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Accelerated Carbonation of Portland Limestone Cement

Yixin Shao 1; Vahid Rostami 2; Zhen He 3; and Andrew J. Boyd 4


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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.

Introduction concrete strength. However, late strength of mortars with 5% lime-


stone addition led to decreased or similar strength while slightly
Accelerated carbonation of concrete can serve as a fast curing re- enhancing early strength (Vuk et al. 2001). The presence of calcium
gime to increase early age strength, improve long term durability, carbonate in cement increased calcium hydroxide (CH) content
and recycle carbon dioxide for emission reduction (Young et al. compared to the reference cement suggesting a contribution of
1974; Rostami et al. 2011; Shao et al. 2006). If ordinary portland the limestone to the hydration reactions (Tsivilis et al. 1998) and
cement (OPC) in concrete can be replaced by portland limestone providing nucleation sites for hydration products (Cyr et al. 2006;
cement (PLC) in an accelerated carbonation process, the carbon Soroka and Setter 1977). However, if the limestone content in
footprint of the cement and concrete industry can be further cement exceeded 10%, both early and late strengths were reduced.
reduced. It was believed that such a high dosage of limestone addition acted
PLC has been extensively studied in the past two decades owing as a diluent (Bonavetti et al. 2003; Dhir et al. 2007; Péra et al. 1999;
to its technical, economic and environmental benefits (Bonavetti Tsivilis et al. 1999, 2002). During the hydration of limestone
et al. 2003; Detwiler et al. 1996; Tsivilis et al. 2003). It has been cement, the calcium carbonate powder was found to react with
found that calcium carbonate filler, once ground to a size smaller the AFm and AFt phases to form carbosilicate and carboaluminate
than 20 μm and blended with hydraulic cement, is not completely hydrates along with conventional hydration products (Kakali et al.
inert during the hydration process. The early and late age strength 2000; Péra et al. 1999).
of concrete is affected depending on the particle size and the Since major components of PLC are similar to those of OPC
content of limestone. Péra et al. (1999) found that adding 10% except the addition of limestone, concrete made with PLC should
limestone to cement, when it was ground to an average size of be able to be treated by accelerated carbonation at early ages to
2.5 μm, resulted in a higher strength of cement paste at 7 days benefit from the advantages of the process. Previous research on
due to accelerated hydration, and comparable strength at 28 days. the accelerated carbonation of OPC paste and mortar immediately
Bonavetti et al. (2003) found that adding up to 10% calcium after casting have suggested that the process has the potential
carbonate interground with clinker led to an equal or even higher to offer improved mechanical properties (Berger et al. 1972;
Goodbrake et al. 1979; Young et al. 1974). The major carbonation
1 reactions occur according to Eqs. (1)–(4) where the final products
Associate Professor, Dept. of Civil Engineering and Applied Me-
chanics, McGill Univ., 817 Sherbrooke St. West, Montreal, QC, Canada
are the hybrid of calcium-silicate-hydrate (C-S-H) and calcium
H3A 2K6 (corresponding author). E-mail: yixin.shao@mcgill.ca carbonate (CaCO3 ) (Berger et al. 1972; Young et al. 1974). Unlike
2
Ph.D. Candidate, Dept. of Civil Engineering and Applied Mechanics, weathering carbonation, accelerated carbonation is performed at
McGill Univ., 817 Sherbrooke St. West, Montreal, QC, Canada H3A 2K6. early age and followed by a subsequent hydration. Recent studies
E-mail: vahid.rostami@mail.mcgill.ca showed that accelerated carbonation curing of concrete after a pre-
3
Professor, School of Water Resources and Hydropower Engineering conditioning can effectively replace steam curing for precast con-
Science, Wuhan Univ., Wuhan 430072, China. crete production (Rostami et al. 2012a; Shi et al. 2012). Concrete
4
Associate Professor, Dept. of Civil Engineering and Applied carbonated in this manner has comparable strength to steam-cured
Mechanics, McGill Univ., 817 Sherbrooke St. West, Montreal, QC, Canada concrete and exhibits an enhanced resistance to permeation, sulfate
H3A 2K6.
attack, and freeze-thaw damage. Subsequent hydration after accel-
Note. This manuscript was submitted on August 28, 2012; approved on
January 3, 2013; published online on January 5, 2013. Discussion period erated carbonation contributes significantly to late strength gain and
open until June 1, 2014; separate discussions must be submitted for indi- maintains concrete alkalinity above the threshold value to protect
vidual papers. This paper is part of the Journal of Materials in Civil En- steel reinforcement from corrosion. The accelerated carbonation of
gineering, Vol. 26, No. 1, January 1, 2014. © ASCE, ISSN 0899-1561/ precast OPC concrete could reduce the carbonation shrinkage of as-
2014/1-117-124/$25.00. sembled concrete structures in service (Toennies 1960). In addition

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J. Mater. Civ. Eng., 2014, 26(1): 117-124


to the technical advantages, accelerated carbonation curing is a CO2 carbonation of concrete requires an initial air curing to reduce free
sequestration process that is capable of utilizing carbon dioxide re- water and allow carbon dioxide diffusion (Rostami et al. 2012a). It
covered from cement kiln flue gas, allowing for carbon recycling was found that a 40% reduction of free water in a concrete made of
within the cement and concrete industry (Shao et al. 2006) 0.36 w/c was necessary to facilitate carbonation. To assure that the
final water content in the cement paste was the same as that in con-
CaðOHÞ2 þ CO2 → CaCO3 þ H2 O ð1Þ crete after initial air curing, the thickness of cement paste was ad-
justed to allow about 40% of free water evaporation during an 18-h
C-S-H þ 2CO2 → SiO2 þ 2CaCO3 þ H2 O ð2Þ initial air curing in an environment of 60% RH and 25°C. It was
found that a thickness of 6 mm was appropriate to serve the pur-
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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

Table 2. Curing Regime


Batch ID Curing ID Initial curing Subsequent curing Test age
a
B1 20A 20-h air curing 0 20 h
B2 20S 20-h sealed curing 0 20 h
B3 18A+2C 18-h air curing+2h carbonationa 0 20 h
B8 20A 20-h air curinga 27 d in sealed bag 28 d
B9 20S 20-h sealed curing 27 d in sealed bag 28 d
B10 18A+2C 18-h air curing+2h carbonationa 27 d in sealed bag 28 d
B11 18A+2C+WS 18-h air curing+2h carbonation+water spraya 27 d in sealed bag 28 d
a
Air curing in RH ¼ 60%, T ¼ 25°C.

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J. Mater. Civ. Eng., 2014, 26(1): 117-124


Table 3. Water Content of PLC Paste after Curing (%)
Batch After After 18-h After 2-h After water After 20-h
ID mixing air curing carbonation spray curing
B1 100 63.5 n/a n/a 63.5
B2 100 n/a n/a n/a 100
B3 100 62.7 56.1 n/a 56.1
B8 100 64.1 n/a n/a 64.1
B9 100 n/a n/a n/a 100
B10 100 62.5 57.3 n/a 57.3
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B11 100 63.8 57.7 100 100

Fig. 1. Setup for accelerated carbonation curing


Table 4. Carbon Uptake, Strength Gain, and pH of the PLC Pastes
was refreshed on each of three consecutive days to make sure all the CO2 uptake (%)
free water was flushed out of the samples. Before making powder Batch Mass IR carbon
samples for analysis, they were dried overnight in an oven at 60°C. ID Age gain Content Strength (MPa) pH
A simple ion extraction method was employed to determine pH B1 20 h n/a 9.9 35.8  4.3 12.4  0.2
values of carbonated and hydrated samples (Heng and Murata B2 20 h n/a 10.2 38.1  1.8 13.1  0.1
2004) at 20 h and 28 days. A volume of 100 μl of distilled water B3 20 h 12.1 20.1 68.1  6.4 10.9  0.2
was dropped on an absorbent paper on the surface of the paste. B8 28 d n/a 7.7 50.4  5.2 12.8  0.2
After 15 min, which was found to be sufficient to produce constant B9 28 d n/a 7.7 104.3  8.8 13.2  0.1
values, the pH of the solution extracted by the paper was measured B10 28 d 12.9 19.5 85.6  11.6 11.2  0.1
using a pH meter (Extech PH110) with a flat sensor head of B11 28 d 12.8 20.8 111.6  13.4 11.9  0.2
9-mm diameter. Three samples in each batch were chosen for the
measurements and the values were averaged.
Phase analysis of the samples was conducted using XRD B9) was maintained at 100% in sealed curing conditions. To com-
(Phillips PW1710, Cu Kα radiation). Powder samples were taken pensate water loss and make it comparable to the reference, carbon-
from the outer 2-mm surface. The same powder sample was also
ated samples in B11 were water sprayed immediately after
examined by TG,FTIR, and NMR. A thermal analyzer (NETZSCH,
carbonation to restore original water content and then kept sealed
TG 449 F3 Jupiter) with a resolution of 0.01 mg was employed to
up to 28 days.
run TG analysis and obtain the mass loss of the samples. The FTIR
Table 4 presents carbon uptake, strength gain, and pH of PLC
spectra of the samples were obtained using a spectrometer
pastes. Carbon uptake was 12.1–12.9%, calculated based on dry
(Model 170SX, Nicolet). Disk specimens were prepared by pressing
cement mass [Eq. (5)]. Carbon content determined by the infrared
a mix of PLC powder with KBr. Spectral analysis was performed
carbon analyzer is also reported in Table 4. The CO2 uptake due to
over the range 4,000 − 400 cm−1 at a resolution of 0.1 cm−1 . The
29 the accelerated carbonation was calculated by subtracting the car-
Si NMR spectra of samples from all batches were obtained to
bon content of the hydrated specimens at 20 h from the carbonated
study the effect of the carbonation treatment on the silicate structure
of C-S-H. The corresponding spectra were obtained at 59.5 MHz ones. It was 10.2%, 9.6%, and 10.9% for B3, B10, and B11, re-
using an Agilent/Varian VNMRS-300 spectrometer. Samples of spectively. They were lower than those obtained by the mass gain
constant mass of 100 μg were collected from the 2-mm surface method. The discrepancy was caused by the denominator in Eq. (5).
layer, packed in 7.5-mm zirconia rotors, and spun at 4,000 Hz. In the mass gain method, the denominator was the dry cement mass
A π=2 pulse of 5 μs was applied with a recycle delay of 5s. [Eq. (5)] while in infrared method, it was the paste mass which
A field emission scanning electron microscope (FE-SEM, Sirion included bound water. It was obvious that the thermal analysis
TMP) was used to study the morphology of fractured surface and of carbon dioxide content was influenced by the initial carbon di-
calcium carbonate crystal formation. The fracture surface was oxide content and dependent on location of sampling. At 20 h, car-
coated by gold and examined in secondary electron mode. bonated PLC (B3) exhibited a compressive strength 79% higher
than the best reference (B2). It was due to a strong carbonation
reaction evidenced by a carbon dioxide uptake of 12.4% in PLC
Results (Table 4). Comparison of PLC pastes B1 and B2, with and without
initial air curing, revealed a strength reduction in 20-h strength
due to the water loss from air curing. The reduction was more con-
Carbon Uptake and Strength Gain siderable after 28 days subsequent hydration. At 28-day, carbon-
Accelerated carbonation is sensitive to water content in cement ated PLC (B10) was stronger than hydrated PLC (B8) with
paste. Initial air curing of 18-h was thus utilized to reduce free water same air curing but was weaker in comparison to a reference with-
and facilitate carbonation. Table 3 presents water content of PLC out air curing (B9). It was apparent that water loss during air curing
pastes after different curing schemes. They are determined by mass had an adverse effect on long term performance. Water compensa-
difference before and after initial air curing and expressed in terms tion after carbonation seemed to be necessary in restoring lost water
of initial mixing water. With reference to a water content of 100% and promoting more strength gain. Despite the carbonation-in-
right after casting, the samples (B1, B3, B8, B10, and B11) cured in duced rapid strength gain at an early age, according to Eqs. (3)
the environmental chamber at 60% RH and 25°C for 18 h, lost and (4), PLC paste after carbonation and water compensation
about 36% of their mixing water. Carbonation of 2 h led to an addi- (B11) exhibited comparable strength to that of the best reference
tional 6% of water loss in batches B3, B10, and B11, according to (B9). It appears that carrying out the carbonation process in a se-
Eqs. (1) and (2). The water content in hydration references (B2 and quence including initial air curing, carbonation curing, and water

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J. Mater. Civ. Eng., 2014, 26(1): 117-124


compensation, is better for ensuring a high early strength, a com-
parable late strength, and a considerable amount of carbon dioxide
uptake.
Table 4 also displays pH values of PLC measured on the surface
after hydration and carbonation. The change in pH was another
evidence of carbonation. The pH of PLC after 2-hr carbonation
was reduced from 12.4 (B1) to 10.9 (B3). The pH of a specimen
hydrated without water loss (B2) was 13.1 at 20-h. The subsequent
hydration to 28 days had increased the pH of carbonated PLC from
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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).

Hydration and Carbonation Products


Fig. 2 shows the XRD patterns of PLC pastes. The peaks
corresponding to CH crystals which were present in the hydration
references (B1 and B2) disappeared in the carbonated PLC (B3 and
B11). Although the CH was not detectable in the carbonated
surface after subsequent hydration (B11), the strength growth after Fig. 2. XRD patterns of PLC pastes
carbonation, comparing B11 to B3 in Table 4, suggested possible
CH formation in the core. The intensity of calcium carbonate peaks
in the hydrated PLC (B1, B2, B8, and B9) confirmed the presence
of limestone in the as-received cement. However, the intensity of
calcium carbonate was noticeably higher in the carbonated speci-
men (B3), evidencing additional formation of calcium carbonates.
It is worth noting that the intensity of calcium silicates (between 32°
and 33°) had a decreasing trend after carbonation (B3), according to
Eqs. (3) and (4). This was suggestive that carbonation of both
hydrates and unhydrated phases occurred simultaneously, leading
to an increase in strength at early age.
TG analysis was also performed. Reference materials, including
as-received PLC cement, 95%-pure calcium hydroxide (CH), car-
bonated 95%-pure CH, and natural calcite, were studied first to
verify the temperature range for each phase. Their DTG curves are
shown in Fig. 3. The decomposition temperature of CaCO3 in the
natural calcite was 908°C, in comparison to 867°C in carbonated
CH (95%) and 816°C in as-received PLC. It seemed that the
decomposition temperature of CaCO3 was proportional to the
crystallinity and the quantity of CaCO3 . Table 5 summarizes
the quantitative results of the reference materials corresponding
to Fig. 3. It was assumed that mass loss in the 105–420°C range
corresponded to decomposition of all hydrates, mass loss in the
420–540°C range to decomposition of CH, and mass loss in the
540–950°C range to decomposition of calcium carbonates. Based
on these temperature ranges, the CaCO3 content in the as-received
PLC was 15%, CaðOHÞ2 content in the CH of 95% purity was
94.5%, and the CaCO3 content in the natural calcite was 98.4%.
This comparison verified the temperature ranges for subsequent
Fig. 3. DTG curves of reference materials
quantitative TG analysis.
DTG curves of all PLC batches at early (20-h) and late (28-d)
age are plotted in Fig. 4 and their mass loss curves are in Fig. 5. The
mass loss below 420°C represented dehydration of several phases higher temperature corresponding to CH around 460°C (B9). They
such as C-S-H, C-A-H, ettringite, and gypsum (Ramachandran and were indicative of formation of more C-S-H phases and a more
Beaudoin 2001). In comparing hydration at 28 d (B9) versus 20 h crystalline CH resulting from subsequent hydration.
(B2), there was a peak shift toward lower temperatures in B9 Carbonation products were characterized by mass loss in the
below 420°C in subsequent hydration and a peak shift toward temperature range of 540–950°C. Decarbonation temperature was

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J. Mater. Civ. Eng., 2014, 26(1): 117-124


Table 5. Phase Analysis of Reference Materials
Water CO2 Calcium Calcium
Reference materials loss % loss % hydroxide (%) carbonate (%)
PLC (as-received) 0.5 6.6 2.2 15.0
CH (95%) 23.0 1.5 94.5 3.4
Carbonated CH (95%) 6.6 31.2 27.1 70.9
Natural calcite 0.3 43.3 0 98.4
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Fig. 6. Water loss and CO2 loss of PLC pastes

Table 6. Calcium Hydroxide (CH) and Calcium Carbonate (CaCO3 )


Content
Batch ID
Phase B1 B2 B3 B8 B9 B10 B11
CH content (%) 6.1 7.8 1.4 7.8 15.2 1.7 2.2
CaCO3 content (%) 19.3 19.8 39.9 15.3 14.9 39.6 41.4
Fig. 4. DTG curves of hydrated and carbonated PLC pastes

Fig. 6 summarizes the mass loss due to dehydration (105–


540°C), mass loss due to decarbonation of amorphous carbonates
(540–720°C) and mass loss due to decarbonation of well crystalline
carbonates (720–950°C) for each batch. At early ages (20-h), the
total bound water in the carbonated PLC (B3) was slightly greater
than air cured (B1) but close to that of the sealed hydrated PLC
(B2). The carbonation reactions at this age can happen to both hy-
drates and anhydrous phases. Although the 2-h carbonation could
convert early developed hydration products, such as C-S-H and CH
into calcium carbonate, it was also capable of producing more
C-S-H by carbonating tricalcium silicates and dicalcium silicates
(Young et al. 1974). Comparing the CO2 loss between the carbon-
ated (B3) and hydrated reference (B2) suggested that calcium
carbonates produced by accelerated carbonation were more amor-
phous than crystalline. In subsequent hydration up to 28 days, car-
bonation products remained almost constant, while hydration
products were increased considerably. This increase was seen more
in hydration references than in carbonation batches. The total solids
Fig. 5. TG curves of hydrated and carbonated PLC pastes were nevertheless still higher in carbonated than in hydrated PLCs.
Although water compensation in B11 made a significant contribu-
tion to strength gain at 28 days, the increase in hydration products
increased from about 800°C in hydrated PLC to over 820°C in car- was not proportional.
bonated PLC, indicating a higher crystallinity in these carbonation Percentage of CH and CaCO3 in PLC pastes was calculated
products. If this range is divided at a temperature of 720°C (Fig. 5), based on mass losses between 420–540°C and 540–950°C, respec-
the slopes in the mass loss curves appear to be horizontal in hy- tively. They are presented in Table 6. The CH content in PLC was
drated batches (B1, B2, B8 and B9) between 540–720°C, but be- significantly reduced right after carbonation (B3) and increased
come significantly steep in carbonated PLC. Since the well slightly in subsequent 28-day hydration (B10, B11). This result
crystalline natural calcite starts to decompose at 720°C (Fig. 3), was in agreement with pH changes (Table 4). The CaCO3 content
it is clear that the mass loss in carbonated PLC pastes in the temper- after carbonation was 39.9% (B3) and remained nearly the same in
ature range of 540–720°C is corresponding to poorly crystalline or subsequent hydration (B10 and B11). However, the CaCO3 content
amorphous calcium carbonates produced by 2-h carbonation. These in hydrated PLC was higher than that in as-received PLC. It was
amorphous carbonates could co-exist with crystalline carbonates 19.5% as an average for B1 and B2 versus 15.0% in as-received
and were imbedded in C-S-H to form an amorphous hybrid of PLC (Table 5). This phenomenon was also observed in CO2 content
calcium carbonates and calcium silicate hydrates. determined by the infrared carbon analyzer in Table 4. It was likely

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J. Mater. Civ. Eng., 2014, 26(1): 117-124


caused by atmospheric carbonation during the 18-h initial open air intensity with the increase of hydration and was converted to Q1 ,
curing. suggesting a C-S-H structure consisting mostly of dimer silicates.
This reduction of Q0 intensity was also observed in carbonated
PLC. However, in carbonated PLC, Q1 was not present. It was re-
Microstructure Change placed by Q2. Obviously, 2-h accelerated carbonation increased the
Typical SEM micrographs of the fractured surface of PLC pastes degree of silicate polymerization and its corresponding early
after 20 h of hydration (B1) and after 18 h of hydration and 2 h of strength. Since Q2 intensity was not strong after 2-h carbonation
carbonation (B3) are shown in Fig. 7. While hydrated PLC paste (B3), it implied that Si-ðOHÞ4 , once it was freed from calcium,
shows a typical hydration microstructure with C-S-H, ettringite and tended to form chains. This formation was interrupted by the re-
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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)

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J. Mater. Civ. Eng., 2014, 26(1): 117-124


PLC in the present study. The 20-h hydration strengths were com-
parable, at 38.1  1.8 MPa in PLC (B2) versus 35.8  2.6 MPa in
OPC. However, the 2-h carbonation strength after 18-h hydration
was higher in PLC, at 68.1  6.4 MPa in PLC (B3) versus 50.0 
5.4 MPa in OPC. After 28-day subsequent hydration, both hydra-
tion and carbonation strengths were statistically of the same order
of magnitude. The hydration reference (B9) had shown a strength
of 104.3  8.8 MPa in PLC and 97.2  5.9 MPa in OPC, while the
carbonation strength (B11) reached 111.6  13.4 MPa in PLC
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compared to 123.7  11.8 MPa in OPC. The main differences


in these two cements are that (1) 15% limestone was interground
with clinker in PLC and (2) the Blaine fineness was 500 m2 =kg in
PLC compared to 390 m2 =kg in OPC. The finer particle size in
PLC played a critical role in promoting higher carbonation reactiv-
ity and higher early strength gain. It was also believed that
limestone powder of 10–20 μm and finer served as a nucleus
for calcium carbonate precipitation.
It was noticed in Table 6 that the total CaCO3 was less in 28-day
hydrated pastes (B8 and B9) than in 20-h hydration (B1 and B2).
The phenomenon was also seen through the IR carbon contents in
Table 4. The reduction of CaCO3 in 28-day hydration was sugges-
tive that some portion of the CaCO3 in the as-received cement
was consumed during subsequent hydration. This confirms the re-
active nature of limestone added to cement to form calcium carbo-
silicate and calcium carboaluminate hydrates during hydration
(Kakali et al. 2000; Péra et al. 1999). However it was not observed
in carbonated PLC after subsequent hydration. Because of
Fig. 9. IR spectra of PLC pastes its strong carbonation and high CaCO3 content, the added lime-
stone became less hydraulically reactive in carbonated PLC in
subsequent hydration.
CaCO3 such as the carbon-oxygen (C-O) band were clearly
observed at 713, 875, and 1,430 cm−1 (Legodi et al. 2001). In
reference to the hydrated PLC (B1, B2, B8, B9), the C-O band Conclusions
became more intense in PLC after 2-h carbonation, as additional
calcium carbonate was produced (B3). The high intensity of the Accelerated carbonation behavior of PLC paste with 15%
C-O band remained in the carbonated PLC at 28-d (B10). In the interground limestone was examined to explore the feasibility of
carbonated PLC, a slight shift in the Si-O band from 975 cm−1 replacing OPC by PLC in carbonation curing of precast concrete
to 1,020 cm−1 was noticed. The wave number corresponding to products. The curing process included initial air curing, carbona-
the Si-O vibrational band was shifted toward a greater wavelength, tion curing, water compensation and subsequent hydration. The
which could be attributed to a higher degree of silicate polymeri- following conclusions are drawn:
zation (Mollah et al. 2000), confirming the NMR results. 1. PLC paste with 15% inter-ground limestone has shown high
carbonation reactivity. PLC paste can uptake 12% carbon di-
oxide based on dry cement mass in an accelerated carbonation
Discussion process and produce an early strength that is 79% higher than
that of hydrated PLC in 20 h. After 28 days subsequent
Accelerated carbonation of portland limestone cement produces a hydration, carbonated PLC pastes obtain a strength which
cement paste with up to 40% calcium carbonates. It exceeds the is comparable to that of hydrated PLC.
limestone limits set by European standard BS EN 197-1 (BSI 2. Although there is evidence of the presence of calcium carbo-
2000) which recognizes two limestone cements with 6–20% and nates produced by accelerated carbonation, the crystals are not
21–35% limestone. Previous research has shown that adding up to detectable by SEM. The higher early strength by accelerated
10% limestone powder to cement does not affect 28-day compres- carbonation is likely attributed to the formation of a hybrid
sive strength, while adding more than 10% up to 45% could lead to microstructure that intermingles calcium carbonates and CSH
a decreased strength (Dhir et al. 2007; Tsivilis et al. 1999, 2002). with a higher degree of silicate polymerization.
The present study shows that the presence of more than 40% cal- 3. Water compensation after initial air curing and accelerated
cium carbonate, which includes 15% limestone additive and 25% carbonation is crucial for PLC to develop comparable long
carbonation-induced CaCO3 , does not reduce the compressive term strength through subsequent hydration. Early carbonation
strength. The carbonation-induced CaCO3 is imbedded in C-S-H doesn’t hinder subsequent hydration.
to form a hybrid hydration-carbonation product. 4. Although the pH value of PLC on the surface is reduced
It is interesting to compare carbonation behavior of portland to 10.9 immediately after carbonation, the subsequent hydra-
limestone cement with OPC. The study on accelerated carbonation tion could however increase the value to 11.9. It is therefore
of OPC was reported elsewhere (Rostami et al. 2012b). Determined possible to perform accelerated carbonation as a fast curing
by the same mass gain method, CO2 uptake was 8.2% in carbon- regime for reinforced concrete production. For thicker con-
ated OPC paste subjected to exactly the same carbonation process. crete products, the pH will be higher at core than on the surface
This was significantly lower than the 12.1–12.9% in carbonated after carbonation.

JOURNAL OF MATERIALS IN CIVIL ENGINEERING © ASCE / JANUARY 2014 / 123

J. Mater. Civ. Eng., 2014, 26(1): 117-124


5. For accelerated carbonation of PLC cement and concrete, mass Heng, M., and Murata, K. (2004). “Aging of concrete buildings and
gain method is proven more efficient than traditional thermal determining the pH value on the surface of concrete by using a handy
analysis in determining calcium carbonate content produced semi-conductive pH-meter.” Anal. Sci., 20(7), 1087–1090.
by carbonation. The mass gain method is independent of Kakali, G., Tsivilis, S., Aggeli, E., and Bati, M. (2000). “Hydration
products of C3A, C3S and portland cement in the presence of CaCO3 .”
the initial carbon dioxide content, insensitive to atmospheric
Cem. Concr. Res., 30(7), 1073–1077.
carbonation during the process, and provides an average value Legodi, M. A., Waal, D., and Potgieter, J. H. (2001). “Quantitative deter-
throughout the entire batch. mination of CaCO3 in cement blends by FTIR.” Appl. Spectrosc., 55(3),
6. Portland limestone cement can effectively replace ordinary 361–365.
portland cement in accelerated carbonation for precast con- Mollah, M. Y. A., Yu, W., Schennach, R., and Cocke, D. L. (2000).
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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
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Rostami, V., Shao, Y., and Boyd, A. J. (2011). “Durability of concrete pipes
subjected to combined steam and carbonation curing.” Constr. Build.
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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.,
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