materials

Article
Properties of Concrete Made with Low-Emission
Cements CEM II/C-M and CEM VI
Anna Król 1, *, Zbigniew Giergiczny 2 and Justyna Kuterasińska-Warwas 3
1 Faculty of Mechanical Engineering, Opole University of Technology, Prószkowska Str. 76,
45-758 Opole, Poland
2 Faculty of Civil Engineering, Silesian University of Technology, Akademicka Str. 5, 44-100 Gliwice, Poland;
zbigniew.giergiczny@polsl.pl
3 Institute of Ceramics and Building Materials, Oświ˛ecimska Str. 21, 45-641 Opole, Poland;
j.kuterasinska@icimb.pl
* Correspondence: a.krol@po.edu.pl




Received: 21 April 2020; Accepted: 11 May 2020; Published: 14 May 2020


Abstract: The paper presents the composition and properties of low-emission ternary cements:
Portland multicomponent cement CEM II/C-M and multicomponent cement CEM VI. In the ternary
cements, Portland clinker was replaced at the levels of 40% and 55% with a mixture of the main
components such as limestone (LL), granulated blast furnace slag (S) and siliceous fly ash (V).
Portland multicomponent cements CEM II/C-M and CEM VI are low-emission binders with CO2
emissions ranging from 340 (CEM VI) kg to 453 (CEM II/C-M) kg per Mg of cement. The results
obtained indicate the possibility of a wider use of ground limestone (LL) in cement composition.
This is important in the case of limited market availability of fly ash and granulated blast furnace
slag. The tests conducted on concrete have shown that the necessary condition for obtaining a high
strength class and durability of concrete from CEM II/C-M and CEM VI ternary cements is low
water–cement ratio. Durability characteristics of concrete (carbonation susceptibility, chloride ion
permeation, frost resistance) made of CEM II/C-M and CEM VI cements were determined after 90 days
of hardening. This period of curing reflects the performance properties of the concrete in a more
effective way.

Keywords: ternary cements; limestone; siliceous fly ash; granulated blast furnace slag; concrete
properties; concrete durability; CO2 emission

1. Introduction
In 2017, the global production of cement, the base component of concrete, amounted to almost
4.65 billion Mg [1]. For the production of 1 Mg of Portland cement clinker, about 1.7 Mg of natural
resources are used, mainly carbonate raw materials such as limestone and marl. Thus, as a result of the
clinker firing process, huge amounts of CO2 are released into the atmosphere, the source of which is
the thermal dissociation of carbonates in the raw material bulk (60%) and the emission of CO2 from the
combustion of technological fuel (40%) [2,3]. It is considered that cement production is responsible for
about 7.4% of the world carbon dioxide emission (2.9 Mg in 2016) [4]. Therefore, the world cement
industry has to meet the constantly growing environmental requirements, which mainly concern
the reduction of dust and greenhouse gas emissions [5]. Unfortunately, the production of the basic
component of cement, i.e., Portland clinker, is associated with the emission of CO2 , which is about
825–890 kg of CO2 per Mg of clinker [6]. The world average is about 840 kg of CO2 but the carbon
dioxide emission level should be lower than 400 kg per Mg of cement. It is suggested that the emission
levels reach around 350–410 kg per Mg of cement [4].

Materials 2020, 13, 2257; doi:10.3390/ma13102257 www.mdpi.com/journal/materials

Materials 2020, 13, 2257 2 of 17

The possibilities of emission reduction include two solutions in the cement production process [2,7]:

• production of multicomponent cements CEM II-CEMV according to EN 197-1 [8] using significant
quantities of main ingredients other than Portland clinker;
• modification of the production process of cement clinker by modification of the raw material
set (belite clinkers, belite-sulphate-aluminate clinkers, etc.) and use of alternative (non-fossil)
biomass-rich fuels.

In the case of production of CEM II-CEM V multicomponent cements, the main components are
usually by-products of industrial processes such as siliceous fly ash (V), calcareous fly ash from coal
dust combustion in the power industry or granulated blast furnace slag from iron metallurgy (S) [2,9,10].
The cements containing significant amounts of fly ashes and slags are characterized by low hydration
heat (a feature important in the implementation of massive concrete structures), higher strength after
longer curing periods and higher resistance to chemical aggression [2,9–11]. To ensure appropriate
durability of concrete made of cement with lower clinker content in the assumed construction
environment, the concrete composition (type and amount of cement, w/c ratio, type of admixtures and
amount of concrete additives) should be properly designed, so that the concrete is characterized by a
tight matrix. Determining the concrete tightness, e.g., by limiting the amount of water in the concrete
mix or using cement with mineral additives, results in limiting the capillary porosity of the hardened
cement slurry [2,12–14]. On the “macro” scale, it directly affects the depth of penetration of aggressive
media and the size of capillary pull, whereas on the “micro” scale, it results in impeding the diffusion of
aggressive ions into the cement matrix. However, the availability of fly ash and granulated blast furnace
slag, with increasing cement production, is limited [15]; therefore, limestone (LL) is used increasingly
often in cement composition. The main advantage of this component is its widespread availability and
the fact that it can be obtained from the cement plants own raw material resources [16–18].
Calcium carbonate, the main component of limestone, reacts with calcium aluminates to form
hydrated calcium carboaluminates. The presence of hydrated calcium carboaluminates inhibits the
transition of ettringite to monosulfate, thus, in hydration products the amount of monosulfate decreases
or disappears while the amount of ettringite increases [19]. The fact that calcite reacts with C3 A to
form carboaluminates means that CaCO3 may play, to a limited extent, the role of a regulator of setting
time. This results in the reduction of the amount of gypsum, which is necessary to regulate the setting
time [20].
In addition to the reaction with calcium aluminate, the addition of limestone to the cement may
accelerate the C3 S phase reaction. This effect is explained by the nucleation effect, in which CaCO3
grains act as additional crystallization germs for cement hydration products [19–21]. Limestone is
a very soft component in comparison to Portland clinker. After the milling process, it has a much
higher specific surface area and, as a micro-filler, influences the properties of cement composites,
e.g., by reducing porosity, increasing strength in the initial period of hardening and improving
workability, reducing water consumption and reducing water draining from the concrete mixture
(so-called “bleeding”) [19–24]. Bearing these facts in mind, the European Committee for Standardization
CEN has undertaken standardization works aimed at extending the range of cements containing
cement components other than Portland clinker in its composition. It is proposed to implement the
non-harmonized standard prEN 197-5 [25], which extends the range of Portland multicomponent
cements (the possibility of using several main components in the composition of cement) by a group of
Portland multicomponent cements CEM II/C-M with a minimum content of Portland clinker of 50%
and a newly created group of multicomponent cements CEM VI, in which the share of non-clinker
components may be a maximum 65%.
This paper presents the results of research on Portland multicomponent cement CEM II/C-M
with 40% of non-clinker main components and multicomponent cement CEM VI with 55% of these
components. Ground granulated blast furnace slag (S), siliceous fly ash (V) and ground limestone
(LL) were used as non-clinker main components. Concrete tests were performed for the analyzed
were determined with a view to future use of cements in construction practice. The level of CO2
emissions originating in the composition of CEM II/C-M and CEM VI cement was also calculated, as
well as the level of CO2 emissions from the production of concrete with the use of tested cements.

2. Materials
Materials and
2020, 13, Methods
2257 3 of 17

2.1. Characteristics of Components and Composition of Tested Cements

cements CEM II/C-M and CEM VI. The basic properties of concrete mixture and hardened concrete
wereThree types ofwith
determined non-clinker
a view toingredient
future usewere
of used in the
cements in study: granulated
construction blast furnace
practice. The levelslagof from
CO2
iron metallurgy, siliceous fly ash from the combustion of coal in power plants, and
emissions originating in the composition of CEM II/C-M and CEM VI cement was also calculated, natural limestone.
Theaschemical
as well the levelcomposition of thefrom
of CO2 emissions cementthecomponents
production of and selected
concrete physical
with the useproperties
of tested are given
cements.
in Table 1. Figures 1 and 2 show diffractograms of ground granulated blast furnace slag (S) and fly
ash (V).
2. Materials and Methods
In the slag phase composition (S), the dominant component is the vitreous phase, the
2.1. Characteristics
quantitative of Components
content and Composition
of which (determined of Tested Cements
microscopically) is 98%. In fly ash, next to the vitreous
phase, the main crystalline components identified are quartz,
Three types of non-clinker ingredient were used in the study: mullite, hematite
granulated and
blast magnetite.
furnace The
slag from
Portland cement CEM I is a semi-finished product with an increased SO content (5.0%)
iron metallurgy, siliceous fly ash from the combustion of coal in power plants, and natural limestone.
3 in order to
obtain a normal
The chemicalSOcomposition
3 content (max. 3.5%)
of the whencomponents
cement mixed with and the other main
selected components
physical of theare
properties cement.
given
Therefore, this cement is a semi-finished product in the process of manufacturing
in Table 1. Figures 1 and 2 show diffractograms of ground granulated blast furnace slag (S) and flymulticomponent
cements.
ash (V). The clinker content in the cement was 90%.
In the slag phase composition (S), the dominant component is the vitreous phase, the quantitative
content ofTable
which 1. Chemical composition
(determined and physical
microscopically) properties
is 98%. In flyofash,
the next
mainto
components of cement.
the vitreous phase, the main
crystalline components identified areContent quartz,
of mullite, hematite
Component, (wt. %) and magnetite. The Portland cement Specific
CEMTypeI of semi-finished product with an increased SO3 content (5.0%) in order to obtain a normalArea
is aRaw Specific SO3
Gravity ACC.
content (max. 3.5%)
Material SiOwhen
2 Almixed
2 O3 with
Fe2O3 theCaO
other main
MgO components
SO3 Na2of
O theKcement.
2O ClTherefore,
− this cement
(g/cm3) Blaine
is a semi-finished product in the process of manufacturing multicomponent cements. The clinker (cm2/g)
content
Limestonein(LL)
the(1)cement5.4 was1.3
90%. 1.1 49.7 1.8 0.03 <0.1 <0.1 0.005 2.70 6150
Granulated blast
40.5 7.4 1.26 43.7 5.0 0.14 0.77 0.45 0.046 2.92 3800
furnace slag (S) 1. Chemical composition and physical properties of the main components of cement.
Table
Siliceous fly ash
52.3 27.5 5.80 Content
3.6 of Component,
2.6 0.29
(wt. %) 0.94 3.15 0.008
Specific 2.14
Specific Area2750
ACC.
(V) (2)
Type of Raw Material
SiO2 Al2 O3 Fe2 O3 CaO MgO SO3 Na2 O K2 O Cl− Gravity (g/cm3 ) Blaine (cm2 /g)
Portland cement (1) 62.9
Limestone (LL) 20.65 5.1
5.4 1.32.57 1.1 49.7 1.4 0.03 5.0 <0.1 0.15
1.8 <0.1 0.63
0.005 0.07
2.70 3.16 6150 4500
CEMblast
Granulated I furnace slag (S) 40.5 7.4 1.26 443.7 5.0 0.14 0.77 0.45 0.046 2.92 3800
Siliceous
(1) CaCO fly ash (V) (2) 52.3 27.5 5.80 3.6 2.6 0.29 0.94 3.15 0.008 2.14 2750
3 content calculated on the basis of the amount of CaO is 89 (wt.%), total organic carbon (TOC)-
Portland cement CEM I 20.65 5.1 2.57 62.94 1.4 5.0 0.15 0.63 0.07 3.16 4500
0.04 (wt.%),
(1) CaCO clay content-0.4 g/100 g, (2) LOI of siliceous fly ash V-2.43 (wt.%) (Category A according to
3 content calculated on the basis of the amount of CaO is 89 (wt.%), total organic carbon (TOC)-0.04 (wt.%),
EN
clay 197-1:2012 [8]). g, (2) LOI of siliceous fly ash V-2.43 (wt.%) (Category A according to EN 197-1:2012 [8]).
content-0.4 g/100

Figure 1. Diffractogram
Diffractogram of granulated blast furnace slag.
Materials 2020, 13, 2257 4 of 17
Materials 2020, 13, x FOR PEER REVIEW 4 of 17
Materials 2020, 13, x FOR PEER REVIEW 4 of 17

Figure
Figure2.2.Diffractogram
Diffractogram of
Diffractogram of siliceous fly ash.
siliceous fly ash.

When
When
Whenanalyzing
analyzing
analyzing the
the properties
propertiesof
properties
the the
ofofthe main
themain components
maincomponents
components of of cement
cementused,
cement used,attention
used, attentionshould
attention should
should be
bebe paid
paid
paid
specific surface 2 /g
to the
to the high
high specific areaofoflimestone
surfacearea limestoneofof6150
6150 cm
cm2/g (Table 1). Obtaining
(Table 1). Obtainingsuch
sucha ahigh
highspecific
specific
surface area
surface is relatively
area easy
is relatively easydue
duetotothethevery
verygood
goodgranularity
granularity of
granularity of the
the limestone.
thelimestone. Thegranulometric
limestone.The granulometric
composition
composition of of non-clinkercement
non-clinker cementcomponents
componentsisisshown
shown in Figure
Figure 3. 3.

Particlesize
Figure3.3.Particle
Figure sizedistribution
distribution of
of supplementary
supplementarycementitious
cementitiousmaterials.
materials.

Two Two
CEMFigure
CEMII/C-M3. Particle
II/C-M cements
cements size
withdistribution
with
a Portland ofclinker
supplementary
a Portlandclinker contentof
content cementitious
of54%
54% and two
and materials.
two CEM
CEM VI
VI cements
cements with
with a
a Portland
Portland clinker
clinker content
content of of
40.5%40.5% were
were prepared
prepared forfor testing
testing thethe ternary
ternary cements.
cements. The
The composition of
composition
Two CEM II/C-M cements with a Portland clinker content of 54% and two CEM VI cements with
oftested
the tested cements and CO 2 emission levels are given in Table 2. The CO2 emission level from 1 Mg
athe
Portland cements and CO
clinker content 2ofemission levels
40.5% were are given
prepared forintesting
Table 2.the
The CO2 emission
ternary cements.level
The from 1 Mg of
composition
of cement was calculated assuming the average CO2 emission level of production of 1 Mg of clinker
cement was calculated assuming the average CO emission level of production
of the tested cements and CO2 emission levels are given in Table 2. The CO2 emission level from 1 Mg
2 of 1 Mg of clinker at
at the level of 840 kg [4] and the clinker content in the composition of the tested ternary cements CEM
the level
of cement of 840 kg [4] and the clinker content in the composition of the tested ternary
was calculated assuming the average CO2 emission level of production of 1 Mg of clinker cements CEM
II/C-M and CEM VI (Table 2). In the calculations, the CO2 emission level related to the transport and
II/C-M
at the and of
CEM VI (Table
[4] and2).theIn the calculations, the composition
CO2 emissionoflevel related to the cements
transportCEM
and
grinding of840
level the kg
components clinker
into cementcontent in the
was omitted. The obtained CO the2tested ternary
emission levels from 1 Mg
grinding of the components into cement was omitted. The
II/C-M and CEM VI (Table 2). In the calculations, the CO2 emission level obtained CO emission levels from 1 Mg
2 related to the transport and of
grinding of the components into cement was omitted. The obtained CO2 emission levels from 1 Mg
Materials 2020, 13, 2257 5 of 17

tested cements at the level of 340.2–453.6 kg allows the inclusion of CEM II/C-M and CEM VI cements
into low-emission cements.
In order to evaluate the synergy effects of cement components, comparative cements containing
one non-clinker component—slag cement C(55S), fly ash cement C(40V) and limestone cement C(40LL)
were also tested (Table 2).

Table 2. Composition of tested cements and CO2 emission level.

Cement Content of Component, (wt. %) CO2 Emission Level

Type of Cement
Marking Cement CEM I Slag S Limestone LL Fly Ash V from Mg of Cement, (kg)
C(30S-10LL) CEM II/C-M (30S-10LL) 60 30 10 - 453.6
C(30V-10LL) CEM II/C-M (30V-10LL) 60 - 10 30 453.6
C(35S-20LL) CEM VI (35S-20LL) 45 35 20 - 340.2
C(35S-20V) CEM VI (35S-20V) 45 35 - 20 340.2
C(40V) (1) CEM (40V) 60 - - 40 453.6
C(55S) (1) CEM (55S) 45 55 - - 340.2
C(40LL) (1) CEM (40LL) 60 - 40 - 453.6
(1) comparative cements.

The properties of cements were determined according to the procedures of EN 196 and the density
according to the standard on the properties of aggregates EN 1097-7 (Table 3).

Table 3. Procedures used to determine the properties of cement.

Property Standard Test Method

Constancy of volume EN 196-3:2016-11 [26]
Initial setting time EN 196-3:2016-11 [26]
Specific surface area EN 196-6:2011 [27]
Density EN 1097-7:2008 [28]
Compressive strength EN 196-1:2016-05 [29]

2.2. Concrete Composition and Properties’ Test Methods

Based on Portland multicomponent cements CEM II/C-M and multicomponent cements CEM VI,
concrete mixes with the following composition, given in Table 4, were designed.

Table 4. Mix proportions of concrete mixtures.

Concrete Cement Water PCE Admixture Coarse Aggregate (kg/m3 ) Sand 0–2 mm
Type w/c
Designation Content (kg/m3 ) (kg/m3 ) (kg/m3 ) 8–16 mm 2–8 mm (kg/m3 )
C(30S-10LL) 300 180 - 680 530 680
C(30V-10LL) 300 180 - 680 530 680
I 0.60
C(35S-20LL) 300 180 - 680 530 680
C(35S-20V) 300 180 - 680 530 680
C(30S-10LL) 340 120 10.2 725 565 725
C(30V-10LL) 340 120 10.2 725 565 725
II 0.35
C(35S-20LL) 340 120 10.2 725 565 725
C(35S-20V) 340 120 10.2 725 565 725

Two types of concrete were prepared—type I containing 300 kg of cement in 1 m3 of concrete

mix at a ratio w/c = 0.60 and type II, containing 340 kg of cement in 1 m3 of concrete mix at a ratio
w/c = 0.35. Natural gravel aggregate with a fraction up to 16 mm and sand 0–2 mm as fine aggregate
were used in the concrete mixture. A superplasticizer (PCE) based on polycarboxylate ether was used
in the composition of concrete with reduced water–cement ratio (w/c = 0.35).
The properties of concrete mixtures and hardened concrete were tested according to the
methodology included in the standards, which are presented in Table 5.
Materials 2020, 13, 2257 6 of 17

Table 5. Procedures used to determine the properties of the concrete mixture and hardened concrete.

Property Standard Test Method (Procedures)

Consistency (fall cone method) EN 12350-2:2011 [30]
Density of concrete mixture EN 12350-6 [29,31]
Air content EN 12350-7:2011 [32]
Compressive strength EN 12390-3:2011 [33]
Absorption PN-B-06250:1988 [34]
Depth of water penetration under pressure EN 12390-8:2011 [35]
Depth of carbonation prCEN/TS 12390-12:2010 [36]
Permeation of chloride ions ASTM C 1202-05 [37]
Ordinary frost resistance PN-B-06265:2018-10 [38]
De-icing salts frost resistance (surface scaling) CEN/TS 12390-9:2007 [39]

3. Results and Discussion

3.1. Properties of CEM II/C-M and CEM VI Cements

The properties of the cements are presented in Table 6. The density of the cements was lowest
for those containing siliceous fly ash (Table 6). The specific surface area of ternary cements ranged
from 4350 to 4750 cm2 /g. Cement slurries with ternary cements did not show volume changes due
to swelling (Table 6). The setting time of cements and other properties are closely related to their
composition and the amount of mineral additives introduced (Table 6).

Table 6. Physical and mechanical properties of cements.

Cement Constancy of Density Initial Setting Specific Surface Compressive Strength (MPa)
No.
Designation Volume (mm) (g/cm3 ) Time (h, min) Area (cm2 /g) 2 Days 7 Days 28 Days 90 Days 360 Days
1. C(30S-10LL) 0.5 3.00 2:15 4750 19.3 36.4 60.1 69.2 74.9
2. C(30V-10LL) 0 2.70 2:40 4700 18.4 28.5 40.9 54.9 64.1
3. C(35S-20LL) 0 2.96 2:45 4600 12.1 25.0 46.8 56.2 61.0
4. C(35S-20V) 0 2.82 3:25 4350 10.7 22.8 45.4 59.1 64.8
5. C(40V) 0 2.64 3:00 4300 15.5 26.4 36.4 49.4 61.3
6. C(55S) 0 2.98 3:10 4330 10.5 25.7 51.5 64.2 71.5
7. C(40LL) 1 2.92 1:55 5765 16.5 27.5 33.2 37.0 39.0

In most cases, the highest increases in strength of standard cement mortars can be observed
between 7 and 28 days of curing (Figure 4). During this period, the strength increases quite significantly
in the case of cements containing blast furnace slag (the slag is hydraulically active and begins to react
with water a long time before the ash pozzolanic reaction begins). The highest strength increase in this
period is observed in comparative slag cement C(55S) on Figure 4. Partial replacement of blast furnace
slag, both with limestone LL and fly ash V, slightly reduces the strength increase between the 7th and
28th days of hardening. Omitting the small influence of limestone on the increase in early strength, it is
a rather chemically inert component in the cement system, and therefore its addition to slag causes a
decrease in later strength. Replacement of slag with fly ash also slows down the dynamics of strength
growth. This can be explained by the fact that the pozzolanic reaction of fly ash begins intensify only
after 28 days of curing (when the amount of Ca(OH)2 from cement hydration increases). The final
strength (after 360 days) of multicomponent cement C(30S-10LL) is similar to that of comparative
cement C(55S), while in the case of cement C(35S-20V) there is a slight decrease in the final strength,
compared to cement C(55S) (Figure 4). This decrease can be explained by the lower activity of fly
ash in relation to ground granulated blast furnace slag, which is a component with latent hydraulic
activity (with a CaO content of approximately 40–44% and after heat treatment in a blast furnace under
conditions similar to those in a rotary kiln for Portland clinker production).
The partial replacement of fly ash by limestone C(30V-10LL) in cement composition, allows a
cement to be made with higher early strength (after 2 days) and higher final strength than the
reference cements C(40V) and C(40LL). The higher early strength in the presence of limestone may
Materials 2020, 13, 2257 7 of 17

Materials 2020, 13, x FOR PEER REVIEW 7 of 17

result from the caulking effect as well as the small amount of carboaluminates formed. On the basis
of the results obtained, it can also be observed that the addition of LL limestone decreases the
of the results obtained, it can also be observed that the addition of LL limestone decreases the strength
strength of cement mortars to a greater extent in combination with siliceous fly ash (C(30V-10LL)),
of cement mortars to a greater extent in combination with siliceous fly ash (C(30V-10LL)), while the
while the use of limestone (even up to 20%) in combination with ground granulated blast furnace slag
use of limestone (even up to 20%) in combination with ground granulated blast furnace slag (cements:
(cements: C(30S-10LL), C(35S-20LL)) gives a much smaller decrease, slightly less than in the case of
C(30S-10LL), C(35S-20LL)) gives a much smaller decrease, slightly less than in the case of using the S
using the S slag composition with fly ash V-cement C(35S-20V).
slag composition with fly ash V-cement C(35S-20V).

Figure
Figure 4.
4. Increase
Increase in
in compressive
compressive strength
strength depending on the
depending on the curing
curing time
time of
of cement
cement mortars.
mortars.

3.2. Concrete Properties

3.2. Concrete Properties with
with CEM
CEM II/C-M
II/C-M and
and CEM
CEM VI
VI Low-Emission
Low-Emission Cements
Cements

3.2.1. Properties of
3.2.1. Properties of Concrete
Concrete Mixture
Mixture
The
The properties
properties of ofconcrete
concretemixture
mixtureare
arepresented
presentedininTable
Table7. 7.The
Theconsistency
consistency(fall cone
(fall conemethod)
method)of
concrete
of concrete mixtures at w/c
mixtures = 0.60
at w/c corresponded
= 0.60 correspondedto class S3 for
to class S3concrete
for concrete mixture with with
mixture cement C(30S-10LL)
cement C(30S-
and classes S2 for other cements. Reduction of the water content to the
10LL) and classes S2 for other cements. Reduction of the water content to the level w/c = 0.35level w/c = 0.35 caused
caused a
decrease in consistency to class
a decrease in consistency to class S1. S1.
The
The density
density ofof all
allconcrete
concretemixtures
mixtureswith
withthe
theratio
ratiow/c
w/c= =0.60
0.60waswassimilar and
similar andranged
ranged from
from2350 to
2350
2360 kg/m 3 . The air content was low and ranged from 0.6% to 1.0%. Decreasing the water-cement ratio
to 2360 kg/m3. The air content was low and ranged from 0.6% to 1.0%. Decreasing the water-cement
level=w/c
to thetolevel 3
ratio the w/c 0.35=resulted in an increase
0.35 resulted in the in
in an increase density of concrete
the density mixtures
of concrete by about
mixtures by 70–80
about kg/m
70–80
and
kg/man increase
3 and in air content
an increase to 1.6–2%.
in air content The increase
to 1.6%–2%. The in aeration
increase inof the concrete
aeration of themixture
concreteismixture
typical of
is
using liquefying admixture.
typical of using liquefying admixture.

Table 7. Properties of concrete mixtures.

Table 7. Properties of concrete mixtures.
Concrete Designation—Corresponding
Concrete to the Composition
Designation—Corresponding of the Cement
to the Composition
Property Ratio w/c
Property Ratio w/c
C(30S-10LL) C(30V-10LL) of the Cement
C(35S-20LL) C(35S-20V)
110C(30S-10LL) C(30V-10LL)
60 C(35S-20LL)
50 C(35S-20V)50
0.60
S3 * 110 S2 * 60 50*
S2 50 S2 *
Consistency, 0.60
S3 * S2 * S2 * S2 *
(mm)
Consistency, (mm) 30 20 30 30
0.35 30 20 30 30 S1 *
0.35 S1 * S1 * S1 *
S1 * S1 * S1 * S1 *
Density, 0.60 2360 2350 2350 2350
(kg/m 3) 0.60 2360 2350 2350 2350
Density, (kg/m0.35
3) 2430 2420 2430 2420
0.35 2430 2420 2430 2420
Air content, 0.60 0.8 0.8 1.0 0.6
0.60 0.8 0.8 1.0 0.6
Air content, (vol.%)
(vol.%) 0.35 1.6 1.8 2.0 2.0
0.35 1.6 1.8 2.0 2.0
* Consistency class acc. EN 12350-2:2011 [30].
* Consistency class acc. EN 12350-2:2011 [30].

3.2.2. Properties of Hardened Concrete

• Compressive strength
Materials 2020, 13, 2257 8 of 17

3.2.2. Properties of Hardened Concrete

• Compressive
Materials
Materials 2020,13,
2020, strength
13,xxFOR
FOR PEERREVIEW
PEER REVIEW 88 of
of 17
17

The
The compressive strength
compressive strength
strength was was determined,
was determined,
determined, after after
after 2, 2, 7,
2, 7, 28
7, 28 and
28 and
and 90 90 days
90 daysdays of of curing,
of curing,
curing, on on
on 1010
10 cm
cm cubic
cubic
The compressive cm cubic
samples.
samples. For For concretes
For concretes
concretes withwith
with w/c w/c = 0.35,
w/c == 0.35, strength
0.35, strength
strength tests tests
tests were were
were also also
also performedperformed
performed after after
after 11 day 1
day ofday of
of curing. curing.
curing. The
samples. The
The results
results are are
are presentedpresented
presented in in Figures
in Figures
Figures 55 and 5 and
and 6. 6. 6.
results
The
The highest
The highest compressive
highest
strength,
compressive strength,
compressive strength, at at w/c =
at w/c
w/c
0.35
== 0.35
0.35 andand 0.60,
and 0.60, was
0.60, was obtained
was obtained
obtained by by concrete
concrete made
by concrete made of
made of
of
Portland multicomponent
Portland multicomponent
multicomponent cement cement C(30S-10LL).
cement C(30S-10LL).
C(30S-10LL). The The lowest
The lowest compressive
lowest compressive
compressive strength strength
strength was was achieved
achieved with
was achieved with
Portland with
C(30V-10LL)
C(30V-10LL)on onPortland
Portlandash ashand
andlime
limecement,
cement,despite
despitethe fact
thefact that
factthat
thatititit contained
containedmore more Portland
morePortland clinker
Portlandclinker
clinker
C(30V-10LL) on Portland ash and lime cement, despite the contained
compared
compared to to the
to the other
the othertwo
other two CEM
two CEM VI
CEM VIcement
VI cementconcretes.
cement concretes. Limestone
concretes. Limestone and
Limestone andsiliceous fly
and siliceous ash
siliceous flyshow a
fly ash synergistic
ash show
show aa
compared
effect only with
synergistic effectearlyonly strength
with early (2 strength
early days) and only
days)with
(2 days) and only10%
only addition
with 10% 10%of limestone,
addition which confirms
of limestone,
limestone, which
synergistic effect only with strength (2 and with addition of which
the resultsthe
confirms obtained
results by De Werdt
obtained et al.
by De
De [40–42].
Werdt et al.The
al. resultsThe
[40–42]. obtained
resultsfrom obtained strength fromtests of concretes
strength tests ofof
confirms the results obtained by Werdt et [40–42]. The results obtained from strength tests
made
concretesof slag-calcareous
concretes made of
made cements provide
of slag-calcareous
slag-calcareous cements
cements a reason
provide
provide foraathe prospective
reason
reason for the
for the wider
prospective
prospective use ofwiderlimestone
wider use in
use of
of
cement
limestone composition.
limestone in in cement
cement composition.
composition.
Decreasing
Decreasingthe
Decreasing the water-cement
the water-cementratio
water-cement ratio(w/c)
ratio (w/c)from
(w/c) from0.60
from 0.60to
0.60 to0.35
to 0.35 resulted
0.35 resultedin
resulted in aaa significant
in significant
significant increase
increasein
increase in the
in the
the
compressive strength
compressive strength
compressive of
strength of concretes
of concretes
concretes made made
made of of all
of all cements
all cements
cements testedtested (Figure
tested (Figure
(Figure 7). 7). This
7). This increase
This increase
increase is is particularly
is particularly
particularly
visible th day. It can be noted that the lowest
visiblein
visible in the
inthe initial
theinitial period
initialperiod
periodof of concrete
ofconcrete hardening,
concretehardening,
hardening,i.e., i.e., until
i.e.,until
untilthe the 77th
the7th day.ItItcan
day. canbe benoted
notedthatthatthe thelowest
lowest
results
results were
results were obtained
were obtained for
obtained for concrete
for concrete using
concrete using cement
using cement C(30V-10LL),
cement C(30V-10LL), however,
C(30V-10LL), however, the
however, the compressive
the compressive strength
compressive strength
strength
after
after 28
after 28 days
28 days was
days was nearly
was nearly 70
nearly 70 Mpa
70 MPa
MPa andand was
and was almost
was almost twice
almost twice
twice as as high
as high
high as as the
as the strength
the strength
strength obtainedobtained
obtained at at w/c =
w/c
at w/c 0.60.
== 0.60.
0.60.
To
Tosum
To sumup,
sum up,it
up, ititshould
shouldbe
should bestated
be stated that
stated that aaa low
that low w/c
low w/cratio
w/c ratio is
ratio is aaavery
is veryeffective
very effectivefactor
effective factorin
factor inshaping
in shaping the
shaping the strength
the strength
strength
characteristics
characteristics of
characteristics of concrete
of concretemade
concrete madeof
made ofcements
of cementswith
cements withlow
with lowPortland
low Portlandclinker
Portland clinkercontent
clinker content(Figure
content (Figure7).
(Figure 7).
7).

Figure5.
Figure
Figure 5. Compressive
5. Compressive strength
Compressive strengthof
strength ofconcrete
of concrete(w/c
concrete (w/c=
(w/c == 0.60).
0.60).
0.60).

..
Figure
Figure6.
Figure Compressive
Compressive strength
6. Compressive
6. strengthof
strength ofconcrete
of concrete (w/c=
concrete(w/c
(w/c 0.35).
== 0.35).
0.35).
Materials 2020, 13, 2257 9 of 17
Materials 2020,
Materials 2020, 13,
13, xx FOR
FOR PEER
PEER REVIEW
REVIEW 99 of
of 17
17

Figure
Figure 7.
The
7. 7.
Figure Theimpact
The impactofof
impact ofreduced
reducedw/c
reduced w/c ratio
w/c ratio on
ratio on the
on the compressive
compressive strength
compressive strength ofofconcretes
strengthof concretes made
concretesmade
madeof of
of tested
tested
tested
ternary
ternary
ternary cements.
cements.
cements.

• •• Water
Water
Water absorption
absorption andwater
and
absorption and waterpenetration
water penetrationunder
penetration under pressure
under pressure
pressure
All tested
tested concretes,
concretes, at
at the same
same w/c,
w/c, show
show similar
similar water
water absorption.
absorption. For
For concretes
concretes with
with w/cw/c ==
AllAll
tested concretes, at thethe
same w/c, show similar water absorption. For concretes with w/c = 0.60
0.60 the absorption varies between 6.6% to 7.0%, while for concretes with reduced
0.60 the absorption varies between 6.6% to 7.0%, while for concretes with reduced w/c = 0.35 it w/c = 0.35 it is
is
themuch
absorption
lower varies
and between
ranges from 6.6%
3.3% toto 7.0%,
4.1% while
(Figure for
8). concretes
Extension of with
the reduced
curing time w/c
to =
90 0.35
days it is
resultedmuch
much lower and ranges from 3.3% to 4.1% (Figure 8). Extension of the curing time to 90 days resulted
lower
in aa and
slightranges from
decrease in 3.3% to 4.1%
absorption of (Figure
the tested8).concretes,
tested Extension of the
most curing for
noticeable time to 90 days
concrete maderesulted
with
in slight decrease in absorption of the concretes, most noticeable for concrete made with
in C(35S-20V)
a slight decrease
cement.in absorption of the tested concretes, most noticeable for concrete made with
C(35S-20V) cement.
C(35S-20V) cement.

(a)
(a)

(b)
(b)
Figure 8.
Figure 8. Water
Water absorption
absorption of
of concrete
concrete after:
after: (a)
(a) 28
28 days of
of curing, (b)
(b) 90 days of
of curing.
curing.
Figure 8. Water absorption of concrete after: (a) 28 days
days ofcuring,
curing, (b)9090days
days of curing.
Materials 2020, 13, 2257 10 of 17
Materials 2020, 13, x FOR PEER REVIEW 10 of 17

The results
The results of
of the
the study
study on
on the
the depth
depth of
of water
water penetration under pressure
penetration under pressure (Figure
(Figure 9)9) show
show that
that
concretes with w/c = 0.35 are characterized by very high tightness, especially after 90 days
concretes with w/c = 0.35 are characterized by very high tightness, especially after 90 days of curing.of curing.
The depth
The depth of
of water
water penetration
penetration under
under pressure
pressure at w/c =
at w/c 0.35 was
= 0.35 was maximum
maximum 15 15 mm
mm forfor concrete
concrete with
with
cement C(35S-20V) after 28 days of curing. Concretes with w/c = 0.60 showed water penetration
cement C(35S-20V) after 28 days of curing. Concretes with w/c = 0.60 showed water penetration depth depth
after 28
after 28 days
days of
of hardening
hardening at at the
the level
level from
from 15.3
15.3 mm
mm toto 43.7
43.7 mm
mm and
and from
from 7.7
7.7 mm
mm to to 14.7
14.7 mm
mm for
for
concrete curing
concrete curing for
for 90
90 days
days (Figure
(Figure 9).
9).

(a)

(b)
Figure 9. Water penetration depth of concrete after: (a) 28 days of curing, (b) 90 days of curing
Figure 9. Water penetration depth of concrete after: (a) 28 days of curing, (b) 90 days of curing

Omitting the influence of the w/c ratio, the differences in the depth of water penetration inside
Omitting the influence of the w/c ratio, the differences in the depth of water penetration inside
the concrete matrices primarily result from the different activity of the main components of cements
the concrete matrices primarily result from the different activity of the main components of cements
used. The most active component, apart from Portland clinker, is ground granulated blast furnace
used. The most active component, apart from Portland clinker, is ground granulated blast furnace slag,
slag, whereas fly ash is a component with pozzolanic activity (ability to react in the presence of
whereas fly ash is a component with pozzolanic activity (ability to react in the presence of moisture,
moisture, with Ca(OH)2 from the hydration of silicate phases of Portland clinker). The impact of this
with Ca(OH)2 from the hydration of silicate phases of Portland clinker). The impact of this reaction on
reaction on the properties of mortar (concrete) is earliest visible about 28 days and later (Figure 9b).
the properties of mortar (concrete) is earliest visible about 28 days and later (Figure 9b). The addition
The addition of limestone improves the porosity of the cement-ash/slag system. Limestone, as a soft
of limestone improves the porosity of the cement-ash/slag system. Limestone, as a soft component,
component, is ground into very fine grains, which fill the voids between cement and ash/slag grains.
is ground into very fine grains, which fill the voids between cement and ash/slag grains. It results in
It results in increased early strength (after 2 days) in relation to the cement included only fly ash.
increased early strength (after 2 days) in relation to the cement included only fly ash. After a longer
After a longer period of time (28 days and later), cements containing granular blast furnace slag in
period of time (28 days and later), cements containing granular blast furnace slag in the composition
the composition with ash (S, V) or limestone (S, LL) have higher strength and tightness.
with ash (S, V) or limestone (S, LL) have higher strength and tightness.
• Carbonation susceptibility
• Carbonation susceptibility
The type of cement used was assessed for its susceptibility to carbonation (Figure 10). The test
was carried
The typeout
ofusing
cementanused
elevated
was CO 2 concentration
assessed 4%, the testtoduration
for its susceptibility was 70
carbonation days 10).
(Figure (accelerated
The test
method).
was Analyzing
carried out usingthe
anresults
elevatedobtained for concretes4%,
CO2 concentration at the
w/ctest
= 0.60, it can was
duration be seen that(accelerated
70 days the highest
depth of carbonation
method). Analyzing theis characterized
results obtainedby for
concrete
concretes w/c = 0.60,
withatPortland multicomponent cement
it can be seen that C(30V-
the highest
10LL),
depth ofafter 28 days of
carbonation hardening theby
is characterized depth of carbonation
concrete reaches
with Portland 29.7 mm, and
multicomponent after C(30V-10LL),
cement 90 days it is
18.6 mm. Reducing the water–cement ratio to the level w/c = 0.35 very effectively lowered the depth
of concrete carbonation (Figure 10). A significant decrease in the depth of carbonation linked with
Materials 2020, 13, 2257 11 of 17

after 28 days of hardening the depth of carbonation reaches 29.7 mm, and after 90 days it is 18.6 mm.
Materials 2020, 13, x FOR PEER REVIEW 11 of 17
Reducing the water–cement ratio to the level w/c = 0.35 very effectively lowered the depth of concrete
carbonation (Figure 10). A significant decrease in the depth of carbonation linked with the extension of
the extension of curing period should be associated with the activity of the cement components used,
curing period should be associated with the activity of the cement components used, mainly ground
mainly ground granulated blast furnace slag (hydraulic activity) and fly ash (pozzolanic activity).
granulated blast furnace slag (hydraulic activity) and fly ash (pozzolanic activity). Additional amounts
Additional amounts of products formed later (after 90 days of curing) from the course of reaction
of products formed later (after 90 days of curing) from the course of reaction between cement hydration
between cement hydration products and active mineral additives, settle in the pores of hardening
products and active mineral additives, settle in the pores of hardening cement slurry and hinder the
cement slurry and hinder the permeation and penetration of aggressive ions [21,23].
permeation and penetration of aggressive ions [21,23].

(a)

(b)
Figure 10. Carbonation
Carbonation depth
depth of
of concrete after: (a)
concrete after: (a) 28 days of curing, (b) 90 days
(b) 90 days of
of curing.
curing.

•
• Chloride
Chloride ions
ions permeation
permeation
The permeability
The permeability limitation
limitation of
of the
the concrete
concrete matrix
matrix is confirmed by
is confirmed the results
by the results of
of chloride
chloride ion
ion
permeation (Figure
permeation (Figure 11).
11). Extending
Extending the
the curing
curing period
period to to 90
90 days
days or decreasing the
or decreasing the water
water and
and cement
cement
ratio to w/c = 0.35 results in a significant decrease in the permeation of chloride ions corresponding to
ratio to w/c = 0.35 results in a significant decrease in the permeation of chloride ions corresponding
to low
low or very
or very low permeation
low permeation class according
class according to ASTMto C ASTM
1202-05 C [37]
1202-05 [37]test
for both for dates.
both test
The dates. The
differences
differences
in chloride inionchloride ion permeability
permeability betweensamples
between concrete concretecan samples can be explained
be explained in the
in the same waysameas way
was
as was described
described in the
in the water water penetration
penetration analysis,analysis, as thisis feature
as this feature strictly is strictly
related to related
tightnesstooftightness
concrete.of
concrete.
Materials 2020,
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12 of 17
17

(a)

(b)

Figure 11. Chloride ions permeation of concrete after: (a) 28 days of curing, (b) 90 days of curing.

•• Freeze–thaw resistance
resistance
An
An important
important feature of concrete,
feature of concrete, used
used inin areas
areas with
with minus
minus temperatures,
temperatures, isis its
its resistance
resistance to
to such
such
environmental impact. Resistance of concrete to cyclic freezing and unfreezing was
environmental impact. Resistance of concrete to cyclic freezing and unfreezing was determined by the determined by
the ordinary
ordinary method
method (150(150 cycles
cycles of freezing
of freezing at −18at −18
◦ °C and
C and unfreezing
unfreezing of concrete
of concrete at 18 atC,18duration
◦ °C, duration
time
time of 1 cycle was 6 h (3 h of freezing and 3 h of thawing)) for concretes with coefficient
of 1 cycle was 6 h (3 h of freezing and 3 h of thawing)) for concretes with coefficient w/c = 0.35. w/c = 0.35.
The test
The test was
was performed
performed after
after 28
28 and
and 90
90 days
days of of concrete
concrete curing.
curing. The
The result
result of
of the
the test
test is
is positive
positive if
if the
the
decrease
decrease ofof compressive
compressive strength is less
strength is less than
than 20%
20% andand the
the loss
loss of
of mass
mass is
is not
not more
more than
than 5%
5% of
of weight.
weight.
The test
The test of
ofconcrete
concretesurface
surfaceresistance
resistancetotofrost
frost
(56(56 cycles)
cycles) in the
in the presence
presence of NaCl
of NaCl de-icing
de-icing salt was
salt was also
performed. Concrete was evaluated after 28 days of curing. The test results are presented in Tablein8
also performed. Concrete was evaluated after 28 days of curing. The test results are presented
Table 8 and Figures
and Figures 12 and 13.
12 and 13.

Table 8. Results
Table 8. Results of
of frost-resistance tests.
frost-resistance tests.

Concrete Concrete Designation,

w/c = w/c
0.35 = 0.35
ConcreteAge
Age Tested Properties
Concrete Designation,
(Days) Tested Properties C(30S-
C(30S-10LL) C(30V- C(35S-20LL)
C(30V-10LL) C(35S- C(35S-20V)
C(35S-
(Days)
Strength of samples after freeze-thaw cycles, (MPa) 86.7 10LL) 63.4 10LL) 77.220LL) 20V)
76.4
Strength of samples
Strength after
of reference freeze-thaw
samples, (MPa) cycles, (MPa)
93.8 86.7 78.5 63.4 83.777.2 76.4
82.7
Decreaseofinreference
Strength strength, (%)
samples, (MPa) 7.6 93.8 19.2 78.5 7.7 83.7 7.7
82.7
28
Loss of sample weight after test, (wt. %) 0.0 0.1 0.1 0.1
Decrease
Scaling of the material afterin
56strength,
freeze-thaw(%)cycles 7.6 19.2 7.7 7.7
28 2 0.12 2.77 0.89 0.55
inLoss of sample
the presence weight
of NaCl salt,after
(kg/mtest,
) (wt. %) 0.0 0.1 0.1 0.1
Scaling
Strength of the material
of samples after 56cycles,
after freeze-thaw freeze-thaw
(MPa) cycles94.8 71.6 84.6 85.7
0.12 2.77 0.89 0.55
Strength
in theof presence
reference samples,
of NaCl (MPa)
salt, (kg/m2) 95.0 84.3 85.9 84.9
90
Strength Decrease
of samples in strength, (%)
after freeze-thaw cycles, (MPa)0.2 94.8 15.1 71.6 1.5 84.6 1.0
85.7
Loss of sample weight after test, (wt. %) 0.0 0.0 0.1 0.1
Strength of reference samples, (MPa) 95.0 84.3 85.9 84.9
90
Decrease in strength, (%) 0.2 15.1 1.5 1.0
Loss of sample weight after test, (wt. %) 0.0 0.0 0.1 0.1
Materials 2020,
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13, xx FOR
FOR PEER
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17
Materials 2020, 13, 2257 13 of 17
The type
The type ofof applied
applied cement
cement affects
affects thethe durability
durability of of concrete
concrete underunder cyclic
cyclic freezing
freezing andand
unfreezing conditions,
unfreezing conditions, especially
especially when when de-icing
de-icing agents
agents are
are used.
used. TheThe worst
worst results
results were
were obtained
obtained forfor
The type of applied cement affects the durability of concrete under cyclic freezing and unfreezing
concrete
concrete made of Portland
madeespecially
of Portland multicomponent
multicomponent cement
cement C(30V-10LL) (Figures 12 and 13; Table 8). The
conditions, when de-icing agents are used.C(30V-10LL)
The worst results(Figures
were12obtained
and 13; for
Table 8). The
concrete
decrease
decrease in compressive strength after the frost resistance test using the normal method reached
made ofinPortland
compressive strength after
multicomponent cementtheC(30V-10LL)
frost resistance test 12
(Figures using theTable
and 13; normal method
8). The reached
decrease in
19.2% for
19.2% for concrete
concrete subjected
subjected to to alternating
alternating temperatures
temperatures afterafter 28 28 days
days of of curing
curing andand 15.1%
15.1% forfor
compressive strength after the frost resistance test using the normal method reached 19.2% for concrete
concrete
concrete subjected
subjected to the test
to the test after 90 days
after 90 days of curing.
of 28
curing. For comparison,
Forcuring
comparison, concretes
concretes made of other
madesubjected cements
of other cements
subjected to alternating temperatures after days of and 15.1% for concrete to the
were
were characterized
characterized by
by strength
strength decreases
decreases at
at a
a much
much lower
lower level
level of
of 7.6%–7.7%
7.6%–7.7%
test after 90 days of curing. For comparison, concretes made of other cements were characterized for
for 28-day
28-day samples
samples and
and
0.2%–1.5%
0.2%–1.5%
by strength for 90-day
fordecreases
90-day at samples.
samples.
a much lower Concrete
Concrete samples
level samples
of 7.6–7.7% after
after the frost-resistance
the frost-resistance
for 28-day test did not
test didfornot
samples and 0.2–1.5% show
show
90-day
significant
significant changes
changes in
in mass.
mass.
samples. Concrete samples after the frost-resistance test did not show significant changes in mass.
When
When analyzing
Whenanalyzing
analyzingthethe results
the results
results of ofthe
of thesurface
the surface
surface resistance
resistance
resistance of concrete
of concrete
of concrete to frost
to
to frost frost inpresence
in thein the presence
the presence of de-
of
of de-icing de-
icing
icing salt
saltsalt (Table
(Table
(Table 8, Figure
8, Figure
8, Figure 13),
13),13), it clear
it isit is clear
is clear that
that
that only
only
only concrete
concrete
concrete made
made
made of
of of Portland
Portland
Portland multicomponent
multicomponent
multicomponent cement
cement
cement
C(30S-10LL)
C(30S-10LL)can
C(30S-10LL) can be
canbe classified
beclassified as resistant.
classified as resistant. However,
resistant. However, remaining
However,remaining
remaining concretes,
concretes,
concretes, especially
especially concrete
concrete
especially made
mademade
concrete of
of Portland
Portland multicomponent
multicomponent cement
cement C(30V-10LL),
C(30V-10LL), showshow
of Portland multicomponent cement C(30V-10LL), show considerable scaling. considerable
considerable scaling.
scaling.

Figure
Figure 12.
Figure12. Frost
12.Frost resistance
Frostresistance of
resistanceof concretes
ofconcretes tested by
tested
concretes tested bythe
by thestandard
the standardmethod
standard method
method [38].
[38].
[38].

Figure
Figure 13.13. Frost
Frost resistanceofofconcretes
resistance concretesin
inthe
thepresence
presence of de-icing
de-icingsalt
of de-icing saltin
inrelation
relationtoto
toresistance
resistancecategory
category
Figure 13. Frost resistance of concretes in the presence of salt in relation resistance category
according
according to toEN
EN13877-2:2013-08
13877-2:2013-08[43].
[43].
according to EN 13877-2:2013-08 [43].

3.2.3. CO
3.2.3. CO22 Emissions
Emissions from
from Concrete
Concrete made
made of
of CEM
CEM II/C-M
II/C-M and
and CEM
CEM VI
VI Cement
Cement
The concrete
The concrete emission
emission level
level was
was calculated
calculated based
based onon the
the level
level of
of CO
CO22 emissions
emissions from
from 11 Mg
Mg ofof
cement (Table
cement (Table 2).
2). The
The results
results are
are presented
presented in
in Table
Table 9.
9. The
The obtained
obtained CO
CO22 emission
emission levels
levels per
per 11 m
m3 of
3 of
concrete are very low (Table 2). When converting the level of CO emission into 1 MPa of compressive
concrete are very low (Table 2). When converting the level of CO2 emission into 1 MPa of compressive
2
Materials 2020, 13, 2257 14 of 17

3.2.3. CO2 Emissions from Concrete Made of CEM II/C-M and CEM VI Cement
The concrete emission level was calculated based on the level of CO2 emissions from 1 Mg of
cement (Table 2). The results are presented in Table 9. The obtained CO2 emission levels per 1 m3 of
concrete are very low (Table 2). When converting the level of CO2 emission into 1 MPa of compressive
strength, it can be observed that an important factor is the w/c ratio in concrete. With a lower w/c ratio
(0.35), the strength levels are much higher and the difference in the level of the obtained compressive
strength depending on the composition of the cement starts to fade. The CO2 emission level per
1 MPa is significantly reduced also, e.g., in the case of CEM II/C-M (30V-10LL) cement from 4.9 kg
(w/c = 0.60) to 2.3 kg (w/c = 0.35). Considering the compressive strength after 90 days, CO2 emissions
are lower, on average by about 0.7 kg at w/c = 0.60 and about 0.2 kg at w/c = 0.35. This is due to the
fact that cements with a high content of the main components other than Portland clinker (mainly
granulated blast furnace slag and/or fly ash) have a significant strength increment between 28 and
90 days of hardening.

Table 9. CO2 emissions from 1 m3 concrete and converted to 1 MPa of 28-day and 90-day concrete
compressive strength.
28-Day Concrete 90-Day Concrete
CO2 Emission (kg) CO2 Emission (kg)
Concrete Cement Content CO2 Emission Compressive Compressive
w/c Ratio Converted into Converted into
Designation (kg/m3 Concrete) (kg/m3 Concrete) Strength fcm,cube 28 Strength fcm,cube 90
1 MPa fcm,cube 28 1 MPa fcm,cube 90
(MPa) (MPa)
C(30S-10LL) 300.0 136.1 42.6 3.2 50.3 2.7
C(30V-10LL) 300.0 136.1 27.9 4.9 38.3 3.6
0.60
C(35S-20LL) 300.0 102.1 33.8 3.0 39.8 2.6
C(35S-20V) 300.0 102.1 33.5 3.0 45.3 2.3
C(30S-10LL) 340.0 154.2 85.8 1.8 95.3 1.6
C(30V-10LL) 340.0 154.2 66.7 2.3 82.6 1.9
0.35
C(35S-20LL) 340.0 115.7 72.6 1.6 83.0 1.4
C(35S-20V) 340.0 115.7 70.4 1.6 82.0 1.4

4. Conclusions
Based on the results of the research carried out, the following conclusions were drawn:

1. The results of the research as well as ecological aspects (mainly reduction of CO2 emissions)
confirmed the advisability of further development of the assortment of general-use cements
with the following ternary cements: Portland multicomponent cement CEM II/C-M and
multicomponent cement CEM VI. The properties of these cements and the concretes made
with them are the result of the properties of the main components and the synergistic interaction
of the composition: granulated blast furnace slag S-limestone LL, siliceous fly ash V-limestone LL,
granulated blast furnace slag S-siliceous fly ash V.
2. When evaluating the synergy effect of additives in the composition of cements, it can be observed
that much better strength effects are obtained in the composition of ground granulated blast
furnace slag (S) with limestone (LL) than fly ash (V) with limestone (LL). This is due to the higher
activity of the ground slag compared to fly ash (V). The results obtained also confirm a very good
synergy effect, known from construction literature and practice, between slag (S) and fly ash
(V). A characteristic feature of CEM II/C-M and CEM VI ternary cements is a low level of early
compressive strength (up to 7 days) and a significant increase in compressive strength at later
stages (especially between 28 and 90 days of hardening).
3. A typical attribute of CEM II/C-M and CEM VI ternary cements is the low level of early compressive
strength (up to 7 days) and a significant increase in compressive strength at a later date (especially
between 28 and 90 days of hardening).
4. The results obtained indicate the possibility of wider use of ground limestone LL in cement
(concrete) composition. This is important in terms of the limited market availability of fly ash
and granulated blast furnace slag.
Materials 2020, 13, 2257 15 of 17

5. The results obtained from tests on concrete showed that a low w/c ratio is a prerequisite for
obtaining high strength class and durability of concrete made of CEM II/C-M and CEM VI
ternary cements. This can be achieved by using the latest generation of liquefying admixtures
(superplasticizers).
6. The durability characteristics of concrete (carbonation susceptibility, chloride ion permeation,
frost resistance) from CEM II/C-M and CEM VI cements should be determined after 90 days of
hardening. This period of curing better reflects the performance properties of the concrete.
7. Portland multicomponent cements CEM II/C-M and CEM VI are low-emission binders with CO2
emissions ranging from 340 (CEM VI) kg to 453 (CEM II/C-M) kg per Mg of cement. Because of a
high content of non-clinker main components, these cements characterize a much lower degree
of hydration after 28 days of hardening than ordinary Portland cement CEM I. The presence of
slag (S) and fly ash (V) results in a significant increase in the strength of low-emission cements
between 28 and 90 days of hardening, and hence a better effect in terms of reducing emissions
per 1 MPa is achieved. In some countries, Poland among others, for this reason the quality of
concrete with low-emission cements is assessed after 90 days.

Author Contributions: Conceptualization, A.K. and Z.G.; Investigation, J.K.-W.; methodology: Z.G.; resources:
A.K. and J.K.-W.; supervision, A.K.; writing—original draft, A.K., Z.G. and J.K.-W.; writing—review & editing,
A.K., Z.G. and J.K.-W. All authors have read and agreed to the published version of the manuscript.
Funding: This research received no external funding.
Conflicts of Interest: The author declares no conflict of interest.

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