Construction and Building Materials 187 (2018) 708–717

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Construction and Building Materials

journal homepage: www.elsevier.com/locate/conbuildmat

Physical-chemical study, characterisation and use of image analysis to

assess the durability of earthen plasters exposed to rain water and acid
rain
Victoria E. García-Vera, Marcos Lanzón ⇑
Departamento de Arquitectura y Tecnología de la Edificación, Universidad Politécnica de Cartagena, Paseo Alfonso XIII 50, 30203 Cartagena, Spain

h i g h l i g h t s

 The binder nature has little influence on physical properties of earthen plasters.
 The curing conditions have an influence on physical properties of earthen plasters.
 Earthen-based plasters have low resistance to rain water and acid rain.
 Gypsum patina formed by sulphuric rain improve the surface resistance of plasters.
 Image analysis allows the assessment of textural alterations produced by acid rain.

a r t i c l e i n f o a b s t r a c t

Article history: This paper aims to determine the physical performance and rain resistance of earthen plasters made with
Received 24 April 2018 a red clayey binder, rich in silico-aluminates and a yellow binder which is mainly calcareous. The nature
Received in revised form 26 July 2018 of the binder had little influence on practical properties of plasters, such as density, consistency, shrink-
Accepted 28 July 2018
age, consumption, thermal conductivity and capillary water absorption. However, important properties
of the plaster as for instance, the cohesion of the surface were affected by the type of binder. In addition,
the plasters durability was evaluated by rain erosion tests conducted with distilled water and acid rain
Keywords:
simulated with hydrochloric and sulphuric acid solutions (5% w/w). It was found that earthen plasters
Earthen plasters
showed a better resistance to sulphuric acid than to hydrochloric acid. Scanning electron microscopy
Surface characterisation
Acid rain and X-ray diffraction analyses confirmed the formation of gypsum coatings on the surface of plasters
Durability attacked by sulphuric acid. In this case, the erosion was smaller due to the passivating role of gypsum,
Image analysis which protects the underneath material from dissolution. The textural alterations assessment, evaluated
by optical microscopy and image analysis software, showed that hydrochloric acid rain was the most
aggressive attack, followed by sulphuric acid rain and rain water.
Ó 2018 Elsevier Ltd. All rights reserved.

1. Introduction often found in heritage constructions, thus motivating further

Earthen materials comprise a wide variety of uses and typolo-
gies, such as adobe, rammed earth and plasters. The rising interest
in earth-based building materials can be explained by a combina-
tion of factors, among which the raw materials availability is
essential. They are abundant, cheap and eco-friendly materials as
lower energy is needed in their quarrying and manufacture com-
paring with common raw materials (e.g. limestone, granite). More-
over, earthen materials are an excellent choice to regulate
temperature and humidity at comfortable levels [1–3]. They are
⇑ Corresponding author.
E-mail address: marcos.lanzon@upct.es (M. Lanzón).
research on both preservation criteria and methods for testing
durability. In this respect, earth-based plasters present inherent
limitations, such as low mechanical strength and limited durability
against atmospheric agents [4]. In addition, during the drying stage
period, cracks may appear due to the volumetric instability of clay
[2,5]. In fact, the occurrence of cracks is a serious limitation in plas-
ters, especially when the binder/sand ratio is not properly adjusted
in the designing phase [2].
The addition of stabilisers like such cement, lime, fly ash, wastes
or coal ash has been proposed to improve a number of features in
earthen materials [3,6–8]. It is worth noting that soils are natural
materials with a heterogeneous composition, including clay, sand
and gravel. Therefore, the optimisation of standard procedures

https://doi.org/10.1016/j.conbuildmat.2018.07.235
0950-0618/Ó 2018 Elsevier Ltd. All rights reserved.
 V.E. García-Vera, M. Lanzón / Construction and Building Materials 187 (2018) 708–717
for preparing plasters, adobe or earthen-walls is more difficult than
that used for cement-based materials. For instance, the chosen soil
(binder) would meet several properties regarding mineralogical
composition, clay/sand ratio and granulometry. Usually, the binder
dosage and aggregates’ grain size must be considered for the
intended use. In plasters, for instance, the amount of binder should
be reduced as much as possible to avoid cracks formation. Simi-
larly, enough compressive strength is required for earthen-walls
or adobe bricks taking part in load-bearing or structural elements
of buildings. In this case, the dose of binder is clearly a conditioning
factor as previously reported by different authors [9,10].
Besides, the mechanical behaviour of earthen materials is influ-
enced by additional factors like manufacturing process, use of sta-
bilisers and curing conditions. Emiroglu et al. [2] evaluated the
effect of the clay/sand ratio on the performance of clay plasters
and found that the compressive strength was lower for samples
with lower clay content. Moreover, samples dried at 60 °C had
lower compressive strength than those dried at 100 °C. El-
Mahllawy and Kandeel [3] studied the characteristics of clay-
sand formulations stabilised with Portland cement and quicklime
in different proportions and humidity (85% and 50%). The best
mechanical performance was found in samples cured at 85% and
moreover, the amount of cement and curing time were critical fac-
tors too.
The low rain water resistance of earthen materials [10] is
clearly an important limitation of earthen plasters. Although speci-
fic tests for measuring the rain water erosion are scarcely
addressed, a number of methods have been proposed in the litera-
ture to extend the durability of earthen materials. For instance, the
use of zinc stearate or polymeric additives has been found to be
effective to extend the lifespan of plasters and adobes [4,11]. In
the same way, natural agents like resins (latex), animal blood, bitu-
men or oil have been proposed as effective solutions to improve a
number of properties in earth-based materials [8,12,13]. The use of
coatings, such as nanostructured emulsions, silane-siloxane emul-
sions and nanolime suspensions has been studied for strengthen-
ing and protecting the surface of earthen materials [13,14].
Finally, phosphogypsum wastes have been confirmed as excellent
admixtures for improving both the mechanical resistance and
durability of adobes [15,16].
The literature on earthen plasters is quite scarce and very few
studies report on durability of plasters, particularly as it relates
to acid rain attack. This paper is focused on three main aspects:
i) the chemical characterisation of the clayey binder, ii) factors that
influence on the physical properties of earthen plasters, and iii)
durability of earthen plasters against rain water and acid rain.
The curing conditions had a significant effect on the compressive
strength, ultrasonic speed, and Young’s modulus of plaster sam-
ples, whereas the nature of the binder had little effect on practical
properties of plasters often provided in technical data sheets. How-
ever, functional properties related to durability, such as hardness
and rain resistance were to some extent affected by the nature of
the binder. The formation of gypsum patina on the surface might
explained the additional resistance of plasters against acid rain.
Microscopy examination and image analysis software are consis-
tent with the erosion data obtained in rain tests.
2. Materials and methods
2.1. Materials and curing
In earthen materials, the binding behaviour is attributed to the clayey phase
and therefore, the terms binder or clay are used interchangeably. The specimens
were made with either red or yellow earth-based binder, two types of sands – ter-
med as sand A and sand B – and distilled water. The binder was a sieved soil fraction
(<0.5 mm) used for the manufacture of industrial bricks. The sands, provided by
Reverté Minerals (Spain), were eminently calcitic and classified according to the
709
EN 933-1 standard [17]. A previous study was carried out for determining the opti-
mal dosage of binder to avoid shrinkage to occur as much as possible. The optimal
composition for the dry mixture consisted of: clay 10% w/w; sand A 30% w/w; and
sand B 60% w/w. To obtain adequate workability water was added in a ratio of 16%
w/w on the amount of the dry mixture.
Several formats of specimens were confectioned depending on the intended use
of the samples. For the mechanical characterisation 4x4x16 cm specimens were
prepared in normalised moulds. The specimens were left in the moulds under lab-
oratory conditions (24 ± 2 °C) for 7 days so that the initial hardening might be
achieved. After that, they were de-moulded and heated at 60 °C for 24 h, thus com-
pleting the hardening process, which basically consists in densification due to water
evaporation. As is the usual practice in plasters, a second set of samples was pre-
pared spreading the fresh paste on 12  24 cm ceramic surfaces using uniform
thickness of 10 ± 1 mm (Fig. 1a–b). Equally, the plaster samples were stored under
laboratory conditions and heated at 60 °C for 24 h.
2.2. Methods
2.2.1. XRD, XRF and TG-MS characterisation
The mineral phases present in the binders were analysed by X-ray diffraction
(XRD) using a Bruker D8 Advance diffractometer in h- h mode. The spectra were reg-
istered from 10 to 70° at 0.05° stepping intervals and the X-ray tube was operated
at 40 kV and 30 mA using the Cu K-alpha line as source of radiation. The diffraction
patterns were evaluated with DIFFRAC.EVA 4.0 software and powder diffraction
database PDF4+ (ICCDD, 2015). In addition, the chemical composition of the binders
was studied by X-ray fluorescence (XRF) with a Bruker S4 Pioneer fluorescence
spectrometer. Finally, thermogravimetric analysis coupled to a QMS 200M3 quad-
rupole mass spectrometer detector (TG-MS) was used for determining volatile com-
ponents like H2O and CO 2. The measurements were performed with a TGA/DSC 1HT
Mettler-Toledo thermogravimetric analyser.
2.2.2. General properties: density, consistency, shrinkage, consumption and thermal
conductivity
The apparent density of the samples was calculated from cured prismatic spec-
imens dividing their mass by the corresponding volume. Flow table measurements
were used to determine the workability of the fresh plasters following the stan-
dardised method for determining mortars consistency [18]. Furthermore, the plas-
ters’ shrinkage was determined from prismatic specimens once the curing period
was completed (n = 3). To do this, the prisms were measured with a calliper along
their axes (±0.01 mm resolution) and the data were expressed as percentage varia-
tion with respect to the initial length of the specimen. Another practical feature of
renders is the actual surface which is coated by the fresh paste, a parameter also
referred to as consumption. To investigate this, the samples were spread on 12 
24 cm ceramic surfaces at uniform thickness as shown in Fig. 1a–c. The thermal
conductivity was analysed using a thermal conductivity analyser C-Therm TCi
equipped with a MTPS sensor accessory.
2.2.3. Ultrasonic propagation speed, Young’s modulus and compressive strength
Ultrasonic propagation speed, Young’s modulus and compressive strength were
conducted for different curing conditions with the aim of studying the influence of
the environment on the materials’ physical properties. In this case, the specimens
were cured for 28 days at: i) 20 °C/30% RH; ii) 20 °C/60% RH; and iii) 20 °C/95% RH.
Ultrasonic speed measurements provide information about the material stiff-
ness i.e., Young’s modulus. The ultrasonic pulse tests were performed following
the UNE-EN 12504-4 standard [19] and three determinations were made per sam-
ple. This test consists in measuring the time, in ms, necessary for the ultrasonic
waves to cross the sample. Contact transducers emitting ultrasonic pulses at 54
kHz were coupled to the lateral sides of the specimens using a coupling agent to
increase the reproducibility of the measurements. The wave speed was obtained
from the size of the specimen and the propagation time. The Young’s modulus
was calculated from the theoretical equation:
E ¼ 10
6
 v2  q ð1Þ
where,
E is the Young’s modulus, in N/mm2.
v is the propagation speed of ultrasonic waves through the material, in m/s.
q is the density of the sample, in kg/m3.
The compressive strength tests were performed on 4x4x16 cm specimens
according to the UNE-EN 196-1 standard [20] at a rate of 1 kg/s using a universal
testing machine. Since earthen materials typically have low mechanical resistance,
a 2 kN load-cell capacity was installed in the testing machine to increase the accu-
racy of the measurements.
2.2.4. Surface properties: peeling test, hardness and capillary water absorption
The peeling test [21,22] was used to assess the cohesion and consolidation char-
acteristics of both red and yellow plasters. For this purpose, equivalent formulations
were spread on clean ceramic substrates as shown in Fig. 1a–d. Three specimens
were confectioned per type of plaster (red or yellow) and three test zones were
defined on the plasters’ surface. Adhesive tapes of 20 x 50 mm were previously
710 V.E. García-Vera, M. Lanzón / Construction and Building Materials 187 (2018) 708–717
Fig. 1. a–b), (10 ± 1 mm); c) cured plasters showing the absence of shrinkage or cracks; d) example of peeling test and small fraction of material adhered to adhesive tapes; e)
device use to simulate water rain and acid rain resistance.
weighed with a resolution of 0.0001 g to perform the peeling test in the selected
zones. The tape was pressed on the plaster and carefully removed for calculating
the adhered material from the mass difference between initial and final weight of
the tape. The process was repeated 10 times per zone of plaster. The average
amount of material adhered to the tape and the standard deviation for 90 tests
(10 data  9 zones) was calculated for both red and yellow plasters. Hardness
was tested at the surface of the specimens using a Shore-A durometer BaxloÒ with
a measuring range from 0 to 100 shore units (resolution ± 1). The tests were carried
out with a truncated cone indenter using a reference material for calibration (60
Shore-A units). The measurements were repeated 10 times per sample.
In the capillary water absorption tests, the specimens rapidly collapse and
hence, a modified method was conducted to assess this feature. Thus, instead of
immersing the specimens in water, they were placed on a wet towel and their mass
variation was measured over time (Fig. 2). The minimal contact between sample
and water allowed measuring the samples’ weight variation with a negligible dam-
age of the specimen. The capillary water absorption was evaluated from the slopes
of water absorption (kg/m 2) vs. time (min0.5) plots using linear regression analysis
[23].
2.2.5. Rain tests: erosion and textural variations
The performance of earthen materials against rain and acid-rain solutions was
investigated for the studied plasters:
 Rain water. The material alteration was simulated by dripping distilled water on
the surface of plasters from a container at constant height for 10 min ( Fig. 1e).
 Acid-rain. Similarly, the specimens were dripped with either sulphuric acid
solutions (H2SO 4, 5% w/w) or hydrochloric acid solutions (HCl, 5% w/w).
After 10 min of dripping, the plasters were dried at 60 °C until a constant mass
was achieved. After this, two tests were investigated for evaluating the alteration
caused by rain. In the gravimetric tests, the plaster’s surface was gently brushed
to eliminate rests of powdered material weakly adhered to the surface. The samples
were weighed before the rain attack, then subjected to the test and after that
weighed again. The average erosion was expressed as a percentage of the weight
loss. The tests were repeated four times per plaster and type of rain simulation
(water, HCl and H 2SO4 solutions). An additional method was used to evaluate tex-
tural variations created on the surface of plasters exposed to rain. The rain action
produced textural alterations on the surface (pores) whose grey level values were
considerably lower than those observed in non-eroded zones. ImageJ 1.50i software
was used to carry out textural analysis of samples attacked by rain water and acid
rain. First, the images were opened in the software and converted into 8-bits grays-
cale images. The low grayscale values of the phase of interest facilitated its separa-
tion by thresholding operations (segmentation). ImageJ provides several methods of
segmentation, among which IsoData (Iterative Self Organising Data Analysis Tech-
nique) is often used. The method uses an algorithm that separates pixels below or
above a certain grayscale value. Then, the mean grayscale values of the separated
pixels are computed and the process is repeated until the variation between consec-
utive iterations is negligible. Finally, the software computes the contribution of the
phase of interest over the total surface.
2.2.6. Optical and Scanning Electron Microscopy (SEM) examination
The images of samples exposed to rain were examined by optical microscopy
using a digital microscope (Dino-Lite Edge) equipped with polariser filter and
brightness adjustable LEDs. The images were captured in high-resolution and
studied with ImageJ software for digital image analysis. To complete the
microstructural analysis, the plasters’ surface was examined by Scanning Elec-
tron Microscopy (Hitachi S-3500N). To do this, small fragments were carefully
removed from the surface and dried at 60 °C. The fragments were metallised
(30 nm coating) with Au-Pd in Argon atmosphere to increase the quality of
the images. The surface was studied in secondary electrons (SE) mode at
ultra-high vacuum using an accelerating voltage of 5 kV and the working dis-
tance was 8 mm.
 V.E. García-Vera, M. Lanzón / Construction and Building Materials 187 (2018) 708–717
Fig. 2. Modified method for measuring capillary water absorption in red and yellow
prismatic samples. Images of capillary water absorption after 10 s. (For interpre-
tation of the references to colour in this figure legend, the reader is referred to the
web version of this article.)
3. Results and discussion
3.1. Chemical-physical characterisation of raw materials: analysis of
binders by XRD, XRF and TG-MS
The plastic limit, liquid limit and plasticity index for the red
binder were, 18.9, 29.5 and 10.6 respectively, and for the yellow
binder 19.2, 33.5 and 14.3. Therefore, according to the Unified Soil
Classification System (USCS), the material has low to medium plas-
ticity [24]. The XRD analysis and mineral composition of the bin-
ders is shown in Fig. 3. The binding phase contains usual
components in raw materials used for bricks manufacturing, such
as quartz, gypsum, calcite, muscovite and kaolinite. In addition,
the colour of the binder suggests the presence of iron oxides phases
(pigments) like hematite, Fe2O 3 and goethite, FeOOH. However,
natural iron oxides are present in low concentration in the binding
phase the reason why they are not easily detected in XRD spectra.
The XRF results show the red binder is more clayey in nature, as it
is mainly composed of SiO2 and Al 2O3 and contains moderate pro-
portions of CaO, Fe2O 3, K2O and MgO (Table 1). In contrast, the yel-
low binder is more calcareous as can be seen from the percentage
of CaO and CO2. The relative proportion of silico aluminates to cal-
careous components, SiO2 + Al 2O3 /CaO, clearly shows the men-
tioned differences.
3.2. Sand particle size grading
Fig. 4 provides the granulometric features of the sands used,
termed as sand A and sand B. The maximum size of the aggregate
(D) is defined as the smallest sieve opening through which more
than 90 wt% of the material passes. In contrast, the minimum size
(d) is the largest sieve opening through which more than 10 wt% of
the aggregate passes. Therefore, the D/d was 0.5/0 mm and
4/0.125 mm for sand A and sand B, respectively. The amount of fil-
ler, which is defined as the percentage of particles passing through
711
the 0.063 mm size were 0.18 and 0.04 wt% for sand A and sand B,
respectively.
3.3. Physical properties
3.3.1. General properties
The physical properties of red and yellow plaster samples are
shown in Table 2. The samples density is consistent with the infor-
mation reported in the literature for earthen materials [4,10]. The
workability of renders and plasters is greatly influenced by the
amount of water used in the mixing. In the flow table tests, the
lower spread on the table, the better workability for plastering
and rendering purposes. For instance, flow table data below 150–
180 mm are adequate for vertical application (walls) [25].
The coated surface by the fresh paste, i.e., the consumption
(24.8 kg/m2 and 24.7 kg/m2) was rather similar to that reported
in technical data sheets of similar materials, as for instance render-
ing and plastering mortars [25]. Shrinkage is generally associated
to the existence of clay minerals in the mixture and measures
the volumetric variation of mortars. The degree of shrinkage is
an important concern in earthen materials as they strengthen by
contraction and densification of clay [26]. Despite this, no cracks
were observed in the studied materials and the observed shrinkage
(1.70% and 1.58%) was analogous to the range of contraction
reported by Deliniere et al. [27] for clay plasters (1.5–2.5%). The
greater shrinkage found in red plasters might be explained by
the major concentration of silicates and aluminates in the binder
(SiO2 + Al2O 3).
Thermal conductivity governs the rate at which heat is con-
ducted through materials, as for instance in the envelope of build-
ings. The conductivity values obtained (1.19–1.17 W/mK) are
relatively low and similar to traditional materials used in the
envelope of buildings (e.g. stone cladding, tiles or glass) [28].
3.3.2. Surface properties
The hardness results tested with the Shore-A durometer
showed earthen plasters are to some extent easily scratched. The
average hardness of yellow plasters (85.3) is slightly higher as
compared to that of red plasters (81.4). In addition, peeling tests
were used for measuring the surface erosion using adhesive tapes.
In this case, the results are expressed in micrograms of plaster
material removed from the surface per square centimetre. The data
confirm that yellow plasters are well-cemented as the surface ero-
sion (peeling) is nearly half of that found for red plasters.
The capillary water absorption was evaluated from the slopes of
water absorption (kg/m2) vs. time (min 0.5) plots using linear regres-
sion analysis [23]. The correlation coefficients obtained in the lin-
ear regression analysis (R greater than 0.99) confirm the reliability
of the proposed method (Fig. 5). The slopes show the plasters’ per-
formance is insufficient in providing adequate protection against
water as reported in previous studies [4,29].
3.3.3. Ultrasonic propagation speed, Young’s modulus and compressive
strength
The propagation speed of ultrasonic pulses through building
materials is dependent on the humidity of the environment [19].
In both plasters, the propagation speed decreases when the relative
humidity of the environment (curing) is increased. This fact can be
explained because the humidity of the environment fills the plaster
voids, thereby increasing the ultrasonic pulse speed. In addition,
the values are comparable to those obtained in earth-based mate-
rials, such as adobe 1235 m/s [4], polymer stabilised blocks 1182–
1298 m/s [30] and soil blocks 1520–1600 m/s [31]. As a conse-
quence of this, the elastic behaviour (Young’s modulus) of the plas-
ters is affected by the curing conditions (Eq. (1)).
712 V.E. García-Vera, M. Lanzón / Construction and Building Materials 187 (2018) 708–717

Fig. 3. X-ray diffraction spectra of red (top) and yellow (bottom) binder sample. (For interpretation of the references to colour in this figure legend, the reader is referred to
the web version of this article.)

In the same way, the plasters strength was affected by the
relative humidity of the environment (Table 3). The best
mechanical performance was found at the lowest relative humid-
ity (30% RH), which is most likely due to higher volumetric con-
traction, which leads to an increase of the material cohesion and
density. However, it is worth stressing that the compressive
strength of red plasters was less affected by the curing condi-
tions than that of yellow plasters. The major proportion of clay
minerals in the red binder could explain the observed differ-
ences. In general, clay minerals have high water retention capac-
ity and the plasters might be more stable to different curing
conditions. The compressive strength of the plasters is below
the range provided by the UNE standard (1.3–5 N/mm2) for
compressed earth blocks [32].
3.3.4. Durability study: erosion and textural variations produced by
rain
Rain simulation tests were used to assess the damage of plas-
ters exposed to rain (Fig. 6). In the gravimetric analysis, the great-
est erosion was produced by HCl rain (2.95% for red plaster and
2.74% for yellow plaster), followed by distilled water rain (1.26%
red plaster and 1.12% yellow plaster) and, finally, H 2SO4 rain
(0.36% red plaster and 0.30% yellow plaster). Although the samples
showed comparable resistance to rain, the yellow plasters were to
some extent more resistant. It must be noted that rain tests com-
bine the dissolving capacity of rain with the local impact (stress)
created by the drop on the plaster’s surface. Therefore, the hard-
ness of the plaster plays as well an important role in the materials
resistance against rain water.
 V.E. García-Vera, M. Lanzón / Construction and Building Materials 187 (2018) 708–717 713

Table 1 Table 2
TG-MS and XRF characterisation of binders. Physical features of plaster samples.

Red binder, % Yellow binder, % Properties Red plaster Yellow plaster

Thermal analysis TG-MS M RSD M RSD
H2O 2.14 1.98 3
Bulk density, g/cm 1.83 3.6 1.81 4.8
CO2 8.55 20.05
Fresh density, g/cm3 2.06 3.4 2.05 2.7
XRF analysis Hardened density, g/cm3 1.87 0.6 1.86 0.3
SiO2 43.92 27.38 Consistency (flow table), mm 123.7 0.8 124.0 1.1
Al2O 3 16.75 10.22 Coated surface (consumption), 24.8 7.7 24.7 2.8
CaO 9.57 29.84 kg/m2
Fe2 O3 7.11 4.09 Shrinkage, % 1.70 7.1 1.58 2.0
K2O 4.97 2.27 Thermal conductivity, W/mK 1.19 0.9 1.17 1.0
MgO 3.64 1.97 Hardness – Shore A 81.4 5.7 85.3 6.0
SO3 1.45 0.87 Hardness – Peeling test, mg/cm 2 871.3 17.8 405.9 19.2
TiO2 0.87 0.54 Capillary water absorption – CWA, 0.594 2.2 0.603 1.9
Na2 O 0.44 0.31 kg/m2min 0.5
P2 O5 0.14 0.11
Others <0.5 <0.5
SiO2 + Al2O3 60.67 37.6
SiO2/Al2O3 2.62 2.68 An additional method, based on image analysis, was used to
SiO2 + Al2O3 /CaO 6.34 1.26 evaluate the alteration of plasters exposed to water or acid rain.
The reason for using this method is that gravimetric measurements
The unexpected behaviour found in plasters attacked by H 2SO4 are not exempt from practical difficulties. For example, the brush-
rain is explained by formation of protecting coatings of gypsum on ing step does not completely remove rests of material accumulated
the plaster’s surface. The results are consistent with previous on the surface leading to an underestimation of the erosion
experiments conducted on adobe samples and rendering mortars (weight loss). Therefore, a second set of experiments was carried
attacked by sulphuric. The formation of gypsum patina is due to out using image analysis software to evaluate textural variations
the following chemical reaction [4,33]: instead of weight variations. In this case, the plasters were not
brushed but dried and directly examined by optical microscopy
CaCO3 þ H2 SO4 þ 2H 2O ! CaSO42H2OðcoatingÞ þ CO2 þ H2 O
combined with image analysis software.
The SEM images corroborated the formation of gypsum crystals Fig. 9 illustrates the process of image analysis in red plasters
in samples attacked by sulphuric acid rain (Fig. 7). In the original attacked by rain. First, high-resolution images were captured with
surface, the binding phase (orange arrows) and sands (white the microscope and calibrated (Fig. 9a–c). The images showed
arrows) are clearly distinguished (Fig. 7; top). In contrast, in rain- qualitative differences between samples exposed to water rain
attacked plasters numerous gypsum crystals cover the plaster sur- and those attacked by acid rain. The existence of gypsum coatings
face due to the chemical process above mentioned (Fig. 7; bottom). on the surface is likely responsible for the textural variations pro-
These coatings behave as an effective barrier against the diffusion voked by H2SO4 rain (Fig. 9b). Then, the calibrated images were
of sufphuric acid, which reduces the rate of the attack. The forma- opened with ImageJ software and converted into 8-bit grayscale
tion of gypsum on plasters attacked by H2SO4 was also confirmed images for evaluating their texture. It was observed that the rain
by XRD analysis (Fig. 8). action produced additional air pores (holes) on the surface of

Fig. 4. Granulometry study.

714 V.E. García-Vera, M. Lanzón / Construction and Building Materials 187 (2018) 708–717

Fig. 6. Mass variation percentage in rainwater and acid-rain erosion tests.

Fig. 5. Capillary water absorption of plaster samples.

plasters. These features were, therefore, an adequate indicator to

assess textural alterations caused by rain. Therefore, the phase of
interest (air) was separated from solid materials in the surface
(Fig. 9d–f). The segmentation process was assisted by the low
grayscale of pores as compared to solid constituents of the plaster,
including darker particles (arrows in Fig. 9). Next, the grayscale
range of the histograms was selected within the same interval to
increase the reliability of the segmentation process. Finally, binary
images were obtained and the area of pores was calculated relative
to the total examined area.
Fig. 10 shows textural variations found for red and yellow plas-
ters using segmentation. Comparing with the gravimetric data
showed in Fig. 6, red plasters were less resistant to water (1.24%
of textural variation) than yellow ones (0.56%). The rain tests com-
bine the dissolving effect of water with the mechanical impact of
the drop. Therefore, image analysis provides more realistic evalua-
tion than gravimetric tests since yellow plasters showed better
performance in Shore A hardness measurements (Table 3). Acid
rain led to similar alteration in yellow and red plasters using
H2 SO4 (2.35% and 2.54%) and HCl solutions (4.47% and 4.68%).
Comparing the three rain simulations, the major variation was
found for hydrochloric acid, followed by sulphuric acid and dis-
tilled water. However, the textural alteration induced by H2SO4
rain (2.35% and 2.54%) is more consistent than the gravimetric Fig. 7. SEM examination: original plaster surface (top); plaster surface after
measurements (0.36% and 0.30%). For the latter tests, the acid conducting sulphuric acid attack (bottom).

Table 3
Influence of relative humidity (RH) on mechanical properties of plasters: ultrasonic speed, Young’s modulus and compressive strength.

Red plaster Yellow plaster

RH 30% RH 60% RH 95% RH 30% RH 60% RH 95%
M (RSD) M (RSD) M (RSD) M (RSD) M (RSD) M (RSD)
Ultrasonic speed, m/s 1864 (1.1) 1799 (0.8) 1559 (0.9) 1973 (1.6) 1805 (0.5) 1361 (0.8)
Young’s modulusa, N/mm2 6500 (2.1) 6055 (1.6) 4550 (1.8) 7233 (3.1) 6051 (1.0) 3439 (1.5)
Compressive strength, N/mm2 1.2 (8.0) 1.0 (10.5) 0.8 (14.9) 1.4 (6.7) 1.2 (6.1) 0.7 (3.7)

Note: M = Mean; RSD = relative standard deviation.

a 2
Young’s modulus using the theoretical formula E = v q .
 V.E. García-Vera, M. Lanzón / Construction and Building Materials 187 (2018) 708–717 715

Fig. 8. X-ray diffraction spectra of fragments removed from the surface of plasters attacked by sulphuric-acid rain. Top: XRD of red plaster specimen. Botton: XRD of yellow
plaster specimen. (For interpretation of the references to colour in this figure legend, the reader is referred to the web version of this article.)

erosion (weight loss) is partially counterbalanced by weight gain
due to formation of gypsum coatings on the surface.
4. Conclusions
 Clayey materials used for the manufacturing of bricks can be
successfully incorporated into earthen plasters. The nature of
the binder has limited influence on practical properties of plas-
ters, such as density, consistency (workability), shrinkage, ther-
mal conductivity or capillary water absorption. However, the
relative proportion of silicoaluminates and carbonates in the
binder may have an influence on surface properties like peeling
resistance or hardness.
 The curing conditions had an impact on mechanical and elastic
properties of earthen plasters. It was found that the higher the
relative humidity, the lower compressive strength, ultrasonic
propagation speed and rigidity.
 Rain erosion experiments conducted with distilled water and
acid rain solutions showed the limited durability of earthen
materials to aggressive environments. The formation of gypsum
patina has been confirmed in the surface of plasters attacked by
716 V.E. García-Vera, M. Lanzón / Construction and Building Materials 187 (2018) 708–717

Fig. 9. Colour images: optical microscopy examination of plaster surface attacked by distilled water (a), H 2SO4 (b) and HCl rain (c). Grayscale images: on the left side, region of
interest to perform the image analysis. On the right side, thresholding process showing histograms and labeled pores. The biggest area of pores was registered for HCl rain (f;
image on the left), followed by H2SO 4 rain (e) and distilled water rain (d). (For interpretation of the references to colour in this figure legend, the reader is referred to the web
version of this article.)

sulphuric acid rain. Nevertheless, patina formation does not  Gravimetric tests and image analysis software are non-
necessarily mean a long-term protection of the plaster as gyp- destructive techniques to assess the durability of plasters
sum is partially soluble in water. exposed to rain. Gravimetric analysis provides precise informa-
 V.E. García-Vera, M. Lanzón / Construction and Building Materials 187 (2018) 708–717
Fig. 10. Textural variation of red and yellow plasters exposed to rainwater and
acid-rain. (For interpretation of the references to colour in this figure legend, the
reader is referred to the web version of this article.)
tion, although the magnitude of the erosion could be underesti-
mated in same cases (e.g. sulphuric acid rain). In contrast, image
analysis is appropriate to assess textural alterations, but the
information is more restricted to particular areas of the surface.
The combination of both techniques might be an excellent
choice to characterise physical and textural alterations of build-
ing materials.
Conflicts of interest
None.
Acknowledgments
The authors express their thanks to the Microscopy Service at
the Technical University of Cartagena, UPCT.
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