Ind. Eng. Chem. Res.

2001, 40, 5861-5877 5861

REVIEWS

Silicon-Based Materials from Rice Husks and Their Applications

Luyi Sun*
Department of Chemistry, The University of Alabama, Tuscaloosa, Alabama 35487-0336

Kecheng Gong
Polymer Structure & Modification Lab, South China University of Technology,
Guangzhou, 510640, P. R. China

Rice husk (RH) has now become a source for a number of silicon compounds, including silicon
carbide, silica, silicon nitride, silicon tetrachloride, zeolite, and pure silicon. The applications of
such materials derived from rice husks are very comprehensive. The methods of synthesizing
these silicon-based materials from RHs and their applications are reviewed in this paper.

Contents 4.3.1. Preparation of Ultrafine 5868

1. Introduction 5861 Silica Powders
4.3.2. Production of Silica Films 5868
2. Structure and Components of RH 5862
4.3.3. Dual-Phase Fillers 5868
3. Silicon Carbide 5862
4.3.4. Energy 5868
3.1. Preparing Silicon Carbide from 5862
RHs 4.3.5. Applications in Alloys and 5868
3.1.1. Pyrolysis Method 5862 Ceramics
3.1.2. Plasma Method 5864 5. Silicon Nitride 5868
3.2. Applications 5864 5.1. Preparing Silicon Nitride from 5869
RHs
3.2.1. Composites 5864
5.2. Summary 5869
3.2.2. Semiconductor Materials 5864
6. Silicon Tetrachloride 5870
3.2.3. Abrasive Materials 5864
6.1. Preparing Silicon Tetrachloride 5870
3.3. Summary 5864 from RHs
3.3.1. Energy 5864 6.2. Summary 5870
3.3.2. SiC Purity 5864 7. Silicon 5870
3.3.3. Whisker Content 5864 7.1. Preparing Silicon from RHs 5870
3.3.4. Improvements on Defects 5864 7.2. Summary 5871
3.3.5. Application of CVD 5865 8. Zeolite 5871
3.3.6. Preparing SiC using 5865 8.1. Preparing Zeolite from RHs 5871
Microwave Radiation
8.2. Summary 5872
3.3.7. Composites 5865
9. Others 5872
4. Silica 5865
10. Conclusions 5872
4.1. Preparing Silica from RHs 5865
11. Literature Cited 5873
4.1.1. Direct Combustion 5865
4.1.2. Combustion after 5866
Pretreatment
1. Introduction
4.1.3. Hydrothermal Method 5866
4.1.4. Reaction with Sodium 5866 The production of rice, one of the major food crops in
Carbonate the world, generates one of the major wastes of the
4.1.5. Reaction with Sodium 5866 world, namely, rice husks (RHs). Efforts to utilize RHs
Hydroxide have been handicapped by their tough, woody, abrasive
4.2. Applications 5867
4.2.1. In Polymer Materials 5867 * Author to whom correspondence should be addressed.
Department of Chemistry, The University of Alabama, Tus-
4.2.2. In Cement 5868 caloosa, AL 35487-0336. Tel.: 205-391-4502. Fax: 205-348-
4.3. Summary 5868 9104. E-mail: sun005@bama.ua.edu.

10.1021/ie010284b CCC: $20.00 © 2001 American Chemical Society

Published on Web 10/31/2001
5862 Ind. Eng. Chem. Res., Vol. 40, No. 25, 2001

Table 1. Analysis of RHA1

component SiO2 K2 O Na2O CaO MgO Fe2O3 P2O5 Cl
content 86.9-97.3 0.58-2.5 0.0-1.75 0.2-1.5 0.12-1.96 trace-0.54 0.2-2.85 trace-0.42

nature; low nutritive properties; resistance to degrada- involved in the production of ultrafine silicon carbide.10
tion; great bulk; and high ash content.1 Such efforts Therefore, there is a need to identify new raw materials
have resulted in minor usage, mostly in low-value and new methods for manufacturing silicon carbide.
applications in agricultural areas or as fuel. Little
advantage is taken of the RHs and pollution is caused 3.1. Preparing Silicon Carbide from RHs
in such disposal processes. However, because of the high
silicon content in RHs, the utilization of RHs has been RHs contain 15-20 wt % silica and a number of
significantly widened in the past few decades. At organic constituents that will yield carbon when ther-
present, RHs are the raw materials for the production mally decomposed. Therefore, RHA contains two neces-
of a series of silicon-based materials, including silicon sary raw materials for the preparation of silicon car-
carbide, silica, silicon nitride, silicon tetrachloride, pure bide: SiO2 and C. With the very high surface area and
silicon, and zeolite.2-4 intimate contact available for the carbon and silica in
RHs, it is possible to form SiC at relatively low tem-
2. Structure and Components of RH perature6 (much lower than indicated by thermody-
namic and kinetic calculations).11 In addition, the silica
Rice husks mainly contain lignin, cellulose, and in the RHs can maintain the initial structure of the RHs.
hydrated silica. Reports have been published on the Both the low density and the space in the raw materials
composition, properties, and intended uses of RHs since facilitate the production of silicon carbide.12 Therefore,
at least as early as 1871.1 Silicon enters the rice plant RHs are the most economical and promising raw mate-
through its root in a soluble form, probably as a silicate rial for producing silicon carbide. Since the pioneering
or monosilicic acid, and then moves to the outer surface work of Lee and Cutler in 1975,13 many studies have
of the plant, where it becomes concentrated by evapora- been reported. The silicon carbide made from RHs is
tion and polymerization to form a cellulose silica mem- usually a mixture of silicon carbide powders and whis-
brane. There is quite general agreement that the silica kers, but through control of the reaction conditions,
is predominantly in inorganic linkages, but some of the silicon carbide whiskers can be obtained as the main
silica is also bonded covalently to the organic com- product. Compared with traditional processing, this
pounds. This portion of the silica cannot be dissolved method is simpler and more economical,14 and it can
in alkali and can withstand very high temperatures.5 dispose of RHs without pollution.
Characterizations by SEM, energy-dispersive X-ray
analysis, AES, etc., suggest that the silica is mainly 3.1.1. Pyrolysis Method
localized in the tough interlayer (epidermis) of the RH
and that it also fills in the spaces between the epidermal Usually, the pyrolysis method of preparing SiC from
cells.1,4,6,7 RHs consists of two stages: first, the RHs are coked at
In general, rice husk ash (RHA) might well be 500-900 °C to obtain coked RHs; then, they are fired
considered slightly impure silica. The content of silica at higher temperatures (1500-1650 °C) in an inert or
and all impurities in RHA vary depending on the reducing atmosphere to form silicon carbide.15-17 How-
variety, climate and geographic location.1 ever, the first stage is not necessary. Some research has
even shown that the yield of SiC from raw RHs is higher
than that from burned RHs.18,19 The produced SiC is
3. Silicon Carbide
usually cleaned with an acid treatment to remove small
Silicon carbide is extremely hard and has a high amounts of amorphous material and wool.20 Because the
thermal conductivity, high thermal-shock resistance, ratio of silica and carbon is less than the optimum ratio
high hot strength, high melting point, a low coefficient for silicon carbide formation, usually either silica is
of thermal expansion, good oxidation resistance, and added or carbon is removed to regulate this ratio.21-23
good corrosion resistance to acid and base. It has been According to whether pretreatment is performed and/
widely used in many industries. The process developed or a catalyst is used, pyrolysis methods can be divided
by Acheson of reacting sand and coke in a resistance into three categories.
furnace to produce silicon carbide is still the basic 3.1.1.1. Direct Pyrolysis. This is the most direct
manufacturing process used today.8 The most critical method, as neither pretreatment nor a catalyst is used.
manufacturing issues in recent years have been the cost A series of experiments have shown that the results of
and availability of coke, the cost of electricity, and this synthesis approach are acceptable.7,15,16,18-20,24-27
environmental considerations.9 For the manufacture of Patel et al. disclosed the reason a catalyst was not
high-performance ceramics by sintering or hot pressing, necessary: the existence of trace elements in RHs, some
other methods of synthesis are sometimes used to of which (Fe, Mg, etc.) can impart a catalytic effect.20,24
prepare high-purity, very fine reactive powders. Such The control of temperature and pressure has always
processes include plasma-arc synthesis, continuous feed been found to be important.13 As reaction conditions
through an induction furnace, batch reaction of silica change, the optimal temperature and pressure for
and carbon in CO or inert gas, decomposition of poly- forming SiC also change. In general, 1550-1600 °C is
carbosilanes, and chemical vapor deposition (CVD).8 favorable.
Note that the variable costs for these fine reactive To increase the reaction rate and the production rate,
powders are an order of magnitude higher than those researchers have regulated the reaction conditions and
for materials produced with Acheson furnace. This has invented some new reaction methods. It was found that,
restricted wide-scale commercialization. The production instead of slow heating and holding for a long time at
of silicon carbide whiskers has problems similar to those pyrolysis temperatures, rapid heating and holding for
 Ind. Eng. Chem. Res., Vol. 40, No. 25, 2001 5863

a short period at high temperatures increases the and mature SiC whiskers were evident. Residual free
production rate in continuous operation, so the rapid carbon in the product was 1/11 of that for RHs that were
heating method was adopted. In this method, raw RHs heat-treated without enzyme treatment.
without any pretreatment are rapidly (300 ( 25 °C/min) Alkali pretreatment has also been reported.5 Strong
heated to high temperature (1300-1600 °C). SiC forms alkalis such as NaOH can dissolve all of the SiO2
from raw RHs heated to 1350 °C, whereas neither silica present in free form but cannot dissolve the SiO2 bonded
nor carbon crystallizes even at 1600 °C. In addition, to the organic molecules, which amounts to about 5%.
some other studies have found that slow heating de- In contrast, weak alkalis such as NH4OH cannot tackle
creases the reactivity of silica and carbon in the RHs the structure of RHs.
by increasing their degree of crystallization.25,28,29 In summary, the main purpose for pretreatment is
In contrast with rapid heating, multistep pyrolysis, to improve the purity of the SiC produced.
which involves the maintenance of different tempera- 3.1.1.3. Pyrolysis with Catalyst. The incorporation
tures for different periods of time during the heating of a catalyst greatly increases the reaction rate. Several
process, was found to result in an even higher produc- types of catalysts, including Fe, Co, Ni, Pd, and Cr, have
tion rate.18,19 been tried.5 The effect of different catalysts on the
The effect of pressure is also significant. It was found formation of SiC from burned RHs was studied over a
that both a high localized CO concentration and its temperature range of 1200-1600 °C. It was shown that
continuous removal help to increase the total SiC catalysts decreased the crystallization of carbon and
yield.26 Therefore, inert gases such as argon and nitro- silica in RHs and accelerated the formation of SiC.28,29
gen have often been used to drive away CO, which Narciso-Romero et al.33 compared the syntheses of SiC
results in the formation of good-quality SiC.15 Krish- from RHs with and without the use of a catalyst (iron,
narao et al.15,17 did systematic studies on the effects of cobalt, and nickel). They found that the introduction of
pressure. By regulating the pressure from 101.3 to 165.5 a catalyst increased the reaction rate and that the yield
kPa, they found that the increase of the pressure was up to 3 times that for the uncatalyzed reaction. The
resulted in (i) an increase in the crystallization of silica general behaviors of the three catalysts were similar,
and carbon in RHs, (ii) an increase in the temperature although nickel was the most effective in terms of
of SiC formation from 1100 to 1150 °C, and (iii) reaction rate and cobalt was best in producing larger
decreases in the formation of SiC whiskers and in the crystal sizes. Other studies have shown that cobalt
total SiC content. They also studied SiC formation catalyst is not advantageous to the formation of SiC
through vacuum pyrolysis and found that, under such whiskers.28,29 The effect of the morphology of the
conditions, the formation of SiC from raw RHs is higher catalyst was also evident. The reaction rate is enhanced
than that from burned RHs.26,30 with increasing surface area of the catalyst.13 Therefore,
3.1.1.2. Pyrolysis after Pretreatment. The most RHs have sometimes been impregnated in FeCl234 or
typical pretreatment is acid leaching, and HCl is most FeSO435 solution to achieve a better catalysis effect.
often used. Krishnarao et al.31 treated RHs by boiling Catalysts can also decrease the reaction temperature.
them in 5 N HCl for 1 h. The washed and dried acid- In the presence of CoCl2, the optimum temperature was
treated raw rice husks (TRRHs) and untreated raw rice g1400 °C, whereas when CoCl2 was not present, con-
husks (RRHs) were directly pyrolyzed (without precok- siderable quantities of SiC formed only above 1500 °C.36
ing) in argon atmosphere at different temperatures New research has shown that alkali metal oxides used
between 1050 and 1600 °C. Silica obtained from TRRHs as catalyst-accelerators can further accelerate the
has a lower level of impurities than that obtained from formation of SiC. The reason is that the addition of
RRHs. Acid treatment was found to decrease the degree alkali metal oxides can lower the melting point of silica,
of crystallization of silica and carbon in RHs, but while the reaction of silica and carbon is the rate-
whisker formation was also decreased in TRRHs. Boric determining step.22 Another study showed that the
acid has also been used to pretreat RHs. Raman et al.32 addition of a mineralizer can further reduce the reaction
mixed RHs with textile-grade polyacrylonitrile (PAN) temperature.34
fibers dissolved in dimethylformamide in a weight ratio When a catalyst is present, control of the temperature
of 10:1. Boric acid was added to the mixture with a is still very important. For example, one study found
silica/boric acid ratio of 10:1, and the mixture was that, when cobalt was present, rapid heating increased
stirred well. The dried mixture was heated in a furnace the formation of SiC whiskers,28 whereas slow heating
fitted with an alumina tube in argon atmosphere to 1450 (5 °C/min) stabilized the silica and carbon by increasing
°C for 4 h. The sample was also cooled in argon. It was their degrees of crystallization.29
found that the incorporation of boric acid into the Another discovery that is worth mentioning is that,
mixture of RHs and PAN yielded SiC whiskers with a during vacuum pyrolysis, the addition of Si3N4 to RHA
better aspect ratio. can increase the yield of SiC whiskers and reduce the
Enzymatic treatments, whose purpose is to remove amounts of SiC particles and excess carbon. At 1400 °C,
excess carbon for silicon carbide formation in RHs, have mixtures with 50 and 60 wt % of Si3N4 were found to
also been used.21 Powdered RHs can be delignified with yield masses of SiC whiskers without any free carbon
NaOH solution and treated with a mixture of cellulases and with about 5 wt % of unreacted SiO2.30 Therefore,
(acucelase and Meicelase) to hydrolyze the cellulose of nitrogen can be considered to substitute the inert gas
the husks. In RHs pretreated with 0.5% NaOH, silica in the reaction to produce some Si3N4, which, in turn,
was enriched to 29.5 wt %, and 288 mg of sugar was can help in the production of silicon carbide whiskers.
recovered from 1.0 g of RHs after a 5-day cellulase In summary, catalysts provide the three advantages
treatment. The C/SiO2 ratio reached 0.74, which is near of (i) increasing the reaction rate, (ii) increasing the
the optimum ratio for silicon carbide formation. When yielding of silica, and (iii) decreasing the reaction
this silica-enriched sample was heated at 1600 °C in temperature. In addition, catalysts can also determine
an atmosphere of argon, R-SiC and β-SiC were formed, the formation mechanism of SiC whiskers.37
5864 Ind. Eng. Chem. Res., Vol. 40, No. 25, 2001

3.1.2. Plasma Method based on SiC’s wide energy band gap, high electron
As mentioned above, the effect of CO from the reaction saturated drift velocity, high thermal conductivity, and
can be sufficiently significant to decrease the reaction other factors. Silicon carbide is also physically rugged
rate; thus, CO needs to be constantly removed with and chemically inert, which is good for semiconductor
argon. In addition, the reaction time can be reduced devices operating in harsh environments. Its excellent
greatly by increasing the temperature. Both of the above properties were identified many years ago, but unfor-
processes can easily be attained in a thermal plasma tunately, the presence of large densities of micropipe
reactor. Moreover, the very high temperatures (104 °C), defects has prevented the routine production of high-
steep temperature gradients (106 °C/min), and high quality silicon carbide crystals.51,52 The silicon carbide
quench rates (106 °C/s) associated with thermal plasmas from RHs has been reported to be used as semiconductor
can be a unique route for the preparation of ultrafine materials,53,54 but because of the high requirements on
SiC from RHs. In contrast to other methods, it is very the purity, some special separation is needed in the
easy to realize continuous production and to control manufacturing process.
reaction parameters in plasma process.38-41
Posttreatment processes such as oxidation and acid 3.2.3. Abrasive Materials
treatment (with H2SO4, HCl, or HF) appear to be
When silicon carbide is used as an abrasive, the
effective in removing the excess carbon, silica, and
requirement on purity is not high. The purity of silicon
mineral oxides. Successive washings can remove chlo-
carbide from RHs is high enough to match this require-
ride and fluoride ions.39,40
ment. The silicon carbide can be either directly used as
3.2. Applications abrasive material or hot-pressed with composites.55
3.2.1. Composites 3.3. Summary
After a lull during the 1960s and early 1970s, interest
in SiC as a fiber reinforcement has experienced a revival Since the first synthesis of SiC from RHs by Lee and
in the past two decades. One of the important reasons Cutler in the 1970s,13 many improvements have been
for this lies in the successful preparation of relatively made, and this technology has been completely indus-
inexpensive high-grade SiC whiskers from RHs.42 Com- trialized. However, further study on the following
pared with many other ceramic materials, silicon car- aspects is necessary.
bide has a relatively high thermal conductivity and low
coefficient of thermal expansion, giving it a relatively 3.3.1. Energy
favorable thermal shock resistance.43,44 The strength
In the first step of the preparation of silicon carbide
and hardness of ceramics and alloys can be greatly
from RHs, making full use of the energy from the
enhanced by the addition of SiC particles into their
combustion of RHs is usually ignored. In fact, by
matrixes. Generally, the reinforcing and toughening
regulating the proper reaction condition, combustible
effects of SiC whiskers are better than those of SiC
gas can be made as a byproduct while the quality of the
particles. The proper aspect ratio is 30-40, aswhiskers
produced silicon carbide is ensured.56 Such energy can
that are too long are hard to distribute. Therefore, a
be used in the other steps of manufacturing.
high content of whiskers is preferred in the production
of SiC from RHs. Usually, thick whiskers are suitable
for ceramic matrix composites, whereas thin whiskers 3.3.2. SiC Purity
are suitable for metal matrix composites.45 RHs contain some inorganic components other than
3.2.1.1. Ceramic Matrix Composites. Upon being silica, which become Fe2O3, K2O, etc., after pyrolysis.
reinforced reinforced by silicon carbide whiskers, a Sometimes, excess carbon is another source of impuri-
ceramic’s fracture toughness can be greatly enhanced, ties. Such impurities have little effect on low-grade
and its flexural strength and thermal conductivity can silicon carbide, but for the high-grade silicon carbide,
also be greatly improved.46 When the whiskers are being particular separation must be carried out.57,58 Now,
introduced into the ceramics, however, attention must more and more high-grade silicon carbide is needed in
be paid to avoid agglomeration, which will result in many fields, which urges the improvement of separation
structural defects.47 Wang et al.44 have successfully techniques and facilities. Some feasible and economic
prepared silicon carbide whiskers from RHs that have technologies for the separation and purification of silicon
good reinforcing properties in ceramic matrix compos- carbide whiskers from RHs have been reported by Xia
ites. et al.,59,60 but even further study to industrialize such
3.2.1.2. Metal Matrix Composites. As early as the technology is necessary.
beginning of the 1980s, the study of aluminum rein-
forced by silicon carbide from RHs was reported. The
3.3.3. Whisker Content
reinforced aluminum not only has a good combination
of room-temperature specific strength and modulus and Because the value of SiC whiskers is higher than that
excellent thermal stability, but it also can be processed of SiC particles, improvements in the technology that
by normal metal working techniques. Such materials increase the whisker content are important.59
are increasingly considered for aerospace applications,
where their high stiffness and strength-to-weight ratios 3.3.4. Improvements on Defects
are additional advantages.48-50
Silicon carbide whiskers produced from RHs contain
3.2.2. Semiconductor Materials a high density of defects. These defects include (i)
Silicon carbide is an important semiconductor for stacking faults and thin twins on close-packed planes
applications in high-temperature electronics, ultraviolet lying normal to the whisker axis, (ii) cavities that are
sensors, and high-speed devices. These applications are 1-20 nm in diameter and are usually confined to a
 Ind. Eng. Chem. Res., Vol. 40, No. 25, 2001 5865

region ∼100 nm wide at the whisker core, and (iii) 4. Silica

partial dislocations lying in radial directions and ap-
parently associated with the presence of cavities. Such Silica not only is an important starting material for
defects greatly affect silicon carbide’s electric properties semiconductors but also plays an important role in the
and thermal conductivity.7,61-63 Selecting the proper plastics, rubber, and photoelectric material industries.74
catalyst and regulating the reaction parameters can There are two kinds of commercial silica: fumed silica
decrease such defects. and precipitated silica. The raw material of fumed silica
is silicon halide. The purity and properties of fumed
silica are excellent, but the amount of energy consumed
3.3.5. Application of CVD and the cost are high. The silica produced through this
CVD has been widely used in the preparation of high- method is mainly used as reinforcement in silicone
grade silicon carbide. At this point, silicon carbide rubber. The raw materials of precipitated silica are
powders,64,65 whiskers,66 fibers,67-69 and even films70 extensive and cheap, and the energy consumed is low.
have been prepared by CVD, although few studies on After modification with a silicon-coupling agent, the
the preparation of silicon carbide from RHs by CVD reinforcing properties of precipitated silica are close to
have been reported. Sharma et al. showed that the those of carbon black, but its general properties are not
silicon carbide whiskers from RHs are very similar to as good as those of fumed silica.75,76
those obtained by CVD with SiO and CO as the primary Because RHs naturally have high contents of silica
reactants.7 Recently, microcoiled silicon carbide fibers and because the silica has a high reactivity, since the
have been prepared by CVD using powder mixtures of beginning of the 1980s, a new way to prepare high-
SiO and coked RHs that were very quickly heated to purity silica from RHs has been intensively investigated.
the reaction temperature.71 Because SiO and CO are the The silicas produced have different applications accord-
intermediate products in the preparation of silicon ing to their qualities.
carbide from RHs, using CVD to prepare high-grade
silicon carbide from RHs should be possible. According 4.1. Preparing Silica from RHs
to the reaction mechanism, SiO and CO can be produced
from the redox of silica and carbon in RHs in the
presence of a catalyst at high temperature. Then, in the 4.1.1. Direct Combustion
second step, the produced SiO and CO can be used to
synthesize silicon carbide whiskers (even film) by CVD. RHs can be directly combusted to produce silica
The technique might be complicated, but considering the without any pretreatment.77-81 In the reaction process,
product’s higher properties, such a method for producing the phase composition of silica in the ash and its surface
silicon carbide should be economical. area depend critically on the combustion temperature
of RHs.77 Combustion instruments also strongly affect
the quality of the silica produced.
3.3.6. Preparing SiC using Microwave Radiation
Properties of the ash obtained by combustion between
Traditional heating usually is done by thermal radia- 400 and 1500 °C have been investigated.78 The SiO2 in
tion or thermal conduction, so the energy only affects RHA formed by combustion below 800 °C was found to
the surface of the sample, which results in a low heating be amorphous. Particles of the ash having an average
rate and long heating period. Considering that the diameter of 20 µm were aggregates of small particles
preparation of silicon carbide from RHs is strict on with a diameter of 2-5 µm. At combustion temperatures
temperature, some new heating methods have been above 900 °C, the SiO2 in RHA consisted of cristobalite
developed, such as fluidized beds and microwaves. and a small amount of tridymite. The surfaces of the
Especially microwave heating, which has been used to ash particles melted, and the particles bonded to each
prepare silicon carbide powders, can achieve total and other. The particle size was 40-60 µm.
rapid heating and creates minimal pollution.72 Because the ash content is relatively high for combus-
tion in a typical furnace, which will strongly affect the
3.3.7. Composites quality, Kapur77 designed a tube-in-basket (TiB) setup
for combusting RHs. In a controlled manner, he found
Compared with silicon-carbide-reinforced metal ma- that the silica in RHs was noncrystalline up to 600 °C.
trix composites and ceramic matrix composites, the The phase transformation in silica began between 600
research on silicon-carbide-reinforced resin matrix com- and 800 °C, with the first appearance of the cristobalite
posites is limited. Considering the high price of the phase in the 800 °C sample. The next transformation
carbon fibers that are used in resin composites, cheap to tridymite started at about 1000 °C and became quite
silicon carbide whiskers from RHs could be a suitable pronounced above 1200 °C. The small amount of quartz
substitute for them. Another advantage of using silicon present in the samples burned at lower temperatures
carbide whiskers as reinforcement lies in the low and disappeared completely by 1200 °C. The cristobalite
requirement on the purity of the silicon carbide whis- and tridymite phases coexisted in the 1400 °C sample.
kers. The main impurities in silicon carbide whiskers The initial increase in the surface area from 60 m2/g in
from RHs are carbon, silica, and silicon carbide par- 350 °C burned ash to 80 m2/g at 600 °C was perhaps
ticles, all of which have little negative effect on resin due to the burnoff of the residual carbon and the
composites’ mechanical properties. opening of new pores. Between 700 and 900 °C, a sharp
Recently, Wang,73 et al. reported the synthesis of drop occurred in the surface area from 40 to only
pentacoordinate silicon complexes from RHA. They are 1 m2/g, which clearly points to the need for controlled
easily hydrolyzed to silica. Such complexes can also be combustion of RHs in order to produce reactive silica
reacted with other reactants to prepare thermally stable ash. Using this TiB burner, the silica ash produced
products. They can also be reacted in situ with SiO2 or consisted essentially of amorphous silica with a rela-
Al2O3 to prepare ceramic matrix composites. tively high surface area of 65 m2/g. In addition to the
5866 Ind. Eng. Chem. Res., Vol. 40, No. 25, 2001

temperature, the duration of heating is also critical to of acid pretreatment. Microbial fermentation has also
the quality of the silica produced .79 been applied to pretreat RHs at low temperatures to
Luan et al.80 studied the combustion of RHs with and release silica in its natural, pure and highly reactive
without coal in the presence of a pilot flame in a form. Such microbiological processes are relatively
modified fluidized bed. The chemical and physical cheap, and if used in combination with acid leaching, it
properties of both the top and the bottom products from can result in the production from RHs of silica that is
the rice husk combustion were strongly influenced by similar to a commercial xerogel. Its purity, specific
two major factors: the feed rate and the feed composi- surface area, and tendency to form fractural structures
tion. The addition of coal to RHs resulted in a much resembles the features of fumed silica.85,93 Bio-pretreat-
smoother temperature distribution in the reactor and ment results in a decrease in organic matter with a
the disappearance of agglomeration. The addition of coal corresponding increase in silica content, greatly de-
also increased the bulk temperature and changed the creasing the carbon content in the silica produced . Its
composition, particle size distribution, and specific disadvantage lies in the long processing time.
surface area of the ash.
4.1.3. Hydrothermal Method
4.1.2. Combustion after Pretreatment In addition to silica, RHs contain organic compounds
and metals. In high-temperature, high-pressure, and
Quite a few kinds of acids (HCl, H2SO4, HNO3, HF)
acidic media with strong oxidation activities, the organic
have been reported to be used in pretreatment,79,82-90
compounds can be decomposed, and the trace metals can
but HCl is surely the most often used.
be turned into soluble ions; then, silica can be obtained.
Chakraverty et al.82,83 found that the leaching of RHs
In this method, the reaction temperature is much lower
in 1 N HCl was effective in substantially removing most
than that used in the combustion method, and it is easy
of the metallic impurities. Acid treatment of RHs prior
to retain the amorphicity of the silica in RHs. Some
to combustion does not affect the structural nature
acids with strong oxidation activities such as H2SO4 and
(amorphicity) of the silica produced . From the stand-
HNO3 are used; sometimes H2O2 is also used as the
point of the amorphicity of the silica produced , mini-
oxidative medium.
mum time, energy requirements, and the cost of pro-
According to Wu’s report,94 by controlling the ratio of
duction, a furnace temperature of 500 °C and combustion
RH, concentrated HNO3, and water at 1:5:5 (by weight)
time of 6 h are considered optimum for converting RHs
and allowing the reaction to proceed for 3 h at 160-
into white amorphous silica. After acid leaching, the
180 °C, high-purity and high-surface-area silica can be
silica produced was completely white in color and had
produced. Longer reaction times and higher contents of
high purity.82
concentrated HNO3 do not affect the reaction results,
The report from Real et al.84 is more attractive. They
but if too much water is added, which leads to a
found that the preliminary leaching of RHs with a
remarkable reduction in the content of concentrated
solution of HCl before combustion at 600 °C could result
HNO3, the result will be the incomplete oxidation of
in relatively pure silica (approximately 99.5%) with a
RHs.
high specific surface area (approximately 260 m2/g) that
Another reported approach95 was similar to that of
was maintained even after being heated at 800 °C. If
Wu, but included the further addition of H2O2. The
the leaching with HCl was performed on the white
weight ratio of H2O2 (30%) to RHA was 5:1, and the
ashes obtained from the combustion of RHs at 600 °C,
volume ratio of concentrated HNO3 to H2O2 was 1:10.
an amorphous silica with the same purity was also
Upon reaction in a sealed vessel at 150 °C for 3 h, high-
obtained, but its specific surface area decreased to
purity (99.99%) silica can be produced.
1 m2/g. Because silica with a high specific surface area
has a high reaction activity, acid leaching greatly 4.1.4. Reaction with Sodium Carbonate
improves the quality of the silica produced , which, in
turn, widens its applications. RHs were first carbonated. The produced RHA was
Other acids, such as H2SO4, HNO3, or their mixture, then reacted with Na2CO3 solution in the proper ratio
have also been used in acid pretreatment.79,82,85-88 for 3 h. After the product was washed, filtered, dried,
The general leaching effects of H2SO4, HNO3 and HCl and ground, silica with acceptable purity was obtained.
are similar, but HCl leaching of RHs is superior to A temperature that is too low will affect the purity of
H2SO4 and HNO3 leaching in removing the metallic the silica produced , whereas a temperature that is too
ingredients.82 In some cases, the chemical posttreatment high will affect the yield and quality of the silica. When
of incinerated RHs has also been performed using HCl.85 the concentration of Na2CO3 is higher than 15%, the
Metal oxides strongly affect the production of silica. yield will be above 90%. The proper reaction tempera-
It has been found that some kinds of metal oxides, ture and time are 600-650 °C and more than 3.5 h,
especially potassium oxide, contained in RHA cause respectively.96
the surface melting of SiO2 particles and accelerate The silica made from this method has good reinforcing
the crystallization of amorphous SiO2 into cristo- properties in rubber. Another advantage of this method
balite.78,79,84,86,91 This behavior is due to the strong lies in the facts that all of the energy in the process is
interaction between the silica and the potassium con- from the energy of the combustion of RHs, no extra fuel
tained in RHs, which leads to a dramatic decrease of is needed, and the main reactant Na2CO3 can be
the specific surface area if K+ cations are not removed recycled. Thus, this method not only is simple and
prior to the annealing of the samples.78,84,92 Therefore, economical but also generates little pollution.96,97
the main effect of acid leaching is to remove metal
oxides, especially potassium oxides. 4.1.5. Reaction with Sodium Hydroxide
Some alkalis, such as NaOH and NH4OH, have also In this method, RHA is first mixed with NaOH to
been used to pretreat RHs.85,87,90 However, the effects produce sodium silicate. Then, the sodium silicate was
of alkali pretreatment are not as obvious as the effects reacted with NH4HCO3, (NH4)2SO4, or H2SO4 to produce
 Ind. Eng. Chem. Res., Vol. 40, No. 25, 2001 5867

SiO2.98-101 The key to this method is the reaction of RHA BRHA has a lower silica content, typically about 54%,
and NaOH. Generally, steam is used to keep the and a substantial carbon content of about 44%. It can
reaction at 150 °C, the reaction lasts 4-5 h, and the also be used as a filler for rubber, but the effect is not
particle size of RHA should be about 100-mesh. The as good as can be obtained with WRHA.113,116
proper concentration of NaOH and mixing speed are 4.2.1.2. As Fillers in Plastics. The application of
also important.98 RHA as a filler in plastics is relatively limited, mainly
If the produced sodium silicate is titrated with 1 N to polypropylene (PP).
HCl, silica gel can be precipitated when the pH falls
With an increase in the RHA loading, a PP compos-
below 10.102-104
ite’s flexural modulus and density increase, whereas its
tensile strength, breaking elongation, and impact
4.2. Applications strength decrease. Yet, RHA still can replace some
The main component of RHA is silica. However, the commercial fillers.117-119
impurities contained in RHA have no obvious negative When a silane-coupling agent is not applied, the melt
effect in many applications; in fact, they even have shear stress and viscosity of PP increase with filler
positive effect on some occasions. Therefore, purification loading. However, if RHA is treated with a silane-
usually is not necessary, and the silica produced can be coupling agent containing the peroxide bis(tert-butyl
used directly. peroxy)diisopropyl benzene, both the melt shear stress
and the viscosity of PP decrease. The degree of viscosity
4.2.1. In Polymer Materials reduction increases with increasing filler, i.e., peroxide,
concentration. A decrease in viscosity is attributed to
Using RHA as a filler in certain polymers results in the peroxide-induced degradation of the PP matrix.120,121
composites with better physical, thermal, moisture This silane-coupling agent can also improve the tensile
resistance, and processing properties, as well as better strength.119 In addition to silane-coupling agents, titan-
economics.105 ate-coupling agents can improve a PP composite’s
4.2.1.1. As Fillers in Rubbers. As early as the impact properties, and zirconate-coupling agents can
1970s, researchers began to perform studies on RHA bring about marginal improvements in the stiffness of
as a filler in rubbers. The combustion conditions are the PP a composite, but their general effects are not as good
key to success in such applications. The carbon-contain- as those of silane-coupling agents.119
ing materials must be burned away, but the use of a
In addition to mechanical and processing properties,
temperature that is too high or a residence time that is
RHA also affects the thermal properties of the compos-
too long will result in a fused crystallized mass with no
useful properties at all.106 Burned RHA yields two ites. The addition of BRHA raises the thermal degrada-
grades of fillers, namely, white rice husk ash (WRHA) tion temperature while maintaining the oxidative sta-
with a high silica content and black rice husk ash bility; the thermal degradation temperature of WRHA
(BRHA) with a low silica content. WRHA can easily be composites was found to be independent of filler loading,
ground to a fine powder. The ground product ranges but the oxidative stability deteriorated with increasing
from 0.1 to 2.0 µm in size (there are some agglomerates, filler content.122 The addition of RHA fillers reduces the
too). It contains 10% carbon (occluded in the ash), as linear thermal expansion coefficient of the composites,
well as trace quantities of various metals, sometimes which improves the dimensional stability of the com-
including iron, which are reported to have little or no posites against thermal effects.122 The stiffness of RHA
effect on its cure or aging properties.107 This WRHA can composites can also be improved by increasing the filler
also be used as a filler in natural rubber (NR), styrene loading, and fillers cause a significant modification to
butadiene rubber (SBR), nitrile butadiene rubber (NBR), the damping properties of the matrix material. Overall,
butyl rubber (BR), ethylene-propylene-diene monomer it can be inferred that the incorporation of RHA fillers
(EPDM), etc.107-111 Especially in epoxidized natural does not result in any detrimental effects to the thermal
rubber (ENR), the addition of WRHA can increase the behavior of the PP matrix and that BRHA composites
tensile strength, tear strength, and hardiness of the seemed to have better thermal degradation and thermo-
rubber.112 As WRHA is predominantly silica, it responds oxidative stabilities than WRHA composites.122 Com-
effectively to silane-coupling agents in improving prop- pared to composites filled with commercial fumed silica,
erties of the rubber compounds. WRHA that has been most of the RHA composites have better impact proper-
modified by silane-coupling agents not only can ef- ties but low tensile and flexural strengths.119
fectively improve ENR’s mechanical properties, such as RHA fillers can also act as weak nucleation agents
tensile and tear strength, but also can improve ENR’s and increase the degree of crystallinity of PP by a small
cure characteristics.107,108,112-114 The cure characteristics margin.122
of WRHA-filled vulcanizates show a close resemblance Studies on polyester filled with RHA have also been
to those of carbon black. This can be attributed to the
reported, but both the tensile and impact strengths of
similarities of filler-related parameters such as surface
the resulting polyester composites decreased with in-
area, surface reactivity, particle size, and metal oxide
creasing filler loading.123
content.113
Generally, WRHA is not as good as fumed silica and In addition to being used in rubbers or plastics, RHA
carbon black, especially in terms of tensile strength and can also be used as a filler in rubber/plastic blends.124,125
tear strength,107,113 but it can replace or partially replace Considering that transferring from RH to RHA results
fumed silica and carbon black on some occasions.114 In in a loss of about 80% of the weight of the RH and that
addition, WRHA can sometimes be combined with other the combustion process can cause pollution, RHs have
fillers, especially with reinforcing blacks. The properties also been directly used as filler in plastics, such as PP126
obtained are linear functions of the amount of the and polystyrene (PS).127 In such cases, the RHs can act
particular filler present in the blend.108,115 as fibers to reinforce the plastics, and the silica in the
5868 Ind. Eng. Chem. Res., Vol. 40, No. 25, 2001

RHs can also have some effect. With chemical modifica- Considering the high value and wide application of
tion of the RHs, the reinforcing effect is acceptable. nanoscale silica, when silica is prepared from RHs,
nanoscale silica is desirable.
4.2.2. In Cement
4.3.2. Production of Silica Films
Because of high energy consumed in cement produc-
tion, some countries short of energy often incorporate Almost all of the silica prepared from RHs is powder;
some other components into cement. RHA from the few reports on silica films are available. Recently,
controlled combustion of RHs is highly pozzolanic.128-134 because of the wide application of silica film in the field
In fact, the incorporation of RHA into cement not only of photovoltaics, such films have attracted increasing
can decrease the cost but can also improve certain attention. At present, the main methods for preparing
properties of the cement. silica films are sol-gel methods, sputtering processes,
The incorporation of RHA into cement paste does not etc., with high technique demands and high costs.154
increase its compressive strength,135-137 but if the RHA One of the methods for makinge silica film involves
is filled in mortar138,139 or concrete,135,140,141 the com- using a sol-gel technique to hydrolyze tetraethyl ortho-
pressive strength of both the mortar and concrete silicate (TEOS), which is expensive. Recently, a novel
increase. The reason might lie in the reduced porosity, pentacoordinate silicon complex73 having properties
reduced Ca(OH)2 content, and reduced width of the similar to those of TEOS has been synthesized from
interfacial zone between the paste and the aggregate RHs. These relatively cheap pentacoordinate silicon
when RHA is present.135 complexes can be substituted for TEOS as the raw
In addition to compressive strength, RHA can also material to for preparing silica films.
increase concrete’s resistance to acid138,142,143 and sul-
fate,138 flexural strength,138 carbonation,143 penetra- 4.3.3. Dual-Phase Fillers
tion,143 etc. One of the main reasons for the improve-
ment of concrete properties upon addition of RHA might In 1995, one kind of new filler, carbon-silica dual-
be the formation of more C-S-H gel and less portlan- phase (CSDP) filler, was developed by Cabot Corpora-
dite in concrete as a result of the reaction occurring tion. This filler, as indicated by its name, consists of two
between the RHA and the Ca2+, OH-, or Ca(OH)2 in phases: a carbon phase, with finely divided silica
the hydrating cement.143 RHA will affect the volume domains dispersed therein. In various polymers, the
changes of the concrete, but the volume changes will CSDP filler exhibits high filler-polymer and lower
be within the limit specified in the American stan- filler-filler interactions.155
dards.136 Considering that RHA also contains both silica and
When expansive cement was partly replaced by RHA, carbon, it might also be able to be used directly as a
its compressive strength increased markedly, and its CSDP filler. Worth mentioning are the intimate disper-
chloride permeability decreased significantly,144 whereas sion and contact of silica and carbon in RHA and the
its total expansion decreased slightly.144,145 fact that the content of silica and carbon in RHA can
Because RHA can react with lime and water, RHA easily be regulated by the combustion conditions. Al-
has sometimes been mixed with lime first and then filled though the silica content is high in RHA but low in
into cement.146-150 The properties of lime-RHA cement CSDP fillers, considering the trend of the replacement
are acceptable. It can be used as the replacement of of carbon by white fillers, RHA might be a kind of filler
portland cement in some application. Sometimes, RHA with huge potential in the future.
has even been directly blended with lime and then used
as a construction material.146 If kaolin clay is available, 4.3.4. Energy
it can be added during the incineration of RHs to All of the methods mentioned above do not consider
improve the binder quality. Blending portland cement the energy produced in the process. Lin et al. designed
with the incinerated kaolin can further increase the a gasification process that can produce amorphous silica
cost-effectiveness.139,151 and, at the same time, generate 10 kW of electric power
by gasifying 28 kg/h of RHs.156 Such a measure, which
4.3. Summary can make full use of the thermal energy produced from
combustion and ensure the good quality of the silica
4.3.1. Preparation of Ultrafine Silica Powders produced , must make the whole production process
more economical. Thus, it is worth popularizing.
Because of their smaller-diameter particles, ultrafine
silica powders have many technological applications,
such as thixotropic agents, thermal insulators, compos- 4.3.5. Applications in Alloys and Ceramics
ite filler, etc. They are widely used in the chemical and The silica from RHs is mainly used in polymer
electrical fields.152 At present, ultrafine silica powders materials and cement, as there are few reports on
are mainly prepared by vapor-phase reaction or the sol- applications in alloys. Compared with silicon carbide,
gel method. The high cost of preparation limits their its range of application is narrower. Some preliminary
wide application.153 Some recently developed methods research on aluminum alloy-RHA composites157 and
using lasers, arcs, plasmas, etc., are hard to industrial- RHA-porcelain composites158,159 has been reported, but
ize at present because of their highly demanding further studies are in process.
techniques and conditions.153 In fact, if the size dis-
tribution of the silica powder is not too wide, when 5. Silicon Nitride
the specific surface area of a silica powder is above
20 m2/g, the powder is considered nanoscale. Based on Silicon nitride is a new structural ceramic with high
the research mentioned above, it is easy to prepare mechanical strength at room temperature and elevated
nanoscale silica from RHs under controlled conditions. temperatures, high thermal shock resistance, good wear
 Ind. Eng. Chem. Res., Vol. 40, No. 25, 2001 5869

resistance, good corrosion resistance, high fracture phology is determined in part by the particle dimensions
toughness, low density, low coefficient of thermal ex- of the milled RHs. Silicon nitride crystals of hexagonal
pansion, and high thermal conductivity. Thus, it has symmetry are obtained from starting powder of dimen-
been under intensive study.160 Several of the most sion ∼53 µm, whereas greater particle dimensions and
important methods for manufacturing silicon nitride are lower packing densities yield silicon nitride with a
the direct nitridation of silicon powders, the carbother- whiskery morphology. The addition of preformed silicon
mal reduction of silica in a nitrogen-based atmosphere, nitride powder results in the formation of fine, equiaxed
and the reaction of chlorosilanes with a gas containing silicon nitride particles, or else undesirable whiskers
nitrogen or a nitrogen compound.161 Because high-purity comprise a substantial part of the product.172,173
fine silica and carbon are commercially available and In addition to nitrogen, purified and dried ammonia
inexpensive, the carbothermal reduction of silica is the can also be used as a nitrogenation atmosphere.35,162
main method for manufacturing silicon nitride pow- Henna et al. impregnated RHs in ferrous sulfate solu-
der.162,163 However, this method has a high requirement tion and then soaked them in an ammonia solution and
on raw materials, as silica with a high reactivity and a coked them at 700 °C for 30 min in the absence of air.
good distribution of the silica and carbon are important Silicon nitride was finally formed by firing the treated
for the reaction. The better the distribution, the more RHs at 1200-1500 °C in an ammonia atmosphere. The
helpful for nitridation.164 Therefore, RHs, which natu- amount of silicon nitride increased with iron content to
rally contain both silica and carbon, came into the reach an optimum value, and beyond this value, an
researchers’ minds. Very high surface area and intimate increase in the amount of silicon carbide formation was
contact available for the carbon and silica mixture can noted.170
be obtained by combusting RHs because RHs contain Some metal oxides, such as Fe2O3, can catalyze the
silica, lignin, cellulose, etc. More importantly, because formation of silicon nitride.163,174 In addition to metal
of the uniform distribution of carbon and silica in the oxides, sodium fluoride has also been reported to have
RHA, the reaction can occur more easily than by the a good catalyst effect.163 Silicon nitride manufactured
conventional mechanical mixing technique.163,165-167 by this method is mainly R phase,11,166,175,176 but in the
presence of V2O5 as a catalyst, β-Si3N4 is the predomi-
5.1. Preparing Silicon Nitride from RHs nant phase in the product.173,177
The production of silicon nitride from RHs was first
5.2. Summary
reported in a U.S. patent, where the reaction temper-
ature was within the range of 1100-1350 °C.168 Several A method for the production of silicon nitride from
other studies on the formation of silicon nitride from RHs has been known for more than 20 years, but it has
RHs have beem reported since then. Some reaction not yet been industrialized. The main reason lies in the
parameters have been identified as having an important difficulty of obtaining high-purity Si3N4 as it is usually
role in the reaction system.165,169 In general, silicon accompanied by SiC. This might be because of the
nitride powders can be prepared from RHs at temper- presence of some alkali metals other than silica in RHs,
atures between 1260 and 1500 °C under a flow of which affect the purity and yield. What is more, the
nitrogen. The reaction temperature is relatively lower carbon-to-silica ratio is above the stoichiometric require-
than that formed from the conventional SiO2/C mixture ment for nitridation, so the extra carbon will result in
reaction, and the nitridation rate of the pyrolyzed RHs SiC during reaction.57 Therefore, effective removal of the
is distinctly faster than that for the conventional SiO2/C impurities before reaction is the key problem inhibiting
mixture process.165,170 Before nitridation, RHs have industrialization. At present, the main method applied
often been treated with acid solution to remove the is acid leaching. Whereas the main effect for acid
metallic impurities and some organic elements (transfer leaching is to remove the metal ions, it has little effect
to soluble ingredients) and then to obtain silicon nitride on organic compounds. The combination of acid leaching
powders of high purity, 57,165,171 although in some and a biochemical treatment that can effectively remove
reports, the RHs have also been used directly without the organic component might solve this problem. On the
any pretreatment.172 Typically, the carbon-to-silica ratio other hand, recently, a SiC‚Si3N4 composite has at-
is such that an excess of carbon above the stoichiometric tracted increasing attention. It has excellent physical
requirement for synthesizing silicon nitride is available and chemical properties and has been widely used in
for reaction.172 some industries.178-181 Therefore, one approach would
Silicon nitride is manufactured by the carbothermal be to produce some SiC on purpose and then directly
reduction and nitridation of silica according to the prepare the SiC‚Si3N4 composite. The SiC and Si3N4
overall reaction165 made in this way should have a good distribution and
intimate contact, which should be helpful for improving
3SiO2(s)+6C(s)+2N2(g) f Si3N4(s)+6CO(g) (1) the SiC‚Si3N4 composite’s properties.
Because the ultrafine Si3N4 powders exhibit even
The generally accepted reaction mechanism is that an better characteristics than normal Si3N4 powders, many
intermediate SiO is formed during the synthesis of methods have been developed for preparing them, but
silicon nitride and that the carbon reduction of SiO2 to with higher costs.182-184 The silicon nitride powders from
SiO is the rate-determining step. RHs usually are not as fine. Methods for improving the
Rahman and Riley173 prepared silicon nitride powder techniques for manufacturing smaller silicon nitride
by nitriding pyrolyzed RHs under 95% nitrogen/5% powders from RHs are worth further investigation.
hydrogen. They found that hydrogen addition is ben- The main content of the Si3N4 made from above
eficial in accelerating the rate of nitride formation. methods is particles; the whisker content is low. In
However, when the reaction temperature is higher than addition, there are few reports on the preparation of
1450 °C, the content of byproduct will greatly increase. Si3N4 fibers or films from RHs. Silicon nitride films are
They also found that the silicon nitride particle mor- widely used in microelectronic device fabrication layers,
5870 Ind. Eng. Chem. Res., Vol. 40, No. 25, 2001

gate dielectrics, and antireflective coatings.185 At present, and alkaline earth compounds such as sodium, magne-
silicon nitride films are mainly made from silane sium, and calcium inhibit the chlorination. The ac-
through some CVD methods, such as low-pressure CVD celeration effect of potassium in the chlorination of SiO2
(LPCVD),186 plasma-enhanced CVD (PECVD),187 and was explained by assuming that the diffusion of K+ ions
laser-assisted PECVD (LAPECVD).187 The direct pro- in the SiO2 lattice causes the distortion of the SiO2
duction of silicon nitride fibers or films from RHs seems lattice and that the chlorinating species such as chlo-
impractical at present. However, RHs can be used as rinated carbon easily diffused into the SiO2 lattice. The
raw materials for producing the starting material for inhibitory effect of the other elements was interpreted
the production of silicon nitride film, silane,188,189 to in terms of the absence of SiO2 lattice distortion, as the
reduce its high cost in other ways. Such studies are ionic radii of these elements are smaller than that of
under way. K+. It was also inferred that the melts of these chlorides
covered the contact points of SiO2 and C.191,192 In
6. Silicon Tetrachloride addition, it was reported that the addition of sulfide
could also increase the yield.193
Silicon tetrachloride is a prominent chemical material
having a major impact in the semiconductor industry. 6.2. Summary
It can be used as a silicon source material for the The attractiveness of the manufacture of SiCl4 from
production of organosilicates, silicon esters, organosili- RHs lies in the low cost, the high reactivity of the silica
con halides, silicone polymer, etc. Recently, silicon content in RHs (low reaction temperature), and the low
tetrachloride has also been used for manufacturing level of impurities that have to be removed from the
solar-grade silicon, high-purity SiO2, SiC, and Si3N4.174,190 product.194 The operation of the process is energetically
In the industrial process, silicon tetrachloride is self-sustaining. Combustion of the carbon residue after
usually produced as a byproduct with other metal chlorination is more than adequate to provide both the
chlorides or by the chlorination of SiC, ferrosilicon, or heat needed for pyrolysis of the RHs and the heat
a SiO2/C mixture with Cl2.190 After pyrolysis at ap- required for the preheating of the chlorine. Because of
propriate temperatures and pressures, the almost-pure the low bulk density of the RHs, the reactor will be
C/SiO2 mixture can be obtained from RHs in a much larger than those of a conventional plant, but the lower
more intimately dispersed form than could readily be temperature of operation and the absence of the need
accomplished by mechanical mixing. The mixture can for electrical heating are expected to lead to comparable
be chlorinated to produce high-purity SiCl4, which reactor costs.194
avoids the separation procedure.190
7. Silicon
6.1. Preparing Silicon Tetrachloride from RHs Low-cost solar-grade silicon is needed for the produc-
tion of solar cells. At present, solar cells are manufac-
Chen et al.190 leached RHs in 3 N HCl in a glass tured using semiconductor-grade silicon. Because the
round-bottomed flask, which was kept at about 100 °C purity level of solar-grade silicon is considerably less
within a thermostat for 1 h. After the leaching, the RHs than that of semiconductor-grade silicon, the cost of
were thoroughly washed with distilled water and then manufacturing solar cells can be considerably reduced
dried. The pyrolysis reaction was conducted in a tubular by investigating new and inexpensive source materi-
reactor under nitrogen atmosphere with heating at 900 als.195 Therefore, worldwide efforts are being directed
°C for 1 h, and the final husk ash contained 51.18 wt % at the development of a low-cost, high-volume, and
silica. The pyrolyzed RHs were chlorinated over the commercially feasible process for the production of high-
range of 700-1100 °C to produce silicon tetrachloride. purity silicon to be used in solar cells. The preparation
The conversion of silica was found to be markedly of pure silicon from RHs is under study. RHs are a
dependent on the temperature of chlorination, and the relatively high-volume, low-cost byproduct commodity
reaction rate was distinctly faster than the rate for the that contains the two basic components needed to
pure SiO2/C mixture. The bulk of the chlorination of the produce silicon: silica and carbon. Impurity analyses
pyrolyzed RHs occurred in about 7 min, and the indicate that RHs from various sources are composi-
subsequent rate of chlorination was very low. It can be tionally similar and that they have low concentrations
inferred that the silica arising from pyrolyzed RHs is (10-20 ppmw) of aluminum and iron, the two major
derived from the original RHs and that the degree of impurities in conventional raw materials used to pre-
contact between SiO2 and C in the pyrolyzed RHs is pare metallurgical silicon. The levels of the major
much more intimate than would be obtained from impurities (Ca, K, Mg, and Mn) in RHs can be reduced
mechanical mixing, giving a high reactivity to the by about a factor of 100 to around 20 ppmw by hot HCl
chlorination reaction. In the process of the chlorination leaching. The doping impurities boron and phosphorus,
reaction, carbon plays the role of reducing agent, and important in silicon intended for solar cells, are less
the part of the silica that is dispersed intimately with affected by acid leaching. Their concentrations were
the carbonaceous material has a higher reactivity. found to be 1 and 40 ppmw, respectively, in leached
Hence, the reaction rate is very fast at the beginning of RHs.196 Other impurities such as Mo, Ti, Ta, Ni, V, and
the reaction, and the reaction is almost complete after Cr are either absent or present in very low concentra-
7 min. tions and can also be easily removed through acid
To produce SiCl4 more efficiently from active SiO2 in leaching. Hence, RH is a potential source for producing
RHs, pyrolyzed RHs can be chlorinated with both solar-grade silicon.197
alkaline and alkaline earth additives such as potassium
compounds in the temperature range of 600-1000 °C. 7.1. Preparing Silicon from RHs
These additives change to chlorides under the condition Several approaches have been developed to produce
of chlorination. Potassium compounds accelerate the silicon from RHs. Among the various methods of reduc-
chlorination of the pyrolyzed RHs, but other alkaline ing the amorphous silica, reduction by metallic magne-
 Ind. Eng. Chem. Res., Vol. 40, No. 25, 2001 5871

sium has been found to be advantageous for the follow- grade silicon is 2:1. However, purified RHs have been
ing reasons: (i) the reduction of silica can be carried pyrolyzed to produce a product containing a C/SiO2 ratio
out at a comparatively low temperature (around 600˚C), of about 4:1; therefore, additional silica was added to
(ii) the supply of reasonably pure magnesium is assured, RHA or controlled combustion was carried out to adjust
and (3) reaction products other than silicon can easily the C/SiO2 ratio to lower values.87,199 Hunt et al.196
be removed by acid leaching.89 Usually, some pretreat- leached RHs in hot HCl and then coked them in inert
ments such as water leaching and acid leaching at high gas to further remove impurities. The coked RHs were
temperature are performed on the RHs before reaction. extruded with sucrose as a binder to produce 5-mm-
The pretreated RHs are first dried and burned to black diameter pellets with an average bulk density of about
ashes at relatively low temperature and then burned 800 g/L. The pellets were pyrolyzed in an arc furnace
to white ashes at high temperature (about 600˚C). The to produce pure silicon.
prepared white ashes are leached with concentrated acid In addition to the above methods, pure silicon can also
(usually HCl) at high temperature to remove any soluble be prepared by hydrolyzing silicon tetrachloride, an
impurities, and were then leached with pure water, intermediate product that can be made from RHs.200
dried, and ground to a fine powder. The prepared fine
powder is reacted with magnesium at about 600 °C. Acid 7.2. Summary
leaching is carried out once more at this point to remove From the above methods, it is easy to see that the
any impurities in the product. Finally, the product is requirement on purity is very strict. Usually, the
leached with pure water and dried to obtain the pure product requires acid leaching at high temperature in
silicon. Ikram et al.195 acid leached and water leached every step to improve the final product’s purity. Only
the products of every step completely. The reduced in this way can the purity of the prepared silicon satisfy
sample was acid leached with HCl to remove MgO and the requirements of solar cells.
other impurities that existed in the oxide form. Next, In addition to pure silicon powders, silicon films have
the sample was leached with HF and then with a also been prepared indirectly from RHs. Nandi et al.
mixture of HF and H2SO4 to remove, more or less prepared hydrogenated amorphous silicon (a-Si:H) films
completely, many impurities that were present in the by the chemical vapor deposition of silanes generated
form of silicates. The sample was then washed with by the acid hydrolysis of magnesium silicide (Mg2Si)
distilled water and dried. The pure silicon (99.95%) was obtained from RHs.201 The growing interest in recent
extracted from RHs at last. Sodium, magnesium, potas- years in a-Si:H thin films is essentially due to the fact
sium, calcium, and iron were found to present in the that it is an inexpensive material for the photovoltaic
range of 50-150 ppm; boron, aluminum manganese, conversion of solar energy as well as for other interest-
and titanium were present in very low concentrations, ing technological applications, such as thin film transis-
each being less than 10 ppm. Phosphorus was not tors, electrophotography, and optical recorders. The
detected in the sample. films are conventionally prepared by (i) glow discharge,
Banerjee et al.89 performed some similar studies. They (ii) photochemical vapor deposition, (iii) laser-induced
found that the silica in RHs can be reduced by magne- CVD, and (iv) plasma CVD of silanes.201 The techniques
sium at an even lower temperature (about 550 °C) than mentioned above, however, require vacuum and expen-
is employed in other conventional methods of reducing sive equipment for deposition. Compared with the above
silica. This saves energy and, more importantly, mini- methods, this method is much more economic. The
mizes the chances of contaminating the silicon by the properties of the resulting a-Si:H films are somewhat
reaction vessel and products. The reduction process is inferior for immediate photovoltaic applications. By
highly exothermic and is completed within a very short further optimizing the deposition parameters such as
time (on the order of tens of seconds). The reaction gas flow rate, substrate temperature, and geometry of
seems to proceed via the interaction of vaporized the reactor, incorporating more hydrogen into the films,
magnesium with silica (gas-solid reaction), indicating and minimizing the impurities contained in the films,
that compaction and effective sealing of the total charge better-quality films can be developed by this simple and
will increase the efficiency of the reaction. The contami- inexpensive method.
nation of silicon was probably mainly due to the labora-
tory-grade magnesium [which contained 0.05% (maxi- 8. Zeolite
mum) of acid-insoluble matter, 0.01% Cu, and 0.02% Fe) Zeolite, a typical microporous crystalline material, is
and the glassware used in the process. This suggests an attractive material because of its solid acidity, ion-
that the purification of magnesium and the use of Teflon exchange capability, adsorption/release capability, and
will lead to better-quality silicon.89,198 Because the molecular-level pores. Zeolite is usually synthesized
reaction is so rapid, MgO is sometimes added as a under hydrothermal conditions from solutions of sodium
moderator in the mixture to dilute the matrix, thereby aluminate, sodium silicate, or sodium hydroxide.202-204
reducing the reaction rate. Natural zeolite was discovered as early as 1756, but the
In addition to magnesium, calcium has also been used synthesis of zeolite was not realized until 1948.205
to reduce the silica in RHs.197,198 Calcium was selected By carrying out base treatment on the combusted
because it is a stronger reducing agent and naturally RHs, high-activity silica that is suitable for zeolite
more abundant than magnesium. When calcium is used synthesis can be obtained.206-209 As of now, morden-
in the reduction action, the reaction temperature is a ite,208,210 NaX zeolite,206,211 and ZSM zeolite207,212,213 have
little higher, at about 720 °C. Theoretically, Al and Ba been successfully synthesized from RHs.
can also be used as reducers in this reaction,197 but few
such reports exist. 8.1. Preparing Zeolite from RHs
In addition to magnesium and calcium, high-purity Bajpai et al. synthesized mordenite using silica from
carbon can also be used to reduce silica to silicon. The RHA for the first time in 1981. The RHs were burned
required ratio of C to SiO2 for the production of solar- for 3 h at 1000 °C to obtain carbon-free ash. The ash
5872 Ind. Eng. Chem. Res., Vol. 40, No. 25, 2001

thus obtained was finely ground and contained 88.86 ranging from 125 to 200 °C and for synthesis durations
wt % silica. The silica solution was prepared by treating of 6-120 h.
RHA with 1-2 N NaOH maintained at 80 °C for a few Recently, ZSM-48 zeolite has also been successfully
hours with continuous shaking. Then, the solution was synthesized from RHs.212 It was prepared from a reac-
filtered through a linen cloth. The silica solution thus tion mixture containing a source of silica (RHA), an
prepared was mixed with a solution containing sodium organic compound (C6DN) having an amine functional
hydroxide and appropriate amounts of aluminum hy- group with pKa > 7, an alkali metal oxide (sodium
droxide. The hot solution of the starting mixture was oxide), and water. The mixture was maintained at 170
kept in an autoclave for the hydrothermal reaction. The °C in a stainless steel autoclave until crystals of ZSM-
desired reaction temperature was attained within 30- 48 were formed.
50 min. At the end of each run conducted for a specific
period of time, the product was filtered and subse- 8.2. Summary
quently washed with hot distilled water until the pH of
the filtrate reached 7. The solid product was then dried Zeolite membranes can be used as catalysts in reac-
overnight at 120 °C and identified. The sequence of tors, as sensors for detection, and/or for liquid separa-
formation of the products with increasing temperature tions. These properties have attracted the interest of
was in the following direction: amorphous to mordenite researchers for several years.215 As the silica film, zeolite
to analcime. It was shown that, when the temperature membrane can also be made from tetraethyl orthosili-
was lower than 135 °C, no mordenite was formed, cate (TEOS),216 so the novel pentacoordinate silicon
whereas when the temperature was higher than 165 °C, complexes can also be used here.73 These relatively
analcime was formed. Therefore, the proper tempera- cheap pentacoordinate silicon complexes can substitute
ture is between 135 and 165 °C. The starting composi- for TEOS as the raw material for preparing zeolite
tion of the mixture is of paramount importance in membrane.
governing the type of zeolite crystallized. Compared to
the synthesis of mordenite using silica from a chemical 9. Others
source, for the synthesis of mordenite with silica from
RHA, relatively less Na2O or a greater SiO2 content in In addition to the materials mentioned above, some
the starting mixture is required. This probably can be other silicon-based materials made from RHs have also
attributed to the form of silica in the initial mixture. been reported, including cordierite,217,218 magnesium
When silica from a chemical source was used, part of it silicide,188,219,220 silanes,188,189 potassium silicate,2 so-
was in the form of sodium silicate in solution, with the dium silicate,2,221,222 forsterite,223,224 Si-O-C fibers,225,226
remaining part as silica gel. In the runs that involved sodium silicofluoride,227 sialon,228,229 and gehlenite.230
silica from RHA, the silica was in the form of a silica
solution. Because the crystallization of mordenite starts 10. Conclusions
from the liquid phase of the starting sodium alumino- Among the silicon-based materials mentioned above,
silicate gel, the solubilities of the materials in the final only silicon carbide has a production method from RHs
mixture to form the liquid phase that contributed to the that has been industrialized. The industrializations of
mordenite crystallization appeared to be different in the the other materials’ productions require further re-
two cases.208,214 search.
Dalai et al.206 synthesized NaX zeolite using RHA as In addition, the products from RHs are mainly
a source of silica for the first time in 1985. The synthesis inorganic materials. In the past few years, Wang et al.
of NaX zeolite is similar to that of mordenite. have performed a series of studies on the organic
Rawtani et al.207 synthesized ZSM-5 zeolite from the applications of RH silica. One of their studies empha-
sodium tetrapropylammonium (TPA) cation system for sized the synthesis of organosilicon complexes from
the first time using silica from RHA in 1989. In this treated RHs.73,231-233 Compared with carbothermal
study, RHA was the only source of the silica and reduction, this method of synthesizing organosilicon is
alumina used in the synthesis. RHs were burned in a simple and economical and generates little pollution.
muffle furnace at 1000 °C for 10 h, and the resultant Although there is general agreement that the silicon
carbon-free ash was ground in a ball mill to a 200-mesh contained in RHs is in the phase of silica,1 because all
size. A stoichiometrically required amount of (TPA)OH of the silica derived from RHs has experienced an
was added to RHA, yielding a viscous TPA-silicate- oxidation process (pyrolysis or oxidative media), no one
aluminate solution. The two solutions were mixed in a can confirm that no organosilicon is contained in RHs.
150-mL stainless steel autoclave, and the lid of the Some of the silica has also been found to be bonded
autoclave was quickly closed to prevent TPA from covalently to the organic compounds.5 Considering that
absorbing carbon dioxide gas from the atmosphere. The the formation of silicon-containing compounds in RHs
reaction vessel was maintained at the desired temper- is a biological process, the existence of organosilicon
ature for a predetermined time. At the end of each run, compounds in RHs is possible. If some of the silicon
the vessel was quenched immediately in cold water to actually exists in the phase of organosilicon, then the
stop the crystallization process. The solid products were direct derivation of organosilicon from RHs will be an
filtered, washed, and dried overnight at 120 °C. When easy and economical method of producing organosilicon.
the mole percent of SiO2 varies from 70 to 80% and that Moreover, with the development of bioengineering,
for (TPA, Na)2O from 20 to 35%, pure ZSM-5 zeolite can direct “planting” of organosilicon in RHs might not be
be obtained as the final product. An increase in the an impossible approach.
hydroxide ion concentration can shorten the induction In the past few years, the biochemistry characteristics
period, whereas higher alkalinity beyond a certain value of silicon have been a hot topic. On the basis of the
will prolong the nucleation in the synthesis of ZSM-5 developments in biomineralized nanostructured mate-
zeolite. The synthesis was carried out for temperatures rial chemistry, scientists are considering the synthesis
 Ind. Eng. Chem. Res., Vol. 40, No. 25, 2001 5873

and assembly of nanaostructured SiO2 using cell mem- (24) Patel, M.; Karera, A. SiC whiskers from rice husk: Role
branes and cell wall templates.234 The direct assembly of catalysts. J. Mater. Sci. Lett. 1989, 8, 955.
of silicon-containing materials from RHs through bio- (25) Subrahmanyam, J.; Krishnarao, R. V.; Mohanarao, R.;
Jagadishkumar, T. Rapid heating of raw rice husks for the
chemistry and nanochemistry might be a most potential formation of SiC whiskers. J. Mater. Synth. Process. 1996, 4, 285.
future use of RHs. (26) Krishnarao, R. V.; Godkhindi, M. M. Studies on the
formation of SiC whiskers from pulverized rice husk ashes. Ceram.
Acknowledgment Int. 1992, 18, 35.
(27) Gorthy, P.; Pudukottah G., M. Production of silicon carbide
The authors thank the four anonymous reviewers for from rice husks. J. Am. Ceram. Soc. 1999, 82, 1393.
helpful comments. L.Y.S. thanks Dr. Qiaoli Liang and (28) Krishnarao, R. V. Effect of cobalt catalyst on the formation
Dr. Joseph S. Thrasher for helpful discussions. K.C.G. of SiC from rice husk silica-carbon black mixture. J. Mater. Sci.
1995, 30, 3645.
acknowledeges the financial support of the National
(29) Krishnarao, R. V. Effect of cobalt chloride treatment on
Natural Science Foundation of China (No. 29974009). the formation of SiC from burnt rice husks. J. Eur. Ceram. Soc.
1993, 12, 395.
11. Literature Cited (30) Krishnarao, R. V.; Godkhindi, M. M. Effect of Si3N4
additions on the formation of SiC whiskers from rice husks. Ceram.
(1) Houston, D. F. Rice: Chemistry and Technology; American Int. 1992, 18, 185.
Association of Cereal Chemists, Inc.: St Paul, MN, 1972 (31) Krishnarao, R. V.; Mahajan, Y. R. Effect of acid treatment
(2) Karera, A.; Nargis, S.; Patel, S.; Patel, M. Silicon-based on the formation of SiC whiskers from raw rice husks. J. Eur.
materials from rice husk. J. Sci. Ind. Res. 1986, 45, 441. Ceram. Soc. 1995, 15, 1229.
(3) Huang, Y. E. Comprehensive utilization of rice husk. Hebei (32) Raman, V.; Parashar, V. K.; Bahl, O. P. Influence of boric
Huagong (China) 1993, (4), 51. acid on the synthesis of silicon carbide whiskers from rice husks
(4) Ding, M. Rice husk silicon and its applications. Inorg. Chem. and polyacrylonitrile. J. Mater. Sci. Lett. 1997, 16, 1252.
Ind. 1992, 24 (6), 36. (33) Narciso-Romero, F. J.; Rodriguez-Reinoso, F. Synthesis of
(5) Patel, M.; Karera, A. SiC whisker from rice husk: Micro- SiC from rice husks catalysed by iron, cobalt or nickel. J. Mater.
scopic study. Powder Metall. Int. 1991, 23 (1), 30. Sci. 1996, 31, 779.
(6) Krishnarao, R. V.; Godkhindi, M. M. Distribution of silica (34) Cheng, X. C.; Shi, P.; Tu, C. W.; Teng, L. Synthesis of
in rice husks and its effect on the formation of silicon carbide. silicon carbide with rice husk. Refractories 1998, 32, 337.
Ceram. Int. 1992, 18, 243. (35) Mansour, N. A. L.; Hanna, S. B. Silicon carbide and nitride
(7) Sharma, N. K.; Williams, W. S.; Zangvil, A. Formation and from rice hulls-II. Effect of iron on the formation of silicon carbide.
structure of silicon carbide whiskers from rice hulls. J. Am. Ceram. Trans. J. Br. Ceram. Soc. 1979, 78 (6), 132.
Soc. 1984, 67, 715.
(36) Krishnarao, R. V.; Subrahmanyam, J. Formation of SiC
(8) Ault, N. N.; Crowe, J. T. Silicon carbide. Am. Ceram. Soc. from rice husk silica-carbon black mixture: Effect of rapid heating.
Bull. 1989, 68, 1062. Ceram. Int. 1996, 22, 489.
(9) He, E. G.; Wang, X. G.; Shang, W. Y.; Chen, W. The
(37) Wang, Q. B.; Guo, M. X. Pilot synthesis of β-SiC whiskers
environment pollution in SiC industry and the prevention mea-
from rice hulls and product analysis. Bull. Chin. Ceram. Soc. 1998,
sure. Environ. Technol. 1999, 17 (3), 39.
18 (2), 9.
(10) Bray, D. J. Silicon carbide whiskers. Am. Ceram. Soc. Bull.
(38) Mishra, P. K.; Nayak, B. B.; Mohanty, B. Synthesis of
1993, 72 (6), 116.
silicon carbide from rice husk in a packed bed arc reactor. J. Am.
(11) Kumar, B.; Godkhindi, M. M. Studies on the formation of
Ceram. Soc. 1995, 78, 2381.
SiC, Si3N4 and Si2N2O during pyrolysis of rice husk. J. Mater. Sci.
Lett. 1996, 15, 403. (39) Stachowicz, L.; Singh, S. K.; Pfender, E.; Girshick, S. L.
Synthesis of ultrafine SiC from rice hulls (husks): A plasma
(12) Wang, Q. B.; Guo, M. X.; Xu, H. Study on synthesizing
process. Plasma Chem. Plasma Process. 1993, 13, 447.
SiC whiskers from rice hulls and to be reinforcement for Si3N4
ceramic matrix composite materials. Adv. Ceram. 1997, 18 (4), 13. (40) Nayak, B. B.; Mohanty, B. C.; Singh, S. K. Synthesis of
(13) Lee, J. G.; Cutler, I. B. Formation of silicon carbide from silicon carbide from rice husk in a dc arc plasma reactor. J. Am.
rice hulls. Am. Ceram. Soc. Bull. 1975, 54 (2), 195. Ceram. Soc. 1996, 79, 1197.
(14) Sacher, I. Contributions to the use of rice husks and rice (41) Singh, S. K.; Stachowicz, L.; Girshick, S. L.; Pfender, E.
husk ash in ceramics. Sprechsaal 1988, 121, 1081. Thermal plasma synthesis of SiC from rice hull (husk). J. Mater.
(15) Krishnarao, R. V.; Mahajan, Y. R.; Kumar, T. J. Conversion Sci. Lett. 1993, 12, 659.
of raw rice husks to SiC by pyrolysis in nitrogen atmosphere. J. (42) Andersson, C.-H.; Warren, R. Silicon carbide fibers and
Eur. Ceram. Soc. 1998, 18, 147. their potential for use in composite materials. Part 1. Composites
(16) Krishnarao, R. V.; Godkhindi, M. M.; Chakraborty, M.; 1984, 15 (1), 16.
Mukunda, P. G. Formation of SiC whiskers from compacts of raw (43) Wang, Q. B.; Zeng, M.; Guo, M. X. Characteristics of SiC
rice husks. J. Mater. Sci. 1994, 29, 2741. whisker and the present situation of its synthesis and application.
(17) Krishnarao, R. V.; Mahajan, Y. R. Formation of SiC New Chem. Mater. 1997, 25 (5), 8.
whiskers from raw rice husks in argon atmosphere. Ceram. Int. (44) Wang, Q. B.; Guo, M. X. Characteristics and application
1996, 22, 353. of multi-node SiC whisker. Diamond Abrasives Eng. 1998, (4), 34.
(18) Krishnarao, R. V.; Godkhindi, M. M.; Chakraborty, M. (45) An, Z.; Guo, M. X. Effects of characters of SiC whisker on
Maximization of SiC whiskers yield during the pyrolysis of burnt mechanical properties of composites. J. Mater. Eng. 1995, (12),
rice husks. J. Mater. Sci. 1992, 27, 1227. 28.
(19) Krishnarao, R. V.; Godkhindi, M. M.; Mukunda, P. G.; (46) Gu, Y. W.; Pan, M. Y.; Zhao, G. Y. Microstructure and
Chakraborty, M. Direct pyrolysis of raw rice husks for maximiza- mechanical properties of SiCw/Al2O3-(Ti, W) C ceramic material.
tion of silicon carbide whisker formation. J. Am. Ceram. Soc. 1991, J. Mater. Eng. 1995, (12), 32.
74, 2869. (47) Liu, Y. X.; Zhao, C. X. Microstructure of the Al2O3-SiCw
(20) Raju, C. B.; Verma, S. SiC whiskers from rice hulls: composite ceramics. Metal Phys. Exam. Test. 1994, 2, 4.
Formation, purification, and characterization. Br. Ceram. Trans. (48) Pickard, S. M.; Derby, B.; Harding, J.; Taya, M. Strain rate
1997, 96 (3), 112. dependence of failure in 2124 Al/SiC whiskers composite. Scr.
(21) Mizuki, E.; Okumura, S.; Saito, H.; Murao, S. Formation Metall. 1988, 22, 601.
of silicon carbide from rice husks using enzymatic methods for (49) Divecha, A. P.; Fishman, S. G.; Karmarkar, S. D. Silicon
carbon control. Bioresour. Technol. 1993, 44 (1), 47. carbide reinforced aluminum-a formable composite. J. Met. 1981,
(22) Wang, Q. B.; Guo, M. X.; Han, M. F. A study on the rate- 33 (9), 12.
determining step of growing SiC whisker. J. Mater. Eng. 1997, (50) Nieh, T. G.; Karlak, R. F. Hot-rolled silicon carbide-
(1), 21. aluminum composites. J. Mater. Sci. Lett. 1983, 2, 119.
(23) Wang, Q. B.; Guo, M. X.; An, Z. Study on the growth of (51) Ishimaru, M.; Dickerson, R. M.; Sickafus, K. E. Ion beam
single β-SiC whisker and the role of catalyst. High Technol. Lett. synthesis of buried oxide layers in silicon carbide. Nucl. Instrum.
1996, 6 (10), 41. Methods Phys. Res. B 2000, 166-167, 390.
5874 Ind. Eng. Chem. Res., Vol. 40, No. 25, 2001

(52) Key, P. H.; Sands, D.; Schlaf, M.; Walton, C. D.; Anthony, (79) James, J.; Rao, M. S. Characterization of silica in rice husk
C. J.; Brunson, K. M.; Uren, M. J. Infrared reflectivity of ion- ash. Am. Ceram. Soc. Bull. 1986, 65, 1177.
implanted and pulsed excimer laser irradiated 4H-SiC. Thin Solid (80) Luan, T.-C.; Chou, T.-C. Recovery of silica from the
Films 2000, 364, 200. gasification of rice husks/coal in the presence of a pilot flame in a
(53) Maeda, E.; Komatsu, M. Thermoelectric performance of modified fluidized bed. Ind. Eng. Chem. Res. 1990, 29, 1922.
silicon carbide semiconductor made from rice hull. Mater. Res. Soc. (81) Wang, N.; Low, M. J. D. Spectroscopic studies of carbons
Symp. Proc. 1996, 410, 77. XVIII: The charring of rice hulls. Mater. Chem. Phys. 1990, 26,
(54) Takeda, S.; Pai, C.-H.; Seo, W.-S.; Koumoto, K.; Yanagida, 117.
H. Thermoelectric properties of porous β-SiC fabricated from rice (82) Chakraverty, A.; Mishra, P.; Banerjee, H. D. Investigation
hull ash. J. Ceram. Soc. Jpn. (Int. Ed.). 1993, 101, 792. of combustion of raw and acid-leached rice husk for production of
(55) Prasad, B. K.; Das, S.; Jha, A. K.; Modi, O. P.; Dasgupta, pure amorphous white silica. J. Mater. Sci. 1988, 23, 21.
R.; Yegneswaran, A. H. Factors controlling the abrasive wear (83) Chakraverty, A.; Banerjee, H. D.; Mishra, P. Production
response of a zinc-based alloy silicon carbide particle composite. of amorphous silica from rice husk in a vertical furnace. AMA
Compos., Part A: Appl. Sci. Manuf. 1997, 28, 301. Agric. Mech. Asia Afr. Lat. Am. 1990, 21 (4), 69.
(56) Chakraverty, A.; Kaleemullah, S. Conversion of rice husk (84) Real, C.; Alcala, M. D.; Criado, J. M. Preparation of silica
into amorphous silica and combustible gas. Energy Convers. from rice husks. J. Am. Ceram. Soc. 1996, 79, 2012.
Manage. 1991, 32, 565. (85) Conradt, R.; Pimkhaokham, P.; Leela-Adisorn, U. Nano-
(57) Li, C. H.; Ni, J. Z. Preparation of SiC and Si3N4 from rice structured silica from rice husk. J. Non-Cryst. Solids 1992, 145,
husks. Shanghai Guisuanyan (China) 1991, (2), 90. 75.
(58) Moustafa, S. F.; Morsi, M. B.; El-Din, A. A. Formation of (86) Proctor, A. X-ray diffraction and scanning electron micro-
silicon carbide from rice hulls. Can. Metall. Q. 1997, 36, 355. scope studies of processed rice hull silica. J. Am. Oil Chem. Soc.
(59) An, Z.; Xia, Y. K.; Ren, Z. M.; Han, M. F.; Jia, R. H.; Guo, 1990, 67, 576.
M. X. Pilot studies of Separation and purification of SiC whisker. (87) Patel, M.; Karera, A.; Prasanna, P. Effect of thermal and
High Technol. Lett. 1995, 5 (7), 6. chemical treatments on carbon and silica contents in rice husk.
(60) Xia, Y. K.; Ren, Z. M.; Li, G. H. A study on the carbon J. Mater. Sci. 1987, 22, 2457.
removing technology on the synthesis of β-SiC particles from rice (88) Sidheswaran, P.; Bhat, A. N. Recovery of amorphous silica
hull. Diamond Abrasives Eng. 1996, (6), 23. in pure form from rice husks. Trans. Indian Ceram. Soc. 1996, 55
(61) Xu, H.; Guo, M. X. A study on the crystal defects in SiC (4), 93.
whiskers from rice hull. New Chem. Mater. 1993, 21 (10), 17. (89) Banerjee, H. D.; Sen, S.; Acharya, H. N. Investigation on
(62) Russell, L. M.; Johnson, L. F.; Hasselman, D. P. H.; Ruh, the production of silicon from rice husks by the magnesium
R. Thermal conductivity/diffusivity of silicon carbide whisker method. Mater. Sci. Eng. 1982, 52, 173.
reinforced mullite. J. Am. Ceram. Soc. 1987, 70, c-226. (90) Yalçin, N.; Sevinç, V. Studies on silica obtained from rice
(63) Nutt, S. R. Defects in silicon carbide whiskers. J. Am. husk. Ceram. Int. 2001, 27, 219.
Ceram. Soc. 1984, 67, 428. (91) Krishnarao, R. V.; Subrahmanyam, J.; Kumar, T. J.
(64) Yang, X. C.; Han, G. R.; Du, P. Y.; Ding, Z. S. Studies of Studies on the formation of black particles in rice husk silica ash.
nucleation and growth of SiC ultrafine powders synthesized by J. Eur. Ceram. Soc. 2001, 21, 99.
chemical vapour reaction. J. Chin. Ceram. Soc. 1997, 25, 332. (92) Real, C.; Alcala, M. D.; Munoz-Paez, A.; Criado, J. M. XAFS
(65) Xu, Y. D.; Zhang, L. T.; Cheng, L. F. Composition, micro- analysis of the potassium-silica interaction in rice husks. Nucl.
structure and thermal stability of silicon carbide chemical vapor Instrum. Methods Phys. Res. B. 1997, 133, 68.
deposition at low temperature. J. Synth. Cryst. 1996, 25, 225. (93) Rohatgi, K.; Prasd, S. V.; Rohatgi, P. K. Release of silica-
(66) Chen, W. W.; Zou, Z. S.; Wang, T. M. New process for rich particles from rice husk by microbial fermentation. J. Mater.
synthetic SiC whiskers by CVD. Acta Metall. Sin. 1997, 33, 643. Sci. Lett. 1987, 6, 829.
(67) Lin, L. The production and market of SiC fiber. New Chem. (94) Wu, X. C. Studies on the hydrothermal conditions of the
Mater. 1998, 26 (9), 28. extraction of high-purity silica from rice husks. Bull. Chin. Ceram.
(68) Shi, N. L. Survey of the development of CVD SiC (C core) Soc. 1996, 15 (4), 36.
filament. Mater. Rev. 1994, 8 (1), 69. (95) Yang, X. H. Production of high-purity silica from rice husk.
(69) Lackey, W. J.; Hanigofsky, J. A.; Freeman, G. B.; Hardin, Chinese Patent CN 1,063,087, 1992.
R. D.; Prasad, A. Continuous Fabrication of silicon carbide fiber (96) Yu, X. W.; Xu, G. H.; Zhou, Y. Y.; Zhao, G. P.; Shang, S.
tows by chemical vapor deposition. J. Am. Ceram. Soc. 1995, 78, N. A new technology of producing high quality white carbon black
1564. with rice husk, rice straw and wheat straw. Bull. Chin. Ceram.
(70) Zheng, Z. X. Study on the silicon carbide films grown by Soc. 1996, 15 (3), 48.
chemical vapor deposition. J. Chin. Ceram. Soc. 1995, 23, 550. (97) Yu, X. W.; Zhao, G. P.; Xu, G. H.; Zhou, Y. Y.; Shang, S.
(71) Motojima, S.; Hamamoto, T.; Iwanaga, H. Preparation of N. Study of factors influencing extraction rate of while carbon
micro-coiled SiC fibers by chemical vapor deposition and their black produced from rice husk. Chem. Eng. (China) 1998, 26 (4),
morphology. J. Cryst. Growth 1996, 158, 79. 51.
(72) Dai, C. H.; Yang, J. Y.; Lin, Y. S. Synthesis of nanometer (98) Lu, F. Y.; Lu, A. J. Comprehensive utilization of rice hull.
SiC powder by microwave method. J. Qingdao Inst. Chem. Technol. Cereal Feed Ind. 1997, (12), 41.
1999, 20 (1), 25. (99) Lu, F. Y.; Yan, J.; Zheng, D. M.; Zhan, X. L.; Liu, X. H.
(73) Wang, W. X.; Sun, L. Y.; Gong, K. C. Synthesis of The process of producing precipitated silica with low cost. Huaxue
pentacoordinate silicon complexes from rice husk ash. In Proceed- Gongchengshi (China) 1996, (3), 18.
ings of the 3rd International Workshop on Green Chemistry in (100) Lu, F. Y.; Lu, A. J. Study on preparation of precipitated
China, Guangzhou, China, May 2000; Guangzhou Institute of silica from ammonium sulfate. Huaxue Gongchengshi (China)
Chemistry, CAS: Guangzhou, China, pp 153-154. 1994, (1), 10.
(74) Zhang, J. M.; Yang, Z. Z.; Tang, A. M.; Tang, Z. W. The (101) Lu, F. Y.; Lu, A. J. Study on preparation of precipitated
study of preparation, determination and dispersivity of SiO2 silica from ammonium hydrogen. J. Chem. Fert. Ind. 1994, 21 (4),
nanometer sized particles. Fine Chem. 1997, 14 (1), 14. 53.
(75) Zhang, Y. C.; Tian, M.; Zhang, L. Q.; Geng, H. P. Progresses (102) Kamath, S. R.; Proctor, A. Silica gel from rice hull ash:
in preparation, modification and application of silicon dioxide. Preparation and characterization. Cereal Chem. 1998, 75, 484.
Mod. Chem. Ind. 1998, 18 (4), 11. (103) Kalapathy, U.; Proctor, A.; Shultz, J. A simple method
(76) Cui, H. Y. The production technology of white carbon black for production of pure silica from rice hull ash. Bioresour. Technol.
and its effect on the property of the product. Guangdong Huagong 2000, 73, 257.
(China) 1997, 24 (1), 24. (104) Kalapathy, U.; Proctor, A.; Shultz, J. Silica xerogels from
(77) Kapur, P. C. Production of reactive bio-silica from the rice hull ash: Structure, density and mechanical strength as
combustion of rice husk in a tube-in-basket (TiB) burner. Powder affected by gelation pH and silica concentration. J. Chem. Technol.
Technol. 1985, 44, 63. Biotechnol. 2000, 75, 464.
(78) Nakata, Y.; Suzuki, M.; Okutani, T.; Kikuchi, M.; Akiyama, (105) Moreland, J. E. The first decade of inorganic and organic
T. Preparation and properties of SiO2 from rice hulls. J. Ceram. surface modification. In Society of the Plastics Industry, Reinforced
Soc. Jpn. 1989, 97, 842. Plastics/Composites Institute, Proceedings of the 34th Annual
 Ind. Eng. Chem. Res., Vol. 40, No. 25, 2001 5875

Conference, Jan 30-Feb 2, 1979; Society of the Plastics Industry: (130) Gram, H. E.; Nimityongskul, P. Durability of natural
New York, Section 14-A. fibers in cement-based roofing sheets. J. Ferrocem. 1987, 17, 321.
(106) Reinforcing fillers: Clays, silicas and silanes; cellulose; (131) El-Hosiny, F. I.; Abo-El-Enein, S. A.; Helmy, I. M.; Khalil,
corn starch; rice husk ash, and carbon black. Eur. Rubber J. 1975, Kh. A. Effect of thermal treatment of rice husk ash on surface
157 (4), 34. properties of hydrated Portland cement-rice husk ash pastes. J.
(107) From nature come new rubber reinforcers. Rubber World. Therm. Anal. 1997, 48, 809.
1974, 171 (2), 42. (132) Rodrigues, F. A.; Monteiro, P. J. M. Hydrothermal
(108) Haxo, H. E. Jr.; Mehta; P. K. Ground rice-hull ash as filler synthesis of cements from rice hull ash. J. Mater. Sci. Lett. 1999,
for rubber. Rubber Chem. Technol. 1975, 48, 271. 18, 1551.
(109) Ismail, H.; Ishiaku, U. S.; Azhar, A. A.; Ishak, Z. A. M. A (133) Yamamoto, Y.; Lakho, S. M. Production and utilization
comparative study of the effect of thermo-oxidative aging on the of active rice husk ash as a substitute for cement. Trans. Japan
physical properties of rice husk ash and commercial fillers in Soc. Civ. Eng. 1982, 14, 386.
epoxidized natural rubber compounds. J. Elastomers Plast. 1997, (134) Jauberthie, R.; Rendell, F.; Tamba, S.; Cisse, I. Origin of
29, 270. the pozzolanic effect of rice husks. Constr. Build. Mater. 2000, 14,
(110) Jain, A.; Rao, T. R.; Sambi, S. S.; Grover, P. D. Energy 419.
and chemicals from rice husk. Biomass Bioenergy 1995, 7, 285 (135) Zhang, M. H.; Lastra, R.; Malhotra, V. M. Rice-husk ash
(111) Mehta, P. K.; Pitt, N. Energy and industry materials from paste and concrete: Some aspects of hydration and the micro-
crop residues. Resour. Recovery Conserv. 1976, 2 (1), 23. structure of the interfacial zone between the aggregate and paste.
(112) Ismail, H.; Ishiaku, U. S.; Arinab, A. R.; Ishak, Z. The Cem. Concr. Res. 1996, 26, 963.
effect of rice husk ash as a filler for epoxidized natural rubber (136) Al-Khalaf, M. N.; Yousif, H. A. Use of rice husk ash in
compounds. Int. J. Polym. Mater. 1997, 36, 39. concrete. The Int. J. Cem. Compos. Lightweight Concr. 1984, 6,
(113) Ishak, Z. A. M.; Bakar, A. A. An Investigation on the 241.
potential of rice husk ash as fillers for epoxidized natural rubber. (137) Ajiwe, V. I. E.; Okeke, C. A.; Akigwe, F. C. A preliminary
Eur. Polym. J. 1995, 31, 259. study of manufacture of cement from rice husk ash. Bioresour.
(114) Ismail, H.; Ishiaku, U. S.; Arinab, A. R.; Ishak, Z. A. M. Technol. 2000, 73, 37.
Epoxidized natural rubber compounds: Effect of vulcanization (138) Kilinckale, F. M. The effect of MgSO4 and HCl solutions
systems and fillers. Polym.-Plast. Technol. Eng. 1998, 37, 469. on the strength and durability of pozzolan cement mortars. Cem.
(115) Ismail, H.; Chung, F. L. Partial replacement of silica by Concr. Res. 1997, 27, 1911.
white rice husk ash in natural rubber compounds: The effects of (139) Boateng, A. A.; Skeete, D. A. Incineration of rice hull for
bonding agents. Iran. Polym. J. (Engl. Ed.). 1998, 7, 255. use as a cementitious material: The guyana experience. Cem.
(116) Costa, H. M. D.; Visconte, L. L. Y.; Nunes, R. C. R.; Concr. Res. 1990, 20, 795.
Furtado, C. R. G. The effect of coupling agent and chemical (140) Mehta, P. K.; Pirtz, D. Use of rice hull ash to reduce
treatment on rice husk ash-filled natural rubber composites. J. temperature in high-strength mass concrete. J. Am. Concr. Inst.
Appl. Polym. Sci. 2000, 76, 1019. 1978, 75 (2), 60.
(117) Fuad, M. Y. A.; Jamaludin, M.; Ishak, Z. A. M.; Omar, A. (141) Zhang, M. H.; Malhotra, V. M. High-performance concrete
K. M. Rice husk ash as fillers in polypropylene: A preliminary incorporating rice husk ash as a supplementary cementing mate-
study. Int. J. Polym. Mater. 1993, 19, 75. rial. ACI Mater. J. 1996, 93, 629.
(118) Fuad, M. Y. A.; Ismail, Z.; Mansor, M. S.; Ishak, Z. A. (142) Mehta, P. K. Properties of blended cements made from
M.; Omar, A. K. M. Mechanical properties of rice husk ash/ rice husk ash. J. Am. Concr. Inst. 1977, 74, 440.
polypropylene composites. Polym. J. 1995, 27, 1002. (143) Yu, Q. J.; Sawayama, K.; Sugita, S.; Shoya, M.; Isojima,
(119) Fuad, M. Y. A.; Ismail, Z.; Ishak, Z. A. M.; Omar; A. K. Y. The reaction between rice husk ash and Ca(OH)2 solution and
M. Application of rice husk ash as fillers in polypropylene: Effect the nature of its product. Cem. Concr. Res. 1999, 29, 37.
of titanate, zirconate and silane coupling agents. Eur. Polym. J. (144) Folliard, K. J.; Ohta, M.; Rathje, E.; Collins, P. Influence
1995, 31, 885. of mineral admixtures on expansive cement mortars. Cem. Concr.
(120) Fuad, M. Y. A.; Zaini, M. J.; Ishak, Z. A. M.; Omar, A. K. Res. 1994, 24, 424.
M. Rice husk ash (RHA)-based silica as filler in polypropylene (145) Ramachandran, V. S. Alkali-aggregate expansion inhib-
composite: Effect of peroxide-containing silane on the rheological iting admixtures. Cem. Concr. Compos. 1998, 20, 149.
behavior. J. Elastomers Plast. 1994, 26, 252. (146) James, J.; Rao, M. S. Reaction product of lime and silica
(121) Fuad, M. Y. A.; Shukor, R.; Ishak, Z. A. M.; Omar, A. K. from rice husk ash. Cem. Concr. Res. 1986, 16, 67.
M. Rice husk ash as filler in polypropylene: Effect of wax and (147) James, J.; Rao, M. S. Reactivity of rice husk ash. Cem.
silane coupling agents. Plast. Rubber Compos. Process. Appl. 1994, Concr. Res. 1986, 16, 296.
21, 225. (148) Khangaonkar, P. R.; Rahmat, A.; Kutty, K. G. J. Kinetic
(122) Fuad, M. Y. A.; Mustafah, J.; Mansor, M. S.; Ishak, Z. A. study of the hydrothermal reaction between lime and rice-husk-
M.; Omar, A. K. M. Thermal properties of polypropylene/rice husk ash silica. Cem. Concr. Res. 1992, 22, 577.
ash composites. Polym. Int. 1995, 38, 33. (149) Sastry, M. V. B. R.; Reddi, M. S.; Gangaraju, C. P.
(123) Chand, N.; Dan, T. K.; Verma, S.; Rohatgi, P. K. Rice husk Comparative study of effect of addition of rice-husk ash and cinder-
ash filled-polyester resin composites. J. Mater. Sci. Lett. 1987, 6, ash to soil-lime mixtures. Indian Highways 1986, 14 (8), 5.
733. (150) de Gutierrez, R. M.; Delvasto, S. A. Production of high
(124) Siriwardena, S.; Ismail, H.; Ishiaku, U. S. Effect of mixing strength cements from rice husk ash. J. Resour. Manage. Technol.
sequence in the preparation of white rice husk ash filled polypro- 1994, 22 (3), 127.
pylene/ethylene-propylene-diene monomer blend. Polym. Test. (151) Stroeven, P.; Bui, D. D.; Sabuni, E. Ash of vegetable waste
2000, 20, 105. used for economic production of low to high strength hydraulic
(125) Ismail, H.; Nizam, J. M.; Khalil, H. P. S. A. The effect of binders. Fuel 1999, 78, 153.
a compatibilizer on the mechanical properties and mass swell of (152) Sadasivan, S.; Rasmussen, D. H.; Chen, F. P.; Kannabi-
white rice husk ash filled natural rubber/linear low-density ran, R. K. Preparation and characterization of ultrafine silica.
polyethylene blends. Polym. Test. 2001, 20, 125. Colloids Surf. A 1998, 132, 45.
(126) Sun, L. Y.; Xiao, M.; Xiao, P.; Song, J. H.; Wang, W. X.; (153) Li, H. T.; Song, X. Q.; Xie, C. L. The industrialization of
Zhang, Y. F.; Gong, K. C. A Preliminary Study on Rice Husk Filled the white carbon black from liquid-phase reaction and the
Polypropylene Composite. Mater. Res. Soc. Symp. Proc. 2001, 661, characterization of the product. Chem. Equip. Technol. (China)
KK5.14.1-KK5.14.6. 1999, 20 (4), 16.
(127) Rozman, H. D.; Lee, M. H.; Kumar, R. N.; Abusamah, (154) Fan, S. S.; Shi, X. N.; Li, C. H.; Wang, J. Q. Study on
A.; Ishak, Z. A. M. The effect of chemical modification of rice husk preparation of silica membrane with ultrafine pore size. J. Inorg.
with glycidyl methacrylate on the mechanical and physical proper- Mater. 1995, 10 (1), 90.
ties of rice husk-polystyrene composites. J. Wood Chem. Technol. (155) Wang, M.-J.; Mahmud, K.; Murphy, L. J.; Pattersor, W.
2000, 20, 93. J. Carbon-silica dual phase filler, a new generation reinforcing
(128) Malhotra, V. M. Fly ash, slag, silica fume, and rice-husk agent for rubber. Kautsch. Gummi Kunstst. 1998, 51, 348.
ash in concrete: A review. Concr. Int. 1993, 15, 23. (156) Lin, K. S.; Wang, H. P.; Lin, C.-J.; Juch, C.-I. A process
(129) Dass, A. Pozzolanic behavior of rice husk ash. Batim. Int. development for gasification of rice husk. Fuel Process. Technol.
Build. Res. Pract. 1984, 17, 307. 1998, 55, 185.
5876 Ind. Eng. Chem. Res., Vol. 40, No. 25, 2001

(157) Das, S.; Dan, T. K.; Prasad, S. V.; Rohatgi, P. K. (185) Kunst, M.; Abdallah, O.; Wünsch, F. The characterization
Aluminum alloy-rice husk ash particle composites. J. Mater. Sci. of silicon nitride films by contactless transient photoconductivity
Lett. 1986, 5, 562. measurements. Thin Solid Films 2001, 383, 61.
(158) Dan, T. K.; Chand, N.; Rohatgi, P. K. Effect of glass, rice- (186) Li, W.-T.; McKenzie, D. R.; McFall, W. D.; Zhang, Q.-C.
husk ash and wollastonite on transverse strength of porcelain. J. Effect of sputtering-gas pressure on properties of silicon nitride
Mater. Sci. Lett. 1987, 6, 277. films produced by helicon plasma sputtering. Thin Solid Films
(159) Ibrahim, D. M.; Sallam, E. H. Suitability of active silica 2001, 384, 46.
from agricultural waste for improving aluminum porcelain. Trans. (187) Tsai, H.-S.; Jaw, G.-J.; Chang, S.-H.; Cheng, C.-C.; Lee,
J. Br. Ceram. Soc. 1980, 79 (6), 154. C.-T.; Liu, H.-P. Laser-assisted plasma-enhanced chemical vapor
(160) Qiu, T.; Xu, J.; Gong, Y. N.; Li, Y. Q. A study of synthesis deposition of silicon nitride thin film. Surf. Coat. Technol. 2000,
of Si3N4 powder by carbothermal reduction. Bull. Chin. Ceram. 132, 158.
Soc. 1995, 14 (5), 14. (188) Acharya, H. N.; Dutta, S. K.; Banerjee, H. D. Production
(161) Lathrop, D. Silcion nitride. Am. Ceram. Soc. Bull. 2000, of magnesium silicide and silane from rice husk ash. Sol. Energy
79 (6), 54. Mater. 1980, 3, 441.
(162) Wang, H.; Dai, Y. N. The character of reaction kinetics (189) Nandi, K. C.; Mukherjee, D.; Biswas, A. K.; Acharya, H.
for producing ultrafine Si3N4 powder with rice husks. Refractories N. A novel and inexpensive method of production of silanes from
1996, 30 (2), 77. rice husk and their gas chromatographic analyses. Sol. Energy
(163) Li, Y.; Liu, L. Q.; Dou, S. X. Kinetics of Si3N4 formation Mater. 1991, 22, 161.
from rice hull. J. Inorg. Mater. 1991, 6 (1), 45. (190) Chen, J.-M.; Chang, F.-W. The chlorination kinetics of
(164) Zhang, S.-C.; Cannon, W. R. Preparation of silicon nitride rice husk. Ind. Eng. Chem. Res. 1991, 30, 2241.
from silica. J. Am. Ceram. Soc. 1984, 67, 691. (191) Okutani, T.; Nakata, Y.; Ishikawa, K.; Takeda, K. Prepa-
(165) Liou, T.-H.; Chang, F.-W. The nitridation kinetics of ration of SiCl4 from rice hull ashes (part 2). Effect of alkaline and
pyrolyzed rice husk. Ind. Eng. Chem. Res. 1996, 35, 3375. alkaline earth metal salt additives on chlorination of rice hull
(166) Rahman, I. A. Preparation of Si3N4 by carbothermal ashes. J. Ceram. Soc. Jpn. (Int. Ed.). 1991, 99, 305.
reduction of digested rice husk. Ceram. Int. 1994, 20, 195. (192) Okutani, T.; Nakata, Y.; Hino, M. Preparation of SiCl4
(167) Addemir, O.; Tekin, A.; Gupta, C. K. Nitridation in the from rice hull ashes (part 3). FT-IR-PAS analysis of chlorination
processing and preparation of metals and ceramics. High Temp. mechanism of rice hull ashes containing alkaline and alkaline
Mater. Processes 1996, 15, 273. earth metal salts. J. Ceram. Soc. Jpn. (Int. Ed.). 1991, 99, 693.
(168) Cutler, I. B. Production of silicon nitride from rice hulls. (193) Zhang, Z. F. The utilization of rice husk and its outlook.
U.S. Patent 3,855,395, 1974. Jingdezhen’s Ceram. (China) 1990, 2, 21.
(169) Kuskonmaz, N.; Sayginer, A.; Toy, C.; Acma, E.; Addemir, (194) Basu, P. K.; King, C. J.; Lynn, S. Manufacture of silicon
O.; Tekin, A. Studies on the formation of silicon nitride and silicon tetrachloride from rice hulls. AIChE J. 1973, 19, 439.
carbide from rice husk. High Temp. Mater. Processes 1996, 15, (195) Ikram, N.; Akhter, M. X-ray diffraction analysis of silicon
123. prepared from rice husk ash. J. Mater. Sci. 1988, 23, 2379.
(170) Hanna, S. B.; Mansour, N. A. L.; Taha, A. S.; Abd-Allah, (196) Hunt, L. P.; Dismukes, J. P.; Amick, J. A.; Schei, A.;
H. M. A. Silicon carbide and nitride from rice hulls-III. formation Larsen, K. Rice hulls as a raw material for producing silicon. J.
of silicon nitride. Br. Ceram. Trans. J. 1985, 84 (1), 18. Electrochem. Soc. 1984, 131, 1683.
(171) Liou, T.-H.; Chang, F.-W.; Lo, J.-J. Pyrolysis kinetics of (197) Bose, D. N.; Govindacharyulu, P. A.; Banerjee, H. D.
acid-leached rice husk. Ind. Eng. Chem. Res. 1997, 36, 568. Large grain polycrystalline silicon from rice husk. Sol. Energy
(172) Weimer, A. W.; Cassiday, J. R.; Susnitzky, D. W.; Black, Mater. 1982, 7, 319.
C. K.; Beaman, D. R. Carbothermal nitridation synthesis of R-Si3N4 (198) Mishra, P.; Chakraverty, A.; Banerjee, H. D. Production
powder from pyrolyzed rice hulls. J. Mater. Sci. 1996, 31, 6005. and purification of silicon by calcium reduction of rice-husk white
(173) Rahman, I. A.; Riley, F. L. The control of morphology in ash. J. Mater. Sci. 1985, 20, 4387.
silicon nitride powder prepared from rice husk. J. Eur. Ceram. (199) Amick, J. A. Purification of rice hulls as a source of solar
Soc. 1989, 5, 11. grade silicon for solar cells. J. Electrochem. Soc. 1982, 129, 864.
(174) Xu, Z. Y. The progress of the chemical applications of rice (200) Hu, C. Z.; Yu, J. S.; Yao, K. H. The status of silane on
husks. Liaoning Huagong (China) 1994, 23 (1), 23. modern technology. Low-Temp. Spec. Gases 1998, (4), 12.
(175) Kaneko, Y.; Ameyama, K.; Iwasaki, H. Formation of (201) Nandi, K. C.; Mukherjee, D.; Biswas, A. K.; Acharya, H.
silicon nitride whiskers from rice hulls. J. Soc. Mater. Sci. (Jpn). N. Characterization of hydrogenated amorphous silicon films
1988, 37, 65. obtained from rice husk. Solid State Commun. 1991, 79, 687.
(176) Toro, P., Wittke, O. Rheological behavior of silicon nitride (202) Dwyer, J. Zeolite structure, composition and catalysis.
whiskers. Mater. Res. Soc. Symp. Proc. 1992, 287, 271. Chem. Ind. 1984, (2), 258.
(177) Rahman, I. A. Formation of different Si3N4 phases in the (203) Fan, E. R. New uses of zeolite. Conserv. Utiliz. Min.
presence of V2O5 during carbothermal reduction of untreated and Resour. 1999, (3), 19.
acid treated rice husk. Ceram. Int. 1998, 24, 293. (204) Deng, S. A. Characteristics and utilizations of zeolite.
(178) Nixon, R. D.; Koester, D. A.; Chevacharoenkul, S.; Davis, Environ. Pollut. Control 1991, 13 (4), 40.
R. F. Steady-state creep of hot-pressed SiC whisker-reinforced (205) Zhao, X. S.; Wang, Q. X.; Li, H. Y. Evolution of zeolite
silicon nitride. Compos. Sci. Technol. 1990, 37, 313. synthesis. Chem. Ind. Eng. Prog. 1994, 13 (3), 32.
(179) Bao, X. J.; Edirisinghe, M. J. Different strategies for the (206) Dalai, A. K.; Rao, M. S.; Gokhale, K. V. G. K. Synthesis
synthesis of silicon carbide-silicon nitride composites from pre- of NaX Zeolite using silica from rice husk ash. Ind. Eng. Chem.
ceramic polymers. Compos. Part A. Appl. Sci. Manuf. 1999, 30, Prod. Res. Dev. 1985, 24, 465.
601. (207) Rawtani, A. V.; Rao, M. S.; Gokhale, K. V. G. K. Synthesis
(180) Nangrejo, M. R.; Bao, X. J.; Edirisinghe, M. J. Preparation of ZSM-5 zeolite using silica from rice husk ash. Ind. Eng. Chem.
of silicon carbide-silicon nitride composite foams from preceramic Res. 1989, 28, 1411.
polymers. J. Eur. Ceram. Soc. 2000, 20, 1777. (208) Bajpai, P. K.; Rao, M. S.; Gokhale, K. V. G. K. Synthesis
(181) Li, X. G.; Nakata, Y.; Nagai, H.; Suzuki, M. Synthesis of Mordenite type zeolite using silica from rice husk ash. Ind. Eng.
and thermal stability of SiC-Si3N4 composite ultrafine particles Chem. Prod. Res. Dev. 1981, 20, 721.
by laser-induced gas-phase reaction. Nanostruct. Mater. 1998, 10, (209) Hamdan, H.; Muhid, M. N. M.; Endud, S.; Listiorini, E.;
1173. Ramli, Z. 29Si MAS NMR, XRD and FESEM studies of rice husk
(182) Luan, S. Y.; Liang, W. H.; Zhu, Z. D.; Qin, R. H.; Jiang, silica for the synthesis of zeolites. J. Non-Cryst. Solids 1997, 211,
C. S.; Duan, X. D. Si3N4 superfine powders prepared by laser 126.
driven gas reaction method. J. Inorg. Mater. 1990, 5, 245. (210) Bajpai, P. K.; Rao, M. S.; Gokhale, K. V. G. K. Thermal
(183) Sheng, L. G.; Luo, X. Y.; Zhuang, H. R.; Li, W. L.; Fu, X. characteristics of mordenite type zeolite. In Proceedings of the
R. Synthesis of ultrafine silicon nitride powder by sol-gel and Seventh International Conference on Thermal Analysis, Kingston,
carbothermal nitridation. J. Inorg. Mater. 1993, 8, 483. Canada, 1982; Wiley: New York, pp 558-564.
(184) Feng, L.; Zheng, T.; Li, D. H. Study on nanometer sized (211) Gokhale, K. V. G. K.; Dalai, A. K.; Rao, M. S. Thermal
R-Si3N4 particles by laser induced chemical vapor deposition characteristics of synthetic sodium zeolites prepared with silica
method. China Powder Sci. Technol. 1999, 5 (3), 30. from rice-husk ash. J. Therm. Anal. 1986, 31, 33.
 Ind. Eng. Chem. Res., Vol. 40, No. 25, 2001 5877

(212) Wang, H. P.; Lin, K. S.; Huang, Y. J.; Li, M. C.; Tsaur, L. (225) Shimokawa, K.; Sekiguchi, I.; Suzuki, Y.; Ueda, Y.
K. Synthesis of zeolite ZSM-48 from rice husk ash. J. Hazard. Synthesis of Si-O-C fibers from rice husk carbide-explanation
Mater. 1998, 58, 147. of formation condition. J. Ceram. Soc. Jpn. (Int. Ed.). 1992, 100,
(213) Kumar, N. L.; Das, D. Zeolite (ZSM-5) synthesis from rice 1111.
husk for xylene isomerization. Res. Ind. 1992, 37 (3), 141. (226) Shimokawa, K.; Sekiguchi, I.; Suzuki, Y.; Yabe, K.; Ueda,
Y. Synthesis of ceramic fibers in the Si-O-C system. J. Ceram.
(214) Bajpai, P. K.; Rao, M. S.; Gokhale, K. V. G. K. Synthesis Soc. Jpn. (Int. Ed.). 1991, 99, 741.
of mordenite type zeolite. Ind. Eng. Chem. Prod. Res. Dev. 1978, (227) Wu, Y. Preparation of sodium fluorodesilicate from rice
17, 223. husk. Hebei Huagong (China) 1993, (1), 62.
(215) Tavolaro, A.; Drioli, E. Zeolite Membranes. Adv. Mater. (228) Rahman, I. A.; Saleh, M. I. Formation of β-sialon in the
1999, 11, 975. carbothermal reduction of digested rice husks. Mater. Lett. 1995,
(216) Nomura, M.; Yamaguchi, T.; Nakao, S. Silicalite mem- 23, 157.
branes modified by counterdiffusion CVD technique. Ind. Eng. (229) Cardile, C. M. Carbothermal synthesis of β prime-sialon
Chem. Res. 1997, 36, 4217. from a byproduct of alumina refining. Key Eng. Mater. 1991, 53-
55, 47.
(217) Naga, S. M.; Mortel, H.; Ibrahim, D. M. Low thermal (230) Han, H.-W.; Huang, C.-Y.; Liu, H.-S. Formation of
expansion honeycomb cordierite containing rice husk ash. Ind. gehlenite (Ca2Al2SiO7) by carbothermal reduction of carbonized
Ceram. 1994, 14 (3), 116. rice hulls. J. Ceram. Soc. Jpn. 1999, 107, 1115.
(218) Naga, S. H.; Sallam, E. H.; Ibrahim, D. M. Effect of (231) Wang, W. X.; Gong, K. C. Organic/inorganic hybrid
mineralizers on the production of dense cordierite bodies. Int. materials on molecular scale from a novel type of precursors.
Ceram. 1994, 43, 243. Presented at the 2000 MRS Spring Meeting, San Francisco, CA,
(219) Ghosh, T. B.; Nandi, K. C.; Acharya, H. N.; Mukherjee, Apr 2000; Paper CC6.25.
D. XPS studies of magnesium silicide obtained from rice husk. (232) Wang, W. X.; Gong, K. C. Novel silicon complexes to
Mater. Lett. 1991, 11, 6. enhance fillers’ interfacial adhesion and processability of polymer.
Presented at the 2000 MRS Spring Meeting, San Francisco, CA,
(220) Bose, S.; Acharya, H. N.; Banerjee, H. D. Electrical, Apr 2000; Paper FF5.6.
thermal, thermoelectric and related properties of magnesium (233) Wang, W. X.; Zeng, X. R.; Liu, A. H.; Gong, K. C. Novel
silicide semiconductor prepared from rice husk. J. Mater. Sci. surface modifying agent from rice husk ash and its application in
1993, 28, 5461. reinforcing silicone rubber. In In Proceedings of the 3rd Interna-
(221) Kalapathy, U.; Proctor, A.; Shultz, J. Production and tional Workshop on Green Chemistry in China, Guangzhou, China,
properties of flexible sodium silicate films from rice hull ash silica. May 2000; Guangzhou Institute of Chemistry, CAS: Guangzhou,
Bioresour. Technol. 2000, 72, 99. China, pp 151-152.
(222) Kalapathy, U.; Proctor, A. A new method for free fatty (234) Wang, L. J.; Guo, Z. M.; Li, T. J. Biomineralized nano-
acid reduction in frying oil using silicate films produced from rice structured materials and plant silicon nutrition. Prog. Chem. 1999,
hull ash. J. Am. Oil Chem. Soc. 2000, 77, 593. 11, 119.
(223) Chakrabarti, M.; Virkar, A. N.; Maiti, H. S. Formation Received for review March 26, 2001
of forsterite using rice husk ash for high-frequency insulation.
Revised manuscript received July 20, 2001
Trans. Indian Ceram. Soc. 1985, 44 (1), 1.
Accepted September 13, 2001
(224) Mondal, B.; Sundaram, S. K.; Virkar, A. N. Studies on
the sinterability of pure and Al2O3 containing forsterite prepared
from rice husk ash. Trans. Indian Ceram. Soc. 1985, 44 (6), 128. IE010284B