The thermal and chemical stability
of limestone aggregates
E. R A A S K (i)
The thermal stability of two limestones of different MgCO3
content was examined by thermogravimetry and by differential
thermal analysis. The chemical stability was studied by measur-
ing the rates of dissolution of MgCO3 fraction of the limestones
in Ca (OH)2 solution. The reaction can cause an expansion and
fracture of limestone aggregates in concrete at elevated tem-
peratures.
INTRODUC~ON
The thermal stability of a concrete made with
Portland cement is influenced by the type of aggregate
used in the mix. Hannant [1] and Imlach and Taylor
[2] have shown that concretes made with limestones
lost strength to a much greater degree than those made
with siliceous aggregates. The strength loss could be
caused by chemical reactions between limestone and
the calcium hydroxide, Ca(OH)a, liberated on hydrat-
ion of Portland cement. Limestones quarried for
use as aggregates in concretes contain some magne-
sium carbonate, MgCO3, which would be the species
first to be attacked in the alkaline media of hydrated
cement paste. This would result from the exchange
reaction,
MgCO3 + Ca(OH)z --~ Mg(OH)z + CaCO3 (1)
(1) Senior Research Officer, Central Electricity Research
Laboratories, Leatherhead, Surrey, England.
The standard free energy (AG ~ of reaction (1), calcu-
lated from the data by Parker, Wagman and Evans [3]
is - - 9.6 kJ at 298 K and at 400 K AG ~ is - - 10.3 kJ.
Moreover, in an aqueous solution the activity of
Mg(OH)2 and CaCO3 are low; the molar solubility
of Mg(OH)z and CaCOz in water is an order of magni-
tude less than that of Ca(OH)2, according to the data
of H o d g m a n [4] (1962), and Linke and Seidell [5].
Calculations with available data show that thei'e
is a driving force for reaction (1) when the molar
concentration of Ca(OH)2 in solution is above
7.5 • 10 -4 m mole, that is when the p H of the solution
is greater than 9. The majority of limestones are stable
in concretes at ambient temperatures presumably
because the rate of conversion of MgCO3 to Mg(OH)z
is insignificant, and the reaction will stop after all the
Ca(OH)z in the concrete has been converted to CaCO3
by the ingress of atmospheric COz. However, in the
U.S.A. and Canada there have been occurrences of
aggregate failure caused by the chemical attack [6, 7].
It has been noted that this type of reaction is more
likely to occur when the O H - ion concentration
in the cement paste is high.
Instead of increasing the chemical potential, an
increase in temperature may have the same effect on
speeding up the rate of conversion of MgCO3 to
Mg(OH)2. This aspect has been studied here and
methods of preventing the attack on MgCOz in the
alkaline media of the cement paste are considered.
387
VOL. 7 . N ~ 4 2 - 1974 . H A T I ~ R I A U X ET C O N S T R U C T I O N S

TABLE I cient to lower the on-set temperature for CO2 -evolu-

CHEMICAL ANALYSIS OF LIMESTONES tion by 50 K (fig. 1) compared with that for Merehead
limestone.
Isothermal decomposition of a solid usually occurs
Constituent Cromhall Merehead in four sequential steps [9] : (a) an induction period,
per cent by weight limestone limestone (b) a slow reaction period, (c) a linear rate period
during which the area of interface between the decom-
CaO 46.2 52.5 posed and undecomposed face does not alter signifi-
MgO 7.5 2.8 cantly, and (d) the period of fall-off in rate as the area
SiOz 3.7 1.3
0.4 0.1 of the interface decreases. Stages (a) and (b) are not
A1203
FeO 0.4 0.3 discernable in figures 2 and 3, but stage (c), the linear
Na20 0.1 0.1 rate period, extends to over 50 % of the total decom-
K20 0.1 0.1 position range.
CO2 42.5 42.8 The linear rates at different temperatures were plott-
Total 100.9 100.0 ed on figure 4 to obtain the temperature coefficient of
decomposition (' activation energy ', E). The value of
Molar E was 176 kJ mole -1 for Cromhall limestone and the
fraction corresponding value for Merehead limestone was
CaCO3 0.808 0.927 190 kJ mole-L
MgCOa 0.174 0.068
FeCO3 Differential Thermal Analysis (DTA)
Na2CO3 0.068 0.006
Silicates A DTA technique was selected which could be
used to estimate the amount of MgCO3 in limestone
when precautions are taken to prevent merging of
the two-stage thermal decomposition of a mixture
of MgCO3 and CaCO3, or double salt of MgCO3.
CaCO3. The MgCO3 fraction decomposes at lower
CHARACTERISTICS OF L I M E S T O N E temperature. When the decomposition takes place in
AGGREGATES a deep bed of ground limestone a partial reverse react-
ion takes place near the surface where CO2 partial
Two samples of limestone aggregate were chosen for pressure is low [10].
the study. Table I shows the chemical analysis of the MgCO3 CaCO3 9 --> MgO + CaO + 2COz (in bed) (2)
two samples. They may be taken to represent typical
high (Cromhall) and low (Merehead) magnesia lime- CaO + CO2 --~ CaCO3 (near surface) (3)
stones. With the Stanton Model 625 DTA apparatus, a
The recent studies of marine sediments [8] suggest 500 mg sample was placed in a 15 mm deep platinum
that a high MgCO3 content in CaCOa deposit (molar
fraction greater than 0.1) suggests a metastable form
of limestone. Over a period of time a ' l e a k a g e '
of magnesium occurs because of higher solubility of 50
MgCO3 compared with that of CaCO3, and the
metastable form changes to stable low magnesium
f,p.~'"
limestone. On this basis Cromhall aggregate having a
high MgCO3 content should have a lower thermal ,0 /:/
stability and would be attacked by Ca(OH)'2 in the
hydrated cement paste. Laboratory experiments were
designed to test the above assumption. //
d
THERMAL DECOMPOSITION
OF L I M E S T O N E S

Thermogravimetrie Analysis
//
For thermogravimetric analysis (TGA) limestone
samples of a narrow size fraction, 53 ~zm to 74 ~tm
10
S"
diameter, were taken to limit any errors which might
arise from size variations. A 200 mg sample was 800 900 i000 ii00
placed in a shallow platinum tray, 1.5 mm deep,
TEMPERATURE, ~
and the furnace was purged with dry nitrogen (N2).
The results shown in figures 1 to 3 show that the Fig. 1. - - Effect of MgCO3 on thermal decomposition of lime-
thermal decomposition of limestone is influenced stone.
by the amount of MgCO3 present. The molar fraction A - CromhaIl limestone - 15.6 ~ MgCOa
of 0.174 of MgCO3 in Oldbury limestone was suffi- B - Merehead limestone - 4.8 % MgCO3

388
 E. R A A S K

966 K 946oK
./" ,O

40 e~ ~ ' 9 9 898 K
40 _

/ / /
/ 30
/ /
30 -
=

/ ~90 K

- / / e 876 K

20
/ R
,-J

F-

./ 9
u.I

10
z.sssK
"~ e ~ 800 K

0.5 1.0 1.5 2.0 2.5 0 0.5 1.0 1.5 2.0 2.5
TIME, sec x 10"4
TIME, sec x 10-4
Fig. 2. - - I s o t h e r m a l C O 2 evolution on heating C r o m h a l l lime- Fig. 3. - - I s o t h e r m a l C O 2 evolution on h e a t i n g M e r e h e a d lime-
stone. stone.

crucible, whereas for the more thermally sensitive
Model 67, only a 45 mg sample was required. In this
case it was necessary to compact the sample to a disc,
4 mm diameter, 1.5 m m deep, in a press. The high
sensitivity of the Model 67 D T A unit is mainly due to
improved thermal contact between the sample and the
thermocouple junction.
Figure 5 shows an endothermic decomposition peak
at 1085 K for Cromhall limestone and there is a
corresponding peak in CO2-evolution rate at 1075 K

|
I
%

(O
-2
Q::
r
-4.5
20
F-

§
g v

<~

A B

I I I L
1.05 1.15 125 1000 1100 1200 1300
TEMPERATURE RECIPROCAL,1/K x 103 TEMPERATURE, K

Fig. 4. - - A r r h e n i u s plot o f decomposition rates. Fig. 5. - - H e a t a b s o r p t i o n on decomposition o f c a r b o n a t e s .

A - Cromhall limestone A - Cromhall limestone
B - Merehead limestone B - Merehead limestone

389
VOL. 7 - N ~ 42 - 1974 - M A T I ~ R I A U X ET CONSTRUCTIONS

8.0 _ /,
.\
=

w
4.0 E 4
>-

/>/
I-
>
z~
_z

c..)
k
I I

I000 II00 1200 1300

TEMPERATURE, K

Fig. 6. - - Evolution of CO2 on thermal decomposition of car-

bonates.
I I
A - Cromhall limestone 0.2 0.4
B - Mereheadlimestone
MgCO 3 ADDED, m mole

Fig. 7. - - Calibration of Ca(OH)2 s o l u t i o n - - 7.5 m molar contain-

(fig. 6). Merehead limestone did not show any features
of the two-stage decomposition. The first, smaller DTA
peak of dolomitic limestone is a useful method of
estimating the amount of MgCO3 if its molar fraction
is greater than 0.1. For smaller quantities chemical
analysis is required and the technique used is described
in the next section.
R E A C T I O N OF D O L O M I T I C L I M E S T O N E
IN Ca (OH)2 S O L U T I O N
The rate of decomposition of the MgCO3 fraction
of dolomitic limestone in calcium hydroxide solution
can be determined by measuring the electrical conduct-
ivity of the solution. After the solubility limit of
ing 0.45 m mole Ca(OH)2 at 350 K.
Mg(OH)2 is reached, the amount of MgCO3 reacted
is proportional to the decrease in conductivity due
to the removal O H - and Ca ++ ions from the solution,
Ca + + 2 [OH]- + MgCO3 --~ Mg(OH)2 + CaCO3 (4)
A conductivity cell, 90 mm deep and 35 mm in
diameter, was constructed from PTFE having a cell
constant of 1.2. An aliquot of 0.007 M solution contain-
ing 31 mg Ca(OH)2 in the cell was heated in an oil-
bath to the required temperature in the range 335 K
to 365 K. Below 335 K the rate of reaction was too
slow for continuous monitoring and the measurement
above 365 K requires an autoclave. The stirred solution

[ I I I

6.0 - 6.0

9 +~ ar""+~ -t- _ at__ + ~ :

Z
_1
4.0
=c
I--

_> A
F-
2,0 z.0
0.5 1.0 1.5 2.0 z 0.5 1.0 1.5 2.0
o
TIME, sec x 10.5 TIME, sec x 10.5

Fig. 8. - - Solubility of MgCO3 fraction of limestone in Ca(OH)2 Fig. 9. - - Solubility of MgCO3 fraction of limestone in Ca(OH)2
solution at 350 K, particle size 5 3 / z m to 74/~m. solution at 350 K, particle size ~ 53 #m.
A - Cromhall limestone A - Cromhall limestone
B - Mereheadlimestone B - Mereheadlimestone

390
 E. RAASK

was saturated with Mg(OH)2 by adding 5 mg of pure
micronized MgCO3 and it was allowed to react for 30
minutes; a 200 mg sample of ground limestone was
then added. Figure 7 is the calibration graph obtained
with pure MgCO3 and the results for two limestones
are shown in figures 8 and 9.
Experimental results suggest that the rate of convers-
ion of MgCO3 fraction limestone to Mg(OH)z in
Ca(OH)2 solution is governed by diffusion inside the
solid particle. Glover and Raask [11] have suggested
that a test for a diffusion-controlled mechanism is to
plot the rate of change &conductivity ~ -
(do)
movement of the latter in the micro channels of the
limestone which controls the rate of change.
To prevent the attack on limestone it is necessary
to remove Ca(OH)2 from the hydrated cement paste.
One possibility is to add a pozzolanic material, for
example p.f. ash, to the mix. A material is said to be
pozzolanic if it is capable of combining with Ca(OH)2
liberated on hydration of Portland cement [I2].
against
STUDY OF PORTLAND CEMENT,
LIMESTONE AND P.F. ASH MIXES

the inverse of the square root of time as in figure 10. A selection of samples was prepared consisting of
The rate of dissolution of the MgCO3 expressed as neat Portland cement paste, mixtures of cement and
dw. ground Cromhall limestone with and without addi-
d-~ ~s given by tion of p.f. ash. The mix composition, curing time
dw (D Dt ) and curing environment are given below. Water to
~- -- 3 wo ~ r:~.a~-~_ (5) cement ratio by weight was 0.3 for all samples.
The cured samples were analysed by DTA technique
where w0 is the original molar fraction of MgCOz in as described previously. Figure 11 shows a typical DTA
the sample and w that at times t, a is the radius of curve of a fully cured OPC paste (Sample 1, Table II).
particles, D is the diffusion constant. Since the conduc- Endothermic decompositions of hydrated silicates,
Ca(OH)2 and CaCO3 are easily noticeable; the latter
tivity change -~- is proportional to the amount are formed by the capture of atmospheric CO2. There
of MgCO3 reacted, eq. (5) can be changed to, is also some evidence for the presence of hydrated
aluminates and Mg(OH)2; the OPC sample used con-
tained 2 % of MgO.
dt - - 3 (20 ~. z:_g~ati: (6) The DTA curve A on figure 12 of partially cured OPC
shows a poorly defined decomposition zone of hydrat-
The experimental results fit the above diffusion ed silicates. On autoclaving a mixture of OPC and
equation (fig. 10), but this does not specify the diffus- dolomitic limestone, a great deal of Mg(OH)z had
ing species which control the rate of conversion of formed (Curve B), but additional p. f. ash prevented
MgCO3 to Mg(OH)z in Ca(OH)2 solution. HO- ions Mg(OH)2 formation (curve C). Most of the Ca(OH)2
have much greater mobility in aqueous solution than liberated from the cement had reacted with ash, and
Mg + and Ca++-ions, therefore it is likely that it is the all the Ca(OH)z was consumed when the autoclaved
sample was cured in water at 300 K for 28 days
(Curve D).
The ash to cement ratio 1 to 1, as in samples 4 and
_e ~ I i i _ 5 (Table III), is too high for use in making structural
0.6
.-r,, \
L i t
Ca(OH]

~
0.4 %

0.2
40
SILICATEHYDRATES
,L
1
uJ
=

CaCO 3 -

4- 9 $
I ALUMINATE [
% HYDRATES l
I I I I
1.0 0.75 0.5 0.25
INVERSEOFSQUAREROOTOFTIME,t x 100 I ] t I
400 600 800 1000
F i g . 10. - - Conductivity changes o f C a ( O H ) 2 solution containing
Cromhall limestone. TEMPERATURE,K
A - P a r t i c l e size < 53 H m Fig. 11. - - Endothermic decomposition on heating hydrated
B - P a r t i c l e size 53 H m to 76 t a n Portland cement paste - cured for four years under water.

391
VOL. 7 - N ~ 42 - 1974 - MATERIAUX ET CONSTRUCTIONS

TABLE II l , r
C O M P O S I T I O N OF C E M E N T , L I M E S T O N E ASH MIXES

Sample Curing time and

No Mix Composition environment

----1 Ordinary Portland

Cement 4 years in water
(oPc)

o P c : limestone 7 days in water

1 : 2

OPC :: limestone2 3 hours in auto- 10

clave at 425 K

OPC : limestone : p.f. ash 3 hours in auto-

1 1 1 , clave at 425 K

C limestone : p.f. ash 3 hours in auto-

1 1 clave at 425 K
q- 28 days in water

OPC : limestone 6 months in water

1 1.35 i
+ 6 months in
autoclave at 425 K
,
I I
OPC : limestone : p.f. ashl 6 months in water
i 1 1.7 0.331 + 6 months in
autoclave at 425 K
concrete. A more realistic ratio of cement to ash is
3 to 1, and this quantity of ash was sufficient to bind
all the Ca(OH)2 liberated from the cement, when the
mixture of limestone, cement and ash was cured at
300 K for six months, followed by another six months
in the autoclave at 425 K (fig. 13). There was no
evidence of an attack on the MgCOa-fraction in
limestone by Ca(OH)~ when p.f. ash was added.
DISCUSSION
In the U.S.A. and Canada there has been much res-
earch to explain the reasons for a large and disruptive
expansion of some of the dolomitic limestone aggregates
when used in Portland cement concrete [6, 7]. It is
generally agreed that a chemical attack on limestone
by the alkaline media of cement paste is the prime
cause for the disruptive effect. Hadley [13] suggested
that the presence of alkali-metal hydroxides is essen-
tial to initiate the reaction at room temperature :
CaCO3 9 M g C O 3 -k N a O H --~ Mg(OH)2 -k
CaCOz + Na2CO3 (7)
In cement paste Na2CO3 reacts with Ca(OH)2 liberated
on hydration of cement and N a O H is generated. As a
consequence of the above reactions, the products
deposited in the veins of limestone have a larger volume
than that originally occupied by the CaCO3. MgCOa
fraction. Sherwood and Newlon [14] postulated that
in addition to Mg(OH)2 alkalis are also precipitated
0
350 150 600 800
TEMPERATURE, K
The effect of p.f. ash on Portland cement and ground
F i g . 12. - -
limestones mixes.
A - Cement/limestone mix culed for seven days in water
B - Cement/limestone mix cured in autoclave
C - Cement/limestone/ash mix cured in autoclave
D - Cement/limestone/ash mix cured in autoclave follow-
ed by 28 days in water
inside limestone as double carbonates, CaCO3.
Na~CO3 9 5H20 and 2CaCOa 9 3K2CO3 9 6H20.
Swenson and Gillott [15] have put forward a differ-
ent explanation. They suggest that the dedolomiti-
zation reactions expose clay impurities in limestone for
moisture penetration and expansion occurs as a result
of water uptake by the clay. O f course, both explana-
tions could be correct to some extent and it would be
difficult to establish whether the expansive effect
caused by precipitation of magnesium hydroxide and
carbonates is greater than that of water uptake by
the clay fraction.
The microstructure of limestone is an important
factor : a fine grained texture of the rock dispersed by
micro channels of MgCO3 and clay impurity are the
characteristic features of expansive limestones [16].
There are some channels in the limestones examined
in this work but the aggregates are stable in the alkali
media of Portland cement at ambient temperature.
The solubility tests described in Section 4 suggest
that the two aggregates are stable up to 335 K; above
this temperature the MgCOa fraction of the limestones
can be attached by Ca(OH)2 released from Portland
cement. A concrete structure made with Merehead
limestone should not be subjected to the expansive
damage resulting from a chemical attack on the
aggregate by the alkali media at any temperature.
The MgCO3 fraction of the limestone is small and
p.f. ash was used in the concrete mix. In the presence
of the additive MgCO3 the limestone will not be attack-

392
 E. RAASK

As a precautionary measure the aggregates likely

! to be used for future designs of the concrete structures
CaCO3
subjected to elevated temperatures should be tested for
60 their thermal stability. Thermal analysis (Section 3.2)
can be used to identify the presence of the potentially
unstable MgCOa fraction, and the conductivity tech-
nique described in Section 4 is a useful method for
studying the reaction rate between MgCOz and
Ca(OH)2. It would be prudent to specify the addition
of p.f. ash to the concrete mix when dolomitic lime-
, stone aggregates are to be used. There are other
advantages when p.f. ash is used in the mix to build
c~ large structures; the ash improves the workability
of the mix, it reduces the temperature peak in the
-
MgCO3 // initial stage of hydration and there can be some savings
< 20 Ca(OH)2 ~ /I in the cost of cement. Excellent guidance on the use of
p.f. ash in concrete mix is given by Barber, Jones,
Knight and Miles [17].

I
TA r

700 900 1100 CONCLUSIONS

TEMPERATURE,K
F i g . 13. - - Stabilizing effect of p.f. ash on dolomitie limestone
concrete.
A - Limestone concrete
B - Limestone concrete with p.f. ash
ed by Ca(OH)2 liberated from Portland cement; the
latter reacts with silica in ash to form an additional
amount of calcium silicates, the bonding species in
the hydrated cement paste. Thus p.f. ash in the con-
crete mix ensures that in case of temperature excur-
sions above 336 K the loss in strength of the concrete
will not be as great.
A concrete structure made with Cromhall limestone
aggregate could show some features of thermal insta-
bility when the concrete is subjected to high tempe-
ratures. The limestone has a comparatively large
MgCO3 content which could be attacked by Ca(OH)2
above 335 K. [mlach and Taylor [2] showed that
there was a loss in strength of small mortar specimens
made with the ground limestone and kept immersed
in water in an autoclave for six months. However,
the risk of aggregate failure due to the attack by
Ca(OH)2 in the concrete is small. The reaction can
take place only via transport of the ionic species in
water and usually will lose free water on heating
before any significant attack can occur; the rate of
diffusion of water in concrete [11] is faster than the
rate of reaction of MgCO3-containing aggregates
with Ca(OH)2.
1) Two limestone aggregates examined in this
work had different magnesium carbonate contents,
the molar fraction of MgCOz in Cromhall limestone
was 0.174 and that in Merehead limestone was 0.068.
The result of thermogravimetric (TG) and differential
thermal analysis (DTA) showed that the MgCOz
fraction in limestone decomposed at lower tempera-
tures than the main constituent (CaCO3). The MgCOa
in Cromhall limestone lowered the temperature by
50 K, and the activation energy for COz evolution was
also smaller by 14 kJ mole -1.
2) The lower thermal instability of Cromhall
limestone was also reflected by the reduced chemical
stability of the material in Ca(OH)2 solution in the
temperature range of 335 K to 365 K. The amount of
reactive MgCO3 in limestone can be determined by
measuring the electrical conductivity of a dispersion of
ground sample in Ca(OH)2 solution. The reaction
between MgCO3 in limestone and Ca(OH)2 is a
diffusion-controlled process, where ionic species
migrate inside the micro channels of limestone.
3) The reaction between the dolomitic limestone
and Ca(OH)2 formed on hydration of Portland cement
can be prevented by addition of a pozzolanic material,
such as p.f. ash, to the concrete mix. Preferential
reaction of Ca(OH)2 with silica in ash leaves the aggre-
gate unscathed and an additional amount of calcium
silicate, the binding constituent of the cement, is
formed.

ACKNOWLEDGEMENT

The work was carried out at the Central Electricity

Research Laboratories, Leatherhead, and the paper is
published by permission of the Central Electricity
Generating Board.

393
VOL. 7 - N ~ 42 - 1974 . HATi~RIAUX ET CONSTRUCTIONS
R~;SUM]~
Stabilit6 thermique et chimique des granulats calcaires
La stabilitJ thermique d'un bJton d ciment Portland
est influenc~e par le type de granulat utilisJ dans le
mJlange : la rJsistance m~canique des bOtons d base
de calcaire diminue beaucoup plus rapidement ~ des
tempJratures JlevJes que celle des bJtons comportant
des granulats siliceux. Cette perte de rJsistance est
peut-~tre due ~ l'attaque chimique des granulats cal-
caires par la pate alcaline de ciment hydratJ.
La stabilitJ thermique de deux types de calcaire dz
teneurs en MgC03 diffJrentes a OtJ examinJe par thermo-
gravimJtrie et par analyse thermique diffJrentielle.
Un accroissement de la fraction molaire du MgC03
dans le calcaire de 0,068 d 0,174 a conduit dune dimi-
nution de la tempJrature de dJcomposition et d u n
accroissement de la vitesse de dJgagement de C02.
Cela indique qu'un calcaire dolomitique & haute teneur
en M g C 0 3 est susceptible de montrer une instabih'tJ
REFERENCES
[I] HANNANT,D.J. - - 1967, Giv. Eng. and Pub., Works
Rev., 62, 665.
[2] IMLACH, B.V., TAYLOR, H.F.W. - - 1972, Trans.
Brit. Cer. Soc., 71 (3), 71.
[3] PARKER, U.B., WAGMAN,D.D. and EVANS, W.H. - -
1971, U.S.A. Nat. Bur. Stand. Technical Note
270-6.
[4] HODGMAN, C.D., - - Handbook Chemistry and
Physics, Chem. Rubber Pub. Co., Ohio, U.S.A.
[5] LINKE, W.F., SEIDELL, A. - - 1965, Sohtbilities of
inorganic and metal-organic compounds, Vol. II Am.
Chem. Soc., Washington.
[6] HADLEY, D.W. u 1964, U.S.A. Highway Research
Board Syrup. on Alkali-Carbonate Rock Reactions,
pp. 1.
[7] SWENSON, E.G., GtLLOTT, J.E. - - 1964, U.S.A.
Highway Research Board Symp. on Alkali-Carbo-
nate Rock Reactions, pp. 21.
[8] LtNOHOLM, R.C. - - 1972, Nat. Phys. Scien., 237, 43.
[9] ECKHARDT, R.C., FLANAGAN, T. - - Trans. Far.
Soc., 1964, 60, 1289.
394
d'origine chimique. On suggbre que la cause en est la
r~action du MgCO3 avec du Ca(OH)z libOr~ par
l'hydratation du ciment Portland. Afin d'en obtenir la
vOrification, on a congu une mdthode bas~e sur la mesure
de la conductivitO Olectro-chimique pour Otudier la
vitesse de dissolution du MgCOa clans des ~chantillons
de calcaire pulvdrisOs et dispersOs dans une solution
de Ca(OH)2. La rdaction est un processus contr6lk
par diffusion, donnant lieu d une migration d'espkces
ioniques dans les microcanaux du calcaire. Dans le
cas du calcaire dt haute teneur en M g C 0 3 (fraction
molaire 0,174), la rdaction pourrait conduire d la dila-
tation et puis d la rupture du granulat.
On peut r~duire le risque d'une telle rupture en ajou-
tant des cendres volantes au mdlange de bOton. La silice
des centres r~agit avec le Ca(OH)2 du bOton, laissant
le granulat intact, et des quantit~s additionnelles de
silicates de chaux (liants du ciment) se forment.
[10] HI~DVALL,J.A. - - 1953, Zeitschr. anurg, allg. chemie,
272, 22.
[11] GLOVER, G.M., RAASK, E. - - 1972, Mat. et Constr.,
5, (29), 315.
[12] TURRIZIAN[, R. - - 1964, The chemistry of cements,
Vol. II, pp. 69. Acad. Press, London, Ed., H.F.W.M.
Taylor.
[13] Hadley, D.W. - - 1961, U.S.A. Highway Research
Board, Proc. 40, pp. 462.
[14] SHERWOOD, W.C., NEWLON, H.H. - - 1964, U.S.A.
Highway Research Board Symp. on Alkali-Car-
bonate Rock Reactions, pp. 41.
[15] SWENSON,E.G., GILLO'rV, J.E. - - 1967, Mag. Concr.
Res., 19 (59), pp. 95.
[16] GmLOTT, J.E. - - 1963, Geol. Soc., Amer. Bull.,
74 (6), 759.
[17] BARBER, E.G., JONES, T., KNIGHT, P.G.K. and
MILES, M.H. - - 1972, P.F.A. Utilization, C.E.G.B.
Publication.