Applied Surface Science 504 (2020) 144195

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Applied Surface Science

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Full Length Article

Calcium hydroxide nanoparticles coatings applied on cultural heritage T

materials: Their influence on physical characteristics of earthen plasters
⁎
Victoria E. García-Veraa, Antonio José Tenza-Abrilb, Afonso Miguel Solakb,c, Marcos Lanzóna,
a
Departamento de Arquitectura y Tecnología de la Edificación, Universidad Politécnica de Cartagena, 30203 Cartagena, Spain
b
Department of Civil Engineering, University of Alicante, Alicante, Spain
c
CYPE Ingenieros S.A., Alicante, Spain

A R T I C LE I N FO A B S T R A C T

Keywords: Calcium hydroxide nanoparticles (nanolime) are a novel solution for consolidating clay-based plasters and
Calcium hydroxide adobes in cultural heritage constructions. The suspension is applied as a coating and fully compatible with
Consolidation calcareous earthen materials. Ca(OH)2 nanoparticles (NPs) are transformed into protective CaCO3 coatings due
Nanoparticles coatings to a carbonation reaction. This work aims to study the effectiveness of Ca(OH)2 NPs coatings in protecting the
Durability
surface of earthen plasters. To do this, the effect of nanolime on surface consolidation, water permeability and
Nanolime suspensions
durability in front of rain action is evaluated. It was found that the treatment improved the superficial cohesion
and reduced water permeability of plasters due to formation of calcareous coatings and partial obstruction of
pores on the surface. In contrast, the effectiveness of the treatment is not demonstrated against rainwater and
acid environments (HCl). Finally, acid rain simulation (H2SO4) led to deposition of protective films of gypsum
that might delay the plaster deterioration in the long term.

1. Introduction because of the high number of coats necessary to achieve consolidation,

Calcium hydroxide (slaked lime) has been traditionally used in a
wide range of applications including soil stabilisation, mortars, stuccos
or lime paint coatings. Saturated solutions of calcium hydroxide in
water – also referred to as limewater – are one of the earliest treatments
for strengthening building materials like porous limestone, lime-based
renders and paintings. Nowadays, calcium hydroxide nanoparticles
suspensions are replacing traditional limewater solutions as protective
coatings for the conservation of historical materials [1–4]. When Ca
(OH)2 is exposed to atmospheric CO2 a carbonation reaction occurs
leading to formation of insoluble CaCO3. The carbonation process cre-
ates relatively hard coatings (consolidation) that strengthen the un-
derneath substrate [5]. The physicochemical similarity between the
consolidating phase (coating) and the treated material (substrate) is one
of the most important aspects in conservation [6]. For that reason, the
evolution of calcium hydroxide into CaCO3 makes it a suitable surface
treatment, particularly in historical building materials with calcareous
nature. In addition, the small size of the nanoparticles facilitates the
deposition and penetration of nanolime suspensions through external
porous of the surface [7,8].
Limewater presents important drawbacks, such as its low effective-
ness due to limited solubility of Ca(OH)2 in water [7]. In addition,
the treatment may produce chromatic alterations of the substrate. The
use of Ca(OH)2 NPs is a promising alternative to traditional limewater
treatments as suggested by some authors [9]. In nanolime-based sus-
pensions treatments, water is replaced by alcohols thereby improving
the stability of the suspension and reducing the coating’s drying time
[6,10,11]. The synthesis, stability and application of calcium hydroxide
NPs have been reported in the literature [11–15]. The consolidation
efficiency of these suspensions is affected by the material’s moisture
and atmospheric factors. Hence, it has been found that moderate to
high relative humidity (75%) facilitate the conversion of portlandite
(calcium hydroxide) into CaCO3. [2]. Also, it must be noted that diluted
Ca(OH)2 NPs suspensions can be more efficient than concentrated ones
[11]. Finally, both the penetration of the coating and CO2 diffusion
through the external pores of the surface are crucial factors to increase
the effectiveness of the Ca(OH)2 NPs treatments [5].
Ca(OH)2 NPs treatments have been successfully applied in wall
paintings conservation [10,16] and artistic surfaces [8] since they do
not produce damaging products that may alter original properties of the
substrate. Likewise, the NPs have been employed on paper consolida-
tion and wood de-acidification obtaining satisfactory results [9,17]. In
architectural conservation, Ca(OH)2 NPs have proven to be effective in
stucco, adobe and stone [5]. López-Arce et al. [2] reported that

⁎
Corresponding author.
E-mail address: marcos.lanzon@upct.es (M. Lanzón).

https://doi.org/10.1016/j.apsusc.2019.144195
Received 16 November 2018; Received in revised form 3 September 2019; Accepted 26 September 2019
Available online 17 October 2019
0169-4332/ © 2019 Elsevier B.V. All rights reserved.
V.E. García-Vera, et al.
nanolime treatments improve physical properties of stones and reduce
both open porosity and pore size. Similar studies have confirmed the
effectiveness of nanolime suspensions in consolidating the surface of a
wide variety of stone materials (Limestone, Pietra di Lecce, Pietra
Serena, Basalto, Perla d’Abruzzo and Poggio Picenze, Pietra Serene and
Estoril stone) [7,11].
Although Ca(OH)2 NPs have been extensively studied in the con-
servation of stone and calcareous surfaces, their consolidation perfor-
mance in earthen materials has been scarcely discussed in the literature.
This paper is focused on testing the efficiency of Ca(OH)2 NPs coatings
on clay-based plasters, and particularly their effect on surface
strengthening, water absorption and resistance to rainwater and acid
rain.
2. Materials and methods
2.1. Materials
Two types of clay-based binders (reddish and yellowish) used in
bricks manufacturing were selected in the study. Heath et al. [18] de-
monstrated the suitability of these materials for the commercial man-
ufacturing of unfired bricks. The clay, which is the binding phase of the
plaster, was mixed with two limestone sands (sand A and sand B) using
the following proportion: 10 wt% clay, 30 wt% sand A, 60 wt% sand B.
Distilled water was added to the mixture to obtain adequate workability
of the plaster (16 wt%).
The particle size distribution of the sands was determined according
to the UNE-EN 933-1 standard [19]. The maximum size of the sand (D)
is defined as the smallest sieve opening through which more than 90 wt
% of the sand passes; the minimum size (d) is the largest sieve opening
through which less than 10 wt% of the material passes. The D/d for
sand A was 0.5/0 mm (medium grain size) and 4/0.125 mm for sand B
(coarse grain size). The percentages of filler, i.e. the amount of sand
passing through the 0.063 mm sieve, were 0.18 and 0.04 wt% for sand
A and sand B, respectively.
2.2. Methods
2.2.1. Specimens preparation, synthesis and use of Ca(OH)2 nanoparticles
Two types of specimens were fabricated to perform the experiments.
The plaster specimens were made by spreading the fresh paste on
12 × 24 cm ceramic surfaces using 1 cm thickness (Fig. 1a and b). Be-
sides, standard 4 × 4 × 16 cm specimens were made to complete phy-
sical characterisation tests [20]. The fresh paste was prepared with a
laboratory mortar mixer, poured in the moulds and after that, the
2
Applied Surface Science 504 (2020) 144195
specimens were kept in laboratory conditions (24 ± 2 °C) for seven
days. Then, the samples were de-moulded and heated at 50 ± 2 °C for
24 h to accelerate their drying.
The Ca(OH)2 NPs were synthesised according to the procedure re-
ported by Lanzón et al. [5]. The synthesis is based on a precipitation
reaction between NaOH 0.6 M and CaCl2 0.3 M solutions to isolate Ca
(OH)2:
2 NaOH + CaCl2 → Ca(OH)2 + 2 NaCl
To perform the synthesis a borosilicate reactor was used and the
process was operated at a temperature of 70 °C under N2 atmosphere to
avoid conversion of Ca(OH)2 into CaCO3 to occur. Next, the excess of
NaCl was eliminated by sequential washing with ultrapure water (Milli-
Q type 1) followed by ultracentrifugation to isolate pure Ca(OH)2.
Lastly, the solid was dispersed in dried 2-propanol (5 g/L) and sonicated
in glass flasks to increase the stability of the suspension. Before the
sonication step, the inner atmosphere of the flasks was purged with N2
to displace air and CO2 and, after that, the flasks were hermetically
closed and sealed with Parafilm®. The morphology and size of Ca(OH)2
NPs obtained by this method has been recently studied by transmission
electron microscopy, TEM. High resolution images of the NPs (HRTEM)
have confirmed that a great majority of Ca(OH)2 NPs are hexagonal
crystals and their size vary between 5 and 600 nm [5]. The earthen
specimens were externally coated with diluted suspensions of Ca(OH)2
NPs (5 g/L) using a small airbrush at a controlled distance of 20 cm
(Fig. 1d). The nanoparticles were applied in five consecutive coats
waiting 90 s to allow alcohol evaporation. Once coated, the specimens
were kept in a climatic chamber for two weeks at 23 ± 2 °C and
90 ± 2% of relative humidity to facilitate the carbonation of Ca(OH)2
NPs. Petri dishes coated with Ca(OH)2 NPs were introduced in the cli-
matic chamber and phenolphthalein solution (1%) was added to
monitor the carbonation extent of the NPs over time. The first two days
of curing, the NPs showed the characteristic pink colour of phe-
nolphthalein due to the alkaline behaviour of Ca(OH)2. After 10 days,
the colour faded considerably and above 14 days the phenolphthalein
solution remained colourless because of Ca(OH)2 conversion into
CaCO3. Finally, the earthen specimens were heated at 50 ± 2 °C for
24 h to eliminate rests of water (humidity) absorbed in the climatic
chamber.
2.2.2. Microscopy examination: TEM and SEM
Transmission electron microscopy TEM (JEOL JEM-1400 Plus) was
used to examine fresh and carbonated NPs. The samples were dispersed
in 2-propanol (0.5 g/L), sonicated 10 min and deposited on 200 mesh
grids. After solvent evaporation, the samples were examined in TEM at
Fig. 1. a and b) plaster preparation; c)
general view of the specimens with the two
test areas: control and the area with the Ca
(OH)2 NPs treatment; d) Application of the
Ca(OH)2 NPs treatment on the specimens; e)
marking process of the areas where the
peeling test was performed; f) 5 × 2 cm ad-
hesive strips used for the peeling tests.
V.E. García-Vera, et al. Applied Surface Science 504 (2020) 144195

an accelerating voltage of 120 kV.

Scanning electron microscopy SEM (Hitachi S-3500 N) was used to
examine the surface of earthen samples coated with Ca(OH)2 NPs. To
examine the samples, small fragments of the specimen were extracted
from the surface and dried at 60 °C. Then, the fragments were me-
tallised with Au-Pd (30 nm coating) in Argon atmosphere and examined
in secondary electrons. The accelerating voltage was 5 kV and the
images were taken at a working distance of 10 mm using several
magnifications.

2.2.3. Peeling test

The peeling test is used to assess the cohesion and consolidation of a
substrate and can be carried out either in laboratory or in situ. Drdacky
et al. [21] define this test as a method for making a quantified assessment
of the adhesion of a surface or near-to-surface layer to a substrate. The test
can be applied to different materials such as calcareous stones, historic
plasters, render surfaces and paint films [22]. The test consists of
measuring the amount of material adhered to a flexible adhesive tape
which is stuck to the surface and then removed. The quantity of ma-
terial adhered to the tape is a measure of the material's surface cohe-
sion.
Three specimens were made per type of clay binder and the Ca(OH)2
NPs were sprayed on a selected area of the sample. Besides, the effec-
tiveness of the treatment was compared to non-coated zones used as
control (Fig. 1c). In each case, three zones were marked on the samples
for conducting the peeling tests using rectangular frames of known area
(Fig. 1e). Therefore, three peeling tests were performed in both control
samples and areas coated with NPs. To perform the test, adhesive tape
strips of 5 × 2 cm were stuck to the surface and removed to produce
peeling on the plaster (Fig. 1f). The process was repeated 10 times in
the selected zone and the amount of adhered material was calculated as
the mass difference of the strip before and after the test.
2.2.4. Water absorption tests: Karsten tube test and capillarity test
The Karsten test, as the peeling test, can be performed both in la-
boratory and in situ. This test allows to determine the permeability of
building materials like stone, bricks, plasters or renders [23,24]. To
perform the test, a 4.5 ml graduated Karsten tube is placed on the
material’s surface and fixed on it with an adhesive to prevent water
leakage (Fig. 2a). Next, the tube is filled with water and the perme-
ability of the studied sample is measured over time. The pressure ex-
erted by the water column is comparable to the rain action on the
material [25]. Using linear regression analysis, the water absorption
coefficient was obtained from the slope of the regression lines that
better fit the observed absorption data [26–28].
Earthen materials have a high capillarity water absorption and they
Fig. 3. Material adhered in the strips of adhesive tape used in the peeling test.
deteriorate when exposed to the action of rainwater for a prolonged
period [25,29]. Hence, performing capillary water absorption tests
according to the UNE-EN 772-11 standard [30] is not always practic-
able in earthen materials as the specimens rapidly decay due to the
water action. Thus, a modified short-duration test was carried out by
placing the samples on a wet towel (Fig. 2b and 2c). The capillary water
uptake was measured over time during 1.5 min and 10 data were re-
corded to obtain a reliable quantification of the slope (R2 > 0.99). This
test is non-aggressive to the samples and allows quantification of ca-
pillary water absorption coefficients using regression analysis (slopes)
when the absorbed water (g/m2) is plotted vs time (min0.5) [26].
2.2.5. Durability tests: water, hydrochloric and sulphuric acid
The test simulates the resistance of earthen plasters formulations in
front of rainwater, acid environments and acid rain. Therefore, both
control specimens and those treated with calcium hydroxide NPs were
exposed to: i) rainwater, simulated by dripping distilled water; ii) acid
environment consisting of hydrochloric acid solution (HCl 5% w/w)
and iii) acid rain simulation using sulphuric acid solution (H2SO4 5%
w/w). In all cases, the liquid was dripped on the specimens’ surface
from a container (Fig. 2d and 2e) at uniform height during 10 min.
Twelve measurements were conducted for each type of rain simulation
and clay type, thus resulting a total of 72 tests. After exposing the
specimens to rain simulation tests, they were gently brushed to remove
rests of non-adhered powdered material on the surface. The specimens
were weighed before and after the simulations to calculate the mass
difference due to rain tests.

Fig. 2. a) Karsten tube on plaster; b) and c) Modified method for testing the capillary water absorption in earthen plasters; the images are taken after 60 s of starting
the test; d) and e) device used for the durability tests (rain, acid-rain and acid environments).

3
V.E. García-Vera, et al. Applied Surface Science 504 (2020) 144195

Fig. 4. Water absorption of plasters using Karsten tubes. a) red clay plaster; 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.)

3. Results and discussion Fig. 5. Capillary water absorption of plasters using a modified method of the
UNE-EN 772-11 standard [30]. a) red clay plaster; b) yellow clay plaster. (For
3.1. Peeling test interpretation of the references to colour in this figure legend, the reader is
referred to the web version of this article.)
The influence of the NPs treatment on the level of cohesion and
consolidation of the clay-based plasters was measured by peeling test.
Table 1
The results showed the yellow clay plaster was better cemented than Effect of Ca(OH)2 NPs coatings on Karsten and Capillary water absorption
the red one since the amount of material removed from the red plaster properties of earthen plasters.
surface was 871 µg/cm2, whereas 406 µg/cm2 were removed from the
Karsten slopes control Karsten slopes coated
yellow plaster (Fig. 3). However, when Ca(OH)2 NPs coatings were
samples, g/cm2min0.5 samples, g/cm2min0.5
nebulized on the plasters, the subsequent erosion was considerably
reduced and similar in both plasters (160 µg/cm2 and 165 µg/cm2). The Karsten tube test
effectiveness of the treatment, expressed as the reduction percentage of Red clay plaster 0.423 0.386
Yellow clay plaster 0.382 0.216
material removed from the surface, was 81.7% and 59.3%, respectively.
Capillary water CWA slopes control CWA slopes coated
The results are consistent with previous studies conducted in lime absorption samples, g/cm2min0.5 samples, g/cm2min0.5
stucco mortars, adobe and calcarenitic stone coated by Ca(OH)2 NPs, in Red clay plaster 0.059 0.053
which the reported consolidation efficiency was above 59% [5]. In Yellow clay plaster 0.060 0.059
addition, similar studies have found greater efficiencies for nanolime
suspensions applied on several types of stone [7,11].
Ca(OH)2 NPs were applied on the plasters, the absorption was reduced
to 0.382 g/cm2 min0.5 and 0.216 g/cm2 min0.5.
3.2. Water absorption: Karsten test

The effect of nanolime coatings was also evaluated by measuring the
permeability of non-coated and coated earthen plasters (Fig. 4a and
4b). The time needed to consume the water column was between 6 and
8.5 min and, therefore, similar to that observed in similar tests con-
ducted for adobe samples (8 min) [25]. The water absorption coeffi-
cients were obtained by linear regression analysis (slopes) by plotting
water absorption against the square root of time [26]. As to the control
sample, the red plaster showed higher absorption (0.423 g/cm2 min0.5)
than the yellow one (0.382 g/cm2 min0.5). The linear regression ana-
lyses (slopes) confirm that clay-based plasters are not adequate mate-
rials to provide long-term protection against water [28,29]. When the
3.3. Water absorption: Capillary tests
Fig. 5 and Table 1 show capillary water absorption results using the
modified method explained in 2.3.2 [30]. As can be seen from Table 1,
the coefficient of water absorption of red and yellow plasters was si-
milar (0.059 g/cm2 min0.5 and 0.060 g/cm2 min0.5). After depositing Ca
(OH)2 NPs, the coefficients were slightly reduced to 0.053 g/cm2 min0.5
and 0.059 g/cm2 min0.5. Although the performance of Ca(OH)2 NPs
coatings is not comparable to that of waterproofing coatings, the results
suggest the NPs may obstruct some pores of the surface. A similar be-
havior of the treatment has been found in water absorption tests

4
V.E. García-Vera, et al.
Fig. 6. a) TEM image of hexagonal Ca(OH)2 nanocrystals; b) a major fraction of Ca(OH)2 NPs is transformed into denser CaCO3 after 12–14 days (darker rhom-
bohedral phase on the left); c) SEM image at 500x showing CaCO3 coatings on plaster samples (arrow); d) Same coating at 2000x.
conducted on nanolime-coated stone samples [7,11].
3.4. TEM and SEM examination
The absorption decrease observed by depositing Ca(OH)2 is attrib-
uted to formation of relatively dense CaCO3 coatings obstructing pores
and voids on the surface. Fresh Ca(OH)2 NPs are initially hexagonal in
shape as corroborated by TEM images (Fig. 6a), but after 12–14 days
they are transformed by CO2 into CaCO3 particles (Fig. 6b). Fig. 6c and
6d show the formation of CaCO3 NPs, thereby reinforcing the surface of
clay-based plasters. As the sprayed coatings are made of pure Ca(OH)2
NPs they are transformed into CaCO3 due to carbonation. It is worth
noting that the characterisation of both clay-based binders has been
previously reported by the authors [28] using X-ray diffraction (XRD)
and X-ray fluorescence (XRF) analysis. The minerals detected by XRD
were quartz, gypsum, calcite, muscovite and kaolinite, whereas XRF re-
vealed that the clay-based binders were mainly composed of SiO2 and
Al2O3 along with common soil constituents, such as CaO, Fe2O3, K2O
and MgO [28]. Therefore, the existence of calcite (CaCO3) in both
plasters is consistent with the applied treatment, which is transformed
on the surface into CaCO3.
3.5. Durability tests: water, hydrochloric (5% w/w) and sulphuric acid (5%
w/w)
The role of Ca(OH)2 NPs in protecting clay-based plasters was
evaluated by rain simulations tests (Fig. 7). The rain erosion was clear
and confirmed the low resistance to rain of clay-based plasters [31].
After 10 min of dripping either distilled water or acidic solutions the
erosion percentage was visible and reached up to 3.0%. The magnitude
5
Applied Surface Science 504 (2020) 144195
of the erosion is explained by the combined action of chemical prop-
erties of water (solvent) and acids (destructive) along with the physical
stress (impact) caused by the drop on the surface [25,28]. Both control
and NPs-coated plasters did not show significant differences in rain
erosion tests and hence, we cannot conclude that Ca(OH)2 NP are ef-
ficient solutions to extend the durability of earthen plasters against
rain. The damaging effect of rain tests was visually confirmed by optical
microscopy examination using a digital microscope Dino-Lite Edge
(Fig. 8). Indeed, a number of voids and defects were observed in all
cases and especially, in plaster’s attacked by HCl rain. In contrast,
plasters attacked with H2SO4 rain showed the best performance
(0.3–0.5% erosion) despite the oxidising nature of sulphuric acid. In
this case, the formation of protecting gypsum layers deposited on the
plaster’s surface may explain the small alteration of samples attacked by
H2SO4 [28]. The gypsum layer creates, however, a fading effect which
is clearly observed under the microscope (Fig. 8c and 8f), and also with
the naked eye. The surface discoloration or fading due to gypsum for-
mation has been confirmed by XRD [28,32]:
CaCO3 + H2SO4 + 2H2O → CaSO4 2H2O (gypsum) + CO2 + H2O
4. Conclusions
The role of Ca(OH)2 NPs coatings on physical characteristics and
durability of earthen plasters is analysed in this paper. The coatings’
performance is evaluated for three important properties of plasters: i)
surface cohesion and consolidation; ii) water absorption; and iii) rain-
water and acid rain resistance. From the obtained results, the following
conclusions can be drawn:
V.E. García-Vera, et al. Applied Surface Science 504 (2020) 144195

• Surface resistance tests confirm that Ca(OH)2 NPs are efficient

coatings to consolidate the surface of earthen materials. The erosion
of coated plasters (peeling tests) is significantly reduced when
compared to non-coated samples used as reference. Therefore, the
coatings can be used in real scenarios to improve the consolidation
of cultural heritage materials made of earth. Moreover, they fulfil a
fundamental principle of conservation science since coating and
substrate are chemically similar and compatible.
• Both Karsten and capillary water absorption tests show that nano-
lime coatings may assist to reduce the water absorption of earthen
plasters. The absorption decrease, which is not comparable to that
observed in waterproofing coatings, might be explained by deposi-
tion of CaCO3 clusters obstructing pores on the surface. Therefore,
the maintenance and conservation of cultural heritage materials
made of adobe or earthen plasters can be improved using the
treatment.
• The efficiency of Ca(OH)2 NPs as protective coatings in front of
rainwater, acid rain and acid environments is not demonstrated.
Rain durability tests showed negligible differences between non-
coated and coated samples.
• An important conclusion of the study is the dissimilar behaviour of
earthen plasters when exposed to distilled water, HCl and H2SO4
rain. In this regard, H2SO4 rain produced the lowest erosion fol-
lowed by rainwater and HCl rain. The small erosion observed in
samples attacked by H2SO4 is explained by formation of protective
coatings of CaSO4 2H2O (gypsum) due to chemical reaction between
H2SO4 and calcium carbonate, CaCO3, from earthen plasters.
However, further studies are needed for confirming the long-term
protection of gypsum coatings since CaSO4 2H2O is partially soluble
in water.

Acknowledgments
Fig. 7. Mass variation percentage in samples exposed to rainwater and acid-
rain a) red plaster; b) yellow plaster. (For interpretation of the references to
The authors want to express their gratitude to Morant Dos S.L. for
colour in this figure legend, the reader is referred to the web version of this
providing the clay used in this study.
article.)

Fig. 8. Erosion tests carried out on non-coated and coated samples: a) effect of distilled water (simulating rainwater) on non-coated samples; b) HCl 5% w/w attack
on non-coated sample produced major erosion on the surface; c) H2SO4 (5% w/w) attack on non-coated samples and formation of beige deposits due to gypsum; d)
effect of distilled water on nanolime-coated samples; e) visible alteration in nanolime-coated samples attacked by HCl (5% w/w); f) gypsum deposits due to H2SO4
(5% w/w) attack on nanolime-coated plasters.

6
V.E. García-Vera, et al.
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