1 s2.0 S1385894714015150 Main PDF

Chemical Engineering Journal 264 (2015) 899935
Contents lists available at ScienceDirect
Chemical Engineering Journal

journal homepage: www.elsevier.com/locate/cej
Review
Review on the physicochemical treatments of rice husk for production

of advanced materials
N. Soltani, A. Bahrami, M.I. Pech-Canul , L.A. Gonzlez
Centro de Investigacin y de Estudios Avanzados del Instituto Politcnico Nacional Cinvestav-Saltillo, Av. Industria Metalrgica No. 1062 Parque Industrial Saltillo-Ramos Arizpe,
Ramos Arizpe, Coahuila 25900, Mexico
h i g h l i g h t s
Applications of rice husk and its derivatives.

Study the available technologies for production of SiC, pure Si, Si3N4, Mg2Si, SiO2 from rice husk.
Explanation of different furnaces for production of rice husk ash.
Study the available technologies for production of activated carbon from rice husk.
a r t i c l e i n f o a b s t r a c t
Article history: Recently, much attention has been focused on the utilization of plant biomass to produce engineering
Received 30 July 2014 materials, encompassing the technological/scientic aspects as well as the economic, environmental
Received in revised form 23 October 2014 and social issues. Amongst the variety of agricultural wastes or biomasses available, rice-husk (RH) occu-
Accepted 6 November 2014
pies a preeminent position, not only in terms of its amount produced worldwide, but also because of its
Available online 3 December 2014
unique chemistry-related features. In this sense, some attempts have been made to produce advanced
materials including SiO2, SiC, Si3N4, elemental Si, Mg2Si and more recently, active carbon , using RH.
Keywords:
The production of those mentioned advanced materials depends largely on the treatments used (physical
Rice husk ash (RHA)
Silicon-based materials
and/or chemical) and the reactions involved in the process, such as pyrolysis, carbothermal and reduction
Physicochemical treatments processes. In this contribution, a critical review on the processing and application of rice husks (RHs) for
Agricultural waste materials the production of various silicon-based materials and of active carbon is presented. The review addresses
Pyrolysis the different processing methods, the effects of various process parameters on the pyrolysis stage, the
Carbon active inuence of physical, chemical and thermal treatments, activating conditions and activated carbon con-
solidation mechanisms. A ow chart with all the possible routes to produce SiO2 was purposely
constructed.
2014 Elsevier B.V. All rights reserved.
Contents
1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 900
2. Biofibers from agricultural by-products for industrial applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 901
2.1. Rice husk . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 901
3. Application of rice husk . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 903
3.1. Absorbent. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 903
3.2. Coatings . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 904
3.3. Pigment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 904
3.4. Cement industry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 904
Corresponding author. Tel.: +52 (844) 4 38 96 00x8678.

E-mail addresses: martin.pech@cinvestav.edu.mx, martpech@gmail.com
(M.I. Pech-Canul).
http://dx.doi.org/10.1016/j.cej.2014.11.056
1385-8947/ 2014 Elsevier B.V. All rights reserved.
900 N. Soltani et al. / Chemical Engineering Journal 264 (2015) 899935
3.5. Insulator. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 905

3.6. Rubber . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 905
3.7. Electronics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 905
3.8. Energy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 905
3.9. Production of potential reinforcement for fabrication of MMCs and CMCs. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 906
4. Production of silica. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 907
4.1. Furnace/reactor for production of RHA . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 908
4.1.1. Rotary kiln. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 908
4.1.2. Fluidized bed process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 908
4.1.3. Inclined grate furnace . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 909
4.1.4. Cyclonic furnace . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 909
4.2. Effect of temperature on the structure of obtained silica from rice husk . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 910
4.3. Pre-purification of thermal treated rice husk . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 912
4.4. Post-purification of thermal treated rice husk . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 914
4.4.1. Precipitation of silica from the sodium silicate solution through acid treatment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 914
4.4.2. Precipitation of silica from sodium solution through injection of CO2 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 915
4.5. Precipitation of silica with NH4F . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 915
4.6. Hydrothermal process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 915
4.6.1. High-temperature hydrothermal process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 915
4.6.2. Low-temperature hydrothermal process. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 915
4.7. Microbial fermentation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 916
5. Silicon carbide . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 916
5.1. Vaporliquidsolid (VLS) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 917
5.2. Frank mechanism (whisker growth from vapor phase) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 917
5.3. SiC formation from rice husk . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 917
5.3.1. Pyrolysis of rice husk at lower temperature . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 917
5.3.2. Carbothermal reaction of rice husk at higher temperature . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 918
5.4. Effect of different parameters on SiC formation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 918
5.4.1. Distribution of silica in rice husk . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 918
5.4.2. Effects of catalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 919
5.4.3. Effect of atmosphere on SiC formation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 920
5.4.4. Effect of chemical pre-treatment of rice husk . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 921
5.4.5. Effect of crystallinty of SiO2 and C . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 921
5.4.6. Effect of milling of starting materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 921
6. Preparation of nano SiC . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 922
6.1. Utilization of agricultural waste materials as source for carbon . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 922
6.2. Arc plasma reactor . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 922
6.3. Microwave heating . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 922
7. Silicon nitride . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 923
7.1. Si3N4 formation through carbothermal reduction and nitridation of rice husk. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 923
7.1.1. Effect of catalysts on Si3N4 formation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 924
7.2. Si3N4 formation through chemical vapor deposition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 925
8. High purity silicon . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 925
9. Magnesium silicide (Mg2Si) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 926
10. Activated carbon . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 927
10.1. Physical activation. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 927
10.2. Chemical activation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 928
10.3. Microwave heating technology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 929
11. Summary and conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 929
Acknowledgments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 930
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 930
1. Introduction appears in the text, we are referring to the vegetable ones, which
are extracted from plants.
Since the 1990s, natural bers started to emerge rapidly for Depending on the part of the plant where they are extracted
industrial applications. Several authors have reported recent pro- from, natural bers can be classied into three categories. When
gresses in the use of natural bers (rice husk (RH), bagasse, bread- determining the properties of natural bers, one has to keep in
fruit, coconut shell and coir, etc.) in composites. Natural ber mind that variability in properties depends on the growing envi-
composites offer environmental advantages such as reduced ronment: temperature, humidity, soil composition, air, age and
dependence on non-renewable energy/material sources, lower pol- body of the plant all affect the height of the plant, density and
lutant emissions, lower greenhouse gas emissions, enhanced the strength of its bers, etc. In addition, the way the plants are
energy recovery, and end of life biodegradability of components harvested and processed results in a variation of properties. Rice
[1]. Based on source and origin of natural bers, they are classied husk is a major agricultural by-product in rice growing countries
into three large groups: animal, vegetable and mineral natural like China and India, with 33% and 22% of the global rice harvest,
bers. Due to the wide usage of vegetables and to their vast avail- respectively. Unique large-tonnage waste material from cultivation
ability and renewability in short time periods as compared to the and processing of crops, dissimilarity in the composition and prop-
others, in this review paper whenever the term natural bers erties to some other plant wastes makes it as a potential material.
N. Soltani et al. / Chemical Engineering Journal 264 (2015) 899935 901
The world rice harvest is estimated in 500 million tons per year. However, it provides rigidity to the structure of the plant. Unlike
Considering that 20% of the grain is husk, and 20% of the husk after hemicelluloses, lignin is composed mainly of aromatic compounds,
combustion is converted into ash, a total of 20 million tons of ash having a small or insignicant inuence on the absorption of water
can be obtained. The ash contains potassium, sodium, magnesium, [4]. The mechanical properties of bers directly relates to their ele-
calcium, iron, and phosphorus, as well as considerably smaller mental composition, components, structure and internal defects.
quantities of copper, iron, manganese, etc. A large quantity of the The percentage of cellulose inuences the structure and properties
world production of rice husk and rice husk ash remains as an of bers such as tensile strength, electrical resistivity, density,
unused waste material. As a result, a large number of possible modulus, and crystallinity. However, it should not be generalized
industrial applications of rice husk ash has been investigated. to all kinds of bers. Those with higher cellulose content and
Extensive research has been carried out on the preparation, prop- higher degree of polymerization of cellulose have better mechani-
erties and applications of RHA during the last three decades and cal properties. By increasing the content of lignin and decreasing
many scientic investigations and patents have been published the length-to-diameter ratio (l/d) of individual cells, the mechani-
on this subject. cal properties deteriorate while extensibility of bers increases.
In this contribution, authors critically analyze the past and pres- High l/d ratio of banana and pineapple bers in comparison with
ent research work carried out so far on the processing and applica- other plants results in the production of long bers. The l/d ratio
tion of rice-husk for the production of various silicon-based of rice straw, wheat straw and corn husk are smaller than those
engineering materials and in addition, of active carbon. The work of the former, therefore relatively ner bers can be formed
addresses the different processing methods, the effects of various through the processes while coir has thick individual cells and
process parameters on the pyrolysis stage, the inuence of physi- therefore cannot form ne bers. Under stress, tensile failure
cal, chemical and thermal treatments, activating conditions and shows two modes: intercellular or intracellular. For instance in
mechanisms of active carbon consolidation. Albeit a number of sci- banana and pineapples intercellular fracture occurs and bers give
entic/technical review articles related to the use of rice-husk for the higher modulus and tensile strength but lower breaking elon-
the development of adsorbents, for polymer green composite con- gation in comparison with coir bers. On the other hand, it has
stituents and for energy applications, have been published, and been reported that the hollow tubular (cellular) structure of the
with the exception of the work by Sun et al. [2] no attempt has plant bers provides excellent insulation against heat and noise
been made to discuss in a comprehensive way the potential of rice for automobile applications [5].
husk for the production of advanced materials, within the frame- Natural bers (derived from vegetables) can be classied into
work of the materials chemistry perspective. It should be pointed four groups depending on the part from which they are extracted:
out that other agricultural residues have also been proposed for
the production of advanced materials, but due to their low SiO2 1. Fruit: This kind of bers are extracted from the fruits of the
content in the ash, they have not been considered for further plant, they are lightweight and hairy, and allow the wind to
studies. carry the seeds.
In this publication, authors make an attempt to gather informa- 2. Bast: They are found in the stems of the plant, providing the
tion from the oldest to the most recent developments regarding plant its strength. Usually they run across the entire length of
the methods to produce silicon-based material from rice husk. the stem and are therefore very long.
More specically, the paper is aimed at discussing in depth about 3. Leaf: This kind of bers are extracted from the leaves; they are
the effect of different catalysts, heat treatments, pretreatments sturdy and form part of the plants transportation system.
and different procedures for the preparation of silicon-based mate- 4. Stalk: These bers are composed of a slender or an elongated
rials, like SiO2 (nanosilica), SiC (nano SiC), Si3N4, Si, and Mg2Si (in structure that holds up an argon or another part of the body.
decreasing order of importance). It also includes the different
extraction routes and the methods for enriching and purifying sil- Fig. 1 presents a owchart, showing a classication of natural
ica in prior and post heat treatment methods. Three main identi- sources depending on the parts from which they are obtained.
ed routes for silica extraction are summarized in a ow diagram Table 1 summarizes the physical and mechanical properties as
purposely designed for this contribution. The characteristics and well as the chemical composition of the aforementioned natural
operation conditions of the different furnace/reactor systems for bers [611].
silica preparation from rice husk are also presented. The produc- Because of its low price and more silica content, as compared to
tion of active carbon from rice husk under special conditions in the other natural bers, rice husk has been found suitable for a
two different methods (either physical or chemical activation) is wide range of manufacturing and application oriented processes.
also addressed. Accordingly, the current critical review focuses on the application
and production of silicon-based materials derived from rice husk.
2. Biobers from agricultural by-products for industrial 2.1. Rice husk

applications
Amongst the various biomasses, with abundant and renewable
Natural bers consist of three major components: cellulose, energy sources, rice husk is not only a potential source of energy,
hemicellulose and lignin. Based on the types of bers and the plant but also a value-added by product [12]. In the last decades, there
source, the relative portion of these components may vary. Cellu- were many reasons associated with rice husk for not being used
lose is a homopolymer of glucose, while hemicellulose is a hetero- effectively like (1) lack of awareness of its potential by farmers
polymer consisting of hexose (glucose, mannose, and galactose) and industry persons, (2) socio-economic problems, (3) penetra-
and pentose sugars (xylose and arabinose) [3]. Cellulose is a semi- tion of technology, (4) lack of environmental concerns, and etc.
crystalline polysaccharide and is responsible for the hydrophilic Solution to the problems associated with utilization of this solid
nature of natural bers. Hemicellulose is a fully amorphous poly- waste needs to be addressed both in quality and quantity aspects.
saccharide with a lower molecular weight compared to cellulose. Recently the efforts have centered mostly in the utilization of rice
The amorphous nature of hemicelluloses comes from the fact that husk to reduce the cost of industrial processing, but due to its hard
it is partially soluble in water and alkaline solutions. Lignin is an surface, high silicon content, small bulk density, and not being eas-
amorphous polymer that does not contain carbon sources. ily decomposed by bacteria, rice husk residues constitute a dra-
Fig. 1. Classication of vegetable source based on the parts from which they are derived.
Table 1
Component percentage, physical and mechanical properties of some natural bers [611].
Natural ber name Cellulose Hemicellulose Lignin Ash Mechanical properties Density (g/cm3) Moisture (wt.%)
Tensile strength El. at break% Young modulus (GPa)
(N/mm2)
Ramie 6891 13.116.7 0.60.7 1 560915 3.0 5.512 1.5 8.5
Flax 65 16 2.5 3.4 3441035 3.0 2628 1.3 4
Coconut 32.65 7.65 59.4 5.1 150180 2040 46 0.61 27.1
Abaca 5663 2025 79 3 400 3.4 14 1.5 14
Banana 70 68 12 1.2 529914 13.7 2732 1.45 13.5
Hemp 70.274.4 1822.4 3.75.7 350800 1.64 3060 1.48 8
Pineapple 64.35 13.85 4.6 0.04 360749 2.8 2435 1.45 91.35
Kenaf 5357 1519 5.99.3 25 400700 2550 1.72.1 1.3 17
Baggase 30.2 56.73 13 4.1 170290 37 1519 0.12 8.8
Rice husk 34.4 24.3 19.2 1520 0.55 6.5
Corn cob 45 29.335 13.715 13 0.50.7 9
Oil palm 56.03 27.51 20.48 2.4 248 25 3.2 0.71.55 1.72
Bamboo 2643 30 2131 1.75 500740 25 3050 0.64 6.2
Cotton 82.7 5.7 0.822 300700 68 610 1.51 8.5
Sisal 6778 711 1024 0.61 300500 25 1013 1.33 11
matic source of pollution which can alter the ecosystem [13]. been reported elsewhere that unlike fossil fuels, rice husk can be
Because of this, numerous criticisms and complaints have been used for reducing the greenhouse effect because trees absorb CO2
reported. In addition, the burned rice husk is associated with car- as they grow and this carbon is released when the biomass is com-
cinogenic and bio-accumulative effects, resulting in silicos is syn- busted. Thus, the net amount of CO2 added to the atmosphere dur-
drome, in other words, a general adverse effect to health. ing energy production through the use of biomass (RH) over the
Furthermore, on the one hand, it has been reported that the utili- entire life cycle is nearly zero [15].
zation of RH in electric power generation is linked to the release Rice husks contain organic substances and 20% of inorganic
of a large number of greenhouse gases that can be a threat to material. The main elemental components of RH are C
humans health and environment [14]. On the other hand, it has 37.05 wt.%, H 8.80 wt.%, N 11.06 wt.%, Si 9.01 wt.% and O
adding a buffer solution of acetic acid, aqueous chlorite and dis-

tilled water. Then, the acid hydrolysis treatment was conducted
by sulphuric acid. Most nanocrystal cellulose displayed a diameter
Fig. 2. Electromeric effect in components of hemicelluloses [16]. and aspect ratio in the range of 1520 nm and 1015, respectively.
Fig. 4 shows the typical structures of rice husk after each step of
the experiment.
3. Application of rice husk
India, Pakistan, Bangladesh, Sri Lanka, Australia, Thailand, Indo-

nesia, and USA were pioneers in the utilization of rice husk during
19701985, which were supported by government and other orga-
nizations. Unique characteristics of rice husk in comparison with
other agricultural residues, such as high silica contents (87
Fig. 3. Possible bonding of silicon with carbohydrate in rice husk [16]. 97 wt.% SiO2), high porosity, lightweight and very high external
surface area make it a valuable material for industrial applications.
Fig. 5 depicts some of the applications of rice husks in different
industrial elds, taking advantages of special characteristics of rice
Table 2
Calculated contents of silicon and SiO2 [16]. husk.
Organic constituent SiO2 (wt.%) Silicon (wt.%)

3.1. Absorbent
D-Xylose 5.179 2.421
L-Arabinose 0.225 0.225
The presence of heavy metals like iron, manganese, nickel,
Methyl glucoronic acid 0.3465 0.162
0.145 0.068 arsenic, cadmium and some anions such as nitrate and uoride
D-Glucose
Total 6.1515 2.876 in aquatic systems is a very serious problem and related to the
prevalence of some diseases like renal failure, liver cirrhosis, hair
losses, cancer, and chronic diseases. Heavy metals are dangerous
for living organisms because of their stability, toxicity, and ten-
35.03 wt.%. The contents of RH are hemicellulose 24.3%, cellulose dency to accumulating in the environment. Adsorption using acti-
34.4%, lignin 19.2%, ash 18.85%, and the else substance 3.25% vated carbon has been found to be an attractive process for the
[10]. The monomeric components of hemicelluloses (monosaccha- removal of heavy metals from industrial efuents. However, the
rides) are resources for producing large-scale commodities such as cost of activated carbon and the loss of adsorption efciency after
xylose, activated carbon, and silicon dioxide, which become polar regeneration of the exhausted activated carbon have limited its use
due to an electromeric effect. The electromeric effect operates as in efuent waste water treatment. Therefore, alternative low-cost,
shown in Fig. 2 [16]. non-conventional adsorbents such as bagasse y ash (BFA), rice
This type of electron transfer is brought into play only under the husk ash, peat, lignite, bagasse pith, wood, saw dust, etc. have been
inuence of an attacking reagent. Therefore it seems that in rice proposed for the treatment of efuents [20,21]. Adsorption proper-
husk, in addition to free SiO2, silicon is bonded with monosaccha- ties of rice husk have been studied because of its low price and
rides [16]. Cellulose, (C6H10O5), the main constituent of rice husk, richness in silica.
being a polysaccharide, does not seem to possess considerable Experimental results done on the adsorption behavior of phos-
bonding property. Lignin, which exists with cellulose, is mostly phate-treated rice husk (PRH) in case of Ni (II), Zn (II), Cd (II) and Cr
inert and therefore it is also not expected to be suitable for bonding (VI) showed that adsorption of Ni (II) and Cd (II) are signicant
[1618]. The possible bonding of silicon with four monosaccharide [22], while the investigation by Rocha et al. [23] showed that the
molecules is shown in Fig. 3. adsorption order was Cd (II) > Cu (II) > Zn (II) > Hg (II) on the rice
Based on the assumption that four monosaccharide molecules straw. In addition, adsorption column methods show the complete
react with one atom of silicon (as silicon is tetravelent), the per- removal of both As (III) and As (V) with rice husk ash [24,25]. It has
centages of silicon that can remain bonded with different mono- also been reported that RHA can remove chromium (III) ion from
meric components of hemicelluloses (monosaccharides) have aqueous solutions, but is not very efcient [26].
been shown in Table 2. It has been reported that RHA produced by heating rice husks at
Johar et al. [19] reported that cellulose bers and cellulose 300 C adsorbs more gold thiourea than the conventionally used
nanocrystals can be extracted from rice husk. They puried the cel- activated carbon [27] and also is an effective adsorbent for the
lulose by removing lignin and hemicelluloses from rice husk bers removal of Brilliant Green (BG) [13] and Congo Red [28] from aque-
with an alkali solution. The bleaching process is completed by ous solution.
Fig. 4. Scanning electron micrograph of (a) untreated rice husk bers, (b) alkali-treated rice husk bers, and (c) bleached rice husk bers [19].
Fig. 5. Schematic of applications of derived rice husk.
In addition to the above-mentioned environmental threats, the silica was synthesized by the hydrothermal treatment method
utilization of dyes in industries such as textiles, rubber, paper, using the silicate supernatant extracted from RHA and cetyltrim-
plastics, cosmetics, etc., to color the products is a serious problem ethyl ammonium bromide (CTAB) as the silica precursor and struc-
for the environment. The dyes are invariably left as the major ture-directing template, respectively [38].
waste in these industries. Many of the organic dyes are hazardous
and may affect aquatic life and even the food chain. For example, 3.2. Coatings
malachite green, a common silk and cotton-dyeing agent, has been
found to be highly toxic in mammalian cells and acts as a liver The presence of RHA in epoxy paints as steel coating can
tumour-enhancing agent. The removal of dyes is an essential task enhance wear resistance, scratch resistance, and elongation. It
for environmental protection. Although activated carbon is the seems that this type of ller in epoxy paints increases paint plastic-
most widely used adsorbent for this purpose because of its ity [39]. In addition, rice husk ash can be used as natural silica
extended surface area, microporous structure, high adsorption (SiO2) source for surface improvement of paper to gain better
capacity and high degree of surface reactivity, the problems asso- printability. This coating layer surface will reduce the ink penetra-
ciated with it makes activated carbon a somewhat undesirable tion into the paper structure by reducing coating permeability,
adsorbent. Abdelwahab et al. [29] have used activated rice husk hence improved water fastness [40].
to adsorb dyes from aqueous solutions. The result demonstrated
that the maximum adsorption capacity was 13 mg of dye per 3.3. Pigment
one gram of dry rice husk. The rice husk also can be used as low-
cost and effective sorbent for the removal of direct F. Scarlet (anio- The synthesis of yellow pigment [(Pr, Zr) SiO4] using RHA to
nic dye Direct Red 23 (DR23)) from aqueous solution. In addition, study the possibility of an agricultural waste as silica precursor,
aluminum hydroxide-coated rice husk ash can remove uoride was evaluated by Bondioli et al. [41]. This pigment is normally pro-
from drinking water [30]. duced by calcining a mixture of monoclinic zirconia (ZrO2) and sil-
Proctor and Palaniappan [31] found that a silicate material ica (SiO2) in the stoichiometry of zircon, together with the coloring
derived from rice husk ash was capable of binding lutein from ion precursor (Pr6O11) and one or more mineralizers, i.e. NaF, NaCl
soy oil in hexane at room temperature. Acid washing lowered or MgCl2. The fabrication of ZrSiO4Fe2O3 inclusion through solid
the ash pH and enhanced lutein adsorption by the ash. In the case state reactions between the mineralizer and both silica (from rice
of gas adsorption it was reported that absorbent prepared from rice husk) and iron oxide precursors was reported by Andreola and
husk ash such as RHA/CaO/CeO2, RHA/CaO, RHA doped with copper co-workers [42].
and RHA-lithium based have a high capacity in sulfur dioxide
(SO2), NO and CO2 absorption [3236]. In addition, with the aim 3.4. Cement industry
of lowering manufacturing cost and green synthesis for CO2 absor-
bant, a series of polyethyleneim-immobilized unimodel and/or Substantial research has been carried out on the use of amor-
biomodal porous silicas were prepared from rice husk ash with phous silica in the manufacture of concrete. RHA is used in the
biopolymer of chitosan as a pore structure-directing agent [37]. manufacture of low cost building blocks and in the production of
Zeng and Bai reported that TEPA-impregnated mesoporous silica high quality cement in two areas. Ordinary Portland Cement
from rice husk treated at 400 C exhibits a good CO2 adsorption (OPC) is expensive and unaffordable to a large portion of the
capacity of 173 mg/g adsorbent under 10% CO2 at 75 C. The porous worlds population. Since OPC is typically the most expensive con-
stituent of concrete, the replacement of a proportion of it with RHA reinforcing ller for styrene-butadiene rubber (SBR), ethylenepro-
offers improved concrete affordability, particularly for low-cost pylenediene elastomer (EPDM), and natural rubber (NR). The
housing in developing countries. The use of pozzolan as alterna- results demonstrated that this ller does not adversely affect either
tives for common Portland cement has been practiced in the past the vulcanization characteristics or aging behavior of mentioned
few decades either for cost reduction, performance and durability materials. On the other hand, Oui et al. [50] investigated the effects
enhancement, or environmental reasons [43]. Pozzolans are sili- of ller loading on the properties of RHA-lled natural rubber (NR)
ceous and aluminous materials, which in themselves possess little materials compared with those of commercial llers. They found
or no cementing property. It can be chemically reacted with cal- that both grades of RHA, low- and high-carbon contents, provided
cium hydroxide in presence of moisture, at ambient temperature inferior mechanical properties (tensile strength, modulus, hard-
to form compounds possessing cementitious properties [44]. Poz- ness, abrasion resistance, and tear strength) compared with those
zolanic materials are added to cement to x the free lime by clinker of reinforcing ller such as silica and carbon black.
silicates during their hydration. It results in insolubility of free lime Fuad et al. [51] reported that incorporation of RHA into polypro-
in water, in some instances providing a stronger bond than cement pylene led to an increased exural modulus of the composites,
without RHA. The amorphous silica in rice husk ash reacts with whereas tensile strength, elongation and impact strength
Ca(OH)2 to form CSH gel (Ca1.5SiO3.5 H2O) in presence of water decreased. Siriwardena et al. [5254] studied the effect of dynamic
at temperature around 30 C. When this product is heated up, it vulcanization and inuence of ller loading of white rice husk ash
losses the water, but maintains an amorphous form up to 750 C. (WRHA)-lled on different polymer blends. They reported that
The ultrane size makes it excellent ller which goes into the WRHA-lled blends can be dynamically vulcanized to achieve
micro voids giving high strength to the concrete [45]. enhanced properties in a manner similar to that of the unlled
Besides, the corrosion performance of concrete can be improved blends. Several researchers studied the poor strength properties
by addition of rice husk ash. As mentioned above, the rice husk ash resulting from a lack of adhesion between the hydrophobic poly-
forms a calcium silicate hydrate gel around the cement particles, mer and hydrophilic ller. They used coupling or compatibilizing
which is highly dense and less porous. This will prevent the crack- agents to improve dispersion, adhesion and compatibility for sys-
ing of the concrete and protect it from corrosion by not allowing tems containing hydrophilic cellulose and a hydrophobic polymer.
any leaching agents to break down the material. The study done These agents modied the interface by interacting with both the
by Saraswathy and Song [46] found that the incorporation of ber and the polymer, thus forming a link between the compo-
RHA up to 30% replacement level reduces the chloride penetration, nents [5557].
decreases permeability, and improves strength and corrosion resis-
tance properties.
3.7. Electronics
3.5. Insulator
Biocon Ltd. in Australia have carried out work on purifying
amorphous RHA but can only get to about 99.9% purity at a great
Because of the low thermal conductivity of rice husk ash, it can
cost, and thus Biocon considers that there are no real market
be used as a raw material for the thermal insulators in a FireBrick.
opportunities with silicon chips [58]. However, The Indian Space
The thermal conductivity of ceramic materials is attributed to crys-
Research Organization has successfully developed technology for
talline lattice vibrations, or phonons [47]. Fabrication of RHA with
producing high purity precipitated silica from RHA, which has a
the highest ux content, results in characteristics like coarse
potential use in the computer industry. American and Brazilian sci-
grains, higher residual carbon content, and low crystallinity. Coarse
entists developed methods to extract and purify silicon with the
grains are favorable for formation of porous structures. By increas-
aim of using it in semiconductors manufacture [59]. Some compa-
ing the porosities content thermal conductivity decreases. Porous
nies are purifying RHA into silica suitable for several industries,
refractories have air entrapped in their pores and this acts as a
including silicon chip manufacture [6062]. Moreover, Bose et al.
non-heat conducting material. The amount of the entrapped air
[63] indicated that magnesium silicide prepared by alloying of
increases with porosity of the refractory and hence its thermal con-
99.9% purity polycrystalline silicon obtained from rice husk ash
ductivity decreases [48]. RHA is also used during the production of
and high-purity magnesium powder, has potential applications
high quality at steel. For instance, RHA is used for insulation of
as a semiconductor devices.
molten metal in tundish and ladle in slab caster. The temperature
of molten metal in the ladle is around 1400 C. When the metal
ows from ladle to tundish, the temperature drops to around 3.8. Energy
1250 C. This reduction in temperature leads to choking and causes
breakdown in the slab caster. Because of separation of RHA as a The fact that the present energy use is largely dependent on fos-
coating over the molten metal in the ladle and tundish, it forms sil fuels makes future sustainable development very difcult. There
a coating that maintains the temperature. Therefore, it reduces are drastic changes in the composition and behavior of our atmo-
the breakdown time of the casting. Moreover, it prevents rapid sphere due to the rapid release of polluting combustion products
cooling of steel and ensures uniform solidication in casting pro- from fossil fuels. There are large quantities of residues, associated
cess [48]. with agricultural production and processing industries that can
be used for energy production. Unlike fossil fuels, which are lim-
3.6. Rubber ited in availability, these residues are not only abundantly avail-
able, but also renewable [64]. Rice husks, as a renewable source
Many attempts have been made to use rice husk ash as ller for of energy, can provide a continuous supply of liquid and gaseous
natural and synthetic rubbers. These kinds of composites have fuels through thermochemical conversion processes. Fig. 6 illus-
experienced an enormous growth in the automotive industry due trates the main conversion technologies that have been used or
to environmentally friendliness, renewability of these bers, good are under development for the production of secondary energy car-
sound abatement capability, and improved fuel efciency resulted riers. Combustion (domestic heating, combined heat and power
from the reduced weight of the components. In one of these (CHP), and co-combustion), gasication (large-scale and small-
attempts, Haxo and Mehta [49] revealed the possibility of using scale), and pyrolysis are known as the main thermochemical con-
ground RHA obtained by a special burning condition as moderately version pathways, while fermentation and transesterication are
produced gas composition which should be maintained between

650 and 850 C [75], besides two other processing parameters
should be satised, actual air to biomass weight ratio divided by
stoichiometric air to biomass weight ratio (ER) and steam to bio-
mass ratio. These ratios should be xed between the range of
0.20.4 [76] and 1.354.04 [77], respectively.
3.9. Production of potential reinforcement for fabrication of MMCs and

CMCs
Because of the high silicon content in RHs, more extensive stud-

ies have been conducted in the past few decades as compared to
other wastes that have signicantly widened its utilization. At
present, RHs are the raw materials for the production of a series
of silicon-based materials including SiO2, SiC, Si3N4, Mg2Si and car-
bon enriched materials which can be used in metal matrix (MMCs)
and ceramic matrix (CMCs) composites [7882].
For instance, in the original work by Das et al. [83] rice husk ash
was used as a reinforcing phase in aluminumsilicon alloys to
investigate the effects of second phases on the alloy solidication
behavior. A reactive inltration processing of SiC/FeSi composites
using preforms made of coked rice husks and SiC powder in differ-
ent proportions is reported by Zhu et al., in which the FeSi2 alloy
Fig. 6. Major conversion technologies for converting biomass into useful energy was used as the inltrating liquid material. The incorporation of
carriers [66].
SiC was conducted in order to improve the wetting and inltration
of the preforms by the alloyed FeSi and thus engineer the
mechanical properties of the composites.
the most common biochemical conversion pathways for ethanol Because of their scientic and industrial signicance, the fol-
and biodiesel production [65,66]. lowing paragraphs are devoted to silicon carbide (SiC) ceramic
The combustion temperature of rice husk is lower than that of matrix composites, specically, to some previous investigations
fossil fuel combustion therefore, it is anticipated that there will where RHA has been used for synthesis of these important materi-
be lower NOx emissions. Since biomass contains little sulphur com- als, although other ceramic matrix composites and different fabri-
pared to coal, it is also expected that there will be lower SOx emis- cation routes have also been included in this review.
sions [67,68]. Moreover, rice husk has an average lower heating The liquid silicon inltration (LSI) route in which liquid Si is
value (LHV) of 1316 MJ/kg, which in comparison is about one- commonly driven to inltrate into carbon porous preforms or a
third of that for furnace oil, one-half that of good quality coal mixture of carbon and SiC powders , and to react with the carbon,
and comparable with sawdust, lignite and peat. Due to its rela- is a promising method to fabricate SiC ceramic composites. SiCw/
tively high caloric value, the combustion of rice husk is autoge- SiCSi composites were fabricated by the inltration of molten Si
nously (self-sustaining) and this minimizes the requirements for into porous preforms prepared from pyrolyzed RHs containing
auxiliary fuel. Apart from offering the benets of energy recovery, SiC whiskers, particles, and carbon. While the amorphous carbon
the combustion of rice husk in thermal treatment units will also would react with molten Si and form new SiC phases, the SiC whis-
solve its disposal problem. It is also more environmental friendly kers in the preform are expected to remain and act as reinforce-
as the combustion process reduces the greenhouse effect by con- ment in the composites. The Vickers hardness, exural strength,
verting emissions that would have been methane due to its elastic modulus, and fracture toughness of the SiCw/SiCSi compos-
slow-rotting into the less potent greenhouse gas carbon dioxide ites inltrated at 1550 C were 18.8 0.6 GPa, 450 40 MPa,
[69]. Gasication as a process of converting carbonaceous materi- 354 2 GPa, and 3.5 0.3 MPa m1/2, respectively [84].
als into gaseous products using a gasifying medium such as air, Addition of Mo powder in different proportions to pyrolyzed
oxygen, steam and etc., that was suggested by Ghaly et al. [70] rice husk up to 11 wt.% was found to cause a suitable residual
as an alternative to combustion of low density biomass materials. stress in the material, and thus enhanced the fracture toughness
Some authors have claimed that uidized bed combustion, with of the composite to 4.1 MPa m1/2 [85]. By the reaction of the Mo
excellent heat and mass transfer characteristics, seems to be a suit- powder and the pyrolyzed carbon in the preform with molten Si,
able technology for converting rice husk and other agricultural res- MoSi2 and SiC can be formed at a much lower inltration temper-
idues into energy [71,72]. The turbulence due to uidization in the ature than that for SiCMoSi2 composites using MoSi alloys as
bed can break the rigid ash skeleton to make the trapped carbon inltration materials [86,87].
available for conversion, although rice husk is difcult to be uid- Recently, it has been considered that multi-carbide ceramics
ized due to its cylindrical shape, nongranular and aky nature. based on B4C and SiC have the potential to provide enhanced
However, uidization behavior of rice husk was improved when mechanical properties compared with those of the single-carbide
it mixed with other solid particles, such as silicon sand and coal ceramics. For instance, SiCB12(C, Si, B)3MoSi2 composites have
forming a multi solid system. Rice husk ash can easily be removed been prepared by the inltration of molten Si into porous preforms
from the uidized bed by entrainment in the gas stream, from prepared from pyrolyzed RH including SiC whiskers and particles,
which it can be collected by a particle-separating system [73]. amorphous carbon and B4C, as well as a little amount of Mo. Mol-
The main goal of the gasication process is the production of a ten Si is supposed to react with carbon and B4C in the preform,
combustible gas that enriched in CO, H2 and CH4 with medium forming new carbides. It is also expected that the SiC whiskers
to high LHV which is suitable for further exploitation in internal and particles in the preforms will remain intact and will preserve
combustion engines and turbines [74]. Bed temperature as one of their properties in the composites. It is intended that by the reac-
the most important parameters that affects heating value and tion with Si, the addition of Mo gives place to MoSi2 formation,
Table 3
Utilization of rice husk in ceramic and metal matrix composite materials.
Composite Fabrication route Starting material Observations Refs.

SiSiC composite Self-propagating high Powder mixture of rice husk ash Microstructure and chemical composition [89]
temperature synthesis activated carbon-Mg
(SHS)
Ferrite composite using At high temperature Pyrolyzed rice husk Fe(NO3)39H2O Enhanced adsorption ability for acid orange II [90]
SiO2 treatment under nitrogen
atmosphere
Al alloy-rice husk ash Stir casting technique A356.2 Al alloy Good interfacial bond between matrix and rice husk [91,92]
ash particles, increment in UTS, hardness and wear
resistance
Alumino silicate Aluminum hydroxide-rice husk ash- Good Compressive strength in 3 vol% H2SO4 solution [93]
composites (ASC) NaOH, Na2SiO3 boric acid
Aluminum-4mass% Powder forging Aluminum, copper, and rice husk ash Maximum hardness of 44 HRA [94]
copper/alumina silica
AlSiFe/Rice husk ash Double stir casting Ferrosilicon, rice husk ash particle, High strength [95]
method aluminum
AluminaMulliteSilicon In situ by carbothermal Al2Si2O72H2O, SiO2 powder, rice husk Obtaining Al2O3Al6Si2O13SiC composite with the [96]
Carbide Composite reduction (SiO2) and activated carbon whiskers SiC
Aluminum alloy-rice Casting Rice husk, LM 13 alloy, Mg [83]
husk ash
Magnesium composite Powder metallurgy(solid- Rice husk silica particles with High density and hardness [97]
with magnesium state reaction) magnesium powder
silicide
Carbon/silica composite Carbonizing and hot- Rice husk Maximum bulk density and Vickers hardness at [98]
pressing sintering temperature of 800 C
SiCw/MoSi2SiC Liquid Si inltration (LSI) Rice husks Mo powder High elastic modulus and fracture toughness [85]
Al/MgAl2O4 In situ Microsilica, rice husk ash, pure Al, Mg Microstructural observations [99]
SiC/FeSi Reactive inltration Cocked rice husks, SiC powder, FeSi2 High Vickers hardness, elastic modulus, three-point [100]
alloy exural strength and indentation fracture toughness
Nano-composites of Solgel technique SnCl22H2O, HCl TiCl3, Rice husk ash, High photocatalytic activity [101]
RHA-10Sn10Ti RHA- cetyltrimethylammonium bromide,
10Sn RHA-10Ti HNO3, NaOH
Nano-composite SiC/ Carbothermal reduction Rice husk ash [102]
Si3N4
Nanocomposite TiO2 Solgel Rice husk High UV absorption efciency [103]
SiO2
Magnesium composite Extrusion HCl solution, Rice husk, AZ31 alloy Having high hardness and Youngs modulus. [104]
alloys dispersed with powder
Mg2Si
SiCw/SiCSi composite Si liquid Inltration Rice husk, carbon, silicon High Vickers hardness, exure strength, elastic [84]
modulus, and fracture toughness
AlSi10Mg/RHA Stir casting Rice husk ash with different size ranges Better wear properties, the coarser and the more rice [105]
(5075, 75100 and 100150 lm), husk ash, the lower wear rate
AlSi10Mg alloy
Al/SiC/RHA Pressureless inltration Recycled aluminum form beverage Presence of the rice husk ash prevent degradation of [106]
containers, SiC, rice husk ash composite through the formation and subsequent
hydration of Al4C3
which would be advantageous to the overall properties of the com- ica is that sodium carbonate powder reacts with quartz sand at
posites. This is because MoSi2 is a less brittle phase compared with high temperature to form sodium silicate, and then the obtained
Si and has a high melting point (2030 C), thus favoring the high- sodium silicate reacts with sulfuric acid in order to precipitate sil-
temperature performance of the composite [88]. A summary of dif- ica. This method was hazardous to the environment because of
ferent fabrication routes and types of ceramic- and metal-matrix production of 0.23 ton carbon dioxide (CO2), 0.74 ton sodium sul-
composites, starting from rice husk is presented in Table 3 [83 fate and 20 tons waste water during the preparation of 1 ton of sil-
85,89106]. ica by using 0.51 ton of sulfuric acid and 0.53 ton of sodium
The following sections are devoted to get an insight into the dif- carbonate. In recent years, one of the worlds primary concerns is
ferent processing methods, the effects of various process parame- the greenhouse effect, especially relating with CO2 [113]. The
ters on the pyrolysis stage, the inuence of physical, chemical main disadvantages of the traditional technique are the high-
and thermal treatments and mechanisms on synthesis of different energy consumption and the high levels of pollution. The processes
silicon based materials including SiO2, SiC, Si3N4, elemental Si, and produce large quantities of CO2 and inorganic salts, which have
Mg2Si. limited their large-scale commercial applications and violated
the principle of sustainable development. It is believed that a
4. Production of silica cheaper and environmental benign route to produce silica powder
with desirable materials attracts much more attention. Therefore,
Various methods have been reported in the literatures for pre- nowadays most of the attention is focused on the utilization of bio-
paring silica materials, such as plasma synthesis [107], chemical masses as silica rich source. A content of 65% silica in rice husk ash
vapor deposition [108], solgel processing [109], micro emulsion produced during burning of rice husk in order to generate energy
processing [110], combustion synthesis [111] and hydrothermal , makes this waste material an economically viable raw material
technique [112]. The traditional industrial method of preparing sil- for production of silica gels and powders [114]. Silica has been
illustrates the division of thermal production of rice husk ash into

two kinds of combustion.
4.1.1. Rotary kiln

When rice husk is used as a heat resource, it is necessary to
blow air to achieve the highest possible combustion temperature.
However, almost all of the rice husk ash obtained by such proce-
dure is crystalline and very low chemically active. It therefore
has few practical uses. Because no method was available for low-
cost industrial production of rice husk ash exhibiting high activity,
there was a need for developing one. In the batch method for pro-
ducing active rice husk, a hollow platform having very small holes
is placed on an enclosed oor slab. A chimney is erected on the hol-
low platform in communication with the interior of the hollow
platform; a cone of rice husk is formed around the chimney to
completely cover the hollow platform. The rice husk at the small
holes is ignited for smolderingly incinerating the rice husk into car-
bonized rice husk, and the carbonized rice husk, and the latter is
Fig. 7. Production of rice husk ash by thermal treatment [117]. allowed to self-burn into ash. In the continuous method for pro-
ducing active rice husk ash, downstream and upstream rotary kilns
widely used in vegetable oil rening [115], pharmaceutical prod-
are connected in tandem; heating of the upstream rotary kiln is
ucts, detergents, adhesives, chromatograph column packing and
controlled to a temperature for burning rice husk into ash. Rice
ceramics [116].
husk is supplied to the upstream rotary kiln to be smolderingly
Depending on the combustion process and RH composition, the
incinerated into carbonized rice husk, then the carbonized rice
rice husk ash may have different colors, which could be, high car-
husk is supplied to downstream rotary kiln to be burned into
bon char, low carbon gray ash, carbon-free pink and white ash. By
ash, and nally, the resulting active husk ash is discharged from
using different treatment temperatures, pre- and post-purication
the downstream rotary kiln [118].
with different agents (acids, bases, etc.), different structures and
In summary, since this procedure rst carbonizes rice husk by
purities can be obtained.
burning it in an incineration furnace without aming and then
burns the carbonized rice husk into ash, it enables easy production
4.1. Furnace/reactor for production of RHA of white rice husk ash exhibiting excellent chemical reactivity. The
schematic of rotary kiln furnace is presented in Fig. 8.
In most of processes used for the preparation of ceramic phases
from rice husk, furnaces play a vital role. The combustion of rice 4.1.2. Fluidized bed process
husk can be divided into two groups: controlled and uncontrolled. In case of completion of mixing and heat transformation during
It should be mentioned that for production of rice husk ash in large the combustion of rice husk, in comparison with the other pro-
scale, controlled combustion procedures should be chosen. cesses, the uidized bed process is more practical. Therefore,
Because of importance of furnaces that work under controlled through modern uidized bed process, it is possible to produce rice
combustion in production of high purity and activated rice husk husk ash with consistently low ash content (<4%), at a very small
ash and also applying special techniques in controlled combustion residence time (<2 min) in the combustion chamber. A simple u-
furnaces, in this part cyclonic furnace, uidized bed furnace, idized-bed reactor consists of a chamber containing a bed of inert
inclined grate furnace and rotary kiln are introduced [117]. Fig. 7 particles such as sand, supported by a distributor plate. Pressurized
Fig. 8. (a) Sectional view of rotary kiln furnace and (b) perspective view of rotary kiln furnace [118].
Fig. 9. Schematic diagram of the uidized bed combustor system developed by Rozainee et al. [120].
air is passed through the distributor plate and the velocity of the - Less excess air, higher CO2 in ue gas.
air is progressively increased to support the entire weight of the - Simple operation, quick start-up.
bed by the uid drag on the bed particles due to the upward ow- - Fast response to load uctuations.
ing air. The bed is then said to be incipiently uidized, and it exhib- - Fluidization of the rice husk and husk char seems to be difcult,
its uid-like properties above this particular velocity, called unless it is mixed with sand and/or char and/or ash to form a
minimum uidization velocity [64,119]. Because of being exother- multi-solid system [64,120,121].
mic reaction with high caloric value, the external heating is
required only during the start-up of the combustion of rice husk; 4.1.3. Inclined grate furnace
the process is later self-sustaining (autogenous). The process can Inclined grate furnace consists of a hull-feeding component, a
be operated continuously for large-scale operation. Rice husk ash combustion chamber, and an ash precipitation chamber. It is sim-
is easily removed from the uidized bed by entrainment in the ple in construction and operation. The air for combustion is sup-
gas stream, from which it can be separated by a simple particle plied by the suction of the dryer fan, while the fuel supply is
separating system such as cyclone. The control of critical process facilitated by the vibration of a feeder connected by a wire to the
parameters, such as temperature and residence time is achieved fan shaft. However, it has incomplete combustion and inefcient
through the control of the ratio of air and rice husk feed in the u- ash separation so that ash and sparks are partially sucked by the
idization chamber. The main advantage of the process is its exibil- fan into the dryer plenum. Despite of similar performance of
ity to produce rice husk ash of different grades (level of carbon inclined grate furnace to at-bed dryers, the former has more dura-
content) depending upon the market demand [117]. Fig. 9 depicts ble steel parts than the later, particularly the grate, which is made
a schematic of uid bed process developed and utilized by Rozai- of mild steel. Two furnace designs are shown in Fig. 10, both with
nee et al. [120] in order to produce high purity silica from rice inclined grates. The box-type furnace does not work appropriately
husk. for settling ashes as the furnace with cylindrical chamber and cen-
In addition to the abovementioned attributes of uidized bed ter pipe [122].
technology, applying this procedure is associated with other signif-
icant advantages and disadvantages as follows: 4.1.4. Cyclonic furnace
In the cyclonic furnace designed and tested by Singh et al. [123]
- Continuous and self-sustainable combustion. husk and air were introduced tangentially to the cyclone chamber.
- High combustion intensity. The air kept the husk rotating in circular motion and accelerated
- Better ash composition and no ash sintering or ash removal combustion in the chamber. It took initial time for the furnace to
problem. attain a self-supporting spontaneous ignition of the husk. The bur-
- Lower operating temperature range. ner was then shut off and the furnace was allowed to run for more
- Optimum opportunities for temperature control. given time to obtain the steady state condition. For recording the
- Easier ash removal, no clinker formation. temperatures at different points in the furnace as shown in
Fig. 10. (a) Schematic of the box-type inclined grate furnace and (b) schematic of the furnace with cylindrical combustion chamber [122].
Fig. 11. Schematic of cyclonic furnace [123].
Fig. 11, thermocouples were used, which were connected to a tem- feeding mechanism. A schematic diagram of the experimental fur-
perature recorder. A burner with compressor was also attached to nace designed by Singh et al. is shown in Fig 11.
the cyclone for ring the furnace. The inside of the furnace was
lined with a mixture of re-clay and refractory bricks. The ash 4.2. Effect of temperature on the structure of obtained silica from rice
was trapped behind a perforated cast iron plate provided in the husk
outlet of the conical bottom. The removal of ash was done inter-
mittently through a side opening. In general, the designation of Calcination of rice husk in static air at temperatures below
system includes determination of the volume of the cyclone fur- 800 C, leads to the amorphous nature of silica, while crystalline
nace, selection of blower capacity, thickness of insulation and the silica occurs at temperatures above 900 C [45].
Table 4 tridymite and quartz in RHA. By increasing the temperature up to

Density and silica content of calcined rice husks [124]. 900 C, the unburned carbon can be removed from the ashes [126],
Temperature (C) Density (g/cm3) SiO2 (wt.%) but this leads to the crystallization of the ash from amorphous sil-
Untreated rice husk 0.559 25.81 ica into cristobalite or tridymite. More investigations have been
500 1.825 83.66 devoted on the formation of cristobalite and tridymite [127
600 1.923 91.50 129]. It has been reported that transformation to b-quartz occure
700 1.938 91.85 at 573870 C, b-tridymite at 8701470 C, and b-cristobalite at
800 1.960 92.90
14701710 C [127]. It has also been reported in the literatures
that formation of crystalline phase is accelerated by the presences
of potassium oxide (K2O) in the RH. Moreover, by increasing the
Yalcin et al. [124] showed that density and silica content concentration of potassium, crystallization of tridymite tends to
increase by increasing temperature; also they indicated that an take a place. Silica is able to incorporate stufng cation such as
increase of oxygen partial pressure helped to reduce carbon and Na+, K+, and Ca2+, into cavities of six-membered rings of SiO4/2 tet-
increment in SiO2 content to 98.32%. Density measurements, silica rahedral. Indeed, these inclusions involve particularly the valence
content of untreated rice husk, and calcined rice husks at 500, 600, compensating elements and require an open structure for transfor-
700, 800 C (for 4 h) are given in Table 4. mation of silica to crystalline forms. Quartz, which is the densest of
Fig. 12 shows the structure of rice husk ash extracted through the structures, cannot accommodate additional elements, while
different incineration temperatures. RHA300 (incinerated at tridymite is the only silica polymorph with the lowest density
300 C) (Fig. 12a) reveals the porous structure of the adsorbent sur- phase that is able to accommodate interstitial K+ cations into its
face and shows the corn cob structure [125]. The SEM structures big cavities. Therefore, the addition of K+ cations to silica stabilizes
of RHA500 and RHA700 are shown in Fig. 12b and c, respectively. the tridymite structures.
Cell walls around pores are fractured and elongated on heating It has been found that some kinds of metal oxides especially
and somewhat ordered reticulated backbones are exposed due to potassium oxide, contained in RHA cause the surface melting of
burning off of less dense materials. RHA700 showed less-fractured SiO2 particles and accelerate the crystallization of amorphous
internal structure and thicker cell walls, giving fewer pores than SiO2 into cristobalite and tridymite. Moreover, alkali metal impuri-
RHA500. Heating to 900 C (RHA900) results in a somewhat ties cause the remained carbons in ashes, originated in organics,
glassy appearance with smooth small pores (Fig. 12d) and the after burning rice husk. This is because the eutectic reaction
internal backbones appear to be fused together. between alkali metals and SiO2 element occurs during burning,
The XRD patterns of RHAs are shown in Fig. 13. The broad and the carbon remains in the melt SiO2 and causes the crystalliza-
smooth hump between 15 and 35 (2h) in the diffractogram in tion of rice husk ash at lower temperature [130133].
Fig. 13(ad) is a characteristic feature of amorphous material, indi- In an investigation on the effect of temperature on the morphol-
cating that pyrolysis converted the crystalline cellulose structure ogy and phase transformations of nano-crystalline silica obtained
to amorphous, random, disordered structure, potentially capable from rice husk, Sarangi et al. reported a graph of the variation of
of adsorption. When the temperature increases from 500 to crystallite size of the calcined materials as a function of tempera-
700 C, there is a little increase of peak intensity at 22 (2h). Heat- ture [134]. This prole shows two regimes: the rst one, for tem-
ing to 900 C increased the intensity of peaks at 22 (2h), in addi- peratures between 500 and 700 C, corresponds to a situation
tion, other peaks were observed at 43, 45, 47 and 49 (2h). where the crystallite size grows slowly with temperature. The sec-
This augment in crystal organization would affect the available ond one, for temperatures higher than 700 C, the aggregation
surface area, resulting in restriction of adsorption capability. effects become very important producing a signicant growth in
Phase analyses of RHA powders show that by increasing tem- the crystallite size. The aggregation processes, produced by the
perature, three crystalline phases are formed, namely, cristobalite, condensation of the silanol groups (SiAOH), become important
Fig. 12. SEM micrographs of rice husk ashes (RHAs); (a) RHA300, (b) RHA500, (c) RHA700 and (d) RHA900 [125].
Fig. 13. X-ray diffraction patterns of rice husk ashes (RHAs); (a) RHA300, (b) RHA500, (c) RHA700 and (d) RHA900 [125].
for temperatures higher than 700 C. It is also showed crystallite amorphous phase was detected in diffractograms. This means
size increases from 4.87 to 18.61 nm with increase in temperature some leached out ions from the husks favored the crystallization
from 700 to 1100 C mainly due to agglomeration. of untreated RHA. Umeda and co-worker [141] also obtained the
high purity silica ashes with 99.3% when using a dilute H2SO4 acid
4.3. Pre-purication of thermal treated rice husk leaching and high temperature combustion.
Chakraverty et al. [135] have studied the effect of different acids
Many authors have suggested that leaching and boiling of rice and their concentration on the combustion product of rice husk.
husk with a solution of HCl, H2SO4, H3PO4, HNO3, NH4OH and HCl, HNO3 and H2SO4 were used for leaching of the rice husk before
NaOH before heat treatment at different ranges of temperature combustion. Table 5 presents the effect of acids and their concen-
and time can be so effective in accelerating the hydrolysis of cellu- trations on the impurity reduction. As it can be seen the leaching
lose and hemicelluloses contained in rice husks and removing most effect of HCl is superior to that of H2SO4 and HNO3 for removing
of the metallic impurities. This allows producing ash-silica com- the metallic ingredients. It was reported that, acid leaching of rice
pletely white in color, with high specic surface area husk in dilute HC1 (1 N) helps in producing ash completely white
[16,130,135139]. in color.
Xiong et al. [140] carried out the preliminary leaching of rice They also evaluated the TG, DTG and DTA analyses of the
husk with a solution of hydrochloric acid before the combustion. untreated and acid-treated husks [142] (see Fig. 14). The TG anal-
It was found that pretreatment is necessary to obtain relatively ysis revealed three distinct stages of mass loss, namely, removal of
pure silica (99.5%) with a high specic surface area (260 m2/g). moisture, release of volatile matter and burning of combustible
This treatment was very effective for removing most of the material. The removal of moisture took place at temperatures rang-
impurities. By increasing the temperature up to 1000 C, only the ing from 40 to 150 C. The volatile matter released from untreated
Table 5
Effect of acid leaching of husk on removal of metallic constituents from rice husk [135].
Treatment Metallic constituents as oxides (ppm)

Na K Ca Fe Mg Mn Zn Cu Total
Untreated 5125 11750 7042 946 2562 1192 179 31 28827
1 N HCl treated 46 50 58 362 187 19 19 6 747
3 N HCl treated 33 33 46 262 146 7 19 6 552
5 N HCl treated 25 ND 25 146 125 3 19 6 349
11.3 N HCl treated 12 ND 8 129 125 3 17 6 300
1 N H2SO4 treated 87 25 2500 233 729 25 102 12 3713
4.5 N H2SO4 treated 92 25 2417 225 646 25 98 6 3534
9 N H2SO4 treated 75 25 2500 229 625 19 85 6 3564
18 N H2SO4 treated 75 50 2667 217 625 24 83 6 3747
36 N H2SO4 treated 117 100 3333 221 437 171 98 6 4483
4.5 N HNO3 treated 17 25 19 500 83 19 17 8 688
9 N HNO3 treated 8 25 11 442 83 12 12 6 599
18 N HNO3 treated 4 25 7 392 62 6 12 HD 508
1 N HCl + 4.5 HNO3 4 25 3 375 52 12 19 6 496
ND = Not Detected.
Fig. 14. TG, DTG and DTA curves of (a) untreated rice husk, (b) treated with 1 N HCl, (c) treated with 3 N HCl, (d) treated with 5 N HCl and (e) treated with 4.5 N H2SO4 [142].
husk is in the range of 215350 C, while that for acid-treated husk that by using this acid and hydrolyzing above 200 C, the metallic
is in the range of 225375 C. In the last stage of mass loss that cor- impurities such as Na, K, Ca, Mg, Fe, Cu, etc could be also removed
responds to the combustion process, DTA records exothermic from the husks via a chelate reaction between carboxyl groups (
peaks for untreated rice husk at 690 C, for treated husk with 1 N COOH) and the metal elements. After acid leaching, it was neces-
and 5 N HCl at 630 and 650 C, respectively and for 5.5 N H2SO4 sary to supply a suitable amount of air to complete organics com-
at 645 C. This shows that treatment with acids of lower concentra- bustion. Thus, high-purity amorphous silica material with 99% or
tion is desirable and the nal temperature of combustion in this more purity were prepared from rice husks by applying the citric
stage decreased with acid-treatment of the husk. However, Car- acid leaching treatment and burning process at 800 C in air. In
mona et al. [137] showed that activation energies for thermal deg- general, the investigation by Real et al. [130] showed that leaching
radation of acid treated rice husk are higher than those from of rice husks with an acid solution before their combustion would
untreated rice husk. It has been reported that the presence of alka- yield silica powder of high specic surface area. However, if the
line and earth-alkaline metals lower the activation energy for ther- acid leaching was performed after combustion, the specic surface
mal degradation of rice husk and decrease the nal temperature area of silica would be poor.
conversion to silica [143]. Liou et al. [144] also showed the weight In some processes besides acid leaching, alkaline treatment was
loss as a function of heating time at a heating rate of 5 C/min for done to purify the rice husk. Ding and Su [148] reported production
rice husk decomposing in N2 and air environment. They showed of native in-situ mastoid SiO2, which in terms of crystal structure is
that the amount of volatile matter evolved in air is greater than different with the other crystalline SiO2. The rst step of their
that from the N2. By increasing the temperature up to 1500 C in experiment was processing of rice husk with 30% H2O2 and 10%
argon atmosphere, rice husk is converted to SiC at 1375 C and HCl mixture and then purifying of rice husk with alkaline water
nothing occurs in weight loss; whereas, in the air atmosphere, compounds 30% ammonia (NH3H2O). The main purpose of pre-
weight loss continues [145]. treatment was to remove the Na, Mg, Ca, Mn, Al, Fe, Zn and other
A strong acid leaching treatment, however, is signicantly haz- elements with acidic water; another purpose was to remove Na,
ardous to environment and human life, and causes an increase of Cl, P, S and other elements with alkaline water. After heating of
the process cost. Therefore, there are some attempts to use an envi- dried rice husk at the temperature of 600 C in a resistance furnace
ronmentally benign, harmless to human and economically effec- for 10 h, the native white silica was obtained. Eventually, nano-
tive process in order to obtain high-purity SiO2 from rice husk SiO2 white powder was obtained by using ultrasonic fragmentation
[146]. method. Patel et al. [16] have shown NH4OH as very weak alkali,
Umeda and Kondoh [146,147] used a carboxylic acid (citric cannot dissolve SiO2 and all the SiO2 remains intact. The amount
acid) leaching in order to produce high purity silica. It was reported of carbon decreased to 76 wt.% in NH4OH.
Javed and co-workers [149] used KMnO4 as oxidizing agent for proposed an improved method for production of silica from rice
preparation of high purity amorphous silica. They mixed rice husk husk ash with lower sodium. They evaluated producing silica in
ash with 0.001 N solution of potassium permanganate for 30 min the form of sodium silicate by adjusting the pH to 4 and 7 with dif-
and then dried it in oven at 105 C for 24 h. It was found that ferent reagents like citric acid, oxalic acid, or hydrochloric acid
KMnO4 reduces the cellulose and organic contents of the rice husk solution and compare the purity of silica xerogels produced. Com-
and acts as an oxidizing agent during thermal degradation. Contri- parison between these procedures shows that at pH = 4, gelation is
bution of cellulose reduction and organic contents and availability slower and hence sodium ions diffuse readily out of gel matrix and
of sufcient oxygen both helps thermal degradation of rice husk therefore, the content of sodium is lower in comparison with
and produces high purity amorphous silica. pH = 7. In both the silica precipitated using citric and oxalic acid
In addition to acid leaching, deionized water can be used as solution has lower sodium content in comparison with the silica
leaching agent. Shen et al. [150] proposed a leaching procedure produced using hydrochloric acid. This can be due to the differ-
with deionized water followed by the low calcination temperature ences in the size of these sodium salts. Because of smaller size of
and the short calcination times (at 600 C in 0.5 h) in order to pre- sodium chloride, it can be absorb on to the surface of micropores
pare more active amorphous silica from the rice husk. Fig. 15 in the silica, and it cannot be washed out from the silica matrix
shows a plot of pore size distribution calculated using the Bar- resulting in higher concentration of sodium. However, Liou et al.
rettJoynerHalenda (BJH) method. The water-rinsed husk sample [152] concluded that larger salts may become embedded in the
shows a narrow peak at the pore diameter of about 3 nm, slightly gel matrix, and hence are not washed out from the gels. They stud-
smaller than that of acid-leached husk sample, which has a value of ied the effect of different gelation pH from 1 to 11 on silica surface
3.5 nm. Liou et al. also showed that water rinsed husk has a specic area. It has been shown that silica surface strongly depends on pH
surface area of only 1.45 m2/g, whereas that of the acid leached value. By decreasing pH, silica surface increases. They showed gela-
husk is increased to 10.39 m2/g. The result indicates that the acid tion does not occur at pH less than 3. At pH 3, solid starts to pre-
can help to decompose the organic matter in the rice husk [144]. cipitate, whereas gel formation is low. Silica yields gradually
increase with increasing pH, with a maximum yield occurring at
4.4. Post-purication of thermal treated rice husk around pH 7. When the pH is greater than 8, formed gels are unsta-
ble and partially redissolved. At pH 11, these gels dissolve almost
4.4.1. Precipitation of silica from the sodium silicate solution through entirely in water. On the other hand, gelation pH has a great effect
acid treatment on porosity and particle size of produced silica. When pH increases
Through low-temperature alkali extraction, puried silica from from 3 to 7, particle size and porosity increase because, during gel
amorphous rice husk ash can be obtained. The solubility of amor- formation, a polycondensation reaction may occur in the following
phous silica at pH = 10 and below is very low and with the increas- two consecutive paths [153].
ing the pH, the solubility increases. This unique solubility behavior
makes silica extractable in pure form of silica gel by solubilizing it
OH3 Si OH OH OH3 Si O H2 O 3
under alkaline conditions, subsequently precipitating it at a low pH
and eventually, drying it. OH3 Si OH OH3 Si O OH3 Si O SiOH3 OH
Valchev and co-workers [79] evaluated the purication of silica 4
from rice husk ash using caustic soda at high pressure. Reaction
between NaOH and SiO2 was conducted at temperature in the where the OH plays an important catalyst role. In the acidic
range of 180200 C and pressure ranging from 6 to 8 atmo- regime, reduced gelation pH leads to the conversion of siloxane
spheres. With burning, the rice husk at 650 C, high reaction pres- bonding (SiOSi) to silanol bonding (SiOH) and gel formation is
sures can be avoided. The reaction is: slow. In this situation, silica is composed of smaller primary parti-
cles and, therefore, possesses high surface area. In the basic regime,
SiO2 2NaOH Na2 SiO3 H2 O 1
the formation of a siloxane linkage from surface silanol groups cre-
Precipitating silica from sodium-silicate is induced using sul- ates negative charges between silica particles and leads to increased
phuric acid at temperature of 90100 C at atmospheric pressure. electrostatic repulsion [154]. The charge catalyzes the particle to
further growth, resulting in increased particle size with increasing
Na2 SiO3 H2 SO4 SiO2 Na2 SO4 H2 O 2
pH. This result causes increased porosity and decreased surface area
Then, the obtained silica was puried in order to remove the of samples.
sulphate impurities. The purity and surface of obtained silica were Porous silica with high specic surface area has been obtained
reported 98% and 150 m2/g, respectively. Kalapathy et al. [151] by Li et al. [155,156]. Pyrolyzed rice husk has been boiled in NaOH
Fig. 15. Differential pore size and cumulative pore volume distribution before and after thermal decomposition of specimens, (a) water-rinsed husk and (b) acid-leached husk
[144].
solution for 3 h to yield sodium silicate solution. pH value was cess of silica dissolution and precipitation is described by reactions
adjusted by ortho-phosphoric acid (H3PO4) to 9.0. Next, polyethyl- (8) and (9), respectively.
ene glycol (PEG) was dissolved in this solution. The acid was again
6NH4 F SiO2 ! NH4 2 SiF6 4NH3 2H2 O 8
added dropwise to decrease the pH value to 4.9 and nally calcined
at 500 C for 1 h. It has been also shown that the amount of PEG
NH4 2 SiF6 4NH3 n 2H2 O ! 6NH4 F SiO2 # nH2 O 9
used for preparation signicantly affects the textural properties
of the porous silica. By decreasing pH to 3.2 signicantly increased
the amount of PEG incorporated into the silica-PEG composites, 4.6. Hydrothermal process
and hence more pores were generated in the lower pH sample
when the PEG was destroyed by calcination. The specic surface The hydrothermal process has been widely used for the synthe-
can be reached to 1018 m2/g. sis of a vast range of solid-state compounds such as oxides, sul-
des, halides, and non-oxide nanomaterials with specic shapes
and sizes, as well as for the synthesis of new solids. Nowadays,
4.4.2. Precipitation of silica from sodium solution through injection of
the hydrothermal process has become an important technique
CO2
for the synthesis of various kinds of inorganic materials, such as
It was reported that by using carbon dioxide at a specic ow
functional oxide molecular zeolites, and other microporous phases.
rate with continuous stirring, silica could be precipitated from
Hydrothermal process can be considered as constituent process
the sodium silicate solution. The precipitated silica is ltered,
for the base and acid treatments. Due to its intrinsic advantages
washed with water to remove the soluble salts and then dried.
such as benign environment due to dissolving of some gases, such
Addition of calcium caused formation of calcium carbonate and
as CO2, nitrogen oxides, and sulfur oxides in water, versatile chem-
sodium hydroxide. The resulting solution is ltered to remove
istry, enhanced reaction rate, and economic cost, it is viable
the solid calcium carbonate. A typical characteristic of silica precip-
method to produce high purity silica from rice husk at industrial
itated is that it is amorphous in nature and the purity is above 98%.
levels. In this respect, a hydrothermal process might have the
The surface area is about 150200 m2/g [157]. An [158] introduced
opportunity to turn into a powerful technique for the synthesis
another green route for purication of silica powders. In this
of valuable silica materials from raw rice husk. According to differ-
method, RHA was added into HCl solution, followed by a treatment
ent experimental conditions and reaction mechanisms, two hydro-
with a solution of HF and H2SO4. Then, certain concentration of
thermal processes can be classied: (1) a high-temperature
Na2CO3 solution was added into the reactor under vigorous stirring
hydrothermal process and (2) a low-temperature hydrothermal
for 4 h. The obtained ltrate was kept at 85 C, and CO2 injects into
process [160164].
the reactor through a tube for 60 min. The purity of obtained silica
was 98.20%. The yield of silica is affected by different factors such
4.6.1. High-temperature hydrothermal process
as impregnation ratio of Na2CO3 to rice husk ash, extraction and
Hydro thermo-baric process was used [165,166] to achieve pure
carbonation time and concentrations of Na2CO3 (as silica extrac-
silica from rice husk. Hydro thermo-baric purication refers to a
tion reagent). Optimal conditions for three factors, impregnation
process that utilizes single or heterogeneous phase reactions in
ratio, extraction and carbonation time, were found to be 5:1, 4 h
aqueous media at high temperature (T > 243 C) and pressure
and 60 min, respectively. They showed that the yield of silica grad-
(P > 3 MPa) to cause leaching or solutionizing of oxide impurities
ually increased with the increasing of Na2CO3 concentration, and
as well as degradation of organic compounds of rice husk. The the-
reached the maximum value (72.52%) at the concentration of
ory behind the process is that water as a sole aqueous medium, can
20 wt.% Na2CO3. Further increment of Na2CO3 concentration did
be dissociated at high temperatures and pressures, forming hydro-
not give an increase in silica yield. This outcome can be explained
nium (hydrated proton or protonized water) (H3O+) ion as well as
as follows: the reactions (5, 6 and 7) occur in the Na2CO3 solution,
the hydroxyl (OH) ion. Thus, this acidbase system is capable of
and the concentrations of HCO3 and OH increase with the increas-
reacting with basic and acidic oxides as well as the organic compo-
ing of Na2CO3 concentration. The increment of OH leads to more
silica leached out from RHA, therefore, the content of SiO2 nents (the hemicellulose, cellulose and lignin). Except for phospho-
3
rous oxide that tends to remain in the solid phase in large
increased, which accelerated the process of the reaction (6). Thus,
the yield of silica was gradually increased. However, the solubility quantities, most of the impurities existing in the rice husk can be
2 removed after 30 min. Silica possessed high surface area, retained
of HCO 3 is weaker than that of CO3 , and the increasing of HCO3

leads to the separating out of silica in the residue before ltering amorphous structure, and has nanometric particle size, though
the product have some residual carbon adsorbed onto its surface.
the suspension. Therefore, the yield of silica slightly decreased
when the concentration of Na2CO3 was above 20 wt.%.
4.6.2. Low-temperature hydrothermal process
CO2 3
OH Mochidzuki et al. [167] treated rice husk under hydrothermal
3 H2 O $ HCO 5
conditions in autoclave and steam-explosion processes. The rice
2 husk ash obtained by this method exhibited some properties that
2OH SiO2 $ SiO3 H2 O 6 are different from those obtained by conventional techniques.
The results show that the hydrothermal reaction hardly affected
2
CO2 SiO3 H2 O SiO2 H2 O CO2
3 7 the local silicate structures within the temperature range tested
(<240 C). Regarding the Si local structure, it consisted not only
of Q4 network but also Q3 and Q2 units, which the rice husk orig-
4.5. Precipitation of silica with NH4F inally possess. Q4, Q3 and Q2 correspond to the silicon oxygen tet-
rahedral frameworks [Si(OSi)4], silanol groups [(OH)*Si(OSi)3] and
Ma et al. [159] proposed the recyclable technology for prepara- silanediol groups [(OH)2*Si(OSi)2], respectively. For instance, Q4: is
tion of silica powder using rice husk ash and NH4F. By dissolving the SiO4 anionic group, or a silicon atom with four surrounding
silica into 5 mol/l NH4F solution at a reaction temperature of oxygen atoms arranged to dene the corners of a tetrahedron. A
110 C for 3 h, (NH4)2SiF6 and NH3 are produced. Addition of silanol (Q3) is a functional group in silicon chemistry with the
(NH4)2SiF6 solution to NH3H2O causes precipitation of high purity connectivity SiOH. It is related to the hydroxy functional
spherical silica powder with the diameter of 5060 nm. The pro- group (COH) found in all alcohols. It is suggested that the
hot-water-treatment residue is applicable to the preparation of 5. Silicon carbide

waterglass like materials that are required in some liquid-phase
syntheses of inorganic materials, e.g., an advanced production Composite materials reinforced with silicon carbide have been
system of mesoporous silicate. the subject of considerable interest in recent years. Silicon carbide
has been increasingly considered for improving the strength, stiff-
4.7. Microbial fermentation ness, wear and corrosion resistance, etc [170,171]. High strength
and stiffness values in combination with large aspect ratios pro-
Rohatgi and co-workers [168] suggested a method to release of vide whiskers of silicon carbide effective means to reinforce mod-
silica-rich particles from rice husk by microbial fermentation. Rice ern metal and ceramic matrix composite materials. They can be
husk, obtained from a local dehusking mill in Bhopal (India) was incorporated into metal matrices, usually by melt inltration or
subjected to microbial fermentations using a locally isolated spe- powder metallurgy.
cies of white rot fungus, Cyathus. Fermentation of the rice husk Silicon carbide has many polytypes arising from the different
was carried out for a period of 60 days under standardized condi- schemes of stacking layers of C and Si atoms; the most common
tions of substrate availability and growth temperature. They (a-SiC, 4H) is formed at temperatures greater than 1700 C and
reported that after harvesting the fermented husk and air dried has a modied hexagonal crystal structure (wurtzite). The beta
at 80 C, rice husks was sieved through different sized sieves to conguration (b-SiC, 3C) exhibits a zinc-blende crystal structure
separate the small particles emancipated from the organic brous (diamond), and can be formed at temperatures below 1700 C
material during microbial fermentation. Then they were burned at [172]. Structure and stacking sequence for 4H-SiC (ABAC. . .),
450 C. The results showed that fermentation resulted in a 3C-SiC (ACBA. . .) and 6H-SiC (ABCACB. . .) are shown in Fig. 17.
decrease in organic matter and increment in SiO2 content. The Conventionally silicon carbide is manufactured from coal and
SiO2 content of the fermented husk was also found to be higher quartz sand in electric furnace by the Acheson process at high tem-
in smaller sieve size fractions in comparison to the untreated perature (around 2400 C) [173]. The large grain size of product
one. Because of utilization of mechanical sieving in their investiga- (>1 mm) decreases the sinterability of the powder. Fine silicon car-
tion, released silica-rich particles separate easily. Extracting SiO2 bide particles can be obtained by solgel techniques and plasma
was more efcient when more effective techniques like oatation chemical vapor deposition at a submicrometer size. Carbothermal
are explored to separate silica-rich particles. Microbial fermenta- reaction of silica can yield SiC particles easily. The primary problem
tion could be advantageously used for producing SiO2 particles of the carbothermal reduction process is the particle size of reac-
from rice husk for commercial applications. tants and the need for an intimate contact among them. The size
Production of silica nano-particles by Californian-red worms of SiC particles can be optimized through the appropriate control
through a bio-digestion process of rice husk has been proposed of the particle size of silica and carbon in the reaction mixture.
by Estevez et al. [169]. Worms were fed with rice husk for During the last four decades, much attention has been paid to
5 months. The excreted humus was neutralized by using CaCO3 the use of rice husks as starting material for the production of sil-
and calcined at different temperatures (500, 600, 700 C) and then icon carbide (particles and whiskers). Lee and Cutler did the rst
digested with a mixture of two acids (HCl and HNO3 in a ratio 1:3 synthesis of SiC from RHs in the 1970s. However, many improve-
vol.). The size of the silica particles was in the range from 55 to ments have been made in further studies, to the point where com-
250 nm depending on calcination temperatures. It was found that plete industrialization of this technology has been achieved. Due to
to obtain single silica nano-particles; the calcined temperature innumerable reasons, rice rice husk shows the encouraging poten-
should be lower than 600 C. tial for being used as a starting material for production of SiC par-
In summary, the structure and properties of obtained silica are ticles at a relatively low temperature (1500 C), much lower than
sensitive to the methods chosen to produce it from rice husk. indicated by thermodynamic and kinetic calculations. Some of
Depending on the temperature or chemical treatments selected, them are facile converting of cellulosic component of RH to carbon
the results can be different, from amorphous to distinct crystal upon pyrolysis, richness in silica (up to 28% in some varieties), high
phases. Fig. 16 summarizes most of the procedures used for the surface area and intimate contact available from carbon and silica
production of silica from rice husk. in the RH [174].
Fig. 16. Different procedures, used for producing silica with different structure from rice husk.
Fig. 17. Structure and the staking sequence of major SiC polytypes [172].
By choosing the optimum conditions for processing parameters, regions of low defect density were identied as 3C-SiC, whereas
both whiskers and particles will be formed. Separation of whiskers the regions of high defect density were consistent with a mixture
from the particulates can be achieved by liquidliquid separation, of SiC polytypes, with the 3C and the 6H polytypes being the most
froth otation, selective occulation, liquid extraction and surface predominant as a result of the formation of microtwins [184].
chemical methods [175,176].
A whisker is usually dened as a single crystal of very high
aspect ratio, i.e. ratio of length to diameter, with l/d > 10 and a 5.3. SiC formation from rice husk
diameter in the range 0.01 lm < d < 10 lm. Such crystal shapes
are highly non-equilibrium, with very large surface area to volume There are several reports, which explain all aspects of formation
ratios. In order for such a structure to be obtained there must be of SiC from rice husk [185194]. In most of the cases, the formation
kinetic factors, which promote a highly one-dimensional crystal of SiC is carried out in two steps. The rice husks are pyrolyzed in
growth [177,178]. Two mechanisms have been suggested for whis- the absence of air at a temperature of 700900 C and then red
kers growth starting from silica and carbon in rice husk [179]: at temperatures of 1500 C in an inert or reducing atmosphere
[195]. Therefore, the carbon/silica ratio of the pyrolyzed rice husks
plays a vital role in the formation of silicon carbide. Liou showed
5.1. Vaporliquidsolid (VLS)
the carbonization of raw rice husk under nitrogen atmosphere.
By comparing the carbon/silica molar ratio in the carbonized husk,
In this mechanism, the presence of a small liquid droplet acts as
it was found that the carbon/silica molar ratio increased with
a preferred site for whisker growth at the tip of each whisker.
increasing the heating rate and the micropore, mesopore and total
Metallic impurities in rice husk are able to act as catalysts in induc-
pore volume decrease with increasing the heating rate. The theo-
ing the growth of SiC. Upon heating, the catalysts decompose, and
retical molar ratio of carbon to silica is 2 for the formation of
metallic silicides in the form of liquid eutectic droplets are formed,
Si3N4 and 3 for SiC [144].
capable of dissolving carbon. The abundance of cavities can be
observed in whiskers that result from the entrapment of carbon
monoxide gas evolved during the rapid growth period. The absence 5.3.1. Pyrolysis of rice husk at lower temperature
of the cavities observed outside the whisker core region can be Because the main constituents of biomass materials are cellu-
attributed to the lateral growth at slower rates [180]. Milewski loses (C) and lignin (L), the pyrolysis reaction reects the behavior
et al. and Petrovic [181,182] did provide a more detailed analysis of these two raw organic materials during the process [196,197].
of the VLS mechanism. The pyrolysis process at the rst stage includes decomposition or
depolymerization of celluloses and lignin into the same intermedi-
5.2. Frank mechanism (whisker growth from vapor phase) ates (I) that may be organic material of smaller molecular weight;
then both gaseous volatiles (V1 and V2) are released from individ-
In this mechanism, whiskers include one or more screw disloca- ual pyrolysis reactants (C and L). There is an overlap of decompo-
tions parallel to their growth axes. The steps or ledges due to the sition of celluloses and lignin in the rst stage. Since the lignin is
dislocations at the whisker tips provide the energetically favored more difcult to decompose than cellulose, greater activation
sites for growth to continue. Frank mechanism was ruled out due energy is observed in the last period of the rst stage. In the second
to the absence of axial screw dislocations in any of the whiskers stage, the residual organic matter (regarded as intermediates, I) is
[183]. It has been shown that the whiskers contain discrete regions further pyrolyzed to form other volatile species (V3), tar and char
of high and low planar defect density. Obtaining SiC at low temper- (P); the latter is composed of a pure mixture of carbon and silica
ature might be associated with planar defects in SiC whiskers. The [197] (see Fig. 18). This material has very high porosity and may
FT-IR spectra of samples heated to 1240 C showed that some

unsaturated CC bonds (13601310 cm1) and carbonyl groups
(15001415 cm1) were formed. When it pyrolyzed at a higher
temperature (1275 C) these compounds progressively trans-
formed to aromatic and condensed aromatic compounds, corre-
sponding to the 1600 cm1 band. This results in a rapidly
growing three-dimensional network polymer, which continuously
grows by trapping small reactive pyrolysis products [200]. As the
temperature is increased from 1240 to 1275 C, a change in absorp-
tion at 1100 cm1 (corresponding to the vibration of SiO bond)
with respect to that at 900 cm1 (SiCO) is observed. There tends
to be stronger absorption at 900 cm1 for the samples heat-treated
to higher temperature, or Fe pretreated. The absorption ratios of
Fig. 18. The pyrolysis process of rice husk at low temperature [197]. the bands SiO/SiCO may be indicative of the progressive
transformation from silica to SiC [201,202].
Silicon carbide (Si-SiC) also was synthesized by self-propagating
be used as a starting material for the synthesis of silicon carbide high temperature synthesis (SHS) from a powder mixture of rice
and silicon nitride [198]. husk ash-C-Mg under pressure of 0.5 MPa. The overall chemical
reactions can be expressed as [89,203]:
5.3.2. Carbothermal reaction of rice husk at higher temperature
2SiO2 s C s 4Mg SiC s Si s 4MgO s 14
It has been reported that the four following stages occur during
carbothermal reaction: (i) crystallization of silica to form cristoba- During SHS process, the mixture of SiO2, Mg and C may have
lite (10001200 C), (ii) graphitization of amorphous carbon interacted to form some possible compounds as the following
(>1300 C), (iii) formation of SiC whiskers (12001400 C) and intermediate chemical reactions.
(iv) formation of SiC particulates (a and b) at higher temperature
SiO2 s 2Mg Si s 2MgO s 15
(>1400 C) [199]. The change in the structure from whiskers to par-
ticles was due to coagulative recrystallization of whiskers. Two fac-
Si l C s SiC s 16
tors that control the carbothermal reaction is the production of CO
and SiO during the process. It was reported that formation of CO is
SiO2 s C s SiO g CO g 17
a desirable condition for formation of silicon carbide whiskers
(SiCw). As long as silica and carbon are in contact, the SiO can be SiO g 2C s SiC s CO g 18
produced. As time passes they no longer remain in contact. The
CO that is produced by reaction (10), reacts with SiO to form SiC
and CO2. By controlling the release of SiO vapor, the formation of 5.4. Effect of different parameters on SiC formation
SiCw from rice husks increases. The SiO absorbed in the pores of
carbon tends to form SiC particles [173]. By controlling both nucleation and growth of SiC whiskers, the
obtainment of SiC can be increased. The thermodynamics and
kinetics aspects, temperature, gas ow rates, availability and con-
centration of growth species, Si/C ratio and a free space to grow
SiO g 3CO g SiC s 2CO2 g 11
are some of the important parameters that should be considered.
It has been recognized that the nal purication, morphology,
SiO g 2C s SiC s CO g 12
structure, and size of SiC ceramic phases depend largely on the
chosen processing conditions and additives. Herein, the effects of
CO2 g C s 2CO g 13
some of these parameters and additives are discussed.
The FT-IR spectrum of carbonized rice husk contains several
absorption bands, which have been assigned to individual struc- 5.4.1. Distribution of silica in rice husk
tural units as listed in Table 6. Composition and topography of both husk surfaces and their
internal tissues are important factors for the properties and perfor-
mance of composite products. Silica distribution plays the main
Table 6
role in formation of SiC. Although, silica exists in all over the rice
Absorption bands in the FT-IR spectra and their assignment.
husk, X-ray point analysis shows that silica is more highly concen-
Region (cm1) Assigned to Refs. trated in regions corresponding to dome-shaped protrusions and
36003100 OAH stretching [200,316] adjoining sloping areas (i.e. protruding inter-dome regions) [204].
30002850 CAH stretching [316,317] A representative FE-SEM image and the results of X-ray point anal-
1600 Aromatic CAC vibrations activated [318]
ysis are shown in Figs. 19 and 20 [204]. The letters (a, b, c,. . .) in the
by neighboring oxygen groups
15001415 CAH deformation [200,316] X axis in Fig. 20 correspond to the silica distribution at various
15001200 CH2, CH3, Si(CH3), C(CH3) [319] locations in the FE-SEM micrograph of Fig. 19.
15001000 Aromatic C@C skeletal vibration [200] The XPS and XRD results indicate that silicon in raw rice husk is
2150 CC [320] bonded to organic material. The SEM analysis of the converted rice
13601310 CAC and C@O skeletal vibration [200]
husks shows that the part of the rice husk that is rich in carbon
11001000 SiAO stretching [321323]
970 SiC (reection) [324] (organic material) tends to form a SiC skeleton structure, whereas
898825 Characteristic SiAC bonds appears [318] the part that is rich in silica is the main source of SiO for the forma-
beside SiAO vibrations tion of SiC whiskers. By growing the whiskers on a carbon surface,
825800 Antisymmetric SiAC stretching [321,325]
the tip of the whisker would no longer be in contact with carbon.
780 SiAC [326]
460, 796, 1093 Characteristic of SiAO bonds [201,318]
The whiskers that formed by the VLS (vaporliquidsolid) mecha-
nism generally show spherical tips. It conrms that the growth of
Fig. 19. High magnication FE-SEM view of outer surface and cross section of rice husk. The points indicated by letters (ah) were analyzed by X-ray point analysis for silica
concentration, as shown in Fig. 20 [204].
namely, oxidation of SiC. In addition, the reduced metal catalyst

particles may re-oxidize if the oxygen is not eliminated.
Therefore, it can be said that the progress of the reaction
depends on how quickly the oxygen can be removed [209]. The
unication of a catalyst greatly increases the reaction rate up to
three times that for the un-catalyzed reaction. Different types of
catalysts, such as Fe, Co, Ni, Pd, and Cr, have been used in order
to achieve high production rate and desirable morphology. It has
been reported that iron, cobalt, and nickel are good catalysts for
the synthesis of SiC and that their effect is more remarkable for
short reaction times. The effect of different catalysts on the forma-
tion of SiC from burned rice husks was studied over a temperature
range of 12001600 C and the increment in proportion of b-phase
from 95% to 99% was observed. Although, using cobalt as a catalyst
causes producing larger crystal sizes and nickel increases reaction
rate more than other catalysts, the general behavior of the catalysts
are very similar [173]. The increasing order of catalytic activity is
Fig. 20. Silica distribution using X-ray point analysis at various locations on the Ni > Co > Fe > un-catalyzed, whereas for SiC crystal size is
outer surface and within internal tissues of rice husk [204].
Co > Fe > Ni > un-catalyzed. In the investigation by Krishnaro
[210] cobalt has been found to accelerate the formation of total
SiC whiskers occurs mainly by reaction between SiO and CO [205 SiC (particulate and whiskers) and decrease the formation of SiC
207]. whiskers from mixture of silicacarbon black. Cobalt acts as a
strong catalyst to the gasication of carbon and decreases the crys-
tallization of carbon black. In the presence of cobalt catalyst, rapid
5.4.2. Effects of catalysts heating has been shown to form larger quantities of SiC whiskers.
Analysis of the progression of reaction rate, morphology of the Without any catalyst, rapid heating has resulted in the formation
whisker formed, evolution of gases during reaction, crystal size of SiC particulates. The effect of Fe content on the formation of
and intermetallic phases, leads to conclusion of a reaction mecha- SiC from rice husk was investigated by Mansour et al. [211]. They
nism based on the formation of an M-Si-C liquid phase, which is reported that the amount of SiC increases with increase in the Fe/
essential for the nucleation and growth of the SiC whiskers. Cata- SiO2 ratio, up to a limiting value of 0.07 [173]. Martinez et al. [206]
lysts and reaction mechanism, which are involved in the formation evaluated the effects of two different catalysts (CoCl26H2O and
of whiskers at elevated temperatures, play complex roles. The FeCl24H2O with NH4OH as a Fe precipitation agent) on the produc-
effect of catalytic elements in chemical reactions above 600 tion of SiC-based materials. It was found that the optimum condi-
800 C are rarely reported [208]. In sight of the melting points of tion was developed using FeCl24H2O as a catalyzer at 1370 C.
the catalysts, it is likely that their role predominates below Mansour et al. [211] also reported elsewhere that by addition of
1000 C. The metallic catalyst may be accelerating reactions iron to the rice husk the volatile matter evolved during the carbon-
between SiO2 and carbon, thus increasing the formation of SiC. ization process would be increased. Furthermore, the iron could
During this reaction, it is necessary to ush out the oxygen con- also act as an inhibitor for the crystallization of silica and carbon,
stantly by argon ow in order to avoid the reverse reaction, leading to an increase in the rate of silicon carbide formation at
higher temperatures. Platinum loaded SiC samples were found to thus preventing the growth of whiskers. On the other hand, if the
be very active by Singh et al. [212] observing a 100% conversion gas ow rate is too slow, most of the CO gas will be concentrated
of CO to CO2 at temperature as low as 175 C in the experiment. at the reaction zone and thus inhibiting the reaction to form SiC.
The activity of the platinum-doped samples did not change with In addition, fast moving gases can also destabilize the liquid drop-
increase in temperature up to 700 C; however, the high perfor- let at the whisker tip and hinder whisker growth [180,215]. The
mance observed was attributed to the uniform distribution of plat- effect of the atmosphere used during pyrolysis, i.e. argon, vacuum
inum on the surface of SiC particles. Kermarec and co-workers was investigated by Zawrah et al. [216]. As it is clear from Fig. 21,
[213] reported that the catalysts added as metal hydroxides are the pyrolyzed samples in vacuum exhibited higher SiC peaks inten-
rst converted to the oxide at around the coking temperature sity than those pyrolyzed in argon atmosphere. During pyrolyzing
and are subsequently reduced to the metal particles using hydro- in argon atmosphere, the furnace chamber pressure increases
gen, CO and CnHm molecules as: because of the development of CO produced from the reactions
between silica and carbon. Increasing the pressure around the sil-
0
NiOH2 ! NiO ! Ni 19 ica and carbon, according to reaction (10) in presence of higher
temperature leads to increasing the crystallinity and the stability
The zero-valent metal particles can impart a high catalytic
of both reactants and consequently leads to decreasing the forma-
property.
tion of SiC. In other words, increasing the pressure results in aug-
Raman et al. [214] increased the yield of SiCw from a mixture of
menting the free energy and the stability of the material
rice husk, textile grade polycarbonitrile (PAN) and boric acid. PAN
according to reaction (10) and the following thermodynamics
was used as an external carbon source in the pyrolysis of rice husks
equations:
to synthesize SiCw. The carbon from PAN is an active form of car-
bon and is produced in situ, and helps in the carbothermal reduc-
tion of silica. In addition, boric acid as catalyst enhances the DG DG0 DnRTln p=p0 20
migration of silica particles, resulting in an efcient contact
between silica and carbon. By increasing the temperature, boric
where DG0 GSiO GCO GSiO2 (Dn = 2, R = gas constant,
acid melts with decomposition to give B2O3B2O3 can be mixed
T = temperature, P = nal pressure, p = initial pressure) [217,218].
with silica due to the formation of a liquid phase, and this helps
In contrast, it was found that the pyrolysis in vacuum guaran-
in bringing silica and carbon in close contact and result in the for-
tees the lower pressure around the reactants and consequently
mation of SiCw at 1450 C. Krishnarao and Godkhindi [170] found
increases the formation of SiC at temperature around 1550 C
that addition of Si3N4 to black milled ash causes in an increment
due to increment of intimate contact between SiO2 and C. More-
in the formation of SiC whiskers and a reduction in the tempera-
over Radhakrishna and Sanghi [179] reported that vacuum pre-
ture of conversion to 1200 C. Silicon nitride is converted to SiC
vents whisker growth since it removes the vapors containing the
rapidly at and above 1300 C.
whisker growth species. Sarangi et al. [219] showed in high-vac-
uum at 1400 C, high crystalline b-SiC particles of very ne size
5.4.3. Effect of atmosphere on SiC formation formed along with some amount of unreacted silica in less than
The chamber atmosphere and the gas ow rate play signicant 5 min.
roles in determining the structure of the nal product and the Fig. 22 shows the relationship between the stable condensed
amount of CO and SiO produced, respectively. Furthermore, the phases, log PN2, log PCO and the temperature for the SiCNO sys-
increment in gasication rate causes an increase in the surface area tem. The atmosphere was considered to be composed of N2 and CO,
of carbon, and thus leads to a high total porosity and adsorption which was formed by the reaction between O2 in the N2 gas cylin-
capacity of carbon. Therefore, the gasication rate should be con- der and carbon black. It indicates that at the heating temperature
trolled. As mentioned before, the produced carbon monoxide dur- (1400 C) and high N2 pressure the a-Si3N4 phase is stable [220].
ing pyrolysis and SiO control the structure of SiC into whiskers. If As it can be seen, by controlling N2 pressure and temperature, it
the CO gas produced is derived away from the reaction zone rap- is possible to reach SiC. However, Ekelund and Forsluhbnd [221]
idly under high gas ow rate, the SiO gas will also be carried away, reported that an increase in N2 pressure does not have any effect
Fig. 21. XRD patterns of SiC prepared from coarse rice husk ash (as is) pyrolyzed at temperature of 1450 C in argon and vacuum atmosphere [216].
impurities in the RH, resulting in higher purity of RHs with a por-

ous structure. Because of porous structure of acid treated rice husk,
the intimacy between silica and carbon eliminates. As a result of
low degree of crystallization, carbon in treated rice husk can form
and absorb a larger quantity of CO and SiO and the produced CO
reacts with SiO2 to form SiO. Thus, the SiC content in the pyrolyzed
treated rice husk was higher than that in pyrolyzed untreated rice
husks. The formation of SiC whiskers in acid treated rice husk is
lower than in un-treated one. Patel and Prasanna [223] reported
the formation of Si2N2O from acid-treated RHs at 13001500 C.
Krishnarao [224] reported that by treating the pulverized burned
RHs with aqueous solution of CoC12, the degree of crystallization
of silica and carbon decreases. They claimed that CoCl2 diffuses
into the graphite and burned rice husk and opens up the layers
of graphite by channeling. It has been reported that the SiC whisker
formed in CoCl2 treated burned rice husks is negligible. Alkali pre-
treatment has also been reported [16]. Patel et al. [16] also showed
that the concentrated (>9 N) NaOH solution cannot penetrate
through the holes of rice husk and the extraction of silica
decreases. Mizuki et al. [80] proposed using an enzymatic method
for formation of SiC. The ground treated powders of rice husk with
NaOH were hydrolyzed with a mixture of Acucelase and Meicela-
sein acetate buffer (pH 45, 20 ml). After treatment with enzymes
the precipitate was dried and pyrolyzed in a two-step process (at
Fig. 22. Relationship between the stable condensed phases, log PN2, log PCO, and 500 C for 1 h in N2 atmosphere and 1600 C for 1 h in Ar atmo-
temperature in the SiCNO system [221]. sphere). The cellulase treatment was developed to control excess
carbon for silicon carbide formation from rice husks. Komatsu
et al. [225] demonstrated that sieving is an easily controlled
on carbothermic nitridation processes in contrast to thermody- method; however, the yield of carbon-controlled rice husks
namic prediction, as shown in Fig. 22 [221]. (45.5%) was lower than that for the enzymatic method (54.0%).
It has been reported that the pyrolysis of rice husk in nitrogen
atmosphere at 1550 C led to the formation of SiCSi3N4 nanocom- 5.4.5. Effect of crystallinty of SiO2 and C
posite. The reported amount of formed SiC was higher than the It has been found that under the same experimental conditions,
amount of Si3N4 [102]. Nitridation of rice husk can be represented formation of SiC from rice husk precursors depends on the charac-
by the following reactions: teristics of the rice husk raw material. The lowest yield and quality
SiO2 s C s SiO g CO g 21 is obtained from pulverized black ash (ground black ash) because
although the C/Si ratio of black ash is adequate for the reaction,
SiO2 s CO g SiO g CO2 g 22 the high aromaticity, less open structure, non-availability of void
spaces and low CO formation, slow down the rate of the reaction.
The subsequent reaction is: While mixtures of white ash and carbon black allow producing
SiO g 2=3N2 g 1=3Si3 N4 s 1=2O2 g 23 intermediate amounts and quality of SiC. The highest ones are typ-
ically obtained using raw rice husk [202,207], where sufcient car-
1=2O2 g C s CO g 24 bonaceous substrate and large enough CO formed from
degradation of cellulose in rice husks and sufcient void space in
SiO g C s 2=3N2 g 1=3Si3 N4 s CO g 25 the husk bed were available. Liou [144] showed level of micropores
in coked rice husk is higher than crystallite rice husk ash. More-
In another investigation, Krishnarao and co-workers [191] pyro- over, it was reported that the intensity of the SiC peak in the mix-
lyzed rice husks without pre-coking in a graphite resistance heat- ture of crystalline white ash with carbon (CWA + C) is higher than
ing furnace at 11001400 C in nitrogen atmosphere. They that of mixture of white ash and graphitized carbon (WA + GC).
reported the formation of good quality (needle-type) SiC whiskers This outcome can be attributed to the production of a large quan-
without the detection of Si3N4. While, small quantities of Si2N2O tity of CO by amorphous carbon. By increasing the heating rate, the
were formed at 11001200 C. The formation of silicon oxynitride carbon in (WA + GC) could absorb less quantity of SiO due to
can be eliminated as long as carbon is present in excess or at least increasing the closed porosity. Thus, the intensity of the SiC peak
in the stoichiometric ratio. The results also illustrated that by in slowly heated (WA + GC) was higher than that in the rapidly
increasing the reaction chamber pressure, the crystallinity of silica heated sample [202].
and carbon in RHs increases, while formation of SiC whiskers
decreases. Hydrogen can also be used, but offers no real advantage 5.4.6. Effect of milling of starting materials
even though it might help to increase the SiO concentration by the It is believed that high-energy milling before carbothermic
reaction [179]: reduction has not altered the reaction mechanism of SiC formation
SiO2 s H2 g SiO g H2 O g 26 and the involvement of gaseous phases, SiO and CO, in the forma-
tion of SiC but greatly enhanced the formation of materials [226
228]. High energy milling leads to the following changes to the
5.4.4. Effect of chemical pre-treatment of rice husk SiO2: (i) formation of amorphous phase in the reactants; (ii) low
It was reported that treating of rice husk with acid and pyrolyz- degrees of long-range order in the remaining crystalline reactants;
ing it in argon atmosphere increases the SiC contents [222]. The (iii) large grain-boundary areas associated with ultrane crystal-
degree of crystallization decreases due to eliminating the lites; (iv) high internal strains in the remaining crystalline reac-
tants; (v) large specic surface areas; (vi) ne particle sizes; and Almost all the processes devoted to the formation of SiC from rice
(vii) intimate mixing of reactants at microstructural levels changes. husk through different routes so far, involve two process steps: (i)
(i) to (vii) can enhance SiC formation by increasing reaction kinet- pyrolyzing at low temperature (400800 C) in a controlled man-
ics via increased diffusivities, increased reaction areas, and ner to remove volatiles, and (ii) reacting the pyrolyzed rice husk
decreased diffusion distance, whereas changes (i) to (vi) can also at high temperature (>1300 C) to form SiC. In a novel approach,
enhance SiC formation by increasing the free energy of the reac- SiC forms from rice husk in a single step [217]. Plasma processes
tants [227]. Lakiza et al. [194] showed at temperature of about are not only suited for operation in a continuous manner but can
1500 C silica begins to evaporate from free surfaces of SiO2 grains. be competitive with the current Acheson-produced material (com-
With increasing specic surface of SiO2 particles, the intensity of mercial route that is used for producing SiC) [240]. The plasma-
this process grows. SiO2 and SiO vapors become adsorbed on the synthesized powder was very ne and dark green in color. Singh
surface of carbon and are reduced by it to Si. The free silicon reacts, et al. [189] used a DC extended arc plasma reactor in order to pro-
either directly or by a vaporliquidsolid (VLS) mechanism with duce b-SiC particles from a mixture of boiler-burned rice husk and
carbon, as a result SiC is formed. The effect of milling process on graphite powder. A SiC yield as high as 72% was achieved at a
particle size of the prepared SiC was also investigated by Zawrah 3.03:1 carbon-to-silica ratio. In another investigation, they synthe-
et al. [216]. They evaluated the effects of three rice-husk ash sam- sized ultrane SiC powders through thermal plasma technique
ples: coarse-grained rice husk ash, ne rice husk ash (hand- using argon as both plasma-generating gas and carrier gas. After
ground) and ball milled one. It was found that the particle sizes pretreatment of rice husk at 550 C under nitrogen atmosphere
of the obtained SiC from ball milled materials were smaller than the sample was treated at very high temperature, steep tempera-
those prepared without milling at 1550 C under vacuum. In addi- ture gradients (106 C m1) and high quench rates (106 C sl).
tion they claimed that mechanical activation of the reactants (rice The plasma-produced powder was then treated in air at 700 C in
husk ashes) at room temperature by high-energy ball milling a tube furnace using natural convection to remove the excess car-
increases the reactivity of the reactants and dramatically reduces bon. The removal of excess silica was carried out by treatment with
the temperature and time for the synthesis reaction of SiC. concentrated HF. The resulted sample shows b-SiC structure.
6.3. Microwave heating

6. Preparation of nano SiC
Recently, the microwave heating method was developed to syn-

In the last decade, efforts have been made by various research-
thesize SiC from rice husk [241244]. In conventional heating, heat
ers to synthesize ne and pure SiC powder by alternative methods
is transferred between objects by the mechanisms of conduction,
like solgel, plasma, laser, chemical vapor deposition (CVD), self-
radiation and convection and both the amorphous SiO2 and carbon
propagating high-temperature synthesis [229233]. Nano-sized
are slowly heated to high temperature. Thus, in the nal product
SiC rods have also been prepared using Si and C as the reactants
both SiC and unreacted SiO2 can be detected. In microwave heating
at the temperature of 1200 C. The availability of nano silicon car-
method, it is known that the exothermic phenomenon of materials
bide commercially could possibly promote more wide spread
in a microwave eld is derived from the effects of Joule loss, dielec-
application of silicon carbide in industry by lower sintering pres-
tric loss and magnetic hysteresis loss. In the case of the carbon and
sure and/or temperature. However, the high cost of the powder
SiO2 powder mixture, the Joule loss becomes important, whereas
may hinder the progress. Recently synthesis of nano SiC from rice
the dielectric loss and magnetic hysteresis loss can be ignored
husk was proposed in order to overcome the high production price
[220]. The carbon is rstly heated to high temperature in a short
of nano SiC through the conventional routes [234,235].
time and the carbothermal reduction of SiO2 is rapidly achieved.
Thus, the crystallization of SiO2 can be ignored. Fig. 23 shows the
6.1. Utilization of agricultural waste materials as source for carbon mechanism for the formation of SiC by the carbothermal reduction
reaction from SiO2 and carbon black using microwave heating.
Recently, formation and growth of SiC nano-wires from mixture Firstly, when microwaves act upon the material, carbon black is
of oil palm and rice husk ash as a carbon and silica sources, respec- heated due to the Joule loss effect. During this time, hot spots at
tively was investigated by Chiew and Cheong [236]. Oil palm bers which exothermic reactions occur begin to appear in some areas
have been reported with high carbon content and low ash content. of the sample. The temperature around the hot spots increases to
It has been shown that the ratio of RHA to oil palm affects the over 1500 C, which results in the generation of SiO (g) from SiO2
growth mechanism. The growth mechanism of nano wire changes and subsequently, the generated SiO (g) moves to carbon black
with increasing of RHA from 20% to 80%. It was shown that the particles at high temperatures over 1500 C where SiC is formed.
optimum amount of RHA to grow SiC nanowires with the mini- Li et al. [245] showed the carbonized rice husk (CRH) at 700 C
mum amount of impurities, with sizes between 30 and 40 nm, for 30 min in an argon atmosphere. The as-received CRH was
and with the maximum yield, is of 40% RHA mixed with oil palm. milled for 1 h at room temperature. Rapid carbothermal reduction
Besides, Kantee et al. [237] have synthesized nanostructured from reactions were achieved in a 2.45 GHz microwave eld in an argon
high silica rice husk ash in combination with Cu or SnO2 powder atmosphere. The complete carbothermal reduction of silica was
and coconut shell charcoal. The mixtures powder and Si substrates achieved at 1300 C for 60 min or at 1500 C for only 15 min by
were heated up to 1250 C in argon atmosphere. The result con- microwave heating, resulting in b-SiC formation. The b-SiC whis-
rmed the presence of SiC and SiO2 nanostructures. kers show diameters of 110170 nm with a length of several to
tens of micrometer. Qadri et al. [243] produced nanoparticles of
6.2. Arc plasma reactor b(3C)-SiC from the agricultural waste of rice husks by microwave
processing in controlled conditions of temperature (1900 C) and
Thermal plasma offers an attractive route for synthesis of ne vacuum. Transmission electron microscopy revealed the presence
and ultrane powders among others methods. Ultrane SiC has of stacking faults along the [111] direction. The presence of 6H/
been prepared by thermal plasma processes, according to several 4H stacking faults in 3C phase is explained in terms of their total
reports [238240]. Some of the advantages of thermal plasma are energies. Fig. 24(a) shows the high density of stacking faults ori-
the reduction of the reaction time signicantly, high operating ented along the (1 1 1) plane. The corresponding selected area elec-
temperature, steep temperature gradients, and high quench rates. tron diffraction pattern from one such particle close to the [0 1 1]
stress applications because of its excellent properties such as high

strength retention at elevated temperature, low thermal expansion
coefcient, good thermal shock resistance, and high corrosion
resistance. It has a much higher creep resistance than metals and
its thermal shock resistance is much better than other ceramics
[246,247]. There are basically four different synthetic routes for
this powder, which differ in purity, morphology and sintering
activity: (i) a direct reaction of elemental silicon with nitrogen that
gives relatively coarse products and have to be milled prior to fur-
ther processing [248]; (ii) carbothermal reduction utilizes a ne
mixture of carbon and SiO2 powders in a owing of N2 at 1500 C
[249]; (iii) the so-called diimide-process is a liquid or gas-phase
route to Si3N4 powders [250]; (iv) CVD techniques using volatile
silicon compounds such as SiCl4, SiH4 or related molecular com-
pounds yield Si3N4 powders upon gas phase reaction with ammo-
nia [251]. Because of the high purity of ne silica and carbon and
their commercial availability, the carbothermal reduction of silica
is the main method for manufacturing silicon nitride powder.
However, this method has a high requirement on raw materials;
high reactivity and a good distribution of the silica and carbon
are important for the reaction. The better the distribution, the
more helpful for nitridation. Therefore, RH, which naturally con-
tains both silica and carbon, is a potential material for producing
Fig. 23. Schematic diagram showing the mechanism for the formation of SiC by silicon nitride [2,81].
carbothermal reduction reaction from SiO2 and carbon black using microwave
heating [220].
7.1. Si3N4 formation through carbothermal reduction and nitridation
of rice husk
zone axis is shown in Fig. 24(b). The diffraction spots, the d-spac-
ing, and the angle between planes conforms b-SiC crystal. The d- Reaction for carbothermal reduction and nitridation of rice husk
spacing of (1 1 1) planes was observed to be around 2.52 . The were suggested by several investigators [252,253]. The factors
streaks along the [111] direction in the diffraction pattern are which have inuence on the overall reaction are characteristics
due to thin stacking faults. In some particles, one could observe of starting materials, temperature, gas ow rate and catalysts
(1 1 1) twins, Fig. 24(c), as well as stacking faults. [254,255]. The homogeneity mixture of carbon and silica, which
occurs naturally in rice husk determine the level of completion of
reaction. In all cases, excess carbon is required to complete the
7. Silicon nitride reaction in a reasonable time and temperature. The role of carbon
in the formation of Si3N4 is to act as a reducing agent to promote
Because of the importance of silicon nitride (Si3N4) in engineer- the nitridation reaction, and also to provide a source of active sites
ing materials, their properties and potential applications at high at which the Si3N4 can nucleate. Lee and Cutler [256] have
temperature, in microelectronics and optoelectronics, in recent attempted to emphasize the important role played by the molar
years there has been a growing interest in this material from differ- C:SiO2 ratio in the formation of silicon nitride. As long as carbon
ent perspectives. Silicon nitride (Si3N4) is one of the most promis- is present in excess or at least in the stoichiometric ratio of the
ing structural materials for high temperature and high mechanical overall carbothermal reductions, the formation of silicon oxynit-
Fig. 24. (a) Particle showing stacking faults, (b) the corresponding diffraction pattern in the [0 1 1] zone, and (c) diffraction pattern from another particle showing twined
spots close to zone [243].
ride can be eliminated [257] by effectively removing the oxygen Rahman and co-workers [146] nitrided the pyrolyzed rice husk
from the system through reaction, at temperatures between 1260 and 1450 C under 95% nitrogen-5%
hydrogen and obtained a-silicon nitride powder of high purity. It
1=2O2 g C s CO g 27 was found that hydrogen addition is benecial in accelerating
the rate of nitride formation. The addition of pre-formed silicon
In order to increase the rate of reaction, the partial pressure of
nitride powder to pyrolyzed rice husk powder before nitridation
produced CO during the reaction must be reduced by introducing a
is noticeably benecial in yielding a product consisting of uniform
higher ow rate of nitrogen. Hence, a higher ow rate of nitrogen
sub-micrometer (<0.5 lm), equiaxed, a-Si3N4 crystals. In addition,
would be favorable in maintaining a low CO concentration and will
they reported that milling of pyrolyzed rice husk has a great effect
also provide a more efcient reaction of silicon dioxide with nitro-
on the crystal size of silicon nitride due to increment in nucleation
gen to silicon nitride.
sites densities for the growth of a-Si3N4. It has also been shown
The general idea about the carbothermal reduction and nitrida-
that, in addition to obtaining a high powder surface area and
tion of rice husk is that SiO gas plays an important role in Si3N4 for-
homogeneous particle distribution, the carbon and silica content
mation. SiO (g) is generated by the reaction between SiO2 and C
of the husk can be controlled through a proper digestion with
(reaction 28) [102].
hot HNO3 [260].
The phase transition from a to b occurs via the diffusion of the
vapor phase or liquid at a temperature greater than 1400 C [261].
The subsequent reaction is:
7.1.1. Effect of catalysts on Si3N4 formation
SiO g 2=3N2 g 1=3Si3 N4 s 1=2O2 g 29
Hashishin et al. [262] evaluated the effect of cryolite in SiO2
One of the problems that is associated with this method is that N2Na3AlF6 system under the presence of graphite. Whiskers were
the nitrogen and the powder are not in contact with each other, synthesized when SiO2/Na3AlF6 molar ratio ranged from 2 to 8. The
indeed the produced SiO cannot take out of the heated sample maximum amount of whiskers was synthesized when the SiO2/Na3
and reacts with nitrogen. Some alternatives proposed to use carrier AlF6 molar ratio was 3. In another report, the same authors [261]
gas are to diffuse into the voids of the heated powder to take out studied the effect of impurities on Si3N4 whiskers via a carbother-
the silicon-containing vapor to react with nitrogen. Passing the mal reduction from SiO2N2Na3 AlF6 system. In this process cryo-
mixture of nitrogen and chlorine or hydrogen through the sili- lite is added as ux in the molar ratio of SiO2/Na3AlF6 = 3. The aim
con-containing material causes removal of vapor from the heated of their study was to investigate the effects of adding impurities
material, but delays or inhibits the reaction between the silicon which are containing Fe2O3, Al2O3, TiO2, MgO, and CaO on the
component and nitrogen so that the silicon nitride does not cover growth of the Si3N4 whiskers. As it can be seen in Fig. 25, Fe2O3,
the reactive material. In these two methods, the purity of Si3N4 is Al2O3, and TiO2 accelerate the growth of the whiskers by the
low; the whiskers grow on ceiling, and side walls of furnace. vaporliquidsolid (VLS) mechanism, CaO and MgO by the
Tanaka and Kawabe [258] prepared the carbonsilica with thin vaporsolid (VS) and VLS mechanisms. It is clear that the shapes
conguration and sufcient porosities and used the moving tray of the Si3N4 whiskers that were synthesized by CaO and MgO con-
for producing Si3N4. By passing the tray through a series of temper- sist of columnar-like and square pole-like. The droplets were found
atures from 400 to 1300 C in the presence of N2, the gas passes on the top of the columnar whiskers but no droplets were observed
into the porosities and provides spaces for growing whiskers. on the top of the square pole. It has also been shown that the addi-
Liou et al. [259] showed that the conversion of silicon dioxide tion of CaO and MgO leads to a decrease in the length and an
increased with increasing gas ow rate up to 200 mL/min. A fur- increase in the diameter of Si3N4. The effects of these impurities
ther increase of gas ow rate has no effect on the conversion. They corresponded to the solubility of the metal in silicon. The compo-
also proposed using pellet-forming pressure for increasing the rate nents of the droplets were mainly the alloys of FeSi and AlSi sys-
of nitradation due to shortening the distance between carbon and tems, and those of TiSi system rarely existed that it can be
silicon dioxide and consequently increasing the contact area of the attributed to the solubility of Si into metal. Darken and Gurry
two components [259]. This method is not practical for samples [263] indicated that the solubility signicantly depended on the
without excess carbon because the naturally distance between car- atomic diameter and electronegativity. The electronegativities of
bon and silicon dioxide is in its minimum level. Si, Fe, Al, and Ti were 1.17, 1.24, 1.43, and 1.47, respectively. There-
Fig. 25. The morphologies and the compositions of the droplets grown on the top of the Si3N4 whiskers synthesized from the mixture of the cryolite-containing silica and
impurities by the carbothermal reduction and nitridation process. (a) Fe2O3 (Fe/Si = 12), (b) Al2O3 (Al/Si = 0.09), (c) TiO2 (Ti/Si = 0.81), (d) CaO (Ca/Si = 0.04), and (e) MgO
[261].
Fig. 26. SEM of powder obtained from nitridation of (a) PRH-V2O5 at 1400 C, (b) PRH-2Fe2O3 and (c) PRH 2NiO at 1500 C in 95% nitrogen 5% hydrogen [174].
fore, the solubility of silicon in Fe is higher than that in Al and Ti. without any excess carbon. Due to consumption of carbon by VC
These results indicated that the diameter of the whiskers is con- and VN, carbon to silica molar ratio is reduced below the stoichi-
trollable. The effect of Fe2O3 addition in SiO2N2Na3AlF6 system ometric ratio. This condition most likely caused the oxygen partial
on the growth mechanism and composition of the droplets has pressure to increase and increase the formation of Si2N2O [257].
been studied by Hashishin et al. [262]. They showed that Al plays By using Si3N4 and rice husk ash with different metal oxides
an important role in the synthesis of Si3N4 whiskers. It has been Y2O3, MgO and A12O3, Si2N2O can be produced by VLS mechanism.
seen droplets of AlSi obtained when Fe2O3: SiO2 ranged from The conversion rate to Si2N2O is much higher for Y2O3 and MgO
3.04.0:100 and 5.06.25: 100. No droplets obtained for other val- additions than for A12O3 additions and maximum amount of Si2N2O
ues. The greatest Al/Si ratio obtained when Fe2O3:SiO2 was 3.5:100 (about 80%) with Y2O3 and MgO obtained at a temperature of about
and 5.63:100. Interestingly, Fe was not contained in the droplets, 1600 C. The decrease in the amount of Si2N2O corresponds well
although Fe2O3 added to the starting material. At high tempera- with the increase in b-Si3N4. At the higher temperatures, Si2N2O
tures such as 1400 C, both AlSi and FeSi droplets can exist. presumably has decomposed to SiO, N2, and Si3N4 [265].
The maximum formation of whiskers has been observed from
the sample of 6% Fe concentration treated at 1400 C by Sarangi
7.2. Si3N4 formation through chemical vapor deposition
[264]. It has been shown that at 1450 C, the amount of whiskers
is gradually changed to globules.
A new method that has been used in order to prepare Si3N4, is
Rahman and Riley [174] produced Si3N4 from rice husk powder
based on chemical vapor deposition. In this method, silicon halides
at temperatures in the range of 12601450 C under a ow of 95%
in atmosphere of N2 can produce silicon nitride powder of very
nitrogen-5% hydrogen by utilization of different catalysts such as
high purity and high specic surface area in a simple and economic
Y2O3, ZrO2, TiO2, CeO2, Fe2O3, NiO and V2O5. It was found that
way. This type of powder is likely to be relatively expensive.
Y2O3 and ZrO2 were not signicantly reduced by carbon or hydro-
Hybrid precursor system-chemical vapor deposition (HYSYCVD)
gen under nitridation conditions and did not have any effects on
is a method recently developed at CINVESTAV1-Saltillo, for the pro-
the amount of fabricated silicon nitride. Both TiO2 and CeO2
duction of advanced ceramics (for example, alpha and beta Si3N4) in
appeared to accelerate silicon nitride formation, and led to higher
which solidgas reaction systems or hybrid systems are used. This
overall yields. TiO2 was easily reduced but CeO2 was also readily
method is based on the ability of some solids like sodium hexauo-
reduced to Ce2O3 with a range of intermediate non-stoichiometric
rosilicate (Na2SiF6) to produce highly reactive gas species (SiF3, SiF2,
oxides CeO2-x. Results by XRD also showed the presence of CeN in
SiF and Si) which, by the reaction with other proper precursors (for
the silicon nitride for the higher nitrogen ow rate. Fe2O3 and NiO
instance, nitrogen precursors), allow the formation of condensed
are easily reduced under low oxygen partial pressure to the metals,
phases like Si3N4 and Si2N2O as stable solids [266]. Sodium hexau-
which in turn yield the liquid silicides at the nitridation tempera-
orosilicate (Na2SiF6, as silicon halides source, was prepared in CIN-
ture. Globules at whisker tips, which are shown in Fig. 26, indica-
VESTAV-Saltillo laboratory by means of the dissolution of SiO2
tive of a vaporliquidsolid (VLS) mechanism of growth, although
(obtained from rice husks) in hydrouoric acid (HF) and the subse-
a signicant amount of SiC was also formed.
quent precipitation with a solution of sodium hydroxide (NaOH).
It was reported that the amount of b-Si3N4 increased signi-
Synthesis tests were carried out in a HYSYCVD reactor at constant
cantly with V2O5 content. It has to be mentioned that VC and VN
pressure and in the atmosphere of nitrogen precursors (N2, 50%
were detected as by-products and VC was found to be the predom-
N2-balance NH3 and, 5% N2-balance NH3) [267].
inant phase due to its greater thermodynamic stability as com-
pared to VN under reaction conditions [257].
8. High purity silicon
V2 O5 l 7C s 2VC s 5CO g 30
The conventional process of manufacturing silicon of reason-
V2 O5 l 5C s N2 g 2VN s 5CO g 31 able purity involves a very high cost of production [268]. Therefore
It was reported that growth of SiC in presence of V2O5 is not as worldwide efforts are being directed to develop a low-cost, high-
favored as in FeSi liquid (iron catalyst). It shows that V2O5 liquid volume and commercially feasible process for production of high
is not able to take into solution a signicant amount of carbon or purity silicon to be used in solar cells for photovoltaic power gen-
carbon monoxide and silicon monoxide through solidliquid eration [269271]. One such process involves reduction of rice
vapor mechanism. However, it was observed that Si2ON7 could
be obtained by utilization digested rice husk in presence of V2O5 1
CINVESTAV is the Spanish acronym of Center for Research and Advanced Studies.
Table 7
Silica-metal reaction thermodynamic data [274].
Reaction Temp. (C) DH (kJ/mol) DG (kJ/mol) Adiabatic Temp. (C)

SiO2 + 2Ca = Si + 2CaO 650 C 363 333 2348
SiO2 + 2 Mg = Si + 2MgO 650 C 312 261 1906
SiO2 + 4/3Al = Si + 2/3Al2O3 650 C 210 180 1477
SiO2 + Ti = Si + TiO2 650 C 34 33 407
Fig. 27. (a and b) High and low magnication bright eld TEM images, respectively, of porous Si prepared via reaction with Mg for 3 h at 300 C and then 12 h at 500 C,
followed by acid dissolution of Mg-bearing product phases. (c) Isothermal nitrogen adsorption and desorption curves of the silicon product at 196 C, and (d) Pore size
distribution (from BJH analysis) of the porous silicon product [275].
husk ash to produce silicon. Several approaches have been devel- teresis loop, indicated that the Si product was largely mesoporous.
oped to produce silicon from RHs. Among the various methods, BET analyses yielded values of 218.4 m2 g1 for the specic surface
reduction of amorphous silica by metallic metals has been dis- area [275].
cussed extensively. The metallic elements Mg, Ca, Al and Ti can In the invention of Sung et al. [276] a method for producing
reduce SiO2 at comparatively lower temperature and forms mix- high purity porous silica and silicon, which are derived from rice
tures of condensed phase products. The relevant overall reactions husk, was presented. In this method, silica was extracted from
and their corresponding free energy change and adiabatic temper- cooking liquor separated in a cooking treatment of rice husk alkali,
ature rise per mole of silicon are shown in Table 7. then silicon was synthesized by performing a reduction reaction. In
Mishra et al. [271] investigated production and purication of this method, improved metallurgical grade silicon that does not
silicon through calcium reduction of rice-husk white ash. They contain boron or phosphorus may be produced through an acid
mixed rice-husk ash obtained at 500 C and commercial grade cal- treatment that greatly reduces the presence of impurities. In addi-
cium thoroughly in stoichiometric proportions. Then the mixture tion, the silicon produced by using this method may be used in the
was reduced at 720 C. The reduced product leached with concen- manufacture of low cost solar cells. Carbon can also be utilized for
trated HNO3 and HF to achieve high purity of 99.9% silicon. Obtain- reduction of silica to silicon. The required ratio of C to SiO2 for the
ing silicon of (99.9999%) purity by reducing white rice husk ash production of solar grade silicon is 2:1. However, purifying RHs
with magnesium at temperature of 800 C followed by several suc- allows obtaining a C/SiO2 ratio of about 4:1 [16,277]. Hunt et al.
cessive acid (mixtures of HF, H2SO4 and HCl) leaching treatments [278] leached RHs in hot HCl and then coked them in inert gas to
were reported in several works [272,273]. With acid treatment, it further remove impurities. The coked RHs were extruded with
is possible to remove MgO, Mg2Si and unreacted Mg as by prod- sucrose as a binder to produce 5-mm diameter pellets with an
ucts. Larbi [274] reported that by utilization of pellet of RHA with average bulk density of about 800 g/L. The pellets were pyrolyzed
magnesium content 5 wt.% in excess of stoichiometry requirement in an arc furnace to produce pure silicon.
and heating in the temperature range of 900 C under owing
argon, it is possible to achieve a maximum silicon yield. The pres-
ence of ne silicon nanocrystals from magnesiothermic reaction 9. Magnesium silicide (Mg2Si)
was conrmed using high resolution transmission electron micros-
copy (see Fig. 27a and b). The surface area and pore size distribu- The intermetallic compound Mg2Si exhibits a high melting tem-
tion of the Si product were evaluated via nitrogen adsorption perature (1085 C), low density (1.99 103 kg/m3), high hardness
desorption analyses. The isothermal adsorptiondesorption curve (4500 MN m2), a low coefcient of thermal expansion
of the silicon product (Fig. 27c) was of type IV with a H1 type hys- (7.5 106 K1) and a reasonably high elastic modulus (120 GPa)
[279,280]. Due to abundance of environment friendly Mg and Si main steps for the preparation and manufacture of active carbon
components in the Earths crust, magnesium silicide (Mg2Si) seems from rice husk: (1) the carbonization of the carbonaceous raw
to be ecologically and economically protable material for elec- material below 700 C, in the absence of oxygen (char), and (2)
tronics. It is a light-weight and indirect-gap narrow-band semicon- the activation of the carbonized product (char), which is either
ductor prospective, in particular, for thermoelectric applications physical or chemical. Carbonization and chemical activation can
[281]. be performed in a single step.
SiO2 could be employed as industrial raw materials to synthe-
size magnesium silicide (Mg2Si) via a deoxidization reaction of 10.1. Physical activation
SiO2 by magnesium in solid-state. Mg2Si intermetallics are suitable
reinforcements for aluminum and magnesium alloys because of The physical activation consists of heating at high temperature
their superior characteristics. In particular, aluminum or magne- under a carbon gasication reactant (H2O, CO2, air). In other words,
sium composite alloys with Mg2Si dispersoids fabricated by pow- carbonization is followed by the activation of the resulting char at
der metallurgy or in-situ casting process show high mechanical elevated temperature in the presence of suitable oxidizing gases. It
properties and a good wear resistance due to the uniform distribu- is possible to attain any degree of conversion of carbon in the rice
tion of ne Mg2Si particles in the matrix [78,282285]. husk by rst pyrolyzing the husk to get reactive char and subse-
The solid-state synthesis of Mg2Si compounds by reaction of quently reacting this char with steam and carbon dioxide at 800
SiO2 with magnesium were suggested by Kondoh et al. [78]. They 900 C. If the nitrogen atmosphere of carbonized rice husk replaces
extruded the compact of mixture AZ31 alloys and rice husk wastes by atmospheric air, carbon dioxide and steam, at various tempera-
burned at 1000 C. It was found that acid treatment of rice husk has tures, different results will be achieved [288]. By increasing the
a dramatic effect on the reaction between magnesium alloy pow- temperature, non-carbonaceous materials are rst removed in gas-
der and rice husk ash. It can be attributed to the reactivity of high eous form. Then freed atoms of elementary carbon are irregularly
purity and ne and amorphous structure of SiO2. grouped into the elementary micro crystallites. The irregular
Bose et al. [63] prepared Mg2Si by alloying technique. Appropri- arrangement creates free interstices that trap tarry hydrocarbon-
ate amounts of prepared white ash and commercially available ates on their way out. Therefore, the resulting carbonized material
99.9% pure magnesium powder were thoroughly mixed and then tends to have low absorption capacity due to blockage of the inter-
tightly packed in an MgO-coated (inside) selemenite crucible and stices. Such carbonized material can only be activated by removing
then red at about 650 C inside a mufe furnace. The amorphous the tray substances through heating them in a steam of suitable
SiO2 was thus reduced to form silicon according to the following oxidizing gases [289]. Ganesh and Dutt Grover [290] reported that
reaction: the samples pyrolyzed under 600 C followed by carbonization
under the air ow, yield carbon free as well as the samples which
SiO2 2Mg Si 2MgO SiO2 unreacted 32 were subjected to steam and carbon dioxide. In this method disor-
The resulting mass after reduction was successively leached ganized carbon is burned-off completely and no trace of carbon is
with HC1 and HF to remove MgO and unreacted SiO2, respectively, detected in the samples. By increasing the pyrolyzing temperature
and then used for preparing Mg2Si by the alloying technique. up to 800 C the carbon disorganized achieve almost micro crystal-
Appropriate quantities of obtained silicon and magnesium powder lite phase. In addition, by subjecting to oxidant gas, the reaction
(both 99.9% pure) were intimately mixed and then red inside an just proceeds on carbon atoms at the edge and corners of elemen-
alloying furnace at 500 C for 24 h under an H2 atmosphere. The tary of micro crystallite, sites which are very reactive [289]. It was
alloying took place according to the reaction: reported that by pyrolyzing rice husk at 900 C, carbon reacts par-
tially with the silica of rice husk. The carbonsilica bonds are
Si 2Mg Mg2 Si 33 strong and stable, consequently combined carbon does not become
oxidized, even under oxygen at temperatures as high as 1200 C. In
Umeda and co-workers synthesized amorphous and porous sil-
the case of the samples that were subjected in the atmosphere of
ica particles originated from rice husks, which were coated with
steam and dioxide carbon, it was explained that the carboncarbon
CNTs, also contained in the pores. The in situ synthesis of Mg2Si
dioxide and carbonsteam reactions are both endothermic and
and MgO via deoxidization and oxidation reaction occurred from
result in two moles of gaseous products for each mole of gaseous
the elemental mixture of pure magnesium and CNTSiO2 compos-
reactant (reactions (34) and (35)). The endothermic reaction
ite particles via the spark plasma sintering process [286]. Although
restricts further increase in the local temperatures of the reactants.
the reports on the preparation of Mg2Si with rice husk is scarce, it
Further, the doubled increase in the volume of the products during
is expected that the growing interest will encourage numerous
these reactions exerts increasing pressure, resulting in progressive
publications in this eld.
fracture of the already fragile char [290].
C s CO2 g 2CO g DH 174 kJ=mol 34
10. Activated carbon
C s H2 O g CO g H2 g DH 131 kJ=mol 35
In addition to silicon, silica, Si3N4 and SiC, activated carbon was
prepared separately from rice husk. According to different burning Since the carboncarbon dioxide reaction is slower than the
temperature of RH in air always silica ash varying in color from carbonsteam reaction under similar conditions, the removal of
grey to black and inorganic impurities along with unburned carbon carbon tends to be partial for the former reaction. Further, the car-
is forming. Very ne and closed pores are created during these bonsteam reaction is catalyzed, owing to the presence of alkali
steps. The purpose of activation is to enlarge the diameter of the metal oxides, especially potash, in ash and therefore is more effec-
pores and to create new pores. According to the International tive in removal of carbon from char. Molina-Sabio and co-workers
Union of Pure and Applied Chemistry (IUPAC), the pores of porous [291] reported that carbon dioxide activation mainly causes the
materials are classied into three groups: micropores (width creation of microporosity. However, steam activation expands
d < 2 nm), mesopores (2 nm < d < 50 nm), and macropores the micro porosity from the early stages of the activation process,
(d > 50 nm) [287]. Therefore, due to extensive surface area, high even in the case in which the removal rate of carbon atoms from
degree of surface reactivity, and favorable pore size distribution, the char is the same for the two activating agents. Then, the
activated carbons absorb many interests. Basically, there are two obtained char was leached with dilute hydrochloric acid at
60100 C for 23 h. During leaching, different impurities like oxi- route is achieved easily. However, Na2CO3 has poor activation
des of sodium, potassium and magnesium were dissolved and then effect and K2CO3 is the optimum activated agent. Different pore
removed from the char by ltration under vacuum. The char was size was found to be linked to the nature of the alkali cation of
then washed thoroughly to remove the remaining acid and then the carbonate in the following order: Li < Na < K < Rb < Cs [302
dried. 304]. The effect of alkali carbonate in the activation process can
be related to formation of porosity due to SiO2 interaction with
the carbonates, which proceeds with formation of potassium and
10.2. Chemical activation sodium silicates and CO2. CO2 reacts with the carbon phase with
formation of CO, according to reactions (36) and (37):
Chemical activation (ChA) can be accomplished in a single step
by carrying out thermal decomposition of raw material with chem- M2 CO3 SiO2 M2 SiO3 CO2 36
ical reagents (dehydration agents) at low temperature. In prepar-
ing of activated carbon, base-leaching and acid-washing as the CO2 C 2CO 37
rst and last stages, respectively, can be done. The base-leaching where M = Na, K. In addition, carbonates can interact with the car-
procedure can effectively remove ash and improve the surface area bon phase from 700 C to 950 C; the process completes in accor-
and pore volume of the simple. The acid-washing procedure can dance with reaction (38):
act as a cleaning process to remove metallic impurities and resid-
ual activating agent [292,293]. However, the pre-treatment of the K2 CO3 2C 2K 3CO 38
rice husk with HF acid can also lead to removal of SiO2 from the Activation reaction between alkali hydroxide and rice husk is
composition of the materials. complicated. Ordinarily, the reaction may be as follows [305,306]:
In comparison to physical activation, chemical activation pro-
vides three important advantages. (i) The lower temperature at 4KOH C K2 CO3 K2 O 2H2 39
which the process is performed, (ii) the global yield of chemical Considering the decomposition of potassium hydroxide and the
activation tends to be greater because burn off char is not required reduction of carbon, some reactions given below may also be fol-
and (iii) obtaining activated carbon with a smaller pore size [294]. lowed simultaneously.
Some special factors dene the quality of obtained activated car-
bon, such as the ratio of the activation agent to rice husks, activa- 2KOH K2 O H2 O 40
tion temperature and time. Experimental results revealed that the
BET surface area, pore volume, and average pore diameter of the C H2 O H2 CO 41
resulting porous carbon generally increase with increasing activa-
tion time, activation temperature and ratio of activation agents.
CO H2 O H2 CO2 42
The mechanism of pore development in active carbon (AC) can
K2 O CO2 K2 CO3 43
be summarized as two main antagonic contributions to SBET: the
formation and disappearance of micropores. Fig. 28 exhibits the
K2 O H2 2K H2 O 44
scheme of the mechanism for pore development in ACs.
On the one hand, appropriate conditions like the mass ratio
K2 O C 2K CO 45
were benecial to the development of pore structure. Under this
condition, the formation rate of micropores was greater than the
K2 CO3 2C 2K 3CO 46
disappearance rate, hence increasing the SBET of AC. When the for-
mation and deformation rates were equal, pore development
K2 O SiO2 K2 SiO3 47
reached a state of dynamic equilibrium with the maximum SBET.
On the other hand, extreme conditions accelerated the widening The reaction (39), is the special characteristic of this method. It
of micropores. Many micropores were destroyed by collapsing or is important in the activation process, amorphous carbon and silica
merging into mesopores and macropores, leading to reduction of in the rice husk disappear through the above reactions and pore
SBET [295]. The most widely used chemical agents include ZnCl2, structure is formed.
H3PO4, H2SO4, KOH and K2CO3 [82, 296299]. ZnCl2 and H3PO4 From both economical and environmental perspectives, phos-
are usually used for activating biomasses which are rich in cellu- phoric acid activation can be another appropriate alternative
lose, hemicellulose and lignin such as wood and nut shell because in this case the activation temperature is much lower
[300,301]. KOH, K2CO3 and Na2CO3 are usually used for activating (usually around 400500 C) than that of physical and alkali
residue, which is rich in ash. Nevertheless, compared with alkali hydroxides activations (>650 C). In addition, phosphoric acid can
hydroxide, the carbonate has lower cost, and the green recycling be recovered and it can be removed easily after activation of the
Fig. 28. The schemic of the mechanism for pore development in ACs [294].
carbon by washing with hot and cold water. The percent of H3PO4 and subsequent chemical activation, produces lower specic area
recovery was calculated with Eq. (48) [307]: than the process where the HF treatment is applied before pyroly-
sis at the same temperature. This outcome on the specic surface
product weight before washing product weight after washing
Recovery area has been observed particularly when ZnCl2 was used as acti-
H3 PO4 weight for impregnation
vating agent [17]. Several authors showed that pre-calcination
100 under N2 has a dramatic inuence on the porosity of nal active
48 carbon activated by agents like NaOH, KOH, K2CO3. However, it
Nevertheless, the pore size due to using H3PO4 is lower in com- was shown pre-calcination under the atmosphere of N2 does not
parison to other activation agents. The lower surface areas of have any inuence on the pores of active carbon activated by phos-
obtained carbon may be due to high retention of phosphates in phoric acid [304,306,311,312]. The change in the value of the spe-
the carbon structure. Reaction of H3PO4 with the precursor matrix cic surface area and the pore volume in the process of treatment
can create phosphate esters and other polymerization by-products and activation of the rice husks are represented in Table 8.
that bind strongly to the solid matrix [308].
Another activated agent was proposed by Uzunova et al. [17]. 10.3. Microwave heating technology
Rice husks were activated with carbamide. The probable mecha-
nism of activation is associated with the interaction of carbamide Recently, microwave heating technology has been applied
with the OH and COOH groups, whereupon the NHCONH2 and instead of conventional heating in chemical activation processes. A
the CONHCONH2 groups are obtained. The latter groups at a tem- comparison of the results of ChA using conventional heating and
perature of 700 C and in the absence of air decomposed into NH3 microwave heating processes for the same precursors revealed that
and CO2. Thereupon part of the nitrogen of the carbamide can be impregnation with the microwave method leads to the development
included in the structure of the carbon, forming the so called diazo of relatively higher surface areas and more economically competi-
groups (N@N). tive than those obtained in impregnation via conventional heating.
In order to obtain activated carbon, in all those mentioned pro- Combination of microwave heating with other activation agents like
cedures, the rice husk was exposed to single step of chemical acti- KOH, NaOH and ZnCl2 have been proposed by some authors [313
vation. However, it has been found pre-calcination in absence of air 315]. This results in a reduction in the processing time, energy con-
before chemical activation has a great effect on the porosity of the sumption and the number of steps involved in the overall process,
porous carbons [309]. Comparison of all resulting porous carbons which eliminates the need for other reagents and devices.
indicates that an activation process can produce carbons with
micro-porosity and meso-porosity. Microporous carbons are pro- 11. Summary and conclusions
duced with higher pre-calcination times. Increment in porosity
due to pre-calcination can help the activating agents to penetrate In recent years as a source of silicon and carbon based mate-
the interior or disperse well. The effect of carbonization tempera- rials , rice husk has been strategically considered and utilized for
ture should also be considered. The carbonization at temperature synthesis of high purity ceramic phases like Si3N4, SiC, silica and
higher than 700 C leads to formation of less stable and inactive nano silica, Mg2Si, porous silicon and carbon materials. Conversion
carbon structure, which is connected with the presence of small of rice husk into value-added engineering materials may have a
quantities of oxygen containing groups, that diminishes the poros- threefold impact: (i) increase in the availability of inexpensive sil-
ity content of the material [310]. It was also reported that rice husk icon based resources, (ii) contribution as part of the solution to the
pyrolysis at 450 C followed by silica removal with HF and a nal waste disposal issue, and (iii) knowledge generation through the
Table 8
The pore volume and specic area of activated carbons derived from rice husk under different activation chemical processes.
Activation agent Process Final temp. (C) Impregnation ratio Pore volume (cm3/g) Specic area (m2 g1) Refs.
ZnCl2 ChA 600 1 0.380 750 [308]
ChA 600 10 wt.% 1.365 480 [327]
ChA 500 2 1.344 2434 [292]
ChA 300 1 0.463 578 [294]
NaOH ChA & Pre-Cal 800 3 0.91.9 >2500 [306]
Dry ChA & Pre-Cal 800 3 1.517 2841 [328]
ChA 800 0.346 933 [82]
H3PO4 ChA & Pre-Cal 900 4.2 0.4 438 [304]
ChA & Pre-Cal 800 4.2 0.373 379 [304]
ChA 500 75% 0.43 376 [329]
ChA 400 649 [307]
ChA 450 1.5 0.735 1295 [330]
ChA 500 2 1.315 1741 [292]
KOH ChA 450 1.5 0.97 1930 [330]
ChA & Pre-Cal 900 4 1.39 2410 [312]
ChA 800 4 0.46 900 [312]
ChA & Pre-Cal 800 4 0.94 1917 [331]
ChA & Pre-Cal 800 4 1.9 3202 [332]
ChA 850 2 1.22 1936 [333]
H2SO4 ChA Under vacuum 100 0.529 704 [334]
K2CO3 ChA & Pre-Cal 900 4 1.54 1676 [311]
FeSO47H2O ChA 600 30% 110 [327]
FeCl36H2O ChA 600 30% 13 [327]
CaCl22H2O ChA 600 30% 53 [327]
KCl ChA 600 30% 64 [327]
Urea ChA & Pre-Cal 700 5 0.81 1259 [17]
ChA: chemical activation.

ChA & Pre-Cal: chemical activation and pre-calcination.
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Chemical Engineering Journal 264 (2015) 899935

Contents lists available at ScienceDirect

Chemical Engineering Journal

Review on the physicochemical treatments of rice husk for production

Applications of rice husk and its derivatives.

Corresponding author. Tel.: +52 (844) 4 38 96 00x8678.

3.5. Insulator. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 905

2. Biobers from agricultural by-products for industrial 2.1. Rice husk

adding a buffer solution of acetic acid, aqueous chlorite and dis-

3. Application of rice husk

India, Pakistan, Bangladesh, Sri Lanka, Australia, Thailand, Indo-

Organic constituent SiO2 (wt.%) Silicon (wt.%)

Fig. 5. Schematic of applications of derived rice husk.

produced gas composition which should be maintained between

3.9. Production of potential reinforcement for fabrication of MMCs and

Because of the high silicon content in RHs, more extensive stud-

Composite Fabrication route Starting material Observations Refs.

illustrates the division of thermal production of rice husk ash into

4.1.1. Rotary kiln

Fig. 11. Schematic of cyclonic furnace [123].

Table 4 tridymite and quartz in RHA. By increasing the temperature up to

Treatment Metallic constituents as oxides (ppm)

hot-water-treatment residue is applicable to the preparation of 5. Silicon carbide

FT-IR spectra of samples heated to 1240 C showed that some

namely, oxidation of SiC. In addition, the reduced metal catalyst

impurities in the RH, resulting in higher purity of RHs with a por-

6.3. Microwave heating

Recently, the microwave heating method was developed to syn-

stress applications because of its excellent properties such as high

Reaction Temp. (C) DH (kJ/mol) DG (kJ/mol) Adiabatic Temp. (C)

ChA: chemical activation.

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