Professional Documents
Culture Documents
Abstract: Accelerated carbonation is a process in which CO2 is intentionally introduced to concrete at an early age for a short period of
time to promote rapid strength gain. The accelerated carbonation of portland limestone cement (PLC) was studied to examine the possibility
of replacing ordinary portland cement (OPC) by PLC in carbonation curing of precast concrete products. Carbonation behavior was char-
acterized by strength gain, CO2 uptake, pH change, XRD, TG, SEM, FTIR, and 29 Si NMR spectroscopy. It was found that PLC was a CO2
reactive material. Its CO2 uptake reached 12% based on dry cement mass. In reference to hydrated PLC, the strength of carbonated PLC was
79% higher at 20 h and of close value at 28 days, even though the ultimate CaCO3 content in carbonated PLC was over 40%. The calcium
carbonates produced by accelerated carbonation were found to be imbedded in calcium silicate hydrates, forming an intermingled micro-
structure. The high carbonation reactivity of PLC was possibly attributed to its fine particle size and the existence of limestone powder nuclei
for calcium carbonate precipitation. The use of PLC in accelerated carbonation of concrete products can significantly contribute to a net gain
in carbon emission reduction. DOI: 10.1061/(ASCE)MT.1943-5533.0000773. © 2014 American Society of Civil Engineers.
Author keywords: Carbon dioxide; Carbonation; Microstructure; Calcium carbonates; Curing; Cement.
C3 S þ ð3-xÞCO2 þ yH2 O → Cx SHy þ ð3-xÞCaCO3 ð3Þ pose. The 18-h was selected to allow initial air curing to be carried
out in an overnight shift. The cement paste was cast in strips
200 mm long, 14 mm wide, and 6 mm thick and, while still in the
C2 S þ ð2-xÞCO2 þ yH2 O → Cx SHy þ ð2-xÞCaCO3 ð4Þ plastic state, cut into samples 14 × 14 × 6 mm. An environmental
chamber was used for initial air curing.
Despite extensive research on accelerated carbonation of OPC Table 2 shows different curing regimes applied to seven batches
paste and concretes, accelerated carbonation behavior of PLC which were cast with the same w/c. For each of the seven batches,
pastes and concretes is not well examined. It is of interest to know ten samples were prepared. The hydration references, B2 and B9,
if PLC can be effective in replacing OPC in carbonation curing were kept in a sealed condition without water loss and tested at 20 h
of dry mix concrete products. This paper presents a study on the and 28 days, respectively. The B1 sample were hydration references
performance and microstructure change of PLC pastes subject to that underwent air curing in an environmental chamber at an RH of
accelerated carbonation curing. The researched PLC paste simu- 60% at 25°C for 20 h, while B8 specimens were sealed for an addi-
lates the paste in a dry mix concrete for precast products such tional 27 days of hydration. The B3, B10 and B11 samples were
as blocks, pipes and hollow core slabs. The curing process includes initially air cured in an environmental chamber at a RH of 60%
18-h initial hydration, 2-h carbonation, immediate water compen- at 25°C for 18 h and then carbonated together for 2 h in a CO2
sation, and subsequent hydration. Comparisons are made between chamber. After 18 h of initial air curing and 2 h of carbonation,
carbonated and hydrated PLC pastes in terms of strength gain, CO2 B3 specimens were tested immediately for 20-h strength and
uptake, and pH value at different ages. The microstructure changes B10 specimens were sealed for an additional 27 days of hydration
are characterized by X-ray diffraction (XRD) analysis, thermog- before being tested at 28 days. To compensate water loss during
ravimetry (TG) analysis, Fourier transform infrared (FTIR) spec- initial air curing and carbonation curing, B11 specimens were water
troscopy, scanning electron microscopy (SEM), and 29 Si nuclear sprayed right after 2-h carbonation curing to restore original water
magnetic resonance (NMR) spectroscopy. content and then sealed for subsequent hydration of 27 days.
The setup for accelerated carbonation is illustrated in Fig. 1. The
initially air cured samples were placed in the chamber and carbon
Experimental Procedure dioxide of 99.5% purity was injected to a constant pressure of
0.15 MPa. The method used to determine CO2 uptake was the mass
Portland limestone cement (PLC) used in this project is a commer- gain method that compares the sample mass before and after car-
cial product manufactured by Holcim Canada. The clinker is inter- bonation. The mass difference represented the carbon dioxide up-
ground with 13–15% limestone by mass, and the resultant Blaine take. The evaporated water during carbonation was collected by
fineness is 500 m2 =kg. Table 1 presents the chemical compositions. absorbent paper and added to final mass after carbonation. Percent
Based on CO2 content, as-received PLC contains approximately CO2 uptakes were thus calculated based on dry cement mass using
15.8% limestone. Cement paste was used in the study instead of Eq. (5). The CO2 uptake was also measured by a commonly used
mortar or concrete in an attempt to avoid inclusion of aggregates infrared based carbon analyzer (CW800, Eltra) through a powder
and their influence on quantitative microstructure analysis. A water- analysis
to-cement (w/c) ratio of 0.36 by mass was used to represent the
paste in typical precast concrete products such as sewage pipes, CO2 uptakeð%Þ ¼ MassCO2 =Masscement ð5Þ
masonry blocks and hollow core slabs. At this w/c, accelerated
Compressive strength tests were conducted after 2 h of carbonation
Table 1. Chemical Composition of PLC Cement (wt%) and 20-h strengths were obtained for B1, B2, and B3 using a com-
CaO SiO2 Al2 O3 Fe2 O3 MgO Na2 Oa SO3 CO2 pression area of 14 × 6 mm. Ten samples of each batch were tested
to produce a representative average. The fractured samples were
59.8 20.6 4.5 2.7 1.7 0.6 3.2 6.6
collected for XRD, pH, TG, FTIR, NMR, and SEM analysis
a
Na2 O alkali equivalent including K2 O. and preserved in acetone to stop further hydration. The acetone
10.9 (B3) to 11.2 (B10) and 11.9 (B11), which were still below the
pH of 13.2 from the most hydrated reference at the same age (B9).
Accelerated carbonation does reduce pH. Water compensation
could enhance the strength of carbonated PLC to a comparable
level to that of the hydration reference, but not the pH values.
However, the pH is still higher than the accepted corrosion thresh-
old value of 10.5 (Pourbaix 1974), and could possibly be improved
with further hydration. Thick concrete specimens have shown
higher pH values in their cores after the same carbonation process
(Rostami et al. 2011).
calcium hydroxide, carbonated PLC displays a more amorphous action between CO2− 3 and labile-Ca and interlayer-Ca in C-S-H,
and denser structure which was responsible for the higher strength. yielding an intermingled network structure of CaCO3 and C-S-H.
Although the existence of calcium carbonates was evident by XRD After 28-day (B10 and B11), Q2 grew stronger, manifesting the
and TG, there were no well-defined crystals observed at 5,000x occurrence of subsequent hydration, which was in agreement with
magnification. It was indicative that calcium carbonates produced the DTG and mass loss results (Figs. 4 and 5).
by carbonation were intermingled with C-S-H. They played a The infrared spectra of different PLC pastes are compared in
critical role in the strengthening of the C-S-H gel. Fig. 9. The vibrational bands after 1,600 cm−1 were assigned to the
The effect of carbonation on amorphous C-S-H structure in PLC chemically bound water, while those smaller than 1,000 cm−1 were
pastes was studied through 29 Si NMR and IR spectroscopy. The mostly corresponding to silicate in the calcium silicate hydrates and
29 Si NMR spectra are plotted in Fig. 8. Qn represents the degree calcium carbonates (Mollah et al. 2000). The bands corresponding
of polymerization of the silicate units in the calcium silicate phase to O-H, C-O (carbon-oxygen)m and Si-O were identified on the
where n shows the number of oxygen bonds between the SiO4 spectra. The vibrational band at 3,640 cm−1 was associated with
units. In hydrated PLC (B1, B2, B8, B9), Q0 was decreased in its the O-H bond in calcium hydroxide, while the other O-H band
at 3; 410 cm−1 could be attributed to O-H in C-S-H. It was found
that the O-H vibrational band was present at 3,640 cm−1 in PLC
after 20-h air curing (B1) but absent in carbonated PLC at 20h (B3)
and after 28 days subsequent hydration (B10). This indicated
the transformation of calcium hydroxide, which was in agreement
with XRD results (Fig. 2). The typical vibrational modes for
Fig. 7. SEM micrographs: (a) hydrated PLC paste (B1); (b) carbonated Fig. 8. 29 Si NMR spectra of PLC pastes (Q0 ¼ −70 ppm,
PLC paste (B3) Q1 ¼ −79 ppm and Q2 ¼ −83 ppm)
crete products. In spite of a high CaCO3 content, the strength “A Fourier transform infrared spectroscopic investigation of the early
of carbonated PLC is comparable to that of carbonated ordin- hydration of portland cement and the influence of sodium lignosulfo-
ary portland cement. The accelerated carbonation curing of nate.” Cem. Concr. Res., 30(2), 267–273.
PLC concrete offers an increased net gain in carbon emission Péra, J., Husson, S., and Guilhot, B. (1999). “Influence of finely ground
reduction as well as an economical means to utilize CO2 in the limestone on cement hydration.” Cem. Concr. Compos., 21(2), 99–105.
Pourbaix, M. (1974). Atlas of electrochemical equilibria in aqueous solu-
vicinity of its source, instead of remote storage in a geologic
tions, National Association of Corrosion Engineers, Houston, TX.
formation. With high CaCO3 in cement, durability properties Ramachandran, V. S., and Beaudoin, J. J. (2001). Handbook of analytical
of carbonated PLC concrete exposed to sulfate attack need an techniques in concrete science and technology, William Andrew
in-depth study. Publishing/Noyes, New York.
Rostami, V., Shao, Y., and Boyd, A. J. (2011). “Durability of concrete pipes
subjected to combined steam and carbonation curing.” Constr. Build.
Acknowledgments Mater., 25(8), 3345–3355.
Rostami, V., Shao, Y., and Boyd, A. (2012a). “Carbonation curing versus
The project is financially supported by Natural Science and steam curing for precast concrete production.” J Mater. Civil Eng.,
Engineering Research Council of Canada (NSERC), Canadian 24(9), 1221–1229.
Concrete Masonry Producers Association (CCMPA), and National Rostami, V., Shao, Y., Boyd, A. J., and He, Z. (2012b). “Microstructure
Basic Research Program of China (973 Program) (Grant No. of cement paste subject to early carbonation curing.” Cem. Concr. Res.,
2009CB623200). The authors would like to thank Holcim Canada 42(1), 186–193.
for providing the portland limestone cement. Shao, Y., Mirza, M. S., and Wu, X. (2006). “CO2 sequestration using
calcium-silicate concrete.” Can. J. Civ. Eng., 33(6), 776–784.
Shi, C., He, F., and Wu, Y. (2012). “Effect of pre-conditioning on CO2
References curing of lightweight concrete blocks mixtures.” Constr. Build. Mater.,
26(1), 257–267.
Berger, R. L., Young, J. F., and Leung, K. (1972). “Acceleration of hydra- Soroka, I., and Setter, N. (1977). “The effect of fillers on strength of cement
tion of calcium silicates by carbon-dioxide treatment.” Nature Phys. mortars.” Cem. Concr. Res., 7(4), 449–456.
Sci., 240(97), 16. Toennies, H. T. (1960). “Artificial carbonation of concrete masonry units.”
Bonavetti, V., Donza, H., Menéndez, G., Cabrera, O., and Irassar, E. F. J. Am. Concr. Inst., 56(2), 737–756.
(2003). “Limestone filler cement in low w=c concrete: A rational Tsivilis, S., Chaniotakis, E., Badogiannis, E., Pahoulas, G., and Ilias, A.
use of energy.” Cem. Concr. Res., 33(6), 865–871. (1999). “A study on the parameters affecting the properties of portland
British Standards Institution (BSI). (2000). “Cement composition, specifi- limestone cements.” Cem. Concr. Compos., 21(2), 107–116.
cations and conformity criteria for common cements.” BS EN 197-1, Tsivilis, S., Chaniotakis, E., Kakali, G., and Batis, G. (2002). “An analysis
London. of the properties of portland limestone cements and concrete.” Cem.
Cyr, M., Lawrence, P., and Ringot, E. (2006). “Efficiency of mineral ad- Concr. Compos., 24(3–4), 371–378.
mixtures in mortars: quantification of the physical and chemical effects Tsivilis, S., Kakali, G., Chaniotakis, E., and Souvaridou, A. (1998).
of fine admixtures in relation with compressive strength.” Cem. Concr. “A study on the hydration of portland limestone cement by means
Res., 36(2), 264–277. of TG.” J. Therm. Anal. Calorim., 52(3), 863–870.
Detwiler, R. J., and Tennis, P. D. (1996). The use of limestone in portland Tsivilis, S., Tsantilas, J., Kakali, G., Chaniotakis, E., and Sakellariou, A.
cement: A state-of-the-art review, Portland Cement Association, (2003). “The permeability of portland limestone cement concrete.”
Skokie, IL. Cem. Concr. Res., 33(9), 1465–1471.
Dhir, R., Limbachiya, M., McCarthy, M., and Chaipanich, A. (2007). Vuk, T., Tinta, V., Gabrovšek, R., and Kaučič, V. (2001). “The effects of
“Evaluation of portland limestone cements for use in concrete construc- limestone addition, clinker type and fineness on properties of portland
tion.” Mater. Struct., 40(5), 459–473. cement.” Cem. Concr. Res., 31(1), 135–139.
Goodbrake, C. J., Young, J. F., and Berger, R. L. (1979). “Reaction of beta- Young, J. F., Berger, R. L., and Breese, J. (1974). “Accelerated curing of
dicalcium silicate and tricalcium silicate with carbon dioxide and water compacted calcium silicate mortars on exposure to CO2 .” J. Am. Ceram.
vapor.” J. Am Ceram. Soc., 62(3–4), 168–171. Soc., 57(9), 394–397.