Characterisation of silica derived from rice husk (Muar, Johor, Malaysia)

decomposition at different temperatures

M. A. Azmi, N. A. A. Ismail, M. Rizamarhaiza, W. M. Hasif. A. A. K., and H. Taib

Citation: AIP Conference Proceedings 1756, 020005 (2016); doi: 10.1063/1.4958748

View online: http://dx.doi.org/10.1063/1.4958748
View Table of Contents: http://aip.scitation.org/toc/apc/1756/1
Published by the American Institute of Physics
 Characterisation of Silica Derived from Rice Husk (Muar,
Johor, Malaysia) Decomposition at Different Temperatures
M. A. Azmi, N. A. A. Ismail, M. Rizamarhaiza, W. M. Hasif. A. A. K

and H. Taib a)

Faculty of Mechanical and Manufacturing Engineering, Universiti Tun Hussein Onn Malaysia, 86400 Batu Pahat,
Johor, Malaysia

Corresponding author: a) hariati@uthm.edu.my

Abstract. Rice husk was thermally decomposed to yield powder composed of silica (SiO 2). Temperatures of 700oC and
1000oC were chosen as the decomposition temperatures. X-Ray Diffraction (XRD), X-Ray Florescence (XRF), Fourier
Transform Infrared (FTIR), and Field Emission Scanning Electron Microscope (FESEM) analyses were conducted on a
synthetic silica powder (SS-SiO2) and the rice husk ash as for the comparative characterisation study. XRD analyses
clearly indicated that the decomposed rice husk yielded silica of different nature which are Crystalline Rice Husk Silica
(C-RHSiO2) and Amorphous Rice Husk Silica (A-RHSiO2). Moreover, it was found that SS-SiO2 was of Quartz phase,
C-RHSiO2 was of Trydimite and Cristobalite. Through XRF detection, the highest SiO 2 purity was detected in SS-SiO2
followed by C-RHSiO2 and A-RHSiO2 with purity percentages of 99.60%, 82.30% and 86.30% respectively. FTIR
results clearly indicated silica (SiO2) bonding 1056, 1064, 1047, 777, 790 and 798 cm-1) increased as the crystallinity
silica increased. The Cristobalite phase was detected in C-RH SiO2 at the wavelength of 620 cm-1. Morphological
features as observed by FESEM analyses confirmed that, SS-SiO2 and C-RH SiO2 showed prominent coarse granular
morphology.

INTRODUCTION
Naturally derived silica (SiO2) can be obtained by extraction of various natural resources. Rice husk, an
agricultural residue are abundantly available in rice producing countries. Currently, majority of the husk yielded
from the processing of rice is either burnt or dumped as waste [1]. Rice husk can be an economically viable raw
material and a sustainable resources for the production of silicates and silica materials. The major components of
rice husk are organic materials such as hemicelluloses, cellulose and lignin totalling about 75 90% and the
remaining ash content of 17 20%. The ash mainly consists of >90% silica and some metallic impurities.
Combustion of rice husk under controlled conditions leads to the productions of rice husk ash containing SiO 2 [2].
Rice husk are potential to produce SiO2 upon several process which are cleaning, purification or modification
and incineration or thermal decomposition process [2,3]. Rice husk, upon thermal decomposition in air at low
temperature (below 700C) produces amorphous SiO2, while crystalline SiO2 may be yielded upon thermal
decomposition at temperatures above 700C. Amorphous SiO2 is mostly present in rice husk ash [3]. Firing rice
husk at different temperatures would influence the existence of amorphous SiO 2 and crystalline SiO2 or both [4].
Transformation of SiO2 phases from amorphous to crystalline has been studied by many researchers [5,6]. Tridymite
and Cristobalite are the phases were found in rice husk ash after firing at 1000 oC [7].
Thus herein, the paper describes a study of the characterisation of synthetic SiO2 (SS-SiO2) and SiO2 obtained
upon thermal decomposition of rice husk ash of in terms of its phase, elemental, functional group and morphological
features.

The 2nd International Conference on Functional Materials and Metallurgy (ICoFM 2016)
AIP Conf. Proc. 1756, 020005-1020005-7; doi: 10.1063/1.4958748
Published by AIP Publishing. 978-0-7354-1414-3/$30.00

020005-1
 INTRODUCTION

Raw Material
Synthetic SiO2 powder designated as SS- SiO2 used in this study was obtained from Unahan-Chem, Korea. Rice
husk as the source of naturally derived SiO2 were obtained from local rice mill, Muar, Johor, Malaysia.

Thermal Decomposition of Rice Husk

Rice husk were firstly washed by using tap water in order to remove dirt and unwanted residues. The cleaned
rice husk was left dried completely under the sunlight for two days. Thermal decomposition or the burning process
of the dried rice husk were conducted in a muffle furnace. Rice husk was gradually heated from room temperature to
700oC and 1100oC with a heating rate of 10oC/minute. Sieving machine (Fritsch, Germany) was then used to obtain
fine rice husk ash powder. The burnt rice husk were then sieved to pass through 25m mesh with maximum
amplitude for 30 minutes. Rice husk powder burnt at 700 oC are designated as A-RHS and 1100oC are designated as
C-RHS. SS.

Characterisation of SiO2
Characterisation of SiO2 was performed by using XRD to identify SiO2 phases present and crystallinity in the
SS-SiO2, C-RHSiO2 and A-RHSiO2. XRD analyses were performed by using Bruker D8 Advance, Germany with
specific Bragg angle 2-theta angle from 10-60 (degree). XRF analyses were conducted using Bruker S4 Pioneer,
Germany as to quantify the concentrations of SiO2. Identification of molecular bonding and properties of SS-SiO2,
C-RHSiO2 and A-RHSiO2 was carried out by using FTIR (Spectrum 100 FT-IR Spectrometer, Perkin Elmer
Precisely, United States). Morphology of SiO2 particles was observed by using FESEM (JEOL JSM-7600F, Japan)
with 1000x magnification. Samples were coated with Platinum (Pt) to enhance conductivity for the morphological
features observation

RESULTS AND DISCUSSION

Phase Identification
The crystalline and amorphous nature of SiO2 derived from rice husk were confirmed by the observation of the
presence of intense and broad diffraction peaks from the XRD analyses, as shown in Figure-1. Broad diffused peaks
with maximum intensity at 2 = 22o observed, are indicating amorphous nature of A-RHSiO2, similar to stusy by
Ayswarya [8]. Intense peak indicates the crystalline nature of SiO2 was observed for samples SS-SiO2 and C-RH
SiO2. Furthermore, it is also worth noting that the intensity of the diffraction peaks of SS-SiO2 are higher than the
crystalline SiO2 derived from rice husk, thus indicating higher crystallinity nature of the synthetic SiO 2 powder.

020005-2
 50000
SS-SiO2

Intensity (counts)
40000
30000
20000
10000
0
10 15 20 25 30 35 40 45 50 55 60
2 (degree)
10000
C-RHSiO2
8000
Intensiti (counts)

6000
Tridymite
Crystobalite
4000

2000

0
10 15 20 25 30 35 40 45 50 55 60
2 (degree)

1000
A-RHSiO2
800
Intensity (counts)

600

400

200

0
10 15 20 25 30 35 40 45 50 55 60
2( degree)

Figure-1. XRD diffractograms for SS-SiO2, C-RH SiO2 and A-RH SiO2

Presence of the crystalline phase, quartz (JCPDS No.: 00-046-1045) was detected in SS-SiO2 while phases of
quartz, tridymite (JCPDS No.: 00-042-1401) and cristobalite (JCPDS No.: 00-039-1425) was detected in the SiO2
derived from rice husk. C-RHSiO2 was found to consist of mainly tridymite and cristobalite phases.

The summary of the nature, phases and 2 peak positions of SS-SiO2, C-RHSiO2 and A-RHSiO2 are as
shown in Table 1.
TABLE 1: Summarised XRD findings for SS-SiO2, C-RHSiO2 and A-RHSiO2
Sample Silica Nature/ Phase Intense peak (2)
SS-SiO2 Crystalline Quartz 21,26,36,39,43,46,50,55
C-RHSiO2 Crystalline Tridymite 21,27
Cristobalite 23,28,31,36,43,45,47,48,54,58
A-RHSiO2 Amorphous SiO2 22

020005-3
 Elemental Analyses
The analyses conducted via XRF determined the percentage of SiO2 purity and the impurities in the samples.
Presence of a total of 13 elements were detected in all samples; SS-SiO2, C-RHSiO2 and A-RHSiO2 as summarised
in Table 2. The presence of impurities such as carbon (C), magnesia (MgO), Sulfphur trioxide (SO3) and
phosphorous petoxide (P2O5) observed only in C-RHSiO2 and A-RHSiO2 suggested that these impurities formations
are due to the thermal decomposition of the rice husk itself and due to the organic nature of the rice husk itself.

TABLE 2: Percentage of SiO2 and impurities in all samples

Concentration, (%)
Elements
SS- SiO2 C-RH SiO2 A-RH SiO2
CaO 0.1533 7.0106 4.0294
Na2O 0.1148 - 4.6888
K2O 0.0736 6.1776 -
MnO 0.0233 - -
Al2O3 0.0181 - -
Fe2O3 0.0093 - -
TiO2 0.0040 - -
Cr2O3 0.0037 - -
C - 0.6941 0.3665
MgO - 2.1518 1.6484
SO3 - - 1.5019
P2O5 - 1.6659 1.4652
Total Impurity, % 0.40 17.70 13.70
Total Purity, % 99.60 82.30 86.30

Purity percentages of SS-SiO2, C-RHSiO2, and A-RHSiO2 were 99.60%, 82.30%, 86.30% and respectively. The
purity of SS-SiO2 is higher than C-RHSiO2 and A-RHSiO2. The impurities of C-RHSiO2 and A-RHSiO2 were
17.70% and 13.70% respectively. Meanwhile, the detected impurity for SS-SiO2 is only of 0.4%. The purity
percentage of SiO2 in C-RHSiO2 and A-RHSiO2 were lower due to the difference in burning temperature during the
thermal decomposition of rice husk. The burning temperature may have affected purity and cause element loss on
fire during burning [9,10].

Molecular Bonding Analysis

Infra-red spectra of the rice husk silica and synthetic silica was recorded by FTIR at wavenumber ranging 550-
4000 cm-1. The FTIR spectra of three different types of silica were similar as shown in Figure-2.

SS

C-RHS
(a.u)

A-RHS

3500 2500 1500 500

Wavenumber (cm-1)
FIGURE 2: FTIR spectra of SS-SiO2, C-RHSiO2 and A-RHSiO2

020005-4
 As can be seen, there are two notable transmittance peaks at certain wavenumber in the spectra. SS-SiO2 FTIR
spectrum observed the lowest peaks intensity among all the samples. The transmittance peaks of SS were recorded at
1056 cm-1 and 777 cm-1. C-RHSiO2 spectrum detected additional weak peak and, C-RHSiO2 featured three peaks at 1064
cm-1, 790 cm-1 and 620 cm-1. While, high intensity transmittance peaks presence in A-RHSiO2 were at 1047 cm-1 and 798
cm-1.
The predominant peaks in the wavenumber range 1000-1100 cm-1 appeared in all samples may be attributed to Si-O-
Si asymmetric bending and stretching vibration bonds, which is the presence of siloxane structural bonding [11,12,13].
Besides that, peaks at wavenumber 700-800 cm-1 in the spectra attributed to stretching of symmetric Si-O bond (Silanol)
[12,14,15]. A single weak peak appeared only in C-RHSiO2 spectrum at 620 cm-1 might corresponds to cristobalite SiO2,
as similarly reported by Haslinawati et al. and Nayak et al.[6,15]. The assignments of individual transmittance peaks of
SS-SiO2, C-RHSiO2 and A-RHSiO2 were tabulated in Table-3.

TABLE 3: Band assignments of SS-SiO2, C-RHSiO2 and A-RHSiO2.

Wavelength Band assignments Wavelength Reference
SS- SiO2 C-RH SiO2 A-RH SiO2
1056 1064 1047 Si-O-Si Asymmetric 1000-1100 [10,11,12]
stretching vibration
777 790 798 Si-O Symmetric stretching 700-800 [11,13,14]
- 620 - Cristobalite SiO2 617,622 [14,15]

High intensity peak in IR spectrum indicated weak bonding strength of Si-O-Si bonds and vice versa [15]. A-RHSiO2
shown the highest intense peak due to the amorphous nature and weak bond strength. Meanwhile, high crystallinity of
SS-SiO2 and C-RHSiO2 can be demonstrated as low stretching and bending vibration and strong bond strength with
lower IR intensity [11]. This fact correlates with XRD analyses which high intense and narrow peak indicated high
crystallinity as recorded by SS-SiO2 powder, sample and vice versa. Furthermore, IR intensity peak decreased resulted
increasing SiO2 purity as discussed in XRF results in which SS-SiO2 powder have highest SiO2 content. C-RHSiO2 and
A-RHSiO2 which have high intense IR peak contained low SiO2 content as compared to SS-SiO2.

Morphological Analysis
The morphological features of SiO2 was observed by FESEM. Micrographs of SiO2 are shown in Figure3(a) to
(c).

020005-5
 FIGURE 3: FESEM micrographs of (a) SS-SiO2, (b) C-RHSiO2, (c) A-RHSiO2

Through morphology observations, it was found that the SS-SiO2 coarse granular particles are clearly seen as
compared to C-RHSiO2 and A-RHSiO2. However, by comparing C-RHSiO2 and A-RHSiO2, the coarse granular
particles in C-RHSiO2 are much more clear compare to A-RHSiO2 which showed particles with irregular geometry.
The coarse granular morphology are affected by the crystallinity level of SiO 2, while the crystallinity in SiO2
affected by following factors; i) burning temperature, ii) elemental composition [15].
As shown in Figure-3(a) and Figure-3(b) which are SS-SiO2 and C-RHSiO2 respectively, the clear coarse
granular shape are caused by their crystalline nature in which also revealed by XRD analysis that showed both SS-
SiO2 and C-HRSiO2 have crystalline phase of quartz and tridymite or cristoballite respectively.
C-RHSiO2 were burnt at 1000C above, while A-RHSiO2 at 700C. Thus the difference of burning temperature
led to difference in coarse granular shape which presents the crystallinity of SiO 2. Burning temperature of A-
RHSiO2 at 700C caused the particles to not completely develop which lead to irregular geometry. In contrast, SS-
SiO2 and C-RHSiO2 with 1000C above burning temperature, show clear coarse particles because of complete
particles development at high temperature [15].
The crystallinity affected by its composition revealed by XRF analysis with presents of potassium (K 2O).
Potassium (K2O) only occurs in SiO2 with crystalline phase [4]. In this study, through XRF analysis, the existence of
K2O only found in SS-SiO2 and A-RHSiO2 which were in crystalline phase as revealed in XRD analysis and
morphology observation.

CONCLUSION
For the XRD analysis, the SS-SiO2 showed only one phase, namely quartz while C-RHSiO2 consist of two
crystalline phases of trydimite and cristobalite. A-RHSiO2 shows non-crystalline phase which are amorphous in
nature. Through elemental analysis it was found that the highest purity detected in SS- SiO2 powder and the purity
decrease in rice husk silica. However, the derived SiO2 from rice husk with high purity concentration at 82.30% in
C-RHSiO2 and 86.30% in A-RHSiO2 showed that it is still possible to be naturally derived. The results found using

020005-6
FTIR well matched with the crystalline phases found XRD and XRF. From the results, SS-SiO2 contains highest
SiO2 purity has strong SiO2 bonding. Natural SiO2 (C-RHSiO2 and A-RHSiO2) show SiO2 bonding and crystalline
characteristic found in C-RHSiO2. Through morphology observation it was found that microstructures of SiO2 were
influenced by phase of crystallinity, burning temperature and elemental composition.

REFERENCES
1. R. M. Mohamed, I. A. Khalid, & M. Barakat. Rice husk ash as a renewable source for the production of zeolite
NaY and its characterization. Arabian Journal of Chemistry, 8(1), 4853 (2015)
2. R. A. Bakar, R. Yahya, & S. N. Gan. Production of High Purity Amorphous Silica from Rice Husk. Procedia
Chemistry, 19, 189195 (2016)
3. J. Nayak and J. Bera,. Effect of Sintering Temperature on Phase-Formation Behavior and Mechanical
Properties of Silica Ceramics Prepared From Rice Husk Ash. Phase Transitions, 879 888 (2009)
4. Y. Shinohara and N. Kohyama. Quantitative Analysis of Tridymite and Cristobalite Crystallized in Rice Husk
Ash by Heating. Industrial Health , 277-285 (2004)
5. A. M.Venezia, V. L. Parola, A. Longo and A. Martorana. Effect of Alkali Ions in The Amorphous to
Crystalline Phase Transition of Silica. J Solid State Chem. , 373-378 (2001)
6. J. P. Nayak and J. Bera. Effect of sintering temperature on phase-formation behavior and mechanical properties
of silica ceramics prepared from rice husk ash, Phase Transitions, 82(12), 879-88 (2009)
7. A. D. Onojah, N. A Agbendeh, C. Mbakaan, B. State, B. S. Polytechnic. Rice Husk Ash Refractory: the
Temperature Dependent Crystalline Phase Aspects. Ijrras, 15(2), 246248 (2013)
8. E. P. Ayswarya, K. F. Francis, V. S. Renju and E. T. Thachil. Rice Husk Ash A Valuable Reinforcement for
High Density Polyethylene. Materials and Design, 1 7 (2012)
9. Omatola, K. M., & Onojah, A. D.. Elemental analysis of rice husk ash using X-ray fluorescence technique.
International journal of physical sciences, 4(4), 189-193 (2009)
10. V. P. Della, I. Khn & Hotza, D. Rice husk ash as an alternate source for active silica production. Materials
Letters, 57(4), 818-821 (2002)
11. S. H. Javed, S. Naveed, N. Feroze, M. Zafar, and M. Shafaq. Crystal And Amorphous Silica From KMnO 4
Treated And Untreated Rice Husk, VI(1), 8190 (2010)
12. S. Sankar, S. K. Sharma, N. Kaur, B. Lee, D. Young Kim, S. Lee, and H. Jung. Biogenerated silica
nanoparticles synthesized from sticky, red, and brown rice husk ashes by chemical method. Ceramics
International, 42(4), 48754885 (2015)
13. M. Sarangi, P. Nayak & T. N. Tiwari. Effect of temperature on nano-crystalline silica and carbon composites
obtained from rice-husk ash. Composites Part B: Engineering, 42(7), 19941998 (2011)
14. D. An, Y. Guo, B. Zou, Y. Zhu, and Z. Wang. A study on the consecutive preparation of silica powders and
active carbon from rice husk ash. Biomass and Bioenergy, 35(3), 12271234 (2011)
15. M. M. Haslinawati, K. A. Matori, Z. A. Wahab, H. A. A. Sidek and A. T. Zainal. Effect of Temperature on
Ceramic from Rice Husk Ash, (09), 19851988 (2009)
.

020005-7