Construction and Building Materials 197 (2019) 175–184

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Construction and Building Materials

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

Geopolymers and polymers in the conservation of tile facades

Sara Moutinho a,⇑, Cristiana Costa b, Ângela Cerqueira c, Fernando Rocha b, Ana Velosa d
a
Civil Engineering Department, RISCO, University of Aveiro, Portugal
b
Geosciences Department, GeoBioTec & RISCO, University of Aveiro, Portugal
c
Geosciences Department, GeoBioTec, University of Aveiro, Portugal
d
Civil Engineering Department, RISCO & GeoBioTec, University of Aveiro, Portugal

h i g h l i g h t s

 Geopolymers visual observation showed that the GEO-MKZL had the better behaviour (without cracking or salt formation).
 Compressive strength showed that Geo-MKZL have a desired compacted structure.
 Polymers showed a better behaviour only in the bonding tile fragments.
 Geopolymers showed a better adhesion to ceramic body than polymers.
 Geopolymers showed potential to be applied into ceramic glazed tiles.

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

Article history: The most commonly used materials to fill gaps/lacunae in glazed tiles are lime mortars or organic resins,
Received 7 June 2018 which have some disadvantages regarding their compatibility and durability, failing to guarantee the
Received in revised form 22 October 2018 desired characteristics. Therefore, there is a need to develop new materials with compatible characteris-
Accepted 7 November 2018
tics, able to withstand exposure to variations in climatic conditions. This scientific work focuses on the
Available online 28 November 2018
possibility of using geopolymers, aiming to evaluate the possibility of the use of these materials in the
intervention process of historic tiles conservation as compatible materials that may be used to fill gaps.
Keywords:
Different geopolymer pastes were developed changing the source of aluminosilicates, the type of alkaline
Tiles
Geopolymers
activators and the pH. To evaluate the geopolymers, polymers and tiles, several tests were carried out.
Polymers The results suggest that the geopolymers are a possible option for the filling of tile gaps, given the char-
Conservation acteristics that can be achieved, ensuring compatibility and durability properties.
Lacunae Ó 2018 Elsevier Ltd. All rights reserved.

1. Glazed tiles as a coating of facades
Glazed tiles (azulejos) are characteristic elements of the Por-
tuguese built heritage, being part of the historical identity of Por-
tuguese culture [1]. They are characterized by their dimensions,
their aesthetic expression and also by the raw materials used
and manufacturing procedures employed [2,3], which condition
the performance of the parts produced in terms of water beha-
viour, wear and resistance. This material that started to be used
in Portugal is composed by two parts – a tardoz (ceramic body) –
and a glazed surface [4]. The composition of the ceramic body
influences the performance of the tile, being evident that a new tile
and an old ceramic tile have different characteristics and conse-
⇑ Corresponding author.
E-mail addresses: sara.moutinho@ua.pt (S. Moutinho), cristianacosta@ua.pt
(C. Costa), angelamcerqueira@ua.pt (Â. Cerqueira), tavares.rocha@ua.pt (F. Rocha),
avelosa@ua.pt (A. Velosa).
quently different performance, due both to an initial difference in
materials and porous structure and the action of degradation
agents and adverse environmental conditions [4]. Therefore, it is
important to study the behaviour of old tiles and to improve the
properties of the materials used in the conservation of the built
heritage, ensuring the compatibility of the employed solutions.
For several centuries Netherlands, Italy, England and Portugal
tile claddings have been used although they express differences
in terms of the decorative elements and also of architectural
expression [5]. Since the 16th century they have been used in
the national territory and it in the mid-19th century were consid-
ered a traditional coating material in several Portuguese cities,
with a particularly pronounced expression in city of Oporto.
In order to meet the evolution in terms of building demands,
there was a differentiation in tile production, resulting from the
technological innovations in ceramic production. Through the
times there have been changes concerning the pictorial layer of
the tile as well as the ceramic body.

https://doi.org/10.1016/j.conbuildmat.2018.11.058
0950-0618/Ó 2018 Elsevier Ltd. All rights reserved.
176 S. Moutinho et al. / Construction and Building Materials 197 (2019) 175–184
The ceramic tile is a material that is surely exposed to degrading
agents, and it is important that conservation and restoration
actions take place in order to preserve the authenticity of the wall
surface respecting the typology and morphological characteristics
of the architecture and to ensure the reversibility of the materials
without compromising the possibility of future interventions.
Simultaneously there is a need to develop new materials present-
ing sustainable properties, compatible with old tiles as long as they
meet the requirements such as to avoid the degradation of pre-
existing materials and contribute to the protection of the walls
regarding water actions, chemical substances and mechanical
actions and contribute to durability of the whole. It was verified
that the absence of materials specifically developed for the inter-
vention in ceramics has led to the selection and use of inadequate
solutions that are readily available in the market. Therefore a vari-
ety of materials, such as organic resins have been used and obtain-
ing compatible solutions is an issue still in the research process.
2. Intervention criteria on tiles
In built heritage intervention action there is a need to identify
all the intrinsic values and to consider the criteria, according to
Athens Charter (1931), Venice Charter (1964), Restoration Italian
Charter (1972) and Krakow Charter (2000). These charters are a
result of the development of international documents by entities
such as ICOMOS and UNESCO [6], based on the respect for the
integrity and authenticity of the built heritage (art°9°, Venice Char-
ter), conservation should be a permanent process (art. 4, Venice
Charter). Taking into account the Athens Charter (point VII) and
the Italian Charter for conservation (art. 2), it is important to con-
sider the environmental aspects in built heritage intervention
actions. In this study the compliance with deontological rules that
aim to ensure authenticity, compatibility, reversibility and durabil-
ity of materials is followed [4,6]. Compatibility is a highly relevant
factor in the context of the present study. It is generally understood
that compatibility is dependent on the characteristics of the archi-
tectural elements and original materials and the specific conditions
to which the building or building element is subject. To follow this
concept that new materials do not lead to degradation of pre-
existing materials. Furthermore, in each particular case it is neces-
sary to take into account issues such as existing humidity, climatic
conditions (relative humidity, variations in temperature, wind,
rainfall intensity) and environmental aspects related to pollution
and the maritime environment [7].
3. Geopolymers applied to ceramic glazed tiles
Geopolymers are inorganic materials from mineral origin, com-
posed of a precursor, an alkaline activator and a solvent. The pro-
cess of geopolymerization involves a chemical reaction that takes
place in an alkaline medium, resulting in the formation of inor-
ganic polymers that have silicon and aluminum as main con-
stituents (Si + Al), connected by oxygen ions. The solution
becomes alkaline through the use of activators such as sodium
and potassium hydroxides and/or sodium and potassium silicates.
Depending on the composition, geopolymer characteristics can be
attained in terms of physical, chemical and mechanical perfor-
mance [8]. One of the most relevant researcher on geopolymers
was Joseph Davidovits [9], who developed binders obtained
through the alkaline activation of kaolin and metakaolin.
The inorganic materials resulting from this activation, com-
pared with organic pastes or with Portland cement present positive
characteristics towards the possibility of use for filling gaps in tiles
[4,10], attaining possible results in terms of compatibility, durabil-
ity and sustainability [11]. Nowadays, Portland cement is still
widely used in the construction industry [9]; however, during its
production there is a significant release CO2 and its use does not
ensure compatibility and durability with the original materials
when applied in conservation/restoration intervention. Compara-
tively geopolymers have an adequate mechanical behaviour, an
adequate ceramic body adhesion, low water vapor permeability
and adequate resistance to chlorides and fire [12]. These character-
istics can be further improved by the use of additives in the formu-
lation geopolymers [13].
This work focused on the study of polymeric materials and
geopolymeric formulations based on research in progress
[4,10,14,15], applied in several tiles in need of intervention and
allowing the analysis of the advantages of the use of this material
in the restoration of ceramic tiles.
4. Materials and methods
4.1. Materials
A group of samples representative of old ceramic tiles and their
use in built heritage were selected. The samples were identified
and distinguished by typology according to the glaze pattern, being
identified by letters (A – N). In this study there are approximately
four samples for each typology (e.g.: F1, F2, F3, F4). The total of
samples was submitted to physical and chemical tests (Table 1).
In the methodology of intervention for tile lacunae filling, some
current products that could be used in the bonding of ceramic frag-
ments were tested in gaps in the ceramic body (Fig. 1). The filling
materials used were organic resins such as an epoxy resin (HB Epo-
surf 2 and Icosit K101N), a polyester resin (Sintolit, Pro-Fill and
Woodfiller), synthetic modeling paste (Darwin paste) and acrylic
resin (Paraloid B-72). The materials were supplied by the company
Sika and their preparation took place according to the technical
data sheets (Table 2).
In the geopolymeric formulations (Table 4) Geo-MKZL [14],
Geo-MK1000 [15] and Geo-MK1000C two variants were consid-
ered: chemical composition and pH value of the system. The con-
trol of this property, assuming values 10–12 (moderately basic)
allows distinct or improved aggregation of the membrane of the
geopolymer during its processing, avoiding the occurrence of
cracks in the material [16].
Metakaolin (Argical-1200S and Argical-1000) was used as main
precursor in the geopolymer formulations. The main constituents
of metakaolin are SiO2 and Al2O3 as shown in Table 3. One of the
formulation employed natural zeolites (clinoptilotite-Na) as addi-
tives due to the adsorbent so as to evaluate the properties of this
material. The zeolite is a group of minerals that has advantages
as a binder in the geopolymer composition, characterized by the
high specific surface, adsorption and cation exchange capacity
[14]. This material has as main constituent SiO2 (Table 3) and with
the feldspars may immobilize materials in the geopolymer matrix
acting as a binder [17]. Chemical composition was assessed by X-
Ray Fluorescence using a Panalytical Axios PW4400/40 X-Ray Flu-
orescence spectrometer for major and trace elements; Loss on Igni-
tion (LOI) was also determinated.
Geopolymers were prepared using commercial metakaolin
Argical-M 1200SÒ (D50 = 1.5, bulk density = 400 g.dm 3) and
Argical-M 1000Ò (D50 = 6, bulk density = 800 g.dm 3), zeolite
(ZeoBau micro 50, Zeocem, Slovakia, CEC = 83 meq/100 g,
SSA = 1663 m2/kg, particle size 0–0.05 mm, bulk density = 500–
600 g.dm 3), sodium silicate (Sigma-Aldrich), and sodium hydrox-
ide (pellets, reagent grade, BASIC) and calcium hydroxide as alka-
line activators for dissolution of aluminosilicate (Table 4). Water
was the reaction medium.
 S. Moutinho et al. / Construction and Building Materials 197 (2019) 175–184 177

Table 1
Physical characteristics of tile samples.

Tile typology Sample Production Application century Localization Dimensions (cm)

Semi-industrial Az-F Fonte Nova (Aveiro) XIX Exterior wall 14,2  14,2  1,0
Az-G Fonte Nova (Aveiro) XIX Exterior wall 14,3  14,3  1,1
Az-L n.d. XIX Exterior wall 14,0  14,0  0,8
Az-M A. Costa, Devesas (Porto) XIX Exterior wall 14,1  14,1  0,6

n.d.- Not defined.

Table 4
Geopolymeric formulation composition.

Geopolymeric formulations composition

Geo-MKZL  Argical-M 1200SÒ and natural Zeolite (ZeoBau micro 50)
 Sodium hydroxide and sodium silicate
 pH 14
Geo-MK1000  Argical-M 1000Ò
 Sodium hydroxide and calcium hydroxide
 pH 14
Geo-  Argical-M 1000Ò
MK1000C  Fly ash (burning of cork - DOFcork)
 pH 11 e pH 12

Fig. 1. Tiles lacunae: collage of fragments and filling gaps.

In the preparation of geopolymers specimens, zeolite (0% and
50%) was added to as metakaolin replacement. Sodium hydroxide
and hydrated sodium silicate were added in the ratio of 1:1.
Geo-MKZL was formulated with metakaolin 1200S and zeolite
(1:1 ratio) with the addition of alkaline activators [14]. Geo-
MK1000 was prepared with the metakaolin 1000 and the addition
of sodium hydroxide and hydrated sodium silicate following molar
ratio 0,4Na:0,5Ca:1Al [15]. Geo-MK1000C was formulated with
metakaolin 1000 with addition of fly ash (burning of cork, provided
by DOFcork) essentially composed of calcium carbonate (Fig. 2) and
a pH control of the final solution (pH of 11 and pH of 12). Fly ash
XRD analysis was determined using a PANalytical diffractometer,
model Empyrean. The share of each phases was determined by
Rietveld method. The measurements were performed using a
monochromatic radiation of a wavelength corresponding to the
Ka1 copper emission line in the range of 5–90°, 2h angular scale.
4.2. Methods
4.2.1. Experimental methodology
Fig. 3 presents the materials and the several tests realized.
4.2.2. Water absorption by capillarity
The capillary absorption test consists in placing the specimens
in contact with water, measuring the variation of mass as a func-
tion of the square root of time. After drying and weighing each
sample, there is an immersion in water for a period of time until
the mass stabilizes and removal from the water followed by weigh-
ing. The difference between the initial mass (dry sample) and the
final mass (saturated sample) provides the value of water absorbed
by capillarity and the capillary coefficient is obtained from the ini-
tial slope of the graph of periodic weighing [18]. Tiles samples and
filling products (Darwin paste, HB Eposurf 2, Pro-fill, Woodfiller
and Geo-MKZL) were tested because the waterproofing efficiency
is analyzed by capillary water absorption test and it was carried
out based on the standard EN 1015-18 [19].
4.2.3. Accelerated artificial ageing
Accelerated artificial ageing was performed under a procedure
adopted in the civil engineering laboratory of the University of
Aveiro to simulate changes in the temperature and relative humid-
ity conditions that may occur when materials are applied on wall
surfaces and ESPEC ARL-680 was used a climatic testing machine.

Table 2
Polymeric pastes characteristics.

Polymeric Resins Resin Composition

Ò
HB Eposurf 2 (A + B) Epoxy A (Resin) 100 g B (Hardener) 30 g
Sintolit (A + B) Polyester A (Resin) 100% B (Hardener) 2–3%
IcositÒ K101N (A + B) Epoxy A (Resin) 79 g B (Hardener) 21 g
Darwin Paste Synthetic modeling paste Paste
ParaloidÒ B-72 Acrylic Dissolution in acetone (50%)
Pro-Fill (A + B) Polyester A (Resin) 100% B (Hardener) 2%
Woodfiller (A + B) Acrylic A (Resin) 100% B (Hardener) 2%

Table 3
Chemical analyses of materials.

SiO2 Al2O3 Fe2O3 MgO CaO Na2O K2O TiO2 P2O5 LOI
% % % % % % % % % %
M 1200S Ò 51,94 39,83 2,09 0,31 0,13 0,09 1,21 1,66 0,07 2,43
M 1000 Ò 53,67 39,88 1,45 0,38 0,14 0,09 0,68 2,22 0,05 1,22
Zeolite 69,68 11,88 1,63 0,92 2,99 0,29 3,75 0,21 0,03 8,42
178 S. Moutinho et al. / Construction and Building Materials 197 (2019) 175–184
Fig. 2. X-Ray Diffraction patterns of fly ash (cork residue by DOFcork).
Samples
collecting
Tiles samples Products
Water absorption
Water absorption by cappillarity artifitial ageing*
by cappillarity
Tensile
strenght*
*Products applied to tiles.
Fig. 3. Materials and methods scheme.
Tile samples were submitted to two sets of summer and winter
cycles consisting of heating/cooling and humidification/cooling.
Each cycle of 7 h and each series was repeated 4 times and had a
duration of 28 h, and a drying time of not less than 8 h. In total
each series lasted at least 36 h. The summer cycle consists of the
variation of temperature and relative humidity, between 10 °C to
60 °C and between 40% to 95% RH. The temperature variation in
the winter cycle occurs between 10 °C and 30 °C, in which the
relative humidity reached 100% for positive temperatures and in
cases where the temperature was negative, there was no relative
humidity.
Accelerated artificial aging allows the study of the performance
of the materials simulating exposure conditions. Tiles samples
were prepared with intervention in the collage of ceramic frag-
ments and volumetric reintegration of the ceramic and glaze body
(Fig. 4). The intervention was performed with different polymeric
and geopolymeric materials (Table 5).
4.2.3.1. Preparation of specimens. The procedure for bonding frag-
ments consisted on the application of organic and inorganic glues,
with/without additives (such as pyrogenic silica and sand), in the
fracture segment and subsequent drying. The filling of the gaps
was due to the loss of ceramic and glaze of the tiles, with applica-
tion of filling materials in the empty space (Fig. 5).
Sample 1. Initially Paraloid B-72 was prepared by dissolution in
acetone (50%) and applied in the bonding zone of fragments. In the
glaze Paraloid B-72 was used as an additive for improvement of the
consistency of the final product. When used as volumetric filling,
Paraloid B-72 was applied with 120/200 sand addition.
Sample 2. The material applied in sample 2 was an epoxy resin
(HB Eposurf 2). In the bonding process this product was applied
without additives. For the reconstitution of the glaze pyrogenic sil-
Accelerated
ica was added to HB Eposurf 2 and in the volumetric filling calcium
carbonate was additionally, leading to a higher degree of com-
paction and a lower shrinkage of the material.
Compressive Sample 3. Sintolit (polyester resin) was applied in this sample. In
strenght the fragments, reintegration of the glaze and volumetric filling this
product was applied with the addition of calcium carbonate in
order to improve the compaction of this filling materials. It was
possible to improve the properties of the product, such as the com-
paction and alkalinity of the solution.
Sample 4. The product used in the restoration of sample 4 was
Pro-fill (polyester resin). This product was supplied by Sika, with
the purpose of studying the applicability of this product in old
materials, such as glazed tiles.
Sample 5. Icosit K101N (epoxy resin) constituted by component
A (resin) and B (hardener) was applied in sample 5. The same mix-
ture was used in the bonding of the ceramic fragments, in the rein-
tegration of the glaze and in the filling of it is not necessary to use
solvents and it a strong bonding was achieved with a ratio of the
mixture being 79:21 (A: B) (safety data sheet of the product).
Sample 6. In sample 6 Sintolit with addition of Darwin paste was
applied in the fracture zone, in the reintegration of the glaze and of
the ceramic body. The proportion of the blend was 62% of Sintolit
and 38% of Darwin’s paste, because it is an amount of additive that
influences the properties of Sintolit increasing its consistency.
Sample 7. In sample 7 geopolymer was applied in order to study
its viability as a filling material. After the degradation analysis of
the geopolymers with different compositions, Geopolymer Geo-
MKZL was applied because it presented higher resistance in the
curing process under influence of temperature and HR.
4.2.4. Tensile strength
The tensile strength standard test [20] was adapted to these
ceramic materials in order to allow the analysis of the maximum
tensile strength that tile sample withholds at the bonding interface
 S. Moutinho et al. / Construction and Building Materials 197 (2019) 175–184
Fig. 4. Tile’s intervention (sample 2).
Table 5
Products applied as filling material.
Tiles samples Products
1 Paraloid B-72 (with sand A120/200)
2 HB Eposurf 2
3 Sintolit (with calcium carbonate)
4 Pro-Fill
5 Icosit K101N
6 Sintolit (with Darwin paste)
7 Geo-MKZL
with the filling material. Making it possible to conclude on the
adhesion strength of the applied materials. For this test the SHI-
MADZU: AG-X/R universal machine was used. The samples ana-
lyzed in the accelerated artificial aging test were prepared for
this test. The samples were cut with dimensions appropriate to
the equipment where the test was performed, with dimensions
of 14  2  1 cm resulting in three samples of each tile (Fig. 6).
4.2.5. Compressive strength
The specimens were prepared into 3  6 cm (b  h) cylindrical
molds (Fig. 7) and exposed to controlled curing conditions,
(23 ± 2)°C and (50 ± 5)% [17]. A specimen of each geopolymeric for-
mulation were tested at 7, 14, 28 and 60 days of curing and the
SHIMADZU: AG-IC universal testing machine was used. The testing
procedure was carried out with a maximum force of 5 kN at the
speed of 50 N/s as per the standard EN 1015-11 [20]. This test
allows to analyze the influence of the composition of the geopoly-
Fig. 5. Filling material used and prepared samples.
179
mers in the compaction of the structure obtained by these materi-
als, factor that influences the formation of resistant structures.
For a better understanding of the tests and samples under study
Table 6 was elaborated with the adopted methods and standards
and the detailed materials.
5. Results and discussion
5.1. Visual observation of the performance of formulations
After 15 days of curing time to control the possible develop-
ment of reactions experienced by the geopolymeric materials
(Fig. 8) exposed to temperature conditions of (23 ± 2) °C and rela-
tive humidity of (50 ± 5)%, deterioration of some materials being
verified by the occurrence of cracking and formation of salts
(Geo-MK1000 and Geo-MK1000C pH 12). However Geo-MKZL
and Geo-MK1000C (pH 11) did not show cracks. Therefore, it is
possible to verify that these temperature and relative humidity
conditions influence the performance of the materials and the cur-
ing temperature is known to be an influencing factor in the synthe-
sis of geopolymers formulations [21–23]. The reaction speed
increases with the curing temperature leading to different proper-
ties such as the compressive strength which usually increases with
the curing temperature [24], being the ideal temperature between
60 °C and 80 °C.
Taking into account that the chemical composition and varia-
tion of pH can result in the formation of salts and appearance of
cracks, it is also clear that water amount can also influence the
structural stability of geopolymers [25–27]. In the formulations
under study, the Geo-mkzl presented a better behavior followed
by Geo-MK1000C that requires a further study in terms of its com-
position to obtain a more compacted structure.
5.2. Water absorption by capillarity
According to standard EN 1015-18 (2002) [19] several tile sam-
ples from different production units and similar glazed units were
tested. For each tile typology, different samples were analyzed con-
sidering the average values obtained, determining a final value of
capillary coefficients between 1 and 6 kg/m2.h1/2 (Table 7).
Tiles usually have a glazed layer leading to low water absorp-
tion values by capillarity and water vapor permeability [16]. The
variation of the capillary values obtained may probably be justified
180 S. Moutinho et al. / Construction and Building Materials 197 (2019) 175–184

Fig. 6. Samples prepared for the tensile strength test.

Therefore, it was possible to study the compatibility between the

Fig. 7. Geopolymer specimens prepared.
by the difference in the manufacturing process and the techniques
used [29].
Filling materials (both polymers and geopolymers) were also
subjected to this test, resulting in a comparative analysis of capil-
lary coefficients between materials and historical tiles (Table 7).
infill materials and the ceramic body.
All materials pastes have higher capillary coefficient (>10 kg/
m2.h1/2) than the historical tiles which can be justified by the exis-
tence of glaze and by closed pore system. According to Table 7 it is
possible to verify that the values obtained for the capillary coeffi-
cient of HB Eposurf 2 as filling material is the closest to that
obtained for the ceramic body being the most compatible material.
The Geo-MKZL presented the highest absorption value obtained
(72,45 kg/m2.h1/2), explained by the geopolymers being character-
ized by open pore system. These microstructural differences could
explain the high capillary coefficient of materials pastes compared
with the ceramic body. The remaining geopolymer formulations
were not tested, since their high absorption capacity led to their
disintegration. In terms of the polymeric materials, the most criti-
cal result of the water action was verified for the Darwin paste
with the highest value (103,21 kg/m2.h1/2) followed by Woodfiller
which can be justified by the degree of porosity that these materi-
als present [28]. The Darwin paste has a high value due to the very
hygroscopic characteristics that it presents. Pro-Fill and HB Eposurf
2 have the lowest values. Therefore it is concluded that the com-
patibility and durability is presented by the epoxy resin HB Eposurf
2 by performance of this material and presents a capillary coeffient
closest to the values obtained by the tiles (11,72 kg/m2.h1/2).

Table 6
Tests performed and materials used.

Methods Standard Tiles Products

Water absorption capillary EN 1015-18 A, B, C, D, E, F, G, H, I, J, K, L, M, N  Profill
 Woodfiller
 HB Eposurf 2
 Darwin paste
 Geo-MKZL
Accelerated artificial ageing Experimental process of Civil department Sample 1 (Tile M) 1- Paraloid B72 + Sand 120/200
Sample 2 (Tile G) 2- HB Eposurf 2
Sample 3 (Tile F) 3- Sintolit
Sample 4 (Tile F) 4- Profill
Sample 5 (Tile L) 5- Icosit K101N
Sample 6 (Tile G) 6- Sintolit + Darwin Paste
Sample 7 (Tile G) 7- Geo MK-ZL
Tensile strength EN 1015-11 Sample 1 (Tile M) 1- Paraloid B72 + Sand 120/200
Sample 2 (Tile G) 2- HB Eposurf 2
Sample 4 (Tile F) 4- Profill
Sample 5 (Tile L) 5- Icosit K101N
Sample 6 (Tile G) 6- Sintolit + Darwin Paste
Compressive strength EN 1015-11 – Geopolymers pastes
 Geo-MKZL
 Geo-MK1000
 Geo-MK1000C
 S. Moutinho et al. / Construction and Building Materials 197 (2019) 175–184
Geo-MKZL Geo-MK1000
(pH 14) (pH 14)
Fig. 8. Geopolymers with 1 day exposure (left) and 15 days exposure (right).
Table 7
Coefficients of water absorption by capillarity obtained.
Capillary coefficients (kg/m2.h1/2)
Tiles Polymers
F 5,79 Darwin paste
G 5,79 HB Eposurf 2
L 2,17 Pro-Fill
M 1,44 Woodfiller
n.d.-Not defined.
5.3. Accelerated artificial ageing
The samples of tiles under study presented a similar state of
degradation prior to the end of ageing cycles. Therefore, restoration
materials were applied to tile samples for volumetric reintegration
and bonding of ceramic fragments. The visual result of the samples
is shown in Fig. 9.
In sample 1 there occurred a deformation in the filling zone and
at the temperature of 60 °C in which the acrylic filling material
enters the plastic phase. For this reason Paraloid B-72 should be
applied and exposed in controlled environmental conditions, for
example, on the interior wall surfaces. In sample 2, it was verified
that the material used resists demanding environments (high tem-
peratures and low temperatures), because it resisted in the collage
of the ceramic fragments and in the filling, presenting only super-
ficial change. As a reintegration material HB Eposurf 2 did not
work, creating detachment of the glaze. In the case of Sintolit
applied in sample 3 it was verified that it did not withstand the
variations of the climatic conditions, showing low resistance both
in the glueing technique and in the filling of gaps, since disintegra-
tion occurred in both cases. However, in the reintegration of the
glaze, despite the presence of air bubbles, the material remained
cohesive and there was no loss of material. Pro-Fill used in sample
4 did not present an adequate performance, since it presented
inadequate tile restoration characteristics, not having compatible
properties in the filling of gaps and adhesion in old semi-
industrial tiles. The compatibility of these materials is ensured
through the performance of filling materials which should present
results similar to old ceramics, not compromising the pre-existing
materials. Regarding the physical and mechanical properties that
this material presents, it becomes clear that they translate higher
values than those of the tile, so there is no compatibility at the
ceramic/material interfaces. In sample 5 with application of Icosit
K101N no loss of product occurred resulting in an adequate binder
for the ceramic. In the filling zone, it registered yellowing without
affecting the characteristics of the tile. Also, volumetric expansion
occurred which is justified by the hydration reaction that occurs
after the application of the material and by the action of heat, this
factor contributes to the occurrence of this degradation in the
materials. In sample 6 in which Darwin’s paste was added to Sin-
tolit, the tile resisted to the alternation of conditions to which it
181
Geo-MK1000C Geo-MK1000C
(pH 12) (pH 11)
Geopolymers
103,21 Geo-MKZL 72,45
11,72
18,49 Geo-MK1000 n.d.
19,47 Geo-MK1000C n.d.
was subjected, not suffering cracks, yellowing, peaks or bubbles.
Only in the last cycle, the material applied in the filling zone disin-
tegrated and the tile underwent degradation in the glaze.
Geo-MKZL, used in sample 7, presented material loss values of
approximately 10% of its initial mass at the end of the test. Photo-
graphic record as shown in the Fig. 10. It was not possible to apply
this test to the other geopolymers, since the curing time of these
materials did not allow this.
In Fig. 11 it is still possible to analyze that in the filling zone the
Geo-MKZL has undergone degradation resulting in cracking of the
filling material, not being a good result. It is important that the
geopolymer exhibited promising properties such as adhesion to
the ceramic body, which was superior to that ensured by the
organic materials.
5.4. Tensile strength
In terms of tensile strength, it was possible to study the mate-
rials used in the bonding of tile fragments (Fig. 12) and the values
obtained are shown in Fig. 13. The materials were applied in the
fracture zone as uniformly as possible, in each sample. The samples
under study were those previously submitted to the accelerated
artificial ageing test. It was not possible to analyze the perfor-
mance of samples 3 and 7, since these tiles did not withstand the
variation of temperature and relative humidity conditions in the
accelerated artificial ageing test, as both of which were frag-
mented. In the remaining samples, the degradation of the materials
is also evident. Sample 2 cracked in the contact surface between
the tile and the fixation of the equipment leading to the conclusion
that the strength of the tile material is lower than that of the
applied glue (HB Eposurf 2, epoxy resin). This is contrary to one
of the principles of restoration under consideration the principle
of reversibility, which is intended to ensure that in any future
intervention the authenticity and integrity of the pre-existing
materials must be respected and restoration materials must have
reversible characteristics in their application. Materials that had
critical resistance results were Icosit K101N and Paraloid B-72. In
sample 6, where the glue applied was to Sintolit with addition of
Darwin paste and Pro-Fill, considerable tensile strength values
were verified. The values obtained with this treatment correspond
to commonly used products by the specialists in preservation and
182 S. Moutinho et al. / Construction and Building Materials 197 (2019) 175–184

Fig. 9. Samples degradation after 20 cycles.

Fig. 10. Accelerated ageing test - Geo-MKZL: a) 1st cycle; b) After 10 cycles.

restoration of tiles and in situ (the acrylic resin and the epoxy
resin) [29].
Fig. 11. Interface between the geopolymer and the ceramic body.
5.5. Compressive strength

According to the graphical representation of the Rc values in
Fig. 14, at 7, 14, 28 and 60 days, the geopolymer with the highest
strength was Geo-MKZL, in the order of 3,0 MPa. Geo-MK1000 pre-
sented lower values of strength, with values around 1.0 MPa.
GeoMK1000C analysis was only possible after 28 days of curing
given its slow consolidation process, registering very low strength
values in the initial phase. The values differed between the
geopolymer formulations, given the variation of their composition.
Welter and MacKenzie [30], investigated the mechanical proper-
ties of a dehydroxylated kaolinitic clay activated with sodium sili-
cate and NaOH solution and found that this activation can promote
a decrease on the compressive strength around 50%. The Geo-
MK1000C had a reduction of activators for pH control which may
justify the low values obtained in mechanical resistance.
 S. Moutinho et al. / Construction and Building Materials 197 (2019) 175–184 183

The increase in the compressive strength values is the result of

more compact structures arising from the higher extent of
geopolymerization. This resulted in a differential mechanical per-
formance, which should be evaluated in the scope of the applicabil-
ity of these materials. It is important that filling materials must
have properties in the order of values of the original materials in
order to ensure compatibility of materials. In this case applied to
the old tiles, materials that have compression values of 3 MPa such
as Geo-MKZL.
The various tests performed including the visual observation of
pastes allowed to analyze the behavior of old materials and
restoration materials. With these tests, we can control the proper-
ties of this category of repair materials as highly promising candi-
dates for ceramic filling materials (Table 8).
The first screening of the pastes efficacy for the infilling of tile
Fig. 12. Methodology applied to determine the tensile strength test on the tiles: a) lacunae was carried out through visual observation. According
Sample in the equipment; b) Sample rupture after application of tensile forces. Table 7, the best performances were obtained using polymer
pastes. Also, these polymeric materials showed low surface crack-
ing and such as the geopolymers a good adhesion to the substrate.
Tensile strenght (Rt) Geo-MK1000 and Geo-MK1000c showed worst results and in some
3.0 tests they were not possible to be tested. This may possibly be
Tensile streght (MPa)

2.3 explained by the higher amount of water required to ensure an

Rt adequate workability. Water excess may compromise the struc-
2.0
tural stability of geopolymers. HB Eposurf 2, Sintolit, Paste Darwin
1.1
additive, Icosit K101N and Pro-fill showed the best performance
1.0 against the action of low and high temperatures.
0.6
0.3 0.3

0.0 6. Conclusions
Sample 1 Sample 2 Sample 4 Sample 5 Sample 6
Samples The tests carried out on the materials under study made it pos-
sible to analyze the behaviour of polymers and geopolymers as fill-
Fig. 13. Values obtained in the tensile strength test.
ing lacunae material in semi-industrial glazed tiles. Tile samples
were physically characterized and it was later possible to develop
compatible and sustainable materials that exhibit considerable
water absorption and resistance characteristics. The geopolymers
Compressive strenght (Rc) were based on metakaolin with the use of alkali activators (NaOH,
6.0 MKZL Ca(OH)2 and fly ash) and had pH adjustment. The characterization
Compressive strenght (MPa)

results shows that these materials have the potential to be applied

5.0 4.6
MK1000 in the filling of tile gaps revealing compatible properties with the
4.0 ceramic body. Water absorption by capillarity showed that the
3.0 MK1000C_pH11
3.0 2.7 highest value was obtained by Darwin paste followed by Geo-
MKZL, determining that these materials have a more porous struc-
2.0 1.6
1.1 ture. Also, the geopolymer has a high capacity to absorb water pos-
1.0 1.0
1.0 0.5 sibly due to the characteristics presented by its chemical
0.3 0.2
0.0 0.0 composition. Through the ageing test it was concluded that Par-
0.0
7 14 28 60 aloid B-72 exhibited a critical performance for application on the
Days exterior facade, showing that it was not a possibility for this type
of application. Pro-Fill and Sintolit with Darwin paste additive
Fig. 14. Values obtained in the compressive strength test. showed adequate strength and compatibility with the ceramic
body according to their performance during the mechanical and

Table 8
Results obtained through tests of the formulation pastes.

Pastes Workability Adhesion to ceramic substrate Efflorescence Cracking Resistance of water action Resistance of temperature Rc Rt
HB Eposurf 2 ++ ++ L L H H Np H
Sintolit ++ L L Np M Np L
Darwin Paste ++ * L L L H* Np M*
Paraloid B-72 ++ ++ L L Np L Np L
Icosit k101N ++ + L L Np M Np Np
Pro-Fill L L M M Np M
Woodfiller Np M L M Np Np Np
Geo-MKZL + + M M L L M L
Geo-MK1000 + Np L L Np Np L Np
Geo-MK1000C ++ Np L L Np Np L Np

++ good, + medium, bad, L-Low, M-Medium, H-High, Np-Not performed, *as additive.
184 S. Moutinho et al. / Construction and Building Materials 197 (2019) 175–184
physical tests, proportioning an adequate solution for filling cera-
mic fragments creating adequate adhesion. Geopolymers pre-
sented an adequate adhesion to the ceramic body, revealing
potential of application in restoration actions on old tiles [31].
Therefore, it is possible to conclude that polymeric materials
have better chemical properties than geopolymers due to their
durability. The characterization results shows that polymer struc-
ture is more compacted and rigid and less porous. There is a need
to improve the geopolymer chemical composition (aluminosilicate
source and alkaline activators) to further assess the durability and
efficacy of geopolymers pastes. However, Geo-MKZL presented
more compatible results with the ceramic body in terms of work-
ability and adhesion to the substrate. Fly ash in geopolymer formu-
lations should continue by testing other molar ratios and other
alkaline activators, in order to optimize these materials.
Conflict of interest
None.
Acknowledgments
The authors acknowledge the availability of materials by Sika
and DOFcork, DDL-Argamassas for the help with materials and
techniques and the DB-HERITAGE Project - Database of building
materials of historical and patrimonial interest (PTDC/EPH-
PAT/4684/2014) funded by the Fundação para a Ciência e Tecnolo-
gia (FCT), Portugal. The second author benefited a PhD scholarship
(SFRH/BD/102837/2014) financed by FCT, Portugal. This work was
partially supported by RISCO (UID/ECI/04450/2013) and Geobiotec
(UID/GEO/04035/2013) Research Centers and funded by FEDER
funds through the Operational Program Competitiveness Factors
e COMPETE and by National funds through FCT.
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