CEMENT and CONCRETE RESEARCH. Vol. 19, pp. 69-80, 1989. Printed in the USA.

0008-8846/89. S3.O0+O0. Copyright (c) 1989 Pergamon Press plc.

INVESTIGATIONS ON THE FLY ASH-CALCiU~ HYDROXIDE

REACTIONS

M.P. Lux~n, M.I. Sgnchez de Rojas and M. Frfas,

Instituto Eduardo Torroja (C.S.I.C.). Apartado 19002.- 28080-Madrid. Spain.

(Refereed)
(Received May 4, ]988)

ABSTRACT
The fly ashes are incorporated to the portland cemen~ and concrete
as active additions, due to their capacity for reacting with the
lime, principally originated during the hydration of the portland
cement, and forming hydraulic compounds.
In this paper a study of the evolution of the fly ash - calcium
hydroxide reaction by the time, is presented.
Ten fly ashes from Spanish power stations are selected. They are
different in "the original coal, chemical composition, ...
No previous treatment (sieving, grinding . . . . ) had been made on the
fly ashes.
The study of the behaviour of every fly ash with the lime are
carried out by a chemical test at several ages.
With the use of the instrumental technique, X-ray diffraction and
infrared absorption spectroscopy, it has been verified the
disappearance of existent mineralogical components in the original
samples as well as the formation of compounds coming from the fly
ash - lime reaction (hydrated calcium aluminates . . . . ). The effect
of the CaO content of the fly ash is observed.
Introduction
Fly ashes are principally used to be mixed with portland cement or are added
directly to concrete in Spain, the same as in other contries; a fact whose
importance will grow even more in the next few years, it is essential
therefore to know the existing fly ashes aiming to obtain a finished product
of good quality. The present study shows a contribution to the study c f
Spanish fly ashes. Ten samples were taken from different power stations using
three types of coal in order to study their reaction capacity and to increase
the knowledge of the products resulting from the treatment of fly ash with
a saturated lime solution for different lengths of time. The X-ray diffraction
and IR absorption spectroscopy techniques rounded off the research.

69
70 Vol. 19, No. I
M.P. Lux~n, et al.

Experimental
Characterization of the fly ashes
* Fineness, the ten fly ashes were not subjected to any grinding process,
so their particle size distribution remained unchanged.
Host international standards restrict the 4 5 ~ m sieve retention and will soon
also be the Spanish standard. Each fly ash was air-sieved on 4 B ~ m and the
percentage retained determined (Table I). This value is basically affected
by the degree to which the original coal is pulverised and not so much by the
source, and also by the thermal process and the characteristics of
precipitator used at the power station (i), (2).
Table I shows that there is no relationship between the percentage of
particles retained on 4 5 ~ m sieve and the type of the original coal.

TABLE I - CHARACTERIZATION OF FLY ASHES

_j FLY RESIDUE CHEMICAL COMPOSITION [%) MINERALOGICAL

8 ASH ON 45/.Lm
u n (%) S A F C M ,~ LO COMPOSITION

QUARTZ
I 19,5 46,9 23,5 7,8 10,6 1.8 0,5 1,4 MULLITE
HEMATITE
u~ QUARTZ
:D MULLITE
o
2 14,0 49,2 29,6 4,2 2,8 1,8 0,9 5,9 HEMATITE
~E CA
:D CALC I TE
l-
aD QUARTZ
MULLITE
3 1.7 50,8 32,1 4.7 1,9 1,8 1,0 4,5 HEMATI TE
CA
o'3 QUARTZ
w
,~ 4 19.5 51,2 30.8 6,4 3,0 1,9 0,4 5,7 MULLITE
HEMATITE
m CALCITE
"r
k- QUARTZ
z MULLITE
< 5 8,5 45,726,9 8,8 9,9 1,6 1,4 4,3i HEMATITE
o ANHYDRITE
2
<[
QUARTZ
6 28~ 49.327,9 6,5 4,5 1,8 0.6 5,3 MULLITE
HEMATITE
$ QUARTZ
51,3 31,1 ,5.9 3,2 1,8i0,7 5,2 MULL ITE
Z 12,0 HEMATITE
=g
ANHYDRITE
QUARTZ
MULLITE
8 40,0 45,0 36,8 7,4 4,4 1,3 1,4 2,9 HEMATITE
ALBITE
ANHYDRITE
QUARTZ
w 9 15~ q5,4 30,0 l~l 4,0 I,I 1,9 0.8 MULLITE
HEMATITE
ANHYORITE
._J QUARTZ
ANHYORITE
i FREE LIME
0 28,O 40,1 20.6 1Z.6;21,1 0,9 3,7 O,3 CS
PORTLANDITE
HEMATITE
CALC I TE
Vol. ]9, No. I 71
FLY ASH, CH, REACTIONS, IR, XRD

A study of Blaine's specific surface was also carried out. It was found that
this method is hard to follow where fly ash is concerned, specially due to
the carbon content which interferes with the measuring process because of
high porosity and the accompanying absorption capacity. This produces results
that are merely indicative. The fly ashes under study have a specific surface
of around 4000 cm2/g u. Blaine, excepting fly ash samples 2, 3 and 7 where
the specific surface is larger.
* Chemical Composition of the ten fly ashes are given in Table I. No
correlations have been found between the chemical composition and the source,
though the highest percentage of CaO and SO 3 is found in fly ash sample i0,
which proceeds from a power station where lignite is used.
Mineralogical composition was studied by X-ray diffraction technique
(Philips model PW-1700 with an X-ray tube containing a copper anode).
It is known that fly ashes are constitued of a glassy matrix with crystalline
phases like mullite, quartz, hematite and unburned coal residue particles.
Several authors (3), (4) have found that the type of mineralogical compounds
of which fly ash consists clearly depends on whether it ash with a high or
low lime content.
Mullite is a compound that is usually found in fly ash with a low lime
content and rarely in those with a high lime content, while the presence of
anhydrite, tricalcium aluminate, portlandite and in some cases calcium oxide
(3), (4), (5), (6) is observed in the latter.
The X-ray diffractograms of the different fly ashes studied here, Figures
la ... lOa show that quartz is the common crystalline compound in every fly
ash sample; whilst mullite does not appear in sample number i0, which the
highest percentage of CaO with a radically different mineral composition.
Anhydrite is found in the ash of lignite as well as in the bituminous and
anthracite combination, not however in bituminous. For fly ashes fron
bituminous source, the presence of calcium aluminate (CA), possibly CaAI407,
had been also detected. Meanwhile, fly ashes from lignites coal contain
calcium silicates, which can be Ca2MgSi207 or Ca2SiO 4 (CS).
Table I shows the mineralogical components of each of the different types of
fly ashes.

Fly ash - lime treatment

The reactivity of the fly ashes basically depends on the particle size,
morphology and surface texture. Thus, the treatment of fly ash with lime
causes the particle surface to change (7).
In order to study the pozzolanic activity of these materials, an accelerated
method was used ~ i c h linked the study of the evolution of the fly ash - lime
reaction along the time. With the techniques used (X-ray diffraction and
IR absorption spectroscopy) the structural changes that take place in the
course of the reaction could be analyzed.
The test consists in putting the different types of fly ashes in contact with
the saturated lime solution at 40 + 1 °C for 7 and 28 days. At the end of
that time, the total alkalinity and the CaO concentration in the solution was
established. The solid residue is studied by X-ray diffraction and IR
absorption spectroscopy.
72 Vol. 19, No. 1
M.P. Lux~n, ec al.

C4AHI$

Ic

M ',I

.
~.~--.--~,~'.~-~
M
A,.o,A i~-u
~
? ~-.~-'~
~r .
H MH ~
M
~
Q g'g lb

u "l
kM

=i°JA o
M
" ~

.. ? ~ Fig lo

45 40 35 30 25 20 15 ~0 5
le

Fig. 1 - X - R A Y D I F F R A C T O G R A M S . a: s a m p l e i;
b: w i t h lime at ? days; c: w i t h lime at 28 days.

/
c,CSH(-)

Fig 2c
O~ l~ M ! L
N& O
u

l/
Fig 2b
N ¢~.CSH(,) IL O
,. o .,o ,o°.".k .:- t~ . k 1\-~.,.~. L~, C,,ACH'H .

. . ~
Q

Fig 2a
M Q.M • HM M |
,. o ..o AoL A AX," k. . ~. _l'v, . A

45 40 ~ 30 2S 20 1S I0 $
ze

Fig. 2 - X - R A Y D I F F R A C T O G R A M S . a: s a m p l e 2;
b: w i t h lime at 7 days; c: w i t h lime at 28 days.
Vol. 19, No. I 73
FLY ASH, CH, REACTIONS, IR, XRD

Fig 3c
c.CS-~.i
u C4:,Cx.
H M A ~ C4~HI. Q " •

I c*CS~ 2eJ I| C A;H

M ~ '~ M H M M CA

oH M M O

~ v ~ / ~ . ~ 1 ~ ~'~..;~..~,~--,'~--"~ " ' ~ - ~ ' ~ . ~ ~ . ~

~0 45 40 3.5 30 2.5 ~0 15 I0 5
~e

Fig. 3 - X - R A Y D I F F R A C T O G R A M S . a: s a m p l e 3;
b: w i t h lime at ? days; c: w i t h lime at 28 days.

C4AHI:

C4 ~,H13

Fig 4c
• M
O M ^ • H M,H c*Cg'~(-)

o
/
Fig. 4 b
- H c.-CS~(-) ~M
C4~.HI3
• .o .. .. ..H

Fig 4 0

20 15 10 S

,e

Fig. 4 - X - R A Y D I F F R A C T O G R A M S . a: s a m p l e 4;
b: w i t h lime at 7 days; c: w i t h lime at 28 days.
74 Vol. 19, No. ]
H.P. Lux~n, et al.

C4Aw~}

Fig 5c

M HM M ¢~., M
M M O,vl H k4 C~H~ ~ Q

M HM M
C,CqH{-)
l
IM
1l;'~ Fig 5b

HM M ~ Fig. 50

~0 45 40 35 30 25 20 15 i0 '~

Fig. 5 - X - R A Y D I F F R A C T O G R A X S . a: s a m p l e 5;
b: w i t h lime at ? days; c: w i : h lime at 28 days.

Q C4 API[3

. c,,A% , Ig 6
o ';', ~ M % M &~(.) Iv~" c,-':p^
~ , 7. ~o ~ Q ~ ?,~" K ' . ~ ~ ~.A
Q

M M M Fig 6b
M
e
~
M~ l o.','
"
ella ~ AH
"
e~ ~ ~
0 ~ , ,,

l
u M ~:~ F;g 6 a
M M O.M M 0 H'H M 0
O 0 0 M

45 40 35 30 25 20 15 IO 5

Fig. 6 - X - R A Y D i F F R A C T O G R A M S . a: s a m p l e 6;
b: w i t h lime at 7 days; c: w i z h lime at 28 days.
Vol. 19, No. ] 75
FLY ASH, CH, REACTIONS, IR, XRD

N N M C M C4 .'HL3
O H H O M

N M
N N
,, A ,, .A ~" , , ~ .... ~ ? ,, Fig Zb
" ..A3LA.j. LYL-2
Q

M M
W U

u N o °N e H N o M Fig. 70

50 45 40 35 30 25 20 15 TO 5
ze

Fig. 7 - X - R A Y D I F F R A C T O G R A M S . a: s a m p l e 7;
b: w i t h lime at 7 days; c: w i t h lime at 28 days.

0
c.CSH(-) J C4~X,3
H , I ~" .
N " I A ," I1J,. C4AC~.C4A",~ . | Fig 8 "

_-/%.-._.__...__._...

N Q
. 0• ? ON
oAN A. =.cs.~-¢ .c'A"' I O

M
A '~'An o Fig 8Q
u o ,.o A o , _ A , o ~ ~ ." ,A , • •

3T . . . . . . . . ~ ,
50r~ . . . . 45 ~ " , T 40' " " ~ 5 30 2 5 20 15 10 5
ze

Fig. 8 - X - R A Y D I F F R A C T O G R A M S . a: s a m p l e 8;
b: w i t h lime at 7 days; c: w i t h l i m e at 28 days.
76 Vol. 19, No. ]
M.P. Lux~n, et al.

Fig 9c
M H M M
M ¢

'L.J H
•
M
C4 ~Ht~

. ~ u ~,~ Fig 9 a
I ~ A." / . o
M,o A o,M i ~ o l ~ /~ u I'~';' ~ I M

50 45 40 35 30 25 20 |5 10
II

Fig. 9 - X-RAY DIFFRACTOGRAMS. a: sample 9;

b: with lime at 7 days; c: whir lime at 28 days.

C4 ,-~(~Mi1
O CIAHI ~C4 ANI'~ "

C4~HI 3

P 0 0 .ll CSap A I I C,A~XVC4'~H~3 C~C~I~ Fig lOb

0 P - _ ~ ) L

c cs ? t
P A~ A~ c An ¢,CS ~ Fig. lOa

50 45 40 35 30 25 20 15 10 $
~e

Fig. i0 - X-RAY DIFFRACTOGRAMS. a: sample i0;

b: with lime at 7 days; c: whir lime at 28 days.
Vol. 19, No. 1 77
FLY ASH, CH, REACTIONS, IR, XRD

TAr'JLE t"I - F L Y A S H - C A L C I U M HYDROXIDE REACTION

REACTIVITY WITH LIME

FLY FIXED LIME M%NERALOG~CAL COMPOSITION
ASH
n. (m M/L) 7 DAYS 28 DAYS
7 D l 28 O REMAINED ! FORMED REMAINED FORMED
"QUARTZ QUARTZ C4A.HI 3
I 2,4 12.2 MULLITE MULLITE CACH
HEMATITE HEMATITE CSH(,)
QUARTZ C4A~;HI~, QUARTZ CSH(,)
MULLITE C4ACHll MULLITE
11,3 15,8 HEMATITE CSH(,} HEMATITE
CA CA
QUARTZ C4AHI~ QUARTZ C4AH13
MULLITE C4A~Hrl MULLITE C4A~HII
13,2 1.5,7 HEMATITE CSH(~,) HEMATITE CSH[.}
CA t CA
QUAF~TZ C4AHI3 QUARTZ C4AH13
O,Z 10,0 MULLITE CSH(,) MULLITE CSH(,)
HEMATITE HEMATITE
QUARTZ CSH(,) QUARTZ C4AHI3
2,5 9,6 MULLITE MULLITE CSH[t)
HEMATITE HEMATITE
QUARTZ QUARTZ C4A.H13
1,5 10,8 MULLITE MULLITE C4ACHu
HEMATITE HEMATITE: C SH(,,,)
QUARTZ CSH(J) QUARTZ C4AH13
0,5 7,4 MULLITE MULLITE CSH (~
HEMATITE HEMATITE
QUARTZ C4AHI3 QUARTZ C4AHI3
MULLITE C4ASHIz MULLtTE C4ACHII
11,5 15o0 HEMATITE CSH(.} HEMATITE CSH(o)
ALBITE ALBITE
QUARTZ C 4 AHI3. QUARTZ C4AH13
3,4 9,6 MULLITE MULLITE CSH(-)
HEMATITE ' HEMATITE

QUARTZ C4AH13 QUARTZ C4AFll}

C4ACHII
10 2.1 7,3 CS C4ACHI! CI AHy
~ORTLANDIT. CSH(,) CSH(.)

{a) The formed CSH con be hidden by the mo,n peok of colcile.

Results and Discussion

Table II shows the CaO values established for the different fly ashes in
mM/L. This value was obtained by the difference between the concentration in
the saturated lime solution and the CaO found in the solution in contacz
with the sample, at the end of the given period.

It can be observed that there is no relationship between the lime fixed by

the fly ash and its chemical composition.
X - r a M d i f f r a c t i o n . The X-ray diffractograms of the residues are shown in
Figures ib . . . . 10b (7 days) and ic . . . . lOc (28 days).
Table II shows all the crystalline products that take shape in the reaction
as well as those mineral components that are initially found in the samples
78 Vol. 19, No. l
M.P. Lux~n, et al.

and still there after the treatment.

Quartz, mullite and hematite are usually present after the treatment with
lime, which is not the case with anhydrite, portlandite and free lime.
It must be underlined that calcium aluminate, found in samples 2 and 3, is
still there after the 28 days treatment and that calcium silicate, found in
sample i0, still appears on the residue X-ray diffractogram of the 7 days
treatment, but has disappeared after 28 days.
Among the reaction products there are calcium aluminium hydrate and more
specifically C 4 A H 1 3 (8), (9), (i0) as well as carboaluminate C 4 A O H I I (9),
(lO) and C 4 A S H 1 2 {monosulfoaluminate), found in sample 2 at 7 days. There is
also evidence that there are formations of other hydrated aluminates that are
hard to describe and which are generally called CxAHy and CACH. The presence
of C - S - H , hydrated calcium silicate, cannot be confirmated by the X-ray
difractograms, because it is hidden by the main peak of calcite. None of the
samples showed any traces of ettringite.
* Infrared absorption spectroscopy. This is an appropiate technique for the
study of fly ashes since it provides information with regard =o their
compos~ion in the vitreous as well as the cristalline phases. The IR
absorption spectroscopy was used to study the pczzolanic materials (Ii), and
both in this field as well as in order to increase the knowledge of fly ash
behaviour, a field hardly covered by literature at all, it seems =~ have a
very interesting future ahead of it. The apparatus used was a Beckman IR
spectrophotometer, model IR-4250 w_~th a double beam and automatic slit, in
the frequency range of 300-1600 cm . The samples were prepared with =he help
of KBr pellets.
The study covered the ten different types of fly ashes and the materials were
analyzed before and after the lime treatment for 7 and 28 days. There is a
great similarity amon~ the different series of IR absorption spectra of the
fly ashes. Therefore only two were selected for description.
Figure ii shows the IR spectra corresponding to fly ash sample i0 (a: without
treatment; b and c: after the treatment with saturated lime solution for 7
and 28 days respectively). The following is found:
-i
i. The absorption band at 1430 cm due tol the presence of carbonate
(calcite) in the sample, as well as the 880 cm band which is very weak and
may come from the carbonatation reaction of the CaO which is part of the fly
ash itself. They have important changes in the samples treated with zhe satu-
rated lime solution. Thus afteq 28 days a very intense absorption band is
observed which reaches 1480 cm maximum. This means that the carbcnate has
possibly combined with another type o f _ ~ o l e c u l e , more specifically with
aluminates. At the same time±ithe 880 cm -- band becomes more intense andla
sharp band appears at 860 cm as well as another smaller one at 735 cm
This phenomenon is observed after 7 days, b~t it is less intense in, a
fashion that the abso~-ption maximum at 1430 cm is still very noticeable.
2. The anhydrite±ithe main compound in this type of fly ash shows @bsorDtion
bands at 1160 cm and 1120 cm as well as at 680, 610 and 590 cm
3. In the area between 900 and 1200 cm -I where, among other absorptions, the
vibrations of silica tetrahedra are observed. The wide absorption range is
due to the presence of distorted tetrahedra with a variable frequency. With
the lime treatment this zone shows noticeable changes that can be a~=ributed
to internal structural reorganization, which becomes even more obvious after
28 days.
Vol. 19, No. I 79
FLY ASH, CH, REACTIONS, IR, XRD

Fig. Ii - INFRARED SPECTRA. a: sample I0; 4. The quartzl absorption bands

b: with lime at 7 days; (795, 780 cm ...) that are
c: with lime at 28 days. found in the original sample are
still thereafter the treatments.
Figure 12 shows the IR spectra
of fly ash sample i (a: without
treatment; b and c: after the
treatment with the saturated
lime solution for 7 and 28 days
respectively). The analysis
states that:
i. The original sample does not
show any carbonate induced
absorption. However, after the
lime treatment, specially after
28 days, since after 7 days they
are hardly noticeable, absorp-
tion bands_~ppear at 1480, 880
and 860 cm The last two are
very weak, and there is another
absorption band in the zone near
1430 cm--. This is very similar
to what happened in the case of
fly ash sample i0.
2. The _{one between 900 and
1200 cm shows a broad band
where it is difficult to appre-
ciate the absorption maxima. It
corresponds to the absorptions of Fig. 12 - INFRARED SPECTRA. a: sample i;
silica tetrahedra with different b: with lime at 7 days;
degrees of polymerization. After c: with lime at 28 days.
28 days the zone is narrower
because of the structural order.
3. Quartz is present in the origi-
nal sample as well as after the
treatment. Its absorption bands
are small (795, 780 cm-Z . . . . ).
Acknowledgements
The authours would like to thank
ASINEL (Asociaci6n de Investiga-
cidn Industrial El4ctrica) for
their contribution to the chemical
analysis of the fly ashes. Dr. Sa-
grera for allowing us to use the
X-ray diffraction equipment and
the CAICYT for financial support
given to the research project of
which this study is a part.
Symbols used to identify the
different minerals
A: ALBITE. An: ANHYDRITE. c: CAL-
CITE. C: FREE LIME. H: HEMATITE. M: MULLITE. P: PORTLANDITE. Q: QUARTZ. CS:
CALCIUM SILICATE. CA: CALCIUM ALUMINATE.
80 Vol. 19, No. 1
M.P. tux~n, et al.

References
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2. R. Helmuth. Ed. Portland Cement Association. (1987).
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Concrete, Materials Research Soc., p.12, Boston (1981).
4. P.K. Mehta, Proc. i st Int. Conf. on the use of Fly Ash, Silica Fume, Slag
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(1983)o
5. S. Diamond, F. L6pez-FZores, Proc. Symp. on Effects of Fly Ash incorpo-
ration in Cement and Concrete, Materials Research Soc., p.34, Boston
(1981).
6. L. Huakun, L. Zhongya, L. Shengjie, Proc. 7 th Int. Congr. on the Chem.
of Cem., V.III, p. IV-7, Paris (1980).
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Int. Congr. on the Chem. of Cem., p.l, Moscow (1974).
8. C. Plowman, J.G. Cabrera, Proc. Symp. on Effects of Fly Ash Incorporation
in Cement and Concrete, Materials Research Soc., p.?l, Boston (1981).
9. P.C. Aitcin, F. Autefage, A. Carles-Gibergues, A. Vaquier, Proc. 2 nd Int.
Conf. on Fly Ash, Silica Fume, Slag and Natural Pozzolans in Concrete,
V.I, p.91, Madrid (1986).
i0. K.G. yon Jeppesen, Zement-Kalk-Gips, n.12, 647, (1984).
Ii. M.P. Lux~n, Cuaderno de Investigaci6n (IETcc-CSIC), n.32, 1976).