Powder Technology 252 (2014) 51–55

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Powder Technology
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Synthesis of Si3N4 powder with tunable α/β-Si3N4 content from waste

silica fume using carbothermal reduction nitridation
Haipeng Ji, Zhaohui Huang ⁎, Kai Chen, Wenjuan Li, Yuanfei Gao, Minghao Fang, Yan-gai Liu, Xiaowen Wu
School of Materials Science and Technology, China University of Geosciences (Beijing), Beijing 100083, China

a r t i c l e i n f o a b s t r a c t

Article history: Silicon nitride (Si3N4) powder with tunable α/β-Si3N4 relative contents was synthesized from waste silica fume
Received 30 July 2013 using carbothermal reduction nitridation (CRN) at a relatively low temperature range of 1400–1500 °C. The ef-
Received in revised form 8 October 2013 fects of the carbon source, CRN temperature and raw materials ratio (Carbon-to-Silica fume) on phase assembly
Accepted 18 October 2013
and micro-morphology of the products were investigated. Fabrication of α-Si3N4/β-Si3N4 from waste silica fume
Available online 29 October 2013
by CRN was achieved at temperatures as low as 1400 °C. Carbon black was found to be more suitable than coke
Keywords:
and graphite for use as the reductant. Elevated temperature was beneficial for the formation of β-Si3N4, whilst
Silica fume excessive carbon black promoted the formation of α-Si3N4. Thus, the α-Si3N4/β-Si3N4 relative contents could
Silicon nitride be effectively tailored by adjusting the CRN temperature and carbon concentration of the initial mixtures. In ad-
Carbothermal reduction nitridation dition, the bi-modal crystals of the whiskers and the short columns strongly influenced the morphologies of the
Morphology product.
© 2013 Elsevier B.V. All rights reserved.

1. Introduction unsatisfactory pozzolonicity has very limited potential application and

Silica fume is an ultrafine powder by-product extracted from gases
produced from silicon or ferrosilicon alloy production. When quartz,
coal, coke and/or woodchips are fired up to 1750 °C in an electric arc
furnace to produce silicon and/or its alloys, the exhaust dust from
smoke is collected on electrostatic filters or filter-bags as silica fume
[1]. In China, the average yield of silica fume has been reported to be
0.2–0.3 ton output along with 1.0 ton ferrosilicon alloy production
(5.11 million tons in 2010, 4.78 million tons in 2012) indicating an
abundant reserve of silica fume. This solid industrial fume consists of
spherical particles less than 1 μm in diameter with the average being
about 150 nm, which if discharged directly into the atmosphere would
aggravate the ambient particulate matter (PM) [2,3]. In recent decades,
the public health effect of ambient PM exposure has become a great so-
cial concern and therefore must be controlled. Due to tougher environ-
mental laws in China, the collection and subsequent utilization of silica
fume are attracting increasing attention.
The SiO2 content and its pozzolanic activity are two dominant factors
affecting the utilization of silica fume. Silica fume with 88–92% SiO2 con-
tent and perfect pozzolonicity can be used as an additive in concrete.
The portland cement based concretes containing silica fume improve
properties such as strength, compaction and durability [4,5]. Silica
fume with SiO2 content of N 92% can be used as additive in refractory cast-
able and as raw materials to synthesize SiC powder [6] and cordierite-
mullite [7]. Nevertheless, silica fume with SiO2 content of b88% and
⁎ Corresponding author. Tel./fax: +86 10 82322186.
E-mail address: huang118@cugb.edu.cn (Z. Huang).
discarded as solid wastes constituting a health and atmospheric hazard.
With a rapidly increasing accumulating waste reserve to dispose, it is
highly desirable to explore feasible routes for the high-efficiency utiliza-
tion of silica fume.
Silicon nitride (Si3N4) is one of the most promising engineering ma-
terials especially for high temperature applications, due to its excellent
thermal shock resistance, good mechanical properties, and chemical
stability at both room and high temperatures [8,9]. Techniques applied
to fabricate silicon nitride include: direct nitridation of silicon [10,11],
high-temperature decomposition of silicon diimide [12], SiO vapor
ammonolysis [13] and carbothermal reduction and simultaneous
nitridation (CRN) of silica [14,15]. Amongst these methods, the CRN
route is one of the most cost-effective routes for industrial production
of Si3N4 powder. Silica fume consists of SiO2 with fine particle size and
high intrinsic chemical reactivity and is a potential candidate for low-
cost production of Si3N4 powder by CRN at relatively low temperatures.
However, few papers dealing with the synthesis of Si3N4 from silica
fume are available, despite of one on the preparation of nanostructured
Si3N4/SiC composites from silica fume with 94.5 % SiO2 content [16], and
another comparing two ways in H2 and in air for the removing excessive
carbon [17]. To our best knowledge, the synthesis of α/β-Si3N4 powder
from waste silica fume with less SiO2 content and unsatisfactory
pozzolonicity has not been previously reported.
In this paper α/β-Si3N4 powder with tunable α/β relative contents
was synthesized from waste silica fume using carbothermal reduction
and nitridation (CRN) method at a temperature range of 1400–1500 °C.
The effects of reductant carbon source, CRN temperature and initial con-
centration of carbon on phase composition and micro-morphology of the
products have been investigated.

0032-5910/$ – see front matter © 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.powtec.2013.10.030
52 H. Ji et al. / Powder Technology 252 (2014) 51–55

2. Experimental

2.1. Material preparation

The chemical compositions of waste silica fume (Shanghai Topken

Silica Fume Co., Ltd., China) measured by X-ray fluorescence (XRF)
are: (wt.%) SiO2 90.26, Al2O3 0.13, Fe2O3 2.46, CaO 0.29, MgO 1.57,
Na2O 0.60, K2O 1.34, SO3 0.29, others 0.26, and loss on ignition 2.80.
The X-ray powder diffraction (XRD) pattern suggests amorphous silica
was the main phase of silica fume used in this research (Fig. 1). Scanning
electron microscopy (SEM) image reveals fine particles of silica fume of
less than 300 nm in diameter (Fig. 2). The reductant carbon sources
employed were: carbon black (average particle size of 100 nm,
Shandong Province, China), carbon coke (granularity ≤74 μm, carbon
content = 88 wt.%, Shanxi Xinshidai Imp. & Exp. Co., Ltd., China), and
flake graphite (N 99wt.% purity, average particle size of 10μm, Shandong
Qingdao Graphite Co., Ltd., China). The CRN synthesis of Si3N4 from silica Fig. 2. SEM image of the as-received silica fume, revealing spherical aggregated particles
less than 300 nm in diameter.
fume plus carbon mixtures was considered to proceed as follows:

3SiO2 ðsÞ þ 6CðsÞ þ 2N2 ðgÞ→Si3 N4 ðsÞ þ 6COðgÞ
According to reaction (1), the compositions and CRN temperature of
silica fume-carbon mixtures were designed, as outlined in Table 1. First-
ly, samples C1, C2 and C3 were used to determine suitable carbon source
for the present study and then, T1, T2, T3 and T4 with stoichiometric
proportion (Carbon:Silica fume = 2:1, molar ratio) were selected to
determine the effect of temperature on the CRN transformation of silica
fume. Finally, to investigate the effects of carbon addition on the
phase composition and morphology of the products and to tailor the
α/β-Si3N4 relative content, 10 wt.% and 30 wt.% excess of carbon black
were added to S2 and S3.
The powders were weighed and dry-mixed using a planetary mill for
12 h in a polyurethane jar with agate balls (ball-to-powder weight ratio
of 6:1). The mixtures held in a graphite crucible were then placed in a
vacuum furnace. The furnace was firstly evacuated to 10 Pa using a rota-
ry vacuum pump and then nitrogen gas (N2, purity 99.999%) was intro-
duced until the furnace pressure reached ~0.14 MPa. The pressure was
maintained throughout the experiment and the N2 flowed at a rate
range of 150–160 L/h. The furnace was initially heated to 1000 °C at
rate of 10 °C/min, and continuously elevated to final temperatures
(1300–1500 °C) at 5 °C/min, holding for 5 h. Finally, the samples were
allowed to furnace-cool to room temperature. The residual carbon in
the reaction products of T1 and S3 was burned off in air at 700 °C for 2 h.
2.2. Characterization
The phase composition was investigated by using X-ray powder dif-
fraction (XRD; Cu target, Kα1 radiation; Rigaku Corporation, Japan). The
ð1Þ micro-morphology was characterized with a scanning electron micro-
scope (SEM; JSM-6460LV, JEOL, Japan). A direct comparison method
proposed by Alcala [18] was applied to determine α-Si3N4 and β
phase percentages in the products based on the intensities Iα and Iβ of
the (201) α-Si3N4 and (101) β-Si3N4 X-ray diffraction peaks. The ex-
pression used for determining the fraction, xα, of α-Si3N4 phase was:
xα = 1/(1 + 0.668 (Iβ/Iα)). For simplicity, the products were assumed
to be pure-phase of silicon nitride, and the validity of the calculated per-
centages restricted to one individual figure. The percentages do not in-
dicate absolute quantities and could not be used for comparisons
among different plots.
3. Results and discussion
3.1. Carbon source selection
Carbon coke, carbon black and graphite were mixed with silica fume
in stoichiometric ratio to form samples C1, C2 and C3, which were then
sintered at 1400 °C for 5 h. The XRD patterns of the products shown in
Fig. 3 were compared to select the most suitable carbon source. When
graphite was used, the products were Si2N2O and cristobalite, whereas
no Si3N4 was obtained. When carbon coke was used, the products
were cristobalite, Si2N2O and β-SiC: cristobalite became more abundant,
Si2N2O got decreased and β-SiC was newly produced. β-SiC could be
formed by the carbothermic reactions of SiO and Si2N2O (reaction (2)
and (3)) [19], respectively.
SiO þ C→SiC þ CO ð2Þ

800
Si2 N2 O þ C→2SiC þ CO þ N2 ð3Þ
Only when carbon black was used, the silica fume was completely
700
transformed into Si3N4: major β phase with minor α phase. Hence, car-
600 bon black was more suitable than carbon coke and graphite for the CRN
Intensity (a.u.)

500
Table 1
Compositions and carbothermal reduction nitridation temperatures of the silica fume-
400
carbon mixtures.
300 Samples no. Proportion Temperature/°C Carbon source

200 C1 S.R.a 1450 Carbon coke

C2 S.R. 1450 Graphite
100 C3 (T3) S.R. 1450 Carbon black
T1 S.R. 1300 Carbon black
0 T2 (S1) S.R. 1400 Carbon black
10 20 30 40 50 60 70 T4 S.R. 1500 Carbon black
2θ (Degree) S2 S.R. + 10 wt.% C 1400 Carbon black
S3 S.R. + 30 wt.% C 1400 Carbon black
a
Fig. 1. XRD pattern of the as-received silica fume, suggesting the phase of amorphous SiO2. S.R. = Stoichiometric Ratio (Carbon: Silica fume = 2:1, molar ratio).
 H. Ji et al. / Powder Technology 252 (2014) 51–55 53

—β-Si3N4 —α-Si3N4 —β-SiC —Cristobalite of both β-Si3N4 and α-Si3N4 phases. As reported, the CRN of SiO2 with
—Si2N2O high purity raw materials usually yields a very high α-Si3N4 content
C1
powder; but in the presence of Fe and alkali elements (such as K2O,
Carbon coke
Na2O, CaO, Al2O3, TiO2 and Fe2O3), β-Si3N4 would be formed associating
with low-melting eutectics [21,24,25]. Chen et al. [26] also reported that
Intensity (a.u.)

Fe2O3 promoted β-Si3N4 formation in the CRN of quartz mineral. Hence,

C2
Graphite
C3
Carbon black
10 20 30 40 50
2 θ (Degree)
Fig. 3. XRD patterns of silica fume plus with different carbon sources sintered at 1400 °C
for 5 h.
transformation of silica fume. Previous researchers have suggested that
the CRN reaction of SiO2 would be enhanced when the total carbon par-
ticle surface area was increased [20,21]. It is also demonstrated that the
physical contact between carbon particles and SiO2 particles was essen-
tial for the SiO formation [22,23]. Amongst the three carbon sources
employed, carbon black has the highest surface area, lowest particle
size and thus the best contact with silica fume particles, which may be
the main reason for the high yield of Si3N4 in sample C3.
3.2. Effect of temperature on the CRN synthesis of Si3N4 powder from silica
fume
To study the effect of temperature on the CRN synthesis of Si3N4
from silica fume, samples T1–T4 with stoichiometric addition of carbon
black were sintered in the temperature range of 1300°C–1500°C for 5h.
XRD patterns of the products are shown in Fig. 4. When sintering at
1300°C the main phase was cristobalite, suggesting that the amorphous
SiO2 was transformed into crystalline silica but with no carbonitriding
reactions occurring. When increasing temperatures to 1400–1500 °C,
conversion of cristobalite vividly proceeded: all the products consisted
—β-Si3N4 —α-Si3N4
JCPDS-ICDD No. 33-1160 JCPDS-ICDD No. 41-360
the presence of Fe and other metallic impurities in the raw silica fume
was therefore the main reason for high β-Si3N4 yield in this study.
To enhance understanding of the phase evolution of CRN process at
1400–1500 °C, the α and β phase percentages in the products were cal-
culated accordingly, as illustrated in Fig. 5. Increasing the temperature
promoted β formation whilst α formation was suppressed. β is the sta-
ble form at all temperatures, whereas α is metastable with respect to β
60 70 but forms due to kinetic reasons. The transformation from α to β, as re-
ported, occurs at temperatures higher than 1600°C. However, due to the
individual and/or synergistical effect of impurities mentioned, α to β
conversion can occur at a much lower temperature, a possible explana-
tion for the relative content evolution between α and β phase observed
in Fig. 5.
SEM images of the products shown in Fig. 6 reveal a bi-modal mor-
phology of both whiskered and agglomerated micro-sized crystals. It
is well known that Si3N4 appears in two crystal forms in powder synthe-
sis, either as high aspect ratios whiskers (fibers, rods) which can easily
grow to centimeter lengths, or as microscopic, short columnar crystals
with hexagonal cross-sections [27]. Whiskers produced by a gas phase
reaction involving SiO are generally accepted as α crystal [25]. The
whiskers observed in Fig. 6 (a) can be attributed as α-Si3N4. Elevating
the temperature to 1450 °C the whisker products evidently decreased
(Fig. 6 (b)), suggesting a decreased yielding of α crystals, which corre-
sponds well with α/β ratio evolution results (Fig. 5). When sintered at
1500 °C, hardly any centimeter scope whiskers but short columnar
micro crystals with particle sizes of 3–10 μm were observed (Fig. 6
(c)), which are attributed to be β-Si3N4 [26].
3.3. Effect of carbon addition on the CRN synthesis of Si3N4 powder from
silica fume
The effect of carbon addition on the phase composition and mor-
phology of the products was further studied at the optimal conditions
of 1400 °C for 5 h using carbon black as reductant. Fig. 7 shows the
XRD patterns of samples S1–S3 with different additions of carbon
black. The intensities of α-Si3N4 diffraction peaks were apparently en-
hanced when carbon black was added in excess of 10 wt.% and 30 wt.%.
This is consistent with the results reported by Suri et al. [17], in which
higher yielding of α-Si3N4 was obtained in case of higher graphite-to-
T4
1500 °C silica fume molar ratios. Fig. 8 illustrates the relative α and β phase con-
tent in different samples sintered at 1400°C, indicating that α-Si3N4 yield

100
Intensity (a.u.)

T3
90
1450 °C
80
Phase composition (%)

70

T2 60 α-Si3N4
1400 °C 50 β-Si3N4
40

—Cristobalite 30
JCPDS-ICDD No. 27-650
T1 20
1300 °C 10
0
10 20 30 40 50 60 70 1400 1450 1500
2 θ (Degree) Temperature (°C)

Fig. 4. XRD patterns of silica fume plus stoichiometric carbon balck sintered at different Fig. 5. α-Si3N4 and β-Si3N4 relative content as function of temperature in samples T1–T4
temperatures for 5 h. with stoichiometric carbon balck.
54 H. Ji et al. / Powder Technology 252 (2014) 51–55

Fig. 6. SEM images of sample T2–T4 sintered at different temperatures: (a) 1400 °C, (b) 1450 °C, and (c) 1500 °C.

varied from as low as 20.7% to as high as 68.1%. α phase formation was
vividly promoted, which would benefit the sintering property of the
synthesized powders. Thus, controlling the carbon black concentration
of the initial mixtures is an effective way of tailoring the relative
α/β-Si3N4 content in Si3N4 products.
As seen in Fig. 7, minor β-SiC was detected in sample S3 with carbon
black in excess of 30 wt.%. The formation of β-SiC could be explained by
multiple mechanisms. When excessive carbon black was added, β-SiC
was formed by reaction (2). Moreover, β-SiC could be also formed by
reaction of C and Si3N4: in the presence of free carbon, the equilibrium
between SiC and Si3N4 can take place via reaction (4) [28].
Si3 N4 þ 3C→3SiC þ 2N2
is in agreement with the observations of Weimer et al. [31] and Vlasova
et al. [32], who have demonstrated in detail of α-Si3N4 growth on carbon
substrates.
SiOðgÞ þ CðsÞ þ N2 →Si3 N4 ðsÞ þ COðgÞ ð5Þ
SiOðgÞ þ COðgÞ þ N2 →Si3 N4 ðsÞ þ CO2 ðgÞ ð6Þ
It is worth noting that the micro-morphology of the α-Si3N4 crystals
changed from straight fibers to curved whiskers on increasing carbon
black (from S1 to S3), indicating that the PCO also greatly affected the
crystal growth of α-Si3N4. In Fig. 9 (c), spherical carbon black particles
decorated with short whiskers distributed in the products were also
ð4Þ observed.

SEM images of sample S1–S3 with different addition of carbon 4. Conclusions

black sintered at 1400 °C are shown in Fig. 9. Previous studies
[15,29] have demonstrated that Si3N4 crystals grown from SiO (g)
supersaturated N2 (g) and CO + N2 (g) were attached to available
surfaces, i.e. nucleation was described as heterogenerous. Under condi-
tions of a high CO content in the reactor, Si3N4 precipitation tends to
occur preferentially close to a reducing agent such as a carbon surface
[30]. Alcala et al. [18] confirmed that the synthesis of α-Si3N4 improved
at increasing partial pressure of CO in the vicinity of the sample. Ekelund
et al. [27] further demonstrated that a high PSiO is insufficient for Si3N4
nucleation, and the PCO determines the nucleation point. The conversion
of SiO2 to Si3N4 can occur through vapor–solid and/or vapor–vapor reac-
tions: in the absence of seeding, Si3N4 will first form on a C site via a
vapor–solid reaction (reaction (5)); subsequently, the gas-phase reaction
may also occur for Si3N4 crystal growth (reaction (6)). The presence of
excessive carbon black can assist both processes by acting as a site for
Si3N4 formation, and by reducing the CO2 produced to CO. This conclusion
Silicon nitride (Si3N4) powder with tunable α/β-Si3N4 relative con-
tents was synthesized from waste silica fume by using carbothermal re-
duction nitridation (CRN) at a relatively low temperature range of
1400–1500 °C with holding time of 5 h in nitrogen flow. Carbon black,
rather than carbon coke or graphite, is recommended as the reductant
due to the high yield of Si3N4 obtained in this study. In the presence of
Fe and alkali, the conversion of α to β is promoted at higher CRN tem-
peratures, favoring the formation of β-Si3N4. Carbon black can serve as
nucleation sites for Si3N4 formation and help to reduce the CO2 pro-
duced to CO. For these kinetics reasons, excessive carbon black pro-
motes the formation of α-Si3N4. Thus, the relative α/β-Si3N4 content
can be tailored by controlling the CRN temperature and the carbon con-
centration of the initial mixtures. The as-synthesized products present
typical bi-modal crystals with whisker and short column morphologies.
This transformation provides a technologically feasible means of

—β-Si3N4 —α-Si3N4 —β-SiC

100
90
S3 α-Si3N4
80
β-Si3N4
Phase composition (%)
Intensity (a.u.)

70
60
S2 50
40
30
20
S1
10
0
10 20 30 40 50 60 70 stoichiometric ratio (S1) excess 10 wt% (S2) excess 30 wt% (S3)
2θ (Degree) Addition of carbon black

Fig. 7. XRD patterns of silica fume plus different carbon balck additions (samples S1–S3) Fig. 8. α-Si3N4 and β-Si3N4 relative content as function of carbon black addition in samples
sintered at 1400 °C. S1–S3 sintered at 1400 °C.
 H. Ji et al. / Powder Technology 252 (2014) 51–55
Fig. 9. SEM images of sample S1–S3 with different carbon black addition sintered at 1400 °C: (a) stoichiometric addition, (b) 10 wt.% in excess, and (c) 30 wt.% in excess.
consuming abundant waste silica fume for low-cost synthesis of silicon
nitride powders.
Acknowledgments
This work was supported by the National Natural Science Foun-
dation of China (Grant No. 51032007), the New Star Technology
Plan of Beijing (Grant No. 2007A080), the Fundamental Research
Funds for the Central Universities (Grant No. 2652013040), and the Re-
search Fund for the Doctoral Program of Higher Education of China
(20130022110006). Y.G. Liu also thanks the Program for New Century
Excellent Talents in University (Grant No. NCET-12-0951).
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