PRODUCTION OF AMORPHOUS AND CRYSTALLINE SILICA FROM

PHILIPPINE WASTE RICE HULL

Emie Salamangkit Mirasol

Department of Mining, Metallurgical and Materials Engineering, College of Engineering,
University of the Philippines, Diliman, Quezon City, Philippines
Email: easm022808@yahoo.com

Abstract

This study is conducted to investigate the production of silica (SiO 2) formed from waste rice hull
(RH) at different processing temperatures and study its structure by x-ray diffraction (XRD),
morphology by scanning electron microscope (SEM), and thermal properties by thermo-gravimetric
analysis (TGA). TGA and derivative thermo-gravimetric (DTG) curves of dried RH showed two
mass-loss steps: release of moisture at 25.26 oC-122.56oC with 7.329% mass loss and thermal
decomposition at 122.56oC-692.21oC with 58.142% mass loss and the maximum mass loss revealed at
343.52oC (position of DTG peak). XRD patterns showed formation of amorphous SiO 2 and some
crystalline SiO2 (cristobalite) in the RHA calcined at 550 oC and 900oC respectively. The SEM images
showed agglomeration of small particles in the RHA calcined at 550 oC while bigger particle
agglomeration was observed in the RHA calcined at 900 oC due to surface melting of SiO 2 particles.
Either amorphous or some crystalline SiO2 can be successfully obtained from waste RH by controlled
heat treatment. Further studies in producing highly crystallize SiO2 of more controlled material and
temperature processing is also recommended.

1. Introduction
Rice hull (or husk) is the covering of rice seeds (palay) and a by-product of milling rice grain.
Rice hull contains 13-29wt% inorganic compounds of which 87-97wt% is silica and composition
depends on the rice variety, climate, geographic location, soil, and quantity of fertilizer used [1-3].
Disposal of rice hull is a substantial problem for rice growers [2] not only because of its high
resistance to breakdown [1] but also because of its resistance to the best effort of man to dispose it [4].
Since rice hull is difficult to use in agriculture in the form of compost [1], it is most often reduced its
volume through open field burning (which creates undesirable atmospheric pollution) or burying [2].
However, studies found that rice hull silica processed through open-field burning can reach 900 oC
temperature are already crystalline in nature consisting cristobalite and small amount of tridymite
[1,4] which is also potentially dangerous to human respiratory system [3]. Philippines as one of the
top rice producers in the world may also suffer from this dilemma.
Silica is a basic material that is widely used in many industries [5]. Silica can be obtained from
pure minerals consisting silica only such as quartz, tridymite, and agate, from typical organisms such
as diatoms, horsetails, and rice [1], rice husk ash, and sand [6]. Among the sources of silica
mentioned, rice husk is the most interesting to study due to its abundance in nature as waste and its
richness in silica. Silica in rice husk can exist in either crystalline or amorphous state over various
temperature ranges and its production is independent of the purification or pre-treatment methods but
it is largely dependent on processing temperature [4]. Therefore, converting this waste to worthy
products may alleviate pollution problem [5] and may reduce production cost of silica for possible
various application.
Rice hull silica have been used in many applications ranges from agricultural as fertilizer and
landfills [2], cement and polymer as fillers[4], heat and energy source, solar technology [5], glasses
and ceramics [6], and even in nanotechnology like SiC whiskers [1]. Studies on the possibility of rice
hulls as raw material source for synthesis of Si nanomaterials were also conducted [7]. With these
numerous possible uses and applications of rice hull and rice hull silica, it is very important then to
study its characteristics and synthesizing desired silica form for optimum utilization.
 Therefore, the objective of this study is to investigate the production of silica formed from waste
rice hull at different heat treatment temperatures and study its structure, morphology, and thermal
properties.

2. Experimental
2.1. Material
The rice hull (Rc18 variety) was collected from a rice miller in Brgy. 21 Quiom, City of Batac,
Ilocos Norte . The as-received rice hull is shown in Figure 1(a) was washed with tap water in a screen
to remove some soils, sand, and other impurities and dried in an oven at 110 oC. The oven dried rice
hull is shown in Figure 1(b).

(a) (b)
Fig. 1. Rice hull (a) as received, and (b) washed and oven dried.

The oven dried rice hull was subjected to two different calcining temperatures. The dried rice hull
sample was then calcined at 550oC for 3 hours [4] and another sample calcined at 900 oC for 1 hour
[1]. The calcining temperatures employed in the samples in order to obtain a white amorphous and
with crystalline silica form were based from the findings of Nakata et al. (1989) and Ugheoke et al.
(2012) respectively. The macroscopic images of rice hull ash calcined at 550 oC and 900oC are shown
in Figure 2(a) and 2(b) respectively. The rice hull ashes were finely ground and ash powder were
pelletized as shown in Figure 2(c) – calcined at 550 oC and Figure 2(d) – calcined at 900 oC for XRD
and SEM characterizations.

(a) (b) (c) (d)

Fig. 2. Macroscopies and powdered and pelletized rice hull ash calcined at 550oC (a and c)
and 900oC (b and d) respectively.

The resulting colors of the RHA are creamish white for calcined at 550 oC for three hours and grey
for calcined 900oC for one hour. An increase in applied temperature appears to have some
accompanying phase changes and holding (or soaking) time as well affect the color of ash produced.
Silica produced between 500-650oC with soaking time of 2.5-6 hr is considered ideal for producing
white amorphous silica [4].

2.2. Characterizations
The thermal behavior of dried rice hull was examined using using TGA-50 by Shimadzu at
Institute of Chemistry (IC), University of the Philippines-Diliman, Quezon City. The analysis was
carried out by heating the sample from 25 to 900 oC temperature in steps of 10 oC/min under nitrogen
gas atmosphere. The dried rice hull sample was introduced into a ceramic (alumina) crucible and
placed in the furnace along with the reference sample.
The structure of silica formed from the RHA calcined at two different calcining temperatures were
determined by x-ray diffraction (XRD) technique and performed at Philippine Nuclear Research
Institute (PNRI), Quezon City. The XRD pattern was obtained with Siemens Kristalloflex 760 X-ray
Generator with Cuk-xray tube (=1.5406Å) and a Philips 1080 vertical goniometer operated at 34kV
voltage and 20mA current. Diffraction patterns were recorded between 10 and 85 o (2θ) with step size
0.02. Identification of the phases formed in the rice hull ash samples was carried out using MacDiff
Peak Database:Complete Minerals [9].
The surface morphology of the rice hull ashes was examined using a scanning electron
microscope (SEM) S-3400N by Hitachi at National Institute of Geological Sciences (NIGS),
University of the Philippines-Diliman, Quezon City.

3. Results and Discussions

3.1. Thermogravimetric and Differential Thermal Analysis (TG-DTA)
The thermo-gravimetric (TG) and derivative thermo-gravimetric (DTG) analysis thermogram
curve of dried rice hull is shown in Figure 3. The TGA curve shows the decomposition of dried rice
hull in a nitrogen atmosphere at a heating rate of 10 oC/min. As can be observed from the curve, there
are two mass-loss steps occurred in the sample: 1 - the release of moisture at temperatures between
25.26oC - 122.56oC which has 7.329% mass loss, and 2 - the process of thermal decomposition began
at 122.56oC temperature and ended at 692.21oC temperature with 58.142% mass loss. The maximum
rate of thermal decomposition in the process is also revealed at 343.52 oC (position of DTG peak
temperature).
The results obtained was in agreement to the findings of other researchers in their previous studies
wherein thermal decomposition or mass loss of untreated rice husk occurred in three distinct stages:
removal of moisture or drying (40-150oC), release or removal of volatile matter (215-315 oC), and
burning of combustible matter (350-690oC) [7].

Fig. 3. The TG-DTG analysis thermogram curves of dried rice hull.

3.2. X-ray Diffraction (XRD) Analyses

 The resulting XRD pattern of the rice hull ash calcined at two different temperatures are shown in
Figure 4. As can be observed in the figure, the silica formed from rice hull ash calcined at 550 oC was
amorphous silica (Figure 4b) as depicted by the broad peak XRD pattern centered at 21.58 deg (2θ)
while some crystalline silica as suggested by the distinct peaks of cristobalite (denoted by C) with
peaks at 21.70 deg (2θ) and 35.92 deg (2θ) can be synthesized at 900 oC (Figure 4a).
These results obtained are in agreement with the results of previous studies wherein the silica
formed by combustion below 800oC was amorphous and at combustion temperatures above 900 oC are
crystalline in nature with the formation of cristobalite and traces of tridymite [1,4].

3.2.Scanning Electron Microscopy (SEM) Analyses

The scanning electron microscopy (SEM) images of rice hull ash (RHA) calcined at 550 oC and
o
900 C are shown in Figure 5(a) and Figure 5(b) respectively, which show agglomerated particles for
both samples. Observing the figures further, particles of RHA in Figure 5(a) seems an agglomeration
of irregular shape particles [10] smaller than 10μm in sizes while Figure 5(b) showed some particles
adhered to each other forming large neck [10] which resulted to agglomeration of bigger particles due
to surface melting of some silica particles [1] and presence of some amorphous silica particles can
also be seen.

Fig. 4. XRD patterns of rice hull ashes calcined at (a) 900 oC and (b) 550oC.

Fig. 5. SEM images of rice hull ashes calcined at (a) 550 oC (b) 900oC.

4. Conclusion and Recommendation

The following results were obtained by investigating the structure, morphology, and thermal
properties of rice hull and rice hull ash calcined at different temperatures:
1) There are two mass loss observed in the TG-DTG curve of dried rice hull, release of moisture and
thermal decomposition.
2) The desired form of silica from waste rice hull can be successfully obtained by controlled heat
treatment producing either purely amorphous or with some crystalline silica.
3) Agglomerated particles were observed in both samples.
The following are also recommended for future study on utilizing rice hull:
1) Additional characterization techniques in investigating the silica formed from rice hull ash.
2) More controlled (homogenized) material and temperatures processing in producing highly
crystallize silica.
Acknowledgment
This study is supported in part by the UP OVPAA Balik-PhD Research Grant (OVPAA-BPhD-
2012-06), CHED-SEGS, and MMSU.

References
[1] Y. Nakata, M. Suzuki, T. Okutani, M. Kikuchi and T. Akiyama, Preparation and Properties of SiO2
from Rice Hulls, J. Ceram. Soc. Jpn, Int’l Ed., Vol.97 pages 830-836, 1989.
[2] O. Olawale, F.A. Oyawale, Characterization of Rice Husk via Atomic Absorption
Spectrophotometer for Optimal Silica Production, Vol.2 No.4, April 2012.
[3] M.F. de Souza, W.L.E. Magalhães, M.C. Persegil, Silica Derived from Burned Rice Hulls, Mat’ls
Res., Vol.5, No.4, 467-474, 2002.
[4] I.B. Ugheoke, and O. Mamat, A critical assessment and new research directions of rice husk silica
processing methods and properties, Maejo Int. J. Sci. Technol. 2012, 6(03), 430-448.
[5] M.M. Haslinawati,, K.A. Matori, Z.A. Wahab, H.A. Sidek, A.T. Zainal, Effect of Temperature on
Ceramic from Rice Husk Ash, International Journal of Basic & Applied Sciences IJBAS-IJENS
Vol:09 No:09, 2009, pages 22-24
[6] A. Onojah, A.N. Amah, and B.C. Ayomanor, Comparative studies of silicon from rice husk ash and
natural quartz, American Journal of Scientific and Industrial Research, ISSN:2153-649X, 2012.
[7] A. Chakraverty, P. Mishara, and H.D. Banerjee, Investigation of thermal decomposition of rice
husk, Thermochimica Acta, Volume 94, Issue 2, pages 267-275, 1985.
[8] N. Liu, K. Huo, M.T. McDowell, J. Zhao & Y. Cui, Rice husk as sustainable source of
nanostructured silicon for high performance Li-ion battery anodes, Scientific Reports, 3:1919,
DOI:10.1038/srep01919.
[9] Mac Diff Peak Database:Complete Minerals
[10] K. Ishizaki, S. Komarneni, and N. Nanko, Porous Materials Process technology and applications,
Materials technology Series, Kluwer Academic Publisher, London, 1998.