producing silicon-based
materials (e.g. solar grade silicon, silicon carbide and silicon nitride
ceramics [4,5]) and concrete additives [6]. However, impurities (e.g.
sands and alkali metals) adhering to the RH debase the quality of
products significantly. Leaching is considered as a promising
technique for removing these impurities from the RH. Although an
acid solution is more effective to remove alkali metals [7–9], leaching
with water is applied more widely due to its acceptable efficiency and
simple process [10–13].
The calcination temperature and time are two important factors to
define whether the silica in the RHA remains amorphous or becomes
crystalline [14]. Some studies have been performed to confirm an
appropriate temperature for preparing the amorphous silica from the
RH. Rozainee et al. [2] found that the temperature of 600–800 °C is
appropriate by reviewing many literatures. However, few studies
have been carried out considering the effects of calcination time.
The aim of this paper is to study the effects of calcination
parameters, including the temperature and time, on the phase of
silica in the original and leached rice husk ash (ORHA and LRHA).
prepare the active amorphous silica from the RH.
2. Materials and methods
2.1. Preparation of the RHA
A specified RH, i.e. Wuyunjing 7# (in China), is used as the raw
material. It is divided into two parts. One is original and the other is
suffered from water leaching. The leaching process is performed in
25 ± 1 °C deionized water with a water application rate 80 ml/g for
4 h. Subsequently, each sample is held at a maximum temperature
(600, 700 and 800 °C) for 0.5, 1.5, 2.5 and 3.5 h. Each RHA sample is
named for clarification, e.g. ORHA600-0.5 which implies the ORHA
calcined at 600 °C for 0.5 h.
2.2. Characterization of the RHA
The surface morphologies of RH and RHA are examined using SEM
(JSM-6380LV, JEOL, Japan). The mineralogical analysis is performed
using XRD (D8 ADVANCE, BLUKER, Germany). Moreover, the specific
surface area of LRHA is determined according to the nitrogen
adsorption method (JW-04, JWGB, China).
3. Results and discussion

Because a small quantity of exterior impurities adheres to the

⁎ Corresponding author. Tel. /fax: + 86 25 84317344. internal surface of RH, only the external surface morphologies of RH
E-mail address: zhushuguang@tsinghua.org.cn (S. Zhu). and RHA are observed in this study. As shown in Fig. 1a, a large

0167-577X/$ – see front matter © 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.matlet.2011.01.034
1180 J. Shen et al. / Materials Letters 65 (2011) 1179–1183
Fig. 1. The external surface morphologies of RH and RHA. (a) ORH; (b) ORHA; (c) LRH; (d) LRHA.
quantity of exterior impurities adheres to the external surface of
original rice husk (ORH). Two factors mainly account for their origin,
i.e. sands [15] and RH powders. They tend to react with potassium to
form alkali rich melts (Fig. 1b). Once carbon is entrapped in these
melts, it cannot be easily oxidized as it is not direct contact with air for
further conversion even at higher calcination temperature or under
higher oxygen gage pressure [1,2,8]. Fortunately, the external surface
of leached rice husk (LRH) is almost free from the exterior impurities
after being leached in the deionized water (Fig. 1c). In addition, no
melts can be found on the external surface of LRHA (Fig. 1d).
Fig. 2 shows the changes of the contents of ORHA and LRHA with
the calcination temperature and time. Because of higher volatility of
some metallic elements at higher calcination temperature [16], a
reduction of the contents of ORHA and LRHA is observed with the
calcination temperature increase. Moreover, the contents of LRHA are
less than those of ORHA due to the removal of impurities (cf. Fig. 2a
and b). As shown in Fig. 2a, the contents of ORHA dramatically
decrease with the calcination time increase, which attributes to the
slow oxidation of carbon residue in ORHA. However, the contents of
LRHA have no obvious change when the calcination time is longer
than 1.5 h (Fig. 2b), which implies no black or gray particles and
almost pure silica existing in LRHA.
Fig. 3 shows the XRD patterns of ORHA and LRHA. The phase
transformation of the silica with the calcination temperature and time
increase can be obviously found from the patterns. As shown in Fig. 3a,
there is no indication of silica presence in crystalline form in
ORHA600, which implies that the exterior impurities adhering to
the ORH are mainly the RH powders. However, the silica in ORHA700
presents in both amorphous and crystalline form. The narrow peaks
about 2θ = 22° are noticed in Fig. 3b, which indicates an incipient
crystallization process. In addition, the silica in ORHA700 shows the
ever severe crystallization with the calcination time increase. Worse
still, the silica in ORHA800 totally presents in crystalline form
(Fig. 3c). The results indicate that the silica phase of the ORHA is
sensitive to both the calcination temperature and time. Although the
LRH is suffered from the same calcination temperature and time, a
broad peaks about 2θ = 22° are noticed in Fig. 3d–f, which indicates an
essentially amorphous form of silica in the LRHA. It can be reasonably
inferred that the sensitivity of the silica phase of ORHA to the
calcination temperature and time may be relevant to the alkali metals
which facilitate the initiation of the formation of cristobalite [17].
Moreover, the RHA which remains amorphous after being calcined at
700 °C for 6 h in literature [2] may refer to the LRHA.
Unfortunately, not all amorphous silica is considered as an active
raw material as the presence of SiOH groups and Si(OSi)4 tetrahedra
makes it less active [18,19]. It is well known that the specific surface
area is one of the most important properties for the active materials.
Therefore, the specific surface area of LRHA is determined according to
the nitrogen adsorption method. As shown in Fig. 4, the specific
surface area of LRHA decreases when the calcination temperature and
time increase. The specific surface area of LRHA600-0.5 is 104 m2/g.
However, it rapidly decreases to 10 m2/g for LRHA800-3.5. The
dramatic decrease in the specific surface area is proportional to the
calcination temperature and time, which is caused by agglomeration
effect and diminishing porosity [3].
4. Conclusions
The silica phase of ORHA is sensitive to the calcination temper-
ature and time by the facilitation of alkali metals. High calcination
temperature or long calcination time leads to the formation of
crystalline silica. However, the silica in LRHA remains amorphous in a
wide range of calcination temperature and time, which confirms the
benefit of leaching on the preparation of amorphous silica from the
RH. Taken activity into account, leaching procedure, as well as the low
calcination temperature and short calcination time is proposed in
order to prepare more active amorphous silica from the RH.
Acknowledgments
This research was supported by the Chinese National Foundation
of Science (No. 50776046).
 J. Shen et al. / Materials Letters 65 (2011) 1179–1183 1181

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Fig. 2. The RHA contents vs. the calcination time at the different calcination
temperatures. (a) ORHA; (b) LRHA.
1182 J. Shen et al. / Materials Letters 65 (2011) 1179–1183

Fig. 3. The XRD patterns of RHA. (a) ORHA600; (b) ORHA700; (c) ORHA800; (d) LRHA600; (e) LRHA700; (f) LRHA800.
 J. Shen et al. / Materials Letters 65 (2011) 1179–1183 1183

Fig. 4. The specific surface area of LRHA.