Ceramics International 42 (2016) 10908–10912

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

Characterization of chemosynthetic H3PO4–Al2O3–2SiO2 geopolymers

Yan He a, Leping Liu a,b,n, Liping He b, Xuemin Cui a
a
School of Chemistry and Chemical Engineering and Guangxi Key Lab of Petrochemical Resource Processing and Process Intensification Technology, Guangxi
University, Nanning 530004, PR China
b
Guangxi Key Lab of Road Structure and Materials, Guangxi Transportation Research Institute, Nanning 530007, PR China

art ic l e i nf o a b s t r a c t

Article history: Pure chemosynthetic Al2O3–2SiO2 powders fabricated by a sol–gel method exhibit high phosphoric acid-
Received 9 March 2016 activated properties and high compressive strengths. The phosphoric acid-activated properties could be
Received in revised form characterized by compressive strength. The phase structure evolution of synthetic powders and the
29 March 2016
resulting geopolymers were investigated by DTA-TG, XRD, FTIR and MAS NMR analysis. These results
Accepted 29 March 2016
show that the phosphoric acid-activation region of the synthetic powders was in the range of 200–
Available online 30 March 2016
800 °C, which was much lower than the temperature at which kaolinite was converted into
Keywords: metakaolinite. 31P MAS NMR analysis revealed that [PO4] tetrahedra were part of the geopolymer
Geopolymers structure.
Phosphoric acid
& 2016 Elsevier Ltd and Techna Group S.r.l. All rights reserved.
Sol–gel method
FTIR
MAS NMR

1. Introduction the source of this mineral [11]. Highly pure chemosynthetic

In comparison with ordinary Portland cements, alkali-activated
geopolymer materials have attracted increasing attention because
of their excellent mechanical properties, chemical stability, fire
resistance, environment friendliness, and low CO2 concentration
[1,2]. Such geopolymers consist of AlO4 and SiO4 tetrahedral units
and can form 3D structures. The negative charges on the AlO4
tetrahedra are balanced with Na þ and K þ ions [1]. However, the
thermal stability and low dielectric properties of the alkali-acti-
vated geopolymers are not ideal because of the presence of alkali
ions. In phosphoric acid-based geopolymers, the positive charges
on the SiO4 tetrahedra maintain neutrality. This new geopolymer
performs better than the alkali-activated geopolymer due to its
excellent mechanical, thermal, and low dielectric properties [3–5].
Currently, metakaolinite is widely used as the main raw ma-
terial in the preparation of phosphoric acid-based geopolymers.
This mineral is formed when kaolinite is calcined within a tem-
perature range of 450–900 °C [6,7]. Due to its relatively simple
chemical composition, metakaolinite is also utilized as the main
raw material in the study of the reaction mechanism of geopoly-
mers [8,9]. Therefore, the change in short-range ordering and in
the local structure of metakaolinite after conversion from kaolinite
has been the subject of considerable research [10]. Unfortunately,
metakaolinite is impure, and the trace components are sensitive to
n
Corresponding author.
E-mail address: liulp84@163.com (L. Liu).
powders were employed in the preparation of phosphoric acid-
based geopolymers in order to understand and control the mole-
cular structure. They are also employed to control the performance
of the phosphoric acid-based geopolymers used in electronic
packaging materials and in insulated encapsulating materials [5].
A type of highly pure chemosynthetic Al2O3–2SiO2 powder that
is synthesized through the sol–gel method possessed a structure
and properties similar to those of metakaolinite [11,12]. The Si/Al
ratio of the synthetic powders could be accurately controlled and
set to 1, and the alkali activation of these powders was enhanced
compared with that of metakaolinite. However, few reports have
been published on the synthesis of phosphoric acid-based geo-
polymers that utilize Al2O3–2SiO2 powders as precursor materials.
In the present work, the structure and properties of Al2O3–
2SiO2 powders and phosphoric acid-based geopolymers were in-
vestigated through scanning electron microscopy(SEM), X-ray
diffraction (XRD), differential thermal analysis-thermogravimetric
analysis (DTA-TG), Fourier transform infrared spectroscopy (FTIR),
and magic angle spinning nuclear magnetic resonance (MAS
NMR).
2. Experimental methods
2.1. Materials
The precursor materials were synthesized through a sol–gel

http://dx.doi.org/10.1016/j.ceramint.2016.03.224
0272-8842/& 2016 Elsevier Ltd and Techna Group S.r.l. All rights reserved.
 Y. He et al. / Ceramics International 42 (2016) 10908–10912
method with tetraethylorthosilicate and aluminum nitrate non-
ahydrate. Anhydrous ethanol (EtOH) and the starting materials
were mixed in the following molar ratios: 1:1 Si/Al; 20:1 EtOH–
SiO2 [11,12]. The gel was stored in a sealed beaker, which was
placed in a water bath at 70 °C for approximately 13 h until a
transparent homogeneous gel was generated. After aging for 36 h
at room temperature, the gel was dried in air at 105 °C for 6 h.
Subsequently, the dried gel was calcined at 200 °C, 300 °C, 400 °C,
500 °C, 600 °C, 700 °C, 800 °C, 900 °C, and 1000 °C for 2 h. The
pure calcined powders were milled and sieved through a 45-μm
mesh sieve. The metakaolinite was derived from kaolinite (Beihai
of Guangxi Province, China) and was calcined at 200 °C, 300 °C,
400 °C, 500 °C, 600 °C, 700 °C, 800 °C, 900 °C, and 1000 °C for 2 h.
The chemical composition of the metakaolinite as measured by
X-ray fluorescence was as follows (mass%): SiO2, 56.91; Al2O3,
42.35; Fe2O3, 0.22; and K2O, 0.49. The metakaolinite was also
sieved through a 45-μm mesh sieve.
2.2. Geopolymer synthesis
The dry gel powders or calcined powders, phosphoric acid, and
deionized water were mixed with SiO2/Al2O3, H3PO4/Al2O3, and
H2O/Al2O3 at ratios of 1:1, 1:1, and 2:1, respectively. After 20 min of
mechanical stirring, the aqueous slurry was poured into cubic
molds measuring 20 mm  20 mm  20 mm. The molds were then
vibrated for another 10 min and subsequently sealed to prevent
water loss. The cubes were cured at 80 °C for 24 h, whereas the
non-molded samples in sealed bags were cured at 60 °C for 3 days.
Both samples were then placed in air at 60 °C for 3 days. The
calcined metakaolin, deionized water, and phosphoric acid were
mixed for 20 min to obtain an aqueous slurry with the following
molar ratios: H3PO4/Al2O3 ¼ 1:1 and H2O/Al2O3 ¼4:1. The pre-
paration process and curing conditions of the specimens were
consistent with those of the synthetic powders.
2.3. Sample analysis
The compressive strengths of various specimens were mea-
sured with a DNS100 electronic universal tester. Three specimens
from each formulation were tested, and the average value was
obtained. The load was applied with an extension rate of 0.5 mm/
min for all tests.
The crystalline compositions of the starting materials and of
the geopolymers were determined with an automated D/Max
2500V instrument (CuKα radiation generated at 40 kV, 100 mA,
and a scanning rate of 10° per min from 10° to 70° [2θ]). The
thermal analysis of the specimens was conducted using a
STA409PC TG-DTA instrument in air with a heating rate of 5 °C/
min. The infrared spectra of the specimens were obtained with a
Nexus470 FTIR spectrometer using KBr pellets.
27
Al, 29Si, and 31P MAS NMR spectra were obtained using a
Bruker AV300 NMR spectrometer with a 4-mm probe spun at 12,
5, and 10 kHz, respectively. The NMR conditions were as follows: a
resonance frequency of 78.2 MHz, a 0.55-ms pulse width, a 1-s
3+
delay, and Al(H2O) as a reference for 27Al; a resonance frequency
6
of 59.6 MHz, a 1.90-ms pulse width, a 15-s delay, and tetra-
methylsilane as a reference for 29Si; and a resonance frequency of
121.5 MHz, a 1.70-ms pulse width, a 30-s delay, and 85% H3PO4 as a
reference for 31P.
3. Results and discussion
The compressive strengths of the geopolymers are plotted in
Fig. 1. The synthetic powders, which were dried at 105 °C for 6 h,
10909
100
synthetic powder-based geopolymers
calcined kaolinite-based geopolymers
80
Compressive strength/MPa
60
40
20
0
0 200 400 600 800 1000
Calcined temperature /
Fig. 1. Compressive strengths of phosphoric acid-based geopolymers.
did not exhibit any strength. The compressive strengths of the
related specimens increased with an increase in the calcination
temperature of the synthetic powders within the range of 200–
800 °C. This strength increased to a maximum of 89.3 MPa at
800 °C. However, the strength of the specimens calcined at 900 °C
was completely lost. The compressive strengths of the calcined
kaolinite-based geopolymers was less than 5 MPa when the cal-
cination temperature was below 500 °C. In the calcination tem-
perature range of 500–1000 °C, the strength trend of kaolinite-
based geopolymers was similar to that of synthetic powder-based
geopolymers. Moreover, the compressive strengths of phosphoric
acid-based Al2O3–2SiO2 geopolymers were higher than those of
alkali-based Al2O3–2SiO2 geopolymers. The strengths of the spe-
cimens synthesized with the synthetic powders calcined at 200 °C
with phosphoric acid reached 40.1 MPa. The synthetic powders
begin to assimilate phosphoric acid-activated properties when
calcined at 200 °C. Kaolin transformed into metakaolin at an initial
temperature of approximately 450 °C [7]. The structural evolution
of metakaolinite from kaolinite was attributed to the evaporation
of hydroxyl water between the SiO4 tetrahedra and the AlO6 oc-
tahedra. Furthermore, Al(IV) and Al(VI) were converted to tetra-
hedral Al(V) sites [13,14]. Therefore, the onset temperature in the
structural evolution of chemosynthetic powders was lower than
that in the conversion of kaolinite to metakaolinite.
Fig. 2 displays the XRD pattern of chemosynthetic powders
calcined at different temperatures. The synthetic powders were
amorphous, with a hump centered at 2θ of 15–35°. The center of
the hump peaks moved to the small angles within the calcination
temperature range of 105–800 °C, and the half high width de-
creased. The amorphous short-range order calculated using the
Scherrer equation increased with calcination temperature [15].
The additional diffraction peaks detected in the patterns at a cal-
cination temperature of 1000 °C reflected mullite (PDF#79-1275).
This result was consistent with the results reported in the litera-
ture [16,17]. The phase transformation of chemosynthetic Al2O3–
2SiO2 powders was similar to that of metakaolin. The phase
transformation accounted for the increase in strength, as depicted
in Fig. 1.
Fig. 3 shows the TG-TDA curves of the dried gel. A mass loss of
approximately 28% was ascribed to hydroxyl water dehydration at
a temperature below 200 °C, and a sharp endothermic peak was
observed between 130 °C and 145 °C. Another small exothermic
peak was observed between 1002 °C and 1008 °C. This peak was
attributed to the mullite formation determined as illustrated in
Fig. 2. Unlike the calcined kaolinite described in the literature [15–
10910 Y. He et al. / Ceramics International 42 (2016) 10908–10912
Fig. 2. XRD pattern of synthetic powders at different calcination temperatures.
Fig. 3. TG-DTA curves of dried gel in air [10].
17], the mass in hydroxyl water was mainly lost at temperatures
below 500 °C. This water was detected in the interlamination be-
tween the Al–O and Si–O layers. The interlayer structure of kaoli-
nite was more obvious than that of synthetic powders [12].
Therefore, the hydroxyl water dehydration in synthetic powders
was less than that in kaolinite. The mass loss in hydroxyl water
suggested that the activation temperature of synthetic powders
was lower than that of metakaolin.
Figs. 4 and 5 show the FTIR spectra of the synthetic powders
and the phosphoric acid-based geopolymers, respectively. The IR
vibrational bands observed at approximately 1380 cm  1 could be
attributed to NO−3 vibration, thereby indicating that the NO−3 group
disappeared between 105 °C and 200 °C. The major peaks detected
at 1074, 809, 669, and 458 cm  1 of the synthetic powders, which
were calcined at 800 °C for 2 h (Fig. 4), were consistent with the
characteristic absorption peaks of metakaolinite [11,12,18–21]. Si-
milar structural characteristics were observed in other synthetic
powders. These results suggested that the synthetic powders he-
ated at 200–800 °C possessed phosphoric acid-reacted properties.
The vibrational bands of these powders, which reacted with
phosphoric acid, shifted towards high wave numbers (Fig. 5). Ta-
ble 1 summarizes the bands of asymmetric stretching vibration (T–
O–Al, T ¼Si, Al, P) and bending vibration (Si–O or Al–O). The vi-
brational bands of the synthetic powders that reacted with alkali
Fig. 4. FTIR spectra of calcined powders heated at different temperatures.
Fig. 5. FTIR spectra of phosphoric acid-based geopolymers with powders calcined
at different temperatures.
solution shifted towards low wave numbers [13,22]. In alkali-
based geopolymer systems, the number of bridging oxygen atoms
(BOs) were less than that of aluminosilicate precursors due to the
excess alkali metal ions. In contrast, the PO4 tetrahedra bonded
with the AlO4 and SiO4 tetrahedra in phosphoric acid-based geo-
polymer systems to form 3D structures. The number of BOs in-
creased more significantly in these geopolymers than in the pre-
cursor materials. This can be attributed to the fact that the
strength of the phosphoric acid-based geopolymers was greater
than that of the alkali-based geopolymers.
Fig. 6 displays the 27Al and 29Si MAS NMR spectra of the dried
gel and the calcined powders as a function of calcination tem-
perature to illustrate the evolution of the local Al and Si environ-
ments. The spectrum of the dried gel signals at 1 and  106 ppm,
which were attributed to 6-coordinate Al [Al(VI)] and Q4(0Al) si-
licon centers, respectively, were similar to those reported in pre-
vious studies on kaolinite [12,13]. The 27Al MAS NMR spectra of
the dried gel powders calcined at 200 °C could be divided into two
new resonance peaks. A peak was detected at approximately
55 ppm and could be attributed to 4-coordinate Al [Al(IV)], while
the other peak was observed at approximately 25 ppm and was
 Y. He et al. / Ceramics International 42 (2016) 10908–10912 10911

Table 1
Characteristic IR vibrational band of chemosynthetic Al2O3–2SiO2 powders and their geopolymer products.

Calcined temperature (°C) 105 200 600 800 900 1000

Asymmetric stretching/cm  1 (Si–O–Al or Si–O–Si) Calcined powders 1074 1066 1067 1074 1095 1100
Phosphoric acid-based geopolymers 1086 1089 1089 1090 / /
Bending (Si–O or Al–O)/cm  1 Calcined powders 456 458 442 458 459 451
Phosphoric acid-based geopolymers 462 461 465 462 / /

Fig. 6. 27Al and 29Si MAS NMR spectra of the dried gel and the powders calcined at different temperatures: (a) dried gel at 105 °C; (b) calcined at 200 °C; (c) calcined at
300 °C; (d) calcined at 600 °C; (e) calcined at 800 °C; and (f) calcined at 900 °C. SSB denotes spinning sidebands.

ascribed to 5-coordinate Al [Al(V)]. Similar peaks in the meta-
kaolinite spectra were usually detected at temperatures over
500 °C. This also suggested that the synthetic powders calcined at
200 °C possessed phosphoric acid-activated properties, thus cor-
responding to the experimental results described above. Such
powders were therefore related to the presence of 5-coordinate Al
[Al(V)]. The peak intensity of Al(V) increased with the calcination
temperature in the temperature range of 200–800 °C, whereas that
of Al(VI) decreased. The 29Si MAS NMR spectra of the calcined
powders (Fig. 6) exhibited a typical broad resonance. These spectra
were centered between 106 and  103 ppm and were assigned
to Q4(1Al) and to Q4(2Al), respectively [23,24]. Notably, the
change from 200 °C to 800 °C was not significant. This outcome
was consistent with the Si resonance peak in metakaolinite

27 29 31
Fig. 7. Al, Si, and P MAS NMR spectra of powders calcined at 800 °C and its phosphoric acid-activated sample: (a) calcined powders; (b) geopolymer materials.
10912 Y. He et al. / Ceramics International 42 (2016) 10908–10912
[23,24]. With an increase in temperature from 800 °C to 900 °C,
the center of gravity of the spectrum reverted to a high magnetic
field, and peaks were observed at approximately  106 and
109 ppm. These peaks were assigned to Q4(1Al) to Q4(2Al), re-
spectively. This result was related to the formation of a few crys-
talline phases when the treatment temperature was increased in
this manner.
Fig. 7 presents the 27Al, 29Si, and 31P MAS NMR spectra of
powders calcined at 800 °C, along with their phosphoric acid-ac-
tivated specimens. These spectra characterized the local environ-
ments of Al, Si, and P atoms in the phosphoric acid-based geopo-
lymers. The 27Al MAS NMR spectra of powders calcined at this
temperature were inhibited at 0, 25, and 50 ppm. These spectra
were assigned to Al(VI), Al(V), and Al(IV), respectively. When these
powders reacted with phosphoric acid, Al(V) and Al(VI) were
converted into the tetrahedral sites of Al(IV). As per the literature,
the broad resonance centered at 43 ppm for the tetrahedral Al
environment of Al(OP)4 was within the range of 35–48 ppm
[25,26]. This range was characteristic of phosphoric acid-based
geopolymers [12]. Moreover, a new peak was observed at ap-
proximately  14 ppm. A shift in this peak implied that this re-
sonance could be assigned to the octahedral aluminum site in an
AlPO4 species. This result was consistent with that of the previous
studies on AlPO4-based molecular sieves [26]. The 29Si MAS NMR
spectrum of phosphoric acid-based geopolymers inhibited a typi-
cal broad resonance that was centered at  92 ppm. As per prior
studies, the broad resonances between  85 and  95 ppm in the
29
Si spectra indicated that the specimens formed a geopolymeric
network structure [1]. The resonance peak centered at  101 ppm
inhibited the unreacted silicate oligomers in the specimens [22].
The 31P MAS NMR spectra of such geopolymers exhibited a broad
peak that was centered at approximately  17 ppm. This peak was
assigned to the tetrahedral P environment [26]. This outcome was
consistent with the results of early studies on AlPO4-based mole-
cular sieve synthesis. A similar broad 31P peak was detected be-
tween  8 and  20 ppm in the gel specimens obtained during the
early stages of crystallization [26].
4. Conclusions
In this study, unlike the metakaolinite converted from kaolinite
in the temperature range of 450–900 °C in previous studies, syn-
thetic powders were heated over a temperature range of 200–
800 °C and were found to exhibit phosphoric acid-reacted prop-
erties. At temperatures below 200 °C, the specimens synthesized
with phosphoric acid and synthetic powders did not exhibit any
strength due to the existence of the hydroxyl water and NO−3 . Based
on the XRD, DTA-TG, FTIR, and MAS NMR analyzes, the phase and
molecular structure evolutions of the chemosynthetic Al2O3–2SiO2
powders suggested that the phosphoric acid activation region was
within the range of 200–800 °C. The number of BOs in the phos-
phoric acid-based geopolymers exceeded those in alkali-based
geopolymers. Therefore, the phosphoric acid-based geopolymers
possessed superior mechanical and low dielectric properties
compared to the alkali-based geopolymers. These results indicated
that the PO4 tetrahedra were part of the geopolymer structure.
Moreover, the molecular structure of the phosphoric acid-based
geopolymers was similar to the molecular structure of the initial
gel in the early stages of crystallization during AlPO4-based mo-
lecular sieve synthesis. Despite the lack of direct evidence con-
firming that phosphoric acid-based geopolymers could be con-
verted into AlPO4-based molecular sieve crystals via the hydro-
thermal method and the addition of template agents, the proposal
in this paper requires further investigation.
Acknowledgments
This work was supported by the Chinese Natural and Science
Fund (Grant no. 50962002), the Guangxi Natural Science Fund
(Grant nos. 2013GXNSFBA019229 and 2014GXNSFBA118250), and
by the Scientific Research Foundation of Guangxi University (Grant
no. XJZ140315).
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