Journal of Wuhan University of Technology-Mater. Sci. Ed. Oct.

2010 889

DOI 10.1007/s11595-010-0114-z

Influence of Absolute Basicity and Capillary Porosity on

Carbonation of Concrete

BA Mingfang1, 2, QIAN Chunxiang1, 2, GAO Guibo1, 2

(1. School of Materials Science and Engineering, Southeast University, Nanjing 211189, China;
2. Jiangsu Key Lab of Construction Materials, Nanjing 211189, China)

Abstract: The single influence of capillary porosity and coupling effects of absolute basicity
and capillary porosity on concrete carbonation were investigated. The experimental results showed that
carbonation rate of concrete at a given absolute basicity (AB) increased moderately with the increase of
the porosity ranging from 6.2% to 9.25%, and increased rapidly with porosity from 9.25% to
12.8%.The coupling effect mainly embodied in disappeared mutation point of capillary porosity, and
the distributing regions of carbonation depth were clearly partitioned in the coupling influence of ab-
solute basicity and capillary porosity. A design method on carbonation related durability of concrete
based on the coupling effects was proposed.
Key words: absolute basicity; capillary porosity; coupling effects; carbonation rate

1 Introduction concrete. Concrete itself is a porous composite material

More and more attention has been paid to the dura-
bility of concrete structure. And carbonation of concrete
is one of the main problems which affect the durability of
concrete structures[1]. In urban and industrial areas, where
environmental pollution results in a significant concen-
tration of CO2, carbonation-initiated reinforcement cor-
rosion prevails. It is well known that carbonation is a
chemical reaction between CO2 from air and the hydra-
tion products of cement in concrete, which causes a re-
duction in the alkalinity of concrete and consequently in
its ability to protect the steel reinforcement from corro-
sion[2]. Factors affecting carbonation rate include the type
and amount of cementitious materials, porosity, curing
time etc[3]. Experimental studies on these influencing
factors were conducted by various researchers[2-4].
Anyway, considering too much factors will make car-
bonation issue even more complicated and difficult for
further research. In fact, the basic factors influencing
carbonation is diffusivity of CO2 in the hardened concrete
and capability of combining CO2[4].
The ingress of CO2 into concrete pore system by
diffusion will react with calcareous hydration products of
©Wuhan University of Technology and Springer-Verlag Berlin Heidelberg 2010
(Received: Mar. 21, 2009; Accepted: June 3, 2010)
BA Mingfang (巴巴巴): Ph D; E-mail: bmf-1@163.com
Funded by the National Basic Research Program of China
(No.2009CB623200) and Nanjing Key Construction Project (No.7612005822)
consisting of mineral aggregates. The porosity of the
concrete allows movement and retention of water and
CO2. So porosity is a critical parameter for diffusivity of
CO2. The size of pores in concrete ranges over several
orders of magnitude, which are classified as gel pores,
micro-pores, and capillary pores. Only capillary pores are
much more correlated with durability[5-7].
The capability of combining CO2 depends not only
on content of Ca(OH)2 but also ones of all the other cal-
careous hydrated compounds of concrete. The reaction
between CO2 and C-S-H produces CaCO3 and a silica
gel[8, 9]. AFt and AFm decompose by carbonation to
CaCO3[10, 12]. As is known that Ca(OH)2, C-S-H, AFm
and AFt come from calcareous phase of cementitious
materials. Thereby in the light of the representation of the
chemical constituent of slag[13], absolute basicity, which
expresses the content of alkalic hydrated compounds in
concrete by Eq.(1), was defined to denote the capability
of combining CO2.
{ }
AB = ∑ Cλ × ⎡⎣ M CaO − (1.65M Al2O3 + 0.35M Fe2O3 ) ⎤⎦ (1)
Where M CaO , M Al2O3 , M Fe2O3 and M SiO2 are the
mass fraction of oxides in cementitious materials, and
Cλ is mass content of certain cementitious material in
per-cubic-meter concrete.
This study was performed to investigate capillary porosity,
AB, accelerated carbonation to ascertain the influence of cap-
illary porosity and AB on carbonation of concrete.
890 Vol.25 No.5 BA Mingfang et al: Influence of Absolute Basicity and C…

2 Experimental to avoid the influence of AB on carbonation, five mix-

tures have the same content of cementitious materials,
2.1 Material and for all mixtures there are very close content of gravel,
The chemical and mineral compositions in per- so the water absorption by the gravel could be neglected
centage by mass of oxides of cementitious materials are here. Table 2 shows the proportions.
expressed in Table 1. The modulus of fineness of the river Table 1 Chemical and mineral constituent of cementitious
sand is 2.6. The grading of gravel is successive and its max materials/wt %
size is 20 mm. The water absorption of gravel is 3.4%. CaO SiO2 Al2O3 Fe2O3 MgO SO3 Loss
2.2 Mix proportions and specimens preparation Cement 63.40 21.00 4.71 4.01 2.52 2.74 2.29
Fly ash 3.20 56.00 28.00 6.20 1.21 0.61 3.21
Five mixtures with different water/binder ratio were
Slag 33.50 35.50 17.00 1.53 6.82 2.39 1.20
prepared obtaining different capillary porosity. In order
Table 2 Mixing proportions of concrete
Number C/B Mixing proportion/(kg/m3)
C FA(I) W G S Superplasticizer
P30 0.30 285 80 109.5 1 041 840 4.74
P35 0.35 285 80 127.8 1 041 859 4.38
P40 0.40 285 80 146.0 1 042 814 4.01
P45 0.45 280 85 164.3 1 044 778 3.65
P50 0.50 280 85 182.5 1 046 758 2.92
In order to reveal the coupling influence of AB and cap- calculated by Eq.(2). This testing method has previously
illary porosity on carbonation, concrete mixtures with differ- been reported[14, 15].
ent AB and capillary porosity have been designed (Table 3). (W − Wdry )
P = sat × 100 (2)
Concrete specimens in all experiments are 100 mm (Wsat − Wwat )
×100 mm×300 mm prisms. Three specimens for each Where P is the capillary porosity (%); Wsat means
mixture were cast and cured in a standard curing room. weight in air of saturated sample; Wwat refers to weight
After 28 days, all specimens were removed and were cut in water of saturated sample; Wdry is weight of
into three 100 mm cubic. The middle cubic were used for oven-dried sample.
porosity measurement and the others for accelerated 2.4 Carbonation testing
carbonation testing. All residual sliced cubes were dried for 48 hours at
Table 3 Experimental proportions/(kg/m3) the temperature of 60 ℃. Then their two lateral faces
w/b Cement Fly-ash Slag Water Gravel Sand SP were retained, others were sealed with paraffin. And then
235 235 0 1 089 752 4.50
they were put into the accelerated carbonation chamber,
330 140 0 1 089 769 4.50
where the temperature was 15 ℃-25 ℃, relative hu-
0.30 330 70 70 140 1 089 758 4.50
400 70 0 1 089 783 4.50
midity was 65%-75% and the carbon dioxide concentra-
330 0 140 1 089 769 4.50 tion was 17%-23%. After 28-day carbonation, the car-
183 182 0 1 079 782 3.65 bonation depth of the specimens was determined by the
263 102 0 1 095 793 3.65 method recommended by RILEM CPC-18 on a vertical
0.40 299 66 0 146.0 1 102 798 3.65 section of the specimen. Each result reported is the av-
336 29 0 1 109 803 3.65 erage carbonation depth “D” measured at two points
365 0 0 1 115 807 3.65 perpendicularly to three faces of the broken concrete
183 182 0 1 022 740 3.65 cube and repeated on three specimens. The mean value of
263 102 0 1 038 751 3.65
the depth carbonation “D” is shown in Fig.1. This method
0.50 299 66 0 182.5 1 045 757 3.65
for measuring the depth of carbonation was reported
336 29 0 1 052 762 3.65
elsewhere[16].
365 0 0 1 057 766 3.65

2.3 Capillary porosity tests 3 Results and Discussion

Capillary porosity of concrete could be obtained
indirectly by hydrostatic weighing. The middle sliced
100 mm specimens were dried at 100±5 ℃ until con-
stant weight achieved and then placed in desiccators
under vacuum for 3 hours, which was finally filled with
de-aired, distilled water. Then the capillary porosity was
3.1 Influence of capillary porosity on
carbonization
Different capillary porosity was obtained from dif-
ferent concrete samples (Table 2). The concrete with high
water/binder ratio has higher capillary porosity. Fig.2
 Journal of Wuhan University of Technology-Mater. Sci. Ed. Oct.2010
shows the changes of porosity with different water/binder
ratio. The result is consistent with the literature reporting
the relationship between water/binder ratio of concrete
and porosity[17].
Fig.1 Measuring of carbonation depth
Fig.2 Relationship between water/binder ratio
and capillary porosity of concrete
According to the obtained accelerated carbonation
depths of concrete samples for different ages, the corre-
sponding carbonation coefficient D f can be calculated
by Eq. (3).
D f = D / t 1/ 2
Where D f is carbonation coefficient (mm/d1/2); D is
mean carbonation depth (mm) and t is carbonation age (d).
The effect of capillary porosity on the accelerated car-
bonation coefficient at different ages is clearly illustrated
in Fig.3.
It can be seen from Fig.3 that the carbonation rate in-
creases with increase of capillary porosity. Moreover car-
bonation rate increases moderately with the porosity rang-
ing from 6.2% to 9.25%, while increases rapidly with po-
rosity ranging from 9.25% to 12.8% at all carbonation ages.
It seems that it is a mutation point at the porosity of 9.25%.
As porosity is lower than the point, CO2 diffuses slowly in
concrete, which results in lower carbonation rate. On the
891
other hand, it is vice versa. Fig.3 also shows that carbonation
coefficient of concrete decreases with prolonged carbonation
age. For concrete with 6.2% porosity, the 3-day D f is 2.51,
and 28-day D f is 1.70. Hereby the decrease of D f is 32%.
The decreasing effect may be caused by the drop of CO2
concentration inside concrete. This finding is in agreement
with the report by D Russell[18].
Fig.3 Capillary porosity versus carbonation
coefficient at different carbonation age
3.2 The coupling effect of AB and capil-
lary porosity on carbonization of
concrete
It is well known that concrete is heterogeneous and
porous composites and porosity and AB are two decisive
parameter of carbonation rate, and, porosity and AB
influence carbonation of concrete jointly. Single influ-
encing factor on carbonation seldom exists in concrete
structures. So the research on the coupling effect of cap-
illary porosity and AB on carbonation has more practical
significance. Fig.4 (a) and (b) show the coupling effect of
AB and capillary porosity on 28-day carbonation depth of
concrete. Fig.4 (a) is a 3-D drawing to express the change
trend of carbonation depth and Fig.4 (b) is a projection
picture, where the contour is the depth of carbonation.
Fig.4 (a) indicates that carbonation depth of con-
crete decreases slowly with the increase of AB, while
decreases greatly with the increase of capillary porosity.
(3)
But there is no mutation point of porosity compared with
Fig.3, which indicates the coupled effects make the car-
bonation change more moderate.
Fig.4 (b) shows the distribution regions of carbona-
tion depth with different AB and capillary porosity. The
AB and capillary porosity could be predicted according
to measured carbonation depth, and the carbonation
depth could also be estimated by the given basicity and
capillary porosity in term of Fig.4 (b). For instance, pro-
viding designed 28-day accelerated carbonation is 21 mm,
the AB1/2 will be between 12 and 14 (kg/m3)1/2 and the
capillary porosity is between 7% and 10%, whose cor-
responding water/binder ratios is between 0.32 and 0.40
referring to Fig.2.
892 Vol.25 No.5 BA Mingfang et al: Influence of Absolute Basicity and C…
Fig.4 The coupling effect of basicity and capillary porosity on carbonization of concrete at 28-dage
4 Conclusions
The capillary porosity has a very important effect on
concrete carbonation. Carbonation rate increases slowly
with the porosity ranging from 6.2% to 9.25%, but in-
creases rapidly with porosity from 9.25% to 12.8%. That
is to say, 9.25% porosity was a mutation point for the
relation between capillary porosity and carbonation.
Carbonation rate decreases with the increase of AB
but was less sensitive to it than to capillary porosity.
Carbonation depth distributing regions are partitioned
clearly in the coupling influence of AB and capillary
porosity on carbonation. A design method of concrete
carbonation durability based on the known basicity and
porosity is proposed. On the other hand, basicity and
porosity could also be deduced likewise in terms of
measured carbonation depth.
References
[1] V G Papadakis, M N Fardis, C G Vayenas. Effect of Com-
position, Environmental Factors and Cement Line Mortar
Coating on Concrete Carbonation[J]. Material Structure,
1992, 149 (25): 93-304
[2] V T Ngala. Effect of Carbonation on Pore Structure and
Diffusion Properties of Hydrated Cement Pastes[J]. Cement
Concrete Research, 1997, 7(27): 995-1 007
[3] V G Papadakis, C G Vagenas, M N Fardis. Fundamental Mod-
eling and Experimental Investigation of Concrete Carbona-
tion[J]. ACI Materials Journal, 1991, 88 (4): 463-373
[4] D C Zhang, D Y Xu, X Cheng, et al. Carbonation Resistance
of Sulphoaluminate Cement-based High Performance Con-
crete[J]. J. Wuhan University of Technology-Mater. Sci. Ed.,
2009, 24 (4): 663-666
[5] Y J Xie, Y H Liu, G C Long. Long-term Durability of Ce-
ment-based Materials with Low w/b[J]. J. Wuhan University of
Technology-Mater. Sci. Ed., 2008, 23 (3): 303-308
[6] J Holly, D Hampton, M D A Thomas. Modeling Relationships
between Permeability and Cement Paste Pore Microstructures[J].
Cement Concrete Research, 1993, 6 (23): 1 317-1 330
[7] H W Song, S J Kwon. Permeability Characteristics of Carbon-
ated Concrete Considering Capillary Pore Structure[J]. Cement
Concrete Research, 2007, 6 (37): 909-915
[8] K Suzuki, T Nishikawa, S Ito. Formation and Carbonation of
C-S-H in Water[J]. Cement Concrete Research, 1985, 15(2):
213-224
[9] K Kobayashi, K Suzuki, Y Uno. Carbonation of Concrete
Structures and Decomposition of C-S-H[J]. Cement Con-
crete Research, 1994, 24 (1): 55-61
[10] T Nishikawa, K Suzuki, S Ito. Decomposition of Synthesized
Ettringite by Carbonation[J]. Cement Concrete Research,
1992, 22(1): 6-14
[11] C Xiantuo, Z Ruizhen. Kinetic Study of Ettringite Carbona-
tion Reaction[J]. Cement Concrete Research, 1994, 24(7):
1 383-1 389
[12] Q Zhou, F P Glasser. Kinetics and Mechanism of the Car-
bonation of Ettringite[J]. Advanced Cement Research, 2000,
12(3): 131-136
[13] H F W Taylor. Cement Chemistry[M]. London: Thomas
Telford, 1997: 122
[14] T Gonen, S Yazicioglu. The Influence of Compaction Pores
on Sorptivity and Carbonation of Concrete[J]. Construction
and Building Materials, 2007, 21 (5): 1 040-1 045
[15] V G Papadakis, M N Fardis, C G Vagenas. Hydration and
Carbonation of Pozzalanic Cement[J] ACI Materials Journal,
1992, 89 (2): 119-130
[16] C D Atis. Accelerated Carbonation and Testing of Concrete
Made with Fly ash[J], Construction Building Material, 2003,
17(3): 147-152
[17] R Kumar, B Bhattacharjee. Porosity, Pore Size Distribution
and In-situ Strength of Concrete[J]. Cement Concrete Re-
search, 2003, 33 (1): 155-164
[18] D Russell, P A M Basheer, G I B Rankin. Effect of Relative Hu-
midity and Air Permeability on Prediction of the Rate of Carbona-
tion of Concrete[J]. Structure Building, 2001, 3(146): 319-326