materials

Article
Calcium Carbonate Cement: A Carbon Capture, Utilization,
and Storage (CCUS) Technique
Craig W. Hargis 1, *, Irvin A. Chen 2 , Martin Devenney 2 , Miguel J. Fernandez 2 , Ryan J. Gilliam 1
and Ryan P. Thatcher 1

1 Fortera Corporation, 251 E. Hacienda Ave, Suite B, Campbell, CA 95008, USA;

[email protected] (R.J.G.); [email protected] (R.P.T.)
2 Calera Corporation, Los Gatos, CA 95032, USA; [email protected] (I.A.C.);
[email protected] (M.D.); [email protected] (M.J.F.)
* Correspondence: [email protected]; Tel.: +1-669-267-6407

Abstract: A novel calcium carbonate cement system that mimics the naturally occurring mineraliza-
tion process of carbon dioxide to biogenic or geologic calcium carbonate deposits was developed
utilizing carbon dioxide-containing flue gas and high-calcium industrial solid waste as raw materials.
The calcium carbonate cement reaction is based on the polymorphic transformation from metastable
vaterite to aragonite and can achieve >40 MPa compressive strength. Due to its unique properties,
the calcium carbonate cement is well suited for building materials applications with controlled
factory manufacturing processes that can take advantage of its rapid curing at elevated temperatures
and lower density for competitive advantages. Examples of suitable applications are lightweight



fiber cement board and aerated concrete. The new cement system described is an environmentally

 sustainable alternative cement that can be carbon negative, meaning more carbon dioxide is captured
Citation: Hargis, C.W.; Chen, I.A.; during its manufacture than is emitted.
Devenney, M.; Fernandez, M.J.;
Gilliam, R.J.; Thatcher, R.P. Calcium Keywords: cement; calcium carbonate; vaterite; carbon capture; industrial ecology
Carbonate Cement: A Carbon
Capture, Utilization, and Storage
(CCUS) Technique. Materials 2021, 14,
2709. https://doi.org/10.3390/ 1. Introduction
ma14112709
Anthropogenic carbon dioxide (CO2 ) is contributing to the rising atmospheric CO2
concentration, which is widely considered to be a leading contributing factor for the
Academic Editor: Jorge S. Dolado
greenhouse effect, ocean acidification, and global climate change [1]. While efforts are
being made to reduce CO2 emissions, global anthropogenic CO2 emissions are projected to
Received: 28 April 2021
Accepted: 20 May 2021
continually increase over the coming decades, mainly driven by the growth of emerging
Published: 21 May 2021
countries [1–9]. Carbonate rocks are estimated to contain approximately 39,000,000 Gt
of terrestrial CO2 and provide a potential pathway for stable, long-term storage of CO2
Publisher’s Note: MDPI stays neutral
resulting from human activities [10]. Furthermore, carbonate rocks, such as limestone
with regard to jurisdictional claims in
and marble, both mainly composed of calcium carbonate (CaCO3 ), have long been widely
published maps and institutional affil- utilized by mankind as construction materials, which offer a potential solution to upcycle
iations. the anthropogenic CO2 into value added materials [11].
CaCO3 , one of the most abundant carbonate species in nature, has three anhydrous
crystalline polymorphs: vaterite, aragonite, and calcite, with vaterite being the least and
calcite being the most thermodynamically stable polymorph [12]. Calcite is the most
Copyright: © 2021 by the authors.
abundant polymorph and is seen in geological formations, such as limestone, chalk, and
Licensee MDPI, Basel, Switzerland.
marble of either biological or geological origin. Aragonite is less common, but abundant as
This article is an open access article
oolitic sand in the Bahamas, while vaterite is observed much less often due to its instability
distributed under the terms and in ambient conditions. However, in nature, many organisms, e.g., coral, first produce
conditions of the Creative Commons metastable amorphous CaCO3 as a precursor and control its transformation to aragonite or
Attribution (CC BY) license (https:// calcite to develop their rigid skeletons [13].
creativecommons.org/licenses/by/ Inspired by the biological use of CaCO3 , Fontaine et al. [14] and Combes et al. [15,16]
4.0/). successfully developed a CaCO3 -based medical cement through an aqueous precipitation

Materials 2021, 14, 2709. https://doi.org/10.3390/ma14112709 https://www.mdpi.com/journal/materials

Materials 2021, 14, 2709 2 of 12

process using calcium chloride (CaCl2 ) and sodium carbonate (Na2 CO3 ) as feedstocks. The
cementing reaction is based on the polymorphic transformation from metastable amorphous
CaCO3 and vaterite to aragonite or calcite through a dissolution–reprecipitation process
in an aqueous medium. However, limited production scale and mechanical properties
(3–13 MPa compressive strength) have restricted larger scale applications in the construction
industry. Nevertheless, the results obtained by Combes et al. provide promising insights
for the development of a nature inspired, synthetic CaCO3 cement system at scale from
anthropogenic CO2 with properties suitable for various building materials applications.
Industrially, three feedstocks are required to produce CaCO3 cement: CO2 , calcium,
and alkalinity. CO2 can originate from CO2 -containing industrial flue gas, e.g., thermal
power plants, chemical plants, and cement kilns. Calcium and alkalinity can come from
industrial waste streams that contain both calcium and alkalinity in the form of calcium
oxide (CaO), calcium hydroxide (Ca(OH)2 ), and calcium silicates. Examples of calcium and
alkalinity-rich industrial waste streams include: carbide lime sludge, an impure Ca(OH)2
by-product of producing acetylene gas (C2 H2 ) from coal and limestone, slag, a Ca/Mg-rich
aluminosilicate glass by-product of iron and steel production, and cement kiln dust, an
impure CaCO3 /CaO by-product of Portland cement manufacturing that is often recycled
in the cement kiln feed [17,18]. An acid can be utilized to extract the calcium from the
waste feedstock and bring it into solution. Ammonium salts, e.g., ammonium chloride
(NH4 Cl), ammonium sulfate ((NH4 )2 SO4 ), and ammonium nitrate (NH4 NO3 ) have been
shown to be effective acids in the production of vaterite from CO2 because they can bring
the calcium into solution (Equation (1)), absorb CO2 from a gas stream (Equation (2)), and
then be regenerated during the formation of CaCO3 (Equation (3)) [17,19,20].

2NH4 Cl(aq) + CaO(s) + H2 O(l) → 2NH4 OH(aq) + CaCl2(aq) (1)

2NH4 OH(aq) + CaCl2(aq) + CO2(g) → (NH4 )2 CO3(aq) + CaCl2(aq) + H2 O(l) (2)

(NH4 )2 CO3(aq) + CaCl2(aq) → 2NH4 Cl(aq) + CaCO3(s) (3)
To promote the formation of metastable forms of CaCO3 over calcite and aragonite,
precipitation is performed at high reactant concentrations, needed to achieve high supersat-
uration and kinetic stabilization [21]. The concentration of carbonate ions is predominantly
governed by (1) the rate of transfer of CO2 across the gas–liquid interface, (2) the rate at
which CO2 converts into carbonate, and (3) the carbonate–bicarbonate equilibrium. The
rate of mass transfer can be increased by increasing the flow rate of gas or by increasing the
gas–liquid interface, for example by high shear mixing. Subsequent conversion of CO2 into
carbonate can occur through the reaction with water (H2 O) or hydroxyl ions (OH− ), but
because the latter reaction is 107 times faster, higher rates can be achieved by performing
the reaction at higher pH. Higher pH also favors higher equilibrium concentrations of
carbonate over bicarbonate. Except for high gas flow rates, these strategies also improve
the CO2 absorption efficiency.
Herein, a novel CaCO3 cement system that mimics the naturally occurring mineral-
ization process of CO2 to biogenic or geologic CaCO3 deposits is described [17,22]. The
CaCO3 cement is produced by capturing CO2 -containing industrial flue gas and utiliz-
ing a calcium and alkalinity-rich industrial waste stream [18]. The result is a cement
with a significantly lower CO2 and energy footprint compared to traditional inorganic
binders, such as Portland cement. Furthermore, the CaCO3 cement offers processing and
performance advantages in a variety of building materials applications over traditional
inorganic binders.

2. Materials and Methods

2.1. Raw Materials
The carbide lime sludge (Gilmour & Company, Inc., Vancouver, WA, USA) contained
25 wt% solids and had silica, alumina, and mixed oxidation state sulfur impurities, e.g.,
S2− and SO4 2− , see Table 1. The CO2 -containing flue gas used was generated from a boiler
 Materials 2021, 14, 2709 3 of 12

simulator (GE Energy and Environmental Research Corporation, Irvine, CA, USA) burning
propane. NH4 Cl (Zaclon, LLC, Cleveland, OH, USA) was used for solubilizing Ca(OH)2 .

Table 1. Chemical composition of the oven-dried carbide lime sludge.

Oxide Mass (%)

CaO 70.0
SiO2 2.4
Al2 O3 1.7
MgO 0.1
Fe2 O3 0.3
SO3 0.7
MnO 0
TiO2 0
P2 O5 0
Cl 0
LOI 1 24.4
1 LOI is mass loss on ignition to 950 ◦ C.

2.2. Aqueous Mineralization Process

To produce CaCO3 cement, the carbide lime sludge is first solubilized with aqueous
NH4 Cl then passed through a leaf filter to remove insoluble impurities resulting in an
aqueous solution of CaCl2 and ammonia (NH3 ), see Equation (1). NH3 dissolved in water
is in equilibrium with ammonium hydroxide (NH4 OH). CO2 -containing flue gas (11 vol%)
is then contacted with the solution in a three-phase continuous-stirred tank reactor (CSTR)
controlled at below 40 ◦ C (Equation (2)), resulting in the precipitation of CaCO3 cement
(Equation (3)). The simulated flue gas was blown from the boiler simulator to the absorber
via a 20 cm steel pipe using a 600 cfm roots style blower. Unlike some other carbon capture
technologies, the CO2 does not need to be concentrated or compressed to high pressures for
storage, which is energy intensive. The CaCO3 cement is then mechanically dewatered by
a filter press (Outotec Oyj, Helsinki, Finland) and thermally dried in a swirl fluidizer (GEA
Processing Engineering, Warrington, UK) to a free-flowing powder. The NH4 Cl solution is
recovered during dewatering and is recycled for the solubilization of additional carbide
lime sludge. Insoluble impurities accounted for 7% of the dry mass of the carbide lime
sludge and were composed of 70% mixed oxides and 30% carbon, see Table 1. The insoluble
impurities were treated as waste at the pilot plant, but, depending on the composition,
could be used in industrial ecology applications, e.g., raw materials for Portland cement
Materials 2021, 14, x production or as supplementary cementitious materials [23]. Figure 1 shows a 4process of 13
block flow diagram of the CaCO3 cement manufacturing process. The CaCO3 cement pilot
plant is shown in Figure 2.

Ammonia
Makeup
Ammonium
Chloride
Baghouse

Absorber
Leaf Filter
Carbide
Lime
Dissolution Absorber Filter CaCO3
Swirl
Reactor Feed Clarifier Press Cement
Fluidizer

Insoluble Gas Flow

Impurities Liquid Flow
Boiler Slurry Flow
Simulator Solid Flow

Figure
Figure 1. Block
1. Block flow
flow diagram
diagram of the
of the CaCO
CaCO 3 cement
3 cement
manufacturing
manufacturing process.
process.
 Reactor Feed Clarifier Press Cement
Fluidizer

Insoluble Gas Flow

Impurities Liquid Flow
Boiler Slurry Flow
Materials 2021, 14, 2709 Simulator Solid Flow 4 of 12

Figure 1. Block flow diagram of the CaCO3 cement manufacturing process.

Figure2.2.CaCO
Figure CaCO3 cement
cement pilot
pilot plant.
plant.
3

2.3.
2.3.Analysis
Analysisand
andTesting
Testing
2.3.1.
2.3.1. Laser ParticleSize
Laser Particle SizeDistribution
Distribution
AAHoriba
HoribaLA-950V2
LA-950V2Laser
LaserScattering
ScatteringParticle
ParticleSize
SizeDistribution
DistributionAnalyzer
Analyzer(two(twolight
light
sources:
sources: 650 nm wavelength laser and 405 nm wavelength LED) was used to studythe
650 nm wavelength laser and 405 nm wavelength LED) was used to study the
particle
particlesize
sizedistribution
distributionof
ofthetheCaCO
CaCO3 3cement.
cement.Measurements
Measurementswerewerecarried
carriedout
outwith
withtest
test
samples
samples dispersed
dispersed in isopropyl alcohol
in isopropyl alcoholusing
usingrefractive
refractiveindexes
indexesofof1.378
1.378
forfor isopropyl
isopropyl al-
alcohol and1.58
cohol and 1.58for
forCaCO
CaCO3.3 .

2.3.2. X-ray Florescence

2.3.2. X-Ray Florescence
An ARL QUANT’X Energy Dispersive X-ray Fluorescence Spectrometer (Thermo
An ARL QUANT’X Energy Dispersive X-Ray Fluorescence Spectrometer (Thermo
Fisher Scientific, Waltham, MA, USA) was used to evaluate the chemical composition
Fisher Scientific, Waltham, MA, USA) was used to evaluate the chemical composition of
of the oven-dried raw materials and the CaCO3 cement. The loss on ignition (LOI) was
the oven-dried
determined raw materials
by measuring the and
massthe CaCO
loss 3 cement. The loss on ignition (LOI) was de-
after heating the samples in an electric muffle
termined by measuring the mass loss after heating
furnace (Thermo Fisher Scientific, Waltham, MA, USA) theatsamples in an
950 ◦ C for 60 electric
min. muffle fur-
nace (Thermo Fisher Scientific, Waltham, MA, USA) at 950 °C for 60 min.
2.3.3. X-ray Diffraction
2.3.3.AX-Ray
X’PertDiffraction
Pro X-ray Diffractometer (Panalytical, Almelo, Netherlands) was used to
A X’Pert
determine Pro X-Ray
the phase Diffractometer
composition (Panalytical,
of the CaCO Almelo,
3 cement and Netherlands)
the transformed was used
cement to
pastes.
determine
The the phase
instrument composition
was operated of the
at 40 kV andCaCO
30 mA 3 cement
(Cu Kα1and
, λ =the transformed
1.5406 Å) using cement
a scan
pastes.ofThe
range ◦ 2θ, a stepwas
5–65instrument of 0.02◦ , at
sizeoperated and40dwell
kV and 30 of
time mA (Cu
4 s. Kα1resulting
The , λ = 1.5406 Å ) using
spectra werea
analyzed using Jade 9 software (Materials Data, Inc., Livermore, CA, USA) for qualitative
phase composition information and MAUD software for quantitative Rietveld analysis
(QXRD) [24].

2.3.4. Scanning Electron Microscopy

A SU-6600 Field Emission Scanning Electron Microscope (SEM) (Hitachi High-Tech,
Omuta, Fukuoka, Japan) was used to collect images of the CaCO3 cement and the transformed
cement paste. The samples were coated with platinum/palladium using a sputter coater
(Electron Microscopy Sciences, Hatfield, PA, USA) prior to secondary electron imaging.

2.3.5. Compressive Strength

Compressive strength development of the CaCO3 cement was evaluated at 4 h, 10 h,
1 day, 3 days, 7 days, and 14 days. Paste cubes (50 × 50 × 50 mm3 ) with a solution-to-solid
ratio (w/c) of 0.35 were utilized. The solution contained 0.1 M magnesium and strontium
chloride. The pastes were mixed according to ASTM C305 and then cast and compressed
according to ASTM C109 [25,26]. The pastes cured inside brass cube molds at the specified
 Materials 2021, 14, 2709 5 of 12

temperature (40, 60 or 80 ◦ C) with >95% relative humidity for up to 1 day. For testing
between 4 h and 1 day, the paste cubes received no additional curing outside their molds.
For 3-, 7-, and 14-day tests, the paste cubes were demolded at 24 h and placed in a bath
with the same composition as the mix solution at the specified temperature (40, 60, or
80 ◦ C). The paste cubes were removed from their curing environments at the specified time
and dried in a 105 ◦ C oven for 4 h before compressive strength testing with a loading rate
of 1 kN/s.

3. Results
3.1. CaCO3 Cement Characteristics
The CaCO3 cement has a median particle size of 15 with a 4 µm standard deviation.
The D90 and D10 for the CaCO3 cement are 19 and 11 µm, respectively. Figure 3 gives
the particle size distribution of the cement. Individual crystals and small agglomerates
make up less than 4% of the material at a median particle size of 0.4 µm. The primary
nucleated crystals agglomerate in the CSTR to minimize their surface energy, forming a
yarn-ball like, spherical morphology assembled of several microplates and lenses (Figure 4).
Ammonium ions have been shown to promote the growth of vaterite into hexagonal plates
and lenses by adsorbing onto the negatively charged (001) plane, which stabilizes the (001)
face promoting the hexagonal crystal growth. Together with the oriented attachment of
amorphous precursors and/or nanocrystals, the lens shaped single crystals are developed
as the crystal grows [27–29]. In Figure 4, an individual lens can be observed above the right
Materials 2021, 14, x most vaterite sphere. In diffusion-based experiments, rosette mesostructures developed 6 of 13
because the crystal structures were grown on a flat surface; whereas, in this study the
mesostructures are spherical because the crystal agglomerates formed in solution.

30

25
Number (%)

20

15

10

0
0.1 1 10
Diameter (µm)
3. Particle
Figure 3.
Figure Particlesize
sizedistribution
distributionof the CaCO
of the 3 cement.
CaCO 3 cement.

Table 2 shows the chemical and mineral composition of the CaCO3 cement. The alu-
mina and silica impurities found in the carbide lime sludge are not found in the resulting
cement because they are relatively insoluble impurities that were removed during the filter-
ing process (Figure 1); however, some magnesium and sulfate from the carbide lime sludge
do make it into the resulting cement. The chloride in the cement comes from the NH4 Cl
solution. The mesostructure of the crystal agglomerates creates porosity and high surface
area that traps solution. When the cement is heated and dried, the NH4 Cl decomposes
into hydrogen chloride (HCl) and NH3 gas. The HCl and NH3 gas are recovered while
scrubbing the flue gas. A portion of the HCl gas contacts water on the drying CaCO3 ,
forming hydrochloric acid, and is neutralized by the CaCO3 cement, leaving a residual
amount of CaCl2 [30]. The CaCO3 cement produced is mainly composed of metastable
vaterite (>99 wt%) with a minor amount of calcite (<1 wt%), see Figure 5. Formation of

10 µm
 15

Num
10

5
Materials 2021, 14, 2709 6 of 12
0
0.1 1 10
Diameter (µm)
amorphous CaCO3 is deliberately avoided as it is difficult to stabilize and process on an
industrial scale. Once
Figure 3. Particle the CaCO3 of
size distribution cement is dried,
the CaCO it is stable under ambient conditions.
3 cement.

10 µm

Figure4.4.SEM
Figure SEMimage
imageofof the
the metastable
metastable CaCO
CaCO 3 cement (vaterite).
3 cement (vaterite).

Table 2. Chemical
Table (XRF)the
2 shows andchemical
mineral (QXRD) composition
and mineral of the CaCO
composition cement.
of3the CaCO3 cement. The alu-
mina and Oxidesilica impurities Weight
found (%) in the carbide lime sludge are not found
Mineral Weightin(%)
the resulting
cement because they are relatively insoluble impurities that were removed during the fil-
CaO 55.1 Vaterite 99.5
tering process
SiO2 (Figure 1); however, 0 some magnesiumCalciteand sulfate from 0.5
the carbide lime
sludge Aldo2 Omake
3 it into the resulting
0 cement. The chloride in the cement comes from the
NH4Cl solution.
MgO The mesostructure 0.1 of the crystal agglomerates creates porosity and high
surface Fe 2 O3 that traps solution.
area 0 When the cement is heated and dried, the NH4Cl decom-
SO3 0.4
poses intoMnO
hydrogen chloride 0(HCl) and NH3 gas. The HCl and NH3 gas are recovered
while scrubbing
TiO2 the flue gas. A 0portion of the HCl gas contacts water on the drying CaCO3,
formingPhydrochloric
O
2 5 acid, and 0 is neutralized by the CaCO3 cement, leaving a residual
Cl 0.2
amount of CaCl2 [30]. The CaCO3 cement produced is mainly composed of metastable
Materials 2021, 14, x 1 44.1 7 of 13
vateriteLOI(>99 wt%) with a minor amount of calcite (<1 wt%), see Figure 5. Formation of
1 LOI is mass loss on ignition to 950 ◦ C.
amorphous CaCO3 is deliberately avoided as it is difficult to stabilize and process on an
industrial scale. Once the CaCO3 cement is dried, it is stable under ambient conditions.
V
1750
V
1500
1250 V
Intensity

1000 V
V
750
500
V
V
250
C V
0
10 20 30 40 50 60
2Θ (degrees)

Figure5.5.XRD
Figure XRDpattern
patternof of CaCO
CaCO 3 cement (V = vaterite; C = calcite).
3 cement (V = vaterite; C = calcite).

Table 2. Chemical (XRF) and mineral (QXRD) composition of the CaCO3 cement.

Oxide Weight (%) Mineral Weight (%)

CaO 55.1 Vaterite 99.5
SiO2 0 Calcite 0.5
 Materials 2021, 14, 2709 7 of 12

3.2. Cementitious Reaction

The cementing reaction in CaCO3 cement is the transformation of vaterite (CaCO3 )
to aragonite (CaCO3 ) or calcite (CaCO3 ). Vaterite dissolves and aragonite and/or calcite
precipitates. Since the cementing reaction is an aqueous dissolution-reprecipitation process,
curing the CaCO3 cement requires high humidity to maintain the transformation of vaterite
to aragonite and/or calcite. If the humidity of the curing environment is not controlled,
the material will desiccate, and the cementing reaction will cease, similar to Portland
cement. Additionally, like Portland cement, the cementing reaction of CaCO3 cement
can be accelerated by increasing the curing temperature. Figure 6 shows the temperature
dependency of the CaCO3 cementing reaction and compressive strength development.
The ultimate compressive strength of the material is 40 MPa, which is 3–13× higher than
the 3–13 MPa compressive strength, previously reported for CaCO3 cement developed
for medical applications [14,15]. At 40 ◦ C, CaCO3 cement paste does not show strength
development through 1 day and takes 14 days to achieve the full strength. By elevating
the temperature, full strength can be achieved by 7 or 3 days for 60 and 80 ◦ C, respectively.
Additionally, at elevated temperature, CaCO3 cement pastes have developed enough
strength by 4 to 10 h (80 and 60 ◦ C, respectively) to be demolded and handled. Fast
Materials 2021, 14, x
early strength is important for manufactured building materials with the need to transfer8 of 13
materials between initial and final curing steps, e.g., from pre-curing in molds at lower
temperatures to autoclaving in stacks at elevated temperatures.

45
40
35
Strength (MPa)

30
25 80 °C
20 60 °C
15
40 °C
10
5
0
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14
Time (days)
Figure 6.
Figure Temperature dependency
6. Temperature dependencyofof
CaCO 3 cement
CaCO strength
3 cement development.
strength development.

During the dissolution of vaterite, aragonite is the preferred precipitate over the most
During the dissolution of vaterite, aragonite is the preferred precipitate over the most
thermodynamically stable calcite, as aragonite exhibits an acicular morphology which can
thermodynamically stable calcite, as aragonite exhibits an acicular morphology which can
lead to an interconnected microstructure. The formation of aragonite can be controlled
lead to an interconnected microstructure. The formation of aragonite can be controlled
through the use of magnesium-based additives (e.g., MgCl2 , MgSO4 , Mg(C2 H3 O2 )2 ), which
through
are knownthetouse of magnesium-based
inhibit additives
calcite growth [31,32]. (e.g.,
The size andMgCl
aspect2, ratio
MgSO , Mg(C
of4the 2H3O2)2), which
acicular arago-
are
nite can be controlled by the use of strontium-based additives (e.g., SrCl2 , Sr(C2acicular
known to inhibit calcite growth [31,32]. The size and aspect ratio of the H3 O2 )2 ),arag-
onite
whichcanarebe controlled
known by the aragonite
to promote use of strontium-based
formation [33], additives
resulting in (e.g., SrCl2aragonite
thinner , Sr(C2H3O2)2),
which are
crystals known
with highertoaspect
promote aragonite formation [33], resulting in thinner aragonite crys-
ratios.
tals with higher aspect ratios.
The interconnection of the aragonite crystals is controlled through the vaterite particle
structure. The spherical vaterite
The interconnection particles have
of the aragonite a large
crystals (15 µm median
is controlled throughsize)the
and hetero-parti-
vaterite
geneous
cle structure.
structure. At all curing
The spherical temperatures,
vaterite particles aragonite
have a largecrystals
(15 µnucleate
m median on the
size)surface
and heter-
of vaterite particles, then grow outward, which results in a dense and interconnected
ogeneous structure. At all curing temperatures, aragonite crystals nucleate on the surface
honeycomb microstructure (Figure 7). This phenomenon is consistent to Nielsen et al.’s [34]
of vaterite particles, then grow outward, which results in a dense and interconnected hon-
observation where they hypothesized that the phenomenon resulted from the high mo-
eycomb microstructure (Figure 7). This phenomenon is consistent to Nielsen et al.’s [34]
bility and exchange of surface ions with solution. For the CaCO3 cement, water is only
observation
a medium for where they hypothesized
the metastable that theand
vaterite to dissolve phenomenon
reprecipitate resulted fromand
as aragonite the does
high mo-
bility and exchange of surface ions with solution. For the CaCO3 cement, water is only a
medium for the metastable vaterite to dissolve and reprecipitate as aragonite and does
not become chemically bonded. All the initial mix water will remain in the system after
the cementing reaction and will become porosity after drying. Therefore, the cemented
 cle structure. The spherical vaterite particles have a large (15 µ m median size) and heter
ogeneous structure. At all curing temperatures, aragonite crystals nucleate on the surfac
of vaterite particles, then grow outward, which results in a dense and interconnected hon
eycomb microstructure (Figure 7). This phenomenon is consistent to Nielsen et al.’s [34
Materials 2021, 14, 2709 observation where they hypothesized that the phenomenon resulted from 8the of 12high mo
bility and exchange of surface ions with solution. For the CaCO3 cement, water is only
medium for the metastable vaterite to dissolve and reprecipitate as aragonite and doe
notbecome
not becomechemically
chemically bonded.
bonded. All initial
All the the initial mix water
mix water will remain
will remain in theafter
in the system system afte
thecementing
the cementing reaction
reaction andandwillwill become
become porosity
porosity after drying.
after drying. Therefore,
Therefore, the cemente
the cemented
materialisisinherently
material inherentlymoremore porous
porous and and less dense
less dense than traditional
than traditional cementscements that are base
that are based
on
onhydration
hydration reactions which
reactions chemically
which bind water.
chemically bindFurthermore, the pore solution
water. Furthermore, of the
the pore solution o
CaCO
the CaCO
3 cement paste is close to neutral compared to the alkaline traditional cements.
3 cement paste is close to neutral compared to the alkaline traditional cements.

Materials 2021, 14, x 9 of 13

100 µm

Figure
Figure
Figure 7.7.SEM
SEM8image
shows
image ofthe
of the the conversion
hardened cement
hardened of the
paste
cement CaCO 3 cement
(predominately
paste (vaterite)
aragonite).
(predominately to aragonite in the
aragonite).
hardened cement paste. Comparing Figure 6 to Figure 8 elucidates that the cementing
Figure
reaction and8 shows the conversion
mechanical propertyof the CaCO3 cement
development of the (vaterite) to aragonite
CaCO3 cement in thedepend-
is entirely
hardened cement paste. Comparing Figure 6 to Figure 8 elucidates that the cementing
ent on the vaterite to aragonite transformation, which is less complex than traditional ce-
reaction and mechanical property development of the CaCO3 cement is entirely dependent
ments and can be easily accelerated through temperature without negative effects on per-
on the vaterite to aragonite transformation, which is less complex than traditional cements
formance. For instance,
and can be easily accelerated at through
80 °C, the CaCO3 cement
temperature without(99% vaterite
negative and
effects on 1% calcite) has fully
performance.
transformed
For instance, atto 8098% aragonite
◦ C, the and 2%
CaCO3 cement calcite
(99% byand
vaterite 3 days of curing;
1% calcite) whereas,
has fully at 40 °C, the
transformed
hardened cement paste is composed of 12% vaterite, 87% ◦
aragonite and
to 98% aragonite and 2% calcite by 3 days of curing; whereas, at 40 C, the hardened cement 1% calcite at 14
days
paste of curing. of 12% vaterite, 87% aragonite and 1% calcite at 14 days of curing.
is composed

100
90
80
70
Aragonite (%)

60
80 °C
50
40 60 °C
30 40 °C
20
10
0
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14
Time (days)
8.Conversion
Figure 8.
Figure Conversionof of
CaCO 3 cement
CaCO to aragonite
3 cement as a function
to aragonite of time and
as a function temperature
of time (quantified (quanti-
and temperature
by QXRD).
fied by QXRD).

4. Discussion
4.1. Raw Materials Availability
Annual global production of carbide lime sludge was estimated at approximately 25
million tons on a dry basis, where >95% is generated in China [23]. Carbide lime sludge
typically contains over 90 wt% Ca(OH)2 on a dry basis with minor impurities such as car-
Materials 2021, 14, 2709 9 of 12

4. Discussion
4.1. Raw Materials Availability
Annual global production of carbide lime sludge was estimated at approximately
25 million tons on a dry basis, where >95% is generated in China [23]. Carbide lime sludge
typically contains over 90 wt% Ca(OH)2 on a dry basis with minor impurities such as
carbon, silica, alumina, iron, and sulfur species depending on the composition of coal and
limestone. Carbide lime sludge is used in China to replace limestone as a raw material for
Portland cement production which can reduce CO2 emissions yet increase energy demand
depending on the additional energy required to dry the carbide lime [35]. However, there
is still a significant amount of carbide lime sludge being landfilled and legacy ponds, which
cause major environmental issues due to carbide lime sludge’s high alkalinity (pH 12.4).
Iron and steel slag production is, on the contrary, more evenly distributed worldwide.
It is estimated that about 510–664 million tons of iron and steel slag were generated
annually in 2019 [36]. Iron and steel slags are composed of about 35–60 wt% CaO with
other constituents such as silica, alumina, magnesia, and sulfur species. Except ground
granulated blast furnace slag, which is used as a supplementary cementitious material to
replace Portland cement in mortar and concrete applications, most iron and steel slags are
landfilled or can only be utilized in low-value applications such as road stabilization or
asphalt aggregates [37]. Based on both the annual production of waste feedstocks (carbide
lime sludge and iron and steel slag) and the CaO extraction efficiency, approximately
100 million tons of CO2 could be captured from industrial facilities and approximately
230 million tons of CaCO3 cement could be produced.

4.2. Building Material Applications

With its unique properties, CaCO3 cement is well suited for building materials ap-
plications with controlled factory manufacturing processes that are typically made from
inorganic binders, such as Portland cement or gypsum. The CaCO3 cement can provide
processing and performance advantages over Portland cement, e.g., shorter production
cycles, lighter weight, and flexibility on fillers and reinforcement elements. Furthermore,
CaCO3 cement is white, which makes it easy to color and texturize for decorative purposes.
Because of its neutral pore solution, CaCO3 cement is not suitable for structural
applications that require mild steel reinforcement but is suited for composite systems
development with the flexibility to incorporate a wide range of reinforcement elements
for superior toughness and flexural properties. The neutral pore solution of the CaCO3
cement also makes it amenable for use in environmentally sensitive areas and applications
that require biocompatibility.
CaCO3 cement’s porosity has inherent advantages and disadvantages. The advantage
is the ability to formulate lightweight products. For example, suitable potential applications
are lightweight fiber cement board and autoclaved aerated concrete due to their manu-
facture in controlled environments that utilize elevated curing temperatures to accelerate
property development. In other applications, the porosity could be a disadvantage, such
as concrete in severe freeze–thaw or physical salt attack environments. The durability of
CaCO3 cement in a range of situations and applications should be investigated in future
research projects.

4.3. CaCO3 Cement Manufacturing Energy and Carbon Footprint

The CaCO3 cement manufacturing process (Figure 1) requires both electrical energy
for mechanical processes (pre-processing, solubilization, filtration, CO2 capture, CaCO3
precipitation, dewatering, and aqueous recycling) and thermal energy for drying at ap-
proximately 130 ◦ C. Based on pilot plant data, production of CaCO3 cement is calculated
to require 2.8 to 3.9 MJ/kg when considering a range of dry and wet raw materials. This
compares to the 4.6 to 5.6 MJ/kg energy consumed during Portland cement production,
mainly from the calcination of limestone at 900 ◦ C and the sintering process at 1450 ◦ C [38].
Since producing CaCO3 cement from waste feedstocks does not require high temperature
Materials 2021, 14, 2709 10 of 12

processes and can capture and store CO2 from industrial emissions, CaCO3 cement has a
significantly lower CO2 footprint compared to Portland cement. The energy and carbon
footprint for CaCO3 cement manufacturing will vary for different sites and plant scales
due to factors such as electricity mix, fuel sources, and operational efficiency.
For the highest energy consumption case (3.9 MJ/kg CaCO3 cement), the electrical
energy consumption is 92 kWh/metric ton of CaCO3 cement, and the natural gas consump-
tion is 3.57 GJ/metric ton of CaCO3 cement. The plant operations that consume the most
electricity are carbide lime sludge dissolution and filtration (39%) and CO2 absorption
including flue gas compression (38%). 88% of the natural gas is consumed in the drying
of the feedstock and product. Using a 2019 California grid carbon intensity of 175 kg
CO2 /MWh, the electricity results in emissions of 16 kg CO2 /metric ton of CaCO3 cement.
With an emission factor of 56 kg CO2 /GJ, the natural gas combustion produces 200 kg
CO2 /metric ton of CaCO3 cement [39,40]. The total emissions are 216 kg CO2 /metric ton
of CaCO3 cement. Figure 9 compares the carbon captured and emitted during CaCO3
cement production to the CO2 emitted during Portland cement production. Since every
metric ton of CaCO3 cement produced captures 440 kg of CO2 and manufacturing CaCO3
cement releases 216 kg of CO2 , CaCO3 cement has a net capture of 224 kg of CO2 /metric
ton of CaCO3 cement produced. Substituting CaCO3 cement for Portland cement, results
Materials 2021, 14, x in a reduction of 882 kg of CO2 /metric ton of cement utilized due to net emissions of
11 of 13
658 kg of CO2 avoided from Portland cement and a net capture of 224 kg of CO2 during
the manufacture of CaCO3 cement when utilizing a waste Ca feedstock.

CaCO3 Cement Portland Cement

208
Emissions
(kg CO2 / metric ton of cement)

100 year
Capture

Direct
866
Capture 658

216 440
Emissions Emissions Net
224
Capture

Emission

Net
Capture

Carbonfootprint
Figure9.9.Carbon
Figure footprintofof the
the pilot-scale
pilot-scale CaCO
CaCO 3 cement
3 cement manufacturing
manufacturing process
process compared
compared to to
Portland
Portlandcement
cementmanufacturing
manufacturingprocess
process(based
(basedon
onthe
theupper
upperrange
rangeofofenergy
energyconsumption
consumptionfor forthe
the
CaCO
CaCO33cement
cementand
andaverage
averagePortland
Portlandcement
cementemissions
emissionsassuming 60%
assuming 60%of emissions
of emissionsare are
from the the
from
calcination
calcinationof
oflimestone
limestoneand
and40%
40%ofofthose
those emissions
emissions are
are recaptured
recaptured over
over 100
100 years
years [41–43]).
[41–43]).

IfIf curing
curing is conducted atat elevated
elevatedtemperature,
temperature,additional
additionalenergy
energyinput
inputis is
required
required to
heat the cementitious 3
to heat the cementitiousmixture
mixturetotothe
thecuring
curingtemperature.
temperature.ForFor example,
example, 11 m of concrete
3 concrete
consistingofof305
consisting 305kg
kgCaCO
CaCO 3 cement,
3 cement, 153153
kgkg water,
water, andand 1978
1978 kg kg of silicious
of silicious aggregate
aggregate re-
requires ◦
quires 147147
MJMJ (0.48
(0.48 MJ/kg
MJ/kg CaCO
CaCO 3 cement)
3 cement) to to heat
heat from
from 2020toto8080°C.C.End
Endofoflife
lifeuses
uses for
for
CaCO33cement
CaCO cementcomposites
compositeswould
wouldbe besimilar
similarto
tothose
thoseofofPortland
Portlandcement
cement composites
composites with
with
thedominant
the dominantrecycling
recycling scheme
scheme being
being crushed
crushed into
into aggregate.
aggregate.

5.5.Conclusions
Conclusions
We have
We have described
described aa method
method of
of converting
converting anthropogenic
anthropogenic CO emissions into
CO22 emissions into CaCO
CaCO33
cement at a pilot scale. The CaCO 3 cement gains approximately 40 MPa of strength during
cement at a pilot scale. The CaCO3 cement gains approximately 40 MPa of strength during
its conversion from vaterite to aragonite, which is 3× higher than previously reported
its conversion from vaterite to aragonite, which is 3× higher than previously reported re-
results. The cement paste hardens and gains strength through the formation of a network
sults. The cement paste hardens and gains strength through the formation of a network of
of interlocking aragonite needles. The conversion and strength gain can be accelerated by
interlocking aragonite needles. The conversion and strength gain can be accelerated by
elevated curing temperatures, e.g., full conversion and strength in 3 days at 80 °C. The
CaCO3 cement system is particularly well-suited in applications that can take advantage
of the inherent porosity, low pH, or rapid kinetics. The new cement system described is
an environmentally sustainable alternative cement that can be carbon negative, meaning
Materials 2021, 14, 2709 11 of 12

elevated curing temperatures, e.g., full conversion and strength in 3 days at 80 ◦ C. The
CaCO3 cement system is particularly well-suited in applications that can take advantage
of the inherent porosity, low pH, or rapid kinetics. The new cement system described is
an environmentally sustainable alternative cement that can be carbon negative, meaning
more CO2 can be captured during its manufacture than is emitted when utilizing a waste
Ca feedstock.

Author Contributions: Conceptualization, I.A.C., M.D., M.J.F., R.J.G., C.W.H. and R.P.T.; methodol-
ogy, I.A.C., M.J.F., C.W.H. and R.P.T.; formal analysis, I.A.C. and C.W.H.; investigation, I.A.C., M.D.,
M.J.F., R.J.G., C.W.H. and R.P.T.; resources, M.D. and R.J.G.; writing—original draft preparation, I.A.C.
and C.W.H.; writing—review and editing, I.A.C., M.D., M.J.F., R.J.G., C.W.H. and R.P.T.; visualization,
C.W.H.; supervision, M.D. and R.J.G.; project administration, I.A.C. and M.J.F.; funding acquisition,
M.D. and R.J.G. All authors have read and agreed to the published version of the manuscript.
Funding: This material is based upon work supported by the U.S. Department of Energy, Office of
Fossil Energy, under Award Number DE-FE-0002472.
Institutional Review Board Statement: Not applicable.
Informed Consent Statement: Not applicable.
Data Availability Statement: All research data are available and can be furnished upon request.
Acknowledgments: The authors express their thanks to their colleagues, scientific advisors, and
investors for their dedicated support of the project. Appreciation for their assistance in conducting
experiments is given to Patricia T. Lee, Samuel O. Morgan, Terilyn Q. Nguyen, Adrian Quiroz, and
Chantel C. Tester. Finally, the authors thank Guillaume A. Calas and Michael J. Weiss for their
assistance modeling the energy demand and CO2 emissions of the CaCO3 cement.
Conflicts of Interest: The authors declare no conflict of interest. The funders had no role in the design
of the study; in the collection, analyses, or interpretation of data; in the writing of the manuscript, or
in the decision to publish the results.

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