Ceramics International 43 (2017) 111

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Ceramics International
journal homepage: www.elsevier.com/locate/ceramint

Review article

Preparation and characterization of whisker-reinforced ceramics from coal

y ash
crossmark

Yang Luoa,b, Shuhua Maa, Zhenqing Zhaoa, Zehua Wanga,b, Shili Zhenga, , Xiaohui Wanga
a
National Engineering Laboratory for Hydrometallurgy Cleaner Production Technology, Key Laboratory of Green Process and Engineering, Institute of
Process Engineering, Chinese Academy of Sciences, Beijing 100190, PR China
b
University of Chinese Academy of Science, Beijing 100049, PR China

A R T I C L E I N F O A BS T RAC T

Keywords: A new type of ceramic is developed based on tobermorite whiskers, in which aluminum replaces some of the
Coal y ash original silicon atoms. These Al-tobermorite whiskers are synthesized from coal y ash through a dynamic
Dynamic hydrothermal method hydrothermal method. Their ne ber morphology and Al-substitution produce bulk ceramics with excellent
Tobermorite ber mechanical properties. When sintered at 900 C, a temperature lower than the one used for conventional
Low temperature sintering
ceramics, these whisker-reinforced ceramics have a exural strength of 52.27 MPa, an open porosity of 9.51%,
Reinforced ceramic
and a bulk density of 2.15 g/cm3. These properties are attributed to the Al/Si ratio in the y ash within an ideal
range to improve the crystal form of the tobermorite as well as the wollastonite produced by sintering, without
leaving residual Al that may aect the mechanical properties of the ceramics.

1. Introduction
Economic development in China has caused energy demands to
soar, with coal being the major fuel for electricity generation in the
country. The total production of coal y ash (CFA) is estimated to
exceed 4.51011 kg per year [1]. Finding a use for this CFA has become
a signicant problem [2,3], especially because the increasing number of
coal power plants entails the production of even greater volumes of
CFA in the future [4]. The CFA not only occupies valuable farmland,
but also can create severe pollution issues in the surrounding environ-
ment [5,6]. While the ecient disposal of CFA is especially challenging
in China, it is also a global issue. The practical use of CFA started in the
1930 s in the USA [3]; since then, many new applications have been
attempted. These include CFA use in construction; as a low-cost
adsorbent for removing organic compounds, ue gases, and metals;
as a lightweight aggregate, mine backll, or road sub-base; and in the
synthesis of zeolites. Despite these eorts, only a small percentage of
CFA (15%) is currently utilized in China [7].
Tobermorite [Ca5Si6O175H2O] is a crystalline calcium silicate
hydrate synthesized by hydrothermal reactions in the CaO-SiO2-H2O
system. Tobermorite synthesis has been studied globally, but generally
only when using raw materials from natural resources [8]. The use of
CFA as a precursor in tobermorite synthesis has not been reported.
Many studies have shown that brous tobermorite-type materials,
and particularly tobermorite whiskers, have great potential for struc-
tural use because they show excellent mechanical properties and
durability. However, the mechanical strength of directly formed
tobermorite-type materials is generally insucient for most applica-
tions. This study therefore combines sintering with a hydrothermal
method for converting CFA into brous Al-tobermorite whiskers, to
be used as reinforcing materials in architectural ceramics. The use of
CFA as a building material has two-fold environmental benets of
reducing the need to mine materials and diminishing the accumulation
of waste CFA. The low cost of CFA could also permit signicant
economic gains.
2. Experimental procedure
2.1. Materials
The CFA used as the primary raw material in this experiment was
sourced from a thermoelectric power plant in Inner Mongolia, China.
The chemical composition is listed in Table 1, which shows that the
Al2O3 and SiO2 contents of 21.47% and 55.57%, respectively, are very
similar to those of conventional raw materials for ceramics [9,10]. Loss
on ignition (LOI), a test where the amount of mass lost after a sample is
exposed to strong heat indicates the prevalence of volatile compounds
in the raw sample, was ~2.83%. The CFA was prepared by planetary

Abbreviations: CFA, coal y ash; TCFA, tobermorite synthesized from CFA; CRE, ceramic; TOB, tobermorite

Corresponding author.
E-mail address: slzheng@ipe.ac.cn (S. Zheng).

http://dx.doi.org/10.1016/j.ceramint.2016.09.211
Received 12 September 2016; Received in revised form 28 September 2016; Accepted 30 September 2016
Available online 07 October 2016
0272-8842/ 2016 Elsevier Ltd and Techna Group S.r.l. All rights reserved.
Y. Luo et al. Ceramics International 43 (2017) 111

Table 1
Chemical composition of CFA.
Calcium oxide Coal fly ash
Composition Al2O3 SiO2 Fe2O3 TiO2 CaO MgO Na2O K2O LOI

Content (wt%) 21.47 55.57 6.8 0.01 5.12 2.97 3.42 1.22 2.83

ball milling for 2 min at a speed of 200 rpm. Hydrothermal reaction

Other reagents, aluminum hydroxide and calcium oxide, were of
reagent grade and obtained from Xilong Chemical Co., Ltd. All were
used as received without further purication.

2.2. Sample preparation

Aluminum substituted tobermorite whiskers
2.2.1. Preparation of aluminum-substituted tobermorite whiskers
A hydrothermal reaction was performed in a 1000-mL stainless
steel autoclave lined with pure nickel and equipped with a mechanical
agitator and a control system used to maintain the desired temperature
within an error of 0.5 C. The milled CFA was treated in the presence
of calcium hydroxide to synthesize Al-tobermorite whiskers via a mild Molding
hydro-chemical reaction, after which the mixture was quickly cooled to
90 C using a cold water ow. The reaction conditions used were those
found in our earlier optimization study [11], namely: mass ratio of
solution to solid reactant (L/S) of 30, temperature of 220 C, Ca/(Al
+Si) molar ratio of 1, and residence time of 2 h. The resulting slurry
was ltered to obtain a solid composite, which was then washed twice Low temperature sintering
with deionized water at 80 C. Finally, the solid composite reinforced
with the whiskers was dried at 105 C for 8 h. A small amount of the
composite was used for subsequent analyses of its physical properties,
while the rest was used to prepare ceramics for testing.
Sodium silicate, calcium oxide, and aluminum hydroxide were Whisker reinforced ceramics
mixed together in the same autoclave described above to synthesize a
series of purer Al-tobermorite whiskers as comparison samples. To
Fig. 2. Schematic for the fabrication of whisker-reinforced ceramics.
investigate the eects of Al2O3 present in the y ash, tobermorite was
also prepared from chemical reagents with varying molar ratios of
Table 2
alumina to silica (Al/Si) of 0 (TOB0), 0.1 (TOB0.1), 0.15 (TOB0.15),
Chemical composition of two kinds of aluminum-substituted tobermorite.
0.2 (TOB0.2), and 0.25 (TOB0.25) by adjusting the amount of
aluminum hydroxide added. All other conditions were kept constant. Composition Al2O3 SiO2 Fe2O3 TiO2 CaO MgO Na2O K2O

Content (wt%) 10.45 35.39 2.46 1.21 30.58 1.32 1.22 0.54
2.2.2. Preparation of whisker-reinforced ceramics
The prepared Al-tobermorites were mixed with deionized water to
achieve a mass ratio of 10:2, and then pressed into 1001004 mm 105 C for 12 h, and then sintered at a temperature between 850 and
cuboids under 20 MPa of pressure using a uniaxial tablet press (Model 1000 C for 2 h in a laboratory-type electrical furnace (Model
WE-300B). The resulting green compacts were dried in an oven at

12
A
A---Quartz
10
B---Mullite
Differencial Volume/%

8
Intensity(a.u.)

A
B 4
B
BB
A
AB A A A 2
A

10 20 30 40 50 60 70 80 90 1 10 100 1000
Diffraction Angle,2 /degree(CuK ) Particle Diameter/m

Fig. 1. Characterization of milled CFA: (a) XRD pattern and (b) size distribution.

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Y. Luo et al. Ceramics International 43 (2017) 111

Fig. 3. Characterization of TCFA: (a, b) SEM images, (c, d) FETEM images, (e) electron diraction pattern, (f) XRD pattern.

HTF1400). Furnace cooling was applied to all samples. Additional
ceramic samples were produced using the same procedure from the
comparison tobermorite synthesized from reagents.
2.3. Characterization techniques
The precursor CFA was analyzed by X-ray diraction (XRD, X'Pert
Pro MPD, PANalytical Company) at 40 kV and 30 mA using Cu K
radiation. After milling, a laser particle size analyzer was used to

3
Y. Luo et al.
Fig. 4. TGDSC spectrum of TCFA.
Fig. 5. XRD patterns of ceramics heat-treated at dierent temperatures.
determine the particle size distribution of the CFA powder.
Inductively coupled plasma-optical emission spectrometry (ICP-
OES, Optimal 5300DV, PerkinElmer Instruments) was performed at
1300 W with a carrier gas ow of 0.08 L/min and a peristaltic pump
ow of 1.5 mL/min to analyze the chemical composition of the CFA
samples. The dried solid composite powders were characterized by
XRD (XPert Pro MPD, PANalytical Company) at 40 kV and 30 mA
within the 2 range of 590 using Cu K radiation to identify the
crystalline phases present. The surface morphology was observed by
scanning electron microscopy (SEM, Sirion 200, FEI), while the
concentrations of individual elements were detected by energy dis-
persive X-ray (EDX) spectroscopy. The morphology and transmission
electron diraction patterns of the bers were characterized by eld
emission transmission electron microscopy (FETEM, JEM-2100,
JEOL).
The exural strength of the ceramic samples was measured by an
electronic universal testing machine (WDW-20E, Jinan Shidai Shijin
Testing Machine Group Co., Ltd.). The bulk density of the samples was
calculated from their weights and dimensional measurements, and the
open porosity was evaluated using the Archimedes displacement
method after ultrasonic processing for 10 min in deionized water.
The particle size distribution of the powders was measured using a
laser particle size analyzer (Beckman Coulter, LS 13320). Nitrogen
adsorption-desorption isotherms were recorded with a nitrogen ad-
sorption apparatus (ASAP 2000) and the specic surface areas were
calculated by the Brunauer-Emmett-Teller (BET) method. The heat
Ceramics International 43 (2017) 111
treatment procedure was conrmed by thermogravimetric dierential
scanning calorimetry (TGDSC, NETZSCH STA 449 C) under owing
air at a heating rate of 10 C/min.
Fourier transform infrared (FTIR) spectra were recorded on a
PerkinElmer Spectrum 100FT-IR spectrometer in the wavenumber
range of 4000400 cm1. For this, 2 mg of each material studied was
mixed with KBr powder in a ratio of 1:100 and pressed into a pellet by
8.9104 N of force, using a manually operated hydraulic press
(Specac). All FTIR measurements were acquired with a 2 cm1 spectral
resolution using a global light source and liquid-nitrogen-cooled
mercury cadmium telluride (MCT) detector.
3. Results and discussion
3.1. Coal y ash characterization and reaction principle
The X-ray diraction (XRD) patterns in Fig. 1(a) show that the
main phases of the raw CFA are quartz and mullite, along with some
amorphous material. The laser particle size analyzer used to determine
the particle size distribution, reveals the milled CFA to have a d(0.5)
size of 75.32 m, as shown in Fig. 1(b).
A schematic showing the fabrication of whisker-reinforced ceramics
is presented in Fig. 2. Under hydrothermal conditions, the highly
reactive silicon dioxide in y ash reacts with calcium oxide when in a
aqueous solution, as per the following reaction:
5CaO+6SiO2+5H2O=5CaO6SiO25H2O
Meanwhile, since silicon and aluminum atoms share very similar
structures and chemical properties, Al3+ can partly replace Si4+ during
the synthesis of tobermorite, resulting the formation of an Al-tober-
morite phase (e.g., Ca5Si5Al(OH)O175H2O) [12]. Though the structure
of crystalline minerals in CFA can be destroyed in a hydrothermal
environment, causing them to gradually participate in the reaction
[13,14], the Al-tobermorite synthesized in the present study has an
excellent whisker structure. It also converts into wollastonite with a
very ne whisker structure after sintering, which gives the nal ceramic
products excellent mechanical properties.
3.2. Characterization of aluminum-substituted tobermorite whiskers
The chemical composition of the tobermorite synthesized from CFA
(hereafter referred to as TCFA) is listed in Table 2, showing that the
aluminum content is relatively high. This is because of the signicant
Al2O3 levels present in the original y ash, which aects the tobermor-
ite [15] as discussed later in Section 3.5. The XRD pattern in Fig. 3(f)
conrms that the hydrothermal product is tobermorite, while the SEM
images in Fig. 3(a) and (b) show that it consists of many tiny dendritic
crystals combined into a porous structure. The synthetic tobermorite
bers are aggregated into balls of uniform size; at high magnication,
the bers are observed to be ne and homogeneous. The FETEM
images clearly conrm that the single whiskers have brous shapes,
with an electron diraction pattern shown in Fig. 3(e) typical of a single
crystal. The width of the ber is less than 200 nm. The draw ratio of
most bers is greater than 25 and the specic surface area, as measured
by the BET method, is 117.8 m2/g.
3.3. Characterization of whisker-reinforced ceramics
In order to identify the most appropriate sintering plan, the Al-
tobermorite powders were subjected to TGDSC analysis (Fig. 4) with
an applied heating rate of 10 C/min. The resulting DSC curve is
divided into three stages:
1) At temperatures from 50 to 350 C, the TG curve slopes to form a
broad endothermic valley. The loss of free water is responsible for
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Y. Luo et al.
Fig. 6. SEM images of typical fracture surfaces of ceramics heat-treated at: (a) 800, (b) 850, (c) 900, (d) 950, and (e) 1000 C.
the 7.12% mass loss and the absorption of heat. In this temperature
range, free water is released through gaps between the dendritic
crystals of tobermorite.
2) Between temperatures of 350 and 650 C, a notable mass loss of
7.84% is associated with an endothermic hump in the DSC curve at
~444 C. This can be explained by the destruction of the phase
structure, with the subsequent loss of water molecules originally
located between layers.
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Ceramics International 43 (2017) 111
3) Between 650 and 1000 C, the exothermic peak at ~819 C is
characteristic of the appearance of an amorphous, disordered, and
metastable state of tobermorite, known as dehydroxylation tober-
morite. The SiOH chemical bond is destroyed at this temperature
and the O and H combine to form water molecules, which then
leave the tobermorite structure. The weak exothermic peak at
~881 C may represent a phase transformation from tobermorite
to wollastonite. The dehydroxylation temperature and wollastonite
Y. Luo et al.
Fig. 7. Flexural strength, open porosity, and bulk density of ceramics as functions of
sintering temperature.
Fig. 8. Comparison of XRD patterns of tobermorite whiskers synthesized at dierent
temperatures.
formation temperature are both higher than those reported else-
where [6,8,16], thus indicating that TCFA is more stable than
naturally formed tobermorite during heating.
The phase transformation of ceramics heat-treated at dierent
temperatures is shown in Fig. 5. The reection peaks indicate that
the main phase is wollastonite, though a small amount of gehlenite is
also present. The crystal structure of wollastonite rst forms at 800 C,
but at this temperature the degree of crystallinity is low. The intensity
of the wollastonite reection peaks increases with increasing the
temperature from 800 to 850 C, with well-crystallized wollastonite
forming at 900 C. This agrees well with the TGDSC analysis, as it
corresponds to the exothermic peak observed at ~895.4 C in stage
three. With an increase in temperature from 900 to 1000 C, the
reection peaks of wollastonite decline and the XRD line broadens,
which is consistent with the emergence and increasing prevalence of an
amorphous phase. This indicates that melting and lattice disturbance of
the ceramic occurs within this temperature range. The reection peaks
of gehlenite, however, change very little during the heating process.
The gehlenite phase may therefore be comprised of impurities in the
tobermorite whiskers [17], and because of its low concentration is
unlikely to aect the mechanical properties of the ceramics.
The SEM images in Fig. 6 show typical fracture surfaces in which
the ber structures of the nal ceramic products are clearly observed.
This structure mimics that of the as-synthesized Al-tobermorite
whiskers, indicating that it is not damaged by the heat treatment
process, despite the resultant phase transformation. In addition, the
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Ceramics International 43 (2017) 111
chemical composition of the bers is consistent with that of wollasto-
nite, as determined by EDX analysis. From 800 to 900 C, the outline of
the bers remains clearly visible and their surface becomes smoother,
which may be attributed to the increase in crystallinity with increasing
temperature in this range. When the temperature exceeds 900 C, an
amorphous phase fuses with the surface of the bers and their contours
become blurred, with gradually more of the glassy phase appearing.
The wollastonite whiskers tend to transform from crystalline to
amorphous in state when the temperature exceeds 900 C, which
causes the ber-based microstructure in the ceramic bodies to dis-
appear.
The exural strength, open porosity, and bulk density of the
ceramics were averaged from three sets of data, and their variations
as functions of sintering temperature are summarized in Fig. 7. When
the temperature is increased from 800 to 900 C, the exural strength
and bulk density are increased, with a small decrease in open porosity.
This means that increasing the temperature from 800 to 900 C can
accelerate the sintering process and promote the densication of the
ceramics. However, when heat treatment is performed at a temperature
greater than 900 C, the strength and density decrease while the open
porosity increases. Based on the previous SEM images and XRD
analysis in this temperature range, the onset of melting clearly
damages the ber-like microstructure of wollastonite whiskers and
reduces the degree of crystallinity. This over-sintering not only
degrades the mechanical properties of the bulk, but also produces
microscale pores within the ceramic and irregular macroscale bulges on
its surface. Among the tested sintering conditions used in this study,
the treatment at 900 C produced the densest and most solid ceramics,
with exural strength of 52.47 MPa, open porosity of 9.51%, and a bulk
density of 2.15 g/cm3. This conrms that the ber microstructure of
wollastonite whiskers in the ceramic body is responsible for the
improved mechanical properties of the ceramic.
From the analyses above, it can be concluded that this new type of
ceramic has a low sintering temperature but better mechanical proper-
ties relative to traditional ceramics. This can be attributed to the high
reaction activity of the raw materials, which is the result of both the
high CaO content of the raw materials ( > 30%) and very small diameter
(~100 nm) of the tobermorite bers [18]. The high reaction activity
permits the optimum sintering temperature of 900 C, approximately
200 C lower than that of traditional ceramics [17,1921].
Signicantly, the reinforcing eect of the whiskers works not only on
the ceramic products, but also on the green bodies. The exural
strengths of the green bodies in this study reach 1520 MPa, which
are very high for the ceramics industry. This strength is attributed to
the water contained within the crystalline structure of tobermorite
[22]. With the brous morphology of the tobermorite whiskers, the
exural strength of the whiskered structure does not decrease during
dehydration.
3.4. Eect of Al-tobermorite morphology on whisker-reinforced
ceramics
The reaction temperature is very important in hydrothermal
synthesis, as it greatly aects the morphology of the Al-tobermorite
produced. Values ranging between 140 and 350 C have been pre-
sented in the literature [13,23], but in the experiments described in the
previous sections, the temperature was maintained at 220 C. The next
logical step in exploration is therefore to examine the inuence of
temperature on the morphology of the Al-tobermorite whiskers pro-
duced while maintaining constant values for all other variables, and to
determine how the morphology aects the properties of the whisker-
reinforced ceramics.
A comparison of the XRD patterns obtained from tobermorite
specimens synthesized at dierent temperatures is shown in Fig. 8. The
diraction peaks become noticeably sharper with increases in the
synthesis temperature, suggesting increases in crystallinity. As increas-
Y. Luo et al.
Fig. 9. SEM images of tobermorite whiskers synthesized at (a) 150, (b) 180, (c) 200, and (d) 250 C.
ing the temperature can improve the rates of mass transfer and
chemical reaction in the hydrothermal process, it follows that the
crystals would grow more completely at higher temperatures.
The SEM images of the tobermorite whiskers synthesized at
dierent temperatures in Fig. 9 show distinct dierences in crystal
morphology. The tobermorite synthesized at 150 C has a poor crystal
structure and ake-like form, as illustrated in Fig. 9(a). When the
temperature is increased to 180 C, the ake-like material is trans-
formed into plate-like strips, as shown in Fig. 9(b). A further increase
in temperature to 200 C causes the tobermorite to grow as needle-like
bers (Fig. 9(c)) with a length-to-diameter ratio of ~15. In Fig. 9(d)
and at 250 C, the width of these bers is ~100 nm and the length-to-
diameter ratio approaches 20.
These dierent morphologies of tobermorite ake-like, plate-like,
needle-like, and brous were used to prepare ceramics sintered at
900 C for 2 h, labeled as CRE150, CRE180, CRE200, and CRE220,
respectively. A comparison of the XRD patterns of these ceramics
(shown in Fig. S1 in the supplementary material) conrms that the
principal crystalline phase of the ceramic products is wollastonite, with
a small amount of gehlenite and some amorphous phase. Increasing
the synthesis temperature is found to sharpen the diraction peaks of
wollastonite. From the SEM images of the typical fracture surfaces of
the ceramics, CRE220 (Fig. 10(d)) has a distinct ber microstructure,
which is less obvious in CRE200 (Fig. 10(c)). Similarly, CRE150 and
CRE180 (Fig. 10(a) and (b), respectively) retain their original ake-
and plate-shaped microstructures.
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Ceramics International 43 (2017) 111
The variations in exural strength, open porosity, and bulk density
of the ceramics are presented in Table 3. These test results agree with
the upward trend seen with increasing reaction temperature in the
XRD and SEM data, and show that CRE220 has the highest exural
strength and bulk density, with the lowest open porosity. From this, we
conclude that ceramics oering outstanding performance can be
successfully produced using Al-tobermorite reinforcing whiskers with
excellent ber morphology.
3.5. Eects of aluminum substitution on whisker-reinforced ceramics
The XRD patterns in Fig. 11 reveal that, with an increase in the Al/
Si ratio from 0 to 0.2, the degree of crystallinity is increased, as shown
by the sharpened diraction peaks of tobermorite. A further increase in
the Al/Si ratio from 0.2 to 0.25 causes no change in the diraction
peaks, possibly because aluminum substitution has become saturated
in the tobermorite crystals. Comparing the enlarged view of the
diraction peaks in the small-angle range, it is evident that greater
aluminum substitution causes the diraction peaks at 27.8 and
28.9 to shift to lower angles. Thus, in the presence of aluminum
hydroxide, the substitution of Si4+ with Al3+ facilitates tobermorite
formation, but induces lattice distortion by increasing the basal spacing
between silicate layers along the c-axis [24]. The XRD pattern of TCFA
is also very similar to that of TOB0.2 and TOB0.25, indicating that the
aluminum substitution rate is very high in TCFA.
Fig. 12 shows the morphological change in the tobermorite with
Y. Luo et al. Ceramics International 43 (2017) 111

Fig. 10. SEM images of ceramics made with dierent morphologies of tobermorite: (a) CRE100, (b) CRE150, (c) CRE200, (d) CRE220.

Table 3
Flexural strength, open porosity and bulk density of ceramics.

Sample Flexural strength (MPa) Open porosity (%) Bulk density (g/cm3)

Max Min Mean Max Min Mean Max Min Mean

CRE 100 32.05 28.34 30.27 25.12 24.63 24.89 1.83 1.75 1.78
CRE 150 39.23 36.81 37.68 15.83 14.89 15.34 2.08 2.01 2.05
CER 200 45.32 44.35 44.98 7.21 6.74 6.98 2.22 2.10 2.18
CER 220 52.71 51.99 52.47 4.53 4.28 4.44 2.35 2.24 2.29

increasing Al/Si ratio. Note that, although the tobermorite whiskers are
generally slender and brous, increasing the Al/Si ratio from 0 to 0.25
causes them to enlarge noticeably. The surfaces of the whiskers also
become smoother and the whiskers are distributed more evenly. The
TCFA whisker size is similar to that of TOB0.2 and TOB0.25.
In order to further understand the impact of aluminum substitution
on the morphology of tobermorite, FTIR spectra were obtained from
dierent samples, as shown in Fig. 13. The stretching, bending, and
deformation vibration modes of the SiO4 tetrahedra are evident in all
spectra at 400600 and 9001200 cm1 [8,25], and a band attribu-
table to the scissoring bending mode of water appears at ~1635 cm1
[25,26]. A broad hydroxyl stretching band is seen at ~3445 cm1. As
the Al/Si is increased from 0 to 0.25, absorption bands gradually
appear at ~1177 and ~912 cm1. The former of these is caused by the
substitution of Si in Q3 sites [6,27] (where it is connected with another
three SiO4 tetrahedra), while the latter is due to the substitution of Si in
Q2 sites [6,27] (where it is connected with two SiO4 tetrahedra). Thus,
an increase in the Al/Si ratio causes incremental substitution of Al for
Si in Q3 and Q2 sites, which induces growth in the crystal structure of
tobermorite [28].
XRD analysis of the nal ceramics revealed that changing the Al/Si
ratio from 0 to 0.25 increases the crystallinity of wollastonite, which
agrees with the XRD results of the Al-tobermorite samples. Subsequent
SEM imaging found that the ceramics retained the ber-like micro-
structures of the Al-tobermorite specimens. These XRD and SEM
results are respectively shown in Fig. S2 and Fig. S3 in the supple-
mentary material. The exural strength, open porosity, and bulk
density of the ceramics were averaged from three sets of data, with
their variation presented in Fig. 14 as functions of the Al/Si ratio. An
increase in the Al/Si ratio from 0 to 0.2 accompanies a signicant

8
Y. Luo et al.
Fig. 11. (a) Comparison of XRD patterns of tobermorite specimens with dierent Al/Si ratios, (b, c) detailed view with enlarged scale.
improvement in the exural strength and bulk density of the ceramics,
along with a great reduction in the open porosity. However, when the
Al/Si ratio reaches 0.25, the high substitution of aluminum negatively
aects the mechanical properties. This can be explained by the upper
limit of aluminum substitution in tobermorite, which has been
reported to reach 20 mol.% (i.e., Al/Si=0.2), with any residual alumi-
num hydroxide in the tobermorite damaging the performance of the
ceramics. Thus, an increase in the Al/Si ratio can benet the mechan-
ical properties of whisker-reinforced ceramics, but only within a
suitable range. When the XRD, SEM, and FTIR analysis results are
considered, it can be inferred that the aluminum substitution level in
TCFA is between 0.2 and 0.3 mol.%.
The eects of aluminum substitution on the mechanical properties
of whisker-reinforced ceramics can be attributed to the promotion of
tobermorite whisker growth by aluminum. These well-developed
tobermorite whiskers are subsequently converted into well-developed
wollastonite whiskers upon sintering and provide good strength
support for the nal ceramic bodies. Notably, the exural strength of
the whisker-reinforced ceramics greatly exceeds the requirement of
15 MPa prescribed in GB/T 4100-2015 (the Chinese national standard
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Ceramics International 43 (2017) 111
for ceramic tiles).
4. Conclusions
In this study, whisker-reinforced ceramics with exural strengths in
the range of 44.9652.47 MPa were successfully produced using
tobermorite whiskers synthesized from CFA using a dynamic hydro-
thermal method. The ne ber morphology of these whiskers and the
eect of aluminum substitution were shown to provide this new type of
ceramic with excellent mechanical properties. The high reaction
activity of tobermorite also permitted a necessary sintering tempera-
ture ~200 C lower than that of traditional ceramics. The optimum
sintering temperature of 900 C produced the reinforced ceramic with
the greatest exural strength (52.47 MPa), highest bulk density
(2.15 g/cm3), and lowest open porosity (9.51%). The morphology of
the tobermorite had a signicant impact on the mechanical properties
of this new type of ceramic, with optimum performance achieved using
Al-tobermorite whiskers with ber-like morphologies. Aluminum sub-
stitution promoted the crystal growth of tobermorite, which improved
the wollastonite whiskers produced by sintering and provided greater
Y. Luo et al.
Fig. 12. SEM images of tobermorite specimens with Al/Si ratios of (a) 0, (b) 0.1, (c) 0.15, (d) 0.2, (e) 0.25, and (f) TCFA.
support for the nal ceramic bodies. Thus, increases in the Al/Si ratio
could benet the mechanical properties of similar whisker-reinforced
ceramics, as long as the ratio does not exceed the upper limit of Al
substitution in tobermorite.
The prepared ceramics could be used as new engineering and
building materials applied in rigor conditions or for specic purposes,
as they showed strengths exceeding national standards for such
10
Ceramics International 43 (2017) 111
components. This study provides a new method for utilization of
CFA, which is of great guiding signicance for high value added
utilization of CFA in ceramic elds.
Although the proposed whisker-reinforced ceramics possess excel-
lent mechanical properties, other properties (e.g., thermal shock
resistance and corrosion resistance) are not investigated in this study.
To expand the application elds of the whisker-reinforced ceramics, a
Y. Luo et al.
Fig. 13. IR spectra of tobermorite with dierent Al/Si ratios.
Fig. 14. Flexural strength, open porosity, and bulk density of ceramics as functions of
Al/Si ratio.
more comprehensive characterization of the ceramics is suggested for
further studies.
Acknowledgements
The authors gratefully acknowledge the nancial support received
from the Major State Basic Research Development Program of China
(973 Program) under Grant no. 2013CB632601. We would like to
thank Editage [www.editage.cn] for English language editing.
Appendix A. Supporting information
Supplementary data associated with this article can be found in the
online version at doi:10.1016/j.ceramint.2016.09.211.
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