Cement and Concrete Composites 111 (2020) 103628

Contents lists available at ScienceDirect

Cement and Concrete Composites

journal homepage: http://www.elsevier.com/locate/cemconcomp

Microstructure as a critical factor of cement mortars’ behaviour: The effect

of aggregates’ properties
Ana Rita Santos a, *, Maria do Rosa
�rio Veiga a, Anto
�nio Santos Silva b, Jorge de Brito c
a
Buildings Department, National Laboratory for Civil Engineering, Avenida do Brasil 101, 1700-066, Lisboa, Portugal
b
Materials Department, National Laboratory for Civil Engineering, Avenida do Brasil 101, 1700-066, Lisboa, Portugal
c
CERIS, Department of Civil Engineering, Architecture and Georresources, Instituto Superior T�ecnico, Universidade de Lisboa, Avenida Rovisco Pais, 1049-001, Lisboa,
Portugal

A R T I C L E I N F O A B S T R A C T

Keywords: The purpose of this work is to assess the influence of the aggregates’ properties on the hygric and mechanical
Aggregate behaviour of Portland cement mortars. This assessment allows the establishment of a close relationship between
Mortar the mortars’ performance and its pore size distribution, which is very sensitive to the aggregates’ characteristics:
Portland cement
It was found that the grain size distribution is the dominant parameter influencing the pore size distribution of
Pore size distribution
Mechanical-properties
the coarse porosity of Portland cement mortars, while the mineralogy and its potential reactivity characteristics
Hygric-properties have an important role on the volume of the coarse and gel porosity. The main outcome shows a remarkable
increase of mechanical strength in mortars with low volume and diameter pore size in the coarse porosity.
Moreover, a high average of connected large capillary diameter pores is, in general, associated with an increase
of the water flow.

use of round-shaped aggregates in the mortars’ composition increases

1. Introduction the volume of the large pores and the connected porosity, due to the
weak interlocking between the particles, thus causing a mechanical
The proper use of materials increases the service life of structures, strength reduction and an increase of the water absorption and capillary
reducing the need of interventions. Thus, it is increasingly important to suction, respectively [3,7,12,18,19].
have a thorough knowledge of the characteristics of the materials in On the other hand, the mineralogical composition of the aggregates,
order to predict their future behaviour. In recent years, the importance and more specifically their degree of alteration and its potential
of careful selection of the type of aggregates and their beneficial effects pozzolanic reactivity, can induce chemical reactions, which may lead to
on the performance and durability of mortars and concrete structures changes in the inter-particle and aggregate-binder transition zones,
has become widely recognized [1–5]: As an integrant part of mortars, reducing the pores volume in this weaker interface. Thus, the ITZ
the characteristics of the aggregates (0–4 mm) have a direct influence on strengthens, due to the continuity and good cohesiveness of the struc­
their pore structure, which in turn influences the physical and me­ ture, which results in an increase of the mechanical strength and dura­
chanical properties, as well as the finishing and the final appearance of bility [17,20–22]. In fact, the use of limestone sand, namely in
renders [6–12]. lime-based mortars or in cements with limestone filler addition mor­
An adequate particle size distribution (PSD) of the sands, due to the tars, leads to a reduction of the pore volume between the aggregate and
“filling action”, where the finer grains allow a denser and more homo­ the matrix, due to the crystallographic continuity between the limestone
geneous matrix of the mortars, due to a reduction of the interfacial particles and the binder, which reinforces the interface and promotes an
transition zone (ITZ) porosity [1,9]. This physical factor of compactness increase of mechanical strength and enhances the in-service perfor­
(or filler effect) leads, in general, to a decrease of the capillary rise ki­ mance [6,12,17,23]. However, it may lead to a decrease of the evapo­
netics [3,13,14] and to the development of high mortars’ mechanical ration of the absorbed liquid water, making the render more vulnerable
strength, namely its compressive strength [9,10,12,15–17]. to damage [6,22–25].
Likewise, some study’s correlated the morphology of the sand grains On the other hand, some forms of silica in the aggregates (called
with the pore size distributions and its behaviour, concluding that the reactive silica forms) can also react, under given conditions of humidity,

* Corresponding author.
E-mail addresses: [email protected] (A.R. Santos), [email protected] (M.R. Veiga), [email protected] (A. Santos Silva), [email protected] (J. de Brito).

https://doi.org/10.1016/j.cemconcomp.2020.103628
Received 15 October 2019; Received in revised form 24 March 2020; Accepted 8 April 2020
Available online 25 April 2020
0958-9465/© 2020 Elsevier Ltd. All rights reserved.
A.R. Santos et al. Cement and Concrete Composites 111 (2020) 103628

Nomenclature

Ci Portland cement (CEM II/B-L 32.5 N)

Al natural siliceous sand
Sb crushed siliceous sand
C crushed limestone sand
B crushed basaltic sand
G crushed granite sand
CP standard grain size distribution
CO optimized grain size distribution

Fig. 1. Particle size distribution of the raw materials.

with the hydroxyl ions and the alkalis sodium and potassium present in
the interstitial solution of the binder paste, producing alkali-silica gels
[5]. However, these gels can swell, causing cracking and other damage grain size distribution (CO) was selected in order to obtain a well packing
on the fine pore structure of the hardened cement mortars, decreasing graded sand, which is supposed to minimize the voids and hence lead to
their mechanical performance and durability [26] or, on the other hand, more compact mortars.
promoting an increase in strength in air lime mortars and a reduction in The particle size distribution (PSD) of the binder and sands, deter­
the large suction-active pores [27,28]. mined with a laser diffraction analyser Coulter LS 230, is presented in
Likewise, increasing the percentages of some secondary minerals, Fig. 1.
such as phyllosilicates (e.g. chlorite, talc and clay minerals), which ab­ A binder/aggregate ratio (b/a) of 1:3 by volume was used in the
sorbs water rapidly [29], can negatively affect the mechanical properties preparation of mortars and the water/binder ratio (w/b) was adjusted to
of mortars [30,31]. The water absorbance and consequent swelling of achieve a good workability fixed by 165 � 5 mm flow diameter for all
these secondary minerals result in stresses in the ITZ, causing increased mortars, as measured by the flow table test [42]. Mortars compositions
potential drying shrinkage volume changes. are presented in Table 1.
Indeed, the important properties of a porous material are strongly All mortars were prepared based on European standard EN 1015-2
affected by the way in which pores of different sizes are distributed [43], using a mortar mixer Controls 65-L0005, and cast in 40 � 40 �
within the matrix: the compressive strength and modulus of elasticity are 160 mm3 non-porous moulds and stored under controlled conditions of
primarily affected by the total volume of pores; however, these char­ temperature and relative humidity, according to EN 1015-11 [44] (20
acteristics can also be influenced by the size and spatial distribution of
�
C � 2 � C and 95 � 5% RH for seven days followed by 20 � C � 2 � C and
pores, maximum pore size and pore shape [32]. The permeability and 65 � 5% RH until the test date).
diffusivity are also influenced by the total volume, pore size, shape and
connectivity [13,33]. On the other hand, shrinkage depends on the total 2.2. Methodology
surface of the pore system [34], while durability to freezing and thawing
cycles is controlled by the volume and the spacing of air voids [25,35]. 2.2.1. Binders and aggregates characterization
In this paper, five aggregates of different mineralogy were selected, The particle size distribution (range between 0.375 and 2000 μm) of
and for each one of them, two distinct grain size distributions were used, the materials employed in the mortars’ formulation and their geomet­
resulting in a total of ten mixes, prepared with the same cement type. rical particle properties, as well as the specific surface area, were
Properties including dynamic modulus of elasticity, and flexural and determined with a laser diffraction analyser Coulter LS 230.
compressive strengths were determined. Additionally, total water ab­ The loose bulk density of the binder and sands, as well as the water
sorption, capillary water absorption coefficient, drying index and drying absorption of the aggregates, were determined according to EN 1097-3
rates were also assessed. The obtained characteristics are discussed and [45] and EN 1097-6 [46] respectively.
linked to the pore structure, in order to fully understand their physical- X-ray powder diffraction (XRD) was performed on a Philips PW3710
mechanical behaviour and finding ways of enhancing their performance X-ray diffractometer, with 35 kV and 45 mA and using Fe-filtered CoKα
by optimizing the various parameters of the aggregates for different radiation (λ ¼ 1.7903 Å), in order to identify the mineralogical
fields of application. composition of the sands. Diffractograms were recorded from 3� to 74�
2θ, at an angular speed of 0.05� 2θ/s and the crystalline phases were
2. Materials and methods identified by comparison with the International Centre for Diffraction
Data Powder Diffraction Files.
2.1. Materials and mortars mix A Zeiss Axioplan optical microscope was also used to determine the
degree of weathering and micro texture of the mineral particles.
A Portland cement CEM II/B-L 32.5 N (Ci), according to European
standard EN 197-1 [36], and five different sands (two siliceous sands, 2.2.2. Microstructure and mineralogical characterization of the mortars
different in shape, a natural one - Al and a crushed one - Sb; a limestone The pore size distribution was determined using mercury intrusion
crushed sand - C; a crushed basaltic sand - B; and a crushed granite sand - porosimetry (MIP). The MIP was performed in a Micromeritics AutoPore
G) have been used to formulate ten mortar types. The different sands IV 9500 with a pressure ranging from 0.0015 to 207 MPa, in a pore size
were selected considering the lithological resources available in range of 0.007–600 μm. The surface tension and the contact angle of the
Portugal (mainland) and their potential exploration for construction mercury with the samples are considered equal to 485 � 10 3 N/m and
works [37,38]. 130� , respectively. In addition, in CO mortars’ specimens, the pore size
To minimize the influence of the grain size on the evaluation of ag­ distribution (PSD) of the small pores was also determined by nitrogen
gregates mineralogy’s effect, the five sands were calibrated in two adsorption isotherms at 77 K (- 196 � C) of temperature of liquid nitro­
different grain size ranges, according to a CEN standardized sand (CP), gen, using a physisorption Micromeritics ASAP 2020 instrument. With
defined in EN 196-1 [39], and according to the Fuller’s distribution (CO), this technique, the smallest pores that are out of range of mercury
assuming a Fuller exponential number of 0.50 [40,41]. The optimized porosimetry can be assessed. The Barret-Joyner-Halenda (BJH) method

2
A.R. Santos et al. Cement and Concrete Composites 111 (2020) 103628

Table 1
Acronyms and composition of the studied mortars.
Acronym’s Composition

Binder Aggregate b/a ratio (by volume) Water(by total weight)

Mineralogy Grain size range w/b ratio % water

Ci Al CP Portland cement, Natural siliceous sand - Al Standard (CP) 1:2.5a 0.9 14

Ci Sb CP CEM II/B-L 32.5 N Crushed siliceous sand - Sb 0.9 15
Ci C CP Limestone sand - C 0.8 13
Ci B CP Basalt sand - B 0.9 14
Ci G CP Granite sand - G 0.9 16
Ci Al CO Natural siliceous sand - Al Optimized (CO) 1:2.3a 0.9 15
Ci Sb CO Crushed siliceous sand - Sb 0.9 15
Ci C CO Limestone sand - C 0.8 14
Ci B CO Basalt sand - B 0.8 13
Ci G CO Granite sand - G 0.9 15
a
Binder/aggregate (b/a) ratio of 1:3 (by volume) were chosen for all mortars’ composition, however, owing to the different percentages of each size fraction of the
sands, and due to the rearranging of particles, the final volume proportion of the total curve resulted in 1:2.5 in the preparation of mortars with standard sands (CP) and
1:2.3 for the mortars with optimized sands (CO).

was chosen to accurately evaluate the distribution of pore size in the their original size (40 � 40 � 160 mm3) and without wrapping them
small mesopore range [47]. with paraffin. During the absorption process, the specimen’s weight was
Additionally, thermogravimetric and differential thermal analysis measured repeatedly until saturation was reached (difference between
(TG-DTA) was also performed on mortar specimens, previously dried at two successive weight measurements less than 1% in 24 h).
40 � C and ground to a grain size up to 106 μm, in order to evaluate the The maximum water absorption per unit area achieved by capillarity
hydration process and the eventual presence of hydrated compounds as is given by the asymptotic value of absorption (Abs) and the rate at which
a result of pozzolanic reaction between the reactive siliceous minerals the capillary absorption occurs in the early stages is given by the capil­
and the alkaline binder. The TG-DTA analysis was performed in a lary water absorption coefficient (CC). The two tangents method, defined in
Setaram TGA analyser, under argon atmosphere (3 L/h) and using Pt/Rh the Italian technical standard Normal 11/85 [50], was adopted for the
crucible, with heating rate of 10 � C/min, from room temperature to estimation of the CC, since this method seems to be the most appro­
1000 � C. priate, especially in cases in which building materials have a first ab­
The measurements were performed for each test in one specimen of sorption stage deviating from linearity [51].
each mortar, at 90 days of curing, since the reproducibility of both The drying process of the specimens, based on EN 16322 [52], was
techniques is extremely high. conducted immediately after the absorption test (with the sample
saturated with water), by measuring the weight loss over time, until the
2.2.3. Mechanical and hygric characterization of the mortars samples reached equilibrium with the environment conditions (differ­
To monitor the mechanical performances in the mortars, the dynamic ence between two successive weightings less than 0.1%).
modulus of elasticity was determined using the fundamental resonance From the drying curve, which shows the amount of water content of
frequency method based on EN 14146 [48], using the equipment of the specimens per unit area as a function of the square root of time, the
frequency of resonance ZRM ZEUS 2005, and the flexural (Rt) and drying index (ID), representing the resistance of a material to the evap­
compressive (Rc) strengths were measured according to the EN 1015-11 oration of water, can be calculated using a simplified method of nu­
standard [44], using an electromechanical testing device, from merical integration, trapezoidal rule. Moreover, the drying rates
PROET, model ETI-HM-S/CPC, with a load cell of 200 kN. The modulus corresponding to the first [D1 in kg/(m2 min)] and second drying phase
of elasticity and flexural tests were performed on 40 � 40 � 160 mm3 [D2 in kg/(m2 min1/2)] were also determined, following EN 16322 [52].
mortar prismatic specimens and the compressive strength tests were All the characterization procedures were performed in three mea­
conducted on half-prisms of each specimen resulting from the flexural surements per mortar type, at 90 days of curing.
test.
The water absorption by capillary action test was performed based
on the EN 1015-18 standard [49], but the specimens were used with

Table 2
Physical properties of the raw materials.
Characteristic Aggregates Binder

Grain size Al Sb C B G Ci

D10 CP 320 � 30 159 � 25 158 � 35 213 � 13 213 � 49 1.5 � 0.1

(μm) CO 135 � 60 41 � 9 22 � 15 91 � 25 60 � 5
D50 CP 963 � 3 916 � 63 966 � 95 969 � 18 886 � 82 12.4 � 0.1
(μm) CO 1045 � 98 838 � 75 971 � 157 896 � 55 800 � 35
D90 CP 1680 � 8 1703 � 45 1735 � 48 1730 � 11 1679 � 55 48.9 � 0.3
(μm) CO 1762 � 31 1711 � 27 1826 � 33 1682 � 12 1721 � 11
SSA CP 0.21 � 0.01 0.57 � 0.10 1.54 � 0.16 0.58 � 0.03 0.36 � 0.05 1.81 � 0.01
(m2/g) CO 0.58 � 0.12 1.16 � 0.17 2.89 � 0.46 0.92 � 0.10 0.79 � 0.04
ρ CP 1490 � 1.0 1480 � 1.1 1460 � 4.6 1640 � 1.3 1430 � 6.4 870 � 3.8
(kg/m3) CO 1580 � 11.2 1500 � 11.1 1430 � 15.0 1640 � 3.6 1490 � 3.4
W (%) - 0.35 � 0.02 0.38 � 0.01 1.87 � 0.08 1.21 � 0.06 0.72 � 0.04 –

D10 - particle diameter corresponding to 10% of the cumulative undersize distribution (by volume); D50 - median particle diameter (by volume); D90 - particle diameter
corresponding to 90% of the cumulative undersize distribution (by volume).
SSA - specific surface area; ρ - loose bulk density; W - water absorption.

3
A.R. Santos et al. Cement and Concrete Composites 111 (2020) 103628

Table 3 registered automatically by the MIP equipment, are presented in

Characterization of the aggregates. Table 4.
Aggregate Morphology, mineralogy and degree of All Ci mortars present a similar unimodal distribution with a wider
alteration range of pores below 1 μm, with the major concentration of porosity
- The grains of the natural siliceous sand between 0.28 and 0.55 μm, which the pore diameter shifts depending on
(Al) have a homogeneous and sub-rounded the grain size of the used sand (Fig. 2 and Table 4). The main diameter of
shape, medium sphericity and smooth the x-axis, which is defined as the critical pore size (dcr), characterize
surfaces. the pore entry size of the connected porosity [9].
- Quartz and feldspar (mainly microcline),
low proportion of mica (mainly muscovite)
Regarding the effect of the grain size of the sands on the pore
and kaolinite. structure of the Ci mortars, it is possible to observe two distinct ranges of
- Quartz crystals with signs of deformation pores (Fig. 2), according the Mindess et al. [1] methodology:
(30%) and presence of microcrystalline
silica (6%).
Al
� Medium capillary pores (approximately below 0.03 μm), where the
- The crushed siliceous grains (Sb) have a pore volume of CP mortars is generally higher than that of CO
heterogeneous and sub-angular shape, low mortars;
sphericity and very rough texture. � Large capillary pores (approximately between 0.03 and 5 μm), which
- Quartz, low proportion of feldspar
could be divided in two distinct subranges:
(mainly microcline), mica (mainly
muscovite), calcite and kaolinite. Large capillary pores below the critical pore size (approximately
- Quartz crystals with signs of deformation between 0.03 μm and dcr), where the pore volume of CO mortars
(22%) and presence of microcrystalline is generally higher than that of CP mortars;
silica (8%).
Large capillary pores above the critical pore size (approximately
Sb between dcr and 5 μm), defined in this investigation by coarse
- The limestone grains (C) have angular porosity, where there is a reduction of the pore volume of the CO
shape and low sphericity and present mortars and the critical pore size diameter.
smooth surface with a few fractures.
- Calcite and low proportion of dolomite.
Traces of kaolinite and quartz. Traces of In the medium capillary pores range (d < 0.03 μm), as expected, the
feldspar and mica (mainly muscovite) lower volume intruded by CO mortars, at 90 days, can be ascribed to the
were also detected in the filler fraction. slightly higher binder content, comparing to CP mortars, since high
binder content leads to high hydration degree, so the medium capillary
pore volume falls, because they become filled with hydration products
C [53], creating a large amount of gel porosity. In this range, with MIP
- The basaltic grains (B) have very angular technique, the influence of the mineralogy and shape is not noticed.
to sub-angular shape and show medium
Regarding the large capillary pores subrange below the critical pore
sphericity and rough surface.
- Quartz, feldspar (plagioclase), mica
size (0.03 μm < d � dcr), a higher amount of Portland cement content in
(namely biotite), pyroxene, olivine and CO mortar composition leads to an increase of volume in this porosity
vermiculite. Also, calcite and range, relative to CP mortars, since this range is attributed to the clinker
montmorillonite were detected. phase [54], thus it decays with age, as present in Fig. 3.
- The degree of alteration of the olivine
In the large capillary pores subrange above the critical pore size (dcr
range from the less altered crystals (21%)
to integral substitution of olivine with its < d < 5 μm), which is closely related with the width of the interfacial
B alteration products (18%). transition zone (ITZ) and with drying shrinkage [55], the pore volume of
- The granitic grains (G) are sub-angular in the CO mortars is reduced and slightly shifted to the lower pore size
shape and show medium sphericity and
diameter, due to the high packing density of the produced mortar.
rough surface.
- Quartz, feldspar (albite and microcline)
Likewise, the dcr of the CP mortars is systematically larger than that of
and mica (muscovite and biotite). Also CO mortars (Fig. 4).
chlorite and some traces of hematite are The large capillary pores range is to a great extent defined by the
present. aggregates’ characteristics: Besides the influence of the grain size of the
- Presence of alkali-feldspars (11%) and
used sand, which can modify the packing density, as stated before, the
plagioclases (5%) severely altered.
influence of the mineralogy is also noted, especially above the critical
G pore size. The chemical and mineralogical composition of the sand
grains can favour the interaction between the binder matrix and the
aggregates’ structure and the formation of hydration products, which
3. Results and discussion improve the hydration and carbonation degree at early ages, reducing
the pores between aggregates and matrix or between the aggregates
3.1. Binder and aggregates properties themselves.
Mortars with limestone sand have the highest volume in the critical
Table 2 shows some physical characteristics of the binder and ag­ pore size diameter and the pore size distribution is shifted to the smaller
gregates and Table 3 shows the aggregates’ mineralogy and morphology pore diameter (Fig. 2). This behaviour of the Ci C mortars corresponds to
determined respectively by XRD and optical microscopy. Some petro­ a refinement and densification of the pore structure, probably because
graphic results (degree of alteration) are also presented in Table 3. limestone particles act as nucleation sites for CaCO3 [56,57]. Indeed,
these mortars present the highest carbonation rate (84–87% compared
3.2. Microstructure characterization to 72–81% of the other mortars, determined by TG-DTA analysis at 90
days), thus may increase the volume of the critical pore size diameter
3.2.1. Mercury intrusion porosimetry (MIP) [12]. Moreover, a high content of fines present in the limestone sand
Fig. 2 shows cumulative pore volume and the pore size distribution (Fig. 1) contributes to particle packing, which promotes the densifica­
curves of Ci mortars at 90 days, determined by MIP. Some parameters of tion of the ITZ [55] and consequently the reduction of the coarse
the microstructure characteristics of Portland cement mortars (Ci), porosity.

4
A.R. Santos et al. Cement and Concrete Composites 111 (2020) 103628

Fig. 2. Differential pore size distribution and Hg-intrusion cumulative curves: (a) CP mortars; (b) CO mortars.

Table 4
Some porosity characteristics of the Ci mortars.
Characteristic Aggregates

Grain Al Sb C B G
size

Total intrusion vol. CP 0.14 0.13 0.11 0.11 0.14

(mL/g) CO 0.13 0.14 0.11 0.11 0.13
Total porosity CP 28.1 24.0 21.8 22.4 26.1
(%) CO 24.6 25.8 22.3 23.6 24.8
Median pore diameter CP 0.37 0.32 0.24 0.39 0.46
(vol.) CO 0.20 0.29 0.22 0.26 0.27
(μm)
Critical pore size diameter CP 0.55 0.43 0.35 0.55 0.55
(μm) CO 0.35 0.28 0.28 0.35 0.35
Fig. 4. Differential pore size distribution of Ci G CP and Ci G CO.

Likewise, mortars with granitic sand also show a high volume of dcr,
but lead to pore diameters that lean towards the larger pores and present
high porosity, for both grain size distributions. A slight increase of the
water content for the preparation of these mortars could increase the
volume of coarse pores, due to drying shrinkage.
Contrarily, the use of basaltic aggregate, in general, shows low vol­
ume below the critical pore size diameter (Fig. 2), notwithstanding, the
mortars show similar carbonation rates than the mortars with granitic
sands. The smaller volume of large capillary pores in the mortars with
basaltic aggregate, despite the dcr shifted toward larger pores, associ­
ated with a low porosity (Table 4), can be due to the formation of
pozzolanic reaction products and, consequently, with an increase of
calcium-silicate-hydrate (C–S–H) gel porosity, which cannot be detected
Fig. 3. Differential pore size distribution of Ci G CO from 28 to 360 days. by the MIP technique. In fact, the chemical and mineralogical compo­
sition of these sands, as well as their degree of alteration (Table 3), in­
creases the degree of pozzolanic reaction which could favour the
formation of high-density C–S–H [58,59]. A more accurate assessment of

5
A.R. Santos et al. Cement and Concrete Composites 111 (2020) 103628

Fig. 5. Pore size distribution of Ci CO mortars at 90 days in the small mesopore Fig. 6. Dynamic modulus of elasticity at 90 days.
range obtained using the BJH method.
create a nuclei effect for precipitation of hydration products and pro­
vides free dispersion of cement particles.
Table 5 On the opposite, mortars with granitic sand showed the lowest vol­
Specific surface area (SSA) of the Ci mortars at 90 days. ume of small mesopores (Fig. 5), which can be associated with the lower
Characteristic Aggregate type degree of hydration (97.8%), when compared to Ci C CO. However, this
Grain Al Sb C B G reduction of volume of the adsorbed gas and the very high surface area
size values (Table 5) combined with the coarsening of the large capillary
BET SSA CO 4.15 � 6.20 � 5.10 � 4.03 � 8.74 �
pore volume (Fig. 2), can be attributed to some carbonation shrinkage of
(m2/g) 0.02 0.06 0.05 0.02 0.11 the C–S–H [61–64]. In fact, very high surface areas (which result from
the low-density of the C–S–H) will experience greater shrinkage strains
[65,66], which reduces the volume of gel porosity, increasing the
the small mesopores is mentioned below. capillary porosity.
The siliceous sands present, in general, a high volume below the On the other hand, mortars with basaltic sand also present a low
critical pore size diameter and lead to pore diameters that are shifted to volume of adsorbed gas in small mesopores range, when compared to Ci
the coarse pores (Fig. 2). Moreover, in the range of macroporosity C CO, although they present the lowest SSA values (Table 5). Due to the
(approximately between 5 and 60 μm), despite a marked reduction of mineralogical composition and the degree of alteration of the basaltic
the pore volume in all mortars, the use of siliceous sand, especially with sand, which favour the formation of pozzolanic reaction products, as
CP grain size distribution, leads to a coarsening of the pores’ diameter. well as the low volume of large capillary pores shown by MIP, this
These behaviours can be attributed to the fact that mortars prepared behaviour can be due to the development of cohesive structures of
with rounded and smoother surface grains have a worse packing and C–S–H (high-density of the C–S–H), which does not allow the nitrogen
cohesion between the binder matrix and sand particles and a consequent gas molecules to enter the structure, resulting in a decrease of the small
higher voids volume [12]. mesopores volume and BET specific surface area [66,67].
Additionally, in general, mortars with CP grain size distributions
show high Hg-intrusion cumulative volume, with the exception of the Ci
Sb mortar, which can be associated to the high level of shrinkage of the 3.3. Mechanical behaviour
matrix of the Ci Sb CO mortar, that could promote micro-cracking of the
aggregate/binder interface, or even cause a partial collapse of the 3.3.1. Dynamic modulus of elasticity
porous network, increasing the volume of the large and macroporosity. From Fig. 6 it results that Portland cement mortars present higher
values than in other studies [68,69], which is attributed to the high
3.2.2. N2 adsorption isotherms cement content (1:2.5 and 1:2.3) of the mortars in this investigation.
The pore size distribution of small mesopores range (from 2 to 200 This high stiffness can cause internal stress and lead to micro-cracking,
nm) was also evaluated on the Portland cement mortars with optimized causing a loss of mechanical characteristics and durability.
grain size aggregates (Ci CO) using N2 adsorption isotherms measured at Considering the effect of the mineralogy of the aggregates, mortars
77 K. The Barret-Joyner-Halenda (BJH) method was applied to obtain the with limestone sand (C), for both grain size distributions, have the
pore size distribution curves presented in Fig. 5. Furthermore, the spe­ highest stiffness. This can be explained by the syntaxial growth of calcite
cific surface area determined through the BET method is shown in particles and C–S–H gel in the interface of the limestone aggregate [70],
Table 5. which improves the higher cohesion between the matrix and the
The pore size distribution of the small mesopores (or small gel cap­ aggregate, and consequently increases E.
illaries porosity) is related with the interstitial spaces of C–S–H grains Contrarily, the use of granitic sand (G) in mortars increases the
and thus has a major effect on hydration rates, since gel porosity exists deformability by approximately 30% in relation to limestone sand
inside the hydration products [32]. Furthermore, this porosity is less mortars, which is in agreement with the pore size distribution (Fig. 2),
connected to the permeability but is affected by shrinkage: any where the volume and pore diameter are shifted to a higher diameter.
shrinkage results in a reduction in volume of fine pore structure, due to Moreover, when analysing the shape of aggregates of similar nature,
the collapse of the small pores, and consequently in an increase in the and considering the same grain size distribution, the use of rounded
volume of larger capillary pores [1]. grains (Al) leads to higher stiffness, when compared with angular grains
Mortar with limestone sand presents the highest volume of small (Sb). This behaviour is in line with the SSA values, since the mortars with
mesopores (Fig. 5), linked to the highest rate of cement hydration of this Al sand present higher-density of C–S–H, i.e. lower SSA than the Sb
mortar (98.6%, determined by TG-DTA, compared to 97.8–98.2% of the mortars. However, the differences are relatively low (<7%).
other mortars), could be attributed to the formation of C–S–H and cal­ Regarding the particle size distribution, different aggregates present
cium aluminium silicate hydrates (C-A-S-H) compounds [9,53], as different behaviours: in general, siliceous aggregates (Al and Sb) show
mentioned. In fact, as Krstulovi�c et al. [60] reported, limestone particles lower flexibility for standard grain size distribution (CP). For mortars

6
A.R. Santos et al. Cement and Concrete Composites 111 (2020) 103628

Fig. 7. Mechanical strengths of Portland cement mortars: a) flexural strength; Fig. 8. Capillary water absorption curves for: a) standard and b) optimized
b) compressive strength. Portland cement mortars.

with C, B and G aggregates, in general, the values obtained for optimized obvious, increasing the volume of the larger pores; therefore, in general,
grain size distribution (CO) are higher, when compared with standard these sands, namely the natural siliceous sands (Al), present low strength
grain size distribution (CP). However, for all compositions, the differ­ values, when compared with the other sands, for both grain size distri­
ence between the grain size distributions is lower than 10%, with the butions. Likewise, the use of aggregates with regular and smooth par­
exception of basaltic sands (B), in which the difference is around 20%. ticles, as Al sand, reduces the cohesion between the matrix and the
The high-density C–S–H phase observed in the microstructure of Ci B CO aggregates and it could cause a strength reduction.
could lead to high stiffness of this mortar, when compared to the stan­ Regarding the particle size distribution, in general, CO mortars
dard mortar [71]. present higher strength than CP mortars (Fig. 7), probably due to their
These small differences (less than 10%) show that, for these Portland well-packed system, in which the voids between grains of the same size
cement mortars, which present very high stiffness, the dynamic modulus are filled with smaller grains, thus inducing better cohesion between
of elasticity values seem to be less affected by the use of different grain aggregate grains and matrix. These results are also in line with the
size distributions than in lime mortars in a previous work [12]. reduction of diameter of coarse range observed in the MIP data. More­
Overall, these data show that the dynamic modulus of elasticity of over, the slight increase of the binder content in the optimized sand
cement mortars is intrinsically related to the mineralogy of the sands mortars could also contribute to the enhancement of the mechanical
grains and consequently to the density of the C–S–H compounds formed strengths.
during the hydration process of these mortars. However, shrinkage Only in mortars with siliceous sand, especially Sb sand, the flexural
could also reduce the mortars’ stiffness. strength shows better performance in CP mortars, as observed in the E-
modulus. In fact, Ci Sb CP shows lower Hg-intrusion volume than the Ci
3.3.2. Flexural and compressive strengths
Fig. 7 summarizes the mechanical properties (flexural strength and
compressive strength) obtained for Portland cement mortars at 90 days.
Considering the effect of the aggregates’ mineralogy, like the values
obtained for the dynamic modulus of elasticity, mortars with limestone
sand (C), for both grain size distributions, have the highest values of
flexural and compressive strengths (Fig. 7). As aforementioned, the
crystallographic continuity between the limestone particles and the
binder, which have limestone filler addition in their composition, pro­
vide a high cohesion between the aggregate particles and the matrix
[70]. Consequently, this continuity decreases the volume of ITZ’s
porosity (coarse porosity) and increases the mechanical strengths.
Furthermore, the high volume of hydrated compounds could also favour
the mechanical performance of these mortars.
Contrarily, in mortars with siliceous sand this continuity is less
Fig. 9. Capillary water absorption coefficient of Portland cement mortars.

7
A.R. Santos et al. Cement and Concrete Composites 111 (2020) 103628

Fig. 10. Desorption curves for: a) standard and b) optimized Portland cement mortars.

Sb CO mortar, as stated in 3.2.1, which could be the result of micro-

Table 6
cracking that affects flexural strength more than compressive strength.
Drying parameters of the Portland cement mortars: drying index (ID) and first
As expected, the obtained results show that the mechanical perfor­
and second drying rates (D1 and D2, respectively).
mance is strongly related with the coarse pore range: a reduction of
Mortar ID D1 (kg/m2.h) D2 (kg/m2.h1/2)
volume and diameter pore size in this range enhances the mechanical
performance, namely the compressive strength. CP CO CP CO CP CO

Ci Al 0.10 � 0.10 � 0.51 � 0.46 � 2.71 � 1.93 �

0.01 0.01 0.07 0.06 0.03 0.05
3.4. Hygric behaviour Ci Sb 0.16 � 0.10 � 0.23 � 0.58 � 1.28 � 2.40 �
0.01 0.01 0.01 0.04 0.01 0.05
Ci C 0.18 � 0.12 � 0.22 � 0.38 � 0.90 � 1.46 �
3.4.1. Water absorption by capillarity 0.02 0.01 0.02 0.02 0.02 0.07
Fig. 8 shows the capillary water absorption curves of Portland Ci B 0.16 � 0.12 � 0.26 � 0.40 � 1.53 � 1.75 �
cement mortars (Ci) at 90 days of curing. The capillary water absorption 0.01 0.01 0.01 0.05 0.01 0.03
coefficients (CC) of mortars are presented in Fig. 9. Ci G 0.13 � 0.12 � 0.49 � 0.49 � 2.12 � 1.89 �
0.01 0.01 0.09 0.04 0.14 0.02
The capillary water absorption curves of Portland cement mortars,
presented in Fig. 8, show a slow initial water absorption rate, followed
by a second section, with a very slight slope, which suggests that mortars Regarding the effect of the aggregates’ mineralogy, the results show
continued absorbing water at a much lower rate during the following that mortars with granitic sand (Ci G CP) and crushed siliceous sand (Ci
days. It is also observed that almost all curves exhibit a first stage not Sb CO) presented the highest rate of capillary water absorption (CC)
sufficiently defined by a straight line. This non-linearity of the cement (Fig. 9), which agrees with the pore size distributions (Fig. 2), since the
mortars means that they have a heterogeneous pore network [72], with main volume of pores is slightly shifted towards a larger diameter,
wider distribution of pores (including capillary and gel pores), which is compared with the other mortars, increasing the capillary water ab­
in agreement with the pore size distribution presented above. sorption coefficient. Moreover, the Ci G CP and Ci Sb CO mortars pre­
From the results presented in Figs. 8 and 9, considering the different sented the highest asymptotic values (Abs) (Fig. 8), which is in line with
grain size distributions, in general, the use of optimized sand (CO) in the the values of capillary porosity data obtained by MIP, where, in general,
mortars with siliceous sands (Ci Al and Ci Sb) induces higher values of the highest connected porosity increases the total water absorption.
water absorption (Abs.) and capillary water coefficients (CC) than the On the other hand, Ci C mortars, for both grain size distributions, in
use of standard sand. On the other hand, in the mortars with limestone general, presented the lowest values of CC as well as Abs., which is
(Ci C), basaltic (Ci B) and granitic sands (Ci G), the total water absorp­ attributed to the low porosity (Table 4) and the fact that the main vol­
tion and water absorption rate are higher in the standard sand (CP) ume of the pores is slightly shifted towards a smaller diameter (Fig. 2).
mortars than in the CO mortars. The presence of macropores, around 10 Concerning the effect of shape, in general, the mortars with rounded
μm, in the structure of the Ca Al CP and Ca Sb CP (Fig. 2a) contribute to siliceous sand (Ci Al) have lower water absorption rate and total water
the total porosity, but they have weak capillary suction and do not in­ absorption than the crushed siliceous sand (Ci Sb) mortars, namely with
fluence the total water absorption by capillarity.

8
A.R. Santos et al. Cement and Concrete Composites 111 (2020) 103628

Table 7
Classification proposal of the pore sizes and their main effect in cement mortar’s performance.
Pores Related to Main effects

Diameter Classification

5 μmto 1 μm Large porosity � grading � extent of ITZ � strength

� mineralogy � capillary water flow
� drying shrinkage
� w/b ratio
1 μmto 0.05 μm Medium porosity High (d > dcr) � grading
� mineralogy
Low (d � dcr) � b/a ratio (grading) � CaCO3 content � capillary water performance
� phenomena of hydration and carbonation � clinker phase
<0.05 μm Microporosity (small capillaries and gel pores) � b/a ratio (grading) � Porosity of C–S–H phases � stiffness
� C–S–H morphologies (mineralogy)
� hydration degree

optimized sand. 4. Conclusions

These trends generally agree with the volume of capillary porosity
and the average pore diameter: high volume of capillary pores and high The study of the pore structure of the Portland cement mortars
average pores diameter are, in general, associated with an increase of formulated with aggregates of different mineralogy and grain size dis­
Abs and CC values. tribution was evaluated and related with the mechanical and hygric
rendering mortars behaviour. The main outcomes are:
3.4.2. Drying Pore size distribution vs mortars’ behaviour:
In Fig. 10, the desorption curves of Portland cement mortars (Ci) at
90 days are presented. Table 6 presents the mean and the standard de­ � The large capillary pores range is to a great extent defined by the
viation values of the drying index (ID) and the first and second drying aggregates characteristics, as they are pores between aggregates and
rates (D1 and D2, respectively) of the Ci mortars at 90 days. matrix or between the aggregates themselves. These types of pores,
Regarding the mineralogy of the sands, a high heterogeneity was especially the coarse porosity, have important variations and they
observed: in general, the mortars with siliceous aggregates (Ci Al CP and influence the mechanical characteristics and hygric properties, as
Ci Sb CO) showed a faster drying (lower ID’s, and higher drying rates D1 shown by the results;
and D2). Mortars with granitic sand also display a fast drying. On the � An increase of volume and diameter pore size of the coarse porosity,
other hand, Ci C mortars, namely with optimized sand, show greater leads to a reduction of the mechanical performance, namely the
drying difficulty (high ID) and a low D1 and D2, which can be attributed compressive strength;
to their lower porosity (capillary and total) and lowest main pore � The increase of water flow by capillarity and the drying behaviour
diameter, by comparison with the mortars with other sands, which are primarily affected by the volume and pore size of the capillary
reduce the mortar permeability and diffusivity. porosity and its connectivity. In the studied mortars, it was found
In general, CP mortars presented a higher drying index (ID) and, in that the capillary pores that most affect the liquid water flow, and
general, lower drying rates D1 and D2, which means that drying occurs especially the capillary water absorption coefficient, range between
slower than in the CO mortars, due to a lower large capillary porosity of dcr and 5 μm, and that the range approximately between 0.05 and 5
the CP mortars. Besides that, the higher content of water absorption of μm is related to the drying behaviour;
the CP mortars relative to the CO mortars could also lead to high ID’s of � The volume of gel capillary porosity and the density of C–S–H are
the former. intrinsically related with the stiffness of Portland cement mortars.
However, for mortars with natural siliceous sand (Ci Al), it is possible
to observe an opposite behaviour, with similar ID and highest drying Aggregates’ characteristics vs pore size distribution:
rates D1 and D2 in the CP mortars, which is also in agreement with the
highest values of porosity (Table 4). � The grain size distribution is the dominant parameter influencing the
The effect of shape on the drying process was also observed: for the size distribution of the large capillary porosity of Portland cement
CP mortars with siliceous round sand (Ci Al), the water flow improves mortars, particularly the coarse porosity: the physical effect of the
due to the slight higher large capillary porosity. For the CO mortars, the finer grains allows denser and more homogeneous mortars with
highest capillary porosity is shown in the mortar with siliceous crushed smaller mean pore diameter - the physical factor of compactness;
sand (Ci Sb), which presents faster drying when compared with the � The mineralogy and its potential reactivity characteristics have an
mortar with Al sand. important role on the large capillary and gel porosity: the occurrence
The results generally show that the first drying phase (D1), which is of chemical reactions between the potentially reactive silica particles
characterized by transport of liquid water to the surface followed by of the aggregate and the binder, may yield high-density C–S–H
evaporation (stage 1), can be attributed to the existence of larger pores compounds, which improves the cohesiveness of the matrix causing
(in the capillary range pores) or the good interconnectivity of the mor­ the reduction of the volume in the ITZ.
tars pore channels [73]: high volume of capillary pores and the main
pores shifted towards coarse pores, increase the water flow, and Therefore, the physical factor of compactness and the chemical fac­
consequently the D1 values. tor of reactivity of small particles, which reduce the volume and diam­
D2 is characterised by a reduction of liquid water transport and eter of coarse porosity, justify the better performance of the optimized
progressive increase in water vapour diffusion (stage 2) and, contrary to mortars, increasing the compressive strength, as well as the resistance to
liquid transport, also occurs through the small capillary pores’ range, in water penetration within the mortars’ pore structure. Likewise, the use
which the gas permeability is also influenced [74,75]: an increase of of limestone sand and optimized basaltic sand, leads to high values of
volume in this range leads to higher water vapour diffusion, which is mechanical strengths and lower values of water absorption content and
reflected in an increase of D2. capillary water absorption coefficient, as well as a greater drying
difficulty.

9
A.R. Santos et al. Cement and Concrete Composites 111 (2020) 103628

On the opposite, with a range of large pores, in general, the use of [10] R. Sugra~nez, J.I. Alvarez,
� M. Cruz-Yusta, I. M�armol, J. Morales, L. S�anchez,
Controlling microstructure in cement based mortars by adjusting the particle size
siliceous sand in mortars’ composition, decreases the mechanical
distribution of the raw materials, Construct. Build. Mater. 41 (2013) 139–145,
strength of Portland cement mortars; however, it promotes a good https://doi.org/10.1016/j.conbuildmat.2012.11.090.
drying of the substrate, which becomes useful for mortars subjected to [11] A. Kalagri, I. Karatasios, V. Kilikoglou, The effect of aggregate size and type of
salt crystallization, water rising damp or wetting/drying cycles. binder on microstructure and mechanical properties of NHL mortars, Construct.
Build. Mater. 53 (2014) 467–474, https://doi.org/10.1016/j.
In cases where a balance between mechanical and weathering conbuildmat.2013.11.111.
behaviour is necessary, namely moderate/high mechanical strength and [12] A.R. Santos, M.R. Veiga, A. Santos Silva, J. de Brito, J.I. Alvarez, Evolution of the
in the presence of rising damp with soluble salts, which require rela­ microstructure of lime based mortars and influence on the mechanical behaviour:
the role of the aggregates, Construct. Build. Mater. 187 (2018) 907–922, https://
tively large interconnected pores, mortars with granitic sands are rec­ doi.org/10.1016/j.conbuildmat.2018.07.223.
ommended, due to their good interconnectivity of the pore channels [13] C. Hammecker, J.D. Mertz, C. Fischer, D. Jeannette, A geometrical model for
(high porosity) and their high average pore diameter. numerical simulation of capillary imbibition in sedimentary rocks, Transport
Porous Media 12 (1993) 125–141, https://doi.org/10.1007/BF00616976.
Concerning all the obtained data, a new pore size range classification [14] T. Casta~no-Cardoza, S. Linsel, A. Alujas-Diaz, R. Orozco-Morales, J.F. Martirena-
can be proposed regarding the effect of the aggregates characteristic on Hern� andez, Influence of very fine fraction of mixed recycled aggregates on the
the pore structure and its effect on the cement mortars’ behaviour mechanical properties and durability of mortars and concretes, Revista Facultad de
Ingeniería, Universidad de Antioquia 81 (2016) 81–92, https://doi.org/10.17533/
(Table 7). udea.redin.n81a08.
[15] T. Von Konow, Aggregate grain size distribution: a major influence on many
Funding properties of lime mortars for restoration, in: Proceedings of Euromat 2003 -
European Congress on Advanced Materials and Processes, 2003. Switzerland,
Lausanne.
This work was supported by the National Laboratory of Civil Engi­ [16] D. Cortes, H. Kim, A. Palomino, J. Santamarina, Rheological and mechanical
neering [grant number 0803/112/19461] and the Portuguese Founda­ properties of mortar prepared with natural and manufactured sands, Cement
Concr. Res. 38 (2008) 1142–1147, https://doi.org/10.1016/j.
tion for Science and Technology [grant number PTDC/EPH-PAT/4684/
cemconres.2008.03.020.
2014]. [17] G. Isaia, A. Gastaldini, R. Moraes, Physical and pozzolanic action of mineral
additions on the mechanical strength of high-performance concrete, Cement Concr.
Compos. 25 (2003) 69–76, https://doi.org/10.1016/S0958-9465(01)00057-9.
Declaration of competing interest [18] M. Stefanidou, Crushed and river-origin sands used as aggregates in repair mortars,
Geosciences 6 (2) (2016) 23, https://doi.org/10.3390/geosciences6020023.
[19] J.P. Gonçalves, L.M. Tavares, R.D. Toledo Filho, E.M.R. Fairbairn, E.R. Cunha,
The authors declare that they have no known competing financial
Comparison of natural and manufactured fine aggregates in cement mortars,
interests or personal relationships that could have appeared to influence Cement Concr. Res. 37 (2007) 924–932, https://doi.org/10.1016/j.
the work reported in this paper. cemconres.2007.03.009.
[20] Y. Knop, A. Peled, R. Cohen, Influence of limestone particle size distributions and
contents on blended cement properties, Construct. Build. Mater. 71 (2014) 26–34,
Acknowledgements https://doi.org/10.1016/j.conbuildmat.2014.08.004.
[21] W.A. Tasong, J.C. Cripps, C.J. Lynsdale, Aggregate-Cement chemical interactions,
This work is part of National Laboratory of Civil Engineering (LNEC) Cement Concr. Res. 28 (1998) 1037–1048, https://doi.org/10.1016/S0008-8846
(98)00067-2.
R&I Project 0803/112/19461 “REUSE-Coatings for Rehabilitation: [22] M. Aly, S. Pavía, Effect of limestone aggregate on the properties of natural
Safety and Sustainability” and is a contribution to the Portuguese hydraulic lime mortar (NHL 5), in: Proceedings of Congreso Euro-Americano
Foundation for Science and Technology (FCT) Project PTDC/EPH-PAT/ Rehabend 2016 Patología de la Construcci� on, Tecnología de la Rehabilitaci�on y
Gesti�on del Patrimonio, Spain, Burgos, 2016.
4684/2014 “DB-HERITAGE - Database of building materials with his­ [23] S. Catinaud, J. Beaudoin, J. Marc-Hand, Influence of limestone addition on calcium
torical and heritage interest”. The authors wish to thank LNEC techni­ leaching mechanisms in cement-based materials, Cement Concr. Res. 30 (2000)
cians for their collaboration in carrying out the tests, as well as to the 1961–1968, https://doi.org/10.1016/S0008-8846(00)00385-9.
[24] J. Pozo-Antonio, Evolution of mechanical properties and dry shrinkage in lime-
MIMED group of the University of Navarra for the MIP and phys­ based and lime-cement based mortars with pure limestone aggregate, Construct.
isorption measurements. They also acknowledge the collaboration of Build. Mater. 77 (2015) 472–478, https://doi.org/10.1016/j.
Lena Agregados S.A., Lusical S.A. and Secil Argamassas in supplying the conbuildmat.2014.12.115.
[25] A.R. Santos, M.R. Veiga, L. Matias, A. Santos Silva, J. de Brito, Durability and
testing materials, as well as the support of the CERIS research centre. compatibility of lime-based mortars: the effect of aggregates, Infrastructure 3 (3)
(2018) 34, https://doi.org/10.3390/infrastructures3030034.
References [26] A. Santos Silva, Concrete Degradation by Alkali-Silica Reaction. Use of Fly Ash and
Metakaolin for its Prevention, PhD thesis, University of Minho, School of
Engineering, 2002 (in Portuguese).
[1] S. Mindess, J.F. Young, D. Darwin, Concrete, second ed., Prentice Hall, New Jersey,
[27] M.R. Veiga, A. Santos Silva, M. Tavares, A.R. Santos, N. Lampreia, Characterization
2002.
of renders and plasters from a 16th Century Portuguese military structure:
[2] P. Quiroga, D. Fowler, The Effects of Aggregates Characteristics on the
chronology and durability, Restor. Build. Monum. 19 (2013) 223–238, https://doi.
Performance of Portland Cement Concrete, Research Report ICAR–104-1F,
org/10.1515/rbm-2013-6603.
University of Texas, 2004.
[28] C. Borges, A. Santos Silva, M.R. Veiga, Durability of ancient lime mortars in humid
[3] S. Pavía, B. Toomey, Influence of the aggregate quality on the physical properties
environment, Construct. Build. Mater. 66 (2014) 606–620, https://doi.org/
of natural feebly-hydraulic lime mortars, Mater. Struct. 41 (2008) 559–569,
10.1016/j.conbuildmat.2014.05.019.
https://doi.org/10.1617/s11527-007-9267-4.
[29] R. Fournari, I. Ioannou, Correlations between the properties of crushed fine
[4] A. Fragata, M.R. Veiga, Air lime mortars: the influence of calcareous aggregate and
aggregates, Minerals 9 (2) (2019) 86, https://doi.org/10.3390/min9020086.
filler addition, Mater. Sci. Forum 636–637 (2010) 1280–1285. https://doi.
[30] P. Petrounias, P.P. Giannakopoulou, A. Rogkala, P.M. Stamatis, B. Tsikouras,
org/10.4028/www.scientific.net/MSF.636-637.1280.
D. Papoulis, P. Lampropoulou, K. Hatzipanagiotou, The Influence of alteration of
[5] V. Ramos, I. Fernandes, A. Santos Silva, D. Soares, B. Fournier, S. Leal, F. Noronha,
aggregates on the quality of the concrete: a case study from serpentinites and
Assessment of the potential reactivity of granitic rocks - petrography and expansion
andesites from Central Macedonia (North Greece), Geosciences 8 (4) (2018) 115,
tests, Cement Concr. Res. 86 (2016) 63–77, https://doi.org/10.1016/j.
https://doi.org/10.3390/geosciences8040115.
cemconres.2016.05.001.
[31] M. Alexander, A. Bentur, S. Mindess, Materials for concretes in relation to
[6] J. Lanas, J.I. Alvarez, Masonry repair lime-based mortars: factors affecting the
durability, in: M. Alexander, A. Bentur, S. Mindess (Eds.), Durability of Concrete:
mechanical behavior, Cement Concr. Res. 33 (2003) 1867–1876, https://doi.org/
Design and Construction. Modern Concrete Technology Series, 20, CRC press,
10.1016/S0008-8846(03)00210-2.
Florida, 2017, pp. 37–51.
[7] J. Lanas, J.L. P�erez-Bernal, M.A. Bello, J.I. Alvarez, Mechanical properties of
[32] K. Aligizaki, Pore Structure of Cement-Based Materials: Testing, Interpretation and
natural hydraulic lime-based mortars, Cement Concr. Res. 34 (2004) 2191–2201,
Requirements. Modern Concrete Technology Series, vol. 12, CRC press, London,
https://doi.org/10.1016/j.cemconres.2004.02.005.
2006.
[8] M. Stefanidou, I. Papayianni, The role of aggregates on the structure and properties
[33] D. Benavente, P. Lock, M.A. � García del Cura, S. Ord� on
~ ez, Predicting the capillary
of lime mortars, Cement Concr. Compos. 27 (2005) 914–919, https://doi.org/
imbibition of porous rocks from microstructure, Transport Porous Media 49 (2002)
10.1016/j.cemconcomp.2005.05.001.
59–76, https://doi.org/10.1023/A:1016047122877.
[9] P. Pipilikaki, M. Beazi-Katsioti, The assessment of porosity and pore size
distribution of limestone Portland cement pastes, Construct. Build. Mater. 23
(2009) 1966–1970, https://doi.org/10.1016/j.conbuildmat.2008.08.028.

10
A.R. Santos et al. Cement and Concrete Composites 111 (2020) 103628

[34] G. Verbeck, Pore structure, in: C. Best (Ed.), STP169B-EB Significance of Tests and [56] K. De Weerdt, M. Ben Haha, G. Le Saout, K. Kjellsen, H. Justnes, B. Lothenbach,
Properties of Concrete and Concrete-Making Materials, ASTM International, Hydration mechanisms of ternary Portland cements containing limestone powder
Pennsylvania, 1978, pp. 262–274. and fly ash, Cement Concr. Res. 41 (2011) 279–291, https://doi.org/10.1016/j.
[35] J. Marchand, R. Pleau, R. Gagne, Deterioration of concrete due to freezing and cemconres.2010.11.014.
thawing, in: J. Skalny (Ed.), Materials Science of Concrete IV, American Ceramic [57] P. Mounanga, M. Khokhar, R. El-Hachem, A. Loukili, Improvement of the early-age
Society, Ohio, 1995, pp. 283–354. reactivity of fly ash and blast furnace slag cementitious systems using limestone
[36] European Committee for Standardization (CEN), EN 197-1, Cement; Part 1: filler, Mater. Struct. 44 (2011) 437–453, https://doi.org/10.1617/s11527-010-
Composition, Specifications and Conformity Criteria for Common Cements, CEN, 9637-1.
Brussels, 2011. [58] Q. Zeng, K. Li, T. Fen-Chong, P. Dangla, Pore structure of cement pastes through
[37] A.R. Santos, The Influence of Natural Aggregates on the Performance of NAD and MIP analysis, Adv. Cement Res. 28 (2016) 23–32, https://doi.org/
Replacement Mortars for Ancient Buildings: the Effects of Mineralogy, Grading and 10.1680/adcr.14.00109.
Shape, PhD thesis, Universidade de Lisboa, Instituto Superior T�ecnico, 2019. [59] K. Scrivener, R. Snellings, B. Lothenbach, A Practical Guide to Microstructural
[38] Laborat� orio Nacional de Energia e Geologia (LNEG) - Portugal, Exploration and Analysis of Cementitious Materials, first ed., CRC Press, Florida, 2016.
mining, accessed in November 2018, http://www.lneg.pt/CienciaParaTodos/edi [60] P. Krstulovi�c, N. Kameni�cK, K. Popovi�c, A new approach in evaluation of filler
coes_online/diversos/ind_extractiva, 2000. effect in cement I. Effect on strength and workability of mortar and concrete,
[39] European Committee for Standardization (CEN), EN 196-1, Methods of Testing Cement Concr. Res. 24 (1994) 721–727, https://doi.org/10.1016/0008-8846(94)
Cement; Part 1: Determination of Strength, CEN, Brussels, 2016. 90197-X.
[40] W. Fuller, S. Thompson, The laws of proportioning concrete, Trans. Am. Soc. Civ. [61] C. García-Gonz� alez, A. Hidalgo, J. Fraile, A. L�
opez-Periago, C. Andrade,
Eng. 59 (1907) 67–143. C. Domingo, Porosity and water permeability study of supercritically carbonated
[41] H. Brouwers, H. Radix, Self-compacting concrete: theoretical and experimental cement pastes involving mineral additions, Ind. Eng. Chem. Res. 46 (2007)
study, Cement Concr. Res. 35 (2005) 2116–2136, https://doi.org/10.1016/j. 2488–2496, https://doi.org/10.1021/ie061571o.
cemconres.2005.06.002. [62] J. Chen, J. Thomas, H. Jennings, Decalcification shrinkage of cement paste,
[42] European Committee for Standardization (CEN), EN 1015-3, Methods of Test for Cement Concr. Res. 36 (2006) 801–809, https://doi.org/10.1016/j.
Mortar for Masonry; Part 3: Determination of Consistence of Fresh Mortar, CEN, cemconres.2005.11.003.
Brussels, 1999 (by flow table). [63] S. Pham, Effects of carbonation on the microporosity and macro properties of
[43] European Committee for Standardization (CEN), EN 1015-2, Methods of Test for Portland cement mortar CEM-I, J. Mater. Sci. Chem. Eng. 2 (2014) 40–52, https://
Mortar for Masonry; Part 2: Bulk Sampling of Mortars and Preparation of Test doi.org/10.4236/msce.2014.27005.
Mortars, CEN, Brussels, 1998. [64] V. Morales-Florez, N. Findling, F. Brunet, Changes on the nanostructure of
[44] European Committee for Standardization (CEN), EN 1015-11, Methods of Test for cementitious calcium silicate hydrates (C-S-H) induced by aqueous carbonation,
Mortar for Masonry; Part 11: Determination of Flexural and Compressive Strength J. Mater. Sci. 47 (2012) 764–771, https://doi.org/10.1007/s10853-011-5852-6.
of Hardened Mortar, CEN, Brussels, 1999. [65] H. Jennings, J. Thomas, D. Rothstein, J. Chen, Cements as porous materials, in:
[45] European Committee for Standardization (CEN), EN 1097-3, Tests for Mechanical F. Schüth, K.S. Sing, J. Weitkamp (Eds.), Handbook of Porous Solids, WILEY-VCH
and Physical Properties of Aggregates; Part 3: Determination of Loose Bulk Density Verlag GmbH, Weinheim, 2002, pp. 2971–3028.
and Voids, CEN, Brussels, 1998. [66] H. Jennings, J. Bullard, J. Thomas, J. Andrade, J. Chen, G. Scherer,
[46] European Committee for Standardization (CEN), EN 1097-6, Tests for Mechanical Characterization and modelling of pores and surfaces in cement paste: correlations
and Physical Properties of Aggregates; Part 6: Determination of Particle Density to processing and properties, J. Adv. Concr. Technol. 6 (2008) 5–29, https://doi.
and Water Absorption, CEN, Brussels, 2013. org/10.3151/jact.6.5.
[47] S. Go~ni, M. Frias, I. Vegas, R. García, R. Vigil de la Villa, Quantitative correlations [67] H. Jennings, Model for the microstructure of calcium silicate hydrate in cement
among textural characteristics of C\S\H gel and mechanical properties: case of paste, Cement Concr. Res. 30 (2000) 101–116, https://doi.org/10.1016/S0008-
ternary Portland cements containing activated paper sludge and fly ash, Cement 8846(99)00209-4.
Concr. Compos. 34 (2012) 911–916, https://doi.org/10.1016/j. [68] R. Oliveira, J. de Brito, M.R. Veiga, Reduction of the cement content in rendering
cemconcomp.2012.05.002. mortars with fine glass aggregates, J. Clean. Prod. 95 (2015) 75–88, https://doi.
[48] European Committee for Standardization (CEN), EN 14146, Natural Stone Test org/10.1016/j.jclepro.2015.02.049.
Methods; Determination of the Dynamic Modulus of Elasticity (By Measuring the [69] C. Farinha, J. de Brito, M.R. Veiga, Assessment of glass fibre reinforced polymer
Fundamental Resonance Frequency), CEN, Brussels, 2004. waste reuse as filler in mortars, J. Clean. Prod. 210 (2019) 1579–1594, https://doi.
[49] European Committee for Standardization (CEN), EN 1015-18, Methods of Test for org/10.1016/j.jclepro.2018.11.080.
Mortar for Masonry; Part 18: Determination of Water Absorption Coefficient Due to [70] D. Bentz, A. Ardani, T. Barrett, S. Jones, D. Lootens, M. Peltz, T. Sato, P. Stutzman,
Capillary Action of Hardened Mortar, CEN, Brussels, 2002. J. Tanesi, W. Weiss, Multi-scale investigation of the performance of limestone in
[50] Instituto Centrale per il restauro, CNR - Centri di studio di Milano e Roma sulle concrete, Construct. Build. Mater. 75 (2015) 1–10, https://doi.org/10.1016/j.
cause di deperimento e sui metodi di conservazione delle opere d’arte & ICR conbuildmat.2014.10.042.
Istituto Centrale del Restauro (CNR-ICR), Normal 11-85, Assorbimento d’acqua per [71] V. Smilauer, Z. Bittnar, Microstructure based micromechanical prediction of elastic
capillarit�
a: Coefficiente di assorbimento capillare, CNR-ICR, Rome, 1985. properties in hydrating cement paste, Cement Concr. Res. 36 (2006) 1708–1718,
[51] N. Karagiannis, M. Karoglou, A. Bakolas, A. Moropoulou, Building materials https://doi.org/10.1016/j.cemconres.2006.05.014.
capillary rise coefficient: concepts, determination and parameters involved, in: [72] J.D. Mertz, Porosity Structures and Transport Properties in Sandstone. PhD Thesis,
J. Delgado (Ed.), New Approaches to Building Pathology and Durability, Building Universit�e Louis Pasteur de Strasbourg, Institut de G�eologie, 1991 (in French).
Pathology and Rehabilitation, vol. 6, Springer, Singapore, 2016, pp. 27–44. [73] M. Karoglou, A. Moropoulou, Z.B. Maroulis, M.K. Krokida, Drying kinetics of some
[52] European Committee for Standardization (CEN), EN 16322, Conservation of building materials, Dry. Technol. 23 (2005) 305–315, https://doi.org/10.1081/
Cultural Heritage; Test Methods: Determination of Drying Properties, CEN, DRT-200047926.
Brussels, 2013. [74] C. Hall, W. Hoff, Water Transport in Brick, Stone and Concrete, first ed., CRC Press,
[53] R.M. Espinosa, L. Frank, Influence of the age and drying process on pore structure London, 2004.
and sorption isotherms of hardened cement paste, Cement Concr. Res. 36 (2006) [75] A. Isebaert, W. De Boever, F. Descamps, J. Dils, M. Dumon, G. De Schutter, E. Van
1969–1984, https://doi.org/10.1016/j.cemconres.2006.06.010. Ranst, V. Cnudde, L. Van Parys, Pore-related properties of natural hydraulic lime
[54] E. Berodier, K. Scrivener, Evolution of pore structure in blended systems, Cement mortars: an experimental study, Mater. Struct. 49 (2015) 2767–2780, https://doi.
Concr. Res. 73 (2015) 25–35, https://doi.org/10.1016/j.cemconres.2015.02.025. org/10.1617/s11527-015-0684-5.
[55] K. Scrivener, A. Bentur, P. Pratt, Quantitative characterization of the transition
zone in high strength concretes, Adv. Cement Res. 1 (1988) 230–238, https://doi.
org/10.1680/adcr.1988.1.4.230.

11