CEMENT and CONCRETE RESEARCH. V o l . 19, pp. 649-656, 1989. Printed in the USA.

0008-8846/89. $3.00+00. Copyright (C) 1989 MaXwel] Pergamon Macmillan

CARBONATION IN A 36 YEAROLD, IN-SITU CONCRETE

L.J. Parrott and D.C. Killoh

British Cement Association
Wexham Springs, Slough SL3 6PL U.K.

(Communicated by S. Pihlajavaara)
(Received Nov. 8, 1988)
&~ ~J~C~I~

Tbez~ogravimetric a n a l y s i s (TGA) o f d r i l l i n g s a t 5~a depth

intervals from a 36 year old in-situ concrete provided
information on the steepness of the carbonation front for
indoor and outdoor exposure. TGA results for indoor
exposure suggested that the cement gel was fully carbonated
to a depth of 45mm but calcium hydroxide was present from
25mm and increased to a maximum at a depth of 65mm: a
gradient covering 40mm. For outdoor exposure the gradient
extended over only 10mm. Phenolphthalein measurements
identified the first drill sample containing calcium
hydroxide and showed neutralization depths of 26 and 38mm
for indoor and outdoor exposure respectively. The phenol-
phthalein results and the TGA data for complete carbonation
indicated that outdoor exposure was more severe but TGA data
for the deepest penetration of carbon dioxide suggested the
reverse. It was recommended that s e r v i c e life studies of
reinforced concrete structures should consider the steepness
of the carbonation front.

Introduction

Carbonation in concrete proceeds inwards from the exposed surface

but does not always exhibit a steep reaction front (1-4) and the
factors controlling the length of the partially carbonated region
are not clear. It seems possible that the moisture conditions
within the concrete could be influential in controlling the
degree of carbonation at a given depth from the exposed surface
(5-10). The 36 year old column selected for this study was
internally exposed on one side and exposed to the UK climate on
the opposite side: these are typical exposure conditions and
might enable the carbonation results from this limited study to
be viewed in a broader perspective. The average relative
humidity in the UK is about 80-85% after diurnal and seasonal
fluctuations are taken into account (11). Thus the concrete
immedlately below the internal face of the column was expected to
be drier than that beneath the external face.

649
650 Vol. 19, No. 4
L.J. Parrot~ and D.C. Killoh

The usual method of studying carbonation is to measure the depth

of neutralization as indicated by a phenolphthalein solution
which has been sprayed onto the fractured concrete surface. This
indicator shows a magenta coloured region on the concrete where
the pH exceeds about 9 and a colourless region at the originally
exposed surface, where carbonation has reduced the pH to below 9
(4). Figure 1 illustrates the data of Ohgishi (2) and shows that
the pH of calcium hydroxide plus calcium carbonate mixtures will
be in excess of 9. ohgishi's data suggests that the
phenolphthalein indicator method will show only the boundary
corresponding to fully carbonated concrete. For this reason it
was necessary to use another method, thermogravimetric analysis,
to examine the regions of partially carbonated concrete.

-r= 13 v~ 2 0 A 0.12%
,2 \ 8%N"c'

11 ~ 15

I0
~~ ~ 10
o
9
5 0 ~

8 X ray intensity rate [%1

0 20 40 60 80 1~ CaCO 3

1~ 80 60 40 ~ 0 Ca (OH) 2 10-5 11.0 H.5 12-0

pH

Fig 1 pH value versus X-ray Fig 2 Effect of pH upon corrosion

diffraction intensity (2) of steel in carbonated mortar (12)

It might be argued that to assess the likelihood of reinforcement

corrosion it is necessary only to detect regions where the pH is
less than 9 (i.e. the value detected by phenolphthalein).
However, the results of Saeki(12) shown in Figure 2 indicate that
corrosion in carbonated concrete (in the absence of chlorides)
can initiate at a pH of about 11.4, although corrosion
intensities are likely to be weak(13). In addition, the
occurrence of corrosion beyond the phenolphthalein neutralization
boundary has been reported in Japanese studies at a variety of
concrete buildings where carbonation had occurred(14,15). The
foregoing discussion suggests that further examination of the
steepness of the carbonation reaction front in field-exposed
concrete would be worthwhile and this report presents an example
of such an examination. Complementary investigations of
carbonation, moisture conditions and corrosion in concrete
specimens exposed indoors and outdoors are currently in progress
at the British Cement Association.
Vol. 19, No. 4 65l
CARBONATION, 36'YEAR OLD, CONCRETE

HOLE B
Nor,. t g

~ ' " 0"

~ ~
~ E T E ~
COLUMN ~ 0'02
I Brick w~ll W1

0-~
~ ~ HOLES A,C,D W 2 ~
~ ~N~S f ~
0.~
D i ~ In~r ~rf~ of 10 ~°C
~ mm ~lumn ~t~ I I f I I I
225 ~ 2~ 400 ~
~ T~
Sample tem~ratur~ ~°CI

~9 3 Sec~ibn ~h~ou~h c o z e n ~ 4 The~oba~ance ou~pu~ ~o~

shov~n~ d ~ ho~e Zoca~ons pa~a~y carbonated concrete

Experimental details

A drawing of a horizontal section through the main column under

investigation is shown in Figure 3. The interior faces of the
column were coated with several layers of paint. The column was
surveyed using a covermeter to locate reinforcement and avoid
drilling through it. Rebound hammer readings (16) were also
taken to obtain an indirect measure of variations in quality of
the concrete surface layers. Samples of concrete were obtained
by drilling, the drill powder being collected over successive
depth ranges of a few millimetres. The 12mm diameter drill hole
was cleaned after each sample was taken to avoid contamination of
subsequent samples. A small portion of each sample was placed on
absorbent paper and lightly sprayed with a phenolphthalein
solutlon (Sg phenolphthalein in 950ml industrial methylated
spirit plus 50ml water). Any magenta colouration of the sample,
signifying a pH greater than 9, was noted.

The drill powder samples of concrete were stored over silica gel
in an evacuated desiccator until required for thermogravimetric
analysis. 20 mil~igrammes of sample were heated at 5°C/minute
from 20 up to 750uC in dry flowlng nitrogen using a computer-
controlled thermobalance (17): a graph of weight change against
sample temperature is shown in Figure 4 for a partially
carbonated sample. The graphical method of obtaining the
required weight loss data is also illustrated. The weight losses
are total weight loss,.lO0-TSO°C, (Wl), carbon dioxide lost from
calcium carbonate (W2), water lost from calcium hydroxide (W3)
and bound water lost from the cement g e l ( W 4 ) . The water lost
from the ~ement gel derives mainly from calcium silicate hydrate
but includes contributions from alumlnate and ferro'alumlnate
hydrates: a portion of it is lost after the c a l c i u m h y d r o x i d e
decomposition and in parallel with the carbon dioxide loss.
652 Vol. 19, No. 4
L.J. Parrott and D.C. Killoh

Results and d i s c u s s i o n

The depths of n e u t r a l i z a t i o n m e a s u r e d by p h e n o l p h t h a l e i n on the

column d e p i c t e d in F i g u r e 3 and on another c o l u m n from the south
side of the same b u i l d i n g are shown in Table 1.

TABLE 1
N e u t r a l i z a t i o n Depths and R e b o u n d H a m m e r results

Phenolphthalein Rebound
Location Exposure Drill hole neutralization number
depth (mm)

N o r t h Side External B 35 - 38.5 61.8

of b u i l d i n g Internal A 26 64.2
Column 1 Internal C 26 64.2
Internal D 25 64.2

South Side External E 20 64.2

of b u i l d i n g External F 18 64.3
Column 2 External G 29 64.3
External H 46 62.3

There were large v a r i a t i o n s of n e u t r a l i z a t i o n depth a s s o c i a t e d

w i t h external exposure, even w i t h i n a single column. T h e s e
v a r i a t i o n s did not c o r r e l a t e w i t h results of the r e b o u n d h a m m e r
tests. A s u b s e q u e n t l a b o r a t o r y e x a m i n a t i o n of a range of
concretes s u g g e s t e d that the rebound h a m m e r results were not very
sensitive to changes of w a t e r / b i n d e r ratio for mature, dried
concretes.

The w e i g h t losses from a concrete sample d u r i n g t h e r m o g r a v i m e t r i c

analysis are d e p e n d e n t upon the d e g r e e of cement hydration, the
degree of c a r b o n a t i o n and the a g g r e g a t e content. The total
w e i g h t loss t e n d e d to be g r e a t e r for samples t a k e n close to the
o r i g i n a l l y exposed surface; this c o u l d be a t t r i b u t e d to an
increased d e g r e e of c a r b o n a t i o n and a reduced a g g r e g a t e content
but was u n l i k e l y to be caused by an increased d e g r e e of cement
hydration. The t h e r m o g r a v i m e t r i c data were u s e d to estimate the
total a m o u n t of w a t e r that had reacted with the cement by
assuming that 6 m o l e c u l e s of w a t e r w e r e lost for every 10
m o l e c u l e s of c a r b o n dioxide reacted. This m o l e c u l a r ratio was
based upon t h e r m o g r a v i m e t r i c results from a m a t u r e sample that
was d e l i b e r a t e l y c a r b o n a t e d at 80% relative h u m i d i t y and upon the
data of Hunt and Tomes (8). The r e s u l t i n g e s t i m a t e s of b o u n d
w a t e r are p l o t t e d against d e p t h from the e x p o s e d surface in
Fiqure 5 and it can be o b s e r v e d that the indoor and outdoor
results are similar. The h i g h v a l u e s close to the o r i g i n a l l y
e x p o s e d s u r f a c e and the s m a l l e r fluctuations w i t h increasing
depth are t h o u g h t to be c a u s e d by v a r i a t i o n s of a g g r e g a t e
content. It was not p o s s i b l e to m e a s u r e the a g g r e g a t e content of
each sample in this study so the effect of v a r i a b l e a g g r e g a t e
Vol. 19, No. 4 653
CARBONATION, 36"YEAR OLD, CONCRETE

--_= 0 08 "~
¢= Hole Exgosure Symbol
~ A Indoor &
o~O B Outdoor i"l
0~n D Indoor 0
~I 00(~
°

~ ~
Average value
o
~ 0~ n . ~ . ~ -~- ~ - - . ~ 0"0393
~ o ~
¢ ~ o~ ~ o o
o
002~ ~
:

I ~ ~ ~ I
O~ 20 40 60 80 100
Depth [mm}

Fig 5 Bound water estimates versus depth from exposed surface

content was allowed for by adjusting the thermogravimetric weight

losses of each sample to give the same total bound water loss of
0.0393 g/g ignited concrete, i.e. the average value in Figure 5.
Thermogravimetric data for mature oement pastes typically give a
total bound water loss of 0.22 g/g of ignited paste so it can be
deduced that an average loss of .0393 g/g for the concrete
implies an aggregate/cement ratio of about 4.6. This figure is
reasonable for a structural concrete of the period (1951) and
provides some support for the method of adjusting the
thermogravimetric results. However, the adjustments to results
for samples within 10mm of the surface should be treated with
caution, because of uncertainty about the duration of initial
moist curing and the associated possibility of a reduction of
bound water in this region.

The adjusted losses from calcium carbonate, calcium hydroxide and

cement gel are shown in Figure 6 together with the depths of
neutralization by phenolphthalein. The results for indoor
exposure in Figure 6 show a region of partially carbonated
concrete between 20 and 65mm from the exposed surface. The
carbon dioxide loss deriving from reacted calcium hydroxide is
shown as a dashed line and accounts for about one third of the
total: other published data also show that reaction with calcium
hydroxide may account for only for about one third of the bound
carbon dioxide (18). The water loss from the cement gel reduced
with carbonation but the gel appears to be fully carbonated at
depths of 20 to 45mm and where calcium hydroxide is still
present. The 25mm depth of phenolphthalein neutralization
corresponds to almost complete carbonation with only a small
portion of the calcium hydroxide remaining.
654 Vol. 19, No. 4
L.J. Parro~t and D.C. Killoh

¢:= [~ Outdoor exposure

"- 0"06 - 0 ; 0"06
~
~ " - ~ L.. Neutralizationof ["] ~ Neutralization
--
~ 0-04 _
- 0 ~ 0,~
, phenolphthalein ~
~ 0.04I, [] alcium ~ of
~'~:~hthelein
~ o ,a~o o
_o I o ~ ~ fromca~oium - Loss fromc
~ 0-02- ! ~ ~carbonate ~ 0.02 carbonete ~
.-= ~,;~-~... ~ h .~
~ ~ro~lgium "-. ~ k
~ 0 hydmxidel ~ - ~ I ~ I ~ ~ 0 I 1 L ~ ~ I
= ~
.~ 0"008 ~ 0'008~
~ ~

0'006 & 0.0061

0.004 /
~ / Loss from
calcium hydroxide
ooo
, Loss from
calcium hydroxide ~
,[
O"002 ~ 0-002 ~
;

, , , , ,

0-01 Loss from 0.01~ Loss from 100_425o C

cement gel 1 ~ - 4 2 5 ° C cement gel ,

l I L l I 0= I l l i I
o~ 20 40 ~ 80 100 0 to 20 30 4~ 50
Depth ~ I o w e x t r a ~urface (mm] Depth below exposed surface [mm)

¥ig 6 T h e r m o g r a v i m e t r i c results for indoor and outdoor exposure

The results for o u t d o o r e x p o s u r e in Figure 6 show many

s i m i l a r i t i e s w i t h the results for indoor exposure, the losses for
u n c a r b o n a t e d and fully c a r b o n a t e d c o n c r e t e b e i n g v i r t u a l l y the
same in each case for calcium carbonate, c a l c i u m h y d r o x i d e and
c e m e n t gel. However, the 35 to 38.5mm d e p t h of n e u t r a l i z a t i o n by
p h e n o l p h t h a l e i n c o r r e s p o n d s a p p r o x i m a t e l y to the m i d d l e of the
10mm wide, p a r t i a l l y c a r b o n a t e d region. In a d d i t i o n there is no
clear r e g i o n w h e r e c a l c i u m h y d r o x i d e is p r e s e n t w h i l s t the cement
gel appears to be fully carbonated.

It could be a r g u e d that the regions of p a r t i a l l y c a r b o n a t e d

c o n c r e t e are a m i x t u r e of u n c a r b o n a t e d and fully c a r b o n a t e d
c o n c r e t e and arise from fluctuations of a locally steep
c a r b o n a t i o n fron£ over the c r o s s - s e c t i o n a l area of the drill
hole. However, this w o u l d not explain the results for indoor
e x p o s u r e w h e r e the cement gel appears to be fully c a r b o n a t e d in
the r e g i o n 20 to 40mm deep w h i l s t the amount of c a l c i u m h y d r o x i d e
c a r b o n a t e d is variable.
Vol. 19, No. 4 655
CARBONATION, 36"YEAR OLD, CONCRETE

Comparison of indoor and outdoor exposure on the basis of the

neutrallzation depth as indicated by phenolphthalein and the
depth of full carbonation suggests that outdoor exposure was more
severe in the column under investigation. If the comparison is
made on the basis of the deepest penetration of carbon dioxide
then indoor exposure seems to be more severe. With regard to the
possibillty of reinforcement corrosion the two exposure
conditions may be comparable if it is assumed that the pH
indicated by a phenolphthalein solution is about 9 and the pH of
uncarbonated concrete is about 13 (4) since a pH value of 11
would be expected at a depth of around 40mm in both cases.
However, the external exposure is more likely to provide the
moist conditions around the reinforcement that would promote
corrosion. The dry conditions inside a building usually lead to
a much greater depth of carbonation than that observed
outdoors(4) but the paint coating on the interior faces of the
column may well have acted as a partial barrier to the ingress of
carbon dioxide.

Concludinu remarks

The data in this report support the idea that carbonation does
not always exhibit a steep reaction front. It was observed for
an internally exposed condition that the partially carbonated
region in a concrete column extended 35mm beyond the 25mm depth
corresponding to neutralization as indicated by phenolphthalein.
The partially carbonated region for outdoor exposure of the same
concrete was only about 10mm long. The results of the present
investigation are consistent with other published literature and
it seems desirable that procedures for the inspection of
carbonated, reinforced concrete should consider the steepness of
the reaction front: it could have practical implications where
carbonation has penetrated a significant portion of the cover and
the projected service life or maintenance schedule needs to be
assessed.

Acknowleduem~nt

The authors are grateful to Mr J H Brown for his help with

sampling and phenolphthalein tests.

References

1. Litvan G. and Meyer A. "Carbonation of gbfs concrete during

20 years of field exposure" ACI SP-91, Madrid Proc, Vol.2,
1445-1462 (1986).

2. Ohgishi S. and Ono H. "Study to estimate depth of

neutralisation on concrete members" Cement Assoc. Japan
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3. Forrester J. "Measurement of carbonation" RILEM symposium on

carbonation of concrete" Wexham Springs, UK, Paper 2.1, 6pp
(19~6).
656 Vol. 19, No. 4
L.J. Parrott and D.C. Killoh

4. Parrott L. "A review of carbonation in reinforced concrete"

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I0. Kroone B. and Blakey F. "Reaction between carbon dioxide gas

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