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CEMENT and CONCRETE RESEARCH. Vol. 17, pp. 489-504, 1987. Printed in the USA.

0008-8846/87 $3.00+00. Copyright (c) 1987 Pergamon Journals, Ltd.

CARBONATION OF CONCRETE AND ITS PREDICTION

D.W.S. Ho and R.K. Lewis


CSIRO Division of Building Research, Melbourne, Australia

(Communicated by C.D. Pomeroy)


(Received March 3, 1987)
ABSTRACT

This paper presents results on carbonation of concrete incorporating


various constituents including chemical admixtures and fly ash. Both
long- and short-term test results are discussed. For concrete with
limited initial curing, it was found that the water/cement (not
water/binder) ratio was the most reliable parameter in predicting the
resistance of concretes to carbonation.

Introduction

Concrete can deteriorate in many ways. Perhaps the greatest concern nowadays
is the corrosion of the reinforcing steel and the subsequent spalling of the
cover concrete. According to the corrosion models put forward by Tuutti (1)
and Browne (2), the ease of penetration of substances such as carbon dioxide,
chlorides, oxygen, and water is of vital importance in the study of concrete
durability. The presence of these substances in concrete determines the
initiation and propagation of reinforcement corrosion.

A preliminary study into this aspect of concrete durability at the CSIRO


Division of Building Research was reported by Ho and Lewis (3). This study has
been extended to cover 16 combinations of mix constituents to represent, as
far as possible, the common materials used in Australia. The aim of this
extended research is to identify the parameters affecting the quality and,
therefore, the durability of exposed reinforced concrete elements such as
building exteriors. The scope of this research was presented earlier (4) and
the influence of mix constituents, curing, and the environment on the
penetrability of water into concrete was reported in terms of water sorptlvity
(5,6). This paper presents results on carbonation of these 16 sets of mix
constituents.

It is important to note that durable concrete cannot be achieved by mix design


alone. Workmanship (i.e., compaction and curing) and possibly the presence of
cracks can also significantly influence the durability of concrete. However,
the discussion of these topics can be found elsewhere (7,22) and is beyond the
scope of this paper.

489
490 Vol. 17, No. 3
D.W.S. Ho and R.K. Lewis

progress of Carbonation

Carbonation is mainly a diffusion process and its progress can normally be


described approximately by

X = Xo + Ct 0 ' 5 , (1)

where X = d e p t h o f c a r b o n a t i o n ,
t = time during which carbonation has been proceeding,
C = carbonation rate, and
Xo = i n i t i a l depth of carbonation which is normally small.

T h e a b o v e e q u a t i o n h a s b e e n p r o p o s e d b y many w o r k e r s ( 9 , 1 0 ) . According to
Tuutti (8), the exponent for time depends on exposure conditions a n d may b e
less than 0.5. Smolczyk (11) summarised research carried out in various
countries and pointed out that carbonation d e p e n d e d o n many f a c t o r s including
the quality of the concrete and the conditions of exposure. The most important
environmental factors that affect carbonation were considered to be carbon
dioxide concentration, humidity, and temperature. However, under similar
conditions of exposure, carbonation was f o u n d t o b e c l o s e l y proportional to
1/F 0"5, where F is the compressive strength of the concrete at the time of
carbonation.

Experimental Procedures

Mix constituents

Materials i n c l u d e d two T y p e h P o r t l a n d c e m e n t s , f l y a s h f r o m two s o u r c e s , and


chemical admixtures such as water-reducing and air-entraining agents. The
aggregate was e i t h e r basalt and natural sand (gap graded), or crushed river
gravel and natural sand having a more continuous combined grading. The d e t a i l s
of the materials and the terminology used in identifying each set of materials
are presented in Tables 1 to 3. For each set of materials a number of mixes
covering a range of compressive strengths was p r o d u c e d . A common s l u m p o f 80
mm was u s e d a s a c o n t r o l for all mixes. These mixes are identical with those
used in other studies (5,6).

TABLE 1 TABLE 2
Compound C o m p o s i t i o n s (%) a n d F i n e n e s s Composition (%) a n d F i n e n e s s (~)
of Cements 1 and 2 of Fly Ashes A and B

1 2 A B

C3S 62 52 CaO 4.7 1.2

C2S 11 24 SO 3 O. 2 O. 04

C3A 10 7 L.O.I. 0.8 3.6

C4AF 10 10 B20 O. 04 O. 2

Fineness index (m2/kg) 340 345 + 45 #m 7.4 20.2


. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

+150 /.xm 1.3 2.4


Vol. 17, No. 3 491
CARBONATION, CHEMICAL ADMIXTURES, FLY ASH

TABLE 3
Identification of Nixes

Coarse Water- Air-


Set Type Cement aggregate reducing entralnfng Fly ash
agent agent
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

1 Plain 1 Basalt - - -
2 WR . . . . Lignln - -
3 WR . . . . Ligpol - -

4 FA . . . . - - A

5 FA . . . . . . A
6 F-W . . . . Lignin - A
7 FA . . . . . . B
8 F-W . . . . Lignin - B
9 AE . . . . . Vinsol
10 F-W-A . . . . Lignin Vinsol B
11 Plain " Gravel - - -
12 AE . . . . . Vinsol
13 W-A . . . . Lignin Vinsol -
14 F-W-A . . . . Llgnin Vinsol B
15 Plain 2 Basalt - - -

16 FA . . . . . . A
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

Notes:

1. Unless stated otherwise, fly ash constitutes 20~ b y w e i g h t of


the total binder.

2. For set 5, fly ash constitutes 40~ by weight of binder.

3. F o r s e t s 10 a n d 1 4 , p a r t o f t h e s a n d i s r e p l a c e d by fly ash
increasing the fly ash content from 20~ to about 25~.

Exposure conditions

C o n c r e t e s p e c i m e n s m e a s u r i n g 75 x 75 x 3 0 0 mm w e r e u s e d . A f t e r i n i t i a l fog
curing for either 1, 7 , 2 8 , 9 1 , o r 3 6 5 d a y s , s p e c i m e n s w e r e c o a t e d o n a l l
sides except the trowelled ( 7 5 x 3 0 0 mm) s u r f a c e w i t h a n e p o x y r e s i n m e m b r a n e
impermeable to carbon dioxide. They were then conditioned in the laboratory
f o r 21 d a y s . The d e p t h o f c a r b o n a t i o n was m e a s u r e d a t t h e e n d o f t h i s d r y i n g
period and the value represented the initial reading before exposure.

For the short-term tests, s p e c i m e n s w e r e s t o r e d i n a c h a m b e r a t a b o u t 23°C a n d


5 0 ~ RH. The e n v i r o n m e n t was c o n t r o l l e d at 4 ± 0.5~ carbon dioxide (by volume).
Carbonation measurements were taken after 1, 4 , 9, a n d 16 w e e k s . R e p l i c a t e
specimens for long-term tests were exposed both under laboratory conditions
( 2 3 ° C a n d 5 0 ~ RH) a n d o u t d o o r s a t t h e CSIRO D i v i s i o n of Building Research,
Melbourne (38°S), either placed vertically facing north (towards equator) or
inclined a t 45 ° f a c i n g s o u t h . The l a b o r a t o r y storage simulated outdoor
exposure except that it provided shelter from rain. These conditions are
likely to be obtained in locations such as the underside of balcony slabs and
the soffit of bridge superstructures. So f a r , t h e 4 " m o n t h a n d 1 - y e a r r e s u l t s
of long-term tests are available and more measurements will be taken after 4
a n d 10 y e a r s o f e x p o s u r e .
492 Vol. 17, No. 3
D.W.S. Ho and R.K. Lewis

The limitations and advantages of the long- and short-term tests have been
discussed previously (4) and the need for short-term tests is highlighted by
Dhir et al. (12).

Measurements

Depth o f c a r b o n a t i o n was d e t e r m i n e d by r e m o v i n g a s l i c e a b o u t 50 mm t h i c k from


t h e end o f t h e s p e c i m e n , s p r a y i n g t h e f r e s h l y b r o k e n s a m p l e s w i t h
phenolphthalein indicator, and m e a s u r i n g t h e d e p t h t o t h e c o l o u r c h a n g e .
A l t h o u g h t h i s t e s t p r o c e d u r e i s r e f e r r e d t o as d e t e r m i n i n g t h e d e p t h o f
c a r b o n a t i o n , i t a c t u a l l y r e v e a l s o n l y t h e l e v e l w h er e t h e pH f a l l s b e l o w a b o u t
9. The b r o k e n s u r f a c e was n o t c o a t e d w i t h ep o x y r e s i n .

I t i s i m p o r t a n t to note t h a t under n a t u r a l e x p o s u r e , the r e d u c t i o n of c o n c r e t e


alkalinity i s n o t n e c e s s a r i l y due t o c a r b o n d i o x i d e a l o n e . S u l f u r d i o x i d e and
n i t r o g e n o x i d e s a r e c o n s i d e r e d as i m p o r t a n t p o l l u t a n t s w h i c h may a f f e c t
concrete (13).

I t ha s b e e n shown t h a t c o r r o s i o n can s t a r t when t h e a l k a l i n i t y of the concrete


f a l l s b e l o w a pH o f a b o u t 11. K a s h i n o (14) f o u n d t h a t c o r r o s i o n o f t h e
r e i n f o r c e m e n t may b e g i n when t h e c a r b o n a t i o n f r o n t i n d i c a t e d by t h e
p h e n o l p h t h a l e i n t e s t was 6 t o 8 mm from t h e s t e e l .

S h o r t - and L o n g - t e r m T e s t s

Rates of carbonation

For t h e m a t e r i a l s u s e d i n t h i s s t u d y , t h e s h o r t - t e r m t e s t r e s u l t s f o l l o w e d t h e
square root relationship as p r e d i c t e d by e q u a t i o n 1. Examples a r e shown i n
F i g u r e 1 wh er e t h e h o r i z o n t a l c o o r d i n a t e i s t h e s q u a r e r o o t o f t i m e . Each
p o i n t on t h e f i g u r e r e p r e s e n t s t h e a v e r a g e o f r e a d i n g s from two s p e c i m e n s .

30
EE
E
Z
ED

GO
tY
<E

"-10
Pt

1 4 9 16
TIME { WEEKS}

FIG. 1
S h o r t - t e r m c a r b o n a t i o n r e s u l t s o f F-W-A c o n c r e t e s ( s e t 14) a t f o u r 2 8 - d a y
s t r e n g t h l e v e l s (F28). Specimens were i n i t i a l l y c u r e d f o r 28 d a y s .
Vol. 17, No. 3 493
CARBONATION, CHEMICAL ADMIXTURES, FLY ASH

For the long-term tests, more results are needed before the rate of
carbonation can be discussed. However, the actual depths of carbonation will
be discussed below.

Correlations between results

An e a r l i e r investigation (3) established a correlation between short-term and


long-term test results. Based on a limited number of mixes with five years of
laboratory storage, the depth of carbonation after o n e y e a r ( y ) was
approximately that obtained after o n e w e e k (w) o f e x p o s u r e t o a n e n r i c h e d
a t m o s p h e r e o f 4~ c a r b o n d i o x i d e .

Results obtained so far from this study support the above approximation. The
depths of carbonation for specimens initially cured for seven days are
presented in Figure 2. Results determined from specimens exposed for one week
i n 4~ c a r b o n d i o x i d e a n d o n e y e a r u n d e r l a b o r a t o r y conditions are compared.
F o r t h e 60 m i x e s c o n s i d e r e d , the line of best fit gives a similar relationship
to that found in the earlier investigation. Hamada ( 2 9 ) a l s o u s e d a n e n r i c h e d
atmosphere of carbon dioxide and found good correlation between results
obtained from short-term tests and natural exposure in Japan.

15
E
E
GRADIENT.~Oo°
~
Z
=1.03
10
o

u.
:o
O
v

I I I
5 10 15
1YEAROFLABORATORC
YARBONATIO(mm)
N
FIG. 2
Comparison of results between short-term test and long-term laboratory
storage. Specimens were initially cured for 7 days.

Typical long-term results are shown in Table 4. During one year of exposure,
depths of carbonation obtained from natural exposure were lower than the
laboratory results. Even under external conditions, carbonation was f o u n d t o
vary, with the vertical specimens carbonating faster than the inclined
specimens. The d i f f e r e n c e s in results may b e d u e t o t h e f a c t t h a t t h e i n c l i n e d
specimens received a b o u t 5 4 0 mm o f r a i n , whereas the vertical specimens
received o n l y 40 mm o v e r t h e same e x p o s u r e p e r i o d a s m e a s u r e d b y a d i r e c t i o n a l
rain gauge. The above findings clearly demonstrate that correlation between
results from short-term tests and outdoor exposure is expected to vary
depending on local climatic conditions.
494 Vol. 17, No. 3
D.W.S, Ho and R.K. Lewis

TABLE 4
Depths of Carbonation (mm) of Fly Ash Concretes (set 16) after 21 Days of
Drying Followed by 1 Year of Exposure (Specimens Initially Cured for 1 Day)

F28 After 21 days 21-day drying + one-year exposure


of air drying ........................................
(MPa) Laboratory N vertical S inclined
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

46 3.0 8.5 4.5 3.0


35 3.5 13.0 7.0 4.0
26 4.0 16.0 10.0 5.5
18 5.0 17.0 11.5 6.5
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

Influence of initial curing

Results from short-term tests on a set of plain concrete mixes are shown in
Table 5. As indicated, carbonation, C, decreased as curing duration was
increased from one to seven days but remained practically unaffected when
curing was extended beyond seven days. Similar conclusions were also drawn by
Nagataki et al. (15) who found that 'after 15 years of outdoor exposure, the
depth of carbonation was greater for concretes initially cured for 1 day,
while the results for 7 and 91 days were similar'

TABLE 5
Carbonation Results (short-term tests) of Set 15 Concretes;
X o (mm), C (mm/w0"5), r (Correlation Coefficient)

Curing 28-day strengths (MPa)


. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

47 38 29 23
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

1 day Xo 3.5 3.5 4.0 4.0


C 5.7 7.1 8.8 9.4
r 0.993 0.996 0.998 0,997

7 days Xo 1.0 1.5 2.0 2.5


C 1.6 4.0 5.5 7.6
r 0.995 0.994 1.000 0,999

28 d a y s Xo 0.5 1.0 1.5 1.5


C 1.1 3.8 5.5 7.3
r 0.998 0,997 0.997 0,998

91 d a y s Xo 0 0.5 1.5 1.0


C 1.2 3.9 5.3 7.4
r 0.989 1.000 0.998 0.998

365 d a y s Xo 0 0.5 1.0 2.0


C 1.0 3.9 5.4 6.9
r 0.989 0.996 0.997 0.965
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Vol. 17, No. 3 495
CARBONATION, CHEMICAL ADMIXTURES, FLY ASH

The above findings also hold for the other plain concretes and concretes
incorporating chemical admixtures. However, for the fly ash mixes, minor
increases in carbonation resistance were observed when curing was extended
from seven days to one year. Typical examples are shown in Table 6.

TABLE 6
Results (short-term tests) from Sets 3, 8, 13, and 16 Concretes having
28-day Strengths between 25 and 30 MPa; X o (mm), C (mm/w 0"5)

Curing NR ( s e t 3) F-W ( s e t 8) W-A ( s e t 13) FA ( s e t 16)


. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

1 day Xo 3.5 4.0 4.5 5.0


C 6.1 8.8 6.3 10.9

7 days Xo 1.5 1.0 2.0 2.5


C 5.2 7.7 5.6 8.0

365 d a y s Xo 1.0 0 0 0.5


C 5.3 7.2 5.5 7.0

In practice, on-site curing is limited and for vertical surfaces exposed in


Melbourne, the amount of improvement in the quality of concrete due to
subsequent wetting (by rain) has been found to be minor (6). Thus, for
building exteriors, it would be prudent to predict the quality of cover
concretes by properties associated with short durations of moist curing, and
for practical purposes, a duration of seven days has been suggested as the
maximum a p p r o p r i a t e .

In the following sections, only short-term test results obtained from


specimens with standard moist curing of seven days will be discussed.

Influence of mix constituents

The current trend (16,17) of durability design is to specify three parameters:


minimum strength grade (i.e., 28-day compressive strength), maximum w a t e r /
cement ratio, and minimum cement content. However, due to the increasing use
of fly ash and other mineral admixtures, there has been a question among
engineers of whether blended cements would provide comparable durability to
equal quantities of pure cement. In drafting the proposals for durability
requirements for the British Standards (16), Beeby (18) pointed out that 'a
fundamental problem with all the discussions on durability was t h e l a c k o f
clear, quantitative data which could be used to test the validity of the
various proposals. It is becoming recognised that obtaining this data is one
of the industry's highest priority'.

In this section the influence of constituents on carbonation is illustrated.


Typical examples are shown in Figures 3(a), (b), and (c) where results are
compared based on three parameters: standard 28-day strength (F28), binder
content (i.e., cement and fly ash), and water/binder (W/B) r a t i o . For the
results shown, the plain concrete of set 1 is used as the control. The
ordinate represents the rate of carbonation, C7, o f s p e c i m e n s w i t h a s t a n d a r d
m o i s t c u r i n g o f s e v e n d a y s . As i n d i c a t e d , the incorporation o f f l y a s h ( s e t 5)
increased the carbonation of concretes, whereas the influence of cement (set
15), water-reducing agent (set 2), and aggregates ( s e t 11) was m i n o r . The
influence of fly ash on carbonation v a r i e d d e p e n d i n g o n many f a c t o r s . This is
discussed further in the following sections.
496 Vol. 17, No. 3
D.W.S. Ho and R.K. Lewis

12i
x SETI PLAIN
10 ~'"" ",~. • SET2 WR
E "-.. a SETS FA
,-8
"".. o SET11 PLAIN
""""a. . . c:} SET15 PLAIN
o_ 6
Z

l I I I I
20 30 ~0 50 60
12
2B-DAY STRENSTH,F2B (MPo)
(o)
10
E
E
-- B

~ 6

5
2

I I I I 1
0
250 300 350 l+O0 ~+50
BINDER CONTENT (kg/m3)
(b)

12

~--10 /p.1/~

/ f ~ // . / /m- ~ - o.,J~
6

I I I I I
~ 05 ~6 ~7 ~8
WATER/BINDER, WIB
(c)

FIG. 3
Short-term carbonation r e s u l t s on specimens i n i t i a l l y cured for 7 days,
based on (a) 28-day s t r e n g t h , (b) binder c o n t e n t , and (c) w a t e r / b i n d e r r a t i o .
Vol. 17, No. 3 497
CARBONATION, CHEMICAL ADMIXTURES, FLY ASH

Design Parameters

The 2 8 - d a y compressive strength, F28

Carbonation results by short-term testing of all mixes considered in this


study are presented in Figure 4. These results can be reduced to three lines
representing fly ash contents of 0, 20 to 25, and 40% by weight of the total
binder. In order to achieve similar resistance to carbonation of, say, 5
mm/w 0"5, concrete needs an average 28-day strength of

30 MPa for 0% f l y ash c o n t e n t ,


35 MPa f o r 20-25% f l y ash c o n t e n t , and
45 MPa for 40% f l y ash c o n t e n t .

10

~ 8
}
G
6
J Vo o °
z"
o_
Z jo 0,o
/o ~ O 25 % FLYASH
m ~ o~y" m 20 % FLYASH
m~V/mD~ o 0 %FLYASH
/ o
°

* , I * i i i l i i i , I
015 020 025
1 / ( F28 )os

FIG. 4
Influence of 28-day compressive strength, F28 (MPa), on carbonation of
concretes. Short-term test results on specimens initially cured for 7 days.

It is important to note that the protection afforded by the concrete to the


reinforcement depends on both the quality and thickness of the cover. For high
quality concretes with large covers, carbonation becomes less significant as a
design criterion. For example, in the absence of chlorides, concrete with a C 7
value of 5 mm/w 0"5 and a cover thickness larger than 35 mm is expected to have
an initiation period of at least 40 years which is often the normal design
life of buildings.

The 7 - d a y c o m p r e s s i v e s t r e n g t h , F7

The s i g n i f i c a n c e o f e a r l y s t r e n g t h d e v e l o p m e n t , as r e p r e s e n t e d by a 7 - t o 28-
day s t r e n g t h r a t i o , is illustrated i n F i g u r e 5 f o r a common 2 8 - d a y s t r e n g t h o f
30 MPa. For m i x e s i n c o r p o r a t i n g t h e same c e m e n t , c a r b o n a t i o n i n c r e a s e s w i t h
d e c r e a s i n g FT/F28 r a t i o .
498 Vol. 17, No. 3
D.W.S. Ho and R.K. Lewis

Results from mixes using cement 1 (sets 1 to 14) are presented in Figure 6.
The linear relationship between C 7 and 1/F70"5 has a high correlation
coefficient of 0.971. It is important to note that the relationship shown in
Figure 6 does not take into account the variations due to the use of different
cements, but does include fly ashes A and B.

10

F28= 30 MPa

E
~ ~EMENT 1
g

Z
0

I I I I J
06 07 08 09 ~0
7-DAY STRENGTH / 28-DAY STRENGTH , F7 / Fz8

FIG. 5
Effect of early strength development on carbonate rate of 30 MPa concretes.

The benefits of high early strength concretes have been recognised by CEB (21)
and various codes of practice {16,17). These documents accept shorter curing
for mixes with faster strength development. Pomeroy (22) explains that 'faster
hydration can ensure the formation of a dense and low permeability concrete
within a few days of casting, thereby reducing the need for prolonged curing'.

Effectiveness of f l y ash

In general, fly ash is used in concrete for economic advantage. Therefore, the
producer needs to know how much cement can be replaced by fly ash while
maintaining strength and/or other specified requirements. In a previous paper
(19), the effectiveness, K c, of fly ash was introduced and defined as the
ratio of the amount (by weight) of cement replaced to the amount of fly ash
added in maintaining the carbonation resistance of concrete. K c would be unity
if fly ash provided the same carbonation resistance as an equal quantity of
cement. It was found that K c varied with the amount of initial curing and the
interaction between mix constituents.

The values of K c for specimens initially cured for 7 days are summarised in
Table 7. For fly ash A, K c varied from 0.35 to 0.60, and for fly ash B, the
range was between 0 and 0.20. For the materials used in this study, fly ash
cannot be regarded as cement in its resistance to carbonation since the values
of K c are less than unity.
Vol. 17, No. 3 499
CARBONATION, CHEMICAL ADMIXTURES, FLY ASH

m•
10 a 40% FLYASH
o 25% FLYASH A/
• 20% FLYASH
o 0% FLYASH ~ ~ •
M

• o
E~
i= &rl~ 0 0 :o o

J /,~OO O
z"
O

l_J
m d~

of ° °
I I I I
15 .20 .25 30
1/(FT) °s

FIG. 6
The influence of 7-day co•pressive strength, F7 (MPa), on the
carbonation of concretes.

TABLE 7
Fly Ash Effectiveness for Carbonation Resistance, Kc

Co•parison Ce•ent Fly Strength levels (MPa)


of •ixes ash .....................................
in sets 25 30 35 40
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

4 and 1 1 A 0.40 0.50 0.50 0.60


5 and 1 1 A 0.40 0.40 0.35 0.35
6 and 2 1 A 0.50 0.50 0.40 0.35
7 and 1 1 B 0.10 0.05 0 0
8 and 2 1 B 0.20 0.15 0.10 0.05
14 and 13 1 B 0 0.20 0.05 0
16 and 15 2 A 0.55 0.50 0.45 0.35

Water/cement (W/C} a n d w a t e r / b i n d e r (W/B} r a t i o s

The w a t e r / c e m e n t ratio of a mlx is generally considered as one of the •ost


important design parameters affecting concrete quality. Since fly ash, in
general, has the ability tb reduce the water demand of a mix, it is often
considered that better quality concrete can be achieved by the incorporation
of fly ash. This would not be disputed if fly ash is used as an addltion
500 Vol. 17, No. 3
DoW.S. Ho and R.K. Lewis

rather than as a partial rep]acement of cement. Confusion often exists when


the two ratios, W/C and W/B, are used loosely.

The relationships between W/B ratio and C 7 for all mixes are presented in-
Figure 7. As indicated, C 7 varied over a wide range for any particular W/B
ratio. However, results could be reduced to four lines representing fly ash
contents of 0, 20, 25, and 40~ by weight of the total binder. At a common W/B
ratio, the highest rate of carbonation was obtained from mixes with the
highest fly ash content. In achieving a common C 7 value of 5 ••/w 0"5, the
required (averaged) W/B ratios are
0.65 for 0~ fly ash content, 0.50 for 20~ fly ash content,

0.45 for 25~ fly ash content, and 0.40 for 40~ fly ash content.

These results demonstrate the deficiency in durability designs based on common


W/B ratios.

10
AS.

~-8 / 7SqS I I0
\
E
E /// o. oo
~6
:7
o / /./
Z
0 0 0 • O
~4
~C
u

rS I I 0 0 I%
SAYLF H j

0/~ 05 0"6 0"7 0-8


WATER I BINDER

FIG. 7
The influence of water/binder ratio on the carbonation of concretes.

For all mixes considered in this study, results fro• 16 sets of materials can
be reduced to a single line (see Figure 8) if the W/C ratio, rather than the
W/B ratio, is considered. There is an excellent correlation (r = 0.982)
between C 7 and W/C ratio. This implies that for concretes to have identical
carbonation resistance, the percentage of cement reduction cannot be greater
than the percentage reduction of water brought about by the incorporation of
chemical admixtures or fly ash. For the materials used, mixes incorporating
fly ash A had a lower water demand than comparable mixes with fly ash B (31).
This may explain why fly ash A had higher K c values than fly ash B.
Vol. 17, No. 3 501
CARBONATION, CHEMICAL ADMIXTURES, FLY ASH

10 a 40 % FLY ASH / a
o 25 % FLY ASH
• 20 % FLY ASH

O ~ AO

/..°
I , I , I , I , I , I , I J
04 0-5 0'6 0-7 0-8 09 10
WATER / CEMENT , W/C

FIG. 8
The prediction of carbonation by considering the water/cement ratio.

Results from Surveys

Many papers have been published reporting greater depths of carbonation with
fly ash concretes. Some of these were discussed by Ho and Lewis (23) in an
authors' closure of an earlier paper (24). Of greater significance are the
findings obtained from surveys of existing structures.
In 1983, Samarin et al. (30) claimed that 'field examination of Australian
concretes in several environments where both plain and fly ash concretes have
been exposed for 10 to 20 years indicate no significance difference in
carbonation depth for concretes (proportioned) on the basis of similar 28-day
strength and slump'. No data or details of 'field examination' were presented.

In the same year, a durability survey of the 20-year old outfall canal at
Munmorah Power Station, Australia, was undertaken. Concretes with and without
fly ash were used in the construction. In the survey, cores were taken from
the walls of the channels. Carbonation measurements were discussed by Munn
(25) and later by Roper et al. (26) who reported that carbonation depths were
higher for the fly ash concretes, the maximum depth being 16 mm in the case of
concretes with fly ash, and 4 mm for concretes without fly ash.

A survey of another Australian structure was also reported (26). Core samples
were obtained from Keepit Dam and the fly ash concrete was found to have a
very high rate of carbonation. After 25 years of service, carbonation ~epths
of 23 and 5 mm were reported for concretes with and without fly ash
respectively. Results indicated a common W/B ratio of 0.56 for both concretes.
502 Vol. 17, No. 3
D.W.S. Ho and R.K. Lewis

Surveys have also been c a r r i e d out in the United Kingdom (27) on s t r u c t u r e s


between 10 and 30 years old. At Poole power s t a t i o n , the f l y ash concrete was
found to carbonate about 50% f a s t e r than comparable concretes without f l y ash.
A summary of r e s u l t s i s shown in Table 8.

TABLE 8
Results from Poole Power Station (Reference 27)

Without f l y ash With f l y ash


. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

Estimated cube s t r e n g t h (MPa) 44 41


Carbonation (mm) 16 22-26
Cover thickness (mm) 22 50-90
Condition of reinforcement Corroded Good
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

I t i s important to note t h a t concretes having a g r e a t e r depth of carbonation


are not n e c e s s a r i l y l e s s durable. This i s because the reinforcement p r o t e c t i o n
depends on both the q u a l i t y and thickness of cover concrete. For the Poole
power s t a t i o n , the f l y ash concrete had a much g r e a t e r cover thickness and
t h a t might explain why i t was more durable than the concrete without f l y ash
even though i t carbonated f a s t e r . Results from t h i s survey c l e a r l y i l l u s t r a t e
t h a t any s t r u c t u r e can be made durable provided the l i m i t a t i o n s of the
m a t e r i a l s used are recognised and proper care has been taken in the design.

I t i s o f t e n argued t h a t carbonation i s not important because of i t s low


magnitude. This would not be disputed for high s t r e n g t h concretes with
s u b s t a n t i a l cover to the reinforcement. The argument i s also v a l i d for
foundations (28) and other s t r u c t u r e s which remain wet or moist during
service.

It must be realised that low strength concretes ( 2 0 t o 25 MPa) w i t h l o w c o v e r


( 1 5 t o 30 mm) h a v e b e e n u s e d f o r m a n y y e a r s i n A u s t r a l i a in the design of
building exteriors. These surfaces a r e wet o n l y when s u b j e c t e d to directional
rain. Rates of carbonation of these exposed surfaces are expected to be faster
than those reported above.

For structures that suffered distress due to reinforcement corrosion, depths


of carbonation have often been measured. Results t h a t h a v e come t o t h e
attention o f t h e a u t h o r s a r e s u m m a r i s e d i n T a b l e 9. The r a t e s o f c a r b o n a t i o n
were determined by a s s u m i n g a s q u a r e r o o t r e l a t i o n s h i p between depth and time.

TABLE 9
Carbonation Measurements from Australian Structures

Structures Age Carbonation


(years) ..........................
D e p t h (mm) R a t e (mm/y 0 " 5 )
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

Building A - facades 13 24 6.5


Building B - facades 25 25 5.0
Building C - facades 6 I0 4.0
Bridge - soffit 12 40 i1.5
Jetty - underside of deck 5 14 6.5
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Vol. 17, No. 3 503
CARBONATION, CHEMICAL ADMIXTURES, FLY ASH

These results indicated that. in practice, carbonation could be fast and


v a l u e s i n e x c e s s o f 5 mm/y 0 " 5 h a s b e e n r e c o r d e d .

Conclusions

The carbonation of concrete as affected b y 16 s e t s o f m a t e r i a l s representing a


broad production range has been investigated. Under short-term test conditions
using an enriched a t m o s p h e r e o f 4~ c a r b o n d i o x i d e , carbonation was f o u n d t o
proceed in proportion to the square root of time. Using the results obtained
so far, the depth of carbonation after one week of short-term testing could be
approximated to that obtained after one year of laboratory storage.

For concrete with 7 days of standard moist curing, carbonation was f o u n d t o


depend mainly on the water/cement (not water/binder) ratio regardless of the
mix constituents considered i n t h i s s t u d y . The i n f l u e n c e of fly ash could also
be discussed i n t e r m s o f i t s Kc v a l u e o r t h e 7 - d a y s t r e n g t h of the concrete.
I f c o m p a r i s o n o f m i x e s was b a s e d o n common 2 8 - d a y s t r e n g t h , binder content, or
W/B r a t i o , then fly ash concretes were found to have lower resistance to
carbonation. This latter f i n d i n g was s u b s t a n t i a t e d by results from surveys of
existing structures.

Acknowledgment

This project is sponsored by the Cement and Concrete Association of Australia.

References

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(1979).

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(1979).

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(1981).

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504 Vol. 17, No. 3
D.W.S. Ho and R.K. Lewis

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27. J.B. Newman, P . J . E . Sullivan a n d A.M. B e l l , Concrete 17 (12), 9 (1983).

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(19851.

29. M. Hamada, V Sym. Chem. o f Cement, 343 (1968).

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(1985).