Ruel J. Arila, Jr.

Essay 3

Statement of the Problem

The problem to be tackled in this study is the feasibility of synthesizing a manganese-

doped zinc silicate phosphor using silicon dioxide from rice hull ash. Specifically, this study
will discuss the morphological and photoluminescent properties of Mn-doped Zn 2SiO4
phosphors synthesized at Mn/Zn/Si molar ratios ranging from 192/8/120 to 199/1/120 using
silicon dioxide derived from rice hull ash burnt at 600, 700, and 800 °C.

Significance of the Study

As a mainly agricultural country, the Philippines is one of the world’s largest producers of
rice, harvesting 19.07 metric tons of rice and accounting for – of the world’s total rice
production. Rice production, however, also produces significant amounts of agricultural waste
in the form of rice hull and stalks. In most areas in the country, these products are often burnt
with no further financial value. This study would like to proposes a value-added application for
rice hulls by utilizing them in the production of Mn-doped Zn 2SiO4 nanophosphors, a high
value product with potential applications in field and plasma emission displays and light
emitting diodes.

For the agricultural sector, this study will explore high-end applications of agricultural
waste in the form of rice hull, potentially adding value to the production of rice. This study also
presents a potential raw material for phosphor production to the developing electronics
industry in the Philippines. This study also aims to add to the body of knowledge of the
scientific community with regards to the newfound interest in nanophosphors and their
potential applications in the field of electronic visual displays.

Review of Related Literature

Due to its silicaceous nature, rice hulls has long been studied for the production of silicon
dioxide, also known as silica. Amorphous silica is a product found in rice hull ash and can be
isolated in a laboratory for several added value applications, among them the synthesis of
silica [1, 2]. Crystalline silica has been synthesized from rice hul ash by burning it at 800 °C
and higher [3] One of the recent added value applications of rice hull is its use in the
synthesis of silica xerogels, which has higher porosity and greater surface area than
crystalline silica [4, 5]. This increased porosity and surface area present more possibilities in
the applications of rice hulls in an industrial sale [2].

Mn-doped zinc silicate (ZSM) phosphors has been studied intensively lately due to its
photodoluminescent properties, emitting light ranging from green to yellow. Light spectra from
excited ZSM phosphors have been measured to have wavelengths ranging between 520 to
574 nm [6, 7, 8, 9]. These studies indicate that ZSM phosphors are ideal phosphors to be
used for green and yellow display electronics and other lighting applications.
 ZSM phosphors can be synthesized through the sol-gel method, using
tetraethylorthosilicate as its silicon source [7, 8, 9, 11.] Due to lack of local industries
producing these precursors, however, the application of this process in an industrial scale is
not viable. ZSM phosphors can also be synthesized through the firing process. This process,
which is an established manufacturing process, uses amorphous silica as its precursor and is
preferred in industrial scale production of ZSM [6, 12].

Methodogy

The study shall be conducted according to the following steps:

I. Synthesis of amorphous silica xerogels

II. Synthesis of Mn-doped zinc silicate phosphors
III. Characterization of Mn-doped zinc silicate phosphors

I. Synthesis of Amorphous Silica Xerogels

A) Washing of Rice Hulls. The rice hulls will be washed with ethanol and water
alternately to remove oil, grease, and other contaminants. The washed rice hulls will be
dried in the furnace at 100 °C for two hours to evaporate moisture.
B) Synthesis of Rice Hull Ash (RHA). The dried rice hulls will be placed in crucibles and
burnt inside a muffle furnace at 500, 600, and 700 °C.
C) Silica Extraction from RHA. 250 g of RHA samples will be treated with one and a half
liters of 1 M NaOH solution and will be boiled for 1 hour. The solution will be filtered
with Whatman ashless filter paper, and the collected residue will be washed with
boiling water then allowed to cool to room temperature.
D) Silica Xerogel Production. An acidic solution with pH 1.5 will be prepared using 1.5 M
oxalic acid and 100 mL deionized water. The silicate solution will be added to the acidic
solution until the pH reaches 4.0. The resulting mixture will be incubated for 12 h to
promote silica gel formation. The gel will be crushed, dispersed, and centrifuged three
times then dried at 80 °C for 24 h to produce silica xerogel.

II. Synthesis of Mn-doped Zinc Silicate Phosphor

A) Material and Precursor Preparation. Zinc oxide, manganese (II) dihydrate, and the
synthesized silica xerogels will be used as the raw materials. The raw materials will be
mixed with an agate mortar and pestle at Zn/Mn/Si molar ratios ranging from 192/8/120
to 199/1/120.

B) ZSM Formation. The prepared precusors are placed in alumina crucibles and fired
inside a muffle furnace at temperatures ranging from 900 to 1,200 °C.

III. Characterization of Mn-doped zinc silicate phosphors

A) X-ray Diffraction. The crystalline structure and crystallite size of the synthesized ZSM
will be identified through X-ray diffraction
B) Scanning Electron Microscopy. The morphological implications of synthesizing ZSM
using silica from rice hull ash will be investigated using SEM analyses.
 C) Photoluminescent Properties. The ZSM samples will be subjected under a 450-W
Xenon lamp and the emitted light will be collected with an optical fiber and analyzed
with a spectrometer. The results will be compared to results obtained by other studies
using the firing process in ZSM synthesis.

Gantt Chart

Project Activities 8 9 10 11 12 1 2 3 4 5 6 7
Preparation of Raw Materials
Synthesis of RHA
Silica Extraction from RHA
Silica Xerogel Production
ZSM Formation
Characterization
Preparation of Dissertation
Thesis Defense
Revisions

References

[1] T. P. Ferolin and R. M. Vequizo, “Synthesis of zinc silicate using silica from rice hull
ash (RHA) through solid-state reaction,” Proceeding of the IETEC, vol. 13, 2013.

[2] R. Pode, “Potential applications of rice husk ash waste from rice husk biomass power
plant,” Renewable and Sustainable Energy Reviews, vol. 53, pp. 1468–1485, 2016.

[3] M. Hamad and I. Khattab, “Effect of the combustion process on the structure of rice
hull silica,” Thermochimica Acta, vol. 48, no. 3, pp. 343–349, 1981.

[4] U. Kalapathy, “A simple method for production of pure silica from rice hull
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[5] U. Kalapathy, A. Proctor, and J. Shultz, “An improved method for production of silica
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[6] M. Takesue, K. Shimoyama, S. Murakami, Y. Hakuta, H. Hayashi, and R. L. Smith,

“Phase formation of Mn-doped zinc silicate in water at high-temperatures and high-
pressures,” The Journal of Supercritical Fluids, vol. 43, no. 2, pp. 214–221, 2007.

[7] K. Omri, A. Alyamani, and L. E. Mir, “Photoluminescence and cathodoluminescence of

Mn doped zinc silicate nanophosphors for green and yellow field emissions
displays,” Applied Physics A, vol. 124, no. 2, 2018.
[8] K. Omri and L. E. Mir, “Effect of manganese concentration on photoluminescence
properties of Zn2SiO4:Mn nanophosphor material,” Superlattices and Microstructures,
vol. 70, pp. 24–32, 2014.

[9] K. Omri, O. Lemine, and L. E. Mir, “Mn doped zinc silicate nanophosphor with
bifunctionality of green-yellow emission and magnetic properties,” Ceramics
International, vol. 43, no. 8, pp. 6585–6591, 2017.

[10] K.-S. Sohn, B. Cho, and H. D. Park, “Photoluminescence Behavior of Manganese-

Doped Zinc Silicate Phosphors,” Journal of the American Ceramic Society, vol. 82, no.
10, pp. 2779–2784, 2004.

[11] Q. Lu, P. Wang, and J. Li, “Structure and luminescence properties of Mn-doped
Zn2SiO4 prepared with extracted mesoporous silica,” Materials Research Bulletin, vol.
46, no. 6, pp. 791–795, 2011.

[12] W. M. Yen, S. Shionoya, and H. Yamamoto, Phosphor handbook. Boca Ratón, FL:

CRC Press, 2007. pp. 318-323