materials

Article
A New, Carbon-Negative Precipitated Calcium
Carbonate Admixture (PCC-A) for Low Carbon
Portland Cements
Lewis McDonald 1 , Fredrik P. Glasser 2 and Mohammed S. Imbabi 1, *
1 School of Engineering, University of Aberdeen, Aberdeen AB24 3UE, UK; l.mcdonald.12@aberdeen.ac.uk
2 Carbon Capture Machine (UK) Limited, Aberdeen AB10 1YL, UK; f.p.glasser@abdn.ac.uk
* Correspondence: m.s.imbabi@abdn.ac.uk; Tel.: +44-1224-272506




Received: 10 January 2019; Accepted: 11 February 2019; Published: 13 February 2019


Abstract: The production of Portland cement accounts for approximately 7% of global anthropogenic
CO2 emissions. Carbon CAPture and CONversion (CAPCON) technology under development by
the authors allows for new methods to be developed to offset these emissions. Carbon-negative
Precipitated Calcium Carbonate (PCC), produced from CO2 emissions, can be used as a means of
offsetting the carbon footprint of cement production while potentially providing benefits to cement
hydration, workability, durability and strength. In this paper, we present preliminary test results
obtained for the mechanical and chemical properties of a new class of PCC blended Portland cements.
These initial findings have shown that these cements behave differently from commonly used Portland
cement and Portland limestone cement, which have been well documented to improve workability
and the rate of hydration. The strength of blended Portland cements incorporating carbon-negative
PCC Admixture (PCC-A) has been found to exceed that of the reference baseline—Ordinary Portland
Cement (OPC). The reduction of the cement clinker factor, when using carbon-negative PCC-A,
and the observed increase in compressive strength and the associated reduction in member size can
reduce the carbon footprint of blended Portland cements by more than 25%.

Keywords: CO2 emissions; carbon CAPture and CONversion (CAPCON); Precipitated Calcium
Carbonate (PCC); limestone; strength; rheology; XRD analysis; Life Cycle Assessment

1. Introduction

1.1. Background
Estimates vary, but the cement industry currently produces at least 2.8 billion tonnes of cement
per annum, accounting for ~7% of global anthropogenic CO2 emissions [1–4]. Cement production is
expected to increase yearly to more than 4 billion tonnes per annum by 2040.
In 2009, the International Energy Agency (IEA) proposed the use of carbon capture and storage
to reduce these emissions [5]. Since the IEA’s proposal to reduce the carbon emissions of the cement
industry, new technologies have been developed to either capture and utilise post-combustion CO2 or
convert it into useful products. Some of these technologies are discussed in Section 1.2.
Calcium carbonate, in the form of limestone, has seen an increase in its use as a cement additive
to reduce the carbon footprint of cement clinker, which is due to the relatively low CO2 output of the
process in comparison to Portland cement manufacture [6]. Most codes of practice allow a maximum
of 5% ground limestone, containing >70% calcium carbonate, to be added to create Portland limestone
cement (PLC) blends as distinct from Ordinary Portland Cement (OPC). Ground limestone has also
been demonstrated to increase workability without impacting strength if used in quantities of less
than or equal to the maximum allowable 5% in accredited PLC blends [7–9].

Materials 2019, 12, 554; doi:10.3390/ma12040554 www.mdpi.com/journal/materials

Materials 2019, 12 FOR PEER REVIEW 2
Materials 2019, 12, 554 2 of 14
been demonstrated to increase workability without impacting strength if used in quantities of less
than or equal to the maximum allowable 5% in accredited PLC blends [7–9].
We present the first results of tests on the use of carbon-negative Precipitated Calcium Carbonate
We present the first results of tests on the use of carbon-negative Precipitated Calcium Carbonate
Admixture (PCC-A), a carbon CAPture and CONversion (CAPCON) product of the Carbon Capture
Admixture (PCC-A), a carbon CAPture and CONversion (CAPCON) product of the Carbon Capture
Machine (CCM) (see http://www.ccmuk.com for more information), to reduce the carbon footprint of
Machine (CCM) (see http://www.ccmuk.com for more information), to reduce the carbon footprint
blended cements. Unlike ground limestone, which is carbon positive, PCC-A from the CCM CAPCON
of blended cements. Unlike ground limestone, which is carbon positive, PCC-A from the CCM
process is carbon negative and sequesters between 100 and 350 kgCO2 per tonne of PCC-A produced,
CAPCON process is carbon negative and sequesters between 100 and 350 kgCO2 per tonne of PCC-
depending on the process inputs. Our proposal for a more sustainable future, where cement production
A produced, depending on the process inputs. Our proposal for a more sustainable future, where
is decarbonised at source, is illustrated in Figure 1.
cement production is decarbonised at source, is illustrated in Figure 1.
CO2

Brine
CCM

PMC
PXC

PCC
PCC

Figure 1. Proposal for the production of a new generation of enhanced performance, low carbon
Figure 1. Proposal
Precipitated Calciumfor the production
Carbonate of a(PCC-A)
Admixture new generation of enhanced
blended Portland performance,
cements low carbon
can be achieved in situ
Precipitated
using Calcium
the Carbon Carbonate
Capture Admixture
Machine (CCM). (PCC-A) blended Portland cements can be achieved in
situ using the Carbon Capture Machine (CCM).
The role of calcium carbonate in blended Portland cements spans chemical and physical properties.
The role role
The chemical of calcium
is throughcarbonate in blended
the formation Portland
of (hemi- cementscarboaluminate
and mono-) spans chemicalphases and physical
during
properties. The chemical role is through the formation of (hemi- and mono-) carboaluminate
hydration [10]. Physically, it is predominantly an inert filler [8,11–13]. Unpublished data suggests phases
that
during
the hydration
control of grain[10].
size Physically, it is predominantly
and the morphology of the PCC-Aan inert
in thefiller
CCM’s [8,11–13].
CAPCON Unpublished
process candata
be
suggests that the control of grain size and the morphology of the PCC-A in the
beneficially used to produce blended Portland cements that do not compromise strength, durability or CCM’s CAPCON
process canwhile
passivation be beneficially used to produce
offering performance benefitsblended Portland
that match cements
or surpass OPC.that do not compromise
strength, durability
The test methods or reported
passivation while
in this offering
paper were performance benefits
used to evaluate, forthat
thematch or surpass
first time, OPC.of
the effects
The test methods reported in this paper were used to evaluate, for the first
adding carbon-negative PCC-A to OPC, potentially leading to the development of new classes of high time, the effects of
adding carbon-negative
performance, low carbon PCC-A to OPC,
Portland cementpotentially
blends. leading to the development
The methods were used toofdetermine
new classes of high
strength,
performance, low carbon Portland cement blends. The methods were used to
rheology, passivation potential and the reduction in embodied CO2 content. It has been shown that thedetermine strength,
rheology,
use passivation
of PCC-A potential
in blended cements and canthe reduction
achieve in embodied
an increased CO2 content.
strength at contents It has
wellbeen shown
beyond thethat
5%
the use
limit forof PCC-Alimestone,
ground in blended cements
while can achieve
concurrently an increased
reducing strength
the embodied COat2 contents
content by well
25%beyond the
or more.
5% limit for ground limestone, while concurrently reducing the embodied CO2 content by 25% or
1.2.
more.Carbon Capture and Utilisation in Cement Production
Portland cement is the most abundantly manufactured material globally and is also one of the
1.2. Carbon Capture and Utilisation in Cement Production
largest sources of CO2 emissions [1–4]; it is thus a prime candidate for the emerging carbon capture
Portland cement
and utilisation industryistothe most abundantly
prioritise. manufactured
A recent report publishedmaterial
by Chathamglobally and[14]
House is also one ofthat,
estimates the
largest
to sources
effectively of COthe
control 2 emissions
impact of [1–4]; it is thusindustry
the cement a prime oncandidate for the emerging
the environment, carbon
the clinker capture
factor (i.e.,
and utilisation
active industry
fraction) in cementstohas
prioritise. A recent
to be reduced report
to 60% published
of the presentby Chatham
value by 2050.House
Once[14]
this estimates
has been
that, to effectively
achieved, control
other methods the to
have impact of the cement
be developed industry
that rely on the
on carbon environment,
capture the clinker factor
and utilisation.
(i.e., An
active fraction) to
alternative in carbon
cementscapture
has to be reducedintothe
outlined 60% of the present
Chatham Housevalue
reportbyis2050. Once
the use of this has
“novel
been achieved, other
cements”—low methods
carbon have to
alternatives to be developed
traditional that relycement
Portland on carbon capture
blends. Theseandcements
utilisation.
include
An alternative
allegedly carbon-freetomagnesium
carbon capture
oxide outlined
derived fromin the Chatham silicates
magnesium House report
(MOMS) is the use ofcalcium
cements, “novel
cements”—low (CSA)
sulfoaluminate carboncements
alternatives
and to traditionalcalcium
carbonated Portland cement
silicate blends.
(CCSC) These cements
cements amongst include
others.
allegedly carbon-free
However, novel cements magnesium
have seenoxide derivedpenetration
little market from magnesium silicates
due to their high(MOMS) cements,
production calcium
costs (MOMS
Materials 2019, 12 FOR PEER REVIEW 3

sulfoaluminate (CSA) cements and carbonated calcium silicate (CCSC) cements amongst others.
Materials 2019, 12, 554 3 of 14
However, novel cements have seen little market penetration due to their high production costs
(MOMS cements), specialty usage (CSA cements), scalability issues (CCSC cements) and resistance
tocements),
change by codes of
specialty practice,
usage (CSAconsumer
cements),groups andissues
scalability standards
(CCSC institutes,
cements) compared to tried,
and resistance tested
to change
and trusted
by codes of Portland cement alternatives.
practice, consumer groups and The Chatham
standards Housecompared
institutes, report claims thattested
to tried, carbonandcapture
trusted
methods
Portlandcould
cement reduce CO2 emissions
alternatives. by 95–100%.
The Chatham House Similarly, a study
report claims ofcarbon
that severalcapture
active carbon
methodscapture
could
plants
reduceconducted
CO2 emissions by David and Herzog
by 95–100%. [15]
Similarly, found
a study of the typical
several activeefficiency to be plants
carbon capture 90% for direct
conducted
emissions.
by David and In both cases,[15]
Herzog thefound
conclusions relate
the typical to high cost,
efficiency to benon-viable
90% for directcarbon capture In
emissions. and storage
both cases,
routes and are therefore of limited value. The estimates also ignore the contributions
the conclusions relate to high cost, non-viable carbon capture and storage routes and are therefore of of secondary
emissions from The
limited value. quarrying,
estimatestransport and grinding,
also ignore where the
the contributions CO2 cannotemissions
of secondary be easily from
captured—see
quarrying,
Figure 2.
transport and grinding, where the CO2 cannot be easily captured—see Figure 2.

Figure 2. Breakdown of CO2 emissions of Portland cement production. Data taken from the Chatham
Figure
House2.report
Breakdown
[14]. of CO2 emissions of Portland cement production. Data taken from the Chatham
House report [14].
Worldwide, CO2 capture and utilisation methods for the cement industry currently include the
production
Worldwide, of carbon-negative
CO2 capture and admixtures
utilisation through
methods mineralisation
for the cement (Carbon
industryCapture Machine)
currently include[6] the
and
carbonation cured cements (Solidia, CarbonCure,
production of carbon-negative admixtures through mineralisation CO 2 NCRETE) [16–18].
(Carbon Capture Machine) [6] and
Carbonation
carbonation cured cements
cured cements (Solidia, were first proposed
CarbonCure, in the 1970s,
CO2NCRETE) but their development has been
[16–18].
stunted due to process
Carbonation curedcomplexity,
cements were cost first
and application
proposed in scope. In the carbonation
the 1970s, curing process,
but their development has CO 2 is
been
converted
stunted dueinto the various
to process polymorphs
complexity, cost of and calcium carbonate—calcite
application scope. In the being the most
carbonation common—through
curing process, CO2
isthe interaction
converted intoof CSH gel withpolymorphs
the various CO2 (gas) proceedingof calcium in carbonate—calcite
two stages: initially beingthe CSHthe“sheds” Ca forming
most common—
CaCO and a low Ca CSH limit is reached at Ca/Si ~1 which, upon continued
through3 the interaction of CSH gel with CO2 (gas) proceeding in two stages: initially the CSH “sheds” carbonation, yields silica
Cagelforming
and calcium
CaCO carbonate
3 and a low [14].
CaThis
CSHdiffers
limit from the normal
is reached at Ca/Si hydration
~1 which, route
uponwhere calciumcarbonation,
continued hydroxide is
formed
yields in place
silica of calcium
gel and calcium carbonate
carbonate [19]. Prior
[14]. Thisto CO
differs
2 exposure,
from the
the free
normal water content
hydration of the where
route cement
is reduced
calcium to ensure
hydroxide is that
formed the CO 2 can of
in place diffuse
calcium efficiently
carbonate throughout.
[19]. Prior The
to cement is then exposed
CO2 exposure, to CO2
the free water
at pressures
content of theup to 5 atm.
cement After exposure,
is reduced to ensure that the unreacted
the CO2 can cement
diffusemay be hydrated
efficiently again toThe
throughout. ensure that
cement
isunreacted
then exposedphasestocan CO continue to hydrate
2 at pressures upand to 5provide further
atm. After increases the
exposure, in strength
unreacted[20].cement
The COmay 2 content
be
of carbonation
hydrated again to cured
ensure cements was verified
that unreacted phasesby Seo
canet al. [21] to
continue through
hydrate XRDandanalysis
provideand determined
further increasesto
inrange from[20].
strength 6.9 to 11%
The CO of2 the cement,
content depending on
of carbonation composition.
cured cements was verified by Seo et al. [21] through
The carbonation
XRD analysis curing process
and determined to rangeisfrom claimed6.9 toto11%
provide
of thecement
cement, with enhanced
depending ondurability,
composition. as the
calcium carbonate precipitation
The carbonation curing process within
is claimedthe CSH gel creates
to provide cementa denser, less porous
with enhanced structure
durability, [22].
as the
However,
calcium carbonation
carbonate reduces the
precipitation alkalinity
within the CSH of the
gelcement
creates paste and in
a denser, turn
less can lead
porous to the [22].
structure early
corrosion carbonation
However, of reinforcingreducessteel, especially
the alkalinityin the of presence
the cementof chloride
paste ions
and [23]. Thecan
in turn combined
lead toreliance
the early on
high pressure
corrosion CO2 infusion
of reinforcing steel,and the accompanying
especially in the presence acidification of the
of chloride ionscement binder
[23]. The with consequent
combined reliance
onpassivation
high pressureloss limits
CO2 the application
infusion and the scope of such carbonation
accompanying methods
acidification to pre-cast,
of the unreinforced
cement binder with
concrete products,
consequent passivationsuchloss as bricks,
limits blocks and paving
the application tiles,ofwhich
scope together account
such carbonation methodsfor notomore than
pre-cast,
20% of all concrete
unreinforced concreteuses [24]. such
products, Such as cements, however,
bricks, blocks andcould
paving potentially
tiles, which betogether
used with non-steel
account for
reinforcement, such as glass fibres.
no more than 20% of all concrete uses [24]. Such cements, however, could potentially be used with
non-steelUnlike carbonation such
reinforcement, curing, mineralisation
as glass fibres. through carbon capture serves more than one role; the
CO2Unlike
is converted into minerals,
carbonation curing, such as calciumthrough
mineralisation carbonate and magnesium
carbon capture serves carbonate, whichone
more than arerole;
used
in aCO
the multitude of industries.
2 is converted The method
into minerals, such as ofcalcium
mineralisation
carbonate canand
include the carbonation
magnesium carbonate, of metal
whichoxide
are
by-products from mining processes [25] or through precipitating the minerals using CO2 absorption
Materials 2019, 12, 554 4 of 14

in an aqueous alkali solution [26]. In the cement industry, calcium carbonate can be used as a clinker
replacement, as described in Section 1.1. Based on theory and experience, the maximum efficiency of
CO2 mineralisation has been estimated at 68% [27].
The use of mineralised CO2 in the form of PCC-A (produced through carbon CAPCON technology
developed by CCM) as a cement admixture is the focus of this paper, where first results have shown
that a significant reduction of CO2 emissions of around 25% can be achieved by the substitution
of clinker with carbon-negative PCC-A (see Section 3.4). The PCC-A in cement reacts with water
during formation to produce hydrated calcium carboaluminates that develop from the hydration and
partial carbonation of C3 A phases. In doing so, the interaction between water and C3 A is modified,
leading to a more rapid formation of ettringite. By stabilising carboaluminates, sulfate is forced to
remain in the ettringite and so conversion back to monosulfoaluminate becomes thermodynamically
unfavourable [8]. This potentially impacts the role of gypsum, a widely used setting retarder [28].
The reference CO2 content of an off-the-shelf PLC was determined in the course of the tests,
using XRD. At 11.4%, it has a comparable CO2 content to carbonation cured cements at 11.0% [21],
but with none of the inherent disadvantages or limitations. Further testing of PCC-A blended cements
is expected to confirm that a significantly higher embodied CO2 content can be achieved without either
detriment to quality or limitation to the range of products made and applications deployed, when
using these new generation Portland cements.

2. Materials and Methods

2.1. Materials
Two types of cement were used in the tests carried out—a CEM I 52.5N OPC and a CEM II/A-LL
32.5R PLC. Hanson Cement UK supplied both products. The main constituents of the cements
were determined through XRD analysis and Rietveld Refinement, as detailed in Sections 2.2 and 3.1.
The manufacturer specifies that both cements have a Blaine fineness between 300 and 500 m2 /kg.
The PCC-A used is a product of the carbon CAPCON process developed by Carbon Capture
Machine (UK) Limited. It was prepared from CO2 -rich flue gas, where CO2 was selectively dissolved
at the point of emission in dilute aqueous alkali (NaOH) solution. The solution was then mixed with
calcium-containing brine to produce the PCC-A, which was subsequently filtered, rinsed and dried
before use to remove contaminants, such as NaCl.

2.2. X-ray Diffraction (XRD) Analysis

Samples of the PCC-A, and both cement types, were tested using a PANalytical X’Pert X-ray
powder diffractometer to determine the composition. Powder specimens were analysed at room
temperature at a 2θ range from 30◦ to 80◦ , Cu K alpha radiation, using a scan period of 10 min.

2.3. Rheological Data

The rheological data of the freshly mixed cement pastes were measured using a continually
increasing shear rate up to 200 1/s over a period of 100 s before decreasing at the same rate to 0.
A 25 mm coaxial cylinder spindle was used in conjunction with a 40 mm sample pot.
The cement and PCC-A were weighed to provide a total solids content of 200 g and the desired
water/solids ratio was also weighed. The PCC-A was added to the water and stirred continuously to
ensure it was evenly dispersed. The PCC-A/water slurry was then combined with the cement in a mixing
bowl and mixed continuously for 90 s; this mixing period was considered sufficient to ensure the hydration
of the cement paste while reducing the risk of early-set formation. Within 30 s of the mixing ending,
the paste was transferred to the sample pot and connected to the rheometer and the test was started.
Data were collected for samples of OPC, PLC and PCC-A blended cement ranging from 0 to
20% PCC-A content. As the water/cement ratio decreased, the range of PCC-A cements that were
sufficiently workable to test also decreased.
Materials 2019, 12, 554 5 of 14

2.4. Compressive Strength

Cement pastes were prepared in the same way as for rheological testing, but with a longer mix
time in accordance with BS EN 196-1:2016 [29]. A longer mix time, compared with the rheological tests,
was used to ensure the PCC-A was well distributed in the paste before casting. The paste was then
cast in 50 × 50 × 50 mm cube steel moulds. Samples were maintained at a constant temperature of
25 ◦ C for 24 h before being demoulded. Samples were thereafter fully submerged in a water bath at an
ambient temperature for 7 or 28 days. It was observed during casting that cement pastes containing
a high PCC-A content were less workable, i.e., they were more viscous than OPC and at the highest
PCC-A content were difficult to cast.
After curing, the samples were wiped dry before being tested. Testing was carried out using
a hydraulic ram at a loading rate of 1 mm/min. The applied load was increased until the sample
fractured. Data were collected electronically with a measurement of displacement and force recorded
6 times per second. The compressive strength was calculated as a variant of the equation provided in
BS EN 196-1:2016 [29] to account for the different cube size tested:

Fc
Rc = (1)
2500
where Rc is the compressive strength (MPa), Fc is the load recorded at the point of fracture (N) and
2500 is the area (mm2 ) that the load was applied to, i.e., 50 × 50 mm.

2.5. Scanning Electron Microscope (SEM) Imaging

Fragments from the compressive strength testing were collected and used for SEM imaging.
Pieces no greater than 10 mm in any dimension were coated using carbon evaporation under vacuum.
The device used was a Zeiss GeminiSEM Field Emission Scanning Electron Microscope, which allowed
for multiple methods of imaging to be used. Images of the fracture surface were obtained using
secondary electron (SE) imaging and electron backscatter diffraction (BSE).
SE imaging is the detection of low energy electrons emitted from the surface of the specimen
exposed to the high energy electron beam and can be used to determine specimen topography. BSE is
the detection of primary electrons that have been diffracted by an angle greater than 90◦ . The angle at
which the electron has been diffracted is related to the atomic structure of the scattering material and
can be used to reveal changes in specimen composition [30].

3. Results and Discussion

3.1. XRD Analysis

XRD diffractograms of the OPC and PCC-A blended cement samples tested were analysed using
Rietveld Refinement, using Profex/BGMN [31] in accompaniment with structure data from ICSD [32].
Tables 1 and 2 provide, in standard notation, the phases identified in the cement clinker and the oxides
present in those phases. The PLC used for comparison interestingly had a calcium carbonate content of
18.27%, which was more than the maximum amount of PCC-A blended with OPC that was tested (15%).

Table 1. Quantitative analysis of Ordinary Portland Cement (OPC) used in tests and oxides present.

Mineralogical Composition Phase Wt. % Chemical Composition Oxide Wt. %

C3 S 59.65 SiO2 20.28
C2 S 15.24 Al2 O3 4.71
C3 A 11.81 Fe2 O3 3.27
C4 AF 8.65 CaO 67.13
CSH2 4.65 SO3 2.54
MgO 0.67
K2 O 1.40
Materials 2019, 12, 554 6 of 14

Table 2. Quantitative analysis of Portland limestone cement (PLC) and oxides present.

Mineralogical Composition Phase Wt. % Chemical Composition Oxide Wt. %

C3 S 60.11 SiO2 15.23
C2 S 7.66 Al2 O3 3.33
C3 A 9.42 Fe2 O3 2.75
C4 AF 1.03 CaO 64.40
CSH2 3.51 SO3 1.41
CaCO3 18.27 MgO 0.64
K2 O 0.83
CO2 11.41

The chemical composition of the PCC-A used in the blended cements is summarised in Table 3.
This PCC-A was comprised of calcite with a very small, residual salt content remaining from the
production process. No other CaCO3 polymorphs were identified using Rietveld Refinement.

Table 3. Quantitative analysis of PCC-A used in cement blends.

Compound Wt. %
Calcite 99.8
Aragonite 0.0
Vaterite 0.0
Halite, NaCl 0.2

The NaCl content attributed to the PCC-A dropped to 0.02% when a 10% blended PCC-A cement
was produced. This is the same as the NaCl content in the fresh tap water used to cure the test samples.
Although the presence of NaCl can lead to an increased compressive strength, at this very low level it
would be limited to no more than ~0.3%. A 10+% relative increase in the 28-day compressive strength
of PCC-A blended cements, therefore, cannot be attributed to the presence of NaCl. The logical
conclusion is that it is attributed to the use of PCC-A.
XRD analysis provides a powerful tool for identifying the purity of PCC-A samples and will be of
great benefit in future when different PCC-A polymorphs and granularities are used.

3.2. Determination of Strength

After 7 days of curing, the PCC-A cement blends showed a reduction in strength with the
carbon-negative Precipitated Calcium Carbonate (PCC) content above 4%. However, after 28 days,
an increase in strength was observed up to 10% PCC. This increase in strength was accompanied
by a decrease in the workability of the cement paste, tentatively attributable to the formation of
carboaluminate phases, which act as a strong binder between the cement paste, unreacted PCC-A and,
in the case of concrete, aggregates [13].
The complete set of results from the compressive strength testing is presented in Figure 3. It can
be seen that an increase in strength is gained after 7 days of curing for PCC-A content between 1 and
4%. Beyond 4% PCC-A, the strength of the cement starts to decrease as the PCC-A content increases.
After 28 days, the strength increase resulting from the inclusion of PCC-A continues up to and beyond
15%, reaching a maximum strength of 54.8 MPa at 10% PCC-A content. This represents an increase of
approximately 20% compared to the OPC reference. A PLC sample was separately tested and found to
have a compressive strength of 18.1 MPa and 22.3 MPa at 7 and 28 days, respectively.
Materials
Materials2019,
2019,12
12FOR
FORPEER
PEERREVIEW
REVIEW 77

increase
increaseof ofapproximately
approximately20%
20%compared
comparedtotothe
theOPC
OPCreference.
reference.AAPLC
PLCsample
samplewas
wasseparately
separatelytested
tested
Materials 2019, 12, 554 7 of 14
and found to have a compressive strength of 18.1 MPa and 22.3 MPa at 7 and 28 days, respectively.
and found to have a compressive strength of 18.1 MPa and 22.3 MPa at 7 and 28 days, respectively.

Compressive
Figure3.3.Compressive
Figure strength
Compressivestrength cements
strengthofofcements containing
cementscontaining PCC-A
containingPCC-A after
after777and
PCC-Aafter and
and2828day
dayofofcuring,
curing,with
withan
an
increase in strength of up to 4% content in the former and
and 10%
10% content
content in
in the
the latter,
latter, respectively.
respectively.
increase in strength of up to 4% content in the former and 10% content in the latter, respectively.

Since
Since all
Sinceall the
allthe tests
thetests were
testswere carried
werecarried out
carriedout on
outon cement
oncement pastes,
cementpastes,
pastes,thethe expected
theexpected 52.5
expected52.5 MPa
52.5MPa compressive
MPacompressive strength
compressivestrength
strength
of
of the
ofthe OPC
theOPC was
OPCwaswasnot not reached—this
notreached—this value
reached—thisvalue is normally
valueisisnormally attributed
normallyattributed to mortar
attributedtotomortar strength.
mortarstrength.
strength.
Future
Futurework
Future workon
work onstrength
on strengthwill
strength willrequire
will requiretesting
require testingsamples
testing samplesatatatlower
samples lower
lowerwater/cement
water/cement(w/c)
water/cement (w/c) ratios
(w/c)ratios and
ratiosand
and
increasing
increasing the
increasingthe curing
thecuring
curingtimetime up
timeup to 365
uptoto365 days.
365days. OPC,
days.OPC, PLC
OPC,PLC and
PLCandand10%10% PCC-A
10%PCC-A will
PCC-Awill also
willalso be
alsobe tested
betested at a similar
testedatataasimilar
similar
workability,
workability,as
workability, asis
as isisshown
shownin
shown inSection
in Section3.3.
Section 3.3.The
3.3. Theuse
The useof
use of PCC-A
ofPCC-A
PCC-Ain in mortars
inmortars will
mortarswill be
willbe studied,
bestudied, as
studied,as the
asthe formation
theformation
formation
of
ofcarboaluminate
of carboaluminate
carboaluminate phases
phaseshashas
phases beenbeen
has documented
been to have
documented
documented totostrong
havebonding
have strong properties
strong bonding between aggregates
bonding properties
properties between
between
and cement
aggregates
aggregatesandpaste
andcement [13].
cementpaste
paste[13].
[13].
3.3. Rheological
3.3. Rheological Analysis
3.3. RheologicalAnalysis
Analysis
Cement
Cement pastes with water/cement ratios of
of 0.5, 0.4
0.4 and 0.3
0.3 were tested
tested using thethe method
Cement pastes
pastes with
with water/cement
water/cement ratios
ratios of 0.5,
0.5, 0.4 and
and 0.3 were
were tested using
using the method
method
described
described in Section 2.3. Data were recorded using a Brookfield R/S+ rheometer in conjunction
describedin inSection
Section2.3.
2.3.Data
Datawere
wererecorded
recordedusing
usingaaBrookfield
BrookfieldR/S+
R/S+rheometer
rheometerininconjunction
conjunctionwith
with
with
the the Rheo3000 software package. The addition PCC-A
of PCC-A to cementcreated
created a more viscous
viscous paste
the Rheo3000
Rheo3000 software
software package.
package. The
Theaddition
addition ofof PCC-A toto cement
cement createdaa more
more viscous paste
paste
(Figures 4–7),
(Figures whereas the PLC tested for comparison was less viscous (Figures 4, 6 and 7).
(Figures4–7),
4–7),whereas
whereasthe
thePLC
PLCtested
testedfor
forcomparison
comparisonwas wasless
lessviscous
viscous(Figures
(Figures4,4,66and
and7).
7).

Figure
Figure
Figure Shear
4. 4. stress
4.Shear
Shear measured
stress
stressmeasuredininin
measured cement
cementsamples
cement sampleswith
samples withwater/cement
with water/cement (w/c)
water/cement(w/c) ratio===
(w/c)ratio
ratio 0.5
0.5
0.5 asas
as rate
rate
rateofofof
shear increases. shear
shearincreases.
increases.
Materials 2019,
Materials 2019, 12,
12 FOR
554 PEER REVIEW 8 of 148

Figure 5. Shear stress measured in cement samples containing high PCC-A content with w/c = 0.5 as
shear rate increases.
Figure 5. Shear stress measured in cement samples containing high PCC-A content with w/c = 0.5 as
shear
As therate
w/cincreases.
ratio of the cement pastes decreases, the PCC-A cement samples over 10% became
too viscous for the rheometer to start and are not included in Figures 6 and 7. This is likely due to the
largeAs the stress
shear w/c ratio
that of
canthe
becement
observed pastes
in thedecreases,
initial partthe
of PCC-A
the tests,cement
where samples
setting ofover 10% became
the cement paste
too viscous for the rheometer to start and are not included in Figures 6 and 7.
starts early. However, the pastes then break down quickly and become fluid and workable again. This is likely due toThe
the
large
overt shear stress
rise in that can
viscosity is be observed
termed in the
“false set”initial
and part
can of the tests, where
sometimes setting of
be overcome bythe cement
using paste
admixed
starts early. However, the pastes then break down quickly and become fluid and workable
plasticiser. The false-setting compositions, assuming that normal strength gain occurs at later stages, again. The
overt rise in viscosity is termed “false set” and can sometimes be overcome
might actually be useful in developing sprayed concretes—exploring this is a task for the future. by using admixed
plasticiser.
However, theseThe false-setting
compositions compositions,
would not beassuming
useful inthat normal strength
conventional gain occurs at later stages,
construction.
might actually be useful in developing sprayed concretes—exploring this is a task for the future.
Figure 5. Shear stress measured in cement samples containing high PCC-A content with w/c = 0.5 as
However,
Figurethese compositions
5. Shear stress measuredwould not besamples
in cement useful in conventional
containing construction.
high PCC-A content with w/c = 0.5 as
shear rate increases.
shear rate increases.

As the w/c ratio of the cement pastes decreases, the PCC-A cement samples over 10% became
too viscous for the rheometer to start and are not included in Figures 6 and 7. This is likely due to the
large shear stress that can be observed in the initial part of the tests, where setting of the cement paste
starts early. However, the pastes then break down quickly and become fluid and workable again. The
overt rise in viscosity is termed “false set” and can sometimes be overcome by using admixed
plasticiser. The false-setting compositions, assuming that normal strength gain occurs at later stages,
might actually be useful in developing sprayed concretes—exploring this is a task for the future.
However, these compositions would not be useful in conventional construction.

Figure 6. Shear stress in cement samples at w/c = 0.4. The 15 and 20% PCC-A samples became
unworkable
Figure at this
6. Shear w/cin
stress without
cementthe use of plasticiser
samples at w/c = and
0.4. have been
The 15 omitted.
and 20% PCC-A samples became
Figure 6. Shear stress in cement samples at w/c = 0.4. The 15 and 20% PCC-A samples became
unworkable at this w/c without the use of plasticiser and have been omitted.
unworkable at this w/c without the use of plasticiser and have been omitted.

Figure 6. Shear stress in cement samples at w/c = 0.4. The 15 and 20% PCC-A samples became
unworkable at this w/c without the use of plasticiser and have been omitted.

Figure 7. Shear stress in cement samples containing w/c = 0.3. The 10% PCC-A became unworkable at
this w/c and are excluded.

As the w/c ratio of the cement pastes decreases, the PCC-A cement samples over 10% became
too viscous for the rheometer to start and are not included in Figures 6 and 7. This is likely due to
the large shear stress that can be observed in the initial part of the tests, where setting of the cement
paste starts early. However, the pastes then break down quickly and become fluid and workable again.
The overt rise in viscosity is termed “false set” and can sometimes be overcome by using admixed
plasticiser. The false-setting compositions, assuming that normal strength gain occurs at later stages,
might actually be useful in developing sprayed concretes—exploring this is a task for the future.
However, these compositions would not be useful in conventional construction.
As the 10% PCC-A cement samples showed the greatest compressive strength of those tested (see
Figure 3), cement pastes of OPC and PLC that provided a similar workability by adjusting the w/c
Materials 2019, 12 FOR PEER REVIEW 9

Figure 7. Shear stress in cement samples containing w/c = 0.3. The 10% PCC-A became unworkable at
this w/c and are excluded.
Materials 2019, 12, 554 9 of 14

As the 10% PCC-A cement samples showed the greatest compressive strength of those tested
(see Figure 3), cement
ratio were found. pastes
These of OPC
w/c ratios and
are PLC in
shown that provided
Figure 8. Thea volume
similar workability by adjusting
of water required for a 10%the
w/c ratio
PCC-A towere found.
obtain Theseworkability
a similar w/c ratios are shown
to OPC is in
25%Figure 8. The
higher. Forvolume
PLC, theof required
water required
volumeforisa2.5%
10%
PCC-A to obtain a similar workability to OPC is 25% higher. For PLC, the required volume
lower. Further work is clearly needed to support the wide use of PCC-A cement blends in future. is 2.5%
lower. Further work is clearly needed to support the wide use of PCC-A cement blends in future.

Figure 8. Workability
Figure 8. Workability of
of three
threedifferent
differentblends
blendstotodetermine
determinethe
thew/c
w/c ratio for
for which
which OPC,
OPC, PLC
PLC and
and
10%
10% PCC-A
PCC-Asamples
samplesexhibit
exhibitsimilar
similarrheological
rheologicalproperties.
properties.

Further
Further work
work isis planned
planned and
and will
will be
be carried
carried out
out on
on the
the rheology
rheology of
of PCC-A
PCC-A cement
cement blends
blends to
to
definitively establish why they behave in a manner dissimilar to what is known for
definitively establish why they behave in a manner dissimilar to what is known for PLC.PLC.

3.4.
3.4. Scope
Scope for
for Emission
Emission Reduction
Reduction of
of PCC-A
PCC-A Cement
Cement Blends
Blends
The
The reduction
reduction inin CO
CO22 emissions
emissions through
through the
the use
use of
of PCC-A
PCC-A can
can be
be calculated
calculated as
as follows:
follows:

CO
CO22 reduction,
reduction, C
C == w
wopc · mopc++w
opc ∙ mopc pcc∙ ·m
wpcc mpcc
pcc,, (2)
(2)

where
where w wopc and w
opc and wpcc arethe
pcc are themass
massfractions
fractionsofofOPCOPCand
and PCC-A
PCC-A respectively,
respectively, and
and mopc
mopc andand mis
mpcc is
pccthe
the mass,
mass, in grams,
in grams, of of
thethe
COCO 2 emitted
2 emitted in in theproduction
the productionofof1 1kg
kgofof the
the respective
respective product.
product. The
The final
final
potential
potential reduction in cement is then calculated using the reduction in clinker required to achieve the
reduction in cement is then calculated using the reduction in clinker required to achieve the
same
same compressive
compressive strength
strengthas asOPC.
OPC.TheThefinal
finalreduction
reductionininCO
CO22 emissions
emissions isis then
thenfound
foundas:as:

%%
reduction COCO
reduction (1(1−−(C
2 =2 = (Ci i·∙(R
(Rc-opc /Rc-ic-i
c-opc/R ))/C))/C opc∙ ))
opc)) · 100,
100, (3)
(3)

where CCii is
where is the
the CO
CO22 reduction of of aa PCC-A
PCC-A with
with ii==1–15
1−15wt.%
wt.%PCC-A,
PCC-A,CCopc is the
opc is the CO
CO22 emitted
emitted from
from
OPC production,
OPC production, RRc-opcc-opc is
is the
the mean compressive
compressive strength
strength of
of OPC
OPC and
and RRc-i is the
c-i is the mean
mean compressive
compressive
strength of the PCC-A blended cement with i = 1−15%. For example, the reduction
strength of the PCC-A blended cement with i = 1–15%. For example, the reduction in CO22 for in CO for the
the 10%
10%
PCC-A cement is calculated as
PCC-A cement is calculated as follows: follows:

COreduction,
CO 2 reduction, C10% = 0.9 ∙ 951.5 gCO2/kg + 0.1∙ (−100) gCO2/kg,
C10% = 0.9 · 951.5 gCO2 /kg + 0.1 · (−100) gCO2 /kg, (4)
(4)
2

CC10% =846.35
10% = 846.35gCO
gCO22/kg,
/kg, (5)
(5)
% reduction CO2 = (1 − (846.35 gCO2 /kg · (44.8 MPa/54.8 MPa))/ 951.5 gCO2 /kg)) · 100, (6)
% reduction CO2 =(1 − (846.35 gCO2/kg ∙ (44.8 MPa/54.8 MPa))/ 951.5 gCO2/kg))∙ 100, (6)
% reduction CO2 = 27.3%. (7)

The reduction in CO2 emission%attributed

reduction to CO2the= use of PCC-A as a carbon-negative clinker
27.3%. (7)
substitute, excluding any embodied CO2 reduction that may be attributed to decarbonising the cement
manufacturing process
The reduction (as 2suggested
in CO emission in Figure 1),toisthe
attributed summarised in Figure
use of PCC-A as a 9.carbon-negative
The values for clinker
clinker
substitution alone are displayed
substitute, excluding as dashed
any embodied CO2lines; the total
reduction reduction
that may bevalues, incorporating
attributed the effectthe
to decarbonising of
the strength
cement increase of PCC-A
manufacturing process cement blends in
(as suggested and the associated
Figure reductionininFigure
1), is summarised the structural member
9. The values for
size/volume, are represented as solid lines.
 Materials 2019, 12 FOR PEER REVIEW 10
Materials 2019, 12 FOR PEER REVIEW 10
clinker substitution alone are displayed as dashed lines; the total reduction values, incorporating the
effect ofsubstitution
clinker the strengthalone increase of PCC-A cement
are displayed as dashed blends
lines;andthethetotalassociated
reductionreduction in the structural
values, incorporating the
Materials 2019, 12, 554 10 of 14
member size/volume, are represented as solid lines.
effect of the strength increase of PCC-A cement blends and the associated reduction in the structural
member Traditionally,
size/volume, theare
production
represented of one kilogram
as solid lines.of OPC clinker emits on average ~950 gCO2 [33].
TheTraditionally,
production
Traditionally, of
the one
the kilogram of
production
production ofofPCC-A
oneone sequesters
kilogram
kilogram ofofOPC ~100–350
OPC clinker gCO
clinkeremits 2, depending
emits onon
average
average on
~950thegCO
~950 alkali
gCO 2 used
2 [33].
[33].
in
The the capture
production ofprocess.
one To
kilogram date,
of the
PCC-A carbon mitigation
sequesters
The production of one kilogram of PCC-A sequesters ~100–350 gCO of
~100–350 two alkalis
gCO , has
dependingbeen examined—sodium
on the alkali
2 2, depending on the alkali used used
hydroxide
inin
the
thecapture
capture and, to a limited
process.
process. ToTodate,extent,
the
date, the ammonia.
carbon
carbon The production
mitigation
mitigation ofof twotwo of sodium
alkalis
alkalis hashasbeen hydroxide
been has a carbon
examined—sodium
examined—sodium
intensity (i.e.,
hydroxide
hydroxide and, the
and,totoaweight
limited ratio
a limited of CO
extent,
extent, emitted in
ammonia.
2 ammonia. Theproduction
The production
production perofunit weighthydroxide
ofsodium
sodium of producthas
hydroxide made) of
hasa acarbon ~870
carbon
gCO
intensity /kg [34]
(i.e., and
the ammonia
weight
intensity (i.e., the weight ratio of
2 ratiohas
of a
CO carbon intensity
emitted in of ~1,600
production gCO
per /kg
unit [35].
weightHowever,
2 emitted in production per unit weight of product made) of ~870
2 of productthere is
made) a body
of
of evidence
~870
gCO gCO
2/kg2 /kg[34]to[34]
suggest
and and
ammonia that 80%
ammonia ofcarbon
has ahas ammonia
a carbon used in ~1,600
intensity
intensity of the
of reaction
~1,600
gCO2gCO could
/kg beHowever,
2 /kg
[35]. regenerated
[35]. However,
thereand is reused,
there
a body is
and
a body so ofthe carbon
evidence intensity
to suggest could
that be
80% reduced
of ammoniato 667 gCO
used /kg
in due
the
of evidence to suggest that 80% of ammonia used in the reaction could be regenerated and reused,
2 to its
reaction lower
could material
be demand
regenerated during
and
the CO
reused,
and soand2 capture
the so the process.
carbon carbon
intensity Forcould
further
intensity be information,
could be reduced
reduced to 667see the
6672Technology
togCO gCO
/kg due2 /kg itsCentre
todue to its Mongstad
lower lower
material (TCM)
material
demand Chilled
demand
during
Ammonia
during
the CO the CO Process
2 capture2 capture (CAP),
process. which
process.
For Forisfurther
further based on the chemistry
information,
information, see thesee of the
the
Technology NHCentre
Technology3-CO2Centre
-Mongstad
NH3 systemMongstad [36].(TCM)
(TCM) Chilled
Chilled
AmmoniaThe final
Ammonia CO
Process sequestered
Process
2 (CAP), whichusing
(CAP), which
is basedeither
on sodium
is based theon thehydroxide
chemistry
chemistry of theor
of
NH ammonia
the is then
NH23- -CO
3-CO NH 100
23 -system
NH gCO
[36]. 2 or
3 system [36]. 350
gCO The
2 , respectively.
ThefinalfinalCO CO The PCC-A
2 2sequestered
sequestered using used in the
using either sodium test results
sodium hydroxide that have
hydroxide or been
orammonia reported
ammoniaisisthen was produced
then100 100gCOgCO using
2 or
2 or 350
sodium
350 gCO
gCO 2, 2 , hydroxide,
respectively.and
respectively. Thethe
The PCC-A values
PCC-A usedin in
used Figure
inthe
the test9 reflect
test results
results that.
thatFigure
have 10 shows
have been
been reportedthe potential
reported was
wasproduced reduction
produced using
using in
emissions
sodium if
hydroxide,recovered
and ammonia
the values is
in used
Figure as 9the alkali
reflect in
that. the
FigurePCC-A10
sodium hydroxide, and the values in Figure 9 reflect that. Figure 10 shows the potential reduction in production
shows the process.
potential Alkalis
reduction from
in
waste could
emissions
emissions if if potentially
recovered
recovered offer equally
ammonia
ammonia is is
used low
used asas carbon
the the alkaliintensity
alkaliininthethe alternatives.
PCC-A
PCC-A production
production process.
process. Alkalis
Alkalis from
from
waste could potentially offer equally low carbon
waste could potentially offer equally low carbon intensity alternatives. intensity alternatives.

(a) (b)

Figure 9. Clinker substitution (a) with PCC-A produced using NaOH:(b) (a) CO2 emissions of PCC-A
cement
Figure
Figure 9.blends
9. Clinker with
Clinker increasing
substitution
substitution PCC-A
withwith
PCC-A content
produced
PCC-A and strength
using
produced NaOH: considerations,
(a)
using NaOH: CO2 (a)
emissionsand (b) percentage
of PCC-A
CO2 emissions ofcement
PCC-A
reduction
blends with in CO 2 emissions
increasing PCC-A of PCC-A
content cement
and blends
strength through clinker
considerations, substitution
and (b) and
percentage strength
reduction
cement blends with increasing PCC-A content and strength considerations, and (b) percentage gain.
in
CO 2 emissions
reduction of PCC-A
in CO cement
2 emissions blendscement
of PCC-A throughblends
clinkerthrough
substitution and
clinker strength gain.
substitution and strength gain.

(a) (b)

Figure Clinker
10.10. substitution(a)
with PCC-A produced using NH 3 : (a) CO2(b)
emissions of PCC-A cement
Figure Clinker substitution with PCC-A produced using NH 3: (a) CO 2 emissions of PCC-A cement
blends with
blends 10.
withincreasing
increasingPCC-A content
PCC-A with and
content strength considerations,
and produced
strength considerations, and (b) percentage
and2 emissions reduction
(b) percentage in in
reduction
Figure Clinker substitution PCC-A using NH3: (a) CO of PCC-A cement
CO 2 emissions
CO of PCC-A cement blends through clinker substitution and increase in strength.
2 emissions of PCC-A cement blends through clinker substitution and increase in strength.
blends with increasing PCC-A content and strength considerations, and (b) percentage reduction in
The 2 emissions of PCC-A cement blends through clinker substitution and increase in strength.
COintroduction of PCC-A blended cements could have a significant impact on the carbon
footprint of the cement industry (and with that the built environment), due to the reduction in CO2
Materials 2019, 12 FOR PEER REVIEW 11
Materials 2019, 12 FOR PEER REVIEW 11

The
Materials introduction
2019, 12, 554
The introduction of of PCC-A
PCC-A blended
blended cements
cements couldcould havehave aa significant
significant impact
impact on on thethe carbon
carbon
11 of 14
footprint of
footprint of the
the cement
cement industry
industry (and
(and with
with that
that the
the built
built environment),
environment), due due toto the
the reduction
reduction in in CO
CO22
emissions
emissions in the PCC-A production process and the subsequent substitution of clinker using PCC-A.
emissions in in the
the PCC-A
PCC-A production
production process
process andand the
the subsequent
subsequent substitution
substitution of of clinker
clinker using
using PCC-A.
PCC-A.
As shown
As shown in Figure
shownininFigure
Figure 9, the
9, the 15% PCC-A blended cement made using a NaOH CAPCON process
As 9, the 15%15%PCC-APCC-A blended
blended cement cement made ausing
made using NaOHa CAPCON
NaOH CAPCON process
process provided
provided a reduction
provided reduction in in emissions
emissions of of 27%
27% compared
compared to to OPC.
OPC. A A PCC-A made made using
using an an ammonia
ammonia
a reductiona in emissions of 27% compared to OPC. A PCC-A made PCC-A
using an ammonia process would
process
process would deliver a 30% reduction. Future work on the use of PCC-A will involve a detailed from
deliver awould deliver a 30%
30% reduction. reduction.
Future work onFuture
the usework on thewill
of PCC-A useinvolve
of PCC-A will involve
a detailed from acradle-to-grave
detailed from
cradle-to-grave Life
cradle-to-grave Life Cycle
Cycle Assessment
Assessment (LCA) of of PCC-A
PCC-A cement
cement blends,
blends, and
and it will
will study
study how how they
they
Life Cycle Assessment (LCA) of PCC-A(LCA) cement blends, and it will study howitthey compare against
compare
compare against
against other cements and cement blends in terms of overall performance, resistance to
other cements andother
cement cements
blendsand cement
in terms blendsperformance,
of overall in terms of overall
resistanceperformance,
to deteriorationresistance
and cost. to
deterioration and cost.
deterioration and cost.
3.5. SEM Imaging
3.5. SEM
3.5. SEM Imaging
Imaging
SEM micrographs were obtained using a secondary electron detector. Figure 11 is of the
SEM micrographs
SEM
non-optimisedmicrographs
PCC-A that werewas
were obtained
obtained using
used tousing
produceaa secondary
secondary
the samples electron
electron detector.
detector.
and test Figure
resultsFigure 11 is
11
reported isinof
of thepaper,
the
this non-
non-
optimised
optimised PCC-A
PCC-A
at progressively
that was used
that magnifications.
higher
to produce
was used to produce Figure the
the samples
samplesand
12 presents
and
andthetest
test results reported
results reported
backscatter
in
electronin
this paper,
this paper,
detector images
at
at
progressively
progressively higher
of the fracturehigher
magnifications.
surfacemagnifications.
of the 15% PCC-A
Figure
Figure 12 presents
12 presents
cement blend.and
and
Both
the backscatter
thelarge
backscatter
and small
electron
electron
PCC-A
detector
detector
crystals
images
images
were
of the
of the fracture
fracture
identified on the
surface
surface of the
of
fracture
the 15% of
15%
surface
PCC-A
PCC-A cementusing
cement
the sample
blend.
blend. Both
Both
SEM
large and
large
imaging,
and small
thesmall
PCC-A
latterPCC-A
crystals
crystals
possibly
were
due towerethe
identified
identified on the fracture
on the area
fracture surface of the
surface required sample
of the sample using SEM imaging, the latter possibly due to the
increased surface for reaction for theusing SEM of
formation imaging, the latterphases.
carboaluminate possibly due 13
Figure to is
the a
increased
increased surface area for reaction required for the formation of carboaluminate phases. Figure 13 is
backscattersurface area
detector for reaction
image required
of the fracture for the
surface offormation
the 10% and of carboaluminate
15% PCC-A cement phases. Figure 13 is
blends.
aa backscatter
backscatter detector
detector image
image of of the
the fracture
fracture surface
surface of of the
the 10%
10% and
and 15%15% PCC-A
PCC-A cement
cement blends.
blends.

(a) 200× (b) 4000×

(a) 200× (b) 4000×
Figure 11.
11. SEM micrographs
micrographs of thePCC-A
PCC-A that was used in cement blends using secondary electron
Figure
Figure 11. SEM
SEM micrographsofofthe
the PCC-Athatthatwas
wasused in cement
used blends
in cement using
blends secondary
using electron
secondary (SE)
electron
(SE) detection.
detection. Grain Grain
size size
was was estimated
estimated to range to range
from less from
than less
100 nm than
to 20 100 (a)
µm. nm200
to×20 µm. (a) 200×
magnification of
(SE) detection. Grain size was estimated to range from less than 100 nm to 20 µm. (a) 200×
magnification of PCC-A
PCC-A and (b)of4000 and
× of and (b)
the same4000×
PCC-Aof the same
sample. PCC-A sample.
magnification PCC-A (b) 4000× of the same PCC-A sample.

(a) 4000× (b) 10,000×

(a) 4000× (b) 10,000×
Figure 12. SE images showing fracture surface topography
topography in a sample of the 15% PCC-A cement
Figure 12. SE images showing fracture surface topography in a sample of the 15% PCC-A cement
blend at different magnifications.
magnifications. (a) 4000
4000××magnification
magnification and
and (b) 10,000×magnification.
(b) 10,000× magnification.
blend at different magnifications. (a) 4000× magnification and (b) 10,000× magnification.
Materials 2019, 12, 554 12 of 14
Materials 2019, 12 FOR PEER REVIEW 12

(a) 4000×, 10% PCC-A (b) 4000×, 15% PCC-A

Figure 13.
Figure Electron backscatter
13. Electron backscatter diffraction
diffraction (BSE)
(BSE) images
images displaying
displaying various
various phases
phaseson
onfracture
fracturesurface.
surface.
Each phase present is displayed by different intensities of black and white, with black representing
Each phase present is displayed by different intensities of black and white, with black representing
unreacted PCC-A
unreacted PCC-A fragments.
fragments. (a) 4000×× magnification
(a) 4000 magnification of of 10%
10% PCC-A
PCC-A cement
cement blend
blend and
and (b)
(b) 4000 ×
4000×
magnification of
magnification of 15%
15% PCC-A
PCC-A cement.
cement.

SEM imaging is a useful tool in determining the presence of PCC-A in cement blends and for
SEM imaging is a useful tool in determining the presence of PCC-A in cement blends and for
grain size determination. Further work to determine the presence of carboaluminate phases and the
grain size determination. Further work to determine the presence of carboaluminate phases and the
progression of phase composition is planned for samples cured from 1, 7, 28 and 365 days.
progression of phase composition is planned for samples cured from 1, 7, 28 and 365 days.
4. Conclusions
4. Conclusions
PCC-A, made using flue gas CO2 in CCM’s CAPCON process, used as a Portland cement
PCC-A, made using flue gas CO2 in CCM’s CAPCON process, used as a Portland cement
admixture, leads to an increased compressive strength that peaks at 10 wt.% PCC-A content.
admixture, leads to an increased compressive strength that peaks at 10 wt.% PCC-A content.
Combined with the carbon-negative nature of PCC-A, the resulting reduction in the clinker factor
Combined with the carbon-negative nature of PCC-A, the resulting reduction in the clinker factor
and the cumulative carbon content, the carbon footprint of a PCC-A blended cement containing 15%
and the cumulative carbon content, the carbon footprint of a PCC-A blended cement containing 15%
PCC-A is equivalent to ~73% of that of the OPC average.
PCC-A is equivalent to ~73% of that of the OPC average.
The strengths of PCC-A cement blends increase with PCC-A content, but the workability reduces,
The strengths of PCC-A cement blends increase with PCC-A content, but the workability
and, speculation notwithstanding, a full and detailed understanding of the processes that are involved
reduces, and, speculation notwithstanding, a full and detailed understanding of the processes that
is needed.
are involved is needed.
To achieve the same level of workability as an OPC paste, a PCC-A cement paste requires 25%
To achieve the same level of workability as an OPC paste, a PCC-A cement paste requires 25%
more water, which is not how a PLC cement behaves (requiring 2–5% less water).
more water, which is not how a PLC cement behaves (requiring 2–5% less water).
Future work to be undertaken on the effects of PCC-A in blended cements will include:
Future work to be undertaken on the effects of PCC-A in blended cements will include:
• The testing of PCC-A for use in mortars to determine the binding effects on aggregates;
• The testing of PCC-A for use in mortars to determine the binding effects on aggregates;
•• Examination ofofPCC-A
Examination PCC-A cements
cements aftercuring
after long long times
curing timesthetoevolution
to study study the evolution of
of carboaluminate
carboaluminate
phases; phases;
•• Investigation of
Investigation of the
the inverse
inverse effects
effects on
on rheology
rheology compared
compared withwith PLC;
PLC;
•• Full LCA of PCC-A blended cements using more alkali-efficient mineralisation
Full LCA of PCC-A blended cements using more alkali-efficient mineralisation processes;
processes;
•• Preparation of PCC-A blended cements containing polymorphs of PCC-A to determine if crystal
structure plays a role in reactivity
reactivity during
during hydration.
hydration.
AuthorContributions:
Author Contributions:TheThe named
named authors—L.M.,
authors—L.M., F.P.G.
F.P.G. and and M.S.I.—all
M.S.I.—all contributed
contributed to of
to the writing the writing
this article.
of this article.
Funding: The first named author L.M., a PhD scholar at the University of Aberdeen working under the supervision
of M.S.I. and
Funding: F.P.G.,
The firstisnamed
sponsored through
author a fully
L.M., a PhDfunded studentship
scholar by CCM (UK)
at the University Ltd.
of Aberdeen working under
The cements
the supervision of M.S.I.
Acknowledgments: used
and F.P.G., in this work
is sponsored were akindly
through provided
fully funded by HansonbyCement
studentship UK.
CCM (UK)
Electron Microscopy was performed in the ACEMAC Facility at the University of Aberdeen.
Ltd.
Conflicts of Interest: The authors declare no conflict of interest.
Acknowledgments: The cements used in this work were kindly provided by Hanson Cement UK.
Electron Microscopy was performed in the ACEMAC Facility at the University of Aberdeen
Conflicts of Interest: The authors declare no conflict of interest.
Materials 2019, 12, 554 13 of 14

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