The role played by the reactive alumina content in

the alkaline activation of y ashes

A. Fernandez-Jimenez
a,
*
, A. Palomo
a
, I. Sobrados
b
, J. Sanz
b
a
Eduardo Torroja Institute (CSIC), P.O. Box 19002, 28080 Madrid, Spain
b
Instituto Ciencia de Materiales (CSIC), Cantoblanco, 28049 Madrid, Spain
Received 14 September 2005; received in revised form 24 October 2005; accepted 8 November 2005
Available online 4 January 2006
Abstract
This study explores the relationship between the chemical composition of y ashes and the microstructural characteristics and
mechanical properties of the cementitious materials resulting from the alkali activation of y ashes (AAFA). Three reactive systems were
prepared by mixing three F ashes, with an 8 M NaOH solution and stored at 85 C. The main reaction product formed in three systems is
an amorphous alkaline aluminosilicate gel. This gel (zeolite precursor), has a three-dimensional framework, with Al occupying Al(4Si)
and Si occurring in a variety of environments Q
4
(nAl). After short thermal activation periods (25 h), an Al-rich gel was formed with
silicon in tetrahedral Q
4
(4Al) units (intermediate phase), yielding low mechanical strengths. When the curing time increase (7 days) the gel
changes into a more stable Si-rich phase with a greater mechanical strength. Finally, it has been shown that the amount of the reactive
aluminium plays an important role in the aluminosilicate gel formation, from a kinetic point of view.
2005 Elsevier Inc. All rights reserved.
Keywords:
29
Si and
27
Al MAS-NMR; Fly ash; Alkali activation; Pre-zeolite binder
1. Introduction
The alkali activation of alumino-silicate materials is a
chemical process that transforms partially or totally amor-
phous, vitreous and/or metastable structures into compact
cementitious skeletons [15]. As a result of the reaction that
takes place between y ashes and alkalis under mild ther-
mal conditions (6090 C), the major reaction product is
an amorphous alkaline aluminosilicate gel [68]. The
29
Si
MAS-NMR analysis [6] of these gels showed the formation
of three-dimensional networks that constitutes the cementi-
tious material that connects unreacted y ash spheres. In
this aluminosilicate gel the Si is found in a variety of
Q
4
(nAl) environments.
On the other hand there is a striking parallelism between
the reaction mechanism involved in zeolite formation from
alkali activation metakaolins and that regulating the alkali
attack of type F y ashes. In this regard, Davidovits [9] and
Palomo et al. [6,7] concluded that the long term formed
products are ultimately related to zeolite phases. The essen-
tial dierence between the two types of material lies in the
properties they exhibit: the nal product of zeolite synthe-
sis is an adsorbent, catalytic powder, whereas the material
obtained with AAFA is cementitious, with high mechanical
strength and considerable stability.
Recent surveys have shown that the Si/Al ratio of the
aluminosilicate gel obtained from the alkali activation of
y ashes depends heavily on the chemical composition of
the starting material, nature and concentration of alkali
activator, synthesis temperature, and thermal curing time
[6,7,1013]. Nonetheless, many questions persist about
the reactivity of y ashes in strong alkaline environments.
For this reason, the aim of our study has been the analysis
of the formation of dierent pre-zeolite gels as a function of
the curing time for dierent y ashes. For this purpose, a
number of dierent techniques have been used for the
structural and microstructural characterization of prepared
1387-1811/$ - see front matter 2005 Elsevier Inc. All rights reserved.
doi:10.1016/j.micromeso.2005.11.015
*
Corresponding author. Tel.: +34 91 302 0440; fax: +34 91 302 6047.
E-mail address: anafj@ietcc.csic.es (A. Fernandez-Jimenez).
www.elsevier.com/locate/micromeso
Microporous and Mesoporous Materials 91 (2006) 111119
materials. Taken into account the vitreous nature of start-
ing ashes as well as the amorphous characteristic of the
formed gels, the MAS-NMR spectroscopy is particularly
adapted to this work.
2. Experimental
2.1. Characterization of the starting materials
Three y ash materials (called P, L and M) from three
dierent Spanish steam power plants were used in this
study. All three were F type ashes (ASTM classication)
consisting primarily of SiO
2
and Al
2
O
3
. Chemical composi-
tions (determined according to Spanish Standard UNE 80-
215-88), the reactive silica (determined according to UNE
80-225-93), and the reactive alumina contents (determined
according to Ref. [14,15]), are shown in Tables 1 and 2. In
Table 2, the relative amount of the vitreous phase in three
ashes is also given.
2.2. Alkali activation of the ash
The three ashes were activated with an 8 M solution of
NaOH. The solution/ash ratio used in each case was
chosen to obtain a paste of standard consistency (UNE
EN 196-3); i.e., 0.33, 0.4 and 0.56 by mass/weight for ashes
P, L and M, respectively. The pastes obtained were cured at
85 C and 98% relative humidity for dierent periods of
time (2, 5, 8 and 20 h and 7 days). After each experiment,
the material was removed from the stove, cooled to labora-
tory temperature, ground and then mixed with small
amounts of acetone to prevent the activation progress.
2.3. Chemical attack
Alkali activated materials were subjected to an acid
attack with a 1:20 solution of HCl to determine the degree
of reaction attaint in each sample (Table 3). The acid solu-
tion dissolves the reaction products formed by alkaline
activation of ashes (aluminosilicate gel and zeolites) but
does not interact signicantly with the unreacted y ash
[6,16]. After ltering, the concentration of the Al dissolved
was determined by ICP-MS on a Spectromass 2000 instru-
ment (Table 4).
2.4. Techniques
All materials were characterized with XRD,
29
Si and
27
Al MAS-NMR and SEM/EDX. X-ray diractograms
of powder samples were recorded on a Philips diractome-
ter PW 1730, with Cu Ka radiation. Magnetic materials
were removed from the samples prior to the NMR spectra
acquisition by exposure the samples to a strong magnetic
eld.
29
Si and
27
Al MAS-NMR spectra of puried samples
were performed with an MSL-400 Bruker apparatus. The
resonance frequencies used in this study were 79.5 and
104.3 MHz, with spinning rates of 4 kHz and 12 kHz. All
measurements were taken at room temperature with TMS
(tetramethylsilane) and AlH
2
O
3
6
as external standards.
The estimated errors in chemical shift values were lower
than 0.5 ppm. A JEOL JSM 5400 scanning electron micro-
scope (SEM), equipped with a LINK-ISIS energy disper-
sive (EDX) analyzer, was used for micro-analysis.
2.5. Mechanical properties
The mechanical properties of resulting products were
studied on prismatic mortar specimens prepared by mixing
sand, y ash, and the activating solution. The sand used
has a 95% quartz content (CEN EN 196-1). The y ash
/sand ratio was 2:1. The fresh mixtures were poured into
metal prismatic moulds (4 4 16 cm) and kept in a stove
at 85 C under relative humidity >95% for up to 168 h. The
mortar prisms were then subjected to exural and compres-
sive test failure as described in the Spanish Standard UNE-
80-101-88.
3. Results
3.1. Degree of reaction (alkali activation)
Table 3 gives the degrees of reaction found by subjecting
the materials to attack with 1:20 solution of HCl [6,16].
The results showed that the degree of reaction increased
with curing time. However, while this parameter rises sub-
stantially in the case of ashes L and P, the degree of reac-
tion in ash M remained essentially unchanged after 8 h.
Table 4, shows the Al
2
O
3
content in the liquid phase,
expressed as a percentage of the Al
2
O
3
content of ashes.
These results indicate that the quantity of Al incorporated
into reaction products increased with reaction time. How-
ever, in the case of the ash M the amount of incorporated
Al is lower than in ashes L and P after 8 h of reaction.
3.2. Structural characterization
Detailed characterizations of the original ashes can be
found in previous published works [7,11,15]. Since the
Table 1
Chemical analysis of y ashes
a
Oxides (%) SiO
2
Al
2
O
3
Fe
2
O
3
CaO MgO Na
2
O K
2
O SO
3
Fly ash P 54.42 26.42 7.01 3.21 1.79 0.59 3.02 0.01
Fly ash L 51.51 27.47 7.23 4.39 1.86 0.70 3.46 0.15
Fly ash M 59.89 27.67 3.02 3.45 1.22 0.94 1.01 0.51
a
Determined as stipulated in Spanish Standard UNE 80-215-88.
112 A. Ferna ndez-Jime nez et al. / Microporous and Mesoporous Materials 91 (2006) 111119
main reaction products are always amorphous to XRD, the
structural characterization of resulting products has been
undertaken with MAS-NMR spectroscopy and SEM.
XRD analysis has been used to conrm the crystalline
character of formed phases. The most relevant data refers
to the detection of the characteristic humps of amorphous
phases in X-ray patterns (not shown) [16,17]. However,
long reaction times give rise to the formation of minor crys-
talline phases, identied asherschelite (JCPDF-19-1178)
and hydroxysodalite (JCPDF 11-401)zeolites [16,18].
3.2.1.
29
Si MAS-NMR spectroscopy
Fig. 1 depicts the
29
Si MAS-NMR spectra of original y
ashes (P, L, and M) and the reaction products formed at
dierent curing times. The wide signals generally observed
in
29
Si MAS-NMR spectra of starting materials are an
indication of the heterogeneous character of ashes. (spectra
in row A, Fig. 1). In these spectra peaks detected at 84,
94, 98 and 103 ppm are attributed to the dierent Si
environments of the ash [6,16]. The peak at around 87/
88 ppm, in turn, is identied as mullite [19], a crystalline
phase present in all ashes. Finally, the peaks with chemi-
cal shifts above 108 ppm are attributed to Q
4
(0Al) envi-
ronments in quartz (108/109 ppm) and cristobalite
(113/114 ppm) [20,21].
It should be mentioned, in connection with the deconvo-
lution of the alkali activated ash spectra, that the relatively
high iron content of starting ashes (7% for ash P and L
and 3% for M) was considerably reduced with the exposure
of samples to a strong magnetic eld. The partial elimina-
tion of iron oxides decrease problems derived from para-
magnetism in NMR spectra. Nonetheless in P sample, the
iron could was not completely eliminated, which led to a
higher broadening of components and a lower signal/noise
ratio than in other pastes. This fact explains that satellite
bands detected in MAS-NMR spectra of P sample are
much more important (not shown).
29
Si MAS-NMR of spectra ashes activated with the
NaOH solution and thermally cured at 85 C between 2 h
and 7 days are also given in Fig. 1 (B, C, D, E and F rows).
As the reaction time increases the intensity of signals attrib-
utable to the reaction products grows at expenses of those
of starting ashes. The most relevant change is observed in
the early stages of the reaction. Between 2 and 8 h of curing
at 85 C, the most intense signal detected is located at
Table 2
Reactive SiO
2
and Al
2
O
3
content of y ashes
Vitreous phase
a
(%) Reactive
b
SiO
2
(%) Reactive
a
Al
2
O
3
(%) Reactive
b
SiO
2
+
a
Al
2
O
3
(%) Si/Al (atomic ratio)
Fly ash P 61.08 45.05 18.04 63.09 1.42
Fly ash L 64.94 42.17 22.46 64.63 1.64
Fly ash M 54.28 45.07 12.60 57.67 2.38
a
Determined by acid attack with HF 1% (see Refs. [13,14]).
b
Determined as stipulated in Spanish Standard UNE 80-225-93.
Table 3
Degree of reaction (% of activated ash) at dierent curing times
a
Ash Thermal curing time
2 h 5 h 8 h 20 h 7 days
Degree of reaction P (%) 33.85 36.36 38.83 42.91 44.50
L (%) 36.01 41.20 44.10 48.00 64.90
M (%) 34.56 37.57 38.35 38.77 38.54
a
Determined by acid attack with HCl 1:20 (see Ref. [15]).
Table 4
Amount
a
of Al
2
O
3
dissolved after acid attack on activated ashes at
dierent curing times
Ash Thermal curing time
2 h 5 h 8 h 20 h 7 days
Dissolved Al
2
O
3
P (%) 8.60 9.6 9.7 10.7 14.3
L (%) 8.66 10.0 11.5 15.1 19.9
M (%) 8.69 9.2 9.8 9.5 11.5
a
Expressed as percent (by wt.) of total ash.
Fig. 1.
29
Si MAS-NMR spectra of starting ashes and AAFA resulting
products in: (a) y ash P; (b) y ash L; (c) y ash M. Row A stands for
starting ashes; row B for samples cured 2 h at 85 C; row C for samples
cured 5 h at 85 C; row D for samples cured 8 h at 85 C; row E for
samples cured 20 h at 85 C; and row F for samples cured 7 days at 85 C.
A. Ferna ndez-Jime nez et al. / Microporous and Mesoporous Materials 91 (2006) 111119 113
around 86/88 ppm. This signal is associated with the
formation of a tectosilicate rich in aluminium with a pre-
dominance of Q
4
(4Al) silicon units [21,22]. The signals
detected at lower values (82/80 and 79/77 and
72/70 ppm) are associated with the presence of less con-
densed, monomer and dimer species, that decrease as the
reaction progresses. The signals appearing above
88 ppm overlap with those of unreacted ash, making dif-
cult their assignment.
A comparison of the
29
Si MAS-NMR spectra of pastes
resulting from three alkali-activated ashes reveals that the
nal and therefore the most thermodynamically stable
compound formed is similar in all cases (7 days at 85 C,
row F, Fig. 1). Nonetheless, the kinetics of the formation
of this compound varies with the nature of the starting
materials, as Fig. 1 shows. In all cases, spectra can be pri-
marily attributed to the formation of an aluminosilicate gel
with a higher Si content than that of the gel previously
detected. The spectra obtained after 7 days of reaction
are formed by ve components associated with the pres-
ence of silicon surrounded by none, one, two, three or four
aluminium tetrahedron in the silico-aluminate gel, whose
signals appear at around 110, 104, 98, 93, and
88 ppm (with an error of 1 ppm). In some cases signals
are detected at 74.5 and 81.0 ppm that are attributed to
the presence of residual less condensed species, probably
monomer or dimer units with silanol groups. For interme-
diate reaction times,
29
Si NMR spectra (rows C and D) are
formed by components of the two formed aluminosilicates.
3.2.2.
27
Al MAS-NMR spectroscopy
The
27
Al MAS-NMR spectra for both the starting ash
and the samples activated for dierent times are given in
Fig. 2. NMR patterns of starting y ashes contain two wide
signals, one centred at +53.86 ppm associated with tetrahe-
dral aluminium (Al
T
) and a second small signal centred at
+4.5 ppm, attributed to octahedral aluminium (Al
O
). The
last component is mainly associated with the presence of
mullite in the starting y ash [20,21].
During alkali activation, the tetrahedral aluminium sig-
nal is observed to shift rst from +53.9 to 60, and nally
from +60 to +59 ppm, indicating that the aluminium
always remains tetrahedrally coordinated. This component
has been ascribed to aluminium surrounded by four silicon
tetrahedra, which is characteristic of Al in zeolites precur-
sors (Alq
4
(4Si) environments).
3.2.3. SEM study
The three studied ashes are formed by hollow or com-
pact spheres of dierent sizes, with a smooth and regular
texture (like most of type F ashes). In Fig. 3(a)(c)
micro-morphological aspects of ashes activated with 8 M
NaOH and cured at 85 C for 7 days are shown. In all cases
an amorphous aluminosilicate gel is formed, which consti-
tutes the cementitious material detected between unreacted
ash spheres. The large number of spherical particles
observed in M pastes corroborate the low degree of reac-
tion attained in this material (see Table 3). EDX technique
was used to nd the average composition of the formed gel.
Deduced Si/Al values were 1.82.0 for sample L, 2.02.3
for sample P and 1.41.5 for sample M.
The crystalline deposits, usually found inside of the par-
tially unreacted ash spheres or between particles, corre-
spond to the zeolites detected with XRD. An example of
these crystalline phases (white arrow) can be seen in
Fig. 3(b). This compound is herschelite crystals having a
Si/Al ratio of 2.2 and a Na/Al ratio of 1.02.
3.3. Mechanical strength
The development of compressive strength in alkaline
activated y ash mortar prisms is plotted against reaction
time in Fig. 4. The most visible change is produced for
short reaction times. The increment of mechanical strength
is similar for the three types of ashes at 5 h, but changes sig-
nicantly for longer reaction times. Between 5 and 20 h, the
compressive strength increases considerably in L and P
ashes but remains almost constant in M pastes. After 168
h (7 days) of thermal curing, the highest mechanical
strength value was obtained in the ash P (80 MPa), fol-
lowed by the ash L (72 MPa). Strength developed in ash
M, is considerably lower, 31 MPa.
4. Discussion
It has been reported in previous papers [6,7] that the
alkali activation of y ashes is a process comprising the dis-
Fig. 2.
27
Al MAS-NMR of starting ashes and AAFA resulting products
in: (a) y ash P; (b) y ash L; (c) y ash M. Row A stands for starting
ashes; row B for samples cured 2 h at 85 C; row C for samples cured 5 h
at 85 C for; row D for samples cured 8 h at 85 C; row E for samples
cured 20 h at 85 C; and row F for samples cured 7 days at 85 C.
114 A. Ferna ndez-Jime nez et al. / Microporous and Mesoporous Materials 91 (2006) 111119
solution of starting materials and the formation of alumi-
nosilicate gels. A similar mechanism was detected during
the formation of zeolites from the alkaline attack of the
kaolinite [22]. The dissolution stage, begins immediately
after the alkali solution comes into contact with the y
ash. In this stage, the high OH

concentration of the alka-

line medium favours the break of covalent SiOSi, SiO
Al and AlOAl bonds present in the vitreous phase of the
ash, releasing the silicon and aluminium ions into the solu-
tion, where they form species with a high number of SiOH
and AlOH groups. During the gelation stage, ionic species
present in the solution (monosilicates and monoaluminates
units) condense to form SiOAl and SiOSi bonds, giv-
ing rise to a three-dimensional aluminosilicate gel with
alkaline cations compensating the decit charges associated
with Al for Si substitution. In these gels, the formation of
AlOAl bonds between contiguous tetrahedra is not
favoured (Loewensteins rule). In the early stages of the
reaction, the speed of formation of dissolved monomers
is greater than the speed of precipitation of the gel.
Actually, the rate of dissolution of ashes strongly
depends on the amount and composition of ashes. Table
1 shows that the three ashes used in this study have very
similar total silica and alumina contents, however not all
silica and alumina are reactive. Taken into account that
mullite and quartz are considered to be inert, our study will
be focused on the amount of silica and alumina reactive
(see Table 2). The reactive silica content is likewise similar,
but the reactive alumina content of the vitreous phase dif-
fers appreciably in the three analyzed ashes. This explains
dierences detected in calculated (Si/Al)
Reactive
ratios.
In Fig. 5(a), the evolution of the reaction degree is given
as a function of the reaction time. In this gure, it can be
observed the existence of two stages in the alkaline activa-
tion of ashes. During the rst few hours the reaction degree
is quite similar; however, as the reaction progresses dier-
ences become evident. In P and L pastes the second stage
is clearly observed; however, in M pastes, the reaction
almost does not progress. The analysis of Fig. 5(b) shows
that during the rst 5 or 8 h of reaction the three ashes
release the same amount of Al (10%); however, after this
stage, dierent amounts of Al are released. In the y ash L,
with an initial amount of reactive alumina of 18.04% (see
Table 2), the amount of Al released into dissolution
increase appreciably as the reaction progress. In the case
of P samples the amount of Al released is considerably
lower in the second stage; nally, in M samples, a very slow
activity is detected after 8 h of reaction. This observation is
explained by assuming that most of reactive alumina of the
M ash has been consumed in the rst stage of reaction
(75% of the reactive alumina). These results provide sup-
port to the hypothesis that a certain minimum amount of
reactive Al is always necessary to favours the formation
of aluminosilicate gels. These results agree with those
reported by Van Deventer et al. in a large number of
mineral aluminosilicates [23]. These authors deduced the
Fig. 3. SEM micrograph and microanalysis (EDX) of (a) P, (b) L and (c) M ashes, activated with 8 M NaOH and cured at 85 C for 7 days.
0 20 40 60 80 100 120 140 160 180 200
0
20
40
60
80
100
P
L
M
C
o
m
p
r
e
s
s
i
v
e

s
t
r
e
n
g
t
h

(
M
P
a
)
Time (hours)
Fig. 4. Compressive strength as a function of the reaction time, for mortar
prisms formed with alkali activated y ashes.
A. Ferna ndez-Jime nez et al. / Microporous and Mesoporous Materials 91 (2006) 111119 115
existence of a correlation between the quantities of Si and
Al dissolved in the reactional medium. According to this
idea, the synchronous dissolution of Si and Al would
explain in our case that the speed with which the unat-
tacked silica of the M ash dissolves is drastically reduced
in the second stage of the reaction, as a consequence of
the reactive Al absence.
In alkaline attack of starting ashes, AlO bonds are
more readily broken than SiO bonds; from this fact, the
rate of reaction will be very high when the amount of reac-
tive aluminium passes through a maximum in the solution.
According to this fact, the probability c
1
of the formation
of AlOSi bonds is higher than that of SiOSi in alumi-
nosilicate gels (see Table 5) at the early stages of activation
[20,21]. This favours the incorporation of Al in the alumi-
nosilicate gels formed (see spectra B and C in Fig. 1). From
this fact, the signal detected around 86/88 ppm has
been associated with the formation of an Al-rich gel [6,7],
in which four Al surrounds a Si tetrahedron and four Si
surrounds an Al. A similar conclusion may be deduced
from the
27
Al MAS-NMR spectra (see Fig. 2). The Al
T
sig-
nal shifts towards more positive positions, characteristic of
tetrahedral aluminium in zeolites (AlQ
4
(4Si)). According to
this fact, the gel detected for short reaction times would
display Si/Al ratios near to 1 (S4R-type intermediate reac-
tion compound) [7]. In addition to the most prominent sig-
nal Si(4Al),
29
Si NMR spectra show other less intense
peaks at lower chemical shift values which are associated
with the presence of less condensed species produced dur-
ing alkaline activation of ashes. Finally, signals detected
at 94, 98 and 104 ppm, correspond to the unreacted
vitreous phase, and signals appearing at around 108
and 112 ppm are due to the Q
4
(0Al) units of the quartz
and cristobalite, present in the starting ash.
As the alkaline activation progresses, aluminosilicate
precipitates covering partially ash particles (see Fig. 3(b)).
However, SEM images have shown that aluminosilicate
gels formed at short reaction times are not homogeneous:
some ash particles, either because of their composition or
because the particles size, react earlier than others (Figs.
3 and 4). Mechanical properties of alkaline activated ashes
depend strongly on the characteristics of the continuous
precipitate that interconnect unreacted ash particles in
resulting prepared composites. In particular, the absence
of the continuity in particles connection between particles
should reduce considerably mechanical performances of
mortars. Dierences on the amount of the deposited alumi-
nosilicate explain dierent compressive strengths measured
in materials prepared for short reaction times in three stud-
ied ashes (Fig. 4).
The coverage of ash particles with formed aluminosili-
cates produces also a substantial slowdown of the reaction,
retarding the dissolution of silicon and aluminium required
0 2 h 5 h 8 h 20 h 7 d
0
4
8
12
16
20
24
28
(b)
(L)
(P)
(M)
U
n
r
e
a
c
t
e
d

[
A
l
2
O
3
]
(
%

i
n

m
a
s
s

f
r
o
m

f
l
y

a
s
h
)
Time of thermal curing
P
L
M
0 2 h 5 h 8 h 20 h 7 d
0
10
20
30
40
50
60
70
(a)
P
L
M
R
e
a
c
t
i
o
n

d
e
g
r
e
e

(
%
)
Time of thermal curing
Fig. 5. (a) Reaction degree versus time; (b) unreacted Al
2
O
3
versus reaction time in the analyzed ashes. The horizontal lines represent the maximum
quantity of aluminium that can react in each ash (see Tables 1 and 2).
Table 5
Si/Al ratio of starting ash, and AAFA pastes at 8 h, 20 h and 7 days of reaction
Reaction product
Ash 8 h 20 h 7 days 7 days
a
(Si/Al)
Reactive
c (%)
b
Si/Al
NMR
c (%)
b
Si/Al
NMR
c (%)
b
Si/Al
NMR
c (%)
c
Si/Al
EDX
P 1.42 70.4 1.40 71.4 1.48 67.6 1.85 54.05 2.02.3
L 1.64 61 1.42 70.4 1.62 61.7 1.71 58.4 1.82.0
M 2.38 42 1.44 69.5 1.48 67.6 1.57 63.7 1.41.5
a
See Table 2.
b
104 ppm Q
4
(1Al) signal, 108 ppm signal disregarded.
c
Value determined by microanalysis (SEM/EDX).
1
c = probability of the formation of SiOAl bonds in the gel, is derived
from c = (1/r) where r = Si/Al. A value of c = 1 indicates that all the
bonds are SiOAl, whilst c = 0.55 indicates that 55% are SiOAl bonds
and 45% SiOSi bonds.
116 A. Ferna ndez-Jime nez et al. / Microporous and Mesoporous Materials 91 (2006) 111119
to the formation of gels. As the reaction progresses, further
amounts of SiO
2
and Al
2
O
3
are dissolved, favouring the
evolution of the initial Gel 1 (Al-rich phase) into a new
Gel 2 (Si-rich phase). This assertion is supported by the
changes observed in the
29
Si NMR spectra. The intensity
of Si(3Al), Si(2Al), Si(1Al) and Si(0Al) signals increases
at expenses of the Si(4Al) signal. Moreover, the line width
of
29
Si MAS-NMR components becomes smaller with
reaction time, indicating that the new-formed phase is
more regular. The Si/Al ratio of the silicon-enriched gel
gradually approaches to 1.8, giving rise to (D6R-type)
structures [7]. In Fig. 6, the intensity of Q
4
(4Al) and
Q
4
(2Al) NMR signals (representative of the two formed
gels) are plotted versus reaction time. In all cases, the inten-
sity of the Q
4
(2Al) band increases at expenses of that
Q
4
(4Al). It is observed that the ash L, with the highest Al
reactive amount, present the quickest transformation, the
P ash display intermediate transformations, and the M
ash shows very low activity after 8 h of reaction.
The Si/Al ratio of the formed gels can be determined by
applying Engelhards equation [21]
Si=Al
NMR

P
n
I
n
Si
n
Al
0:25
P
n
nI
n
Si
n
Al
n 0; 1; 2; 3; 4
where I
n
(Si
n
Al) stands for the intensity of the component
associated with silicon surrounded by nSi and (4 n)Al.
The analysis of values given in Table 5, conrm the obser-
vation that the Si/Al ratio of the formed gel increases with
the reaction time. In this table, the (Si/Al)
Reactive
values,
deduced by EDX, corresponding to starting ashes and pre-
zeolite gels formed after 7 days of reaction are given. De-
spite dierences observed in values obtained with NMR
and EDX, the same trends are observed. Taken into ac-
count experimental conditions required to form the cemen-
titious material (very alkaline systems, very low liquid/
solid ratios, relatively short working times, low tempera-
tures), the zeolite crystallization process is extremely unfa-
voured. According to this fact, the amount of zeolites
detected in this work is very low.
A deeper analysis of Table 5 shows an inverse relation-
ship between the (Si/Al)
Reactive
values deduced in start-
ing y ashes and the Si/Al ratios of the alkaline
aluminosilicate gels obtained after 7 days of reaction.
These observations result from two dierent facts: (i) the
more stable aluminosilicate gels nally formed display Si/
Al ratios near 1.8; (ii) the incorporation of Si in absence
of Al is considerably retarded [24,25]. According to these
facts, composition of aluminosilicate gels obtained in L
and P ashes are similar; however, slow kinetics prevent to
attain this composition in M samples. The reaction kinetics
depends on a series of intrinsic and extrinsic variables (par-
ticle size, chemical composition of the ash, pH of the med-
ium, nature and concentration of the activator, curing time
and temperature, etc.), which dier in analyzed systems. In
the case of the M ash, the kinetic is considerably slowdown
as a consequence of the fast consumption of the reactive
Al
2
O
3
in the rst formed gel.
In Fig. 7, it is analyzed the relationship between
mechanical strengths and the relative amount of Q
4
(4Al)
versus Q
4
(3Al) + Q
4
(2Al) units in gels. From these results,
it can be concluded that the mechanical strength of the
material increases during formation of the gel in rst stage
of the alkaline activation (coating of ash particles with an
Al-rich aluminosilicate gel, Gel 1), but increases further
as a result of the Si enrichment of the cementitious materi-
als (formation of the Si enriched aluminosilicate gel, Gel 2).
In the case of the ash M with the highest (Si/Al)
Reactive

ratio, the lowest mechanical strength (see Fig. 5) is

obtained as a consequence of the smaller amount of Si
incorporated into the aluminosilicate gel (low degree of
reaction attained) (see Table 3). Focusing specically on
the present research, it can be concluded that the most suit-
able ashes for the manufacture of alkaline cement with
2 5 8 20 168
0
5
10
15
20
25
30
35
40
(a)
(b)
FA P
A
r
e
a

(
%
)
Time (hours)
(a)=Q
4
(4Al) (b)=Q
4
(2Al)
2 5 8 20 168
0
5
10
15
20
25
30
35
40
FA L
(b)
(a)
A
r
e
a

(
%
)
Time (hours)
2 5 8 20 168
0
5
10
15
20
25
30
35
40
FA M
(b)
(a)
A
r
e
a

(
%
)
Time (hours)
(a)=Q
4
(4Al) (b)=Q
4
(2Al)
(a)=Q
4
(4Al) (b)=Q
4
(2Al)
Fig. 6. Evolution of signals intensity of
29
Si MAS-NMR Q
4
(4Al) and Q
4
(2Al) components as function of the reaction time in the three analyses ashes.
0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0
0
10
20
30
40
50
60
70
80
90
Gel 2 Gel 1
P L M
C
o
m
p
r
e
s
s
i
v
e

S
t
r
e
g
t
h

(
M
P
a
)
[Q
4
(2Al) +Q
4
(3Al)] / Q
4
(4Al)
Fig. 7. Mechanical strength versus Q
4
(2Al) + Q
4
(3Al)/Q
4
(4Al) ratios
deduced by NMR spectroscopy in the three y ashes.
A. Ferna ndez-Jime nez et al. / Microporous and Mesoporous Materials 91 (2006) 111119 117
good cementitious properties are of type F, with (Si/
Al)
Reactive
ratios below 2.
Results of this investigation have clearly shown that the
availability of dissolved Al and Si at a given moment highly
inuences the kinetics of the alkaline activation of y ashes.
Other variables, as concentration of the activator, curing
temperature and curing time, play also a signicant role
in kinetics of gels formation [10,13]. From a thermody-
namic point of view the process of activation of y ashes
can be divided up to three main stages (see Fig. 8):
Stage 1 (Dissolution stage): Most of the vitreous compo-
nent of the y ash is dissolved. No mechanical strength
development is observed during the dissolution process.
Stage 2 (Induction period): During the induction period a
massive precipitation of a metastable Gel (named Gel 1)
takes place, that produces the coating of unreacted y
ash particles. This gel display the singular characteristic
of incorporate (into the microstructural framework) a
big part of the reactive aluminium existing in the ash,
but not all the silicon. The beginning of this stage is
associated to the initial setting of the paste. In this case
a real degree of reaction
2
around 7080% (the apparent
degree of reaction
3
has been estimated about 3040%),
is obtain but the mechanical strength development of
the material is not important [6,7].
Stage 3 (Silicon incorporation stage): Finally, stage 3 cor-
responds to a period in which Gel 1 is transformed into
Gel 2. This new gel is a Si-rich material since it accom-
modates into the structural framework that silicon
which is more slowly dissolved in the alkaline medium.
Naturally, during the time in which Stage 3 is running
the reaction degree continues advancing till reaching
values >90% (real degree of reaction). At the same time,
mechanical strength increases considerably. When the
content of Gel 1 in the alkali activated y ash is higher
than the content of Gel 2, the mechanical strength devel-
opment is low, 2025 MPa, however when the content of
Gel 2 Gel 1, then the mechanical strength gain nota-
bly increases to 80 MPa (see Fig. 8).
5. Conclusions
The analysis of the mechanical strength, degree of reac-
tion and microstructural characteristics of alkaline-acti-
vated ash pastes has shown that y ashes that best
perform under alkaline activation are: (i) ashes with a high
reactive SiO
2
and Al
2
O
3
contents and (ii) ashes with (Si/
Al)
Reactive
ratios below 2.
In all analyzed cases an alkaline aluminosilicate gel is
formed as the major reaction product regardless of the
composition of the ash. For short reaction times, formed
gels are constituted by an Al-rich phase, in which Si tetra-
hedra are surrounded by four Al tetrahedra (Q
4
(4Al)
units). As the reaction progresses, this phase evolves into
a more stable Si-rich phase, in which a higher amount of
Si occupy Q
4
(3Al) and Q
4
(2Al) environments. In these
materials, the increment of Si/Al ratios, improve consider-
ably mechanical properties of aluminosilicate gels formed.
Acknowledgements
This study was funded by the Spanish Department Gen-
eral of Scientic Research, under Project BIA2004-04835.
Fig. 8. Schematic description of mechanical properties evolution to the reaction time. The increment of mechanical performances is related to the Si/Al
ratio in the gel.
2
Real degree of reaction (only the reactivevitreouscomponent of the
y ash is taken into account for the calculations).
3
Apparent degree of reaction (100% of the y ash is considered to
contribute to the alkaline activation reactions).
118 A. Ferna ndez-Jime nez et al. / Microporous and Mesoporous Materials 91 (2006) 111119
Authors thank CSIC and European Social Fund for the
I3P Contract (Ref. 13P-PC2004L) co-nanced by the Euro-
pean Social Fund.
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