Materials and Structures
DOI 10.1617/s11527-014-0350-3
ORIGINAL ARTICLE
Synthesis, characterization and mechanisms of one-part
geopolymeric cement by calcining low-quality kaolin
with alkali
Mei Xun Peng Zheng Hong Wang
Shao Hua Shen Qiu Guo Xiao
Received: 21 December 2013 / Accepted: 29 May 2014
RILEM 2014
Abstract Precursors for the preparation of one-part
geopolymers were synthesized by calcining low-
quality kaolin, which containing a lot of quartz, with
NaOH or Na2CO3, then the cement pastes of ground
precursor powders were synthesized by only adding
water and cured at 80 C for 3 days followed by
curing at ambient environment for 25 days. The
geopolymeric cement pastes obtained reasonable dry
compressive strengths, though they were not quite
resistant to water. Alkalis seriously alter the thermal
decomposition course of kaolin, and the octahedral-
coordinated Al in kaolin also turns into tetrahedral-
coordinated Al according to Fourier transform infrared
spectroscopy analysis. By using X-ray diffractions, it
is discovered that nearly all minerals convert into
X-ray amorphous substances and nepheline when the
low-quality kaolin is thermally treated with alkalis at
950 C though most kinds of minerals except kaolinite
are stable after the thermal treatment without alkali at
750 C. P-zeolite is produced during the hydration of
the precursors, and the optimized precursor shows
partly dissolving characteristics in water under scan-
ning electronic microscope. It is supposed that the
hydrolysis of sodium silicates and glassy substances
induces the crystallization of P-zeolite and facilitates
M. X. Peng (&)  Z. H. Wang  S. H. Shen  Q. G. Xiao
School of Chemistry and Chemical Engineering, Hunan
University of Science and Technology, Xiangtan 411201,
China
e-mail: orally@163.com
the hydrated pastes cementing, on the other hand, the
delayed hydrolysis of sodium silicates with high SiO2/
Na2O ratio after solidification might make the one-part
geopolymers expand and reduce the softening
coefficients.
Keywords Low-quality kaolin  One-part
geopolymer  Calcination  Hydration  Mechanism
1 Introduction
Portland cement (PC) contributes substantial carbon
dioxide emissions as well as causes other environ-
mental problems such as the emissions of dusts,
oxynitrides and oxysulfides [1, 2]. Geopolymer is
framework structure generally synthesized from a
two-part mixture, which consists of solid aluminosil-
icate raw materials. This synthesis occurs by using
thermally dehydroxylated aluminosilicate and alkali
silicate solution [35]. Geopolymeric cement (GC) is
considered more environmentally friendly [6] because
of their low energy consumption, good mechanical
properties and low pollution emissions.
However, the two-part GC which contains alkaline
solution and aluminosilicate has several limitations.
Caustic and sticky alkalis could complicate the prepa-
ration and the application of geopolymers [7]. Compared
with PC, GC is relatively costly because it uses industrial
alkalis and/or water glass as activating agents. Kaolin is

almost the only practical one used for geopolymerization
among the natural raw materials. Therefore, raw mate-
rials choices are still limited. A new processing method
of synthesizing one-part (simple water addition) GC
similar to PC was introduced. In 2008, Duxson P and
Provis JL [8] recommended the preparation of an ideal
geopolymer glass precursor to synthesize one-part GC,
though the detailed method was not given. Geothermal
silica and sodium aluminate were combined with water
to form a solid binder [9]. Kolousek et al. proposed a new
method for synthesizing geopolymer and the method
involved a reactive precursor by calcining low-quality
kaolin with sodium and potassium hydroxide at 550 C.
However, the compressive strength was considerably
low [10]. Solid-state synthesis through thermal reaction
of halloysite with LiOH followed by hydration of the
product resulted in fragile and crumbly products [11].
Kaolin was calcined with K2CO3 to form KSiAlO4
products as the starting materials for the synthesis of
zeolites [12]. Feng et al. [13] synthesized one-part
geopolymers through thermal activation of albite with
alkali at 1,000 C, and the compressive strength of the
geopolymeric sample reached 30 MPa after cured for
7 days. However, the alkali content was much higher
than that of the typical GC.
It seems that the one-part GCs have great potential
to develop. However, their properties and the mech-
anisms related to calcination and hydration have not
been explored deeply, and the studies on various low-
cost aluminosilicate clays as raw materials have just
begun to apply to the one-part GC technology. The
common low-quality kaolin with high Si/Al ratio is
abundant, inexpensive, and more compatible with GC
in terms of their chemical compositions compared
with high-quality kaolin. Unlike pure kaolinite (2SiO2-
Al2O32H2O) with Si/Al ratio equal to 1, low-quality
kaolin are usually composed of other minerals such as
quartz, feldspar and muscovite besides kaolinite, so it
has high Si/Al ratio similar to geopolymers with a Si/
Al ratio of 26 [14]. When quartz is thermally
activated with alkali, the sodium silicate added in
two-part GC as part of the activator can be synthesized
during calcination (Reaction [1]):
SiO2 Na2 CO3 =NaOH ! Na2 O  nSiO2
CO2 =H2 O 1
Through the thermal treatment with alkali for low-
quality kaolin, the resulting product will be active
alkaline aluminosilicate glass. Thus, the common low-
Materials and Structures
quality kaolin with high Si/Al ratio can be a potential raw
material during one-part geopolymerization. The current
study focuses on the suitability of low-quality kaolin to
form one-part GC through thermal activation with alkali
(NaOH or Na2CO3). X-ray diffraction (XRD), scanning
electron microscopy (SEM), Fourier transform infrared
spectral (FTIR) analysis, thermogravimetry (TG) and
differential scanning calorimetry (DSC) are adopted to
explore the calcination and hydration reactions for
discuss the mechanisms being involved in.
2 Experimental section
2.1 Materials
Low kaolinite content clay acquired from Pingxiang
China was ground to obtain 90 % of particles that
measure\75 lm. The full silicate analysis, which is a
kind of quantitative chemical analysis method accord-
ing to JC/T1021-2007 in China, ascertained the
chemical composition of the clay as 70.11 % SiO2,
19.07 % Al2O3, 4.29 % K2O, 1.03 % Fe2O3, 0.33 %
Na2O, 0.32 % CaO, and 0.10 % MgO (on a mass
basis). Both sodium carbonate and sodium hydroxide
were of analytical reagent grade and supplied by
Guangfu, ShangHai. Industrial water glass (soluble
sodium silicate) (WG) with the Na2O/SiO2 mol ratio
of 3.0 and the density of 1,350 kg/m3 (8.5 % Na2O,
24.5 % SiO2 and 67 % H2O) was adjusted to the
Na2O/SiO2 mol ratio of 1.5 by adding NaOH.
2.2 Thermal treatment
The kaolin powder, which was ground to obtain 95 % of
particles that measure\75 lm, was mixed with specific
amounts of NaOH or Na2CO3 with respect to the mass
of the dry clay. The mixtures were heated in a laboratory
muffle furnace to the desired temperature (650, 750,
850, 950 or 1,050 C) at an increment of 10 C/min,
then held at this temperature for 3 h before being cooled
down to room temperature in the furnace. The ground
clinkers were sealed against atmospheric carbonation
and hydration prior to analysis and synthesis.
2.3 Geopolymerizing and curing
The clinker powders were directly mixed with water at
a water/solid mass ratio of 0.3 and stirred for 3 min in
Materials and Structures

a cement paste mixer to form one-part GC pastes. Leiz PHS-3C pH-meter to explore the hydration
Otherwise, the two-part GC pastes were synthesized reaction.
with thermally calcined kaolin and adjusted WG. The
pastes were placed in 40 9 40 9 36 mm3 molds,
sealed with plastic bags, and cured at 80 C for 3 Results and discussion
3 days?20 C for 25 days in air with [90 % humid-
ity. The pastes were subjected to compressive strength 3.1 Compressive strength and softening
test for 3, 4, 7, and 28 days before wiped out the water coefficient
on the surfaces of the pastes with wrung wet cotton
cloth. The 4 day compressive strength was obtained The cement products are asked to be subjected to cruel
from the pastes immersed in water at 20 C for 1 day natural environment, so they should resist attacks of
after cured at 80 C for 3 days to calculate the the alternations between dry and wet weather. The
softening coefficient. strengths of dry cement products are often higher than
those of wet ones, so the softening coefficients, which
Softening coefficient 4 day compressive strength=
are the ratios of the wet strengths to the dry strengths,
3 day compressive strength can measure the applicability for the cements. No one-
2 part GC paste cured at room temperature gained
reasonable strength though all the pastes cured at
2.4 Sample characterization
80 C formed successful hardened geopolymers. The
highest dry compressive strength for one-part GC is
The kaolin, the calcined clinkers (precursors), and the
much higher than the two-part GC prepared with
cured geopolymer samples were analyzed by using
optimized activator, and some of wet strengths for the
FTIR. The spectra were recorded from 4,000 to
one-part GC are higher than that for the two-part GC
450 cm-1 by using a PE2000 FTIR Spectrum Spec-
also, but the softening coefficients for the one-part GC
trometer, and the specimens were prepared by using
are lower than the two-part ones obviously (to see
the KBr pellet technique. Powder XRD was con-
Table 1). The one-part GC paste using kaolin calcined
ducted on a Bruker D8-Advance diffractometer from
with 25 % NaOH at 950 C has the highest dry/wet
Germany with Cu Ka radiation at 35 kV and 40 mA.
compressive strength 63.0/16.4 MPa among the pastes
Each sample was scanned with 2h between 3 and
made from precursors of the kaolin calcined at 650,
70, a step increment of 0.01 with a scanning rate of
750, 850, 950 and 1,050 C adding NaOH 15, 20 and
8/min. SEM was conducted by using JSM-6380LV
25 % mass of the kaolin respectively. Furthermore,
from JEOL Japan to characterize the microstructures.
33 % Na2CO3 replacing 25 % NaOH according to
Energy disperse spectroscopy (EDS) was adopted to
equal content of Na2O hardly alter the strengths of the
analyze the chemical composition of the microdo-
geopolymers. It seems that the compressive strengths
main by using EDX-Genesis 60s from EDAX in
of the one-part geopolymers increase with the eleva-
USA. TG/DSC was conducted at 10 C/min from 30
tion of NaOH content and calcination temperature
to 1,300 C in air by using a Mettler Toledo TGA/
(\1,050 C). But the calcination temperature higher
DSC1/1600HT. Compressive strength was deter-
than 950 C reduces the compressive strength drasti-
mined by using a NYL-600 pressure testing machine
cally, and the dry/wet compressive strength of
from WuXi.
hydrated paste is only 6.4/2.4 MPa when the precursor
is calcined at 1,050 C with 25 % NaOH.
2.5 pH value measurements of one-part GC
precursor dispersed in water 3.2 Thermal analysis

One gram of cooled kaolin calcined at 750 C with
15 % NaOH and ground to 100 % of particles\75 lm
was dispersed in 100 ml distilled water at 80 C in a
closed retort cooled with circulating water. The pH
values at different stirring times were checked with
Figures 1 and 2 show the derivative thermogravimet-
ric (DTG) and DSC curves respectively for raw kaolin
and the kaolin mixed with 25 % sodium hydroxide or
33 % sodium carbonate. The only obvious weight loss
of about 3.5 % is observed for the raw kaolin between
 Materials and Structures

Table 1 Compressive strengths and softening coefficients of the geopolymeric pastes

Calcination Thermal Hydration Dry compressive Wet compressive Softening
temperature activation activator strength (MPa) (3d) strength (MPa) (4d) coefficient
(C) addition

750 Na2O1.5SiO2nH2O 16.3 15.0 0.92

650 15 % NaOH nH2O 1.3 0.7 0.54
750 15 % NaOH nH2O 22.5 2.3 0.10
850 15 % NaOH nH2O 16.4 8.3 0.51
950 20 % NaOH nH2O 22.4 10.3 0.46
950 25 % NaOH nH2O 63.0 16.4 0.26
1,050 25 % NaOH nH2O 6.4 2.4 0.38
950 33 % Na2CO3 nH2O 47.7 15.5 0.32

0.02
440 and 530 C, corresponding to an endothermic
kaolin valley in DSC curve. The small DSC valley at 573 C,
0.00 which appears in all three samples, is reasonably due
-0.02
to the reversible ab quartz transition. The wide DSC
endothermic valley at approximately 1,200 C for the
DTG/%/ C

-0.04 33%Na 2CO3

kaolin indicates the fusion of orthoclase in the kaolin.
-0.06
The kaolin adding 25 % NaOH exhibits two
defined weight loss valleys before 750 C. The
-0.08 strongest valley accompanies 23.8 % weight loss at
-0.10
25%NaOH 110 C, with a sharp endotherm in the heat flow,
caused by evaporation of the strongest adsorbed water
-0.12 associated with NaOH among three samples. Approx-
0 200 400 600 800 1000 1200
T/ C imately 2.9 % weight loss occurs in the range of 530
and 750 C because of the dehydration of NaOH,
Fig. 1 DTG of kaolin, kaolin?25 % NaOH and kaolin?33 % accompanied with a DSC endothermic valley at
NaCO3
704 C. A broad and shallow endothermic valley at
890 C is ascribed to the gradual reaction of kaolin
with alkali and the formation of sodium alumina
silicate glassy phases. Compared with the raw kaolin,
there was no sharp dehydration around 485 C for
kaolin with 25 % NaOH. The evident endotherm at
1,160 C is attributed to the melting of all minerals.
Therefore alkali seriously alters the thermal-decom-
position of kaolin and reduces the temperature for clay
to vitrify.
For the clay adding 33 % Na2CO3, the features of
DTG and DSC are similar to those for the clay adding
25 % NaOH. Approximately 3.7 % weight loss of
absorbed water occurs in the range of 60 and 113 C
and exhibits most drastic at 85 C, but is more
moderate than that of the sample with 25 % NaOH
at 110 C. Approximately 12.8 % mass loss between
Fig. 2 DSC of kaolin, kaolin?25 % NaOH and kaolin?33 %
Na2CO3 300 and 790 C is observed as a result of the release of
Materials and Structures
CO2 by the decomposition of sodium carbonate
accompanied with a broad endothermic valley.
Above 790 C, no further notable weight loss is
found, while an endothermic valley at around 910 C
is more evident than that one with 25 % NaOH, which
is attributed to the formation of sodium alumina
silicate glassy phases via the reaction between the
kaolin and the free alkali released by the thermal
decomposition of Na2CO3. Compared with NaOH, the
kaolin with Na2CO3 melts also at 1,160 C with
endothermic valley in DSC curve. Thus, Na2CO3 as
alkali is as effective as NaOH on activating kaolin with
equivalent content of alkali.
3.3 FTIR analysis
Figure 3 shows the FTIR spectra comparison of the
specimens including the raw kaolin, the calcined
kaolin with (and without) alkali and the hydrates.
Kaolin depicts characteristic peaks at 3,694 and
3,625 cm-1, which correspond to the OH- stretching
vibration. The valley at 1,013 cm-1 is attributed to the
SiO bonds in the SiO4 molecules, and the valley at
910 cm-1 corresponds to exterior OH vibrations.
The bands at 793 and 687 cm-1 are both due to SiO
symmetric stretching. Absorption at 535 cm-1 is
contributed by SiOAlVI, in which the Al is in
octahedral coordination. A weak valley near
1,640 cm-1 in all formulae is caused by the bending
vibrations of water. Except for the raw kaolin, all
formulae of the calcined kaolin and the hydrates do not
exhibit a SiOAlVI valley at 535 cm-1. This indi-
cates that the octahedral coordinated Al in kaolinite
turns into the tetrahedral coordinated Al [14] after
being thermally disposed between 750 and 950 C. All
valleys related to structural water such as 910, 3,622
and 3,706 cm-1 are not found in the curves of
disposed kaolin with thermal history, while both
valleys near 1,640 cm-1 (which is weak in the kaolin)
and 3,450 cm-1, which are related to the absorbed
water weakly bound with aluminosilicates, appear in
the precursors of one-part GC (to see Fig. 3d) and their
hydrates (Fig. 3c, e). The calcined kaolin at 750 C
exhibits weakest water absorption because of very
weak 1,640 and 3,450 cm-1 valley (Fig. 3b). Both
the one-part geopolymer (Fig. 3e) and the two-part
mix geopolymer (Fig. 3c) exhibit a sharp valley at
around 1,458 cm-1 which is attributed to the influence
of the CO32- ions during curing [15]. The strong water
e
d
c
b
a
500 1000 1500 3200 4000
-1
Wave number/cm
Fig. 3 FTIR spectra comparison of a the kaolin, c the kaolin
calcined at 750 C, e the hydrate of (c) with WG, d the kaolin
calcined with 25 % NaOH at 950 C and b the hydrate of (d)
absorption and hydration ability of the kaolin ther-
mally treated with alkali at 950 C are probable the
cause to explain the bound water in it. Using Na2CO3
instead of NaOH as alkali, the IR characteristics of
clinkers calcined with alkali are identical, as well as
the hydrated geopolymers (not graphically show here).
3.4 XRD analysis
Figure 4 presents the XRD patterns of raw kaolin,
the kaolin calcined at 750 C with or without 25 %
NaOH and the corresponding hydrates. The kaolin
calcined at 750 C without alkali has the same
mineral composition with raw kaolin, but the
kaolinite content in the former is less than in the
latter. Only the diffraction peak at 19.75, which is
attributed to kaolinite, remains for the calcined
kaolin. The contents of orthoclase and muscovite are
also reduced according to diffraction peak strength,
but the content of quartz is still high, so quartz
seems inert during calcination. Nepheline (NaAl-
SiO4) and little amount of anhydrous sodium
aluminosilicate Na2(Al2Si3O10) (?) are found in the
kaolin treated with 15 % NaOH at 750 C, and the
contents of all raw minerals are reduced according
to the highness of the diffraction peaks. With
Na2(Al2Si3O10) disappearing, a new crystal phase
P-zeolite (Na3.6Al3.6Si12.4O3214H2O) is found in
the one-part GC hydrated from the kaolin calcined
with 15 % NaOH at 750 C (seen in Fig. 4).
 Materials and Structures

P
(750 )
P P QP
P
N N
P P ( )
N N 750
D P
P
)
P P N P
750 N P PP
Q ( )
Q Q PN Q Q
M K Q Kaolin M P PN Q Q Q Q Q
K M OO QQ Q O PM PM Q
M M OMM QQ Q Q Q
Q
10 20 30 40 50 60 70
10 20 30 40 50 60 70
2 2

Fig. 4 XRD patterns for kaolin at different conditions includ- Fig. 6 XRD patterns for the hydrates of kaolin calcined at
ing raw kaolin, kaolin calcined at 750 C with or without NaOH different temperatures
and the hydrate. Peaks marked with letters are: Q-quartz
(PDF#89-1961), K-kaolinite (PDF#80-0886), M-muscovite 750 C disappears when the calcination temperature
(PDF#07-0025), O-orthoclase (PDF#71-0957), D-Na2(Al2Si3- elevates to 950 C. Most phases in the precursors
O10) (PDF#87-1276), N-nepheline (PDF#35-0424), P-zeolite treated at 1,050 C appear glassy with little content of
(PDF#44-0052)
quartz and nepheline, for the base line of the XRD
pattern indicates a smooth broad peak (to see Fig. 5).
The hydration of thermally treated kaolin with
alkali cured at elevated temperature 80 C produces
P-zeolite, and except for it, the characteristics of XRD
QN N
patterns for the one-part geopolymers shown in Fig. 6
1050 are very similar to their precursors calcined at different
calcination temperature shown in Fig. 5. The calcina-
QN
NN 950 tion temperature 950 C leads to the highest content of
N N N
Q Q Q Q Q P-zeolite in the hydrates among 750, 950 and
Q
Q
750
1,050 C.
Q
M O
D MNN
NN QQ Q Q
Based on the results in Table 1, it can be seen that
M N M QQ Q Q
Q the precursors calcined with more alkali at moderately
10 20 30 40 50 60 70 higher temperature (B50 C) contain more nepheline,
and the corresponding hydrates contain more P-zeo-
Fig. 5 XRD patterns for kaolin calcined with alkali at different lite, that lead to better compressive strength. So the
temperature hydrated paste of the clinker calcined at 1,050 C
containing most content of glassy phases seems quite
inert compared with those containing more crystalline
The phase characteristics of one-part GCs and their phases given the fact that the former possesses lowest
precursors vary with the calcination temperature and compressive strength. Since the one-part GC with
the alkali content according to Fig. 5. After calcina- optimal calcination conditions can convert all other
tion, the contents of all the raw minerals are lessened, minerals besides kaolinite in the clay into cementitious
and some of them disappear. At the same time, the and moderately glassy substances and result in much
glassy phases are generated and the contents of them higher dry compressive strength than two-part GC, it is
increase with the elevation of both calcination tem- more effective on activating the cementing activity of
perature and alkali content, though the nepheline does low-quality kaolin.
not vary its content with calcination temperature in Based on the information of the XRD (to see
this way and is at most content in the precursor Figs. 4, 5, 6) and the compressive strengths (to see
calcined at 950 C. Na2(Al2Si3O10) found in the Table 1), it is concluded that the precursors and the
thermally treated kaolin with 15 wt% NaOH at hydrates of one-part geopolymers are much better
Materials and Structures

Fig. 7 SEM morphologies of raw kaolin, calcined kaolin with of c; e kaolin calcined with 25 % NaOH at 950 C; f geopolymer
alkali and the related one-part geopolymers. a raw kaolin; hydrated from e; g kaolin calcined with 25 % NaOH at
b muscovite in raw kaolin; c Geopolymer from kaolin calcined 1,050 C; h geopolymer hydrated from g. The white crosses
at 750 C with 15 % NaOH; d muscovite in the geopolymer mark the positions where the local compositions were analyzed

crystallized than those of two-part geopolymers which precursor treated at 1,050 C as well as the corre-
are composed of amorphous silicates. And as shown in sponding hydrate for the one-part GC is very similar to
Figs. 5 and 6, the hump between 20 and 30 of the that for two-part geopolymer attributed to amorphous
 Materials and Structures

Table 2 Element atom contents of the microdomains by EDS

Graph number of Calcination and hydration condition Atom content
microdomain in Fig. 7
Na K Al Si Approximate ratio
of (Na?K):Al:Si

b Muscovite in raw kaolin 0 0.37 1.51 1.69 1:3:3

c 15 % NaOH?750 C 12.23 0.45 5.78 12.87 2:1:2
d (15 % NaOH?750 C)?H2O 8.00 1.45 8.35 16.40 1:1:2
e 25 % NaOH?950 C 7.25 1.39 5.31 18.66 2:1:3
f (25 % NaOH?950 C)?H2O 7.99 1.28 4.71 15.75 2:1:3
g 25 % NaOH?1,050 C 8.96 1.31 4.97 20.02 2:1:4
h (25 % NaOH?1,050 C)?H2O 4.47 0.14 4.92 25.22 1:1:5

silicates, but the cementing property of the former is
much worse than the latter (to see Table 1). We are
expecting to reveal the cause in the subsequent
researches.
3.5 SEM and EDS analysis
Figure 7 presents the SEM morphologies of the raw
kaolin, the thermally treated kaolin adding alkali and
the hydrates. The positions of the microdomains for
EDS are also marked in Fig. 7. Compared with the
raw kaolin (seen in Fig. 7a), the aggregated particles
in the hydrated kaolin calcined at 750 C with 15 %
NaOH exhibit cementing characteristics, though the
morphologies of the raw minerals remain in the
particles and do not fully hydrate. For example, the
muscovite piece remains (seen in Fig. 7d) with
dirty corroded morphology different from that in
Fig. 7b. The kaolin calcined at elevated temperature
950 C with 25 % content of NaOH exhibits a kind
of homogenized glassy morphology without any raw
mineral remaining, and the corresponding geopoly-
meric particles agglomerate with smooth morpholo-
gies without acute edges. This indicates extensive
dissolution of the precursor particles in water in
consistent with the excellent strength property (to
seen in Table 1). The calcined kaolin at 1,050 C
with 25 % NaOH completely reveals the glassy
morphology (Fig. 7g), and its hydrated particles are
very angular (to see Fig. 7h), indicating that the
clinkers hardly react with water. No crystal mor-
phologies of new minerals including nepheline and
P-zeolite are found in all samples by SEM. Com-
bining the strength properties of the pastes in
Table 1 with XRD and SEM information, it can be
summarized that the porous moderately glassy
clinkers containing nepheline bring about well
binding pastes containing P-zeolite.
The EDS chemical analysis of microdomains in
Table 2 proclaims that all the calcined kaolin with
NaOH and their hydrates have similar chemical com-
positions as geopolymers, and they contain excessive
alkalis (Na2O or K2O), that is to some extent different
from the raw kaolin without Na2O. The Si/Al ratios of
both the one-part geopolymers and their precursors
increase with the calcination temperature. It is consis-
tent with the fact that more quartz in the clay melts into
the precursors at high calcination temperature.
3.6 pH value measurements of one-part GC
precursors dispersed in water
The pH values of the kaolin calcined at 750 C with
15 % NaOH dispersed in water at 80 C are shown in
Fig. 8. The chemical course in this test is similar to the
hydration course of the precursors, though the water/
solid ratio here is much higher than that in the cement
pastes. The hydration mechanisms can be penetrated
from the change of pH values. The pH value elevates
quickly before 30 min, and decreases before increas-
ing secondly until 90 min and decreases afterwards.
The drop of pH value becomes gentle after 500 min
and continues to the end.
The first increase of pH value might be ascribed to
dissolution of the free alkali remaining in the clinker
particles, and the second pH elevation could be
attributed to the hydrolysis of the sodium silicate and
sodium aluminosilicate. Feng et al. [13] found poorly
crystallized anhydrous sodium silicate when thermally
treated albite with alkali, and the sodium silicate might
Materials and Structures
Fig. 8 pH value related to hydration time of thermally
activated kaolin with alkali
exist in the clinkers of kaolin calcined with alkali,
though it is hard to be found out by XRD for it is
almost X-ray amorphous. The kaolin with high quartz
content calcined with less content of alkali often
produces sodium silicate with high ratio of SiO2/Na2O
that hydrolyses in water very slowly.
The formation of the zeolite reduces the pH value in
the end. Ma HC et al. [16] synthesized zeolite of type A
from bentonite by thermal activation using Na2CO3.
Na2SiO3, Na2Al2O4 and Na2Al2Si2O9 were found in the
bentonite through alkali fusion activation using Na2CO3
at 830 C, and zeolite of type A was produced during the
following hydration process of the treated bentonite in
water at 90 C for 6 h. The thermally treated albite with
alkali also generated zeolite when hydrated [12]. Na2
(Al2Si3O10) was also found when low quality kaolin was
calcined with alkali at 750 C. The hydrolysis of clinkers
in excessive water will be accompanied with the
production of P-zeolite since its existence in the one-
part GC was ascertained by using XRD.
3.7 Calcination and geopolymerization
mechanisms for one-part geopolymers
In our experiments, when alkali is added much
enough, the calcination reaction for kaolin containing
quartz could be proposed as Eq. (3).
Al2 O3  2SiO2  2H2 O SiO2 NaOH
! Na2 O  Al2 O3  nSiO2 amorphous H2 O 3
According to thermodynamic law, nepheline is then
produced if sodium aluminosilicate Na2OAl2O3-
nSiO2 is active:
Na2 O  Al2 O3  nSiO2 amorphous
! Na2 O  Al2 O3  2SiO2 nepheline 4
The kaolin containing more quartz and calcined at
higher temperature with alkali will produce the
amorphous sodium aluminosilicate with larger n,
which was proved with EDS analysis, and the
precursors calcined at too high temperature, for
example at 1,050 C, will melt and turn into compact
glass. It is proposed that this compact vitrification
weakens its reaction activity and will neither turns into
nepheline nor hydrolyzes in water to geopolymerize.
Independent quartz will turn into sodium silicate as
Eq. (1), so quartz in the kaolin will turn into sodium
silicate when calcined with alkali at 750 C, and the
hydrolysis of the precursors in water might follow:
Na2 O  nSiO2 H2 O ! SiO2  H2 O Na OH
5
Na2 O  Al2 O3  nSiO2 amorphous H2 O
! Na OH AlO 2 SiO2  H2 O 6
When the precursor powders disperse in water, pH
value increases accompanied with the hydrolysis of
Na2OnSiO2 and Na2OAl2O3nSiO2. It is well know
that the hydrolysis rate of Na2OnSiO2 is seriously
affected by modulus n and is negatively related to n.
The hydrolysis elevates pH value and supports gen-
eration of zeolite as reaction (7) [16]:

AlO
2 SiO2  H2 O Na OH
! Na2 O  Al2 O3  pSiO2  qH2 Ozeolite 7
The generation of zeolite reduces the pH value and
makes the pastes cementing. The hydrolysis of the
precursors might be quite slow and control the geopoly-
merization processes. The practical hydration and geopo-
lymerization reactions take place in more dense solution,
so the reaction rate will be quicker. But the condition with
excessive water such as being dipped in water will inspire
the hydrolysis of the precursor as Eqs. (5) and (6), but
restrain the geopolymerization as Eq. (7), for low density
of (OH)- slows down the generation of zeolite. So the
pastes will swell and break. This might explain the rather
low softening coefficients of the one-part geopolymers.
4 Conclusions
Thermal stimulation of low-quality kaolin with alkali
for geopolymeric precursors was used as a step in the

evolution of one-part geopolymer cements. Only
adding water, the pastes formed from ground precur-
sor of low-quality kaolin calcined with 25 % NaOH at
950 C gains rather high dry compressive strengths
though they are not quite resistant to water. The TG/
DSC predicts that alkali alters the thermal decompo-
sition of kaolin, and the octahedral coordinated Al in
kaolin also turns into tetrahedral coordinated Al
according to IR analysis. During thermal activation
with alkali at 950 C, most other minerals besides
kaolinite dissolve though they are stable when
calcined at 750 C without alkali. Moreover, nephe-
line and glassy phase sodium aluminosilicate are
generated during calcination with alkalis, and P-zeo-
lite is produced during the hydration of the precursors
cured at 80 C. The optimized one-part GC precursors
show partly dissolving characteristics in water under
scanning electronic microscope. It is supposed that the
hydrolysis of XRD-amorphous sodium aluminosili-
cate induces the crystallization of P-zeolite and makes
the hydrated pastes cementing, although the delayed
hydrolysis after consolidation might make the one-
part geopolymers swell and reduce the wet strengths.
Acknowledgments The work was funded by the natural
science foundation of Hunan Province China (Project No:
11JJ5025). The authors are grateful to the College of Chemistry
and Chemical Engineering, Hunan University of Science and
Technology for providing access to the equipments used in this
investigation.
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