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NCPCM 2017 IOP Publishing
IOP Conf. Series: Materials Science and Engineering 338 (2018) 012007 doi:10.1088/1757-899X/338/1/012007
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Pore Structure Characterization in Concrete Prepared with

Carbonated Fly Ash

Sanjukta Sahoo*
Head, Department of Civil Engineering, KIIT Polytechnic, KIIT (Deemed to be
University), Bhubaneswar: 751024, Odisha, India
*E-mail: [email protected]

Abstract. Carbon dioxide capture and storage (CCS) is a technique to address the global
concern of continuously rising CO2 level in the atmosphere. Fly ash is considered as a suitable
medium for CCS due to presence of metal oxides. The fly ash which has already sequestered
carbon dioxide is referred to as carbonated fly ash. Recent research reveals better durability of
concretes using carbonated fly ash as part replacement of cement. In the present research pore
structure characterization of the carbonated fly ash concrete has been carried out. Mercury
Intrusion porosimetry test has been conducted on control concrete and concrete specimens
using fly ash and carbonated fly ash at replacement levels of 25% and 40%. The specimens
have been water cured for 28 days and 90 days. It is observed that porosity reduction rate is
more pronounced in carbonated fly ash concrete compared to control concrete at higher water
curing age. Correlation analysis is also carried out which indicates moderately linear
relationship between porosity % and pore distribution with particle size and water curing.

1. Introduction
Recently the CO2 concentration in atmosphere already crossed the value of 403.38 PPM [1] and is
projected to touch the value of 800 PPM by 21st century. The predicted consequences of rising CO2
level in the atmosphere include dramatic change in climate, leading to predictions of devastating
consequences for both human and biota [2]. This motivated the research world to think about a safe
and suitable strategy to mitigate the challenge. Strategies to reduce the CO2 content of atmosphere
include limiting the CO2 production, adopting fuels having less carbon, enhancing the use of alternate
energy sources [3, 4], utilising the produced CO2 in different fields and capturing and storing the CO2
safely through various technology. CCS (carbon capture and carbon storage) is one of the most
promising approaches to reduce the carbon dioxide (CO2) content in the atmosphere and thus the
greenhouse effect [5-7]. Mineral carbonation comes under the chemical storage of CO2, where both
carbon capture and carbon storage is being done by solid carbonation. It is one of the most promising
options for the permanent CO2 fixation by forming stable carbonate mineral such as calcite,
magnesite, siderite and dolomite etc. Fly ash (FA), the residue of coal power plant, has abundant
availability and toxic nature. Being a hazardous pollutant, it is a great threat to the society. This needs
safe disposal or productive reutilisation. FA after sequestering carbon dioxide is referred to as
carbonated FA. Recently researches undertaken by the author to utilize carbonated FA as part
replacement of cement in concrete have established the relevance of the cementitious nature exhibited
by the material. Research indicates better alkali, acid and sulphate resistance by concrete which uses
FA [8] and carbonated FA as part replacement of cement [9]. Porosity is one of the major parameters
of the concrete influencing its behaviour related to both strength and durability. Pore structure is one
of primary deciding factors for permeability [10] of the concrete, which influences the aggressive

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NCPCM 2017 IOP Publishing
IOP Conf. Series: Materials Science and Engineering 338 (2018) 012007 doi:10.1088/1757-899X/338/1/012007
1234567890‘’“”

ingress of deteriorating ions and thus may be used as a predictor of structural durability. Concrete has
a complex internal pore system. The capillary pores arising from cement particle spacing in the
dispersion, smaller gel pores in inter layers of the C-S-H or other hydrate products, air voids and
porous zone at aggregate cement interface [11] constitute the pore system.
The objective of the present research is to characterize the pore structure of carbonated FA concrete.
The characterization will include determination of porosity % and pores distribution. The objective
also includes finding the existence of correlation of these parameters with water curing age,
proportion of the FA and carbonated FA used in the concrete.
2. Experimental Program
In this research work three cementitious materials such as commercially available ordinary Portland
cement (43 grade as per IS: 8114-1978), low Calcium FA (ASTM Class F) from national thermal
power corporation (NTPC), Kaniha, Odisha and carbonated fly ash (CFA), prepared through mineral
carbonation of FA through atmospheric carbonation ([9], [12] ) are used. Crushed granite (20mm
maximum size) and river sand conforming to zone III of nominal maximum size of 4.75mm were
used as coarse aggregate and fine aggregate respectively in the concrete mixture. Commercially
available poly-carboxylic based super plasticizer and normal tap water was used in the experiment.
The specific gravities of cement, FA and CFA were found as 3.1, 2.33 and 2.31, respectively. Their
particle-size was analysed using Mastercizer-2000 (Malvern Instruments, Malvern, U.K.). Their
respective granulometric data are also reported in Table 1.
Table 1: Granulometric data for cement, fly ash, carbonated fly ash and their size fractions
Constituent D10 (µm) D50 (µm) D90 (µm) Mean size (µm)
Cement 1.860 8.939 31.946 16.79805
Fly Ash 0.719 5.914 24.714 13.09198
Carbonated fly ash 0.060 8.329 32.416 15.89338
The mix design calculations for M30 grade concrete were performed as per IS: 10262 (BIS 2009).
Total five types of concrete were prepared in the laboratory for investigation in accordance with IS:
516-1959. Control concrete (CC) was made using 100% cement as binding material and two set (Low
and High) of fly ash concrete (LFC and HFC) as well as carbonated fly ash concrete (LCFC and
HCFC) were cast using FA and CFA at cement replacement level of 25% and 40%, respectively. A
constant water/ binder ratio of 0.38 with slump value of around 100 mm was used in the experiment.
The total 24 numbers of concrete cubes (150 mm) from each type were cast to perform the
compressive strength, durability and pore structure characterisation test. After 24 h, they were
removed from the mould and kept in the water curing chamber for curing period of 28 and 90 days.
To conduct the compressive strength test of the concrete six numbers of cubes from each type were
taken out of the curing chamber and dried in shade at the end of 28 and 90 days of water curing. The
test was carried out in a compressive testing machine of 2000KN capacity (CTM Digital) in the
concrete laboratory of SCE, KIIT University at the loading rate of 0.2-0.4 N/mm2/s. To determine the
durability characteristics of the concrete against chemical attack, each type of concrete cubes were
allowed to immerse in three chemicals such as 5% Sodium chloride, 5% Sodium sulphate, and 1%
Sulphuric acid at the end of 28 and 90 days of water curing. After 120 days of chemical curing the
compressive strength of the concrete were measured following the similar procedure. The
compressive strength value was considered as the average of strength value of three samples. For the
pore structure characterisation, slices of 8 mm and 2mm thickness concrete specimens have been
obtained from the core of the 28 and 90 days water cured concrete cube. The specimens were
immersed in ethyl alcohol for eight days and dried in oven at 600C for mercury intrusion porosimeter
(MIP) test by Quantachrome Poremaster.
3. Experimental Results
3.1 Particle size distribution:
From the granulometric data along with their size fractions as presented in Table 1 it is observed that
the D90 and D50 values of all the samples are ranging between 24.741µm - 32.416µm and 5.914µm -

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NCPCM 2017 IOP Publishing
IOP Conf. Series: Materials Science and Engineering 338 (2018) 012007 doi:10.1088/1757-899X/338/1/012007
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8.939µm, respectively, hence all the samples have the capacity of adequate hydration as all have the
mean particle size less than 45µm [13, 14]. Both the FA and carbonated FA have finer particles than
the cement [15] and the smaller particles add to fineness and strength on hydration as the pozzolanic
reaction can be highly activated when the particle size is small.
3.2 Compressive strength of concrete under normal water and chemicals:
As presented in the Table 2, the compressive strength value for CFC though less for 28 days water
curing, but with increasing water curing period it behaved in a better manner showing significant
higher strength value. Further, it displayed best resistance to chemicals for both the water curing ages.
Though CC performed better in initial ages, but both the FA and CFC have shown much higher
resistance to chemicals compared to that of CC. This is due to the filling of smaller size pores, voids
and air spaces of cement particles by the FA and carbonated FA. This results in packing of the
concrete material tightly, restricting the permeation of harmful ions.
3.3 Mercury intrusion porosimetry (MIP) test:
From MIP test information on several parameters related to porosity are obtained. These parameters
include total intrusion volume, total pore area, median pore radius, average pore radius, bulk density,
apparent skeletal density and porosity %. The porosity % and pore size distribution are two critically
studied factors which influence utility aspects of concrete specimens in structural usages. Information
retrieved relating to these important parameters are tabulated in Table 2. Figure 1 and Figure 2
represent the histogram of total intrusion volume and porosity percentage in concrete specimens for
28 and 90 days of water curing period, respectively. The intrusion volume vs pore diameter plots from
the machine generated data for concrete specimen water cured for 28 and 90 days have been furnished
in Figure 3 and Figure 4, respectively. The pore percentage distribution in three major influencing
zones for concrete specimen water cured for 28 and 90 days have been tabulated in Table 3. Figure 6
illustrates the pore percentage distribution of concrete specimens over volume, water cured for period
of 28 and 90 days.
Table 2. Test results for concrete specimen water cured for 28 and 90 days
Compres Compressive strength under
Water strength chemical attack for 120 MIP Test Results
curing Type (MPa) days (MPa)
period of Salt Sulphate Acid Total Total
in concrete intrusion pore Bulk
days volume area density Porosity
(ml/g) (sqm/g) (gm/cc) %
CC 43.62 32.35 30.89 25.99 0.0673 7.627 1.981 13.332
LFC 39.9 34.18 34.01 28.03 0.052 6.568 1.892 9.838
28 HFC 38.76 25.4 24.85 22.8 0.05 4.509 1.796 8.98
LCFC 31.96 23.98 33.82 30.51 0.052 4.505 1.924 10.158
HCFC 25.45 20.61 26.77 26.56 0.068 7.162 1.822 12.480
CC 49.36 35.94 31.41 35.64 0.0646 6.427 1.972 12.739
LFC 51.62 47.79 40.4 43.38 0.0405 3.254 1.861 7.537
90 HFC 52.01 50.07 47.23 47.39 0.0430 3.868 1.794 7.714
LCFC 42.88 39.04 51.01 44.12 0.0420 4.642 1.931 8.110
HCFC 38.92 35.88 44.4 43.02 0.0431 3.230 1.826 7.870
4. Discussion on MIP test results
4.1 Variation of total intruded volume and porosity %:
It can be observed from Figure 2, that FC show the best performance followed by CFC at 28 days
water curing. HCFC show the highest cumulative intruded pore volume percentage as almost
approaching 70%. A decrease in total intrusion volume has been observed for all the concrete
specimens with increasing water curing age, the decrease of intrusion volume in CC is much low, thus

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NCPCM 2017 IOP Publishing
IOP Conf. Series: Materials Science and Engineering 338 (2018) 012007 doi:10.1088/1757-899X/338/1/012007
1234567890‘’“”

indicating almost a slow release of hydrate products during 28 to 90 days water curing. However, in
FC and CFC the difference in the intrusion volume is appreciably larger compared to CC. The CFC
display the best performance with a higher degree release of hydrate products compared to all other
concrete. This indicates accelerated chemical transition, formation and deposition of the extra
hydrated product within this curing period those are responsible for densification of the CFC and FC
specimens in a faster rate.

Figure 1. Histogram of total intrusion volume in concrete Figure 2. Histogram of porosity % in concrete specimens
specimens

Figure 3. Cumulative intruded volume vs pore diameter Figure 4. Cumulative intruded volume vs pore diameter for
for concrete specimen water cured for 28 days concrete specimen water cured for 90 day
From Figure 3, it can be inferred that for specimens water cured for 28 days, CC displayed the highest
porosity % followed by the HCFC, LCFC and LFC, the HFC being the lowest. Low porosity
associated with FC may be explained in light of denser pore structure arising from low particle size
and secondary hydration of FA. With the FA addition to the cement, physically it serves as the
nucleation sites for the cement hydration products. Thus, it helps the cement grain to achieve a higher
degree of hydration. In addition, chemically FA particles also undergo the hydration process
(pozzolanic reaction) in presence of water and Ca(OH)2 thus giving the extra C-S-H gel. Due to these
dual effects of FA, the extra gel formed helps in increasing the solid volume of the cement paste and
adds extra solids to the concrete material. These extra solid deposited in the pore space filling the
capillary pores and thus the making the microstructure packed and dense [16]. An improvement in
porosity through decrease in porosity % is also noticed with increase in curing period. It is seen that
the CFC performs in a better way to reduce its porosity % with water curing age in comparison to that
of FA concrete and the CC. This is due to the continuous and gradual increase of hydration rate with
time thus developing the microstructure more and more with the global refinement of continuous
pores filling. In case of CFC along with the extra hydration products, the calcite (CaCO3) present in
carbonated FA, additionally fill the micro pores of the material helping dense packing of the
microstructures in a higher degree.

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NCPCM 2017 IOP Publishing
IOP Conf. Series: Materials Science and Engineering 338 (2018) 012007 doi:10.1088/1757-899X/338/1/012007
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Figure 5. Pore % distribution for concrete specimen water cured for period of 28 days
4.2 Pore size distribution:
As observed from Figure 3 to Figure 5 the 28 days water cured samples, with respect to the pores in
the size range from 0 to 106 nm, HCFC has the highest proportion followed by LFC, CC, LCFC and
HFC. Regarding the pores in the size range of 107 to 1051 nm, HFC leads followed by LCFC, LFC,
CC and HCFC. For the pore diameter > 1051 nm, HCFC has the highest proportion and LCFC, the
lowest. With increase in water curing period, it is observed that pore % in larger size is also higher in
CC and CFC, when compared to the FC specimens. For CC and LFC, the percentage of macro pores
(107 to 1051 nm) only, increased whereas for all other concrete it decreased whereas for the mega
pores of pore diameter > 1051nm, in FC only it has decreased. It is also noted that the micro pores %
increases with water curing days with a faster rate in case of HFC and LCFC, and its rate is lowest for
the CC. The percent of mega pores for CC also increases but for FC it is greatly reduced with curing
period. It indicates the fine pores filling in case of CC is the slowest and for HFC it is the highest. It
can be inferred that inclusion of FA lead to the densification of pore structure of the concrete.
Table 3. % distribution of pores in concrete specimen water cured for 28 and 90 days
Range of 28 days Water Curing 90 days water curing
Pore sizes CC LFC HFC LCFC HCFC CC LFC HFC LCFC HCFC
0-106 nm 67.16 67.31 62 64.02 67.88 65.94 67.9 67.44 69.05 69.84
107-1051nm 25.37 26.92 34 32.2 23.36 26.32 29.88 30.23 23.81 20.88
>1051 nm 7.47 5.77 4 3.78 8.76 7.74 2.22 2.33 7.14 9.28
5. Correlation Analysis
To determine the existence and significance of a linear relation between dependent and independent
variable, the correlation analysis is performed and a relationship between volume fraction, water
curing age and porosity parameters related to the various concrete is obtained. The volume fraction
denotes the ratio of volume of cementitious materials to the volume of cement in concrete specimens
without any replacement. The concrete specimens prepared constitute of cement, FA and carbonated
FA as cementitious materials. Assuming spherical shape of the particle, the volume of the particles
can be computed using the Eqs. 1-3. Vi is the volume of any cementitious particle, whose radius is ri,
xi is the proportion of the cementitious particle in terms of percentage and rc is the mean particle size
of the OPC 43. VF   xiVi Vc ; where, Vi  4 3 ri 3 and Vc  100  4 3 rc 3 (1)
The Pearson product moment correlation coefficient (PCC) between two parameters is calculated as
ratio of the covariance to the product of standard deviations of the two variables. The PCC of porosity
% with respect to the water curing age and volume fraction is provided in Table. 4
Table 4. Pearson Correlation coefficient for porosity % with Volume fraction and Water Curing Age
Volume fraction Water curing age Porosity %
Volume fraction 1
Water curing age -9.59215E-18 1
Porosity % 0.616162478 -0.509437784 1

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NCPCM 2017 IOP Publishing
IOP Conf. Series: Materials Science and Engineering 338 (2018) 012007 doi:10.1088/1757-899X/338/1/012007
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The above table indicates a moderately positive correlation between volume fraction and porosity %
and thus, an increase in volume fraction will result in higher porosity %. This clearly establishes that,
the replacement of cement with smaller particles of FA or carbonated FA will reduce the porosity %
in concrete specimen thus will reduce the permeability. Reduction in permeability results in improved
resistance against the chemical attack. The experimental results of reduced strength loss in FC and
CFC against acid, sulphate and chloride attack are set of the evidences. Table 5 offers the PCC
relating the volume fraction and water curing age with the distribution of pore sizes. The data offer a
moderate positive correlation between volume fraction and the pore % at higher size. The distribution
is more towards higher size pores at higher volume fraction i.e. in CC. Similarly, water curing age has
a moderate positive correlation with the pore size distribution favouring to smaller pores.
Table 5. Pearson correlation coefficients for pores distribution to water curing age and volume fraction
Volume fraction Water curing age
Volume fraction 1
Water curing age -9.59215E-18 1
Pore distribution 0-106 nm 0.290566975 0.533294782
Pore distribution 107-1051 nm -0.586587493 -0.270035599
Pore distribution >1051 nm 0.681325048 -0.043190589
6. Conclusion
The conclusions drawn from the porosity test performed on the concrete specimens are outlined in the
following lines. The porosity percentage at 28 days of water curing is the least for the high FC and the
highest for the control concrete. However, at 90 days of water curing the porosity % remained high
for control concrete whereas both the FC and CFC show almost nearly equal value with very low
porosity %. With water curing age, the porosity of control concrete slightly decreased whereas the rate
of decrease in case of FC was found medium and for CFC was the fastest. This may be predicted due
to the high rate of hydration in case of CFC and FC in the later water curing age. Further, with water
curing age the total intrusion pore volume decreases at high rate in case of CFC than that of FC and
CC. The Pore distribution in CFC and FC tends to be more in the finer zone (<106nm) compared to
those in control concrete. From the correlation analysis, it was concluded that a moderately positive
linearity exists between volume fraction and porosity % and a moderately negative linearity exists
between water curing period and porosity %.
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