CEMENT and CONCRETE RESEARCH. Vol. 19, pp. 821-826, 1989. Printed in the USA.

0008-8846/89 $3.00+00 Copyright (c) 1989 Pergamon Press plc

INFLUENCE OF ALKALI ON CARBONATION OF CONCRETE, PART I ,

PRELIMINARY TESTS WITH MORTAR SPECIMENS

K.Kobayashi and Y.Uno

Institute of Industrial Science, University of Tokyo
~-22-i, Roppongi, Minatu-ku, Tokyo, Japan

(Communicated by M. Daimon)
(Received Dec. 29, 1988)
ABSTRACT
Mortar specimens were made using a total of five kinds of ordinary
portland cement including two of different Na20-equivalent alkali
content (R20) and three kinds of varying R20 to a maximum of 1.5 %
through addition of NaOH, and accelerated carbonation tests were
performed. I t was found that the rate of carbonation becomes higher
the greater the alkali content of cement, and i t was shown through
simulation experiments that this trend becomes prominent when there
is movement of pore solution
Introduction
Environmental factors such as humidity, temperature, and C02 concentration, and factors concerning materials, mix proportions, and execution of
work such as kind of cement, water cement ratio, curing conditions, and degree
of consolidation have been known as agents affecting the progress of carbonation of concrete. However, according to reports of investigations on the
situation concerning deterioration of concrete structures in Japan, i t is indicated that carbonation of structures b u i l t since 1970s, a period when the
method of manufacturing cement in Japan was converted to a dry system using
SP kilns, has been progressing at an abnormally high rate.
This paper points out that alkali supplied from cement is one of the main
causes of the extreme acceleration of such concrete carbonation, and moreover, reports how i t is shown through simulation tests that this influence
appears prominently at locations in the structures where migration of pore
solution goes on actively.
Carbonation and Pore Solution Composition
In the presence of water carbonation of concrete proceeds through the
reaction below.
Ca(OH)2 + CO2

, CaCO3 + H20

821

( l )

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K. Kobayashi and Y. Uno

Eq. (1) can be also expressed as follows :

Ca2+ +

C032- (or HCQ3-) ~

CaCO3

( ~ )

The reaction equation above Suggest that carbonation has a close r e l a t i o n

with the chemical composition of pore solution in concrete. The ingredients
of pore s o l u t i o n , as is clear from Table I . are mostly sodium ion and potassium ion, and hydroxide ion which are in a state of equilibrium with the f i r s t
two, the concentration of calcium ion being only about 0.0004 to o.0036 mol.
I t is known that the pH of pore solution having such ingredients is f a i r l y
high, generally around 12 to 13. Since hardly any CaC03 w i l l dissolve in a
solution of high pH, the CaC03 produced according to Eq. (2) is p r e c i p i t a t e d
as a solid phase. The concentration of calcium ion is lowered because of
t h i s , and s o l i d Ca(OH)2 as a hydration product is dissolved in pore solution
by j u s t the amount of decrease in concentration. Carbonation of concrete progresses as the above process is repeated so that i t s speed w i l l depend of pH.
In e f f e c t , carbonation of concrete w i l l occur at a high rate the higher the
pH of pore solution and the longer that such a high value of pH is maintained.
This report summarizws the results of experiments on mortar conducted to confirm whether the abovementioned reasoning was v a l i d .
Experimental
Experiments were conducted using the two kinds of specimens below. One
kind consisted of @5 x lO cm cylinders, the other of cylinders of the same
size provided with c y l i n d r i c a l hollow parts of 8 mm diameter at t h e i r centers
to form t h i c k - s h e l l cylinders. The cements used were ordinary portland cement
(A) of RzO = 0.57 % with NaOH added to vary equivalent NazO content at the
end of 0.9 %, 1.2 %, and 1.5 %, and ordinary portland cement (B) of low-alkali
type of R20 = 0.31% used in part. The chemical composition of these cements
Table I . - Chemical Analysis of the Cement used ( % by weight )

CaO

Si02

64.9

22.1

4.8

64.3

21.2

5.7

Table 2.

A1203

Fe203

S03

MgO

Na20

KzO

2.9

1.9

1.4

0.24

0.50

I.I

3.4

1.9

1.8

0.16

0.23

0.7

Analysis of Pore Solution Expressed

From High-Alkali Cement Mortars I)

Age,

Concentration E q u i v a l e n t s / l i t e r (N)

Days

Ca++

Na+

15

0.001

0.22

0.55

0.77

0.73

49

0.002

0.24

0.59

0.83

0.77

7O

0.000

0.22

0.57

0.79

0.75

149

0.002

0.23

0.60

0.83

0.80

585

0.000

0.24

0.58

0.82

0.78

K+

Na+ K+

OH-

Ig.Loss

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CARBONATION, ALKALI EFFECT, ACCELERATION

are given in Table 2. Silica sand (Toyoura standard sand} was used as the
aggreqate. ,Mortar mixes were of three levels of water cement r a t i o , 0.40,
0.50, and 0.60, with unit water contents respectively determined so that flow
would be 18O mm.
Soecimens, after casting, were moist-cured for 28 days in a fog curing
room of temperature 2OC. This was followed by accelerated carbonation tests
using under conditions of C02 concentration IO %, temperature 20C, and humid i t y 60 % RH. However, specimens with hollow spaces at t h e i r centers, which
were for modelling migration of pore solution were subjected to accelerated
carbonation tests under conditions of sunplying solutions of pH = 7 or 13
from the hollow portions throughout the period of accelerated carbonation
(Fig. l ) to maintain pH of pore solution at a high value all of the time. The
depth of carbonation of these specimens were determined as averages performing
s p l i t t i n g tests, spraying phenolphthalein 1% ethanol solution on the fracture
planes, and measuring the areas of non-colored parts by image analysis apparatus. Further, measurements of pore size distributions by mercury porosimeter
and thermal analyses were performed on a part of the specimens.
Results of Experiments and Discussion
Fig. 2 gives the results of experiments using cylinder specimens and
shows the influence on carbonation of alkali in cement. With the ratio of
average carbonation depth under various conditions to the average carbonation
depth in case of water cement ratio 0.50 and R20 = 1.5 % as the carbonation
r a t i o , the relation of this and R20 is i l l u s t r a t e d , these being the results
at 16 weeks of accelerated carbonation. As this figure clearly shows, carbonation increases with the value of R2O in case water cement ratio is constant,
and this tendency is seen prominently especially in case of water cement ratio
0.60. Fig. 3 shows the relation between carbonation ratio and R20 in case of
using thick-shell cylinder specimens modelling the migration of pore solution,
the carbonation ratio indicated with water cement ratio of 0.50 and R20 of
0.57 % in case of cylinder specimen as the basis. This figure indicates that
carbonation is greatly accelerated when water is continuously diffused from
the center portion of the specimen toward the periphery, with this trend becoming prominent as the value of R20 increases. As for Fig. 4, i t shows the
relation between Period of accelerated carbonation and average carbonation
and average carbonation depth indicating that diffusion of water from the
center of the specimen sharply accelerates carbonation. What draws attention
in this figure is that a differece in progress of carbonation can be recognized between the cases of pH 7 and 13 of the water diffused. At the i n i t i a l
stage of accelerated carbonation the speed of carbonation is higher for the
case of pH = 7 than pH = 13, but the speed of the former gradually decline
u n t i l the relation is reversed along the way. The change in a l k a l i concentration d i s t r i b u t i o n in the specimen as water moves from the center portion
is conceivable as the reason for t h i s . That is, when water..of pH = 7 is d i f fused soluble a l k a l i s inside the specimen are concentrated toward the surface,
but when pH = 13, since i t is an aqueous solution of about the same degree of
concentration as the pH of the pore solution, a change in the alkali concentration d i s t r i b u t i o n in the specimen does not occur. I t is thought that
because of t h i s , carbonation is greatly accelerated at the i n i t i a l stage when
water of pH = 7 is supplied, but as carbonation progresses to the i n t e r i o r ,
the concentration of alkali is lowered so that the speed of carbonation f a l l s ,
and at a certain point the depth of carbonation in case of pH = 13 in which
carbonation is progressing at a roughly constant speed becomes greater for
the reversal to occur.

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Vol. 19, No. 5

K. Kobayashi and Y. Uno

~ H20(pH=7/13)

FIG. 1

..ol.-co.

Specimen modelling migration of

pore solution
(Thick-shell cylinder)

co,,ol.gN
5.0

FIG. 2

o 4.0
o
n-

Carbonation ratio - R20 rela-

cO

,,.
o
c-

Thick-she.l I c~'1 ' ~ n d e r ~ / T h l c k . s h e l 1 cy]Inder

3.C

tionship as influenced by water

cement ratio (16 weeks acceler-

~ 2.Q

ated carbonation)

1.0

0 013 0'.s

0 .'9

1.2
'

1'.5

R20 (%)

6.0
o

5.O

FIG. 3

n.,
cO

4.0

Carbonation ratio - R20 rela-

3.0

tionship as influenced by specimen type

,e,=.

e=
0
e~

B 2.0
1.0
l
0.5

w,~c~o,
0.9

,
1.2

R20 (%)

1.5

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825
CARBONATION, ALKALI EFFECT, ACCELERATION

Fig. 5 shows the results of investigations on pore structures of carbonated and non-carbonated. This figure shows that total volume was greatly
reduced by carbonation, with the reductions of pores of diameter in a range
of 20 to 300 A being prominent. In carbonation tests of ordinary specimens
the influence of carbonation appears prominently in pores of diameters in a
range of lO0 to lO00 A, and i t is pointed out that pores in this range are
decreased (2,3). The reason for this is thought to be that pores in a range
of lO,O00 to lO0,O00 A are reduced in diameter due to solute ingredients from
migration of pore solution and CaC03 due to carbonation being adhered to pore
walls and the pores in the abovementioned diameter range having been increased.
That is, when carbonation occurs under conditions of using cement of high
alkali and of pore solution migrating, the pore volumes in a range of pore
diameters smaller in comparison with ordinary cases are reduced. The results
mentioned above indicate that carbonation was not accelerated due to the
structure becoming oorous because of leaching of dissolved ingredients accompanying migration of pore solution.

120

Thick-shelI cylinder

100

80

cylinder

FIG. 4
Progress of carbonation

60

of thick-shell cylinders
and of cylinder

40

~ 2o
0

dr

1 2
4
8
16
Period of AcceLerated Corbonation (week)

"]
Non-carbonated
part
~TJ~.V.:O.O954(cc/g)

\c~c)o.m ~

Fig. 5
Pore size distributions of
carbonated and of non-car-

bonated part in thick-shell

cylinder (pH = 13)

Carbonated part

+-~

TJ:.V.=O.O602(cc/g)

_c

o.

Pore Radius (A)

- ~

W/C = 50 %, R20 = 1.5 % -

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Vol. 19, No. 5

K. Kobayashi and Y. Uno

Concl usion
This paper has pointed out that carbonation of cement mortar and concrete
is governed by the alkali contained, in effect, the pH of pore solution.
Furthermore, i t has been ascertained through simulation experiments that carbonation due to this factor is greatly accelerated by migration of pore solution.
References
I. S.Diamond, Proc. 6th Int. Conf. on Alkalies in Concrete, Copenhagen, 155165 (1983)
2. R.Kondo,M.Daimon and T.Akiba, Proc. 5th Int. Symp. on Chemistry of Cement,
Vol.3, Tokyo, 402-409 (1968)
3. S.E.Philajavaara, Materials and Construction, Vol.l,No.6, 521-528, (1968)