Construction and Building Materials 291 (2021) 123363

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Construction and Building Materials

journal homepage: www.elsevier.com/locate/conbuildmat

Carbon sequestration in cementitious composites using biochar and fly

ash – Effect on mechanical and durability properties
Souradeep Gupta, Alireza Kashani, Aziz Hasan Mahmood, Tianhao Han
School of Civil and Environmental Engineering, The University of New South Wales, Sydney, Oval Ln, Kingsford, NSW 2032, Australia

h i g h l i g h t s g r a p h i c a l a b s t r a c t

Biochar enhances carbon

sequestration through mineralization
in cementitious mixes.

Higher strength than control is
maintained in biochar-added mortar
after carbonation.

Chemical contaminants in biochar
can increase drying shrinkage.

Biochar addition to fly ash-mix
reduces water absorption and
chemical shrinkage due to
carbonation.

a r t i c l e i n f o a b s t r a c t

Article history: A possible reduction in high CO2 emission associated with cement production can be achieved by seques-
Received 26 January 2021 tering CO2 as carbonate mineral in hydrated cement matrix. This study aims to investigate application of
Received in revised form 8 April 2021 biochar and its combination with fly ash to improve CO2 uptake and carbonate mineralization in cement
Accepted 12 April 2021
mortar. Effect of fly ash and biochar, from waste peanut shell, on carbonate mineralization, strength, per-
Available online 3 May 2021
meability and shrinkage of mortar are investigated. Experimental findings show that combination of bio-
char and fly ash, used to replace 23% of cement by mass, enhances carbon sequestration through
Keywords:
mineralization by 7–13 % (by weight of cement) than control. Biochar addition at 3% contributes to higher
Biochar
Carbonation
carbon sequestration than plain mortar, while improving strength and reducing capillary water absorp-
Cement tion. Although relatively high content of sodium (42%) and potassium (8%) in the produced biochar lead
Shrinkage to 39% higher drying shrinkage than control, addition of biochar reduces the chemical shrinkage associ-
Carbon sequestration ated with only carbonation reaction by 30–60%. 23–25% of carbonation shrinkage in biochar-mortar can
be recovered through 4–7 days of rewetting. Overall, the research suggests a strong possibility of devel-
oping low carbon building materials using biochar as supplementary admixture, while offering improved
mechanical and durability performance.
Ó 2021 Elsevier Ltd. All rights reserved.

1. Introduction (for example, limestone) at high temperature to produce clinker,

leading to release of carbon dioxide (CO2) to the environment.
Cement consumption has increased significantly in the last cen- CO2 released during cement manufacturing contributes to 5–7%
tury with rapid rise in urbanization and increase in built-up areas. of global anthropogenic CO2 emission depending on boundary con-
Cement manufacturing involves calcination of carbonate minerals ditions [1,2]. Therefore, strategies to mitigate net CO2 emission

https://doi.org/10.1016/j.conbuildmat.2021.123363
0950-0618/Ó 2021 Elsevier Ltd. All rights reserved.
S. Gupta, A. Kashani, Aziz Hasan Mahmood et al.
associated with production of cement and concrete must be con-
sidered for sustainability of this industry in long term.
Accelerated carbonation curing (ACC) is a potential way to
reduce net emission by capturing CO2 and storing it in mineral
form (carbonates) in the cementitious matrix. Portland cement-
based materials present a viable means of capturing and sequester-
ing carbon dioxide emitted from different industrial sources
through ACC [3]. ACC involves exposing cementitious building
materials to relatively high level of CO2 (up to 20%), which reacts
with unhydrated components (i.e. calcium disilicate and calcium
trisilicate) and hydration products leading to formation of stable
carbonates in the matrix [4]. Carbonation initiates with dissolution
of CO2 in the pore solution resulting in formation of carbonic acid
and reduced pH of the pore solution. Hydration products including
calcium hydroxide (Ca(OH)2), commonly referred to as ‘‘CH”) and
calcium silicate hydrates (C-S-H) react with carbonic acid to form
calcium carbonate [5]. The reaction pathways are shown in Eqs.
(1)–(3). Although diffusion of CO2 is high in gas-filled pores, mois-
ture is necessary for the carbonation of CH [6].
CO2 + H2 O !H2 CO3 ð1Þ
Ca(OH)2 + H2 CO3 !CaCO3 + 2H2 O ð2Þ
C-S-H + H2 CO3 ! SiO2 + 2CaCO3 + H2 O ð3Þ
However, carbon sequestration through ACC is effective only
when the cementitious building materials are exposed to CO2 at
early age because substantial diffusion can take place through
the pores in cementitious matrix [4]. In case of matured matrix,
diffusion of CO2 is limited only to the top layer, and may cause high
shrinkage and restrained cracking [7]. It shall be noted that the
process of ACC can only be applicable to prefabricated units and
unreinforced cement-based materials, for instance, façade panels,
drain channels, road kerbs etc. This process can be detrimental to
steel reinforced concrete because lowering of pH during carbona-
tion may damage the passive layer on steel bars, thus triggering
corrosion [8].
Effect of carbonation and carbonate mineralization of cementi-
tious composites depend on its composition, which influence the
mechanical properties, diffusion of CO2 and amount of hydration
products that may carbonate during ACC. Rostami et al. [4,9] inves-
tigated effect of carbonation curing at early stage (18 h from mix-
ing) for only 2 h on compressive strength development of cement
paste. The authors reported 30% improvement in strength at
28 days compared to control paste subject to air curing. Carbon
dioxide uptake determined by change in weight was 7.3% of the
mass of cement paste. Souto-Martinez [10] highlighted that addi-
tion of pozzolanic admixtures may reduce the amount of calcium
hydroxide in hydrated pastes, which may result in 20–60% reduc-
tion in carbon sequestration potential of Ordinary Portland Cement
(OPC) concrete. However, Papadakis [11] reported that addition of
pozzolanic admixtures including silica fume and fly ash respec-
tively at 10% and 20% by weight of cement increased the rate of
carbonation and carbonation depth compared to control (without
admixture). This is attributed to simultaneous carbonation of cal-
cium hydroxide and calcium silicate hydrate in cementitious com-
posites with pozzolans [11]. Furthermore, due to porous nature of
fly ash, diffusion of CO2 may increase leading to higher rate of car-
bonate mineralization. Reducing cement demand by 20% using fly
ash can lead to reduction in CO2 emission by at least 300 million
tonnes per year [12].
One of the potential means to enhance carbon sequestration
potential of cementitious composites is by adding biochar, pro-
duced by pyrolysis of waste biomass. Biochar has been widely
explored as an excellent adsorbent of CO2 due to polar groups on
2
Construction and Building Materials 291 (2021) 123363
its surface and high micro-pore surface area [13–15]. Gupta et al.
[16] and Dixit et al. [17] found that addition of biochar to cement
mortar generate more hydration products, that may increase the
carbonate mineralization sites in biochar-cementitious compos-
ites. Similar findings were reported by Wang et al. [18] – addition
of 2% wood biochar led to slight increase in total hydration, evident
from higher heat of hydration after 48 h from mixing. The micro-
porous channels in biochar may also provide the diffusion pathway
for CO2 into the cementitious matrix, thus increasing rate of car-
bonation during ACC. Biochar has been extensively explored as
supplementary cementitious admixture by several researchers,
and findings suggest that addition of biochar at 1–5% by weight
of cement can lead to improvement in compressive strength and
durability [16,19,20].
Addition of biochar has substantial environmental benefits. The
carbon ‘‘locked in” the chemical structure of biomass is seques-
tered in the produced biochar during pyrolysis, which otherwise
would be released to the environment during incineration or nat-
ural decay of biomass in landfills [21]. Depending on feedstock
and preparation conditions, carbon sequestered in the biochar
can contribute to reduction in greenhouse gas emission by 535–
570 kg CO2-eq [21]. Application of biochar as a construction mate-
rial is also an effective means of utilizing waste biomass. For exam-
ple, about 72 million tonnes of food waste is annually generated in
Australia and India [22,23]. One of the major contributors to this
food wastage is the nut production and processing industry. Aus-
tralia and India annually produce 8 million tonnes of peanut
[24]. The peanut hull weighs about 20–25% of the total weight,
indicating a waste generation of 1.5–2 million tonnes annually
from this industry alone. Processing and pyrolyzing of peanut hull
to make biochar and applying it as a cementitious admixture can
increase sustainability of cement-based materials and offer high-
volume recycling of this biomass waste.
Prolonged exposure to CO2 starting at initial stage will increase
diffusion of CO2 through pore channels, that may enhance carbon
sequestration capacity of biochar-cement composites. Despite ben-
efits of using biochar and fly ash as construction materials, there is
a dearth of systematic investigation into their influence on carbon-
ate mineralization during prolonged exposure to CO2 (7 days and
28 days) and its effect on strength, permeability and shrinkage of
Portland cement – mortar. Application of biochar and fly ash in
manufacturing of prefabricated blocks are gaining industry inter-
ests; thus, understanding the effect of carbon sequestration on
the mechanical and durability properties of cementitious compos-
ites with these materials would boost confidence in their perfor-
mance and open up a new direction for developing low carbon
building materials. To the best of authors’ knowledge, this is the
first holistic assessment of carbon sequestration and its impact
on physical properties of biochar-mortar and biochar-fly ash mor-
tar. Adding biochar and biochar-fly ash combination would induce
different physical and chemical effects on hydration, which influ-
ence the diffusion kinetics and capture of CO2 in the form of cal-
cium carbonate. Therefore, this study aims to quantify and
compare the rate of carbon dioxide uptake and carbonate mineral-
ization in mortar with biochar and biochar-fly ash. Effect of carbon
uptake on shrinkage, mechanical strength, porosity and rate of
water absorption are also assessed and discussed.
2. Materials, mix proportions and methods
2.1. Materials
2.1.1. Cement, fly ash and sand used
Portland cement (also called general purpose (GP) cement in
Australia), conforming to AS 3972 [25] is used in this study. The
S. Gupta, A. Kashani, Aziz Hasan Mahmood et al. Construction and Building Materials 291 (2021) 123363

used cement contains a proprietary blend of Ordinary Portland
cement and limestone, up to maximum 12% by weight of the clin-
ker [26]. The composition and physical properties of the cement
are presented in Table 1. The X-ray diffractogram of the cement
is presented in Fig. S1a (supplementary information), showing
peaks of alite, belite and calcite present in the clinker compounds.
Sydney sand with specific gravity of 2.65 and water absorption of
3.8–4% is used as fine aggregates. The sand contains 95.90% silica,
3% alumina and trace amount of calcium carbonate and iron oxide.
The loss on ignition (L.O.I) of the sand is 1.10%. Class F fly ash with
silica content of 66% is used (Table 1). X-ray diffractogram of the fly
ash, presented in Fig. S1b (supplementary info) shows the domi-
nant presence of quartz and mullite, typical of fly ash from coal-
based power plants [27]. This means a fraction of the silica in fly
ash is crystalline, which might lead to low rate of pozzolanic reac-
tion at early stage, especially under dry curing conditions.
2.1.2. Preparation of biochar
Biochar is produced from unwashed hull of processed peanut
collected from a local food and beverage industry in Sydney. The
hull is broken into smaller particles before pyrolysis. The pyrolysis
is carried out in a muffled furnace with a specially designed venti-
lation system to allow for smooth escape of the organic vapours
and volatiles. The peanut hull is placed in aluminium tray and
the temperature in the furnace is ramped up at 10 °C/min from
room temperature (23–25 °C) until it reaches 500 °C. The pyrolysis
temperature is selected based on the decomposition temperature
of hemicellulose and cellulosic components in the biomass. Cellu-
lose and hemicellulose are sources of sugars including sucrose and
glucose, which leads to retardation of hydration and slow strength
development. Furthermore, some of these sugars have strong cal-
cium chelating groups, which can slow down the formation of bin-
der gel (calcium silicate hydrates) [28]. Hemicellulose decomposes
in the temperature range of 220–315 °C, while cellulose and part of
lignin decompose between 300 and 500 °C into organic vapours
and non-condensable gases [29]. The pyrolysis is conducted for
1 h at steady state temperature of 500 °C. The produced biochar
is then taken out from the furnace and immediately covered with
aluminium sheets to allow cooling and prevent oxidation on the
surface.
The produced biochar is ground into finer particles using agate
balls in a planetary ball mill with biochar to ball ratio of 1:70 by
mass. The grinding process is carried out for 15 min at 300 rpm,
comprising of clockwise and anticlockwise motion.
2.2. Mix proportions and curing methods
Five mixes are investigated in this study. The proportion of
components are shown in Table 2. The control mortar comprises
of cement, sand and water in the ratio of 1:2.50:0.50. The produced
biochar is added at 1% (BC1) and 3% (BC3) by weight of cement. Fly
ash is used to replace 20% by weight of cement (FA20) with water
to binder ratio maintained at 0.50. However, due to reduction in
cement content by 20% the dilution is higher in FA20 compared
to biochar-mortar, leading to water-cement ratio of 0.63. Combina-
tion of biochar and fly ash is also investigated (FA20BC3), where
20% fly ash is combined with 3% biochar to replace 23% of cement.
Representative cement paste samples corresponding to each
mortar mix are used for quantification of calcium carbonate, cal-
cium hydroxide and degree of hydration. Paste samples are used
to avoid the dilution effect of sand on precise determination of
hydration phases. The paste samples comprise of cement, biochar
and fly ash at same proportions as the mortar mixtures. The
water-binder ratio (w/b) for the paste samples is 0.40, taking into
account the water absorption of the sand (4% in this case). The
paste samples are denoted with suffix ‘‘-CP” (for example, PCP
(control), BC1-CP, BC3-CP, FA20-CP and FA20BC3-CP).
All samples are tightly sealed with polythene sheets and stored
at constant temperature of 23 °C for first 23–24 h after casting. This
is to prevent evaporative moisture loss and ensure that all the sam-
ples are under similar moisture state during the initial hardening
period. After demolding (at 1-day age), part of the samples are sub-
ject to water curing (referred by ‘WC’), while the rest are immedi-
ately stored in carbonation chamber, maintained at 1% CO2 (100%
purity) supplied at 0.20 MPa (2 bar), 23 °C temperature and 55%
relative humidity (referred by ‘CC’). The samples are exposed to
CO2 for continuous period until the time of testing (for example,
after 6 days and 27 days of carbonation, which correspond to 7 days
and 28 days age of mortar from the time of casting). The exposure
concentration of CO2 is selected based on the duration of exposure
(6 days and 27 days) and the effect of elevated CO2 concentration

Table 1
Proportion of components in the studied mortar mixes.

Mix code Mix description Cement Sand Fly ash Biochar Water Water-binder ratio Water-Cement ratio
(g) (g) (g) (g) (g) (w/b) (w/c)
Plain mortar Control mortar with only cement and sand 100 250 0 0 50 0.50 0.50
(control)
BC 1 Mortar with 1% biochar by weight of cement 99 250 0 1 50 0.51
BC 3 Mortar with 3% biochar by weight of cement 97 250 0 3 50 0.52
FA20 Mortar with 20% fly ash by weight of cement 80 250 20 0 50 0.63
FA20BC3 Mortar with 20% fly ash and 3% biochar by 77 250 20 3 50 0.65
weight of cement

Table 2
Proportion of components in the studied mortar mixes.

Mix code Mix description Cement Sand Fly ash Biochar Water Water-binder Water-Cement ratio
(g) (g) (g) (g) (g) ratio (W/C)
Plain mortar Control mortar with only cement and sand 100 250 0 0 50 0.50 0.50
(control)
BC 1 Mortar with 1% biochar by weight of cement 99 250 0 1 50 0.51
BC 3 Mortar with 3% biochar by weight of cement 97 250 0 3 50 0.52
FA20 Mortar with 20% fly ash by weight of cement 80 250 20 0 50 0.63
FA20BC3 Mortar with 20% fly ash and 3% biochar by weight 77 250 20 3 50 0.65
of cement

3
S. Gupta, A. Kashani, Aziz Hasan Mahmood et al.
on the stability of binder gel. For example, Castellote et al. [30]
reported complete decomposition of C-S-H after exposure to 10%
CO2 for 103 days, which can lead to drastic loss in mechanical
properties of cement-based composites. Findings show that CO2
concentration up to 3% would mimic the natural carbonation pro-
cess, maintain structural integrity and does not affect relative car-
bonation resistance of normal cement-based composites and those
containing siliceous admixtures (for example, fly ash and silica
fume) [30,31]. Similar to carbonation curing, mortar samples are
cured in water for 6 days and 27 days from the time of demolding.
Investigation into shrinkage is carried out under two exposure
conditions – (i) drying shrinkage where mortar samples are
allowed to dry at constant temperature and humidity conditions
(23 °C and 55% RH), and (ii) carbonation curing in chamber main-
tained at the previously mentioned conditions.
2.3. Test methods
2.3.1. Characterization of biochar
Scanning electron microscope (SEM) imaging is used to investi-
gate the morphology of the prepared biochar particles. Biochar par-
ticles are coated with platinum using sputter coater, and the
imaging is conducted at 20 kV potential.
Stability of biochar is generally estimated from the molar ratio
of oxygen to carbon (O:C) and hydrogen to carbon (H:C) [32]. The
carbon content of biochar is determined using Carbon-Hydrogen-
Nitrogen-Sulfur (CHNS) analysis using elemental analyser (Vario
MicroCube). The oxide composition of biochar, including oxides
of calcium, sodium, silicon, potassium, aluminium, sulfur and mag-
nesium and those of heavy metals, are investigated using X-ray flu-
orescence (XRF). Details on the method are provided in
supplementary information (section 1). Particle size distribution
and external surface area of biochar, fly ash and cement are deter-
mined using laser diffraction analysis. External surface area for bio-
char, cement and fly ash are determined based on their respective
specific gravities  600 kg/m3, 3150 kg/m3 and 2300 kg/m3 respec-
tively. The surface area of biochar and fly ash calculated by this
technique is compared to surface area determined by nitrogen
adsorption.
Pores of biochar and fly ash play important role in moisture
redistribution, diffusion of CO2 and hydration of biochar-cement
composites [33]. Median pore size, total porosity and permeability
in the meso to macro-porous range of the produced biochar are
investigated by mercury intrusion porosimetry (MIP, AutoPore IV
9500). The external surface area, pore surface area and pore vol-
ume of the fly ash and biochar in the meso-porous range
(<100 nm) are determined based on nitrogen adsorption isotherm.
The powders are degassed at 80 °C for 8 h prior to analysis.
pH of bio-based fillers influence cement hydration and stability
of cementitious mixes [34]. Addition of biochar must not signifi-
cantly reduce pH of the pore solution during hydration of cement
paste. In order to simulate pore solution, slurry comprising of
20 g of cement with 200 g water (pH ~ 6.70) (1:10 by weight) is
mixed at room temperature (23 °C). The prepared mix is allowed
to rest for 24 h before obtaining the filtrate using a pre-wetted fil-
ter paper. The water-cement ratio of the slurry is designed in
accordance with Snoeck et al. [35,36], in order to maintain a pH
of at least 12 after 24 h [35] and extract sufficient filtrate for pH
testing. Similarly, 10 g of biochar is mixed with 100 g of water
(pH ~ 6.70) and the filtrate is obtained after 24 h. In case of
biochar-cement combination, 3% of cement by weight is replaced
by biochar (19.40 g cement and 0.60 g biochar) and mixed with
water in the ratio 1:10 for obtaining the filtrate. pH measurement
is conducted using pH meter at room temperature (23 °C).
Carbon dioxide capturing capacity of biochar is determined
using thermogravimetry analysis (TGA). 5 g of produced biochar
4
Construction and Building Materials 291 (2021) 123363
is stored in carbonation chamber for 28 days to allow adsorption
of CO2 in the biochar pores. Thereafter, 30 mg of biochar is subject
to TGA in the temperature range of 25 °C to 1000 °C under nitrogen
purge (50 mL/minute). The mass loss is compared to that of as-
produced biochar (not exposed to CO2) to calculate the CO2 adsorp-
tion capacity (mmol/g of biochar), A using Eq. (4)
M BC;CO2  M BC
A¼ ð4Þ
Minitial x MLCO2
Where, MBC;CO2 and MBC are the mass loss (mg) of CO2-saturated bio-
char and as-produced biochar at 1000 °C respectively. Minitial is the
initial mass (mg) of as-produced biochar). MLCO2 is the molecular
weight of carbon dioxide (44 g).
2.3.2. Characterization of mortar samples
Strength of mortar samples at 7th and 28th day subject to wet
(WC) and CO2 curing (CC) are tested using a load controlled set-up
according to ASTM C109 [37]. 50 mm cube samples are used. The
surface of wet samples are wiped with a towel before compression.
For each curing condition, 3 to 4 samples per mix are tested.
Drying (air), carbonation and sealed shrinkages of mortar bars
are tested according to ASTM C596 [38]. Three samples per mix
are tested for each exposure condition. Shrinkage of samples over
eleven-week (77 days) period are recorded. Thereafter, the samples
are stored in water for 7 days to monitor the recovery of drying and
carbonation shrinkage.
Capillary absorption and water accessible porosity of mortar
samples subject to WC and CC are tested at 28 days according to
ASTM C1403 [39]. The detailed procedure is stated in section 2 of
supplementary information. Water accessible porosity, P wa ð%Þ, is
calculated according to Eq. (5)
mssd  mOD
Pwa ð%Þ ¼ x100 ð5Þ
mssd  mI
Where, mssd , mOD , mI are saturated surface dry mass, oven dry mass
and water-immersed mass of mortar samples respectively. All the
tests are carried out in triplicates (n = 3). Statistical significance
between results due to difference in treatment (biochar dosage or
curing condition) is calculated based on p-value from t-test at 95%
confidence interval (pcritical = 0.05).
Depth of carbonation in carbonated samples are determined
after 28 days of carbonation using 40  40  160 mm3 prism.
The prisms are broken into halves using centre-point loading over
a span of 100 mm. Phenolphthalein solution is sprayed over the
broken faces and the change in colour is observed for next 2–
3 min. Then the maximum depth of carbonation front is measured
from each of the four edges of the samples and the average and the
standard deviation are then calculated. Two samples are tested for
each mix.
Microscopic analysis of the mortar samples after carbonation is
carried out using scanning electron micrography. The samples are
collected by wet cutting from the top 4–5 mm of the mortar sam-
ples. The samples were pasted on carbon tape and coated with
platinum before imaging.
2.3.3. Degree of hydration and carbon dioxide mineralization potential
Thermogravimetry analysis (TGA) is used to quantify the chem-
ically bound water, degree of hydration and carbonation products
in both sealed and CO2 exposed samples at 7-day and 28-day
age. 35–40 mg of powder paste from top 4 mm (minimum depth
of carbonation) of 50 mm cube samples is used for
thermogravimetry.
Decomposition of carbonated products, more particularly poly-
morphs of calcium carbonate (CaCO3), in the temperature range of
550 °C–1000 °C can be used to quantify the CO2 mineralization
S. Gupta, A. Kashani, Aziz Hasan Mahmood et al. Construction and Building Materials 291 (2021) 123363

potential of carbonated cementitious composites [4,40,41]. This Table 3

can be quantified using Eq. (6) [4] CHNS composition of biochar.

CHNS composition % by mass

2:27  ðM 550  M 1000 Þ
CaCO3 ð%Þ ¼ x100 ð6Þ Carbon (C) 56.00
Mcp
Hydrogen (H) 2.60
Nitrogen (N) 5.20
where, M550 and M1000 , are mass of cement pastes at 550C and
Sulfur (S) 0.50
1000 °C respectively. M cp is the mass of anhydrous cement paste, Oxygen (by difference) 35.70
after heating to 1000 °C and corrected for the loss of ignition of
cement and that of admixtures (biochar and fly ash) used in this
study [42]. Decarbonation of calcium carbonate takes place in two
Table 4
steps – decarbonation in the range of 550–720 °C, corresponding Oxides (only) composition of biochar.
to decomposition of poorly crystalline carbonates (for example,
vaterite and aragonite), and decarbonation in the range of 720– Chemical composition (%) Peanut shell
biochar
1000 °C, corresponding to degradation of well crystalline calcite
[4,43]. Sodium Oxide (Na2O) 41.53
Magnesium oxide (MgO) 8.18
The CO2 uptake by the cement pastes as percentage of cement Aluminum oxide (Al2O3) 1.01
weight, CO2 ð%Þ, can be quantified using Eq. (7) Silica (SiO2) 1.42
Phosphorus oxide (P2O5) 9.05
M550  M1000
CO2 ð%Þ ¼ x100 ð7Þ Sulfur oxide (SO3) 1.50
M cp Potassium oxide (K2O) 9.62
Calcium Oxide (CaO) 4.48
Calcium hydroxide content, CHð%Þ, is calculated from dehy- Other chemicals including heavy metals: Oxides of Copper, < 0.01
droxylation of cement pastes between 420 and 540 °C [4,40], using Chromium, Lead, Nickel, Copper, Zinc, Zirconium,
Eq. (8) Hafnium, Barium
Loss on ignition (L.O.I) 21.20
4:12  ðM 420  M540 Þ
CHð%Þ ¼ x100 ð8Þ
Mcp
surface (Fig. 1b) which is generally inherited from the original
Degree of hydration, að%Þ is calculated from the mass loss in the
structure of biomass.
range of 105 °C to 1000 °C based on Bhatty’s method [44] using
Based on Carbon, Hydrogen, Nitrogen and Sulfur (CHNS) analy-
Eq. (9)
sis (Table 3), the produced biochar has carbon content of 56% with
Ldh þ Ldx þ 0:41Ldc oxygen to carbon molar ratio (O:C) of 0.45. O:C is considered for
að%Þ ¼ x100 ð9Þ estimating the stability of biochar. The general trend suggests that
0:26
reduction in oxygen content with increase in carbonization lead to
Where, Ldh ; Ldx andLdc are mass losses due to dehydration (105– biochar with higher stability [32]. According to Spokas [32], bio-
420 °C), dehydroxylation (420–540 °C) and decarbonation (550– char with O:C ratio of 0.45 has an estimated half-life of about
1000 °C) respectively. 0.26 in Eq. (9) is the chemically bound water 100 years. However, this is based on stability of biochar under soil
at an infinite time (assuming complete hydration) estimated from conditions and natural environment, and therefore further investi-
the theoretical stoichiometry of cement (Bogue’s formulae) [45]. gation can be considered for stability of biochar in alkaline condi-
tions. The produced biochar has relatively high nitrogen content
3. Results and discussion (5.20%) compared to biochar from wood and rice husk [33,46],
which is attributed to nitrogen fixing by bacteria in leguminous
3.1. Characterization of prepared biochar peanut plants [47].
Chemical composition (oxides only) of biochar (Table 4), shows
3.1.1. Morphology and composition of biochar high content of sodium, potassium and magnesium. This is linked
Fig. 1a shows the morphology of peanut shell particles after to additives and salts (sodium chloride) being used in processing of
grinding. The particles are irregular in shape comprising of elon- peanut for dietary consumption purpose. Sodium chloride decom-
gated and angular particles of different sizes. Although grinding poses only around 800 °C [48]. This means that peanut biochar pre-
was conducted, some particles retained the macro-pores on the pared at 500 °C (as in this case) will inherit the sodium chloride

Fig. 1. (a) Morphology of biochar particles (b) Macro-pores in produced biochar.

5
S. Gupta, A. Kashani, Aziz Hasan Mahmood et al.
from parent biomass. Presence of sodium, potassium and magne-
sium salts in the biochar are also confirmed from the XRD spectra
(Fig. S1c, supplementary information), showing peaks correspond-
ing to sodium chloride (2h = 31.69°, 45.42°), potassium chloride
(2h = 45.42°, 28.31°, 40.57°, 66.21°) and magnesium chloride
(2h = 27.33°, 56.41°) respectively. Phosphorus is also present in rel-
atively high amount, reflected in 9.05% phosphorus oxide by mass
of biochar, which could be inherited from the parent feedstock.
3.1.2. pH, particle size and porosity
pH of biochar in tap water (pH ~ 6.70) is recorded as 8.17, while
pH of 3% biochar in cement filtrate (pH ~ 12.86) is 12.46. This
shows that the produced biochar is alkaline in nature, which is
due to formation of basic oxides on biochar surface and removal
of organic acids at high temperature [49]. Although biochar is rel-
atively less alkaline than cement, addition of 3% biochar does not
significantly affect the pH of pore solution.
Based on laser diffraction (Fig. 2a), particle size of biochar ran-
ged from 1 mm to 70 mm with d50 and d90 of 14 mm and 40 mm,
respectively. The produced and ground biochar is finer than Port-
land cement (d50 = 23 mm and d90 = 60 mm) and fly ash
(d50 = 22 mm and d90 = 80 mm) used in this study. In the pore radius
Fig. 2. a. Particle size distribution of biochar, fly ash and Portland cement; b. Pore volume of the biochar and fly ash in the meso-porous range.
6
Construction and Building Materials 291 (2021) 123363
range of 1.57 nm to 30 nm, the produced biochar has substantially
higher pore volume than fly ash (Fig. 2b). This is also reflected in
three times higher pore surface area of biochar than fly ash
(Table 5). Higher pore volume may enhance carbon dioxide diffu-
sion and sequestration in biochar-based composites than control.
The produced biochar has total porosity of 34.59% and perme-
ability of 1.86 (Table 5), which is higher compared to ground wood
biochar prepared under similar temperature and heating rate
(500 °C and 10 °C/min) [33,50]. Permeability is contributed by con-
nectivity of pore system in the biochar particle. This will contribute
to absorption and subsequent desorption of moisture during hard-
ening phase of cement mortar.
The external surface area of biochar particle (2.15 m2/g) is lar-
ger than the fly ash (1.07 m2/g) used in this study (Table 5), attrib-
uted to finer particle size of biochar (Fig. 2a). This trend is similar
to the external surface area measured by laser diffraction 
1.58 m2/g, 1.08 m2/g and 0.81 m2/g for biochar fly ash and cement
respectively. High surface area of admixtures added to cementi-
tious composites contributes to hydration and development of
mechanical properties [33,50].
Based on thermogravimetry analysis and Eq. (4) (Fig. S1 in sup-
plementary information), the prepared biochar has CO2 adsorption
S. Gupta, A. Kashani, Aziz Hasan Mahmood et al. Construction and Building Materials 291 (2021) 123363

Table 5 capacity is calculated as follows. Considering 3% biochar in mortar

Porosity of biochar and external surface area of cement, fly ash and biochar based on containing 800 kg/m3 of cement (as in this study) i.e. 24 kg of bio-
mercury intrusion porosimetry and nitrogen adsorption. char in 1 cubic meter of mortar can sequester (24  0.86  42) g of
Technique Porosity and surface area of biochar CO2 ~ 866 g of CO2 if the all the pores contribute to adsorption. This
indicates the potential of biochar as active sites for carbon dioxide
Mercury intrusion Total porosity (%) 34.59
porosimetry Median pore diameter (mm) 3.59 capture during ACC.
Permeability (darcy) 1.86
Nitrogen adsorption External surface area (m2/g)
Biochar 2.15 3.2. Characterization of biochar-cement after water curing and
Fly ash 1.07 carbonation
Micro-pore volume (x 10-3 cm3/g)
Biochar 6.55
Fly ash 1.87
3.2.1. Change in mass and depth of carbonation
Pore surface area (m2/g) Fig. 3a shows the change in mass (%) due to exposure to car-
Biochar 2.78 bon dioxide during 27 days of the monitoring period. All mortar
Fly ash 0.88 mixes show steep reduction in mass during the initial 5–7 days,
which is due to accelerated drying of pore water under high
moisture gradient between the sample and the surrounding.
capacity of 0.86 mmol/g. Based on this, the carbon dioxide capture Moreover, the pores in cementitious paste filled with water
potential of biochar-mortar only due to biochar’s adsorption offer sites for dissolution of carbon dioxide, which drives the

Fig. 3. (a) Mass change of cement mortar subject to CO2 curing (b) Depth of carbonation in cement mortar after 28 days of CO2 curing.

7
S. Gupta, A. Kashani, Aziz Hasan Mahmood et al.
carbonation reaction [11]. In case of mortar with fly ash, there is
higher free water in pores compared to plain mortar due to
reduced cement content and higher water to cement ratio
(Table 2). Therefore, fly ash-mortars (FA20 and FA20BC3) show
relatively high loss in mass due to accelerated drying during
the initial stage of carbonation. Drying of pore water leads to
an unsaturated system of capillary pore channels, which provide
pathway for further diffusion of carbon dioxide. A steady increase
in mass can be observed in all samples after the initial drying per-
iod, attributed to increase in diffusion of carbon dioxide and car-
bonation of hydration products to form calcium carbonate. This is
congruent with the findings by Metalssi et al. [51] – mortar with
0.27% cellulose shows steep mass loss during the initial 7 day
period followed by 1–1.50% mass gain due to carbonation
between 7th and 28th day mark. BC1 shows 0.50% increase in
mass between 6-day mark and 27-day mark compared to 0.30%
in case of plain mortar. This is indicative of higher initial porosity
of BC1, that leads to increased diffusion of carbon dioxide and
consequent carbonation. However, as the dosage of biochar is
increased to 3% of cement by weight (BC3), the increase in mass
between 6th and 27th day has reduced compared to BC1. This can
be explained by lower free water in capillary pores of cementi-
tious paste due to higher moisture retention in pores of biochar
as the dosage is increased from 1% to 3%. Moreover, due to fine
particle size and high surface area (Fig. 2 and Table 5), biochar
particles can reduce interconnectivity of pore system [33,52],
thereby reducing CO2 penetration into cement-mortar. This is
confirmed by lower depth of carbonation in biochar-mortar. BC1
and BC3 shows reduction in carbonation depth of 28% and 54%,
respectively, compared to plain mortar (Fig. 3b). Similar effect
can be observed when comparing FA20 and FA20BC3. FA20 shows
increase in mass by 1.05% from 6th day to 27th day, while
FA20BC3 shows an increase by 0.60% within the same period.
Higher mass increase in case of FA20 compared to plain mortar
is contributed by the pozzolanic conversion of calcium hydroxide
(CH) to calcium silicate hydrate (C-S-H), leading to less CH per
mol of CO2. Lower quantity of reactants is reported to drive the
forward reaction and increase the rate of carbonation [11,53].
Moreover, higher porosity due to increased loss in moisture at
early stage and porous nature of fly ash also contribute to
increased diffusion of CO2 [11]. This is reflected in 20% higher car-
bonation depth in case of FA20 compared to plain mortar
(Fig. 3b). Combination of biochar with fly ash (FA20BC3) reduces
the rate of CO2 diffusion due to improved packing, attributed to
difference in particle sizes of these two admixtures (Fig. 2). Dif-
ference in particle sizes can offer better binary packing [54],
which is expected to block the capillay porosity needed for
ingress of CO2. This is further supported by lower initial sorptivity
and water accessible porosity of FA20BC3 compared to FA20 after
carbonation, discussed later in the article.
However, it is interesting to note that biochar has consider-
able effect on reducing carbonation depth in normal mortar,
although it does not reduce carbonation depth in fly ash mor-
tar. Addition of 20–30% fly ash to mortar introduces porous
zones, especially due to accelerated moisture loss under dry
CO2 environment, which dominates over the pore-refinement
effect [55]. Fig. S3 (supplementary materials) shows that the
carbonation front (colourless areas) in FA20BC3 samples pro-
gressed to greater depths in localized regions around voids
marked in yellow. This indicates that localized porous zones
due to fly ash addition might enhance penetration of carbon
dioxide leading to increase in average depth of penetration.
Addition of 3% biochar may not have blocked all such macro-
porous channels, which facilitate penetration of CO2. This is also
supported by similar secondary sorptivity of FA20 and FA20BC3
after 28 days of carbonation, discussed later in the article.
8
Construction and Building Materials 291 (2021) 123363
3.2.2. Carbonate mineralization and CO2 uptake
Fig. 4a and b show the amount of mineral carbonate formed as
percentage of cement mass after 7 days and 28 days of carbona-
tion. This is compared with that of carbonate formed under sealed
curing conditions to determine the net amount of calcium carbon-
ate formed due to carbonation. Net carbonate mineralization,
CCnet (% of cement), is determined from the calcium carbonate con-
tent under CO2 exposure, CCCO2 and that under sealed curing,
CC sealed (determined using Eq. (3)), respectively (Eq. (10)).
CCnet ¼ CCCO2  CC sealed ð10Þ
The amount of calcium carbonate under sealed conditions is
contributed by decomposition of blended limestone in Portland
cement, inorganic minerals and carbon in the added biochar [17].
Two different ranges of decarbonation, i.e. 550 to 720 °C and 720
to 1000 °C, are determined from DTG shown in Fig. S4 (supplemen-
tary information). DTG of sealed cured cement pastes at 28 days
shows two prominent peaks in the ranges of 30–105 °C and 420–
540 °C, which correspond to dehydration of pore water and dehy-
droxylation of calcium hydroxide, respectively. These peaks are
noticeably diminished after carbonation with a drastic increase
of peaks between 550 and 1000 °C (Fig. S4, supplementary infor-
mation). This is due to loss of moisture from cement samples dur-
ing carbonation and conversion of calcium hydroxide to calcium
carbonate. All pastes show higher calcium carbonate contents after
7 days and 28 days of carbonation compared to sealed curing,
shown in Fig. 4a and b.
In the temperature range of 550–720 °C, PCP (control), BC1-CP
and BC3-CP show net carbonate content of 6.75%, 10.78% and
15.71% after 7 days of carbonation curing. This indicates higher
mineralization of poorly crystalline carbonates due to addition of
biochar. Similar trend is observed after 28 days of carbonation
where BC1-CP and BC3-CP show 13.10% and 15.05% carbonate
mineralization compared to 8.55% in PCP (control). Early age car-
bonation converts both CH and C-S-H into calcium carbonate;
however, carbonation at early age is capable of producing more
carbonates from C-S-H, which are less crystalline and relatively
unstable compared to calcite formed from carbonation of CH
[56]. In the range of 720–1000 °C, which corresponds to decompo-
sition of calcite, BC1-CP and BC3-CP show content of 17.90% and
17.58%, respectively, compared to 21% in case of control. This sug-
gests that addition of biochar leads to higher carbonate mineraliza-
tion mainly through formation of poorly crystalline carbonates.
Fig. 5 shows the reduction in calcium hydroxide after 7 days and
28 days of carbonation compared to sealed curing. It can be
observed that reduction of CH in PCP (control), BC1-CP and BC3-
CP are similar at 7 days; however, BC1-CP and BC3-CP show sub-
stantially lower loss in CH after 28 days of carbonation compared
to PCP. This trend confirms that lower amount of CH is being car-
bonated in these samples, leading to reduced content of calcite in
BC1-CP and BC3-CP. Thus, it indicates that carbonation of C-S-H
is the major contributor to carbonate formation in BC1-CP and
BC3-CP.
After 7 days and 28 days of carbonation, BC3-CP shows total net
calcium carbonate of 26.50% and 32.60% by mass of cement
respectively compared to 22% and 29% in case of PCP (control).
The enhancement in carbonate mineralization due to addition of
3% biochar compared to control is statistically significant, deter-
mined using p-value from t-test at 95% confidence interval
(pcalculated < 0.05). The findings suggest that biochar-cement com-
posite has higher carbonate mineralization potential compared to
control. A plausible explanation is the role of biochar in generating
more hydration products through nucleation and internal curing
action compared to control pastes [16,33], demonstrated by the
lead author of this research. This is also confirmed from higher
S. Gupta, A. Kashani, Aziz Hasan Mahmood et al. Construction and Building Materials 291 (2021) 123363

Fig. 4. Net calcium carbonate formation and CO2 uptake after carbonation curing during (a) 7 days (b) 28 days based on TGA results and Eqs. (6) and (7); (c) Net CO2 uptake by
carbonated cement pastes.

9
S. Gupta, A. Kashani, Aziz Hasan Mahmood et al.
Fig. 5. Reduction in calcium hydroxide content after 7 days and 28 days of carbonation based on TGA results and Eq. (7).
degree of hydration in biochar-cement pastes, discussed later in
the article. Increase in amount of hydration products means more
carbonatable products during CO2 exposure. Moreover, due to the
meso-porous nature and high pore surface area (Table 5), biochar
acts as sites for carbon dioxide adsorption (Fig. S2 in supplemen-
tary information), which can enhance carbonate mineralization
and sequestration potential of cementitious composites. Overall,
the findings show that even if depth of carbonation may be
reduced in biochar-mortar (Fig. 3b), it may sequester higher carbon
dioxide per unit mass of cement through carbonate mineralization
than control (without biochar).
Fly ash–cement mix (FA20-CP) shows net carbonate mineraliza-
tion of 9.14% and 23.45% in the temperature range of 550–720 °C
and 720–1000 °C respectively after 7 days of carbonation, com-
pared to 6.75% and 15.16% in case of PCP (control). Overall, addi-
tion of fly ash increases net carbonate mineralization and CO2
uptake by 10.70% and 4.70% respectively with respect to mass of
cement compared to control (Fig. 4a and c). However, at 28 days
the difference in net mineralization between FA20-CP and PCP
(control) is reduced to only 6%. Thus, the trend suggests that addi-
tion of fly ash accelerates rate of carbonation and sequestration at
early stage. This is expected due to dilution and pozzolanic effect of
fly ash [11,53]. Dissolution and diffusion of CO2 depend on the pore
connectivity, which increases at early stage due to 20% replace-
ment of cement by fly ash [11,55]. Higher initial porosity due to
reduced cement content (and increase in water-cement ratio)
and porous nature of fly ash facilitate increase in CO2 dissolution
and diffusion into the cementitious matrix, reflected from 4.60%
higher CO2 uptake in FA20 than PCP (Fig. 4c). Therefore, carbona-
tion tends to proceed at a faster rate than control. However, at later
stage due to pozzolanic reaction of fly ash, CH is converted to C-S-
H, which promotes a disconnected pore structure and reduce the
amount of reactive CH for carbonation in the mix [10,11]. This
leads to a reduction of CO2 diffusion and mineralization of FA20
at 28 days compared to PCP (control).
Addition of biochar to fly ash–cement mix (FA20BC3-CP) leads
to an increase in net carbonate mineralization by 7% and 5.20%
compared to FA20-CP at 7 day and 28 day mark, respectively. This
translates into increase in carbon dioxide uptake by 2.5–3% in case
of FA20BC3-CP compared to FA20 after 7 days and 28 days of car-
bonation (Fig. 4c). This implies sequestering of 7.20–9.40 kg of car-
bon dioxide in a concrete component of of 1 m3 volume designed
with a binder content of 390 kg/m3 and 20% cement replaced by
10
Construction and Building Materials 291 (2021) 123363
fly ash, which is typical for high-strength constructions [57]. This
trend indicates that addition of biochar has a positive influence
on carbon sequestration of fly ash - cement mix. This is attributed
to higher meso-porous volume and pore area of biochar than fly ash
(Fig. 2b and Table 5), which enhance diffusion of carbon dioxide
into the matrix leading to higher mineralization. It is interesting
to observe that the reduction in calcium hydroxide in FA20BC3-
CP is substantially lower than FA20-CP after 7 days and 28 days
of carbonation (Fig. 5). This can be explained by the fact that pres-
ence of porous admixtures, biochar in this case, promote poz-
zolanic reaction of fly ash to generate C-S-H from CH through
regulating moisture and generating internal curing effect [58,59].
This is evident from the reduced CH content in FA20BC3-CP –
14.13% and 17.40% by mass of cement after 7 days and 28 days
respectively (based on Eq. (8)), compared to 17.28% and 19.16%
in the case of FA20-CP. Therefore, carbonation of C-S-H is a more
prominent contributor to calcium carbonate than CH for
FA20BC3-CP.
3.2.3. Compressive and flexural strength
Fig. 6a and b compare compressive strength development after
7 days and 28 days of water curing and carbonation curing, respec-
tively. It can be observed that addition of biochar at 3% of cement
by weight (BC3) leads to improvement in strength by 24% and 21%
after 7 days and 28 days of water curing (WC) respectively com-
pared to control. This is attributed to filler effect of biochar due
to its fine particle size and its contribution in enhancing degree
of hydration of cement. Biochar addition at 1% and 3% also leads
to higher degree of hydration at 7 days compared to control
(Fig. 7), which is statistically significant (p = 0.025 < 0.050 at 95%
confidence interval). This is expected due to internal curing effect
of biochar [17,19] contributed by retention and release of moisture
from the pores of biochar during hardening of cementitious com-
posites. Furthermore, the biochar particles in the vicinity of cement
particles, serve as additional surfaces for precipitation of hydration
products [60], leading to increased hydration. The mentioned
mechanisms improve densification of cement matrix and contibute
to improvement in strength.
However, addition of biochar at 1% and 3% dosage do not have
significant improvement on flexural strength at 28-day age
(Fig. 6c). This is in agreement with findings by Khushnood et al.
[61] – addition of 1% peanut shell biochar (maximum size 6 mm)
reduced flexural strength by 6% although low addition (0.25–
S. Gupta, A. Kashani, Aziz Hasan Mahmood et al. Construction and Building Materials 291 (2021) 123363

Fig. 6. Compressive strength at (a) 7 days and (b) 28 days and (c) flexural strength after 28 days of wet and CO2 curing (d) left: SiO4 tetrahedra represented by blue triangles
and calcium atoms represented by green circles in C-S-H gel; right: depolymerization by replacing SiO4 bridges by alkali metal atoms (Na, K), represented by red diamonds (e)
Correlation betwwen 7-day strength and mass change during first 7 days of CO2 exposure. (For interpretation of the references to colour in this figure legend, the reader is
referred to the web version of this article.)

11
S. Gupta, A. Kashani, Aziz Hasan Mahmood et al. Construction and Building Materials 291 (2021) 123363

Fig. 6 (continued)

Fig. 7. Degree of hydration of cement pastes after 7 days and 28 days of sealed curing.

0.50% of cement by weight) increased flexural strength by 20–80% composites is sensitive to the resistance offered by its tensile
compared to control. Cement based composites are weak under plane. High dosage of biochar tend to increase inhomogeneity in
tension. Under flexural loading, the strength of cement-based the tensile plane of mortar due to different properties of biochar

12
S. Gupta, A. Kashani, Aziz Hasan Mahmood et al.
and the surrounding cementitious matrix [61]. This contribute to
propagation of tensile cracks through weaker interfacial zones,
thus reducing flexural strength.
In case of fly ash–cement mortar, addition of biochar
(FA20BC3) does not show statistically significant improvement
in strength after 7 days and 28 days of water curing compared
to FA20 (without biochar). This is unlike the case of plain mortar
(without fly ash), where 3% biochar addition showed improve-
ment in compressive strength. Presence of fly ash along with suf-
ficient wet curing results in precipitation of C-S-H gel with
consequent reduction in calcium hydroxide (CH) through poz-
zolanic reaction. C-S-H is primarily responsible for strength devel-
opment of cementitious paste. Presence of alkali metals including
sodium and potassium in biochar (Table 4) can influence the
structure and stiffness of C-S-H gel. Sodium (Na+) and potassium
(K+) ions adsorbed in C-S-H can attract additional water mole-
cules in the intralayer, thus increasing the stiffness of the gel
[62]. The increased stiffness reduces lateral deformation under
compressive loading leading to positive effect on strength [62].
However, this effect is offset by the effect of sodium in depoly-
merizing the silicate network and reducing the density of
C-(Na)-S-H gel compared to C-S-H [62,63]. This is explained
through the schematics presented in Fig. 6d. Sodium ions can
break the silicate tetrahedra bridges by inserting into the layer,
leading to less stable C (Na,K)-S-H gel and increased depolymer-
ization. Moreover, Na+ leads to swelling of C(Na,K)-S-H layer
compared to C-S-H which may induce additional stress in the
cementitious matrix. Thus, the net effect of sodium and
potassium would depend on which of the mentioned effects is
more dominant. In this research, this effect is manifested in
statistically similar strength of FA20 and FA20BC3 at 28-day age
(p-value > 0.05, tested at 95% confidence interval) although
FA20BC3 shows 13% higher strength than FA20 at 7-day age. This
might be explained by higher degradation to C-S-H gel due to
dissolution of sodium and potassium ions from biochar with the
age of mortar. Therefore, sodium and potassium content of bio-
char must be taken into account for application in cementitious
composites containing pozzolanic material.
Plain mortar shows 42% improvement in compressive strength
after 7 days of carbonation compared to its water cured samples,
while BC1 and BC3 show similar strength development under
water curing and carbonation curing. This is contrary to the find-
ings observed by Wang et al. [64] - cement blocks (50 mm cube)
with 1% wood-based biochar showed 70% increase in compressive
strength subjected to 24 h of carbonation and 6 days of air curing
compared to 7-day air cured samples. This difference in findings
could be attributed to the duration of carbonation, which is 7 days
in this case compared to 1-day in case of Wang et al. [64]. Fig. 8a
and b compare the micro-structure of water cured and carbonated
BC3 respectively after 7 days. It can be seen that the C-S-H gel in
carbonated BC3 is porous and not as dense as in the case of
water-cured sample. This is attributed to prolonged carbonation,
that leads to moisture starvation, impeding hydration and increas-
ing porosity. Although long exposure to CO2 can enhance carbonate
mineralization and sequestration, degraded binder gel-structure
can negatively affect strength development.
FA20BC3 shows 22% higher strength compared to FA20 after
7 days of carbonation although 28 day strengths are similar. The
strength development of mortar mixes after 7 days of carbonation
is closely related to the mass loss due to consumption of moisture
during carbonation (R2 = 0.95, Fig. 6e). Fig. 8c shows that the car-
bonation process leads to formation of carbonation products in
macro-void spaces (in FA20), which are otherwise occupied by cal-
cium hydroxide during hydration. However, high early loss in
moisture creates additional porosity and affect the strength devel-
opment [4]. For instance, FA20BC3 shows 0.70% lower loss in mass
13
Construction and Building Materials 291 (2021) 123363
than FA20 after 7 days of carbonation, which leads to 22% higher
strength although both these mixes show similar strength after
7 days of water curing. This is congruent with findings by Rostami
et al. [4] that loss of moisture by 3.70% led to 60% lower strength
after carbonation compared to samples receiving water spray to
replenish moisture loss subsequent to carbonation.
After 28 days of carbonation, BC1 and BC3 show 14% (pcalclated =
0.035 < 0.050) and 25% (pcalclated = 0.010 < 0.050) higher strength
than plain mortar. Similar trend can be observed for flexural
strength (Fig. 6c) – carbonated BC1 and BC3 show 17% and 7%
improvement in strength than plain mortar. While compressive
strength increases by 59% for BC1, and 43% for BC3 from 7 days
to 28 days of carbonation curing, plain mortar does not show any
noticeable increment in strength. Strength development after
28 days of carbonation is an interplay of adverse degradation of
C-S-H and positive effect of densification by calcium carbonate in
pores of cement matrix. Prolonged exposure to carbon dioxide
leads to decomposition of C-S-H into cross-polymerized gel with
low Ca:Si ratio and reduces binding capacity [65]. This is reported
to cause loss in structural integrity in carbonated matrix [66]. The
control matrix shows higher carbonation depth compared to BC1
and BC3 at 28-day age (Fig. 3b), meaning the degradation due to
carbonation took place in a larger volume of the control sample
compared to biochar-mortar. In case of BC1 and BC3, the mass
change from 7 days of carbonation to 28 days are higher than plain
mortar, meaning the top 4–7 mm depth of the samples (depth of
carbonation shown in Fig. 3a) are more densified by calcium car-
bonate than in case of plain mortar. This is expected to densify
macro-pores and contribute to strength. Furthermore, Gupta
et al. [67] found that under humidity gradient the retained water
in biochar pores is released, that can improve hydration of cement
pastes. Therefore, the loss in moisture due to carbonation can be
replenished by the internal curing action of biochar, thus con-
tributing to better strength development than plain mortar.
In presence of 20% fly ash, addition of biochar does not lead to
any significant improvement in compressive and flexural strength
after 28 days of carbonation (Fig. 6b and c). Furthermore, the
strength increment from 7th day of carbonation to 28th day of car-
bonation is 2.11 times in case of FA20, which is higher than 1.60
times for FA20BC3. This implies that despite higher carbonate min-
eralization in FA20BC3, the strength development is retarded com-
pared to FA20. This is attributed to higher contribution of C-S-H to
carbonate mineralization in case of FA20BC3 than FA20 (discussed
in Section 3.4). After 28 days of carbonation, the CH content in
FA20BC3-CP is 13.94 ± 0.12% by mass of cement, whereas FA20-
CP shows a much reduced CH content at 9.81 ± 0.20% (calculated
based on Eq (8)), suggesting lower conversion of CH to calcium car-
bonate during carbonation. CH may reduce porosity of cementi-
tious composites by blocking the macro-pore spaces but does not
contribute to strength development [68]. Thus, conversion and
degradation of C-S-H in FA20BC3 is a more prominent contributor
to calcium carbonate than in the case of FA20. Furthermore, it can
be seen from Fig. 8d that fly ash particles in carbonated FA20BC3
after 28 days are partially consumed with only traces of hydration
products on the surface. As a result, pores at the interface of fly ash
and cementitous matrix and the bulk matrix (Fig. 8e) remain
unfilled although intermingled carbonate crystals of calcium car-
bonate and needle-shape crystals, which may be ettringite or elon-
gated CH crystals, densify part of the matrix. Although some
hydration can be seen on the biochar surface, much of the particle
is not covered by hydration products (Fig. 8d). Biochar particles can
enhance strength through filler effect; however, low hydration on
its surface during carbonation may affect long-term strength
development. Therefore, even though carbonated FA20BC3 shows
similar strength as carbonated FA20 after 28 days, the strength
development from 7-day age to 28-day age is retarded.
S. Gupta, A. Kashani, Aziz Hasan Mahmood et al.
(e)
Macro-
pores
Fig. 8. SEM micrograph of (a) C-S-H gel in water-cured BC3; (b) porous C-S-H gel structure in carbonated BC3; (c) Carbonate minerals in macro-voids of FA20 (d) Partially
reacted fly ash particles in carbonated FA20BC3 after 28 days; (e) Macro-pores around carbonated zones in FA20BC3; (e1) Zoomed in micrograph of calcium carbonates
intermingled with hydration products.
3.2.4. Capillary water absorption
Fig. 9a and b compare capillary water absorption of mortar sam-
ples after 28 days of wet curing and carbonation. The initial
absorption during the first 4 h (shown in Fig. S5, supplementary
information) is attributed to rapid absorption by capillary pores,
while the secondary absorption between 24th and 168th hour is
contributed by macro-voids [16,69]. The slope of the absorption
curve during these two periods can be used to calculate the initial
sorptivity and secondary sorptivity, respectively. The results are
presented in Fig. 9c and d.
It can be observed that addition of 1% and 3% biochar do not sig-
nificantly influence initial absorption although 1% addition of bio-
char leads to 11% increase in total absorption compared to control.
However, increase in biochar dosage to 3% leads to 16% reduction
in total absorption than plain mortar after 28 days of water curing.
This suggests reduction in open porosity by filler effect of biochar
with increase in dosage. It is also supported by 6% reduction in
water accessible porosity of BC3 compared to plain mortar after
28 days of wet curing, which is statistically significant (pcalculated =
14
Construction and Building Materials 291 (2021) 123363
(e1)
Calcium
carbonate
Ettringite or
needle-shape
C-S-H
0.045 < 0.050, at 95% confidence interval). Similar trend can also be
observed in 23% reduction in water absorption in case of FA20BC3
compared to FA20 (Fig. 9b). This is also reflected in lower water
acccessible porosity of FA20BC3 compared to FA20, both subject
to wet curing (Fig. 10).
After carbonation, all mixes show substantial increase in total
absorption (g/cm2) (Fig. 9a and b), which is mainly contributed
by increase in initial sorptivity (Fig. 9c and d) compared to those
under water curing. Fig. 9e shows that initial sorptivity of mortar
mixes after carbonation is strongly correlated with the mass loss
due to drying during the 28-day carbonation period. The moisture
stored in fine capillary pores of cement matrix supports hydration,
which refine the pore structure with age of concrete. Accelerated
carbonation and drying consumes the water in fine capillary and
gel pores, reducing hydration and thus increasing the water sorp-
tivity of the matrix. This is congruent with findings from Tracz
and Zdeb [70]. They investigated carbonation under natural envi-
ronment for 2 years which led to doubling of medium capillary
pores (50 nm–100 nm) compared to water curing. These pores,
S. Gupta, A. Kashani, Aziz Hasan Mahmood et al. Construction and Building Materials 291 (2021) 123363

Fig. 9. Capillary water absorption of (a) plain mortar, BC1 and BC3 and (b) FA20 and FA20BC3 after 28 days of water curing and CO2 curing. (c) Initial sorptivity of water cured
samples and carbonated samples (d) Secondary sorptivity of water cured and carbonated samples (e) Relation between initial sorptivity and mass loss due to carbonation
during 28 days.

15
S. Gupta, A. Kashani, Aziz Hasan Mahmood et al.
Fig. 9 (continued)
due to stronger capillary suction, contribute to increase in initial
sorptivity. This is observed in case of BC1 showing 29% increase
in initial sorptivity due to higher drying rate compared to plain
mortar (control) and BC3.
It can be seen from Fig. 9e that reduction in mass loss by only
0.36% in FA20BC3 compared to FA20 due to carbonation, led to
reduction in initial sorptivity by 27%. The slope of reduction
(shown by black arrow in Fig. 9e) is steeper than in the case of
BC3 compared to plain mortar (shown by blue arrow in Fig. 9e).
Porous cementitious composites (for example, fly ash -cement
mortar) suffer more from prolonged carbonation compared to nor-
mal mortar due to higher ingress of CO2 resulting in degradation of
binder gel and pore coarsening [6]. Therefore, addition of biochar
to fly ash-mortar has a more significant effect on reducing water
absorption after 28 days of carbonation compared to that in the
case of plain mortar. Lower mass loss due to combination of bio-
char and fly ash (FA20BC3) than FA20 would reduce capillary
porosity, while the fine biochar particles can block pore channels,
thus contributing to reduction in water sorptivity.
Carbonation in case of plain mortar and BC1 leads to reduction
in water accessible porosity compared to water cured samples
(Fig. 10), attributed to deposition of calcium carbonates in
16
Construction and Building Materials 291 (2021) 123363
macro-pores of mortar [51]. However, BC3 shows similar porosity
after water and carbonation curing (Fig. 10). This is due to lower
carbonation depth and lower permeability of BC3 compared to
BC1. It suggests that carbon dioxide could not diffuse into the
internal pore network of BC3 and as a result, blockage of internal
macro-pores by calcium carbonate is less effective than BC1.
Both FA20 and FA20BC3 show about 3.20 times increase in ini-
tial sorptivity after carbonation compared to wet curing (Fig. 9c),
which is significantly higher compared to 1.50–1.80 times increase
in plain mortar, BC1 and BC3. This is attributed to aggravated pore
coarsening due to carbonation in mortar containing pozzolanic
mineral admixture, fly ash in this case [66]. Bier [71] attributed this
to the pozzolanic action converting CH to C-S-H, which suffers sev-
ere decalcification and increase in porosity due to prolonged car-
bonation. However, FA20BC3 shows 33% lower initial sorptivity
and 10% lower water accessible porosity (Fig. 10) compared to
FA20 after carbonation, suggesting that addition of biochar reduces
the permeability of fly ash-mortar. This is attributed to filler effect
of biochar and lower mass loss due to drying of FA20BC3 mortar
compared to FA20 during the carbonation period (Fig. 3a).
However, carbonation leads to significant reduction in sec-
ondary sorptivity (Fig. 9d). Lower secondary sorptivity is caused
S. Gupta, A. Kashani, Aziz Hasan Mahmood et al.
Fig. 10. Water accessible porosity of mortars after 28 days of water curing and CO2 curing.
by blockage of macro-pores (>100 nm) by calcium carbonate
formed through reaction of calcium hydroxide with diffused car-
bon dioxide [51]. Metalssi [51] reported that accelerated carbona-
tion substantially reduce macro-porosity of cementitious
composites (pore size between 0.90 and 2.50 mm). Secondary sorp-
tivity is applied for prediction of service life of concrete structures
[72], and therefore lower value would indicate improved durability
due to enhanced water tightness. Due to higher diffusion of carbon
dioxide and carbonate mineralization (Figs. 3a and 4b), carbonated
FA20 and FA20BC3 show 78–79% reduction in secondary sorptivity
compared to water cured samples, while BC3 shows only 60%
reduction. The secondary sorptivity is also reduced by 18% in car-
bonated FA20BC3 compared to BC3 (Fig. 9d), indicating its
improved resistance to migration of external moisture during ser-
vice life.
3.2.5. Drying and carbonation shrinkage
3.2.5.1. Drying shrinkage. Fig. 11a and b show drying shrinkage (air
drying) and carbonation shrinkage of mortar over 11 week
(77 days) period. It also shows the reversibility of shrinkage due
to rewetting subsequent to shrinkage. Due to rewetting after air-
drying and carbonation, all the mortars show expansion, observed
in Fig. 11a and b.
It is found that drying shrinkage increases with increase in bio-
char dosage, evident from 31% and 39% increase after 77-day per-
iod compared to plain mortar due to addition of 1% and 3% biochar,
respectively. Similar trend can be observed when comparing FA20
and FA20BC3. It is expected that salt content (sodium chloride) in
peanut contributed to sodium in peanut biochar, which is also sup-
ported by the XRD spectra of the produced biochar (Fig. S1b, sup-
plementary info). Assuming all the sodium is sourced from sodium
chloride, 1% and 3% biochar amount to 0.42% and 1.26% sodium
chloride by mass of cement in BC1 and BC3 mortar based on oxide
only composition (Table 4). Park et al. [73] observed 30% and 47%
higher drying shrinkage in concrete containing 0.60% and 1.20%
sodium chloride at 77-day age. Higher shrinkage due to presence
of sodium compounds is attributed to role of alkali cations (Na+,
K+) in increasing the visco-plastic/visco-elastic compliance and
reduction of creep resistance under drying induced stresses [74].
This is attributed to rearrangement of micro-structural configura-
17
Construction and Building Materials 291 (2021) 123363
tion of C-S-H due to spatial arrangement induced by cations [74].
Deprotonation of -SiOH- to -SiO- leads to negatively charged
C-S-H surface. Thus, the positively charged cations are adsorbed
onto the C-S-H gel and induce electrostatic attractions leading to
a denser micro-structure. This mechanism induces stresses in the
micro-structure and may lead to deformation of C-S-H by shorten-
ing the chain length of silicate [75]. Drying shrinkage is also influ-
enced by disjoining pressure. Beltzung et al. [76] found that
increased cationic concentration destabilizes the adsorbed water
close to the solid skeleton in C-S-H, resulting in release of disjoin-
ing pressure. This reduces the distance between solid layers, lead-
ing to higher shrinkage.
Upon rewetting for 7 days, plain mortar, BC1 and BC3 show 32–
34% recovery in shrinkage (expansion) from the 77-day mark;
however, FA20BC3 shows only 24% recovery. Higher reversibility
of shrinkage represents the elastic response of mortar, that can
be instrumental in minimizing shrinkage cracking through curing.
The trend shows that combination of fly ash and biochar reduce
reversibility of drying shrinkage. Reversible shrinkage due to wet
curing is dependent on penetration of external water, that replen-
ishes internal moisture in cement matrix, leading to hydrationof
unhydrated cement particles. The generated hydration products
reduce capillary porosity, resulting in recovery of a fraction of
the total shrinkage. Pozzolanic action of fly ash and filler effect of
unreacted fly ash and biochar particles can minimize porosity of
mortar, thus limiting penetration of external moisture. Subject to
similar curing conditions, FA20BC3 show lower water accessible
porosity and water absorption (%) (Fig. 10) compared to plain mor-
tar, BC1 and BC3.
3.2.5.2. Carbonation shrinkage. After carbonation, all mortars show
increase in shrinkage (comparing Fig. 11a and b), which is due to
coarsening of fine pores, decalcification (chemical effects) and
accelerated drying during carbonation (physical effect) [74]. Since
the environmental conditions (temperature and humidity) for air-
drying and carbonation were similar (23 °C and 55% RH), the effect
of only carbonation on change in shrinkage, e; can be determined
from the difference between carbonation shrinkage and drying
shrinkage, using Eq. (11).
e ¼ cc  D ð11Þ
S. Gupta, A. Kashani, Aziz Hasan Mahmood et al. Construction and Building Materials 291 (2021) 123363

Fig. 11. (a) Drying shrinkage (air drying), (b) Carbonation shrinkage of mortar and (c) Shrinkage due to only carbonation process.

18
S. Gupta, A. Kashani, Aziz Hasan Mahmood et al.
ecc is the carbonation shrinkage (micro-strain) and eD is the dry-
ing shrinkage (micro-strain) for the same mortar mix. cc and D are
negative (not absolute values). e after 3 days, 7 days, 28 days,
56 days and 77 days of carbonation are shown in Fig. 11c. It is
interesting to note that BC1 and BC3 show 32–65% reduction in
carbonation-only shrinkage compared to plain mortar (control)
depending on the exposure age. Therefore, the differences in
shrinkage between control and BC1, and control and BC3 up to
77-day period, shown in Fig. 11b, are mainly due to the physical
drying effect. This trend suggests that biochar-mortar would be
less vulnerable to detrimental effects of carbonation reaction,
including cracking and dimensional instability during carbon
sequestration, than control mortar. Reduced carbonation-only
shrinkage in biochar-mortar can be attributed to the reduced depth
of carbonation compared to plain mortar (Fig. 3b). Chen et al. [77]
suggested that carbonation shrinkage is mainly caused by decalci-
fication of C-S-H, and this leads to increase in irreversible shrink-
age. Therefore, reduced penetration of CO2 in BC1 and BC3 would
lead to lower volume of decalcified C-S-H compared to plain mor-
tar, resulting in lower carbonation-only shrinkage.
However, depth of penetration may not be the only reason for
reduction in carbonation-only shrinkage. Despite similar depth of
carbonation, FA20BC3 shows 63–77% reduced carbonation-only
shrinkage compared to FA20 beyond 7th day mark (Fig. 11c). A
possible explanation, mooted by Ye et al. [74], is the crystallization
stress generated by calcium carbonate crystals in cementitious
matrix containing sodium salts. Formation of calcite and aragonite
are associated with about 12% and 3% expansion in volume.
According to Power’s theory [78], formation of calcite do not lead
to forced increase in volume because it is formed in the pore spaces
occupied by calcium hydroxide (CH). However, presence of sodium
compounds (as in the case of peanut shell biochar in this study),
leads to refined pore structure, which suffers from expansive crys-
tallization stress due to generation of calcium carbonates during
CO2 exposure [74]. Secondly, FA20BC3 shows substantially lower
water accessible porosity than FA20, meaning the densified matrix
may be a restraint to growth of calcium carbonate resulting in
large expansive stresses. This plausible volume expansion due to
carbonation in biochar-mortar may reduce the carbonation-only
shrinkage.
Carbonation followed by rewetting leads to expansion and net
reduction in shrinkage. Plain mortar, BC1 and BC3 lead to 22–
25% reversibility in shrinkage, while FA20 and FA20BC3 show
20% and 16% reversibility. This shows that combination of biochar
and fly ash leads to higher fraction of irreversible shrinkage after
rewetting compared to cement mortar with only fly ash. Higher
carbonate mineralization potential of FA20BC3 compared to FA20
reduces water accessible porosity (Fig. 10) which can reduce the
penetration of moisture during rewetting and lead to lower recov-
ery of shrinkage by further hydration. Furthermore, the reduction
in CH is substantially less in FA20BC3 than FA20, indicating that
carbonation of C-S-H could be the major contributor to formation
of carbonates. Prolonged carbonation of C-S-H lead to removal of
interlayer calcium and formation of silica gel, which contract by
10–12% by volume [79]. Moreover, presence of alkali compounds,
including compounds of sodium and potassium in biochar, can
enhance decalcification leading to collapse of layered structure in
C-S-H [74]. Such degradation of the gel structure has been reported
to cause irreversible shrinkage during carbonation in alkali-rich
cement pastes [74].
4. Conclusion
This study investigates the influence of biochar and combina-
tion of biochar and fly ash on carbonate mineralization in
19
Construction and Building Materials 291 (2021) 123363
cement-mortar through accelerated carbonation curing. The find-
ings demonstrate that addition of 3% biochar, prepared and pro-
cessed from peanut shell, increases the rate of carbonation of
cement mortar, although it reduced the depth of carbonation.
Addition of 3% biochar contributes to generation of more hydration
products and improves degree of hydration than control. This
increases the products participating in carbonation reaction, lead-
ing to higher carbonate mineralization and CO2 uptake by 5–7%
than control.
Combining biochar and fly ash increases the carbonate mineral-
ization and rate of CO2 uptake of cement blocks by 5–7% compared
to fly ash–cement (without biochar) at early age (7 days), suggest-
ing addition of biochar has a positive influence on rapidly captur-
ing and sequestering carbon dioxide. Carbon sequestration
through carbonation of binder gel is higher in biochar-fly ash
blocks than fly ash–cement blocks.
Higher initial moisture loss, due to carbonation, negatively
affects 7-day compressive of biochar mortar. However, increased
carbonate mineralization and reduced depth of carbonation after
28 days in biochar-mortar (BC3) compared to control leads to
24% improvement in compressive strength.
Adding biochar to fly ash mortar reduces rate of water ingress
by 33%, which will enhance durability of concrete constructions.
Combination of biochar and fly ash in mortar demonstrates sub-
stantially lower (by 27%) initial sorptivity than fly ash-mortar after
carbonation, attributed to filler effect of biochar and higher carbon-
ate mineralization.
High salt content (sodium and potassium salts) as contaminants
in biochar can substantially increase drying shrinkage (by up to
33%) of biochar-mortar compared to control. Addition of biochar
can reduce the carbonation-only shrinkage (due to chemical reac-
tion) by 32–77% depending on mix composition and exposure age.
22–25% of the carbonation shrinkage can be recovered in plain
mortar and biochar-mortar by short period (7 days) of rewetting.
Combination of fly ash and biochar can lead to higher irreversible
shrinkage than fly ash – mortar due to higher carbonation and
degradation of binder gel.
In summary, the research highlights a potential means of devel-
oping low carbon biochar-cement material, which can offer high
carbonate mineralization with some improvements in mechanical
and durability properties.
CRediT authorship contribution statement
Souradeep Gupta: Conceptualization, Methodology, Investiga-
tion, Writing - original draft, Writing - review & editing. Alireza
Kashani: Funding acquisition, Resources, Writing - review & edit-
ing. Aziz Hasan Mahmood: Investigation. Tianhao Han: Data cura-
tion, Investigation.
Declaration of Competing Interest
The authors declare that they have no known competing finan-
cial interests or personal relationships that could have appeared
to influence the work reported in this paper.
Acknowledgements
The authors would like to thank Center for Infrastructure Engi-
neering and Safety (CIES) for supporting with materials and equip-
ment resources for this research. Assistance from technical officers
Mr. Paul Gwynne and Mr. William Terry is also appreciated.
S. Gupta, A. Kashani, Aziz Hasan Mahmood et al. Construction and Building Materials 291 (2021) 123363

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