Construction and Building Materials 236 (2020) 117445

Contents lists available at ScienceDirect

Construction and Building Materials

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

The effectiveness of ethyl silicate as consolidating and protective coating

to extend the durability of earthen plasters
Victoria E. García-Vera a, Antonio J. Tenza-Abril b, Marcos Lanzón a,⇑
a
Departamento de Arquitectura y Tecnología de la Edificación, Universidad Politécnica de Cartagena, 30203 Murcia, Spain
b
Department of Civil Engineering, University of Alicante, 03690 Alicante, Spain

h i g h l i g h t s

 Ethyl silicate significantly improves the physical resistance of earthen plasters.

 Water absorption properties are clearly enhanced with ethyl silicate coatings.
 Earthen plasters present limited durability against rain water and acid rain.
 Ethyl silicate-treated samples show much better resistance to acid rain.
 The plasters’ porosity is substantially reduced with ethyl silicate coatings.

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

Article history: In the heritage protection, one of the most interesting scenarios is the preservation of the original mate-
Received 15 May 2019 rials. In this case, the surfaces are generally treated to consolidate them. The aim of this paper is to eval-
Received in revised form 8 October 2019 uate the effect of ethyl silicate coatings on surface consolidation, water absorption and porosity of
Accepted 2 November 2019
earthen materials. Peeling tests, water absorption measurements (capillary and Karsten) and textural
alteration analyses were conducted by optical microscopy. In addition, the protective role of the ethyl sil-
icate coatings against rainwater, HCl rain and H2SO4 rain was evaluated to compare the durability of
Keywords:
coated and control samples. It was found that ethyl silicate substantially improved the above properties
Earthen plasters
Ethyl silicate
as well as microstructural features of the samples. Scanning Electron Microscopy and EDX mapping
TEOS revealed the coating was not regularly spread on the surface. Despite this, Mercury Intrusion
Consolidation Porosimetry tests showed the total porosity of samples coated with ethyl silicate was clearly reduced.
Acid resistance Ó 2019 Elsevier Ltd. All rights reserved.
Durability
Microstructure

1. Introduction
Earth-based constructions are traditional solutions for building
because of their availability and easy handling. Nowadays, there
are historical earthen constructions that are relatively well pre-
served, despite anthropogenic and weathering factors. These con-
structions are part of our cultural heritage and must be
preserved to leave this legacy to future generations. Earthen mate-
rials by their own nature are weak and consequently very sensitive
to external agents, such as pollutants and atmospheric effects,
especially rain [1,2]. These agents cause decay processes including
a significant softening and deterioration on the surface. Therefore,
as regards earthen materials exposed to outdoor environments, the
use of protective treatments is beneficial to delay the above pro-
⇑ Corresponding author.
E-mail address: marcos.lanzon@upct.es (M. Lanzón).
cess. For this reason, further research is needed to ascertain the
performance of protective coatings (e.g. ethyl silicate [3,4], sodium
silicate [5], hydroxyapatite [6], nanolime [7], oils [8]) in front of
water and acid rain aggressions. This study is focus on ethyl silicate
applied on earthen plasters.
The most damaged areas of earthen plasters in historical con-
structions are usually rebuilt. In this case, the materials used in
the reconstruction might be manufactured with stabilisers (i.e.
lime, cement, wastes, fly ash or coal ash) to enhance their proper-
ties, such as increase mechanical strength, decrease erosion against
rain and water absorption, and increase water vapour permeability
[8–10]. However, from the heritage point of view the most inter-
esting scenario is the preservation of the original materials. In this
case, the materials are generally consolidated with the aim of
strengthening eroded zones on the surface. Both in the restoration
process and consolidant selection, close attention should be paid to

https://doi.org/10.1016/j.conbuildmat.2019.117445
0950-0618/Ó 2019 Elsevier Ltd. All rights reserved.
2 V.E. García-Vera et al. / Construction and Building Materials 236 (2020) 117445
avoid undesired effects [11,12] such as surface glazing, chromatic
change, water vapour permeability decrease.
According to [13], the preservation of historical heritage is still
based on conventional techniques and products, usually charac-
terised by a lack of compatibility with the substrate to be treated,
and by low performances under environmental conditions. How-
ever, modern techniques and products are accepted by Venice
Charter [14], which includes the use of any modern technique for
conservation and construction when more suitable for conserva-
tion. On the other hand, the chemical industry has been studying
and manufacturing waterproofing and consolidants since the
beginning of the 20th century to prevent the decay of architectural
heritage [15]. At present, nanomaterials are being studied for the
conservation and restoration of building heritage. These nanoma-
terials can act as consolidants (inorganic nanomaterials and
silicon-based hybrid polymer nanocomposites), water repellents
or as protective treatments (self-cleaning coatings and antimicro-
bial coatings) [16].These consolidants have been applied mainly
on stony materials but little has been studied on earthen materials.
Among the actions aimed at using consolidating materials, [17]
shows that silicon-based consolidants (such as ethyl silicate,
sodium silicate or colloidal suspensions of silica) may deposit a
gel of amorphous silica within the pores of stone. This gel strength-
ens the surface of the material and increase its acid resistance due
to deposition of SiO2 gel, which is not attacked by acid rain and pro-
vides certain hydrophobicity by blocking pores of the material. An
additional advantage of inorganic consolidants is that they are more
compatible with the substrate although they have worse cohesion
properties than the organic ones [17]. Despite the current interest,
the use of the aforementioned consolidants (ethyl silicate, sodium
silicate, and colloidal suspensions of silica) is not a novelty of the
last years in the heritage restoration, because they were already
used in the 20th century for the consolidation of stones [18].
Other than silica-based consolidants have been used on stone
materials, such as calcium alkoxides [19], hydroxyapatite [6], oxa-
lates [20], etc. Nevertheless, ethyl silicate (i.e. tetraethyl orthosili-
cate or TEOS) is currently the consolidant most extensively used on
stones [4,15], which has been used since the beginning of the 20th
century not only as consolidant on stones but also as binder for
ceramics, adhesive for coverings in precision casting, raw material
for obtaining amorphous silica, gelling product to obtain alcohol
fuels, and in the preparation of glass adherent lacquers [21]. Ethyl
silicate, in addition to being used on stones with good results
[12,19,22], has also been applied successfully in the consolidation
of bricks [15,23] and lime mortars [24,25].
The consolidation of earthen plasters has been little studied.
However, some examples have been found in the scientific litera-
ture, such as the earthen finishes at Mesa Verde national park of
Colorado that were consolidated with alkoxysilanes and gelatin
[26]. Also, treatments indicated to protect the surfaces of porous
building materials against weathering (silicon nanoparticles, tita-
nia and silica nanoparticles, silane–siloxane, beeswax) were used
for the consolidation of earthen plasters [27]. In addition, nanolime
has been applied successfully for the consolidation of other earthen
materials such as adobes [1]. However, more research on the con-
servation and consolidation of earthen materials is needed, since it
is a material widely used in the construction of historic buildings
(e.g. Alhambra of Granada, Roman theatre of Cartagena, Punic wall
of Cartagena).
This study focuses on the use of ethyl silicate in the consolida-
tion of earthen plasters. The aim of this study is to evaluate the
consolidation effects of the ethyl silicate (ES) on earthen plasters.
For this purpose, a set of specimens treated with ES and control
samples were studied. To evaluate the consolidating effectiveness,
several tests were conducted including peeling test (also called
Scotch tape test), water absorption, durability tests consisting of
rainwater, HCl rain and H2SO4 rain simulation. Furthermore, Mer-
cury Intrusion Porosimetry (MIP) analyses were performed to
assess the microstructural variations induced by the treatment in
the pore system. Finally, the surface of treated and control earthen
plasters were examined with Scanning Electron Microscopy (SEM)
using EDX mapping analyses.
2. Materials
Each specimen was made with a clayey binder, a mix of two
limestone sands (A and B) and distilled water. The raw materials
and the final paste of this study were analysed in a recent study
[28]. Two types of clayey binders (yellowish and reddish) were uti-
lised which are commonly employed in the manufacture of
extruded fired bricks. These clayey binders are usually named with
the word clay in the industry. Henceforth, in this context the terms
binder and clay will be indistinctly used to refer to any type of
clay-based binders. The binders have been studied by X-ray diffrac-
tions (XRD) confirming the existence of quartz, gypsum, calcite,
muscovite and kaolinite as main minerals. Similar X-ray fluores-
cence (XRF) studies have found SiO2 (43.9%) and Al2O3 (16.8%) as
major components of both binders. Finally, the thermogravimetric
analysis showed the yellow binder has higher carbonate concen-
tration (20.1%), most likely associated to calcite and dolomite, than
the red binder (8.6%), being the H2O concentration similar for both
binders, yellow (2.1%) and red (2%). Also, the Atterberg limits were
obtained, for the red clay, the plastic limit, liquid limit and plastic-
ity index were 18.9, 29.5 and 10.6 respectively, and for the yellow
clay 19.2, 33.5 and 14.3.
The particle size distribution study of the sands was carried out
according to the UNE-EN 933-1 standard [29]; for sand A, the max-
imum size (D) was 0.5 mm, the minimum size (d) 0 mm and the fil-
ler percentage 0.18% (filler defined according to [30] as the
percentage passing through the 0.063 mm sieve); for sand B the
values found were: D = 4 mm, d = 0.125 mm, filler = 0.04%. The par-
ticle size distributions of the binders were determined by laser
diffraction (Fig. 1). The dosage used was: 10 wt% binder, 30 wt%
sand A, and 60 wt% sand B. Water was added to this mixture
obtaining 0.16 ratio of water to solid. This dosage has been utilised
in previous studies [1,28,31,32] leading to minimal shrinkage dur-
ing the samples hardening. Estel 1000Ò (CTS Spain), a commercial
consolidant with a 75% of tetra-ethyl-ortho-silicate (TEOS) as active
ingredient, was used as consolidating treatment.
3. Methods
3.1. Samples preparation.
Two types of specimens were manufactured to meet the needs
of the tests performed, prismatic specimens using standardised
moulds for cement mortars (4  4  16 cm), and 1 ± 0.1 cm thick
plasters were applied on ceramic surfaces (12  24 cm) (Fig. 2a,
2b and 2c). The specimens were stored for seven days under labo-
ratory conditions (24 ± 2 °C) and then dried at 60 °C for 24 h to
accelerate the process of water evaporation and densification of
the mixture. After that, the samples were kept for 1 h under labo-
ratory conditions to acclimatise, and then the ethyl silicate (Estel
1000Ò) treatment was applied. This consolidant reacts with the
atmospheric humidity and is transformed into silica gel SiO2
releasing ethanol. A single coat of ethyl silicate was applied on
the surface with the aid of a nebuliser at a distance of 20 cm from
the surface (Fig. 2e). Cardboard frames were used to delimit the
area where the treatment was to be applied (Fig. 2d). Once the
treatment was applied, the samples were kept for two weeks in a
humid chamber at 80% ± 2% RH, and at the end of this period they
were reintroduced in the oven at 60 °C for 24 h.
 V.E. García-Vera et al. / Construction and Building Materials 236 (2020) 117445 3

Fig. 1. Particle size distribution of the red and yellow clay. (For interpretation of the references to colour in this figure legend, the reader is referred to the web version of this
article.)

Fig. 2. (a) process of plaster preparation; (b) red plaster samples; (c) yellow plaster samples; (d) plaster covers with cardboard frames to apply the treatment; (e) nebuliser
used to apply the ES treatment. (For interpretation of the references to colour in this figure legend, the reader is referred to the web version of this article.)

3.2. Peeling test 3.3. Water absorption tests

The level of consolidation of the studied plasters was assessed
with the peeling test (Fig. 3a, 3b, and 3c). This technique can be
performed in situ and under laboratory conditions and it is suitable
for assessing the cohesion qualities of paint films, stones, historic
renders and plasters [33–35]. The method measures the amount
of material adhered to a flexible adhesive tape (5  2 cm) which
is attached to the tested surface and then removed (Fig. 3c). The
detached material is calculated as the difference between the orig-
inal and final weight of the tape. Therefore, the amount of
extracted material reflects the cohesion of the substrate and can
be used to evaluate the effects of consolidation after restoring
the surface [12]. Three plasters were manufactured for each type
of clay (Fig. 2b and 2c). The samples were divided into two areas,
one without treatment (control) and another with the ethyl silicate
(ES) treatment. Three regions were chosen on the surface and 10
peeling tests were performed on them so that 180 tests were car-
ried out in total (90 coated samples + 90 control samples).
The water absorption capacity of the plasters was evaluated
using a modified version of the UNE-EN 772-11 standard [28,36].
This modification prevents samples collapse to happen due to the
water action by placing the specimen on a wet towel (Fig. 3d).
The mass variation per unit of area of the sample as a function of
square root of time is monitored. The absorption coefficient was
obtained from the slopes of the curves using linear regression anal-
ysis [28,37,38]. The water absorption capacity was also assessed
with the Karsten test that simulates the water penetration due to
water column pressure. The test can be performed either in situ
or laboratory conditions in a wide set of materials, such as stone,
brick and renders [39,40]. A graduated tube is fixed to the surface
with an adhesive to avoid water leakage and filled with water. The
absorbed water was measured periodically until the 4.5 cm3 mark
on the tube was reached, then the water absorption coefficient
(WAC) was obtained by linear regression from the slope of the
curves.
4 V.E. García-Vera et al. / Construction and Building Materials 236 (2020) 117445

Fig. 3. (a and b) preparation of the adhesive strips to carry out the peeling test; (c) 5x2 cm adhesive strip glued to the plaster surface; (d) modified method of the UNE-EN
772-11 standard [36] to measure capillary water absorption for earthen materials; (e) devise used to perform the durability tests (simulation of rainwater, HCl rain and H2SO4
rain).

3.4. Durability tests microscope was equipped with polariser filter to eliminate possible
light refections and the images were captured in high-resolution.
The tests to evaluate the resistance to the action of rain, HCl rain
and H2SO4 rain were conducted by dripping the specimens (control 4. Results and discussion
and treated) from a container at a constant height for 10 min
(Fig. 3e). The dripping speed was approximately one drop every 4.1. Consolidation treatment: peeling test
5 s. The action of rainwater was simulated dripping distilled water
and the action of acid rain was simulated dripping two types of The peeling test results (Fig. 4) show that the yellow plaster has
acid solutions: sulphuric acid solution H2SO4 0.9 M and hydrochlo- higher consolidation efficiency than the red plaster, since the
ric acid solution HCl 0.6 M. Twelve specimens were made for each detached material for the red plaster was 50% higher (871.3 mg/
clay formulation and treatment i.e.12 control specimens and 12 cm2; RSD 17.8) than that of the yellow one (405.9 mg/cm2; RSD
treated specimens with ES. Therefore, four specimens were used 19.2). The effectiveness of the treatment was important in both
in each rain simulation experiment. After dripping the specimens, plasters: 94% (52.9 mg/cm2; RSD 13.3) and 92.5% (30.4 mg/cm2;
they were gently brushed in order to remove non-adhered rests of RSD 16.5) for the red and yellow plasters, respectively. The results
eroded material on the surface. The specimens were weighed are coherent with other studies [17] conducted on stone where
before and after being dripped to obtain their mass variation due ethyl silicate also improved the surface cohesion. The ethyl silicate
to rain action. effectiveness is higher than that achieved by Ca(OH)2 nanoparticles
coatings when the treatment is evaluated for similar earthen mate-
rials (adobe) [1]. The good performance of the ethyl silicate is due
3.5. Mercury Intrusion Porosimetry (MIP)
to the amorphous silica gel, produced by the chemical reactions of
the ethyl silicate with the atmospheric humidity that strengthen
MIP is commonly used to assess consolidation efficiency
the surface of the material.
[12,17]. Hence, the microstructural properties of control and trea-
ted plasters were studied by MIP using a Poremaster-60 GT
4.2. Capillary water absorption tests
porosimeter. The technique allows obtaining information about
the pore structure of materials with accessible pores ranging from
The water absorption coefficient (WAC) was calculated as the
4 nm to 900 lm. The MIP analyses were conducted on samples
regression line slope. The results (Fig. 5) showed that both clay-
taken from the surface of plasters and the working conditions var-
ied from atmospheric pressure to 60.000 psi (413.7 MPa). Four
samples were analysed: red plaster (1.0758 g; 0.5343 cm3); coated
red plaster (1.7526 g; 0.8490 cm3); yellow plaster (1.2883 g;
0.6584 cm3); coated yellow plaster (1.2610 g; 0.6078 cm3).

3.6. Scanning electron and optical microscopy

Semi-quantitative analysis (mapping) and morphology exami-

nation of the samples were studied by Scanning Electron Micro-
scopy (SEM) (Hitachi S-3500N) equipped with an X-ray detector
Bruker XFlash 3001 for microanalysis EDX. The fragments were
extracted from control and coated plasters and dried at 60 °C for
24 h. The working conditions in SEM were 20 kV using back-
scattered electrons (BSE mode) and a working distance of 15 mm.
Moreover, an optical microscope (Dino-Lite Edge) was used to
study the physical changes on the surface produced by rain. The Fig. 4. Material adhered on the adhesive tape strips used in the peeling test.
 V.E. García-Vera et al. / Construction and Building Materials 236 (2020) 117445 5

Fig. 5. Capillary water absorption of the red clay plaster (a) and yellow clay plaster (b) using a modified method of the UNE-EN 772-11 standard [36]. (For interpretation of
the references to colour in this figure legend, the reader is referred to the web version of this article.)

based plasters have similar WAC (red-clay plaster: 0.67 kg/

m2∙min0.5; yellow-clay plaster: 0.60 kg/m2∙min0.5). The ES treat-
ment reduced WAC in both plasters (0.39 kg/m2∙min0.5 for the
red-clay plaster and 0.3 kg/m2∙min0.5 for the yellow one). The
WAC reduction is consistent with previous studies performed on
limestone materials treated by ethyl silicate [41]. The yellow-clay
plasters showed lower water absorption, for both control and trea-
ted samples, which might be due to two reasons. Firstly, the red
binder was mainly composed of clay-based minerals often suscep-
tible to absorb water, and therefore, they increase the water capil-
lary uptake. Secondly, the greater presence of calcitic phase
(CaCO3) in the yellow binder (clearly identified with larger peaks
in the XRD analysis [28]), which is associated with lower water
absorption.

4.3. Water absorption: Karsten tube

The Karsten water absorption (KWA) was also studied from the
slope of regression lines, calculated over the entire time interval
shown in Fig. 6. The KWA data were similar for both plasters
(red-clay plaster: 5.38 kg/m2∙min0.5; yellow-clay plaster: 4.87 kg/
m2∙min0.5). After applying ethyl silicate, KWA was reduced in both
materials (red-clay plaster: 1.80; yellow-clay plaster: 1.84). When
the test was conducted on control plasters the material was dis-
solved by water and partially filled the Karsten tube (Fig. 7a) [2].
However, when the test was performed on the surface treated with
ES, the decaying effect of the surface did not occur (Fig. 7b) due to
the consolidating properties of the treatment.
4.4. Durability tests: rain simulation
The durability tests confirmed that earthen materials are sensi-
tive to the action of rain water and acidic environments (Fig. 8).
The control plasters behaved similar and the highest erosion was
Fig. 7. Tests of water absorption using Karsten tubes. (a) test conducted on the red
clay plaster without treatment; (b) test perfomed on the red-clay plaster treated
with ethyl silicate. (For interpretation of the references to colour in this figure
legend, the reader is referred to the web version of this article.)
observed for HCl rain simulation, followed by distilled rainwater
simulation and, finally, H2SO4 rain simulation [28], the RSD for
the control samples ranged between the values of 5.9% and
10.3%. An important finding of the study is that ethyl silicate signif-
icantly improved the rain resistance in all cases (water, HCl and
H2SO4), the RSD for the treated samples ranged between the values
of 5.1% y 16.8%. It must be emphasised, however, that for the H2SO4
simulation the weight of the specimens increased due to gypsum
formation on the surface [32,38,42].

Fig. 6. Water absorption using Karsten tubes. (a) red-clay plaster, and (b) yellow-clay plaster. (For interpretation of the references to colour in this figure legend, the reader is
referred to the web version of this article.)
6 V.E. García-Vera et al. / Construction and Building Materials 236 (2020) 117445

Fig. 8. Percentage of mass variation in plasters exposed to rainwater, HCl rain and H2SO4 rain for the red clay plaster (a) and yellow clay plaster (b). (For interpretation of the
references to colour in this figure legend, the reader is referred to the web version of this article.)

Fig. 9. Colour and textural variations caused by rain (water, HCl and H2SO4) in red-clay plasters; (a) to (c) control plaster exposed to distilled water, HCl and H2SO4 rain; (d) to
(f) plaster coated with ethyl silicate exposed to distilled water, HCl and H2SO4 rain. (For interpretation of the references to colour in this figure legend, the reader is referred to
the web version of this article.)

The effect of rain was also examined by optical microscopy
using a digital microscope equipped with image software (Dino
Capture 2.0). The effect of HCl and H2SO4 acid solutions was visible
in non-treated samples (Fig. 9b and 9c). However, it is worth
stressing the protective role of ethyl silicate in samples exposed
to all types of acid environments as shown in Fig. 9e and 9f. The
deposition of gypsum in samples attacked by H2SO4 acid was con-
firmed by deposition of thin white rests on their surface (Fig. 9c
and 9f). Finally, HCl solution produced an important alteration on
the surface of the samples where large cavities were observed,
thereby confirming the results observed in Fig. 8.
4.5. Mercury intrusion porosimetry
MIP data (Fig. 10) showed that the ethyl silicate treatment
decreased the total volume of pores in both plasters. In the red
plaster the total pore volume was reduced from 0.1214 cm3/g (con-
trol) to 0.1044 cm3/g (ES coated), whereas in the yellow one a sim-
ilar reduction was observed (control: 0.1391 cm3/g; ES treatment:
0.1096 cm3/g). The predominant pore diameter in both plasters
was in the 10–100 mm interval, in which the porosity reduction
was clearly reduced. In this interval, the pore volume was reduced
by 11.08% and 21.76% for red and yellow plasters, respectively. The
results are coherent with previous studies where ethyl silicate was
found to reduce the volume of pores in fired-clay bricks [23] and
limestones [41].
4.6. Scanning electron microscopy
The objective of SEM-EDX examination was to determine
whether the ethyl silicate was distributed uniformly on the plas-
ter surface. (Fig. 11). Since calcium is a major constituent in the
studied plasters, the emission of the element was used to visu-
alise changes induced by ethyl silicate treatment, in which silicon
is the major element. Using mapping analysis, the calcium signal
(X-ray emission) was represented in red whereas the silicon one
was displayed in blue. As shown in Fig. 11a, an important fraction
of the X-ray emission is due to calcium (aggregates) with a minor
contribution of the binding phase (clay). On the other hand, the
emission due to silicon (blue) is increased after applying the coat-
ing (Fig. 11b), since the ethyl silicate transforms into silicon.
Moreover, this image shows the irregular pattern of silicon distri-
bution, revealing that the treatment did not cover the surface
completely.
5. Conclusions
The study confirms ethyl silicate improves physical and
microstructural features of the earthen plasters studied. There-
fore, the durability of heritage materials like adobe, earthen
plasters or tapial can be improved using the consolidant. Accord-
ing to the results obtained in this study, the following can be
concluded:
 V.E. García-Vera et al. / Construction and Building Materials 236 (2020) 117445 7

Fig. 10. Porosimetry study for (a) red-clay plaster (control and treated) and (b) yellow-clay plaster (control and treated). (For interpretation of the references to colour in this
figure legend, the reader is referred to the web version of this article.)

Fig. 11. (a) red-clay plaster without treatment; (b) red-clay plaster treated with ethyl silicate. (For interpretation of the references to colour in this figure legend, the reader is
referred to the web version of this article.)

 Ethyl silicate coatings consolidated the surface of earthen mate-
rials and peeling tests confirmed a significant contribution of
the consolidant with effectiveness above 92%.
 Both capillary water and permeability absorption of earthen
plasters were reduced by ethyl silicate coatings. This improve-
ment is beneficial for earthen materials due to the fact they
are highly sensitive to the water action. In addition, Karsten
tube experiments demonstrated the consolidating effect of
ethyl silicate when applied on earthen materials surfaces.
 Durability tests confirmed the protective effect of ethyl silicate
coatings against rain, HCl rain and H2SO4 rain. The reduced
impact of rainwater is due to the consolidating effect of the
ES treatment, whereas in acidic environments the lack of reac-
tivity of SiO2 in front of HCl and H2SO4 solutions is a positive
factor to consider. The lower erosion observed with sulphuric
acid solution is explained by formation of gypsum layers on
the plasters’ surface
 Mercury Intrusion Porosimetry analyses showed that ethyl sili-
cate reduced the total volume of pores in earthen plasters,
which is consistent with both capillary water absorption and
Karsten tests.
8 V.E. García-Vera et al. / Construction and Building Materials 236 (2020) 117445
 Although nebulisation methods are, in theory, appropriate to
provide uniform spray and deposition, Scanning Electron Micro-
scopy examination combined with EDX mapping analyses
showed the coating is not homogeneously spread on the
surface.
The good results obtained with the ethyl silicate as a consoli-
dant of earthen materials and its easy application show that it
could be a useful tool in the heritage preservation.
Declaration of Competing Interest
The authors declare that they have no known competing finan-
cial interests or personal relationships that could have appeared
to influence the work reported in this paper.
Acknowledgments
This study is part of the project entitled NanoHeritage: develop-
ment, application and characterisation of novel consolidating coat-
ings for Heritage Conservation - funded by Fundación Séneca,
Regional Government of Murcia, Spain.
References
[1] M. Lanzón, J.A. Madrid, A. Martínez-Arredondo, S. Mónaco, Use of diluted Ca
(OH)2 suspensions and their transformation into nanostructured CaCO3
coatings: A case study in strengthening heritage materials (stucco, adobe
and stone), Appl. Surf. Sci. 424 (2017) 20–27, https://doi.org/10.1016/j.
apsusc.2017.02.248.
[2] G. Minke, Building with earth, Base, Berlin, 2006.
[3] E. Franzoni, G. Graziani, E. Sassoni, G. Bacilieri, M. Griffa, P. Lura, Solvent-based
ethyl silicate for stone consolidation: influence of the application technique on
penetration depth, efficacy and pore occlusion, Mater. Struct. 48 (2015) 3503–
3515, https://doi.org/10.1617/s11527-014-0417-1.
[4] G. Graziani, E. Sassoni, E. Franzoni, Consolidation of porous carbonate stones
by an innovative phosphate treatment: mechanical strengthening and
physical-microstructural compatibility in comparison with TEOS-based
treatments, Herit. Sci. 3 (2015) 1, https://doi.org/10.1186/s40494-014-0031-0.
[5] K.B. Ren, D.A. Kagi, Upgrading the durability of mud bricks by impregnation,
Build. Environ. 30 (1995) 433–440, https://doi.org/10.1016/0360-1323(94)
00056-X.
[6] G. Graziani, E. Sassoni, E. Franzoni, G.W. Scherer, Hydroxyapatite coatings for
marble protection: Optimization of calcite covering and acid resistance, Appl.
Surf. Sci. 368 (2016) 241–257, https://doi.org/10.1016/J.APSUSC.2016.01.202.
[7] G. Taglieri, C. Mondelli, V. Daniele, E. Pusceddu, G. Scoccia, Synthesis, textural
and structural properties of calcium hydroxide nanoparticles in hydro-
alcoholic suspension, Adv. Mater. Phys. Chem. 04 (2014) 50–59, https://doi.
org/10.4236/ampc.2014.43008.
[8] R. Eires, A. Camoes, S. Jalali, Enhancing water resistance of earthen buildings
with quicklime and oil, J. Clean. Prod. 142 (2017) 3281–3292, https://doi.org/
10.1016/j.jclepro.2016.10.141.
[9] R. Eires, A. Camoes, S. Jalali, Earth architecture: ancient and new methods for
durability improvement, Struct. Archit. Concepts Appl. Challenges. (2013)
962–970.
[10] D. Maskell, A. Heath, P. Walker, Inorganic stabilisation methods for extruded
earth masonry units, Constr. Build. Mater. 71 (2014).
[11] F. Pinto, D. Rodriguez, The action of inorganic consolidants in limestones, in: J.
W. Lukaszewicz, P. Niemcewicz (Eds.), 11th Int. Congr. Deterior. Conserv.
Stone, Toruń, Poland, 2008.
[12] S.A. Ruffolo, M.F. La Russa, M. Ricca, C.M. Belfiore, A. Macchia, V. Comite, A.
Pezzino, G.M. Crisci, New insights on the consolidation of salt weathered
limestone: the case study of Modica stone, Bull. Eng. Geol. Environ. 76 (2017)
11–20, https://doi.org/10.1007/s10064-015-0782-1.
[13] D. Chelazzi, G. Poggi, Y. Jaidar, N. Toccafondi, R. Giorgi, P. Baglioni, Hydroxide
nanoparticles for cultural heritage: Consolidation and protection of wall
paintings and carbonate materials, J. Colloid Interface Sci. 392 (2013) 42–49,
https://doi.org/10.1016/j.jcis.2012.09.069.
[14] ICOMOS, International charter for the conservation and restoration of
monuments and sites (The Venice charter 1964) 1964 Venice.
[15] G. Cultrone, V. Sánchez-Ibáñez, Consolidation with ethyl silicate: how the
amount of product alters the physical properties of the bricks and affects their
durability, Mater. Construcción. 68 (2018) 173, https://doi.org/10.3989/
mc.2018.12817.
[16] A. Sierra-Fernandez, L.S. Gomez-Villalba, M.E. Rabanal, R. Fort, New
nanomaterials for applications in conservation and restoration of stony
materials: A review, Mater. Construcción. 67 (2017) 107, https://doi.org/
10.3989/mc.2017.07616.
[17] E. Zendri, G. Biscontin, I. Nardini, S. Riato, Characterization and reactivity of
silicatic consolidants, Constr. Build. Mater. 21 (2007) 1098–1106, https://doi.
org/10.1016/J.CONBUILDMAT.2006.01.006.
[18] A. Moropoulou, T. Tsiourva, P. Michailidis, G. Biscontin, A. Bakolas, E. Zendri,
Evaluation of consolidation treatments of porous stones-Application on the
Medieval City of Rhodes, in: Fourth Int. Symp. Conserv. Monum. Mediterr.,
1997: pp. 239–256.
[19] M. Zuena, E. Zendri, D. Costa, J. Delgado-Rodrigues, N. El Habra, P. Tomasin,
Calcium ethoxide as consolidant for porous limestones: influence of the
solvent, Coatings 9 (2019) 83, https://doi.org/10.3390/coatings9020083.
[20] C. Conti, I. Aliatis, M. Casati, C. Colombo, M. Matteini, R. Negrotti, M. Realini, G.
Zerbi, Diethyl oxalate as a new potential conservation product for decayed
carbonatic substrates, J. Cult. Herit. 15 (2014) 336–338, https://doi.org/
10.1016/J.CULHER.2013.08.002.
[21] H. Cogan, C. Setterstrom, Ethyl silicates, Ind. Eng. Chem. 39 (1947) 1364–1368,
https://doi.org/10.1021/ie50455a002.
[22] D. Ciofini, A.A. Mencaglia, S. Siano, A photoacoustic pulse-echo probe for
monitoring surface stone mechanical properties: Validation tests in
consolidation of Carrara marble, Constr. Build. Mater. 187 (2018) 610–619,
https://doi.org/10.1016/J.CONBUILDMAT.2018.07.225.
[23] P. Martinez, M. Soto, F. Zunino, C. Stuckrath, M. Lopez, Effectiveness of tetra-
ethyl-ortho-silicate (TEOS) consolidation of fired-clay bricks manufactured
with different calcination temperatures, Constr. Build. Mater. 106 (2016) 209–
217, https://doi.org/10.1016/J.CONBUILDMAT.2015.12.116.
[24] J. Delgado Rodrigues, A.P. Ferreira Pinto, R. Nogueira, A. Gomes, Consolidation
of lime mortars with ethyl silicate, nanolime and barium hydroxide.
Effectiveness assessment with microdrilling data, J. Cult. Herit. (2018) 43–
53, https://doi.org/10.1016/J.CULHER.2017.07.006. 29.
[25] C.A. Grissom, A.E. Charola, A. Boulton, M.F. Mecklenburg, Evaluation over Time
of an Ethyl Silicate Consolidant Applied to Ancient Lime Plaster, Stud. Conserv.
44 (1999) 113, https://doi.org/10.2307/1506723.
[26] A. Ferron The Consolidation of Earthen Surface Finishes: A Study of
Disaggregating Plasters at Mesa Verde http://repository.upenn.edu/
hp_theseshttp:// 2007 National Park, University of Pennsylvania repository.
upenn.edu/hp_theses/74.
[27] F. Stazi, A. Nacci, F. Tittarelli, E. Pasqualini, P. Munafo, An experimental study
on earth plasters for earthen building protection: The effects of different
admixtures and surface treatments, J. Cult. Herit. 17 (2016) 27–41, https://doi.
org/10.1016/j.culher.2015.07.009.
[28] V.E. García-Vera, M. Lanzón, Physical-chemical study, characterisation and use
of image analysis to assess the durability of earthen plasters exposed to rain
water and acid rain, Constr. Build. Mater. 187 (2018), https://doi.org/10.1016/
j.conbuildmat.2018.07.235.
[29] AENOR, UNE-EN 933-1:2012. Tests for geometrical properties of aggregates -
Part 1: Determination of particle size distribution - Sieveing method., AENOR,
Madrid. Spain, 2012.
[30] AENOR, UNE-EN 13139:2003. Aggregates for mortar, AENOR, Madrid. Spain,
2003.
[31] M. Lanzón, V.E. García-Vera, A.J. Tenza-Abril, V. De Stefano, Use of image
analysis to evaluate surface dispersion and covering performance of nanolime
coatings sprayed on heritage material substrates, Appl. Surf. Sci. 480 (2019)
962–968, https://doi.org/10.1016/J.APSUSC.2019.03.066.
[32] M. Lanzón, E. Martínez, M. Mestre, J.A. Madrid, Use of zinc stearate to produce
highly-hydrophobic adobe materials with extended durability to water and
acid-rain, Constr. Build. Mater. 139 (2017) 114–122.
[33] M. Drdacky, J. Lesak, S. Rescic, Z. Slizkova, P. Tiano, J. Valach, Standardization of
peeling tests for assessing the cohesion and consolidation characteristics of
historic stone surfaces, Mater. Struct. 45 (2012) 505–520, https://doi.org/
10.1617/s11527-011-9778-x.
[34] ASTM, D 3359-02. Standard Test Methods for Measuring Adhesion by Tape
Test, 2004.
[35] M. Drdácký, Z. Slížková, In situ peeling tests for assessing the cohesion and
consolidation characteristics of historic plaster and render surfaces, Stud.
Conserv. 60 (2015) 121–130, https://doi.org/10.1179/
2047058413Y.0000000116.
[36] AENOR, UNE-EN 772-11:2011. Methods of test for masonry units - Part 11:
Determination of water absorption of aggregate concrete, autoclaved aerated
concrete, manufactured stone and natural stone masonry units due to
capillary action and the initial rate of water, AENOR, Madrid. Spain, 2011.
[37] C. Hall, W.D. Hoff, Water Transport in Brick, Stone, and Concrete, Spon Press,
London, 2002.
[38] V.E. García-Vera, A.J. Tenza-Abril, M. Lanzón, J.M. Saval, Exposing sustainable
mortars with nanosilica, zinc stearate, and ethyl silicate coating to sulfuric
acid attack, Sustainability. 10 (2018), https://doi.org/10.3390/su10103769.
[39] RILEM COMMISSION 25 PEM, Test No I.1 – Porosity accessible to water, Mater.
Constr. RILEM 13. (1980) 177–179.
[40] D. Vandevoorde, V. Cnudde, J. Dewanckele, L. Brabant, M. de Bouw, V. Meynen,
E. Verhaeven, Validation of in situ applicable measuring techniques for
analysis of the water absorption by stone, Proc. Chem. (2013) 317–327.
[41] V. Vitry F. Dagrain D. Fabienne V.P. Laurent Characterization of the
consolidation effect of ethyl silicate on Maastricht limestone, in:
ConserStone 2011 – Conserv. Stone Herit 2011 Orléans, France
[42] M. Lanzón, P.A. García-Ruiz, Deterioration and damage evaluation of rendering
mortars exposed to sulphuric acid, Mater. Struct. 43 (2010) 417–427, https://
doi.org/10.1617/s11527-009-9500-4.