materials

Article
Potential Role of GGBS and ACBFS Blast Furnace Slag at
90 Days for Application in Rigid Concrete Pavements
Liliana Maria Nicula 1,2, *, Daniela Lucia Manea 1 , Dorina Simedru 3 , Oana Cadar 3 ,
Mihai Liviu Dragomir 1 , Ioan Ardelean 4 and Ofelia Corbu 1,5, *

1 Faculty of Civil Engineering, Technical University of Cluj-Napoca, 28, Memorandumului,

400114 Cluj-Napoca, Romania; [Link]@[Link] (D.L.M.);
[Link]@[Link] (M.L.D.)
2 Faculty of Construction, Cadastre and Architecture, University of Oradea, 4, B.S. Delavrancea Street,
410058 Oradea, Romania
3 Research Institute for Analytical Instrumentation Subsidiary, National Institute for Research and
Development for Optoelectronics INOE 2000, 67 Donath Street, 400293 Cluj-Napoca, Romania;
[Link]@[Link] (D.S.); [Link]@[Link] (O.C.)
4 Department of Physics and Chemistry, Technical University of Cluj-Napoca, 28, Memorandum Street,
400114 Cluj-Napoca, Romania; [Link]@[Link]
5 Research Institute for Construction Equipment and Technology, ICECON S.A. Bucharest,
266, Pantelimon Road, 2nd District, CP 3-33, 021652 Bucharest, Romania
* Correspondence: [Link]@[Link] (L.M.N.); [Link]@[Link] (O.C.)

Abstract: Incorporating blast furnace slag into the composition of paving concrete can be one of
the cost-effective ways to completely eliminate by-products from the pig iron production process
(approximately 70% granulated slag and 30% air-cooled slag). The possibility to reintroduce blast
furnace slag back into the life cycle will provide significant support to current environmental concerns
and the clearance of tailings landfills. Especially in recent years, granulated and ground blast furnace
slag (GGBS) as a substitute for cement and air-cooled blast furnace slag (ACBFS) aggregates as
a substitute for natural aggregates in the composition of concretes have been studied by many
researchers. But concrete compositions with large amounts of incorporated blast furnace slag affect
Citation: Nicula, L.M.; Manea, D.L.;
the mechanical and durability properties through the interaction between the slag, cement and water
Simedru, D.; Cadar, O.; Dragomir,
M.L.; Ardelean, I.; Corbu, O.
depending on the curing times. This study focuses on identifying the optimal proportions of GGBS
Potential Role of GGBS and ACBFS as a supplementary cementitious material (SCM) and ACBFS aggregates as a substitute to natural
Blast Furnace Slag at 90 Days for sand such that the performance at 90 days of curing the concrete is similar to that of the control
Application in Rigid Concrete concrete. In addition, to minimize the costs associated with grinding GGBS, the hydration activity
Pavements. Materials 2023, 16, 5902. index (HAI) of the GGBS, the surface morphology, and the mineral components were analyzed via
[Link] X-ray diffraction, scanning electron microscopy (SEM), energy dispersive spectrometry (EDX), and
Academic Editors: Safat Al-Deen and nuclear magnetic resonance relaxometry (NMR). The flexural strength, the basic mechanical property
Biruk Hailu Tekle of road concretes, increased from 28 to 90 days by 20.72% and 20.26% for the slag concrete but by
18.58% for the reference concrete. The composite with 15% GGBS and 25% ACBFS achieved results
Received: 31 July 2023
similar to the reference concrete at 90 days; therefore, they are considered optimal percentages to
Revised: 24 August 2023
replace cement and natural sand in ecological pavement concretes. The HAI of the slag powder with
Accepted: 25 August 2023
a specific surface area equivalent to that of Portland cement fell into strength class 80 at the age of
Published: 29 August 2023
28 days, but at the age of 90 days, the strength class was 100. The results of this research present three
important benefits: the first is the protection of the environment through the recycling of two steel
industry wastes that complies with European circular economy regulations, and the second is linked
Copyright: © 2023 by the authors. to the consequent savings in the disposal costs associated with wastefully occupied warehouses and
Licensee MDPI, Basel, Switzerland. the savings in slag grinding.
This article is an open access article
distributed under the terms and Keywords: environmentally friendly road concrete; granulated and ground blast furnace slag (GGBS);
conditions of the Creative Commons air-cooled blast furnace slag (ACBFS) aggregate; durability; hydration activity index (HAI)
Attribution (CC BY) license (https://
[Link]/licenses/by/
4.0/).

Materials 2023, 16, 5902. [Link] [Link]

Materials 2023, 16, 5902 2 of 25

1. Introduction
Portland cement production requires a significant energy input that contributes to
releasing a large amount of carbon dioxide into the atmosphere, about 7% of total global
greenhouse gas emissions [1,2]. The consumption of raw materials adds 1/3 to air pollution
(1 ton of cement is obtained from about 2.8 tons of limestone/shale), a process of depletion
of natural resources. In addition, each tone of cement produced consumes 110–120 kWh
of energy [2–4]. The world production of Portland cement (OPC) was 4.2 billion tons in
2021 and is expected to increase to 4.4 billion tons by the end of 2022 [5,6]. The European
Union presented the circular economy as a viable alternative to the production model with
an excessive and sometimes unnecessary consumption of natural resources that prevails
worldwide, especially in developed countries [7,8]. The transition to regenerative systems,
designed to conserve the value of resources (materials, water, land, and energy) and
products, will reduce the use of raw materials and energy while reducing waste generation
and negative impacts on the environment, climate, and human health [8,9].
Therefore, efficient use of renewable and non-renewable raw materials is essential
for economic development [10]. Multiple wastes (fly ash, blast furnace slag, construction
and demolition waste, municipal solid waste incineration ash, metallurgical and mining
waste, etc.) [11–17] have been studied as raw materials for cement-based materials. Of
these, blast furnace slag represents a sustainable source to replace conventional materials
in concrete compositions. The slag can have a crystalline or glassy, amorphous structure in
its solid state. GGBS is obtained by cooling liquid slag under a powerful jet of cold water,
which vitrifies during the granulation process. Air-cooled blast furnace slag (ACBFS) is
obtained by slowly cooling liquid slag. The resulting material crystallizes and retains a
small portion in the glassy state [8]. The properties of ACBFS, its stability, and the leaching
of heavy metals meet all the requirements as a building material [18] and are often used
both as fine and coarse aggregates in concrete compositions [19–21]. ACBFS particles
have a very rough texture due to their vesicular structure, but the pores present in ACBFS
particles are not interconnected. However, the water absorption is higher, reaching up to
8% compared to natural aggregates where the upper limit is 4% [20]. A beneficial effect
for concrete curing can be achieved in composite materials by carefully designing the
mixing ratios to account for the water absorbed by the lightweight fine aggregates (LWAs)
before the cement sets. These beneficial aspects include increased hydration, leading to a
higher compressive strength, reduced water absorption, and reduced electrical conductivity
(permeability). These advantages also include lower autogenous shrinkage and a lower
tendency to early cracking [22,23].
With the development of high-performance green concrete, GGBS has become an
important auxiliary material in cement concrete, also known as the “sixth ingredient” of
concrete [24]. The widespread use of GGBS as a cement substitute in concrete composition
is currently leading to technological, economic, and environmental benefits. GGBS is
widely recommended, as it improves mechanical properties, corrosion resistance, and
chloride ion penetration. In addition, well-proportioned and well-preserved slag concretes
have been shown to prevent harmful alkali–silica interactions during the curing period
and increase sulfate resistance. The pozzolanic action of slag used as a micro aggregate
and filler (fine mass integrated into the cement matrix) resulted in a higher performance
in the concrete with GGBS. At 56 days, its strength development matched conventional
cement concrete’s [25]. The incorporation of fly ash (FA) or GGBS into concrete resulted
in 91-day compressive strengths similar to conventional concrete. In addition, the pore
structure of the concrete was changed, and the volume of capillaries larger than 0.05 µm
was reduced [26]. Moreover, GGBS plays an important role in filling voids between raw
materials and reducing porosity so as to increase the compactness of concrete [27,28].
Adding GGBS decreases the permeability and increases the chemical stability of self-
consolidating concrete (SCC) due to the reaction of blast furnace slag with excess soluble
calcium hydroxide [29,30], while ACBFS aggregates affect the flexural strength, but they
improve other properties, such as the compressive strength and drying shrinkage [31].
Materials 2023, 16, 5902 3 of 25

The original contribution of this study lies in the detailed analysis of some concretes
containing GGBS as supplementary cementitious material (SCM) together with this type
of ACBFS as a fine aggregate in order to obtain an ecological and economical material
without sacrificing mechanical performances or the durability of the obtained concrete.
This work complements the current research, which is mainly concerned with the separate
incorporation of GGBS or ACBFS into concrete compositions at 28 days of curing age.
The results show the optimal percentages of substituting conventional materials with
blast furnace slag whose performances at 90 days of age are similar to those of the control
concrete. The HAI of the GGBS was evaluated, and the slag mortars’ microstructure was
analyzed via X-ray diffraction, energy dispersive electron microscopy (SEM), and nuclear
magnetic resonance (NMR) relaxometry [32,33]. In addition, the influence of the specific
surface area of the slag powder on the HAI and the degree of crystallinity compared to the
standard mortar was analyzed up to an age of 90 days, similar to the study [34].
This research has significant implications for developing slag concrete for road paving.
The extension of the reference tests from 28 to 90 days confirms the performance improve-
ment, encouraging its use in the composition of road concretes with slag.

2. Materials and Methods

2.1. Materials
The Portland cement -CEM I 42.5R supplied by Romcim Targu-Jiu, CRH Romania
Company is defined according to SR EN 197-1 [35], and the granulated blast furnace slag
sourced from Combinatul Siderurgic in Galati is defined according to SR EN 15167-1 [36].
GGBS has a vitreous mass content of 95%, and the oxide composition is made up as in
Table 1. A greater than 70% concentration of silicon, calcium, aluminum, magnesium, and
iron oxides in GGBS indicates that it is a suitable pozzolanic material for use as a cement
replacement according to ASTM D6868 [37,38]. A calcium-oxide-to-silicon ratio above one
indicates effective hydraulic activity for GGBS [37,39].

Table 1. Oxidative analysis of GGBS and ACBFS (%).

Element SiO2 Al2 O3 MnO MgO CaO Fe2 O3 FeO Na2 O K2 O Other
GGBS (%) 38.10 9.50 0.23 8.10 40.80 0.56 0.30 0.68 1.73
ACBFS (%) 39.01 9.14 0.51 7.57 41.37 0.58 0.01 0.64 1.17

River sand and ACBFS in size (0/4) mm were used as fine aggregates according to SR
EN 12620 [40]. The oxide composition of the ACBFS aggregates in Table 1 is similar to that
of GGBS, the difference being in the predominance of the crystalline phase. The total sulfur
content was determined to be less than 1%, which is below the limit of 2% according to
SR EN 12620, and the determined iron oxide content (0.58%) is also less than the 3% value
according to IS: 383 [41]. The two components are limited to eliminating the expansive
reaction and disintegration of the ACBFS slag particles. The water absorption coefficient
WA24 determined according to SR EN 1097-6 [42] on found aggregates in the saturated dry
surface (SSD) state was 2.02% for natural sand and more than 2.56% for ACBFS [43]. The
quality assurance of the coarse aggregate from gravel (4/8) mm and for crushed quarry
stone (8/16) mm was controlled according to SR EN 12620 [40] and according to SR 667 [44]
for crushed quarry stone (8/25) mm.

2.1.1. Mortar Mixes

The amounts of material for the mortar production are listed in Table 2. Three mortar
mixes were prepared, a standard M I with 100% Portland cement and two with 50% GGBS
and with different specific surface areas, 360 m2 /kg and 330 m2 /kg, called M II/360 and
M III/330. For the specific surface area, the air permeability method (Blaine) was used on
cement particles with GGBS below 63 µm in comparison to a reference material sample
according to SR EN 196-6 [45]. The 40 × 40 × 160 mm prismatic samples were preserved
and tested for up to 90 days according to SR EN 196-1 [46], as seen in photo (Figure 1a,b).
Materials 2023, 16, 5902 4 of 25

Table 2. The composition of mortars.

Materials MI M II/360 M III/330

Materials 2023, 16, x FOR PEER REVIEW 4 of 5
Binder-specific surface area 331 m2 /kg 360 m2 /kg 330 m2 /kg
Portland cement, (g) 450 ± 2 225 ± 1 225 ± 1
(GGBS < 63 µm), (g) - 225 ± 1 225 ± 1
according to SR
(NA_0/4 mm),EN(g)
196-6 [45]. The 40±× 540 × 160 mm 1350
1350 prismatic
± 5 samples were1350 preserved
±5
and tested for up
Water, (mL)to 90 days according225to SR EN 196-1 [46],
225as seen in photo (Figure
225 1a,b).

(a) (b)
Figure 1.
Figure 1. (a)
(a) Compressive strength test
Compressive strength test on
on mortars;
mortars; (b)
(b) mortar
mortar samples
samples after
after testing.
testing.

Table 2.
2.1.2. The composition
Concrete Mixes of mortars.
The material proportions of the poured concrete in this experiment are listed in Table 3.
Materials MI M II/360 M III/330
Three road concrete mixes were prepared, one reference and two containing 15% GGBS with
Binder-specific
a specific surface
surface area area
equal to that of 331 m /kg
cement
2
and 25% or360
50%mACBFS
2 /kg aggregate330 m 2/kg
crushed to
Portland
size (0/4) mm. cement,
To achieve(g) the desired 450 ±2
workability, 225 ± 1
superplasticizer additive 225 ± 1 used
SP was
instead(GGBS ˂ 63 excess
of adding µm), (g) -
water [47]. Superplasticizer 225 MasterGlenium
additive ±1 225
SKY± 527
1 and
(NA_0/4
air-entraining mm), (g)
additive Master Air 9060, 1350 ± 5 Builders1350
Master ± 5 Romania1350
Solutions ± 5 with
group,
Water,
characteristics in (mL)
accordance with SR EN225 225 water in accordance
934-2 [48] and potable 225 with
SR EN 1008 [49] were used. In the concrete manufacturing process, the aggregates were
2.1.2. Concrete
saturated Mixes
with the SSD dry surface to prevent reduced workability, rapid stiffening, cement
hydration delay, and
The material the occurrence
proportions of the of concrete
poured shrinkage
concrete in thiscracks [50]. are listed in Table
experiment
3. Three road concrete mixes were prepared, one reference and two containing 15% GGBS
Table 3. Concrete composition kg/m3 .
with a specific surface area equal to that of cement and 25% or 50% ACBFS aggregate
crushed to size (0/4) mm. To achieve the desired workability, superplasticizer additive SP
S 0/0 S 15/25 S 15/50
Material (kg/m3 ) was used Reference
instead ofConcrete
adding excess (15%GGBS_25%ACBFS)
water [47]. Superplasticizer(15%GGBS_50%ACBFS)
additive MasterGlenium
SKY 527 and air-entraining additive Master Air 9060, Master Builders Solutions Romania
Cement (C) 370 314.50 314.50
(GGBS < 63 µm) group, with characteristics
- in accordance with SR EN 934-2 [48] and potable
55.50 55.50water in ac-
Binder (b) cordance with SR370 EN 1008 [49] were used. In the
370 concrete manufacturing process, the ag-
370
Water (w) gregates were saturated
151.68 with the SSD dry surface
154.51 to prevent reduced workability,
155.92 rapid
w/b stiffening, cement0.41
hydration delay, and the occurrence
0.418 of concrete shrinkage
0.421cracks [50].
(ACBFS_0/4 mm) - 163.44 326.90
Natural sand (AN_0/4 mm)Table 3. Concrete 654.70
composition kg/m3. 490.33 326.90
Coarse aggregate (AC_4/25 mm) 1215.88 1214.16 1214.18
Aggregate total S 0/0
1870.58 S 15/25
1867.94 S1867.97
15/50
Material (kg/m 3)
Admixtures (SP-SKY 527) Reference Concrete (15%GGBS_25%ACBFS)
5.55 6.18 (15%GGBS_50%ACBFS)
6.29
Admixtures (MA 9060) 0.74 0.74 0.81
Cement (C) 370 314.50 314.50
(GGBS ˂ 63 µm) - 55.50 55.50
The design parameters for the pavement concrete were set for class BcR 5.0, which
Binder (b) 370 370 370 according to
corresponds to very heavy traffic, commissioning in the system with slip form
Water (w) 151.68 154.51 155.92
the requirements specified in NE 014 [51] and SR EN 206 [52]. The flexural strength (fct, fl)
w/b 0.41 ratio was adjusted to
was 5.5 MPa, the w/b 0.418
0.41, the binder dosage was0.421
370 kg/m3 , and
(ACBFS_0/4 mm) the occluded air content
- was in the range163.44
(5.0 ÷ 6.5)%. The results of 326.90
the fresh concrete
Natural sand (AN_0/4 mm) 654.70 490.33 326.90
were within the specified limit values, and the compressive strength (fc) already reached
Coarse aggregate (AC_4/25the
mm) 1215.88
minimum value 1214.16
of 50 MPa at the age of 7 days [43], see Table 4. 1214.18
Aggregate total 1870.58 1867.94 1867.97
Admixtures (SP-SKY 527) 5.55 6.18 6.29
Admixtures (MA 9060) 0.74 0.74 0.81
Materials 2023, 16, 5902 5 of 25

Table 4. Design parameters of road concrete composites.

Parameters Min. Dosage Compaction Density Occluded fcm fcf, fl

(w/L)
Design Cement (%) (kg/m2 ) Air (%) 28 Days MPa 28 Days MPa
NE 014 and
360 kg/m3 max. 0.45 1.15 ÷ 1.35 2390 ± 30 5.0 ÷ 6.5 min. 50 min. 5.5
SR EN 206
Results 370 kg/m3 0.41 ÷ 0.42 1.26 ÷ 1.33 2392 ÷ 2394 5.1 ÷ 6.4 - -

2.2. Methods
2.2.1. The Influence of HAI of GGBS on the Composition of Mortars
The hydration activity index (HAI) of GGBS was calculated with Equation (1) as
the ratio between the compressive strength of 50:50 slag cement mortar (fcGGBS ) and the
compressive strength of cement mortar (fcC ).

HAI = (fcGGBS /fcC ) × 100, (%), (1)

The strength class for GGBS according to ASTM C989 and the HAI according to SR
EN 15167:1 have the values given in Table 5.

Table 5. The minimum value of the HAI of the GGBS at 28 days.

ASTM C989 ASTM C989 ASTM C989

SR EN 15167:1
(Clasa 80) (Clasa 100) (Clasa 120)
70 75 95 115

2.2.2. Characterization of the Microstructure of Standard Mortar and Mortars with GGBS
X-ray diffraction (XRD) was performed for phase composition analysis and scanning
electron microscopy coupled with energy dispersive spectroscopy (SEM) (EDX) was per-
formed for microstructure analysis. Fragments from the compression test on standard
mortar (M I) and mortar with 50% GBS (M II/360, M III/330) up to the age of 90 days
were examined.

X-ray Diffraction on Mortars

XRD patterns were performed on powder samples using a D8 Advance diffractometer
(Bruker, Karlsruhe, Germany) with CuK α1 anode (λ = 1.5418 Å), operating at 40 kV and
35 mA at room temperature. Conventional reference–intensity ratio (RIR) method [53] was
used for the semi-quantitative analysis. The degree of crystallinity of the mortar samples
was calculated based on the ratio between the area of diffraction peaks over the total area
of the diffraction peaks and amorphous halos.

Scanning Electron Microscopy (SEM) and Energy Dispersive X-ray Spectroscopy

(EDX) Measurements
SEM-EDX analysis was performed at room temperature using a scanning electron
microscope (VEGAS 3 SBU, Tescan, Brno-Kohoutovice, Czech Republic) with a Quantax
EDX XFlash (Bruker, Karlsruhe, Germany) detector. Samples of ~4 mm2 were mounted
with carbon tape on an SEM stub.

2.2.3. NMR Relaxometry Measurements of the Prepared Mortars

From intact prismatic samples prepared for standard mortar and mortar with 50%
GGBS, a cylindrical sample with a length of 20 mm and a diameter of 9.5 mm was extracted
to determine the relative pore size distribution with the NMR relaxometry technique [32].
After drying in the oven, the samples were placed in 10 mm diameter glass tubes and
sealed. The first NMR measurement was performed to highlight the intra-C-S-H pores
followed by the second measurement on cyclohexane-saturated samples to highlight the
 2.2.3. NMR Relaxometry Measurements of the Prepared Mortars
From intact prismatic samples prepared for standard mortar and mortar with 50%
GGBS, a cylindrical sample with a length of 20 mm and a diameter of 9.5 mm was ex-
tracted to determine the relative pore size distribution with the NMR relaxometry tech-
Materials 2023, 16, 5902 nique [32]. After drying in the oven, the samples were placed in 10 mm diameter 6glass of 25
tubes and sealed. The first NMR measurement was performed to highlight the intra-C-S-
H pores followed by the second measurement on cyclohexane-saturated samples to high-
light the inter-C-S-H pores and the capillary pores [33]. NMR measurements were per-
inter-C-S-H pores and the capillary pores [33]. NMR measurements were performed at
formed at 90 days of age with a low-field instrument (Minispec MQ20, Bruker, Karlsruhe,
90 days of age with a low-field instrument (Minispec MQ20, Bruker, Karlsruhe, Germany)
Germany) using the
using the CPMG CPMG technique
technique [32,33].
[32,33]. Before Before
each each measurement,
measurement, the samples
the samples were
were brought
brought into thermal equilibrium with a temperature ◦ of 35 °C. Relaxation time distribu-
into thermal equilibrium with a temperature of 35 C. Relaxation time distributions T2
tions
were T 2 were extracted from the CPMG series using a numerical Laplace inversion [54,55].
extracted from the CPMG series using a numerical Laplace inversion [54,55].

2.2.4.
2.2.4. Road
Road Concrete
Concrete Mixes
Mixes with
with Incorporated
Incorporated SlagSlag (GGBS
(GGBS andand ACBFS)
ACBFS)
A total of nine prisms measuring 150 × 150 × 600
A total of nine prisms measuring 150 × 150 × 600 mm were castmm were castand
andleft
leftininair
airfor
for
2424h.
h. They
They were
were thenthen preserved
preserved in water
in water at a at a temperature
temperature of (20of±(20
2) ±C2)until
◦ °C until
they they
werewere 90 days90
days
old. old. According
According to SR
to SR ENEN 12390-5
12390-5 [56],
[56], flexural
flexural strengthwas
strength wastested
testedon on three
three prismatic
prismatic
specimens
specimens forfor each
eachcompound,
compound,and andthe
theaverage
averagevalue
value waswasformed
formed (Figure 2a,b).
(Figure TheThe
2a,b). re-
maining
remaining samples
samples from thethe
from flexural strength
flexural strength testing were
testing wereused for for
used further teststests
further in this ex-
in this
perimental
experimental study.
study. From
Fromthis,
this,cubes
cubeswith
witha aside
sidelength
lengthofof150
150mm,
mm,cubes
cubeswith
with aa side
side length
length
of
of 70
70 mm,
mm, and
and strips
strips with
with aa thickness
thickness ofof 50
50 mm
mm were
were cut.
cut.

(a) (b) (c) (d)

(e) (f) (g) (h)

Figure
Figure 2.2. (a)
(a) Concrete
Concrete poured in 150
poured in 150 ×
× 150
150 ××600
600mm
mmprisms;
prisms;(b)
(b)flexural
flexuralstrength
strength test;
test; (c)
(c) measuring
measuring
and weighing cubes of 150 mm side; (d) compressive strength test; (e) 150 × 150 × 50 mm strips tested
and weighing cubes of 150 mm side; (d) compressive strength test; (e) 150 × 150 × 50 mm strips
at 56 freeze–thaw cycles; (f) collecting the exfoliated mass from the surface of the sample; (g) Böhme
tested at 56 freeze–thaw cycles; (f) collecting the exfoliated mass from the surface of the sample;
abrasive wheel wear resistance test; (h) hydrostatic weighing of the 70 mm side cube.
(g) Böhme abrasive wheel wear resistance test; (h) hydrostatic weighing of the 70 mm side cube.
The compressive strengths according to SR EN 12390-3 [57] and the loss of compres-
The compressive strengths according to SR EN 12390-3 [57] and the loss of compressive
sive strength between
strength between the the control
control samples
samples preserved
preserved inin waterand
water andthe
thesamples
samples tested
tested with
with
100 freeze–thaw cycles were determined on cubes with a side length of 150 mm according
to SR 3518 [58], (Figure 2c,d).
Mass loss due to exfoliating in the presence of de-icing agents (3% NaCl) after 56 freeze–
thaw cycles according to SR CEN/TS 12390-9 [59] was determined on strips with a cross-
section of 150 × 150 mm and a thickness of 50 mm (Figure 2e,f). On the samples tested
with 56 freeze–thaw cycles, the migration coefficient of the sodium chloride solution was
determined using the colorimetric method according to the NT BUILD 492 test [60].
Materials 2023, 16, 5902 7 of 25

The volume loss from wear according to SR EN 1338 [61] (Figure 2g) and the permeable
pore content according to ASTM C 642 [62] were determined on cubes with a side length of
71 mm (Figure 2h).
The freshly split fragments were sprayed with 1% phenolphthalein solution to deter-
mine the carbonation corrosion resistance in accordance with SR CR 12793 [63].
The quality of the concrete was assessed according to the requirements indicated in
Table 6 for freeze–thaw resistance and the conditions indicated in Table 7 for wear resistance.

Table 6. Acceptance criteria for frost resistance of concrete SS 13 72 44 [64,65], NE012-1 [66], and SR
3518 [58].

Frost-Thaw Resistance Requirement SS 13 72 44 Requirement NE 012-1 Requirement SR 3518

Very good m56 < 0.10 kg/m2
Hi m56 < 0.20 kg/m2 m56 < 0.50 kg/m2 -
(Raised) or m56 < 0.50 kg/m2 and m56 /m28 < 2
or m112 < 0.50 kg/m2
m56 < 1.00 kg/m2 and m56 /m28 < 2
Acceptable (Moderate) m56 < 1.0 kg/m2 -
or m112 < 1.00 kg/m2
Unacceptable m56 ≥ 1.00 kg/m2 and m56 /m28 ≥ 2
m56 < 2.0 kg/m2 -
(Low) or m112 ≥ 1.00 kg/m2
Loss of compressive
Degree of gelling G100 - -
strength (η) < 25%

Table 7. Wear resistance classes SR EN 1338 [61].

Class 1 3 4
Marcare F H I
Criteria No measured performance ≤20,000 mm3 /5000 mm2 ≤18,000 mm3 /5000 mm2

Chloride corrosion resistance was evaluated on cylindrical specimens 100 mm in

diameter and 50 mm thick using the RPCT test according to ASTM C 1202 [67] (Figure 3).
At the end of the RCPT test, the samples were split axially and sprayed with silver nitrate
(AgNO3 ), a 0.1 mol/dm3 (0.1 M) solution, to determine the penetration depth of chlorine
(Xd) according to the NT BUILD 492 test [60]. Chlorine ion migration coefficients (D) were
then calculated with the Nernst–Planck Equation (2) [60,68]:
s
0.0239(273 + T ) L (273 + T ) Lxd
D= ( xd − 0.0238 ) (2)
(V − 2) t V−2

were:
D—Migration coefficient in non-equilibrium state (×10−12 m2 /s);
V—Applied voltage (V);
T—Mean value between initial and final temperature in the anolytic solution, (◦ C);
L—Sample thickness (mm);
Xd—Average chlorine penetration depth (mm).
The correlation between the past electrical charge Q and the penetrability of chlorine
ions is presented in Table 8:

Table 8. Interpretation of results according to ASTM C 1202 [67].

Past Electrical Charge (Coulomb) High Moderate Low Very Low

Penetrability of chlorine ions > 4000 2000–4000 1000–2000 100–1000
Materials 2023,
Materials 16, 5902
2023, 16, x FOR PEER REVIEW of25
8 of 9

(a) (b) (c)

Figure 3. (a) Specimens protected with epoxy material on the side surface; (b) image during RCPT
test; (c) the electric charge passed through the sample S 0/0 after 6 h.

The correlation between the past electrical charge Q and the penetrability of chlorine
ions is presented in Table 8:

Table 8. Interpretation of results according to ASTM C 1202 [67].

(a) (b) (c)
Past Electrical Charge (Coulomb) High Moderate Low Very Low
Figure
Penetrability of [Link]
Figure 3. (a) Specimens
(a) Specimens protected with
with epoxy
protected˃4000 epoxy material on
on the
2000–4000
material the side surface; (b)
side1000–2000
surface; image100–1000
(b) image during RCPT
during RCPT
test;
test; (c)
(c) the electric charge
the electric charge passed
passed through
through the
the sample
sample SS 0/0
0/0 after
after 66 h.
h.
3. Results and Discussion
The correlation
3. Results between the past electrical charge Q and the penetrability of chlorine
and Discussion
3.1. Mortar
ions
3.1. Mortar Mixes
is presented with
Mixes in GGBS
Table
with GGBS8:
3.1.1. The
3.1.1. The Influence
Influence of
of HAI
HAI of
of GGBS on the
GGBS on the Composition
Composition ofof Mortars
Mortars
Table 8. Interpretation of results according to ASTM C 1202 [67].
The compressive
The compressive strengths
strengths ofof the
the standard
standard mortar
mortar MI
MI and
and the
thetest
testmortars
mortarsMII/360
MII/360
and(Coulomb)
Past Electrical Charge
and MIII/330 are
MIII/330 are shown
shown in
in Figure
High4a.
Figure 4a. The
The values determined
determined for
Moderate
values Low
for the
the tests
tests at
at 28 days
Very
28 days of
of age
Low age
on
on cement
cement mortars
Penetrability of chlorine ions
mortars were
were taken
taken from
from
˃4000 the
the previous
previous work
2000–4000
work [69].
1000–2000
[69]. 100–1000

3. Results and Discussion

3.1. Mortar Mixes with GGBS
3.1.1. The Influence of HAI of GGBS on the Composition of Mortars
The compressive strengths of the standard mortar MI and the test mortars MII/360
and MIII/330 are shown in Figure 4a. The values determined for the tests at 28 days of age
on cement mortars were taken from the previous work [69].

(a) (b)
Figure 4.
Figure 4. (a)
(a) The
The compressive strengths of
compressive strengths of mortars;
mortars; (b)
(b) evolution
evolution (HAI)
(HAI) as
as aa function
function of
of age
age from
from 28
28 to 90 days.
to 90 days.

As can
As can be
be seen,
seen, the
the highest
highest increase
increase in the compressive
in the compressive strengths
strengths from
from 28 to 90
28 to 90 days
days
was 22.90% for the MIII/330 mortar and 13.62% for MII/360, respectively,
was 22.90% for the MIII/330 mortar and 13.62% for MII/360, respectively, while the increase while the in-
crease
for for MI
MI was was 7.13%.
7.13%. In FigureIn 4b,
Figure
it can4b,beitseen
can be seen
that the that
HAIthe HAI
of the of the
50% GGBS50% GGBSsamples
mortar mortar
samples increased
increased with agewith[24].age
The[24].
slowerThe hydration
slower hydrationreactionreaction
and lower andheat
lower heat release
release rate ofrate
the
of(a)
the GGBS
GGBS comparedcompared to Portland
to Portland cementcement [70] resulted
[70] resulted in a low (b)HAI
in a lowatHAI at 28ofdays
28 days age. of age.
But at
But at 90 days of age, the HAI for the slag mortar reached a value close to
Figure 4. (a) The compressive strengths of mortars; (b) evolution (HAI) as a function of age from
90 days of age, the HAI for the slag mortar reached a value close to a a strength
strength class
class of
of to
28
10010090according to ASTM
days. to ASTM
according C989 C989
[71],[71], exceeding
exceeding the the
valuevalue
at 28atdays
28 days (strength
(strength classclass 80).
80). The
higher specific surface area of the MII/360 mortar had a significant impact on increasing the
As can
reaction be seen,
capacity andthe highest increase
hydration in theat
rate [24,72,73] compressive
the reference strengths from
ages of 28 and2856todays
90 days
but
was
had a22.90%
slightlyfor the MIII/330
smaller impact atmortar and 13.62%
the 90-day age. Thefor MII/360,
value of the respectively,
HAI of 97 forwhile the in-
the MIII/330
crease
mortarforandMI wasto
close 7.13%. In Figure
the value of 99 4b,
for it can be seen
MII/360 that the
confirms the HAI of the
increase in 50% GGBS mortar
the hydration rate
samples increased with age [24]. The slower hydration reaction and lower heat release rate
at 90 days.
of theFor
GGBS compared
quality to the
control in Portland cement
production of [70] resulted in asamples,
mortar/concrete low HAIthe at standard
28 days ofdevia-
age.
But at 90 days of age, the HAI for the slag mortar reached a value close to avary
tion has been plotted in Figure 4a to show how much the individual values strength class
compared
of 100 mean
to the according to ASTM
compressive C989 [71],
strength [Link]
In addition,the value at 28ofdays
the values (strength
the CoV, class 80).
the coefficient
 days but had a slightly smaller impact at the 90-day age. The value of the HAI of 97 for
the MIII/330 mortar and close to the value of 99 for MII/360 confirms the increase in the
hydration rate at 90 days.
For quality control in the production of mortar/concrete samples, the standard devi-
ation has been plotted in Figure 4a to show how much the individual values vary com-
Materials 2023, 16, 5902 9 of 25
pared to the mean compressive strength value. In addition, the values of the CoV, the
coefficient of variation (%), in Table 9, calculated by dividing the standard deviation by
the mean, show that most of the results are below the 10% limit [74,75] with the exception
ofofMII/ 360 at(%),
variation 28 days and9,MIII/330
in Table at 90
calculated by days, which
dividing the are belowdeviation
standard 15% as inbythe papers
the mean,
[74,76].
show that most of the results are below the 10% limit [74,75] with the exception of MII/360
at 28 days and MIII/330 at 90 days, which are below 15% as in the papers [74,76].
Table 9. Coefficient of variation (CoV) (%) of compressive strengths for mortars.
Table 9. Coefficient of variation (CoV) (%) of compressive strengths for mortars.
Mix MI MII/360 MIII/330
Mix MI MII/360 MIII/330
Coefficient of variation CoV (%) CoV (%) CoV (%)
Compressive strength
Coefficient at 28 days-fc (MPa) CoV (%) 10
of variation 11
CoV (%) CoV8(%)
Compressive strength at 28 days-fc (MPa) 10 11 8
Compressive strength at 56 days-fc (MPa) 6 4 7
Compressive strength at 56 days-fc (MPa) 6 4 7
Compressive strength at 90 days-fc
Compressive strength at 90 days-fc (MPa)(MPa) 8 8 7 7 13
13

3.1.2. X-ray Diffraction

3.1.2. X-ray Diffraction
Figure
Figure5a5A shows
shows thetheXRDXRDpatterns of the
patterns mortar
of the samples
mortar at theatage
samples theofage
90 of
days. The
90 days.
XRD patterns of the mortar samples at 90 days presented in Figure 5a indicate
The XRD patterns of the mortar samples at 90 days presented in Figure 5A indicate the the pres-
ence of quartz
presence (SiO(SiO
of quartz 2) as the main crystalline phase, accompanied by albite (NaAlSi3O8),
2 ) as the main crystalline phase, accompanied by albite (NaAlSi3 O8 ),
orthoclase K(AlSi 3O3), and traces of calcium silicate hydrate (CaH2O4Si). At the age of 90
orthoclase K(AlSi3 O3 ), and traces of calcium silicate hydrate (CaH2 O4 Si). At the age of
days, the the
90 days, portlandite andand
portlandite ettringite, which
ettringite, areare
which characteristic ofof
characteristic early
earlycement
cementhydration,
hydration,
were
werenotnotremarked
remarked[77].
[77].

(A) (B)
Figure
Figure5.5.(A) XRD
(A) patterns
XRD of (a)
patterns M I,M(b)
of (a) I, M
(b)II/360, and (c)
M II/360, andM(c)
III/330 mortarmortar
M III/330 samples at 90 days.
samples at 90Note:
days.
Q—quartz, A—albite, O—orthoclase, and C—calcium silicate; (B) degree of crystallinity
Note: Q—quartz, A—albite, O—orthoclase, and C—calcium silicate; (B) degree of crystallinity at 28 and
at 28
90 days on mortar samples (%).
and 90 days on mortar samples (%).

Figure
Figure5b
5Bshows
showsthe
the evolution of the
evolution of the degree
degreeofofcrystallinity
crystallinityfor
forthe
the investigated
investigated sam-
samples
ples up to the age of 90 days and those previously reported at 28 days [69], the difference
up to the age of 90 days and those previously reported at 28 days [69], the difference up to
up to 100%
100% representing
representing the amorphous
the amorphous fraction
fraction [78]. [78].
The results indicate that replacing cement with 50% GGBS increases the degree of
crystallinity from 28 to 90 days, while the degree of crystallinity decreases for the standard
mortar, on the degree of reaction of the binder [79]. For the MII/360 slag mortar with a
higher specific surface at the age of 28 days, it approaches that of the standard mortar. In
MIII/330 slag mortar, the degree of reaction has a high growth rate from 28 to 90 days
above that of MII/360 mortar and standard mortar.
The decrease in the degree of crystallinity from 28 to 90 days in the MI standard sample
indicates a slowing down of the reaction rate of the binder and thus implicitly a slower
development of the resistance structure. However, in the slag samples, the continuation of
these reactions allows the resistance structure to develop after a longer curing time [80].
 The results indicate that replacing cement with 50% GGBS increases the degree of
crystallinity from 28 to 90 days, while the degree of crystallinity decreases for the standard
mortar, on the degree of reaction of the binder [79]. For the MII/360 slag mortar with a
higher specific surface at the age of 28 days, it approaches that of the standard mortar. In
Materials 2023, 16, 5902 10 of 25
MIII/330 slag mortar, the degree of reaction has a high growth rate from 28 to 90 days
above that of MII/360 mortar and standard mortar.
The decrease in the degree of crystallinity from 28 to 90 days in the MI standard sam-
The concentration
ple indicates a slowing down of defects
of the in the crystal
reaction structures
rate of the binder andandthethus
relative solubility
implicitly of the
a slower
different minerals also influence the development of the mechanical
development of the resistance structure. However, in the slag samples, the continuation strength [81].
of theseThe XRD results
reactions allowscorrelate with the
the resistance rate of to
structure increase
develop inafter
the mechanical
a longer curingstrengths of the
time [80].
mortars, which is lower for the standard mortar and higher for the
The concentration of defects in the crystal structures and the relative solubility of theslag mortars over the
period from 28 to 90 days. The higher increase in compressive
different minerals also influence the development of the mechanical strength [81]. strength at 90 days in the
slagThe
mortar
XRDisresults
supported by an
correlate additional
with the rate cementitious
of increase in and pozzolanic reaction
the mechanical strengthsatofa the later
age, which
mortars, which is influenced
is lower forbythe thestandard
GGBS [82–84].
mortar and higher for the slag mortars over the
period from 28 to 90 days. The higher
3.1.3. Scanning Electron Microscopy (SEM) and increase inEnergy
compressive strength
Dispersive X-ray at Spectroscopy
90 days in the
slag mortar is supported
(EDX) Measurements by an additional cementitious and pozzolanic reaction at a later
age, which is influenced by the GGBS [82–84].
On the mortar samples, the SEM technique was used to characterize the structure
and elemental composition on the surface of the examined samples. The images of the
3.1.3. Scanning Electron Microscopy (SEM) and Energy Dispersive X-ray Spectroscopy
mortar samples M I, M II/360, and M III/330 aged 90 days (Figure 6) show that their
(EDX) Measurements
surfaces are irregular and inhomogeneous with pore-like defects. Since the SEM technique
On the
is better mortar
suited forsamples,
the study theofSEM technique
macropores was used
(pores > 50 to
nm)characterize
[85] and isthe structure
limited due to and the
elemental
properties composition
of the materialon the surfacethe
studied, of the examined
defects samples.
observed were in The images
the categoryof the mortar
of air voids
samples
(>severalM µm)
I, M [86–88].
II/360, and Some M III/330
authorsageduse 90 days (Figure
methods such as6)mercury
show that their surfaces
intrusion porosimetryare
irregular and inhomogeneous with pore-like defects. Since the SEM
(MIP) and fractal dimensions [89–91] for a more complex characterization of the pore struc- technique is better
suited
ture, for
butthethestudy of macropores
SEM technique was (pores
used for > 50 nm)
this [85] as
work, and is limited additional
it provides due to the properties
information
ofabout
the material
the surfacestudied, the defects observed were in the category of air voids (>several
structure.
µm) [86–88].
Table 10 Someshowsauthors use methods
the measured poresuch
sizeasand
mercury intrusionbetween
the distances porosimetry (MIP) of
the pores and the
fractal dimensions
examined samples[89–91]
aged 90 fordays.
a more complex characterization of the pore structure, but
the SEM technique
Larger was at
air voids used for this
smaller work, as
spacings it provides
indicate a moreadditional information
porous surface, and about the
conversely,
surface structure.
small pore sizes at larger spacings indicate a more compact surface [92].

(a)
Figure 6. Cont.
Materials2023,
Materials 16,x5902
2023,16, FOR PEER REVIEW 1111ofof12
25

(b)

(c)
Figure
[Link]
SEMimages
imagesof
of(a)
(a)M
MI,I,(b)
(b)M
MII/360,
II/360,and
and(c)
(c)MMIII/330 mortar
III/330 samples
mortar atat
samples 9090
days.
days.

Table 10 shows the measured pore size and the distances between the pores of the
examined samples aged 90 days.
Materials 2023, 16, 5902 12 of 25
Materials 2023, 16, x FOR PEER REVIEW 12 of 13

Table 10. Pore measurements of mortar samples M I, M II/360, and M III/330, at 90 days.
Table 10. Pore measurements of mortar samples M I, M II/360, and M III/330, at 90 days.
Sample Pore Identification Code Pore Radius (µm) Distance Code Li(Ci–Ci + n) Distance (µm)
Distance
Sample Pore Identification
C1 Code Pore Radius (μm) Distance22.19
(μm)
MI 6.04 Code Li(Ci–Ci + n)
L1(C1–C2)
C2 5.72
MI C1 C3 6.04 5.06 L1(C1–C2)
L2(C3–C4) 22.1957.31
C2 C4 5.72 5.95
M II/360 C3 C1 5.06 7.40 L2(C3–C4) 57.31
C4 C2 5.9510.20 L1(C2–C3) 26.96
M II/360 C1 C3 7.40 5.31
C2 C4 10.205.16 L2(C4–C6)
L1(C2–C3) 205.25
26.96
C5 7.48
C3 C6 5.31 6.66
C4 5.16 L2(C4–C6) 205.25
M III/330 C1 6.57 L2(C1–C6) 209.19
C5 C2 7.4811.58
C6 C3 6.66 6.69 L1(C3–C4) 32.44
M III/330 C1 C4 6.57 6.27 L2(C1–C6) 209.19
C2 C5 11.5811.29
C6 14.18
C3 6.69 L1(C3–C4) 32.44
C4 6.27
At 90 days, the M I standard mortar sample (Figure 6a) shows a surface with air voids
C5 11.29
(with radii ranging from 5.06 to 6.04 µm) spaced at intervals (from 22.19 to 57.31 µm).
C6 The slag samples M 14.18 II/360 (Figure 6b) and MII/330 (Figure 6c) show slightly larger air
voids ((radius from 5.16 to 10.20 µm) or (from 6.27 to 14.18 µm)) compared to the standard
Larger
mortar. air voids
However, theatairsmaller
voids arespacings indicate
at larger spacingsa more
in theporous
MII/360surface,
sample and conversely,
(from 26.96 to
small pore sizes at larger spacings indicate a more compact surface
205.25 µm) and intervals in the M III/330 slag sample (from 32.44 to 209.19 µm) compared [92].
to theAtstandard
90 days,sample.
the M I standard
This behavior mortarmaysample
be due (Figure
to the 6a) shows a surface
modification with air voids
of the microstructure
(with
of theradii
cement ranging
paste from
due to5.06theto 6.04 µm)
ability spaced
of GGBS at intervals
to fill the vacant (from
pores22.19
and to 57.31 µm).
effectively The
reduce
slag samples
the pore volumeM II/360
of the(Figure
matrix [84].6b) and MII/330 (Figure 6c) show slightly larger air voids
((radius from 5.16 to 10.20
Energy-dispersive EDX µm) or (from 6.27was
spectroscopy to 14.18
usedµm))to mapcompared to theand
the surfaces standard
identify mor-
the
tar. However, the air voids are at larger spacings in the MII/360
elemental composition of the samples previously studied via electron microscopy. The sample (from 26.96 to
205.25 µm) and intervals in the M III/330 slag
resulting images at 90 days are shown in Figures 7 and 8. sample (from 32.44 to 209.19 µm) compared
to theFor
standard
the threesample.
samples This behaviorthe
analyzed, may be due to the
predominant modification
elements at 28- andof the microstruc-
90-days-old are
ture of Ca.
Si and the Aluminum
cement paste was due to the ability
identified in theof
slagGGBS to fillMII/360
samples the vacant
andpores and effectively
M III/330 due to the
reduce the pore volume
higher amounts of aluminum of thepresent
matrixin [84].
the GGBS compared to the Portland cement [93,94].
The Energy-dispersive
development of the EDX twospectroscopy
main elements was(Caused andto map thetheir
Si) and surfaces
ratioand
from identify
28 to the
the
elemental
90 days are composition
shown in Figureof [Link] previously
The values recorded studied via electron
at 28 days of age weremicroscopy.
taken from Thea
resulting
previous images at 90 days are shown in Figures 7 and 8.
study [69].

(a) M I (b) M II/360 (c) M III/330

Figure
Figure 7.
7. Surface
Surface mapping
mapping of
of (a)
(a) M
M I,I, (b)
(b) M
M II/360,
II/360,(c)
(c)M
MIII/330
III/330mortar
mortarsamples
samplesatat9090days.
days.
Materials
Materials2023, 16,16,
2023, x FOR
5902PEER REVIEW 13 of 14
13 of 25

(a)

(b)

(c)
Figure 8. EDX
Figure spectrum
8. EDX of (a)
spectrum of M
(a)I,M(b)
I, M
(b)II/360, (c) M(c)
M II/360, III/330 mortar
M III/330 samples
mortar at 90 days.
samples at 90 days.
 For the three samples analyzed, the predominant elements at 28- and 90-days-old are
Si and Ca. Aluminum was identified in the slag samples MII/360 and M III/330 due to the
higher amounts of aluminum present in the GGBS compared to the Portland cement
[93,94]. The development of the two main elements (Ca and Si) and their ratio from 28 to
Materials 2023, 16, 5902 14 of 25
the 90 days are shown in Figure 9. The values recorded at 28 days of age were taken from
a previous study [69].

(a) (b)

(c)
Figure
Figure 9.
9. (a)
(a)Ca
Cacontent;
content;(b) SiSi
(b) content; (c)(c)
content; Ca/Si ratioratio
Ca/Si for mortar samples
for mortar M I, M
samples MII/360, and M and
I, M II/360, III/330
M
up to 90 days.
III/330 up to 90 days.

In
In Figure
Figure 9a,
9a, aa high
high concentration
concentration of of Ca,
Ca, the
the predominant
predominant phasephase forfor Portland
Portland cement,
cement,
is
is observed
observed in in the
the MI standard mortar
MI standard mortar at at 28
28 days
days [95].
[95]. The
The formation
formation of of calcium-rich
calcium-rich gels
gels
in
in the
the standard
standard MI mortar resulted
MI mortar resulted in in increased
increased strength
strength at 28 days
at 28 days compared
compared to to the
the slag
slag
mortars
mortars [96].
[96]. The
TheSiSicontent
contentofofthe theslag
slagmortars
mortarsisisclose toto
close that
thatof of
thethe
standard
standard mortar at
mortar
28 days
at 28 andand
days decreases
decreasesslightly at 90atdays
slightly (Figure
90 days 9b). At
(Figure 90 At
9b). days,
90 more
days, pronounced
more pronounceddiffer-
ences in the in
differences C/S
theratio
C/Sare observed
ratio in Figure
are observed in 9c, which
Figure 9c,differentiates the hydrated
which differentiates calcium
the hydrated
silicate
calcium(C-S-H)
silicate into different
(C-S-H) phases. The
into different standard
phases. mortar with
The standard C/S <with
mortar 1 frames
C/S <the C-S-H
1 frames
hydrate
the C-S-H in hydrate
phase (α) inwith
phase a [Ca2+]
(α) with ion concentration
a [Ca2+] less than 2 mmol/L,
ion concentration less than while for thewhile
2 mmol/L, slag
mortars withmortars
for the slag 1 < C/Swith< 1.5,1 it< frames
C/S < 1.5,the C-S-H
it framesin phase (β) with
the C-S-H a [Ca2+]
in phase concentration
(β) with a [Ca2+]
that is betweenthat
concentration 2 and 22 mmol/L
is between [96].
2 and 22 mmol/L [96].
The morphology of
The morphology the hydrated
of the hydrated calcium
calcium silicate
silicate changes
changes from
from weakly
weakly crystalline
crystalline
fibers to a reticular network [97]. The presence of the C-S-H compound in the slag mortars
fibers to a reticular network [97]. The presence of the C-S-H compound in the slag mortars
over
over aalong
longperiod
period of time
of time contributed
contributed significantly
significantly to increasing
to increasing the compressive
the compressive strengths
strengths
and almost and almostthe
reaching reaching
strength theofstrength
the standardof themortar
standard mortarat[96,98,99]
[96,98,99] at 90behav-
90 days. This days.
ior can be attributed to the formation of additional C-S-H gel due to the hydraulic and
pozzolanic reactivity of the GGBS [84].
The EDX results correlate with those of the XRD and show the continuation of the
hydration–hydrolysis reactions and the development of a strength structure after longer
curing times for the slag mortar.
 Thisbehavior
This behaviorcan
canbe
beattributed
attributedtotothe
theformation
formationofofadditional
additionalC-S-H
C-S-Hgel
geldue
duetotothe
thehy-
hy-
draulic and pozzolanic reactivity of the GGBS
draulic and pozzolanic reactivity of the GGBS [84]. [84].
TheEDX
The EDXresults
resultscorrelate
correlatewith
withthose
thoseofofthe
theXRD
XRDand
andshow
showthe
thecontinuation
continuationofofthe
the
Materials 2023, 16, 5902 hydration–hydrolysis reactions and the development of a strength structure after
hydration–hydrolysis reactions and the development of a strength structure after longer longer
15 of 25
curing times for the slag mortar.
curing times for the slag mortar.

3.1.4. NMRRelaxometry
3.1.4. Relaxometry Measurements
[Link]
NMR RelaxometryMeasurements
Measurements
Thedevelopment
The developmentofofthe
the CPMGechoecho seriesininthe
the caseofofthe
the baremortar
mortar samplesand
and
The development of theCPMG
CPMG echoseries
series in thecase
case of thebare
bare mortarsamples
samples and
cyclohexane-saturated
cyclohexane-saturated samples at 90 days is shown in Figure 10.
cyclohexane-saturated samples
samples atat 90
90 days
days is
is shown
shown in
in Figure
Figure 10.
10.

1
1

(a.u.)
Intensity(a.u.)
0.1
0.1

Intensity
MI
MI
0.01 MII/360
0.01 MII/360
MIII/330
MIII/330
MI-cyclo
MI-cyclo
MII/360-cyclo
MII/360-cyclo
MIII/330-cyclo
0.001 MIII/330-cyclo
0.001
−20 0 20 40 60 80 100 120 140 160 180
−20 0 20 40 60 80 100 120 140 160 180
Echotime
Echo time(ms)
(ms)

(a)
(a) (b)
(b)
Figure 10.(a)
Figure (a) Thesamples
samples onwhich
which theNMR
NMR relaxationmeasurements
measurements wereperformed;
performed; (b)series
series
Figure10.
10. (a)The
The sampleson on whichthe
the NMRrelaxation
relaxation measurementswere
were performed;(b) (b) series
of
of CPMG echo trains for bare and cyclohexane-saturated mortar samples M I, M II/360, M III/330 at
ofCPMG
CPMG echo
echo trains
trains for
for bare
bare and
and cyclohexane-saturated mortar samples
cyclohexane-saturated mortar samples M
M I,I, M
MII/360,
II/360, M
M III/330
III/330atat
90
90 days.
90days.
days.

AA clearerinterpretation
interpretation ofthese
these resultscomescomes fromthe the numericalLaplace
Laplace transfor-
A clearer
clearer interpretationof of theseresults
results comesfrom
from thenumerical
numerical Laplacetransfor-
transfor-
mation
mation of the CPMG echo trains to reveal the distribution of the relaxation times [54,55].
mationof ofthe
theCPMG
CPMGecho echotrains
trainstotoreveal
revealthethedistribution
distributionofofthetherelaxation
relaxationtimes
times[54,55].
[54,55].
Figure11
Figure
Figure 11shows
11 showsthe
shows thedistributions
the distributions
distributions ofofof the
the
the relaxation
relaxation
relaxation times
times
times ininthe
in the theempty
empty
empty mortar
mortar
mortar samples
samples
samples after
afteroven
after
oven ovendrying
drying drying and
and
and the thesamples
the
samplessamples saturated
saturated
saturated withcyclohexane,
with cyclohexane,
with cyclohexane, which
whichwhich weredetermined
were determined
were determined using
using
using
the thenumerical
the numerical
numerical Laplace
Laplace
Laplace inversion
inversion
inversion technique.
technique.
technique.

(a)
(a) (b)
(b)
Figure 11. (a) Distribution of T2 relaxation times in blank samples; (b) distribution of T2 relaxation
times in cyclohexane-saturated samples at 90 days.

The values for the transverse relaxation time T2 plotted on the horizontal axis are
proportional to the relative pore size, and the values plotted on the vertical axis represent
the probability density for a specific relaxation time and are expressed in arbitrary units
(a.u.). The probability density indicates the probability with which a given relaxation time
 Materials
Materials 2023, 16,16,
2023, x FOR PEER REVIEW
5902 16 of1617
of 25

isFigure
present 11. (a) Distribution
in the of T2 relaxation
investigated sample. timesIn Figurein blank
11,samples; (b) distribution
three peaks of T2 relaxationthe
can be distinguished,
times in cyclohexane-saturated samples at 90 days.
position of which can be assigned to the three pore types: intra-C-S-H gel pores (Peak 1)
with sizes up to 2 nm, inter-C-S-H gel pores (Peak 2) with sizes up to 10 nm, and capillary
The values for the transverse relaxation time T2 plotted on the horizontal axis are
pores (Peak 3) with sizes between 50 nm ÷ 1 µm [33]. The peak area is proportional to the
proportional to the relative pore size, and the values plotted on the vertical axis represent
amount of water or cyclohexane absorbed by the pores.
the probability density for a specific relaxation time and are expressed in arbitrary units
It can be seen in Figure 11a that in slag samples MII/360 and MII/330, the area of
(a.u.). The probability density indicates the probability with which a given relaxation time
Peak 1 is smaller than in control sample MI, but the pore size distribution curve is slightly
is present in the investigated sample. In Figure 11, three peaks can be distinguished, the
shifted to higher values for T2 . In the cyclohexane-saturated samples, in Figure 11b, in
position of which can be assigned to the three pore types: intra-C-S-H gel pores (Peak 1)
the
withMII/360
sizes upslag to 2 mortar, the area gel
nm, inter-C-S-H of Peak
pores1(Peak is identified as having
2) with sizes a higher
up to 10 nm, and intensity
capillary and
translates
pores (Peak 3) with sizes between 50 nm ÷ 1 µm [33]. The peak area is proportional to thethe
to higher values than in the control sample, while in the MIII/330 sample,
area
amountof Peakof water1 is or
similar to the absorbed
cyclohexane control sample. It is known that intra-C-S-H gel pores
by the pores.
(PeakIt1)can with
be seen in Figure 11a that in slag samples MII/360 to
dimensions < 2 nm do not cause damage and the structure
MII/330, of the
the area of cement
Peak
paste because they are characterized by a low permeability
1 is smaller than in control sample MI, but the pore size distribution curve is slightly to liquids and gases [100,101].
The inter-C-S-H
shifted to highergel pores
values forinT2Figure
. In the 11b, corresponding to samples,
cyclohexane-saturated Peak 2, have a smaller
in Figure 11b, insurface
the
area for the
MII/360 slagsamples
mortar, withthe areaslagofand
Peak a 1distribution
is identifiedwith loweravalues
as having higher of T2 compared
intensity and trans-to the
standard sample.
lates to higher values than in the control sample, while in the MIII/330 sample, the area of
PeakThe 1 isarea
similar to the
of Peak control [Link]
3 corresponding is known
capillary that intra-C-S-H
pores gel poresand
for the MIII/330 (Peak 1) withslag
MII/360
dimensions ˂ 2 nm do not cause damage to the structure of the cement paste becausedistribu-
samples in Figure 11b is smaller than the area of the standard MI mortar, while the they
are characterized
tion of the T2 relaxation by a low permeability
times is [Link] liquidsNMR andmeasurements
gases [100,101].show The inter-C-S-H gel
a lower capillary
pores inin
porosity Figure
the slag11b,samples
corresponding
compared to Peak
to the2,standard
have a smaller
[Link]
Fewerarea for the
capillary samples
pores reduce
with
the slag and
damage a distribution
to the cement stone with lower values
structure caused of by
T2 the
compared to the phenomenon
freeze–thaw standard sample. [101,102].
The area of Peak 3 corresponding to the capillary pores for the MIII/330 and MII/360
3.2.
slagRoad
samplesConcrete Mixes11b
in Figure withisIncorporated
smaller thanSlag the (GGBS
area of and
the ACBFS)
standardTested at 90 Days
MI mortar, while the
distribution of the T2 relaxation times is similar. The NMR measurements show a lower
3.2.1. Mechanical Resistances, Mechanical Wear, Freeze–Thaw, and Permeable
Pore Content
capillary porosity in the slag samples compared to the standard sample. Fewer capillary
pores Thereduce the damage
evolution to the cement
of the flexural strengths stoneat 90structure
days, thecaused by the freeze–thaw
compressive strengths of the phe-con-
nomenon
trol kept in[101,102].
the thermostatic chamber, and the loss of compressive strength after 100 freeze–
thaw cycles are shown in Figure 12. The flexural strengths at the reference age of 28 days of
[Link]
the Roadconcrete
Concrete SMixes15/25 withandIncorporated
S 15/50 were Slag 5.0(GGBSMPa, andcorresponding
ACBFS) Tested to at 90
theDays
requirements
3.2.1. Mechanical Resistances, Mechanical Wear, Freeze–Thaw, and Permeablethe
for the very heavy traffic class BcR 5.0 [51] and the same traffic class as Porereference
Con-
tent
concrete [69].
An increase in flexural strength from 28 to 90 days by 20.72% or 20.26% can be observed
The evolution of the flexural strengths at 90 days, the compressive strengths of the
for
control keptconcrete
the slag and by 18.58%
in the thermostatic for the
chamber, andreference
the lossconcrete (Figurestrength
of compressive 12a). Inafter
the case
100 of
the slag concrete, the flexural strength is only 1.47% lower for
freeze–thaw cycles are shown in Figure 12. The flexural strengths at the reference age of S15/25 and 7.7% for S15/50
compared
28 days oftothe theslag
reference
concrete concrete.
S 15/25 Increasing
and S 15/50the dosage
were to 50%
5.0 MPa, ACBFS led totoathe
corresponding decrease
re-
in flexural strength [97], which is due to the higher absorption
quirements for the very heavy traffic class BcR 5.0 [51] and the same traffic class as the and porosity c natural sand
and implicitly to
reference concrete [69]. the increase in water demand to maintain a desired workability [19,103].

(a) (b)

Figure 12. Cont.

Materials 2023,
Materials 16,16,
2023, 5902
x FOR PEER REVIEW 17 18
17 of of 25

(c)
Figure 12. (a) The flexural strengths at 28 and 90 days; (b) the compressive strength of the reference
samples and the compressive strength at 100 freeze–thaw cycles, (c) loss of compressive strength at
100 freeze–thaw cycles.

An increase in flexural strength from 28 to 90 days by 20.72% or 20.26% can be ob-

served for the slag concrete and by 18.58% for the reference concrete (Figure 12a). In the
case of the slag concrete, the (c) flexural strength is only 1.47% lower for S15/25 and 7.7% for
S15/50 compared
Figure12.
12.(a)
(a)The to the strengths
The flexural
flexural reference concrete. Increasing the dosage strength
to 50% ofACBFS led to a
Figure strengths atat 28
28 and
and9090days;
days;(b)
(b)the
thecompressive
compressive strength thethe
of reference
reference
decrease
samples andin flexural strength
the compressive [97], at
strength which is due to cycles,
100 freeze–thaw the higher
(c) lossabsorption andstrength
of compressive porosity at c
samples and the compressive strength at 100 freeze–thaw cycles, (c) loss of compressive strength at
100 freeze–thaw
natural sand and cycles.
implicitly to the increase in water demand to maintain a desired worka-
100 freeze–thaw cycles.
bility [19,103].
An
In increase
Figure 12b,intheflexural
the strength strength
compressive from 28 to 90 days bydays
20.72%for or
the20.26% canwith
be ob-
In Figure 12b, compressive strength value
value atat 90
90 days for the samples
samples slag
with slag
served
compared for the
of theslag concrete
the reference and
reference composition by 18.58%
composition is for
is the the
the lower reference
lower by by1.48 concrete
1.48(S15/25) (Figure
(S15/25) and 12a).
and 2.32% In the
2.32% (S15/50).
(S15/50).
compared of
case of the slag concrete, the flexural strength is only 1.47% lower for S15/25 and 7.7% for
The loss
The loss of
of compressive
compressivestrength strengthafter
after100100freeze–thaw
freeze–thawcyclescyclesforfor
thethe slag
slag concretes
concretes is sim-
is similar
S15/50 compared to the reference concrete. Increasing the dosage to 50% ACBFS led to a
ilar to that
to that of S0/0
of the the S0/0 reference
reference concrete,
concrete, see Figure
see Figure 12c. 12c. All values
All values obtained
obtained at 90atdays
90 days of
of age
decrease in flexural strength [97], which is due to the higher absorption and porosity c
age are below
are below the limit
the limit of 25%
of 25% specified
specified in SRin3518
SR 3518
[58].[58].
natural sand and implicitly to the increase in water demand to maintain a desired worka-
The
The total
total exfoliated
exfoliated mass mass SS atat 56
56 freeze–thaw
freeze–thaw cycles,
cycles, the
the wear
wear volume
volume loss, and the
loss, and the
bility [19,103].
permeable pore
permeable pore content
contenttested
testedatat9090days
daysofofageageshowed
showedhigher
higher performance
performance values
values than
In Figure 12b, the compressive strength value at 90 days for the samples with than
slag at
at 28 days,
28compared
days, Figure
Figure 13. 13.
of the reference composition is the lower by 1.48 (S15/25) and 2.32% (S15/50).
The loss of compressive strength after 100 freeze–thaw cycles for the slag concretes is sim-
ilar to that of the S0/0 reference concrete, see Figure 12c. All values obtained at 90 days of
age are below the limit of 25% specified in SR 3518 [58].
The total exfoliated mass S at 56 freeze–thaw cycles, the wear volume loss, and the
permeable pore content tested at 90 days of age showed higher performance values than
at 28 days, Figure 13.

(a) (b) (c)

Figure 13. (a)
Figure 13. (a) Total exfoliated mass
Total exfoliated mass after
after 56
56 freeze–thaw
freeze–thaw cycles;
cycles; (b)
(b) volume
volume loss
loss after
after mechanical
mechanical
wear test; (c) permeable pore content.
wear test; (c) permeable pore content.

The
The cumulative
cumulative value
value ofof the
the exfoliated
exfoliated mass
mass ofof the
the slag
slag samples
samples is
is lower
lower than
than that
that of
of
(a) the reference sample (Figure
the reference sample (Figure(b) 13a); S56 is ˂0.1 kg/m 22, which corresponds to a very good
13a); S56 is <0.1 kg/m , which corresponds(c) to a very good
resistance to exfoliation according to SS 13 72 44 [64,65]. The loss of wear volume showed
Figure 13. (a) Total exfoliated mass after 56 freeze–thaw cycles; (b) volume loss after mechanical
up to 3.98% higher values for the composite material S 15/25 compared to the reference
wear test; (c) permeable pore content.
composite material S 0/0 but falls within the same wear resistance class (class 4, marking
I, withThe
values ≤18,000 mmof3 /5000 mm2 ) [61] (Figure 13b). The permeable pore content
cumulative value the exfoliated mass of the slag samples is lower than that of
recorded low values
the reference samplebetween 1.39%S56
(Figure 13a); andis 1.23% at 902, days,
˂0.1 kg/m whichwhich corresponds
corresponds to compact
to a very good
concretes. Slag concrete S15/25 has an 8.21% lower content of permeable pores than the
reference concrete S0/0 (Figure 13c). A partial replacement of natural sand with a lower
 resistance to exfoliation according to SS 13 72 44 [64,65]. The loss of wear volume showed
up to 3.98% higher values for the composite material S 15/25 compared to the reference
composite material S 0/0 but falls within the same wear resistance class (class 4, marking
I, with values ≤18,000 mm3/5000 mm2) [61] (Figure 13b). The permeable pore content rec-
Materials 2023, 16, 5902 orded low values between 1.39% and 1.23% at 90 days, which corresponds to compact 18 of 25
concretes. Slag concrete S15/25 has an 8.21% lower content of permeable pores than the
reference concrete S0/0 (Figure 13c). A partial replacement of natural sand with a lower
proportion
proportion ofofACBFS
ACBFS(25%)(25%)could
couldlead leadtotoan
anoptimal
optimalbalance
balancebetween
betweenthethepacking
packingdensity
density
and
and void content in the composite, thus creating a denser microstructure [23,104].
void content in the composite, thus creating a denser microstructure [23,104]. The
The
reduction
reduction inin the
the performance
performance parameters
parameters of of concrete
concrete S15/50
S15/50 compared
compared to to concrete S15/25
concrete S15/25
can
canbebeexplained
explainedby bythe
theincrease
increasein inporosity.
porosity. AtAt9090days
daysof ofage,
age,the
theincrease
increaseininporosity
porosityin in
the
theSS15/50
15/50composite
compositewas wasnotnotaffected
affectedby bythe
theslower
slowerhydration
hydrationof ofGGBS
GGBS[105].
[105].The
Thereason
reason
for
forthis
thiswas
wasthe
theincrease
increasein inthe
thepercentage
percentageof ofthe
thesubstitution
substitutionof ofnatural
naturalsand
sandbybythe
theACBFS
ACBFS
aggregate, which has a higher water absorption coefficient
aggregate, which has a higher water absorption coefficient than natural [Link] natural sand.
Figure
Figure 14
14 shows
shows thethe penetration
penetration depthdepth (Xd)
(Xd) ofof the
the sodium
sodiumchloride
chloridesolution
solutionused
usedasasa
athawing
thawingagent
agentinina atest
testofof5656freeze–thaw
freeze–thaw cycles.
cycles. The
The measurement
measurement waswas
mademade after
after split-
splitting
ting
and and spraying
spraying the the concrete
concrete strips
strips withwith a size
a size of of
150150× ×150
150×× 50
50 mm
mm with
with silver
silver nitrate
nitrate
(AgNO
(AgNO33).).Compared
Comparedtotothe thereference
reference concrete
concrete S0/0,
S0/0,a decrease of 11.14%
a decrease waswas
of 11.14% observed
observedfor
sample S15/25
for sample and and
S15/25 a decrease
a decreaseof 6.77% for sample
of 6.77% for sampleS15/50, which
S15/50, indicates
which a better
indicates re-
a better
sistance of the slag concretes to repeated freeze–thaw cycles with deicing agents.
resistance of the slag concretes to repeated freeze–thaw cycles with deicing agents.

Depth Xd (mm) of penetration with

(3%NaCl) solution
Xd (mm)

13.73
16

12.8
12.2
14
Xd (mm)

12
10
8
6
4
2
(Mix) S 0/0 S 15/25 S 15/50

(a)

(b) (c) (d)

Figure
Figure14.
14.(a)
(a)Penetration
Penetrationdepth
depthofof(3%NaCl)
(3%NaCl)solution
solutionininsamples
samplestested
testedwith
with5656freeze–thaw
freeze–thawcycles;
cycles;
images
imagesof
ofXd
Xd measurement
measurement (b)
(b) for
for sample
sample SS 0/0;
0/0;(c)
(c)for
forsample
sampleSS15/25;
15/25;and
and(d)
(d)for
forsample
sampleSS15/50.
15/50.

3.2.2. Resistance to Corrosion from Chlorides and from Carbonation at 90 Days

The average values of the electrical pass-through charges Q resulting from the rapid
chlorine penetration test (RCPT) and the average penetration depth of the chlorine ions
measured on three samples are shown in Figure 15. The pass-through electrical charges
recorded values between (2316 ÷ 2485) Coulombs for all the prepared mixes (Figure 15a),
falling within the moderate class of chloride ion permeation concretes according to ASTM
C 1202 [67].
 3.2.2. Resistance to Corrosion from Chlorides and from Carbonation at 90 days
measured on three samples are shown in Figure 15. The pass-through electrical charges
The average values of the electrical pass-through charges Q resulting from the rapid
recorded values between (2316 ÷ 2485) Coulombs for all the prepared mixes (Figure 15a),
chlorine penetration test (RCPT) and the average penetration depth of the chlorine ions
falling within the moderate class of chloride ion permeation concretes according to ASTM
measured on three samples are shown in Figure 15. The pass-through electrical charges
C 1202 [67]. values between (2316 ÷ 2485) Coulombs for all the prepared mixes (Figure 15a),
recorded
Materials 2023, 16, 5902 19 of 25
falling within the moderate class of chloride ion permeation concretes according to ASTM
C 1202 [67].

(a) (b)
(a) (b)
Figure 15. (a) Electric charge Q recorded at 6 h; (b) penetration depth Xd and migration coefficient
Dx Figure 15.
(10−12 m
Figure (a)ofElectric
2/s)
15. (a) Electric
chlorinecharge Q recorded
ions.Q
charge recorded at
at 66 h;
h; (b)
(b) penetration
penetration depth
depth Xd
Xd and
and migration
migration coefficient
coefficient
Dx (10−
Dx (10
−12 m2/s) of chlorine ions.
12 m2 /s) of chlorine ions.

At the age of 90 days, the passing electrical charges Q decrease by up to 6.8%, the
At the
At the age
ageofof9090days,
days,
thethe passing
passing electrical
electrical charges
charges Q decrease
Q decrease by up toby6.8%,
up tothe
6.8%, the
penetra-
penetration
penetration depth
depth ofofchlorine
chlorine ions
ions Xd by
Xd byupuptoto6.18%,
6.18%,andandthethe migration
migration −12 coefficient
coefficient2 /s)Dx Dx
tion depth of chlorine ions Xd by up to 6.18%, and the migration coefficient Dx 10 (m by
10−12
10 (m
up to(m
−12
2/s) by up to 7.39% (S15/50) compared to the reference concrete (Figures 15b and
2 /s) by
7.39% up to 7.39%
(S15/50) (S15/50)
compared compared
to the referencetoconcrete
the reference concrete
(Figures 15b and (Figures
16). The15b and
results
16).16).
The results obtained show that the concretes with incorporated
obtained show that the concretes with incorporated GGBS have an increased resistancein-
The results obtained show that the concretes with incorporated GGBSGGBShave have
an toan in-
creased
creased resistance
resistance totothe
thepenetration
penetration of
of chlorine
chlorine ions
ions compared
compared to to conventional
conventional
the penetration of chlorine ions compared to conventional concretes, which is similar to the concretes,
concretes,
which
which is similar
is similar
investigations totothe
theinvestigations
[37,106]. [37,106].
investigations [37,106].

(a) (b) (c)

(a) (b) (c)
Figure 16. Chlorine ion migration front at the age of 90 days (a) for sample S 0/0; (b) for sample S
15/25;
Figure [Link]
Figure 16. (c) for sample
Chlorine
Chlorine ion S 15/50. front
ionmigration
migration atthe
front at theage
ageofof9090 days
days (a) (a)
for for sample
sample S 0/0;
S 0/0; (b)sample
(b) for for sample
S S
15/25; andand
15/25; (c) (c)
forforsample
sampleS S15/50.
15/50.
3.2.3. Carbonation Corrosion Resistance at 90 Days
3.2.3. Carbonation
3.2.3. image inCorrosion
Carbonation
The Figure 17 Resistance
Corrosion Resistance
shows the at at90
90Days
samples Days
after one hour of spraying the phenol-
phthalein
The image in Figure 17 shows the samples after(red-purple)
solution. The color of thethe
indicator solution on the the
contour areas
The image in Figure 17 shows samples after one hour of spraying phenolph-
one hour of spraying the phenol-
of the surfaces
thalein solution. remained
The color identical to the interior
of the indicator area(red-purple)
solution of the testedon samples. The diffusion
the contour areas of
phthalein solution. The color of the indicator solution (red-purple) on the contour ofareas
of
thecarbon dioxide
surfaces remainedfromidentical
the cement matrix
to the was area
interior hampered
of the by the samples.
tested increasedThe
compactness
diffusion of
of the
the surfaces
cement
carbon dioxide remained
paste in the
from identical
concrete
the to thewas
cement[107,108].
matrix interior area
Thehampered
image of
bythe
below tested
shows
the thatsamples.
increased Thetested
thecompactness
samples diffusion
of
of carbon
were dioxide
not affected
the cement paste infrom
bythe the cement
carbonation matrix
corrosion.
concrete [107,108]. The image below shows that the samples tested of
was hampered by the increased compactness
thewere
cementnot paste
affected inbythecarbonation
concrete [107,108].
[Link] image below shows that the samples tested
were not affected
The results by carbonation
obtained corrosion.
as the average of the three samples tested for each mixture and
the standard deviation are shown in Figures 12–15. The CoV (%), coefficient of variation,
shown in Table 11 is below 10% for most of the results with the exception of two results
that are below the accepted limit of 15% according to Appendix B of SR EN 206 [52].
Materials2023,
Materials 16,5902
2023,16, x FOR PEER REVIEW 20
20 of 21
of 25

Figure17.
Figure 17. Carbonation
Carbonation progress
progressafter
afterone
onehour
hourof
ofspraying
sprayingthe
thephenolphthalein
phenolphthaleinsolution.
solution.

Table The results obtained

11. Coefficient as the
of variation average
(CoV) (%) ofofphysical–mechanical
the three samples characteristics
tested for each mixture and
determined for
the standard deviation
concretes at 90 days. are shown in Figures 12–15. The CoV (%), coefficient of variation,
shown in Table 11 is below 10% for most of the results with the exception of two results
that are below the accepted
Mix limit of 15% according to Appendix
S 0/0 B of SR EN 206S[52].
S 15/25 15/50
Coefficient of variation CoV (%) CoV (%) CoV (%)
Table 11. Coefficient
The tensileofstrength,
variation-fct,
(CoV) (%) of physical–mechanical
fl (MPa) 6.1 characteristics
10.4 determined
4.4 for
concretes at 90 days.
Reference compressive strength, fc (MPa) 7.0 4.0 1.0
Compressive strength at 100 freeze–thaw, fc (MPa) 12 9.0 2.0
Mix
The exfoliated mass at 56 freeze–thaw cycles (kg/m2 ) S 0/0
8.2 S8.8
15/25 S13.3
15/50
Loss ofCoefficient
volume from ofwear
variation
(mm ) 3 CoV
5.7 (%) CoV 2.6 (%) CoV7.7 (%)
The tensile strength,
Permeable -fct,fl
pore content (%) (MPa) 7.36.1 10.4
3.3 4.4
8.9
Passing charge at 6 h (Q)
Reference compressive strength, fc (MPa) 0.7 7.0 1.7
4.0 0.6
1.0
Penetration depth Xd (mm) 2.3 8.8 1.4
Compressive strength at 100 freeze–thaw,
Migration coefficient of chlorine ions (Dx (10 − 12 fc
2 (MPa)
m /s)) 2.6 12 9.0
9.7 2.0
1.5
The exfoliated mass at 56 freeze–thaw cycles (kg/m2) 8.2 8.8 13.3
Loss of volume from wear (mm ) 3 5.7 2.6 7.7
4. Conclusions
Permeable pore content (%) 7.3 3.3 8.9
The purpose of this paper is to show the potential role of GGBS and ACBFS in the
Passing charge at 6 h (Q) 0.7 1.7 0.6
composition of pavement concretes after a longer curing period. The optimal proportions
Penetration depth Xd (mm) 2.3 8.8 1.4
of GGBS as an SCM and ACBFS aggregate as a−12substitute for natural sand in the paving
Migration coefficient of chlorine ions (Dx (10 m2/s)) 2.6 9.7 1.5
concrete composition were determined with the performance at 90 days being similar to
that of the reference concrete. To obtain a clearer picture of the influence of the GGBS on
4. Conclusions
the concrete composite, mortars containing 50% GGBS were prepared, and the behavior
The purpose
was highlighted byof this paper
evaluating theisHAI
to show
and thethemicrostructure
potential role of of the
GGBS and ACBFS
composite usingin the
SEM,
composition
XRD, EDX, and of pavement
NMR. Theconcretes
performanceafter aoflonger curing
the road slagperiod.
concreteThewas
optimal proportions
evaluated using
of GGBS
two mixesas inan SCMGGBS
which and ACBFS
replacedaggregate
the cement as in
a substitute for natural of
the same percentages sand
15%,inand
the ACBFS
paving
concrete composition
aggregates replaced 25% wereanddetermined
50% of naturalwithsand.
the performance at 90 days being similar to
that In
of the reference
summary, theconcrete.
results ofTothe
obtain
testsa carried
clearer picture
out on of the influence
mortar of theshow
and concrete GGBSthe on
the concrete composite, mortars containing 50% GGBS were prepared, and the behavior
following:
was The
highlighted
GGBSs with by evaluating the HAI
specific surface areasand of the
360 microstructure
m2 /kg and 330of m2the
/kgcomposite using
were classified
SEM, XRD,toEDX,
according the HAI and at NMR. The class
strength performance
80 at 28 of the and
days roadstrength
slag concrete
class 100wasatevaluated
90 days
using twoto
according mixes
ASTM in which
C989. GGBS replaced the cement in the same percentages of 15%, and
ACBFS aggregates replaced 25%
The degree of crystallinity and 50% of
determined vianatural sand.
X-ray diffraction correlates with the rate of
In summary, the results of the tests carried out on mortar and
increase in the mechanical strength of the mortars and is lower for theconcrete
standardshowmortartheand
fol-
lowing:
higher for the slag mortars at 90 days.
The air
The GGBSs
voidswith specific
identified viasurface
the SEMareas of 360 m2/kg
measurements andslag
in the 330mortars
m2/kg were classified
are larger than
according
in to the
the standard MIHAI at strength
mortar class widely
but are more 80 at 28spaced,
days and strengthaclass
suggesting more100 at 90 days
compact ac-
surface.
cording to ASTM C989.
The presence of different C-S-H forms in the slag mortars, identified via EDX measure-
mentsThe degree
at 90 days,of crystallinity
justifies determined
the increase via X-ray
in mechanical diffraction
strength correlates
to values similarwith the rate
to those of
of increase in the mechanical strength of the mortars and is lower for the standard mortar
the standard mortar.
and higher for the slag mortars at 90 days.
Materials 2023, 16, 5902 21 of 25

The NMR measurements show a lower content of capillary voids compared to the
standard mortar, resulting in a better resistance to repeated freeze–thaw cycles.
The durability parameters (strength losses and the amount of exfoliation after the
freeze–thaw cycles, as well as their resistance to corrosion by chlorine ion penetration and
by carbonation) at 90 days of the two composites S15/25 and S15/50 were at the same level
or higher than the reference concrete value.
The S15/25 composite achieved similar mechanical strengths and volume loss from
wear as the reference concrete, but the values were lower for the S15/50 concrete.
This study confirms optimum proportions for the S15/25 composite when the Portland
cement replacement is 15% GGBS and natural sand is 25% ACBFS. In addition, the use of
GGBS with a specific surface area equal to that of Portland cement results in environmen-
tally friendly road concrete with low production costs.
The hydration reactions of GGBS as a cement substitute continuate over a longer
curing period, so the reference age of 90 days is the appropriate option. This experimental
study responds to the desires of the circular economy, and the results can be successfully
used to obtain ecological and economical road concretes.

Author Contributions: Conceptualization, L.M.N., D.L.M., D.S., O.C. (Oana Cadar), I.A., M.L.D.
and O.C. (Ofelia Corbu); methodology, L.M.N., D.S., O.C. (Oana Cadar), I.A. and O.C. (Ofelia
Corbu); investigations, L.M.N., D.S., O.C. (Oana Cadar), M.L.D. and O.C. (Ofelia Corbu); writing—
preparation of the original project, L.M.N.; writing—review and editing, L.M.N., D.L.M., D.S., O.C.
(Oana Cadar), I.A., M.L.D. and O.C. (Ofelia Corbu); surveillance, D.L.M., D.S., I.A., M.L.D., O.C.
(Ofelia Corbu). All authors have read and agreed to the published version of the manuscript.
Funding: This research was funded by the project the “Network of excellence in applied research
and innovation for doctoral and postdoctoral programs/InoHubDoc”, a project co-funded by the
European Social Fund financing agreement no. POCU/993/6/13/153437.
Institutional Review Board Statement: Not applicable.
Informed Consent Statement: Not applicable.
Data Availability Statement: All the required data that support the findings are presented in
this manuscript.
Acknowledgments: This paper was financially supported by the Project the “Network of excellence
in applied research and innovation for doctoral and postdoctoral programs/InoHubDoc”, a project
co-funded by the European Social Fund financing agreement no. POCU/993/6/13/153437. D.S. and
O.C. (Oana Cadar) acknowledge financial support from the Ministry of Research, Innovation, and
Digitization through Program 1—Development of the national research and development system,
Subprogram 1.2—Institutional performance—Projects that finance the RDI excellence, Contract no.
18PFE/30 December 2021.
Conflicts of Interest: All authors confirm that they have no conflict of interest.

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