Fuel 291 (2021) 120220

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Fuel
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Full Length Article

Study on the pozzolanic activity of ultrafine circulating fluidized-bed fly

ash prepared by jet mill
Duanle Li a, b, Rui Sun b, Dongmin Wang b, *, Caifu Ren b, Kuizhen Fang b
a
Key Laboratory for Thermal Science and Power Engineering of the Ministry of Education, Department of Energy and Power Engineering, Tsinghua University, Beijing
100084, China
b
School of Chemical & Environmental Engineering, China University of Mining & Technology, Beijing 100083, China

A R T I C L E I N F O A B S T R A C T

Keywords: The pozzolanic activity of ultrafine circulating fluidized-bed (CFB) fly ash prepared by jet mill has been inves­
Circulating fluidized-bed fly ash tigated in this research. The ultrafine powder properties and the hydration heat release process of the cement
Cement blended with ultrafine CFB fly ash have been obtained. Furthermore, the dissolution characteristics of SiO2 and
Ultrafine grinding
Al2O3, the Ca2+ absorption capacity in saturated Ca(OH)2 solution, and the polymerization degree of Si-O and Al-
Pozzolanic activity
O polyhedrons have been studied to further clarify the mechanism of ultrafine grinding on pozzolanic activity.
Polymerization degree
Compared to raw CFB fly ash (RCFA), the particle morphology, the pore structure of ultrafine CFB fly ash (UCFA,
D50 ≤ 5 μm), and the pozzolanic activity of UCFA are significantly improved. The hydration rate of cement
blended with UCFA is accelerated, and the total heat release is close to that of pure cement within 72 h. Ultrafine
grinding increases the SiO2 and Al2O3 dissolution rate of CFB fly ash and Ca2+ absorption capacity in saturated
Ca(OH)2 solution, mainly due to the decrease of polymerization degree of Si-O and Al-O polyhedrons and particle
size of CFB fly ash.

1. Introduction [21–23]. In the aspect of efficient mechanical grinding, however, the

In recent years, circulating fluidized-bed (CFB) combustion boiler
has been developed rapidly in power generation and waste treatment
sector, resulting in the formation of a large amount of CFB fly ash [1–5].
The metakaolin contained in CFB fly ash, whose potential pozzolanic
activity is similar to that of pulverized coal (PC) boiler fly ash, can be
used as supplementary cementitious materials for cement or concrete
[6–8]. However, many researchers [4,9–15] suggest that raw CFB fly ash
may have harmful effects on workability, mechanical properties and
volume stability to concrete, due to its high water-demand ratio, poor
pozzolanic activity and high expansion rate. This drawback has signif­
icantly limited the application of CFB fly ash. CFB fly ash is formed
approximately under 800–900 ◦ C [3], whilst PC fly ash is often formed
under 1200–1400 ◦ C [16]. In CFB combustion, excessive limestone is
usually added into furnace for desulfurization purposes [17,18]. The low
combustion and desulfurization process result in the defects of CFB fly
ash of loose and porous structure, irregular particle shape, large particle
size, and high sulfur and calcium content [19–21].
For solid wastes with poor pozzolanic activity, mechanical grinding
might reduce the particle size and improve the pozzolanic activity
linkage between grinding technics and the physical and chemical
properties of solid wastes is a main decisive factor [24,25]. Ball mill,
impact mill and jet mill are the most commonly used mechanical
grinding equipment. Jet mill is one of the most effective machineries for
ultrafine grinding of solid waste [23–29]. Compared to the ball mill and
impact mill, the powder particles ground by jet mill were reported to
have smooth surface and smaller particle size (1–10 μm) with a narrower
particle size distribution [8,23], while the phase transitions can be
avoided by the cooling effect of jet mill in the grinding process [27].
With the development of large-scale grinding technology, the energy
consumption of ultrafine grinding has been greatly reduced, which
makes it possible to use industrial equipment to produce ultrafine
ground solid waste [30–32]. By ultrafine grinding, the particle size could
be reduced rapidly and the lattice structure could be optimized [33,34].
In the hydration process, the smaller the particle size, the faster the
dissolution rate and the higher the hydration degree [21,35]. Ultrafine
grinding has been widely used in solid waste treatment [36–39]. Re­
searches indicate that ultrafine powder, such as ultrafine slag and PC fly
ash, is a kind of high quality supplementary cementitious materials that
can significantly improve the workability, compressive strength and

* Corresponding author.
E-mail address: wangdongmin@cumtb.edu.cn (D. Wang).

https://doi.org/10.1016/j.fuel.2021.120220
Received 27 July 2020; Received in revised form 7 December 2020; Accepted 13 January 2021
Available online 5 February 2021
0016-2361/© 2021 Elsevier Ltd. All rights reserved.
D. Li et al. Fuel 291 (2021) 120220

durability of concrete, and has been widely used in concrete [38,40,41].
Some researchers [42–44] have attempted to improve the perfor­
mance of CFB fly ash in application by mechanical grinding. It has been
approved that mechanical grinding can change the powder properties
and improve the dissolution rate and pozzolanic activity of CFB fly ash
[45–47]. Ultrafine grinding provides a promising technique to improve
the performance of CFB fly ash in application. However, there are few
studies on ultrafine grinding of CFB fly ash and the corresponding effects
on its pozzolanic activity. The jet mill has been successfully used in ul­
trafine grinding of other solid wastes [24,25,28,29], but the suitability
of CFB fly ash is still unclear. Therefore, it is necessary to discuss the
suitability of jet mill when used in ultrafine grinding of CFB fly ash
through the pozzolanic activity.
In this research, the effect of ultrafine grinding on CFB fly ash’s
pozzolanic activity and hydration heat release process of cement has
been studied to identify its improvement from raw CFB fly ash (RCFA).
Meanwhile, SiO2 and Al2O3 dissolution characteristics, Ca2+ absorption
capacity in saturated Ca(OH)2 solution, and the chemical structure of Si-
O and Al-O polyhedron of CFB fly ash have been studied to further
clarify the affecting mechanism of ultrafine grinding on pozzolanic ac­
tivity, with the hope to provide useful information for its application as a
cement-based material.
2. Experimental
2.1. Raw materials
The cement was a reference cement (P⋅I 42.5) following the Chinese
national standards of ‘Concrete Admixtures’ (GB 8076-2008) and
‘Mineral Admixtures for High Strength and High-Performance Concrete’
(GB/T 18736-2017), produced by China United Cement Corporation,
which is specially used for the detection of concrete admixtures. It is
made by grinding Portland cement clinker and gypsum. The RCFA came
from a power plant in Shanxi province, China. The UCFA was prepared
by RCFA through ultrafine grinding in an industrial jet mill, the chem­
ical compositions and physical properties of above materials are shown
in Tables 1–3 and Fig. 1, respectively. Compared to RCFA, UCFA pos­
sesses similar chemical compositions, but its particles size has been
greatly reduced to less than 32 μm with very narrow size distribution,
which belongs to the category of ultrafine fly ash. The percentage of
particles of less than 3 μm is increased from 8.45% to 27.91%, and the
median diameter (D50) is lowered from 31.11 μm to 4.25 μm. In addi­
tion, the specific surface area of UCFA is significantly larger than that of
RCFA, and its 45 μm fineness is almost zero, which is consistent with the
test results of particle size distribution.
2.2. Testing methods
The fineness, specific surface area and pozzolanic activity index of
CFB fly ash were measured according to the Chinese national standard of
‘Fly Ash Used for Cement and Concrete’ (GB/T 1596-2017). The parti­
cles size distribution was measured by a laser particle size analyzer (LS-C
(IIA), OMEC Instrument Co.) according to the Chinese industry standard
of ‘Testing Method for Particle Size of Cement (Laser-based Methods)’
(JC/T 721-2006).
The self-hardening compressive strength of CFB fly ash was
measured as follows: 300 g CFB fly ash and 195 g water (weighing
Table 2
The physical properties of cement.
Specific surface area Standard Setting time Compressive
(m2⋅kg− 1) consistency (%) (min) strength
(MPa)
Initial Final 3d 28 d
347 27.2 155 215 28.3 51.2
accuracy: ±0.1 g, water/CFB fly ash = 0.65) were mixed by NJ-160
cement paste mixer (Wuxi Jianyi Experimental Equipment Co., Ltd.,
program control: slow stirring 120 s, stopping 15 s and fast stirring 120
s) and formed by molds (sample size: 30 mm × 30 mm × 30 mm). The
formworks were removed after 24 h, and the samples were cured in
water (curing temperature: 20 ± 3 ◦ C).
The mortar compressive strength of cement was measured according
to the Chinese national standard of ‘Method of Testing Cements –
Determination of strength (ISO)’ (GB/T17671-1999). 90 g CFB fly ash,
360 g cement, 1350 g standard sand (followed Chinese national stan­
dard of ‘Standard sand for cement strength test’(GB 178-1997) and 225
g water (weighing accuracy: ±0.1 g) were mixed by JJ-5 cement mortar
mixer (Wuxi Jianyi Experimental Equipment Co., Ltd., program control:
slow stirring 30 s, adding standard sand and slow stirring 30 s, fast
stirring 30 s, stopping 90 s and fast stirring 60 s) and formed by molds
(sample size: 40 mm × 40 mm × 160 mm). The curing conditions were
consistent with the previous paragraph. The activity index of CFB fly ash
was characterized by ISO mortar strength, which was calculated ac­
cording to Formula (F1).
R
activity index = × 100% (F1)
R0
where R represents the compressive strength of cement blended with 30
wt% CFB fly ash, and R0 represents the compressive strength of cement.
The pore structure of CFB fly ash was measured by a specific surface
area and pore analyzer (TRISTAR II 3020M, Micromeritics Instruments
Co., method: BET (Brunauer-Emmett-Teller), adsorbate: N2).
The chemical composition of CFB fly ash was analyzed by an XRF-
1800 spectrometer (Shimadzu Co.).
The mineral composition of CFB fly ash was analyzed by a SMAR­
TLAB polycrystalline X-ray diffractometer (XRD, Rigaku Analytical De­
vices, Inc.) with Cu radiation in continuous scan mode with a step size of
0.02◦ in the 2θ range of 3–135◦ .
The morphology of CFB fly ash was investigated by a S3400N field
emission Scanning Electron Microscope (FESEM, Hitachi Co.).
The polymerization degree of Si-O and Al-O polyhedrons of CFB fly
ash were analyzed by an solid state nuclear magnetic resonance
(SSNMR, VNMRS-600, Agilent Technologies, Inc.) operated with the
main magnetic field intensity of 14.09 T. The proton resonance fre­
quency was 600.13 MHz with the magnetic field drift less than 60 Hz/h
and the resolution of <0.005 Hz.
The dissolution characteristics of SiO2 and Al2O3 of CFB fly ash were
measured as follows: 2 ± 0.001 g CFB fly ash was dissolved in 100 ml
NaOH solution with the NaOH concentration of 0.2 or 2 mol/L. The
solution was maintained at 25 ◦ C while under magnetic stirring for a
certain time. The solid particles were separated from the solution by a
centrifuge at a rotating speed of 8000 r/min for 10 min, which was then
filtered by a 0.22 μm filter membrane. The contents of Si, Al and Ca in

Table 1
Chemical compositions of cement and CFB fly ash (wt.%).
Samples SiO2 Al2O3 Fe2O3 CaO MgO TiO2 SrO P2O5 SO3 LOI

Cement 21.73 4.60 3.45 64.55 3.56 / 0.24 0.12 0.46 /

RCFA 43.19 35.67 6.11 8.10 0.78 2.12 0.23 0.13 2.90 5.62
UCFA 43.35 35.77 6.33 8.26 0.66 1.96 0.24 P2O5 2.93 5.37

Note: LOI- loss on ignition (950 ◦ C).

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D. Li et al. Fuel 291 (2021) 120220

Table 3
The physical properties of CFB fly ash.
Samples Specific surface area (m2⋅kg− 1) Fineness (45 μm, %) Particle size distribution (%) D50 (μm)

<3 μm 3–32 μm 32–65 μm >65 μm

RCFA 346.1 29.0 8.45 41.15 23.45 29.65 31.11

UCFA 766.8 0.5 27.91 67.80 4.29 0 4.25

3. Results and discussions

3.1. Powder characteristics

The effects of ultrafine grinding on the appearance, pore structure

Fig. 1. Particle size distribution curve of CFB fly ash.
the filtrate were analyzed by an inductively coupled plasma optical
emission spectrometer (ICP-OES, Thermo Fisher Scientific Co. Ltd.).
The chemical activity index was determined by the saturated Ca
(OH)2 solution absorption method. The operation procedure was as
follows: 1 ± 0.001 g CFB fly ash was dissolved in 100 ml saturated Ca
(OH)2 solution which was maintained at 60 ◦ C under magnetic stirring.
The suspension was centrifuged and filtered to get the clear filtrate. The
pH value of the filtrate was adjusted to 5–6 with dilute nitric acid. The
concentration of the residual Ca2+ in the filtrate after pH regulation was
measured by the ICP-OES. The chemical activity index was calculated
according to Formula (F2).
( [ ])
C Ca2+
chemical activity index = 1 − [ ] × 100% (F2)
C0 Ca2+
where C[Ca2+] represents the residual Ca2+ concentration in solution,
and C0[Ca2+] represents the initial Ca2+ concentration in solution.
The hydration heat release of cement was measured by an 8-channel
isothermal micro-calorimeter (7338 ToniCAL TRIO, TA Instruments-
Waters, LLC, water/cement: 0.45).
and mineral composition of CFB fly ash are shown in Figs. 2–4 and
Table 4, respectively.
Fig. 2 shows the SEM images of CFB fly ash particles. The particle
shape of RCFA is irregular, the large agglomerated particles coexisted
with fine particles, and the particle size changes greatly. Most of the
particles are presented in a cohesive state, and there are obvious pores
on the surface of particles. However, the particle shape of UCFA are
relatively regular and uniformly sized. There are almost no large-scale
agglomerated particles, and the pores on particle surface are signifi­
cantly reduced. Ultrafine grinding has obviously reduced the particles
size and optimized the particles morphology and pore structure of CFB
fly ash.
Fig. 3 shows the adsorption and desorption isotherm and pore size
distribution of CFB fly ash. As shown in Fig. 3(a), the hysteresis rings in
the adsorption-desorption isothermal curves belongs to H3 type, which
is the typical feature of non-rigid aggregates of flake or layered particles
[48]. It has been shown that CFB fly ash contains a large number of pores
of slit hole type. The pores of powders could be divided into three cat­
egories according to their sizes: micro-pores (pore size: ≤2 nm), meso-
pores (pore size: 2–50 nm) and macro-pores (pore size: ≥50 nm) [42].
As shown in Fig. 3(b), the pore size distribution of RCFA is mainly larger
than 200 nm, while that of UCFA is mainly in the range of 2–50 nm. The
particle size of UCFA decreased and the pore size distribution of UCFA
moved to the left. Table 4 shows the pore structure parameters of CFB fly
ash, compared with RCFA, the total pore volume, average pore diameter
and the most probable pore diameter of UCFA particles decreases
significantly, and the large pores of CFB fly ash have been destroyed by
ultrafine grinding, which is consistent with SEM result. It has been
revealed that the pore structure of CFB fly ash has been obviously
optimized by ultrafine grinding, its pore size and total pore volume have
been reduced, and then lead to the high particle bulk density.
Fig. 4 shows the XRD analysis of CFB fly ash. The main minerals of
CFB fly ash are quartz, hematite, anhydrite, lime and calcite. Compared
with RCFA, the positions of diffraction peak of UCFA do not change at
each diffraction angle, suggesting no phase change after ultrafine
grinding. The diffraction peak intensity of quartz and anhydrite of UCFA

(a) RCFA (b) UCFA

Fig. 2. SEM images of CFB fly ash particles.

3
D. Li et al. Fuel 291 (2021) 120220

Fig. 3. Adsorption and desorption isotherm (a) and pore size distribution (b) of CFB fly ash.

is lower than that of RCFA, and some diffraction peaks are widened. It
might be that ultrafine grinding has destroyed the ordered structure of
some quartz and anhydrite crystals of CFB fly ash and lead to the
increasing of lattice defects and the thickening of amorphous layers.

3.2. Pozzolanic activity and hydration heat release

The effects of ultrafine grinding on the activity index and self-

hardening compressive strength of CFB fly ash, and the hydration heat
release process of cement blended with CFB fly ash have been presented.
The results are shown in Figs. 5–7 and Table 5.
Fig. 5 shows the active indexes and self-hardening compressive
strength of CFB fly ash. As shown in Fig. 5(a), compared with RCFA, the
activity indexes of UCFA at 3 d, 7 d and 28 d are significantly increased
by 17%, 13% and 20%, respectively, especially the activity index of
UCFA at 28 d is 113%. UCFA is a kind of supplementary cementitious
material with high activity. The effect of ultrafine grinding on the ac­
tivity index of CFB fly ash is significant. Mechanical grinding could
Fig. 4. XRD analysis of CFB fly ash.
reduce the particle size, and increase the lattice defect and surface-active
site of CFB fly ash, which might lead to the increase of its pozzolanic
Table 4 activity [45,48], and greatly improving its activity index at each age.
Pore size distribution parameters of CFB fly ash. As shown in Fig. 5(b), CFB fly ash demonstrates self-cementitious
Sample Total pore Average pore The maximum Bulk density
activity, and its hardened paste has a certain self-hardening compres­
volume diameter (nm) diameter of a few (g⋅cm− 3) sive strength. Compared with RCFA, the self-hardening compressive
(ml⋅g− 1) holes (nm) strength of UCFA is increased from 0.78 MPa (7 d) and 0.92 MPa (28 d)
RCFA 0.1948 91.41 303.88 0.51 to 1.71 MPa (7 d) and 2.06 MPa (28 d), respectively. CFB fly ash contains
UCFA 0.0620 41.70 2.59 0.92 a certain amount of calcium compounds, such as CaSO4 and f-CaO,
which would react with water to generate Ca(OH)2, and then react with
the dissolved SiO2 and Al2O3 to form C-S-H gel and C-A-H gel [6,7].
Meanwhile, SO2- 4 produced by CaSO4 dissolution could react with the C-
A-H gel to form ettringite [9,49], which further increases the

Fig. 5. The active indexes and self-hardening compressive strength of CFB fly ash.

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D. Li et al. Fuel 291 (2021) 120220

Fig. 6. Heat release rate (a) and total heat release (b) of cement blended with 30% CFB fly ash.

The hydration induction period of cement blended CFB fly ash is

Fig. 7. The ratio of (CFB fly ash + cement)/cement of total heat release.
compressive strength of the hardened paste of CFB fly ash. Therefore,
CFB fly ash demonstrates a certain degree of self-cementitious activity.
Fig. 6 shows the hydration heat release rate and total heat release of
cement blended with 30% CFB fly ash, whilst the characteristic pa­
rameters of hydration heat release curves are presented in Table 5. As
shown in Fig. 6 and Table 5, the hydration processes of cement blended
with CFB fly ash are similar to that of pure cement, which includes the
following five processes, i.e. the pre-induction, induction, acceleration,
deceleration and stabilization period [50]. The total heat release of
cement blended with CFB fly ash is decreased. In 12 h, the contribution
rate of CFB fly ash to hydration heat is close to zero, and it was almost
non-hydrated, especially RCFA that inhibits the hydration of cement
before the end of acceleration period. With the continuous hydration of
cement blended with CFB fly ash, the contribution rate of CFB fly ash to
hydration heat is gradually increased. The total heat release (72 h) of
cement blended with UCFA is 94.5% of that of pure cement, which is
about 10% higher than that of cement blended with RCFA.
longer than that of pure cement, especially for the cement blended with
UCFA. The hydration induction period of cement is controlled by
nucleation [51,52]. Before nucleation formed and converted into hy­
dration products, the concentration of Ca2+ in the solution should be
reached a certain level until saturated precipitation. Compared with the
pure cement, the Ca2+ produced by clinker dissolution decreases with
decreasing clinker content in the cement blended with CFB fly ash, and
the Ca2+ in the solution is delayed to reach the saturation concentration,
leading to a prolonged hydration induction period. After the induction
period, the hydration heat release rate of cement increases rapidly to the
second (maximum) heat release peak and then decreases rapidly.
Compared with pure cement, the second heat release peak of cement
blended with CFB fly ash is delayed, the peak value is reduced, and a
third exothermic peak appeared in the hydration deceleration period.
During the hydration deceleration period, SiO2 and Al2O3 dissolved
from CFB fly ash would react with Ca(OH)2 produced by cement hy­
dration to release heat. Meanwhile, the dissolution rate of II-anhydrite in
CFB fly ash is very slow [49]. SO2-4 is continuously released due to the
slow dissolution of II-anhydrite, and the concentration of SO2- 4
constantly keeps at a high value, which would delay the conversion of
ettringite (AFt) to monosulfate (AFm) [15,34]. The hydration heat
release of CFB fly ash and the delayed decomposition heat release of AFt
increases the heat release rate, leading to the third heat release rate
peak. Compared with RCFA, the second heat release peak appears at the
same time, the maximum heat release rate is increased by 5.6%, and the
third exothermic peak is advanced by 6 h. It might be due to the smaller
particle size, easier wetting, and faster dissolution rate of SiO2, Al2O3
and II-anhydrite of UCFA, which leads to the advance of the third
exothermic peak. To summarize, the hydration process of cement
blended with CFB fly ash is accelerated by ultrafine grinding, the third
exothermic peak is greatly advanced, and its hydration rate and total
heat release is greatly enhanced.

Table 5
Characteristic parameters of cement hydration.
Sample t1 (h) t2 (h) t3 (h) V2 (J⋅(g h)-1) Total heat release (J⋅g-1)

8h 12 h 24 h 72 h

Cement 0.90 7.15 9.05 13.7326 60.8074 111.8775 174.9806 247.0571

+30% RCFA 1.60 8.10 17.65 10.1191 40.45573 78.3199 143.8727 211.1332
+30% UCFA 1.75 8.05 23.6 10.6837 43.29679 83.12477 157.8736 233.4560

Note: t1 – the ending time of induction period, t2 – the appearing time of second exothermic peak, t3 – the appearing time of third exothermic peak, V – maximum heat
release rate.

5
D. Li et al.
3.3. Dissolution characteristic of SiO2 and Al2O3 and chemical activity
index
In order to discuss the mechanism of ultrafine grinding on pozzolanic
activity, the dissolution amount of SiO2 and Al2O3 of CFB fly ash in alkali
solution and its absorption capacity of Ca2+ in saturated Ca(OH)2 so­
lution (chemical activity index) have been characterized. The results are
shown in Figs. 8 and 9.
Fig. 8 shows the dissolution of SiO2 and Al2O3 of CFB fly ash in
different concentrations of NaOH solution (0.02 mol/L and 2 mol/L),
respectively. The dissolution amount of SiO2 and Al2O3 in NaOH solu­
tion increases with the increase of stirring time. In 0.2 mol/L NaOH
solution, which simulates the aqueous alkali environment of cement
hydration, SiO2 and Al2O3 dissolution rates are higher in first 6 h, and
then slows down. However, the dissolution rates of SiO2 and Al2O3 in the
2.0 mol/L NaOH solution have been maintained at a high level,
constantly higher than that in 0.2 mol/L NaOH solution. It appears that
the alkaline environment has great influence on the dissolution char­
acteristics of SiO2 and Al2O3 of CFB fly ash. The higher the alkali con­
centration, the higher the dissolution rate and dissolution amount.
Compared with RCFA, the dissolution amounts of SiO2 and Al2O3 of
UCFA have been increased by about 45% and 20% in 0.2 mol/L and 2.0
mol/L NaOH solution, respectively. Ultrafine grinding could promote
the dissolution of SiO2 and Al2O3 of CFB fly ash.
In alkaline solution, SiO2 and Al2O3 of CFB fly ash could react with
OH− to form silicate and aluminate, which dissolves in solution. The
main reaction equations are presented as Eqs. (1) and (2) [11]. With the
increase of OH− concentration, the reaction rate of Eqs. (1) and (2) in­
creases, leading to the increase of both the dissolution rate and disso­
lution amount of SiO2 and Al2O3 in the same time. This is due to that,
ultrafine grinding has significantly increased the specific surface area
and reduced the particle size of CFB fly ash. When mixed with NaOH
solution, the contacting areas between UCFA and NaOH solution is
Fig. 8. Dissolution of SiO2 and Al2O3 of CFB fly ash in different concentrations of NaOH solution.
6
Fuel 291 (2021) 120220
much larger than that of RCFA, which promotes particle wetting and
dissolution and increases reaction rate.
Al2 O3 (s) + 2OH − (aq)→2AlO−2 (aq) + H2 O (1)
SiO2 (s) + 2OH − (aq)→SiO2−3 (aq) + H2 O (2)
The pozzolanic activity of CFB fly ash mainly comes from the reac­
tion of its own active components (i.e. SiO2 and Al2O3) with Ca(OH)2
produced by cement hydration [20]. The products of the pozzolanic
reaction are C-S-H gel and C-A-H gel. In the hydration process of cement
blended with CFB fly ash, the hydration products of clinker minerals
coexist with the products of pozzolanic reaction of CFB fly ash. It is
difficult to accurately characterize the reaction capability of SiO2 and
Al2O3 in CFB fly ash with Ca(OH)2. Therefore, the absorption capacity of
saturated Ca(OH)2 solution has been used to evaluate its reaction
capability [53].
Fig. 9 shows the absorption of Ca2+ by CFB fly ash in saturated Ca
(OH)2 solution. The absorption rate of Ca2+ increases with reaction time,
and the pH value of the solution decreases gradually. The absorption
rate of Ca2+ is accelerated after 3 h. Combining with Fig. 8, it seems that
the dissolution of active SiO2 and Al2O3 in CFB fly ash in alkaline so­
lution, especially at low concentration, requires a certain time. The
dissolution amount obviously increases with reaction time. With the
consumption of dissolution reaction, the pH value of saturated lime
solution gradually decreases (Eqs. (1) and (2)). Meanwhile, the SiO2-3 and
AlO-2 reacts with Ca2+ in the solution, Ca2+ in the solution would be
consumed and its concentration would decrease. Within 3 h, the disso­
lution amount of SiO2 and Al2O3 of CFB fly ash is lowered, and the
consumption of Ca2+ becomes less and less. After 3 h, the subsequent
dissolution amount gradually increased, the reaction rate increased, and
then the consumption rate of Ca2+ increased. Compared with RCFA,
UCFA has its Ca2+ absorptivity increased by 8.63% at 6 h. Ultrafine
grinding has enhanced the dissolution rate of SiO2 and Al2O3 of CFB fly
D. Li et al.
Fig. 9. Absorption of Ca2+ (a) and pH value (b) in saturated Ca(OH)2 solution.
ash. The concentration of SiO2- -
3 and AlO2 in the solution is increased, and
2+
the absorption capacity with Ca in the solution is increased as well. It
means that the pozzolanic reaction ability of CFB fly ash could be
improved by ultrafine grinding, which is consistent with the change of
activity index and hydration heat release rate.
3.4. Polymerization degree of Si-O and Al-O polyhedrons
The pozzolanic activity of fly ash mainly depends on the content of
soluble SiO2 and Al2O3, the polymerization degree, and the
29
Fig. 10. NMR spectra of
7
Fuel 291 (2021) 120220
depolymerization ability of Si-O and Al-O polyhedron structures [54].
Ultrafine grinding can obviously increase the dissolution rate of SiO2
and Al2O3 of CFB fly ash, and thus increase its pozzolanic activity. To
better understand the mechanochemical effect of ultrafine grinding, the
influence of ultrafine grinding on the polymerization degree of Si-O and
Al-O polyhedrons have been analyzed. The results are shown in Fig. 10.
Fig. 10 shows the NMR spectra of 29Si and 27Al of CFB fly ash. As can
be seen from Fig. 10(a) and Fig. 10(b), the chemical shifts of 29Si is
around − 110, and the peaks of chemical shifts are generated by reso­
nance with the three-dimensional network structure composed of four
27
Si and Al of CFB fly ash.
D. Li et al.
[SiO4], indicating that 29Si is in the chemical environment of Q4, and it is
four-coordination structures [55,56]. Compared with RCFA, the 29Si
resonance peaks of UCFA are apparently degenerated and broadened,
and the chemical shifts are moved from − 109.763 to − 107.303, The 29Si
resonance peaks in NMR spectra of RCFA around − 106.893 is dis­
appeared in the 29Si NMR spectra of UCFA, indicating that the poly­
merization degree of Si-O polyhedron in UCFA has been decreased. The
changes of 29Si chemical shift and the spectral shape of UCFA indicate
that ultrafine grinding has changed the chemical structure of Si-O
polyhedron. Its chemical structure has been cracked by mechanical
force and moved towards the direction of low polymerization degree,
and its pozzolanic activity is enhanced as the consequence [55]. As
shown in Fig. 10(c) and (d), the 27Al resonance peaks of CFB fly ash are
around 60 and 5, suggesting that the chemical structure of Al-O poly­
hedron is [AlO4] at low polymerization state and [AlO6] at high poly­
merization state, respectively [56,57]. Compared with RCFA, the 27Al
chemical shifts of UCFA have been moved towards the oligomeric state.
Ultrafine grinding has destroyed the chemical structure of Al-O poly­
hedron and transform it to the oligomeric state with higher activity.
To summarize, ultrafine grinding has an efficient mechanical force
effect on CFB fly ash. The chemical structure of some Si-O and Al-O
polyhedrons in CFB fly ash might be destroyed, and their polymeriza­
tion degree might be decreased to show a higher reaction activity.
Combined with XRD pattern, the results have revealed that ultrafine
grinding destroys the ordered crystals structure in CFB fly ash and in­
creases lattice defects, thus its pozzolanic activity would be improved.
The active SiO2 and Al2O3 in UCFA are at the oligomeric state with
higher reaction activity, and the particle sizes of UCFA are smaller than
RCFA, leading to the increase of the dissolution rate and dissolution
amount of active SiO2 and Al2O3, the absorption capacity of Ca2+ in
saturated Ca(OH)2 solution, pozzolanic activity index, self-hardening
compressive strength, and hydration heat release rate. Ultrafine
grinding reduced the particle size and the polymerization degree of Si-O
and Al-O polyhedrons of CFB fly ash in the same time, and thus improves
its pozzolanic activity.
4. Conclusions
(1) Ultrafine grinding optimizes the particle morphology and pore
structure of CFB fly ash, and improves its pozzolanic activity
index and self-hardening compressive strength.
(2) Ultrafine grinding improves the hydration heat release rate and
the total heat release of cement blended with CFB fly ash. The
hydration rate of cement blended with UCFA is accelerated, and
the total heat release within 72 h is close to that of pure cement.
(3) Ultrafine grinding improves the dissolution rate of SiO2 and
Al2O3 of CFB fly ash and the absorption capacity of Ca2+ in
saturated Ca(OH)2 solution, which is mainly due to the decrease
of polymerization degree of Si-O and Al-O polyhedrons and par­
ticle size of CFB fly ash, thus further improves its pozzolanic
activity.
CRediT authorship contribution statement
Duanle Li: Conceptualization, Data curation, Formal analysis,
Investigation, Methodology, Project administration, Resources, Soft­
ware, Validation, Visualization, Writing - original draft, Writing - review
& editing. Rui Sun: Formal analysis, Validation, Writing - original draft.
Dongmin Wang: Funding acquisition, Supervision, Conceptualization.
Caifu Ren: Formal analysis, Writing - original draft. Kuizhen Fang:
Formal analysis.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
8
Fuel 291 (2021) 120220
the work reported in this paper.
Acknowledgment
This work was supported by the National Key Research and Devel­
opment Program of China (No. 2019YFC1904302).
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