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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.
489
490 Vol. 17, No. 3
D.W.S. Ho and R.K. Lewis
progress of Carbonation
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
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
C2S 11 24 SO 3 O. 2 O. 04
C4AF 10 10 B20 O. 04 O. 2
TABLE 3
Identification of Nixes
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:
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.
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
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.
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)
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)
47 38 29 23
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
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)
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
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.
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
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.
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
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.
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
TABLE 8
Results from Poole Power Station (Reference 27)
TABLE 9
Carbonation Measurements from Australian Structures
Conclusions
Acknowledgment
References
11. H.G. Smolczyk, RILEM I n t . Sym. Carb. of Concr. Fulmer Grange, 1.1 (1976).
504 Vol. 17, No. 3
D.W.S. Ho and R.K. Lewis
12. R.K. Dhir, M.R. Jones, and J.G.L. Munday, Concrete 1 9 (I0), 32
{1985).
14. N. Kashino, 3rd Int. Conf. on the Durability of Build. Mat. and
Components, Finland, 176 (19841.
15. S. Nagataki, H. Ohga and E.K. Klm, ACI SP91-24, 521 (1986).
19. D.W.S. Ho and R.K. Lewis, Cem. Concr. Res., 1_55 (5), 793 (19851,
20. D.W.S. Ho and R.K. Lewis, Inst. of Eng. Australia Conf., Brisbane, 95
(1985).
25. R.L. Munn, 2nd Int. Conf. on Ash Tech. and Marketing, London, 403 (1984).
28. J.G. Cabrera a n d G.R. Woolley, Proc. Inst. Cir. Engrs, Pt 2 (79), 149
(19851.
30. A. Samarin, R.L. Munn and J.B. Ashby, ACI SP-?9, 143 (1983).
31. D.W.S. Ho and R.K. Lewis, Inst. of Eng. Australia Conf., Brisbane, 95
(1985).