Construction and Building Materials

Characterization of the historical mortars concerning ancient monuments-Experimental

approach
--Manuscript Draft--

Manuscript Number: CONBUILDMAT-D-22-02274

Article Type: Research Paper

Keywords: Mortar; monuments; characterization of the materials

Corresponding Author: ΠΑΝΑΓΙΩΤΗΣ ΚΑΚΑΒΑΣ

University of Peloponnese
GREECE

First Author: Panayiotis kakavas

Order of Authors: Panayiotis kakavas

S. A. Lycourghiotis

N. A. Kalapodis

Abstract: The scope of this paper is the investigation of the physicochemical characterization of
historical mortar of the masonry of a 19 th century Byzantine Temple using various
experimental methods e.g. SEM, SEM-EDS, XRD, FT-IR(ATR), TGA, nitrogen
adsorption – desorption isotherms, microelectrophoresis and determination of
equilibrium pH of water suspensions of the mortar samples. The church located in the
area of “Ilia”, near to the ancient Olympia, Peloponnese, Greece, presents important
cultural and architectural ineptest and it has been designated as a monument by the
Greek authorities. This has been severely damaged and needs to be restored. An
essential perquisite is the evaluation of the composition, quality and degree of
disintegration of the masonry mortar. It was found that the mortar mixture is mainly
composed from quartz (mean crystal size 46 nm) and amorphous alumina included in
sand used upon the construction and calcite (mean crystal size 43 nm) resulted from
the reaction of atmospheric CO 2 with Ca(OH) 2 also had used in the construction of
the masonry. Very small amount of Na 2 O, K 2 O, MgO and Fe 2 O are also
present. The mortar presents morphology of overlapping tiles allowing the
development of mesoporous between these tiles centered at about 25nm. The porous
texture of the mortar facilitates rising the soil moisture from the bottom to the top of the
masonry which cause, through dilution, the decrease of the amount of calcite along this
direction and thus disintegration of the mortar, mainly in relatively low heights from the
ground. In contrast, the relatively low surface electrical charge developed in the very
weak “mortar – adsorbed water liquid interface” and the slight surface acidity of the
mortar do not practically allow its corrosion by the SO 2 and NO atmospheric pollutant
gases. The above results could be useful upon the monument restoration. Designing
repair mortars for monuments and historical buildings one must ensure the
compatibility with the old material. The compatibility depends on many parameters
such as: colour, texture, porosity, composition, size and type of aggregates as well as
the mechanical characteristics.

Suggested Reviewers: antonia moropoulou

amoropul@central.ntua.gr

Q Shen
qshen@sdu.edu.cn

S Thaomola
suky_2547@yahoo.com

T Schmid
thomas.schmid@bam.de

m jordan
manuel.jordan@umh.es

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Cover Letter

Dear Editor,

I will be highly obliged if you consider our submitted article entitled “Characterization of the
historical mortars concerning ancient monuments-Experimental approach’’ for review in
your respectful scientific periodical “Construction and Building Materials”

With respect

P Kakavas-Papaniaros, Professor
Manuscript (For revision, remove the original version and upload Click here to view linked References
clean version of revised paper)

1
Characterization of the historical mortars concerning ancient
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3
monuments-Experimental approach
4
5 S. A. Lycourghiotis1,2, N. A. Kalapodis1, P. A. Kakavas-Papaniaros1*
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7 1
Department of Civil Engineering, University of the Peloponnese, 1 M. Alexandrou, 26334
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9
Koukouli, Patras, Greece
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2
11 School of Science and Technology, Hellenic Open University, 18 Par. Aristoteles Str, Patras, GR
12 26335, Greece
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14 *Corresponding author Email: kakavas@uop.gr
15
16
17
18 Abstract
19
20
21 The scope of this paper is the investigation of the physicochemical characterization of
22 historical mortar of the masonry of a 19th century Byzantine Temple using various
23 experimental methods e.g. SEM, SEM-EDS, XRD, FT-IR(ATR), TGA, nitrogen adsorption –
24
25 desorption isotherms, microelectrophoresis and determination of equilibrium pH of water
26 suspensions of the mortar samples. The church located in the area of “Ilia”, near to the ancient
27
Olympia, Peloponnese, Greece, presents important cultural and architectural ineptest and it
28
29 has been designated as a monument by the Greek authorities. This has been severely
30 damaged and needs to be restored. An essential perquisite is the evaluation of the
31
32 composition, quality and degree of disintegration of the masonry mortar. It was found that
33 the mortar mixture is mainly composed from quartz (mean crystal size 46 nm) and amorphous
34 alumina included in sand used upon the construction and calcite (mean crystal size 43 nm)
35
36 resulted from the reaction of atmospheric CO2 with Ca(OH)2 also had used in the construction
37 of the masonry. Very small amount of Na2O, K2O, MgO and Fe2O are also present. The mortar
38 presents morphology of overlapping tiles allowing the development of mesoporous between
39
40 these tiles centered at about 25nm. The porous texture of the mortar facilitates rising the soil
41 moisture from the bottom to the top of the masonry which cause, through dilution, the
42
decrease of the amount of calcite along this direction and thus disintegration of the mortar,
43
44 mainly in relatively low heights from the ground. In contrast, the relatively low surface
45 electrical charge developed in the very weak “mortar – adsorbed water liquid interface” and
46
47 the slight surface acidity of the mortar do not practically allow its corrosion by the SO2 and NO
48 atmospheric pollutant gases. The above results could be useful upon the monument
49 restoration. Designing repair mortars for monuments and historical buildings one must
50
51 ensure the compatibility with the old material. The compatibility depends on many
52 parameters such as: colour, texture, porosity, composition, size and type of aggregates as well
53 as the mechanical characteristics.
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55
56 Keywords: mortar, monuments, characterization of the materials
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 1. Introduction
1
2 The study of mortars of historical monuments has developed significantly in recent
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decades [1-21]. The use of advanced techniques of physical and chemical characterization has
5 provided very useful tools to conservationists and engineers involved in the restoration and
6 preservation of cultural heritage. Specifically, characterization techniques have been used in
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8 prehistoric monuments [3], monuments of the Roman period [4], as well as in the monuments
9 of medieval and Byzantine times [8, 9]. Assessing the dangers of monuments due to natural
10 or biological erosion is an important aspect of modern research in this domain [9]. It is, in
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12 effect, important the contribution of these studies to the reconstruction of historic mortars in
13 order to restore monuments respecting old materials and construction conditions.
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15 Ιn the present work we are studying a Byzantine church located in the area of “Ilia”, in the
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17 village of Schini, near to the ancient Olympia, Peloponnese, Greece. The church is called
18 “Aghios Ioannis-Saint John” and has been designated as a monument by the Greek authorities.
19 The architectural style of the church belongs to the Byzantine “basilica rhythm”. It began to
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21 be built in 1850 and was completed between 1894-1896. Due to the intense seismic activity
22 of the wider area, the monument has suffered serious damage and needs restoration. Its
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masonry has suffered many penetrating cracks. It is probable that the significant damage of
25 the building is to some extent due to the earthquakes of 1965 [27]. Then the building has been
26 roughly repaired. Following the earthquake that year, most of the houses in the village of
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28 Schini were demolished. As can be seen from the field observation, the damages seem to have
29 worsened due to the differential subsidence of the soil under the foundations of the
30 monument as well as due to the erosion and disintegration of the mortars. Finally, due to the
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32 earthquake on 15-2-2016, which had its epicenter near the monument, the building was
33 considered dangerous by the Greek authorities and the church ceased to operate. Figure 1
34 illustrates the location of the temple as well as various characteristic damages that we find
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36 today.
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57 Figure 1. Location map and characteristic fracture positions of the masonry
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 Today an effort is taking place by the scientific community and the local authorities for the
1 restoration of the temple. In the context of this effort, it is very important to study the
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3 traditional mortars used upon the construction of the temple and also the erosion that they
4 present mainly due to humidity. In the presence of work, we carry out a detailed physical and
5 chemical characterization of traditional mortars. This is indeed very useful allowing the
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7 utilization of compatible materials upon the future restoration. The corrosive effect of
8 moisture on the disintegration of the mortar is also studied.
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10 2. Experimental
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13 2.1. Sampling
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15 Three samples of historical mortar were taken from different heights of the outer wall
16 of the Byzantine church monument (sample 1 from 0.77 m, sample 2 from 2.11 m and sample
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18 3 from 3.94 m, (Figure 2). The different heights of sampling allow monitoring the eventual
19 effect of emerging moisture.
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41 Figure 2. Sampling positions in the front outer wall of the Byzantine church monument
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under investigation
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45 2.2. Characterization of the samples.
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47 The morphology of the samples was studied by scanning electron microscopy (SEM)
48 images and its chemical composition by scanning electron microscopy-energy –dispersive X-
49
50 ray spectroscopy (SEM-EDS). A Scanning Electron Microscope (SEMJEOL JSM6300) equipped
51 with an Energy Dispersive Spectrometry accessory has been used. Microanalysis was
52 performed on gold coated samples.
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55 The crystal phases in the samples were investigated by X- ray powder diffraction (XRD) and
56 Fourier transform infrared attenuated total reflectance spectroscopy ATR-FTIR. The XRD
57 patterns were recorded in the range of 10° ≤ 2θ ≤ 70o. A Bruker D8 Advance diffractometer
58
59 was used. This is equipped with nickel - filtered CuKα (0.15418nm) radiation source. The mean
60 crystallite size was estimated using Scherrer’s equation.
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 The Scherrer equation, in X-ray diffraction and crystallography, is a formula that relates the
1 size of sub-micrometre crystallites in a solid to the broadening of a peak in a diffraction
2
3 pattern. It is often referred to, incorrectly, as a formula for particle size measurement or
4 analysis. It is named after Paul Scherrer and It is used in the determination of size of crystals
5 in the form of powder [39]. The Scherrer equation can be written as:
6
7 𝑘𝜆
8 τ=
𝛽𝑐𝑜𝑠𝜃
9
10
11
where:
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13 τ is the mean size of the ordered (crystalline) domains, which may be smaller or equal to the
14 grain size, which may be smaller or equal to the particle size;
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16 𝑘 is a dimensionless shape factor, with a value close to unity. The shape factor has a typical
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18 value of about 0.9, but varies with the actual shape of the crystallite;
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20 𝜆 is the X-ray wavelength;
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22 𝛽 is the line broadening at half the maximum intensity (FWHM), after subtracting the
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24 instrumental line broadening, in radians. This quantity is also sometimes denoted as 𝛥 = (2𝜃)
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26 𝜃 is the Bragg angle.
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28 The ATR-FTIR spectra were recorded in the range 800-4000cm-1 by a FTIR Perkin-Elmer
29
Spectrum 100 spectrophotometer equipped with a multi-reflection horizontal ZnSe ATR
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31 accessory (Specac's Gateway ATR Accessory Kit).
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33 Thermogravimetric analysis (TGA) of the solids was performed using a Diamond TGA/DTA
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Perkin Elmer instrument.
35
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37 The texture of the samples [specific pore volumes, mean pore diameters and specific surface
38 areas in the pore range 1.7- 100nm (BJH parameters) as well as the total -BET specific surface
39 areas and the specific surface areas in the range of micropores, (below 1.7nm)] was
40
41 determined by nitrogen adsorption - desorption isotherms using a Micromeritics apparatus
42 (Tristar 3000 porosimeter).
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44 The surface charge of the samples at various pH values was estimated by determining the
45
46 corresponding values of j-potential determined by micro electrophoretic measurements at 25
47 °C using a Zetasizer NanoZS, Malvern. Very dilute solid/electrolyte suspensions (10 mg/100
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mL) were prepared with constant ionic strength,0.01M NaNO3. The pH of the suspensions was
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50 adjusted by small additions of a 1M HNO3 solution.
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52 The surface acidity-basicity of the solids was estimated by determining the equilibrium pH of
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sample/water suspensions. 0.02 g of the solid sample was dispersed in 2 mL of distilled water
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55 under stirring. After 10 min without stirring the liquid was separated from the solid and the
56 pH of the liquid was measured using a pH-meter (Radiometer Copenhagen ABU901
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Autoburette) equipped with a combination pH electrode. More details concerning the
59 characterization methods have been reported elsewhere (28- 30).
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 3. Results and Discussion
1
2 3.1. Morphology and chemical composition
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4 Τhe images of the three samples studied in different magnifications at micrometric
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6 and near nanometric scale are illustrated in Figure 3
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37 Figure 3. SEM images of the samples studied taken at three different magnifications increasing
38 from the top to the bottom.
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40 It is seen that the mortars studied have the form of overlapping tiles, irrespectively of the
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42 magnification. This form, but also the spherical form, is characteristic of many mortars with
43 significant presence of calcite (CaCO3). This morphology is generally vulnerable to corrosion
44 due to the relatively high porosity it creates being permeable to significant amounts of water
45
46 – moisture.
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48 The chemical composition of the mortar samples was determined by SEM-EDS in
49 microphotographs with x250 magnification. Figure 4 illustrates typical SEM-EDS spectra for
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51 the samples studied. The chemical composition is illustrated in Table 1. The chemical analysis
52 was performed in six different regions for each sample and showed uniform composition.
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 cps/eV
1.00 * Acquisition 14779
1
5
2
4 K O Mg
3 Fe Na Al Si Au K Ca Fe Au
4 3 Ca

5 2

6 1
7 0
8 2 4 6 8 10 12 14
keV
9
10
11 Sample #1
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13 cps/eV
14 4.5 1.00 * Acquisition 14780
4.0
15 3.5
16 3.0 K O Mg
17 2.5 Ca
Fe Na Al Si Au K Ca Fe Au

18 2.0
1.5
19 1.0
20 0.5
21 0.0
22 2 4 6 8 10 12 14
keV
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25 Sample #2
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27
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29 cps/eV
1.00 * Acquisition 14783
30 5
31 4 K O Mg
32 Fe Na Al Si Au K Ca Fe Au
3 Ca
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2
34
35 1

36 0
2 4 6 8 10 12 14
37 keV
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40 Sample #3
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45 Figure 4. SEM-EDS spectra of the samples studied in different heights upon the mansory of
46 the monument
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48 Table 1. Percentage atomic composition (%) of the samples determined by SEM-EDS
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50
51 Si Al Na K Mg Ca Fe O
Sample
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53 1 13.37 5.64 0.39 2.83 0.49 10.5 0.91 64.6
54
55 2 10.66 1.52 1.22 0.38 0.89 9.75 0.57 73.2
56 3 4.75 2.30 0.73 0.54 0.96 16.61 0.83 72.1
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 Elemental analysis shows the presence of significant amounts of Si, Al and Ca indicating the
1 presence of significant amounts of the corresponding solid phases in the mortar mixture.
2
3 Smaller amounts of Na, K, and Fe are also detected. It seems that the atomic composition is
4 different in these samples indicating the effect of moisture. We shall return to this point after
5 the identification of the crystal solid phases present in the mortar mixture.
6
7
8 3.2. Identification of solid phases.
9
10 Figure 5 shows the XRD patterns of the samples studied. The large number of sharp
11 peaks indicates that the mortar mixture is largely crystalline. We also notice that the position
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13 of the peaks does not change practically due to the positions of the sample on the wall of the
14 monument suggesting that emerging moisture from the ground did not affect the crystal
15 structure of the mortar.
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42 Figure 5. XRD patterns of the samples studied.
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44 The XRD patterns reveal the presence of two crystal phases in the mortar mixture, namely
45 calcite [CaCO3, peak positions at 2θ equal to 23.1 (1 0 2), 29.4 (0 0 6), 36.0 (1 1 0), 39.4 (1 1
46
47 3), 43.2 (2 0 2), 47.6 (1 0 8) and 48.40 (1 1 6), COD 9016706] and quartz [SiO2, two main peak
48 positions at 2θ equal to 20.9 (1 0 0) and 26.70 (1 0 1), COD 1011176]. The above results show
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50
that the Ca(OH)2 had used for constructing the masonry of the monument has been gradually
51 transformed into calcite via penetration of the atmospheric CO2 through the porous texture
52 of the mortar (see below) and reaction with Ca(OH)2. In fact, it is known that when the
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54 masonry has been laid, the slaked lime in the mortar slowly begins to react with carbon
55 dioxide to form calcium carbonate (limestone) according to the reaction: Ca(OH)2 + CO2 →
56 CaCO3 + H2O [31]. The application of Scherrer’s equation on the peak at 2θ equal to 29.40
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58 and 26.70 allowed determining the mean crystal values for calcite and quartz at 43 and 46
59 nm, respectively.
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 The ATR-FTIR spectra of the samples studied are illustrated in Figure 6. According to the
1 literature the absorption bands at 1410/1460 and 874 cm-1 may be assigned to calcite [32,33]
2
3 and the absorption bands at 2930 and 2850 and 1160 cm-1 to the silicon phase [34]. Thus, the
4 ATR-FTIR spectra are in line to the XRD results. The TGA curves of the samples studied are also
5 compatible to the main solid phases deduced by XRD. In fact, the TGA curves (Fig. 7) show
6
7 that the samples maintain their weight percentage intact up to 100 ° C followed by a slight
8 drop (2.5-4%). This is obviously due to the evaporation of very small amounts of water that is
9
trapped in the pores of the mortar (see below). Significant loss of weight is observed in the
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11 temperature range 650 - 800° C effortlessly attributed to the decomposition of CaCO3 to CaO
12 [ CaCO3 (s) → CaO (s) + CO2 (g)] [35]. It is well known that the quartz is quite stable in the
13
14 temperature range studied [36].
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36 Figure 6. ATR-FTIR spectra of the samples studied.
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 Figure 7. TGA curves of the samples studied.
1
2 Taking into account the absence of additional peaks on the XRD patterns (besides those of
3
4
calcite and quartz), confirmed by ATR-FTIR spectra, as well as the elemental analysis (Table 1)
5 we are assuming the presence of amorphous alumina (Al2O3) and small amounts of
6 amorphous Na2O, K2O and Fe2O2 in the mortar mixture, in addition to calcite and quartz sand.
7
8 This allows us to transform the percentage atomic composition (Table 1) to the corresponding
9 weight composition of the solid phases present in the samples. This is illustrated in Table2. It
10 is noticeable that the calculated weight composition is fully compatible with the oxygen values
11
12 illustrated in Table 1. Inspection of Table 2 shows that the mortal is mainly composed from
13 quartz and amorphous alumina included in sand used upon the construction and calcite
14
resulted from the reaction of atmospheric CO2 with CaO/Ca(OH)2 also used in the construction
15
16 of the masonry. The remaining oxides in smaller quantities are also contained in the quartz
17 sand used upon the construction of the masonry.
18
19 Table 2. Percentage weight composition (wt %) of the solid phases determined for the
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21 samples studied using the elemental atomic composition values compiled in Table 1
22
23 SiO2 Al2O3 Na2O K2O MgO CaCO3 Fe2O3
24 Sample
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26 1 33.8 12.1 0.5 5.6 0.8 44.2 3.1
27 2 35.0 4.2 2.1 1.0 1.9 53.3 2.5
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29 3 12.9 5.3 1.0 1.1 1.7 75.0 3.0
30
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32 It is moreover seen that the weight composition of the mortar somewhat depends on the
33
34
height from the ground where the mortar sample has been taken. This is more pronouncing
35 concerning calcite. We are observing a considerable decrease in the amount of calcite going
36 from the high to low value of the height from the ground (sampling point 3 to 1, Figure 2). This
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38 is bringing about changes in the whole composition. We attribute this decrease in the
39 progressive removal of calcite from the mortar through its dilution in the soil moisture rising
40 slowly from the bottom to the top of the masonry. This process is causing a progressive
41
42 disintegration of the masonry mainly near to the bottom of the masonry and should be taken
43 into account when restoring the monument. Suspecting that climbing moisture is related to
44
the texture of the mortar it seemed to us useful studying the texture of the mortar samples.
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46
47 3.3. Investigation of the texture of the mortar samples
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49 The texture of the mortar samples was estimated by determining the nitrogen
50 adsorption-desorption isotherms (Fig. 8a). The isotherms belong to type IV indicating
51
52 mesoporous material with most pores ranged between 1.7 and 100nm [31]. This is confirmed
53 by the pore volume distribution curves determined by elaborating the desorption isotherms
54 (Fig. 8b). Moreover, the hysteresis loop of type H3 indicates the presence of aggregates of
55
56 plate like particles forming pores between them [31]. This is in full agreement to the
57 morphology deduced by the SEM images (Fig. 3).
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34 Figure 8. (a) Nitrogen adsorption -desorption isotherms and (b) pore volume distribution
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36 curves of the samples studied.
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38 Moreover, the elaboration of the desorption curves allowed determining critical parameters
39 concerning texture. These are compiled in Table 3. Inspection of this table shows that the
40
41 mortar mixtures exhibit a mesoporous texture with mean meso pore diameters around 25nm
42 and a rather low specific pore volume near to 0.1 cm3/g. These mesopores are inserted
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between the overlapping tiles. This is more clearly visualized by further magnification of the
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45 SEM image concerning sample 2, taken as an example. The size of these mesopores is much
46 higher than that of the water molecules (about 0.27nm) allowing moisture and gases to
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48 penetrate the mortar mixture.
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50 Table 3. Textural parameters of the sample studied.
51 Specific Specific pore
52 Total specific surface of Specific surface of volume of Mean meso
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54 surface area mesopores micropores mesopores pore diameter
55 Sample ΒΕΤ (m2/g) BJH (m2/g) (<1.7nm ) (m2/g) BJH (cm3/g) BJH (nm)
56 1 23.3 21.3 1.9 0.13 25.8
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58 2 17.8 16.7 1.1 0.12 22.8
59 3 15.9 15.6 0.2 0.12 26.6
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 Due to their mesoporous texture, the surface area of the samples is largely developed inside
1 the mesopores as it is inferred by the very similar values obtained for the BET and the
2
3 corresponding BJH specific surface areas as well as from the very low values determined for
4 the micropores. It is well known that the silica even in the form of quartz is more porous than
5 calcite. Therefore, the porous texture and thus the specific surface area of the mortar studied
6
7 is mainly due to quartz. Thus, the decrease in the amount of the calcite in the mortal mixture
8 (deduced by SEM –EDS and XRD) due to its dilution in the soil moisture rising to the top of the
9
masonry, is expected to lead to the increase in both mesoporous and microporous specific
10
11 surface. This is indeed the case as it can be seen by inspecting Table 1. The above indicate that
12 the porous texture of the mortar mixture is closely related to the progressive disintegration
13
14 mainly near to the bottom of the masonry.
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16 3.4. Surface charge and surface acidity - basicity of the samples studied
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18 A less important reason, but not a priori negligible, for the mortar disintegration would be its
19 uptake of pollutant gases such as SO3 and NO2 These could be adsorbed and then transformed
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21 into SO4 2- and NO3- inside the “mortar – adsorbed water liquid interface”. The later could in
22 turn attack the mortar resulting to the formation of sulfur or nitrogen salts such as CaSO4 or
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24
Ca (NO3)2. The absence of these solid phases in the XRD patterns as well as the absence of
25 sulfur or nitrogen in the SEM-EDS spectra of the samples studied shows that these processes
26 are negligible, if any, in our case. In order to rationalize the durability of the mortar against
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28 this type of corrosion we are studying the characteristics of the aforementioned interface by
29 determining the interface ζ-potential at various pH values as well as by determining the
30 equilibrium pH of the mortar samples/water suspensions as a measure of their surface acidity-
31
32 basicity.
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34 Inspection of Figure 9 shows that the ζ- potential determined at various pH values is ranged
35 between +15 and -17mV. These limiting values are considered to be very low indicating very
36
37 low surface charge of the mortar mixture and the formation of a very weak “mortar –
38 adsorbed water liquid interface”. This behavior is usual for SiO2 [38], the component which
39 mainly contribute to the development of the high surface of the mortar. The low negative ζ-
40
41 potential and thus the low negative surface charge even at pH near to 7 is not sufficient to
42 actually facilitate the SO3 /NO2 (drawn from the oxidation of the SO3 /NO2) to be transformed
43
in to SO42- /NO3- by attracting the released proton ions [ SO3+H2O →SO42- +2H+, NO2 + H2O →
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45 NO3-+H+].
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 1
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21 Figure 9. ζ- potential determined at various pH values for the samples studied
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24 The same conclusion can be drawn from the values of the Equilibrium pH determined for the
25 mortar samples/water suspensions and compiled in Table 4. These values indicated that the
26 surface of the mortar mixture is acidic and thus not suitable to induce the aforementioned
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28 reactions by attracting the released proton ions.
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30 Table 4. Equilibrium pH of the mortar samples/water suspensions
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32 Sample Equilibrium pH
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34 1 5.52
35 2 5.25
36 3 4.66
37
38
39
40 4. Conclusions
41
42 The mortar mixture is mainly composed from quartz (mean crystal size 46 nm), amorphous
43
alumina and calcite (mean crystal size 43nm). The later was slowly derived upon the reaction
44
45 of atmospheric CO2 with Ca(OH)2 which had been used in the construction of the masonry.
46 Very small amounts of Na2O, K2O, MgO and Fe2O are also present in the mortar mixture. The
47
48 morphology of overlapping tiles of the mortar mixture allows the development of mesoporous
49 between the tiles with a mean size around 25nm. These porous facilitates rising the soil
50 moisture from the bottom to the top of the masonry. The moisture dilutes calcite causing the
51
52 decrease of its amount along this direction and thus the disintegration of the mortar. This is
53 more pronounced in relatively low heights from the ground. The no observation of corrosion
54 due to the SO2 and NO pollutant gases were attributed to the relatively low surface electrical
55
56 charge developed in the very weak “mortar – adsorbed water liquid interface” and the slight
57 surface acidity of the mortar.
58
59
60
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Declaration of Interest Statement Click here to view linked References

Declaration of interests

☒The authors declare that they have no known competing financial interests or personal relationships
that could have appeared to influence the work reported in this paper.

☐The authors declare the following financial interests/personal relationships which may be considered
as potential competing interests: