Progress in Organic Coatings 57 (2006) 140148

Evaluation of silicon-based strengthening agents on porous limestones

P. Maravelaki-Kalaitzaki a, , N. Kallithrakas-Kontos b , D. Korakaki b ,
Z. Agioutantis c , S. Maurigiannakis c
a

Ministry of Culture, 25th Ephorate of Prehistoric & Classical Antiquities, Stoa Vardinogianni, 4th oor, 73100 Hania, Crete, Greece
b Technical University of Crete, Department of Science, 73100 Hania, Greece
c Technical University of Crete, Department of Mineral Resources Engineering, 73100 Hania, Greece
Received 20 December 2005; accepted 7 August 2006

Abstract
Deteriorated porous bioclastic limestones from the archaeological area of Aptera, Crete, Greece, were treated with silicon-based strengthening
products, tetraethoxysilanes, elastified silicic acid ethyl esters, an aqueous colloidal dispersion of silica particles, as well as an oligomeric siloxane
water repellent. Changes in color, water vapor permeability, water absorption by capillary suction, porosity and pore size distribution were evaluated
after treatment. Energy dispersive X-ray fluorescence and Fourier transform infrared spectroscopy indicate the penetration depth of the applied
products. The effectiveness of strengthening was also evaluated by measuring the tensile strength. The pore size distribution was insignificantly
modified decreasing only the ratio of coarse pores. The applied products penetrated up to a depth of 30 mm. All the studied products create linkages
across the interface between calcite and the alkoxysilanes-derived gels, due to the hydroxyl groups of the quartz included in the limestones. Better
reinforcing results were obtained by applying the elastified silicic acid ethyl ester. The elastified silicic acid ethyl ester confers chromatic stability
on the stone, shows insignificant modification of the water vapor permeability and reduces the absorbed quantity of water.
2006 Elsevier B.V. All rights reserved.
Keywords: Strengthening agents; Porous limestones; Penetration depth; EDXRF; Pore size distribution; Elastified silicic acid ethyl ester

1. Introduction
The use of strengthening agents for improving the physicochemical and mechanical properties of deteriorated exposed
stone is an irreversible intervention. Therefore, particular attention should be paid to the assessment of the possible strengthening agents. Stone consolidation is performed when serious
decay patterns and loose cohesion is encountered down to a certain depth [1]. Stone strengtheners slow down the rate of surface
loss by binding loosened grains. Consolidation should improve
internal cohesion without altering other physical properties of
the stone. The penetration depth of stone strengtheners through
the deteriorated zone is critical for achieving a successful consolidation. The penetration of the consolidant depends on the
microstructural characteristics of the stone and especially the
pore size, as well as the intrinsic properties of the consolidant
like viscosity and surface tension of the liquid.

Corresponding author. Tel.: +30 28210 37661; fax: +30 28210 94487.
E-mail address: nmaravel@electronics.tuc.gr (P. Maravelaki-Kalaitzaki).

0300-9440/$ see front matter 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.porgcoat.2006.08.007

On the other hand, water repellents are intended to prevent

or reduce water penetration into stone and minimize the rate of
decay. Reduction in water absorption is desirable, since in most
cases deterioration is associated with the water. However, water
vapor transmission rates should not be reduced during treatment,
allowing moisture to evaporate from the stone.
Inorganic consolidants fail to achieve a strengthening effect
due to the formation of shallow hard surface layers [2], as
a result of the insufficient penetration depth of the product.
Another group of the organic compounds used for the stone consolidation include alkoxysilanes [3]. Alkoxysilanes have been
used worldwide for decades; their widespread application is
due to their abilitiy to penetrate deeply into porous stone, be
weather-resistant and slightly reduce the water vapor permeability [3,4]. After hydrolysis and condensation alkoxysilanes
deposit colloidal silica inside the porous structure. Although silica molecules show a great chemical affinity to the siliceous
sandstones, alkoxysilanes have been frequently used as consolidants for carbonate materials. Important drawbacks of alkoxysilanes are the poor chemical bonding to calcite, and the tendency
to crack during shrinkage and drying due to their brittleness.

P. Maravelaki-Kalaitzaki et al. / Progress in Organic Coatings 57 (2006) 140148

The choice of alkoxysilanes for the consolidation of carbonate stones relies on the current absence of adequate products. In
an attempt to improve the insufficient binding of the gel to the
carbonic surface, some research groups have altered the minerals surface by creating hydroxyl groups that can react with
alkoxysilanes [5]; this process consumes some calcite. Another
approach is to employ alkoxysilanes coupling agents, in which
the R group is compatible with the calcite substrate and the
silanol or silicate groups on the coupling agent are compatible
with the alkoxysilanes-derived gels [6].
The second drawback of alkoxysilanes associated with their
tendency to crack with drying and shrinkage has been addressed
by introducing segments of linear siloxanes that link up with the
larger silicate networks of the gel [7]. In this way, thin elastic
films (elastified silicic acid ethyl esters) develop on the surface
of the macropores, and bind the components together by forming bridges of bigger gel flakes. Another research group noted
that capillary pressure competes with the elastic modulus of the
gels shrinkage [8]; they proposed the addition of small particles (2 m) in silica sols in order to increase the moduli and
therefore, the resulting gels experience reduced shrinkage.
The aim of this work was to investigate the performance of
certain consolidants, such as tetraethoxysilanes, elastified silicic
acid ethyl esters, an aqueous colloidal dispersion of silica particles, as well as an oligomeric siloxane water repellent applied on
bioclastic micritic porous limestones. The criteria for the selection of the products for stone treatment were the frequency of
their use and the suggestions of the recent literature. The evaluation was based on measuring chromatic parameters, water
vapor permeability and water absorption by capillarity, porosity
and pore size distribution, and tensile strength. Special attention
was devoted to the determination of the penetration depth of the
consolidants through the non-destructive analytical technique
energy dispersive X-ray fluorescence (EDXRF). This technique,
if combined with a micro-drilling process providing powder of
the sample at different depths from the surface, can be also
applied in situ. The product penetration depth determined by
EDXRF was compared with Fourier transform infrared spectroscopy (FTIR) and scanning electron microscopy with energy
dispersive X-ray analysis (SEM-EDS) analyses. An evaluation
of the mechanism of the treatment is suggested, in order to
improve the requirements for an efficient application.
2. Experimental
2.1. Stones
The examined porous stone of carbonate nature frequently
occurs in the historic masonry of Crete, Greece. The studied
samples originate from the archaeological area of Aptera, Hania,
Crete, Greece. The examined lithotype (40 samples) is a bioclastic micritic limestone, which consists mostly of calcium
carbonate (approximately 95%) with small amounts of quartz
and plagioclases.
The mineralogical characterization of the stone was carried
out by X-ray diffraction analysis (XRD, Siemens D-500) of
finely pulverized samples for the identification of the mineral

141

crystalline phases. Infrared spectroscopy (FTIR, Biorad FTS 40)

was used for gathering qualitative information on some of the
characteristic minerals contained in stone (calcium carbonates,
quartz, clays, etc.) and for determining the presence of salts
(nitrates, sulphates, oxalates, etc.) and consolidants. Chemical
analysis was also carried out using inductive-coupling plasma
with atomic emission spectrometry (ICP-AES).
2.2. Products
Composition, codename, characteristics and the way of application of the four selected products are shown in Table 1.
Keim-Silex OH (KS) is a tetraethylsilicate dissolved in
methylethylketone (butanol) and acetone, while ES (tetraethylsilicate), HP (oligomeric siloxane) and PP (tetraethylsilicate and
silane) are dissolved in isopropyl alcohol, which is considered
less toxic and ecological solvent. Ludox HS30 (LD) is an aqueous colloidal dispersion of very small silica particles (12 nm
diameter). The product was used as a 20% per weight solution
of SiO2 . The LD has a high specific surface area. The particles are dispersed in an alkaline medium (sodium hydroxide),
which reacts with the silica surface to produce negative charges.
Because of the negative charges, the particles repel one another
resulting in stable products. During drying, the hydroxyl groups
on the surface of the particles condense by splitting out water
to form siloxane bonds (SiOSi), resulting in coalescence and
interbonding.
Consolidants were applied on the dry material under laboratory conditions. After treatment, test specimens remained under
laboratory conditions until constant weight. Treatment with KS
was applied by capillary absorption, while treatment with ES
and HP was applied by brushing the consolidant solution on the
sample surface and after the surface drying the pure solvent was
applied to enhance the product penetration depth. The PP and
LD were deposited on the sample surface with a pipette, alternately with the solvent. Specimens designed for measuring the
water vapor permeability, were treated by brushing the product
on one face until total saturation.
2.3. Methods for evaluation of the applied products
To evaluate color changes of the treated samples the chromatic parameters were obtained by reflectance using a colorimeter (Minolta, CR-200), calibrated to a white tile standard surface
(L* = 97.55, a* = 0.02, b* = 1.56) at channel 00. Random readings were taken from the treated and untreated area, at three
locations and the results were expressed as L* (lightness), a*
(redness) and b* (yellowness) values [9].
The petrophysical characterization was carried out by determining the capillarity coefficient [10], water vapor permeability
[11] and porosity with pore size distribution on the untreated and
treated stones. The water vapor permeability of the samples was
evaluated by measuring the mass of water vapor passing though
the unit surface in 24 h, at 30 C, under control conditions. Determination of porosity and pore size distribution were carried out,
before and after application of the products, by means of mercury intrusion porosimetry (MIP, Micromeritics 9320).

142

P. Maravelaki-Kalaitzaki et al. / Progress in Organic Coatings 57 (2006) 140148

Table 1
Properties of the used consolidation products
Product

Application mode

Manufacturer/supplier

Composition

SiO2 (%,
w/w)

Viscosity
(25 C, cp)

Specific gravity
(15 C, g/cm3 )

KEIM-Silex OH (KS)
Ethyl silicate PHASE (ES)
PHASE PLUS 5035 (PP)
Hydrophase -Plus (HP)
Ludox HS30 (LD)

Capillarity
Brushing
Pipette
Brushing
Pipette

KEIM FARBEN
PHASE Srl
PHASE Srl
PHASE Srl
GRACE

Tetraethylsilicate
Tetraethylsilicate
Tetraethylsilicate and silane
Oligomeric siloxane
Colloidal silica (water solvent) 12 nm

33
40
40
45
30

<2
3.3
3.3
3.8
6.4

0.940.97
0.70
0.90
0.75
1.201.22

EDXRF with 55 Fe and 109 Cd radioactive sources, Si(Li)

semiconductor detector (resolution 150 eV at 5.9 keV) was also
employed for the identification of the penetration depth of the
consolidants. The main advantages of the applied EDXRF technique are the capability of direct analysis of solid samples, the
simultaneous detection of almost all the elements with atomic
number higher than aluminium, and the short analytical time.
EDXRF was performed both at the treated surface and in several depths from the stone surface. In particular, about 15 mg of
powder were extracted from several depths from the surface by
means of a dentists wheel and were subsequently analyzed by
EDXRF. Therefore, a distribution of the silicon and a measurement of the penetration depth of the consolidant were achieved.
FTIR analysis of the EDXRF-analyzed powders was used to
compare the analytical results of both techniques. SEM analyses
were performed in cross sections of treated samples for investigating the penetration depth of the applied products by detecting
the distribution of silicon inside the treated limestone.
The mechanical properties of untreated and treated stones
were evaluated using the indirect tension test (Brazil test) on
cylindrical specimens prepared by wet coring. Specimen diameter was approximately 51 mm and specimen thickness was
26 mm. Experiments were performed based on the International
Society of Rock Mechanics (ISRM) guidelines where each specimen was mounted in curved jaws and loaded under a constant
load rate of 200 N/s until failure. Testing was performed in an
MTS loadframe with closed loop servohydraulic control.
3. Results and discussion
3.1. Characterization of the studied lithotypes
The building material from the fortified wall of Aptera used
for the tests is a bioclastic magnesium calcite (95.1%) with
quartz (4.9%). FTIR analysis reveals nitrates in almost all analyzed samples which are related to the presence of animals
in the archaeological area. Mirabilite, thenardite, gypsum and
epsomite were formed in several samples, as a result of the sea
spray action. Table 2 shows the complete chemical analysis of
the studied lithotype. The high sodium oxide content measured
in the samples indicates the risk of salt crystallization and subsequent decay. The main cause of decay of the studied lithotype is
the eroding effect of water and sea-salt spray inducing salt crystallization, dissolution of the cementing material and grain loss.
The results of the microstructural characteristics of the stone
as well as some mechanical properties are reported in Table 3. As

far as porosity and pore size distribution are concerned, the studied limestone has been differentiated into two categories (AM1
and AM2) by the average pore radius, which is quadruple in
one category (AM1) as compared to the other (AM2). The other
properties reported in Table 3, such as bulk density and specific surface area are in close relationship with the average pore
radius. High specific surface is associated with low pore radius
and low bulk density. The building stones AM2 characterized
by a low average pore radius show good construction properties as they register higher tensile strength and therefore behave
properly in the fortification walls against mechanical stress.
3.2. Efciency of the applied consolidants
3.2.1. Changes of the chromatic coordinates, water vapor
permeability and capillarity coefcients
Table 4 shows the changes of the chromatic coordinates for
the treated stones originating from monuments (AM1 and AM2).
For the calculation of the chromatic variations the untreated
stone was selected as reference area. L* refers to the brightness, while a* and b* to the redgreen and yellowblue color,
respectively. The
L = Lt Lun value describes a change in
brightness, where positive values of
L* correspond to treated
samples (index t), which reflect more light than untreated samples (index un). Positive values of
a* and
b* indicate that the
treated samples are more red and yellow, respectively, than the
untreated. The
E* value, given in Eq. (1), represents the color
change between the treated and the untreated surface.

E = (
L )2 + (
a )2 + (
b )2

(1)
The chromatic variations induced by the applied products
range in acceptable limits when the parameter
E* is <2.5. The
most significant decrease in lightness was observed with the
Table 2
Chemical composition of bioclastic monument limestones by ICP-AES
SiO2
Al2 O3
Fe2 O3
MgO
CaO
Na2 O
K2 O
IL

1.05
0.29
0.06
0.31
52.44
2.11
0.75
42.35

Total

99.36

IL: ignition loss.

P. Maravelaki-Kalaitzaki et al. / Progress in Organic Coatings 57 (2006) 140148

Table 3
Petrophysical properties of monument limestones

(g/cm3 )

Bulk density
Specific surface area (m2 /g)
Average pore radius (m)
Total porosity (%)
Capillarity coefficient (kg/m2 h1/2 )
Water vapor permeability
coefficient (g/m2 24 h mmHg)
Tensile strength (MPa)

Table 5
Variations (% reduction) of the water vapor permeability (WVP) and capillarity
absorption coefficients (CA) of treated limestones

AM1

AM2

2.10 (0.05)
1.3 (0.3)
1.8 (0.3)
22.9 (3.2)
0.0036 (0.0001)
0.18 (0.01)

2.06 (0.11)
2.2 (0.5)
0.5 (0.1)
21.1 (2.9)
0.0032 (0.0002)
0.16 (0.01)

2.8 (0.9)

4.5 (0.9)

AM1 and AM2: bioclastic monument.

application of LD. A decrease in lightness was also registered

for the treatment with ES + HP for both monument limestones.
Other chromatic variations include a slight increase in red (
a* )
and yellow hues (
b* ) for the case of the AM1 category treated
limestones; the highest increase in yellow hues was induced by
LD on AM1 limestones.
AM2 limestones show an increase in yellow hues when applying LD, ES + HP and KS alone or in combination with PP and
HP. Concerning the chromatic variation, the best performing
products were: PP, PP + HP and KS, as well as KS + PP applied
to AM1 samples. The treatments responsible for the most significant changes in chromatic parameters were LD and ES applied
alone or in combination with PP or HP.
The reduction induced by the applied products in the water
vapor permeability and capillarity coefficients is shown in
Table 5. In general, the water vapor permeability coefficients
decreased after treatment of limestones. The most significant
decrease was registered after application of KS + PP, LD and
HP. As far as water vapor transmission is concerned only PP
behaves properly, since it induces a reduction lower than 25%
when applied alone.
The capillarity coefficient measured on treated stones was
lower than the untreated stones. However, this property was not
considered when studying the efficiency of the applied consolTable 4
Variation of the chromatic parameters of treated limestones

L*

a*

b*

Sample

WVP (%)

CA (%)

AM1
KS
KS + PP
ES + HP
ES + PP
PP + HP
PP
LD

53.33
66.67
78.57
62.55
52.63
22.82
64.44

16.67
29.27
51.87
33.12
69.70
38.46
12.06

AM2
KS
KS + PP
KS + HP
ES + HP
PP + HP
PP
LD

58.67
63.75
73.83
49.00
52.08
24.33
75.76

11.11
34.58
63.09
60.38
54.55
32.31
15.25

AM1 and AM2: bioclastic monument.

idants, since low coefficients have also been recorded in the

untreated stones. Furthermore, it is desirable for a consolidant
to be capable of reducing the water absorption, but it is not a
main requirement of the consolidation. The water absorption by
capillarity was significantly reduced when applying the water
repellent HP, as it was expected [12].
3.2.2. Evaluation of the penetration depth of the
consolidants through EDXRF
The silicon K yield at 1.74 keV, was used for the identification of the silicon-based products. This analysis revealed that
silicon was uniformly distributed on the treated surface and was
detected up to a depth of 30 mm from the surface. In Fig. 1 the Xray yield of silicon and calcium is shown for the treated surface
(0 mm) and at a depth of 10 mm for an AM1 limestone treated
with PP.
The ratio of X-ray yields of Si to Ca, obtained during the
EDXRF analysis of the treated surface, at various depths from

E*

AM1
KS
KS + PP
ES + HP
ES + PP
PP + HP
PP
LD

2.31
1.36
7.73
6.02
0.56
1.02
16.00

0.87
1.86
0.86
1.45
0.60
1.53
2.54

0.25
1.29
1.46
1.25
0.33
0.24
2.25

2.48
2.64
7.91
6.32
0.88
1.85
16.36

AM2
KS
KS + PP
KS + HP
ES + HP
PP + HP
PP
LD

1.11
1.49
0.99
5.89
0.76
1.00
15.98

0.14
0.97
0.70
0.93
0.38
0.16
0.79

3.07
3.84
2.97
3.17
0.82
0.09
4.14

3.27
4.23
3.21
6.75
1.18
1.02
16.53

AM1 and AM2: bioclastic monument.

143

Fig. 1. X-ray yield of silicon and calcium is shown for the treated surface (0 mm)
and at a depth from the surface of 10 mm for an AM1 limestone treated with PP.

144

P. Maravelaki-Kalaitzaki et al. / Progress in Organic Coatings 57 (2006) 140148

Fig. 3. Absorbed product amount (mg/cm2 0.01) and ratio of the tensile
strengths of treated and untreated samples.
Fig. 2. Absorbed product amount (mg/cm2 0.07) and silicon yield (SY) measured by EDXRF at depths from the surface of 0, 1, 10 and 30 mm.

the treated surface and the opposite untreated side, were used in
order to estimate the penetration depth of the studied products.
The ratio of the EDXRF Si and Ca yields was introduced in all
calculations, in order to minimize errors involved in the quantification of these elements. Furthermore, the EDXRF Si/Ca ratio
of a treated sample divided by the same ratio of the untreated
material was defined as silicon yield (SY) at various depths from
the surface. The division of treated to untreated material was
necessary, since the studied limestones also contain a quantity
of silicon-based minerals, which should be considered in the
overall calculation of the silicon.
Fig. 2 illustrates the mean values of SYs obtained for different products and at different depths from the surface for the
AM1 and AM2 treated limestones. In Fig. 2 the amount of the
applied product is also reported. The SY at 30 mm from the surface corresponds to the opposite of the treated side and usually
shows values higher than 1, implying that a part of resin has
reached the untreated side. Limestones treated with PP (pipette)
and HP (brushing), as well as the AM2 limestones treated
with KS (capillarity) show a poorer penetration of the applied
products.
The obtained SYs of the treated samples were not always
proportional to the quantity of the applied resin. The lower
absorbed amounts of the applied products were recorded for
PP, LD and ES applied either by a pipette or brushing. Even
though LD and ES were applied by depositing the solution and

consequently the solvent, nevertheless, the product was accumulated on the surface, as indicated by the corresponding SYs.
The SYs identified in samples treated with PP show the lowest values at all depths, being proportional to the low quantity
of the absorbed product. It is important to emphasize that the
SYs identified on samples treated with PP at depths from the
surface of 0, 1, 10 and 30 mm show similar trends, indicating
that the resin has been evenly distributed in the whole matrix of
limestone.
Conversely, high absorbed product amounts were registered
for the samples treated with KS by capillary absorption, followed by comparable SYs at all depths from the surface. Samples
treated with KS, as well as KS + PP also show an even distribution of the product in depth; the obtained SYs were higher than
the corresponding of the samples treated with PP, as a result of
the higher absorbed amount. The AM2 limestones (with smaller
pores than AM1), absorbed less product and generally exhibited
lower SYs than AM1 limestones. Therefore, the resin quantity
which is spread deeply into the sample depends upon the resin
composition, the application mode and the microstructural characteristics of the limestone.
3.2.3. Evaluation of the mechanical characteristics of
treated limestones
The absorbed amount of the products on the treated samples
was compared with the ratio of the tensile strength obtained
between treated and untreated samples and the results are
illustrated in Fig. 3. There is some correlation between these
values, especially in cases treated with KS and PP in which

P. Maravelaki-Kalaitzaki et al. / Progress in Organic Coatings 57 (2006) 140148

Fig. 4. Porosity (% 0.1), specific surface area (m2 /g) and average pore radius
(m) for treated and untreated samples.

the consumed product is proportional to the measured tensile strength. The values of the tensile strength corresponding to samples treated with PP are a bit lower or the same
with the untreated ones, indicating that the applied consolidant
has not induced an over-strengthening. This is an important
property of the elastic silicic acid ester, like the PP, which
does not modify the mechanical characteristics of the limestone. KS, however, produced over-strengthening, but this is
mostly related to the high consumed product by capillarity
absorption.
3.2.4. Mercury intrusion porosimetry
After treatment, the AM1 and AM2 limestones show a
decrease in porosity, specific surface area and average pore
radius (Fig. 4). The decrease of the average pore radius is
due to deposition of the consolidants into the pores. These
properties are desirable, since they contribute to a decrease of
the decay susceptibility of the limestones, provided that the
pore size distribution has not been modified to a great extent
[13]. As an example, the percent relative volume distribution
of the AM1 and AM2 treated with KS + PP and the corresponding untreated samples as a function of pore radius are
illustrated in Fig. 5. After treatment, the pore size distribution
shifts towards small radii without observing an occlusion of
pores.

145

Fig. 5. Percent relative volume as a function of pore radius (m) for the AM1
and AM2 samples treated with KS + PP and the corresponding untreated ones.

In the case of the high average pore radius AM1 limestones

porosity, specific surface area and average pore radius were more
reduced, while lower differences between treated and untreated
samples were observed for the AM2 limestones with small average pore radius.
The specific surface area was increased only in samples
treated with LD. The increase in the specific surface area induced
by LD can be explained by the nature of the product which produced itself new surfaces due to the deposition on the stone
surface of silica particles. Carretti and Dei [14] also found that
the specific surface area of treated mortars with excess of Paraloid was increased.
The decrease in the specific surface area indicates that fine
pores were reduced. The stone susceptibility to weathering, taking into consideration the salt crystallization pressure along with
structural and mechanical parameters, is well documented in the
literature [1517]. Damage of stone due to mechanical actions
of crystallized salts into the pore network occurred, when crystallization pressure exceeds the tensile strength. The smaller the
pore size, the higher the pressures caused by salt crystallization.
However, the results obtained in this work showed that the AM2
limestones with small pore radii show better mechanical properties than the AM1 limestones, since in the AM2 limestones
the pore system may have been built up by small isolated pores
which do not favour the access and transport of salt solutions

146

P. Maravelaki-Kalaitzaki et al. / Progress in Organic Coatings 57 (2006) 140148

Fig. 6. FTIR spectra of an AM1 limestone treated with KS + PP at depths from the surface of 1 and 30 mm, as well as the untreated limestone.

towards the interior. The same was observed in the study of

Cardell et al. [17], where a micritic limestone with pores in the
range from 0.01 to 0.1 m resisted salt weathering better than
stones with coarse pores.
3.2.5. Comparison of the penetration depth of the
consolidants identied by EDXRF with FTIR and SEM-EDS
Two characteristic infrared absorptions were taken into consideration (Fig. 6), which are related to the presence of both the
carbonatic matrix (877 cm1 corresponding to the CO3 2 bend)
and the silica gel (peak at 1100 cm1 corresponding to the
SiOSi stretching vibration). Fig. 6 depicts the infrared spectra of an AM1 limestone treated with KS + PP at depths from the

surface of 1 and 30 mm, as well as the untreated limestone. The

spectra indicate that SiOSi silicate linkages were developed,
as a result of the low quartz quantity of the limestones; quartz
provides hydroxyl groups capable of creating linkages across the
interface between calcite and the alkoxysilanes-derived gels.
Table 6 shows the calculated areas of the absorptions corresponding to CO3 2 bend at 877 cm1 and the SiOSi stretching
vibration at 1100 cm1 , as well as the FTIR SiOSi/CO3 2
ratio between treated and untreated stone and the corresponding
ratio of EDXRF Si/Ca X-ray yields. By dividing the FTIR to the
EDXRF ratios an almost stable value is obtained indicating that
both techniques are in accordance concerning the measurement
of the product penetration depth.

Table 6
Comparison of the penetration depth of products evaluated with FTIR and EDXRF
Limestones
and products

Depth from the

surface (mm)

CO3 2

SiOSi

FTIR SiOSi/CO3 2 t/un

EDXRF Si/Ca t/un

EDXRF/FTIR

AM1
KS
KS
KS + PP
KS + PP
ES + HP
ES + HP

1
30
1
30
1
30

23.60
20.20
21.57
17.99
22.24
23.44

51.65
39.14
46.96
49.36
30.24
35.47

10.94
9.69
11.46
14.44
3.02
3.36

4.89
4.00
5.13
6.14
1.49
1.62

0.45
0.41
0.45
0.43
0.49
0.48

AM2
KS
KS
KS + PP
KS + PP
KS + HP
KS + HP

1
30
1
30
1
30

20.77
22.61
21.28
19.85
25.98
20.80

20.34
6.32
40.96
43.47
40.12
25.63

1.46
0.42
4.94
5.62
3.96
3.16

0.62
0.17
1.96
2.09
1.51
1.11

0.42
0.40
0.40
0.37
0.39
0.35

AM1 and AM2: bioclastic monument.

P. Maravelaki-Kalaitzaki et al. / Progress in Organic Coatings 57 (2006) 140148

Fig. 7. Area analyzed by SEM, the corresponding SEM-EDS spectrum and the
semi-quantitative analysis of an AM1 sample treated with KS.

147

The least chromatic variations were induced by PP, HP and

KS. LD and ES, alone or in combination with PP or HP alter
significantly the chromatic parameters of the limestones.
Consolidants and the water repellent obstruct the water vapor
transmission rate. The worst performance was noted after
application of KS + PP, LD and HP. As far as treatment criteria
are concerned, only PP reduces the water vapor permeability
coefficient to acceptable limits.
The water absorption capillarity coefficients were reduced
after treatment, especially when applied the water repellent
HP.
EDXRF showed that the applied products reached a penetration depth of 30 mm. KS and PP were evenly distributed
inside the limestone, while ES and LD accumulated on the
surface.
Samples treated with PP are characterized by mechanical
properties similar to the untreated material, while ES and KS
produce an over-strengthening.
After treatment, the AM1 and AM2 limestones show a
decrease in porosity, specific surface area and average pore
radius. The pore size distribution was insignificantly modified
decreasing only the ratio of coarse pores.
All the studied products create linkages across the interface
between calcite and the alkoxysilanes-derived gels, due to the
hydroxyl groups of the quartz included in the limestones.

Fig. 7 illustrates the area analyzed by SEM, the corresponding SEM-EDS spectrum and the semi-quantitative analysis of
an AM1 sample treated with KS. The Si/Ca obtained SEMEDS intensities (equal to 0.081) are in close relationship with
the corresponding EDXRF Si/Ca X-rays yields (equal to 0.093)
indicating that EDXRF can be used for evaluating the penetration depth of the consolidants.

From the above studied products Ludox and ethyl silicate,

which remain on the surface and create an over-strengthening,
are not recommended as consolidants for this kind of porous
limestones. The elastified silicic acid ethyl ester (PP) behaves
properly and can be used for a consolidation treatment.

4. Conclusions

The authors would like to acknowledge the valuable contribution of Prof. A. Tsetsekou (Department of Mineral Resources
Engineering, Technical University of Crete) for the MIP measurements.

The selection of the most efficient consolidation treatment

takes into consideration the following criteria: least chromatic
variation, lowest decrease in water vapor permeability, highest
liquid water-repellence, highest consolidant penetration depth
and moderate increase of the mechanical resistance (tensile
treated/tensile untreated <1.5 [18]).
In the present work bioclastic limestones were consolidated
and protected with certain conservation materials in order to
achieve reduction of the decay phenomena. The treatment of
limestones with various products and combination of these products provide interesting information on the performance of the
consolidants, concerning SYs, consumed product amount, application mode and tensile strength. From the comparative assessment of the data obtained in this study, the following can be
pointed out:
KS applied by capillarity showed the higher quantity of the
absorbed product in almost all samples, while ES, LD and
PP applied by brushing or a pipette were absorbed to a lesser
extent.

Acknowledgement

References
[1] J. Delgado Rodrigues, A.P. Ferreira Pinto, A.E. Charola, Int. J. Restor.
Buildings Monuments 4 (6) (1998) 653666.
[2] I. Maxova, Proceedings of the Ninth International Congress on Deterioration and Conservation of Stone, 2000, p. 395.
[3] G. Wheeler, Alkoxysilanes and the Consolidation of Stone, The Getty Conservation Institute, 2005.
[4] M. Camaiti, G. Borselli, U. Matteoli, L Edilizia e l industrializzazione 10
(2) (1988) 435445.
[5] N.R. Weiss, I. Slavid, G. Wheeler, Proceedings of the Ninth International
Congress on Deterioration and Conservation of Stone, 2000, p. 533.
[6] G. Wheeler, J. Mendez-Vivar, E.S. Goins, A. Fleming, C.J. Brinker, Proceedings of the Ninth International Congress on Deterioration and Conservation of Stone, 2000, p. 541.
[7] M. Boos, J. Grobe, G. Hilbert, J. Muller-Rochholz, Proceedings of the
Eighth International Congress on Deterioration and Conservation of Stone,
1996, p. 1179.
[8] M. Escalante, J. Valenza, G. Scherer, Proceedings of the Ninth International
Congress on Deterioration and Conservation of Stone, 2000, p. 459.

148

P. Maravelaki-Kalaitzaki et al. / Progress in Organic Coatings 57 (2006) 140148

[9] Misure colorimetriche di superfici opache, I.C.R.-C.N.R. Doc. NORMAL

43/93, 1994.
[10] Assorbimento dacqua per capillaritaCoefficiente di assorbimento capillare, I.C.R.-C.N.R. Doc. NORMAL 11/85, 1986.
[11] Permeabilita al vapor dacqua, I.C.R.-C.N.R. Doc. NORMAL 21/85, 1986.
[12] M. Alvarez de Buergo Ballester, R. Fort Gonzalez, Prog. Org. Coat. 43
(2001) 258266.
[13] A. Moropoulou, N. Kouloumbi, G. Haralampopoulos, A. Konstanti, P.
Michailidis, Prog. Org. Coat. 48 (24) (2003) 259270.

[14] E. Carretti, L. Dei, Prog. Org. Coat. 49 (2004) 282289.

[15] P. Theoulakis, A. Moropoulou, Construct. Building Mater. 11 (1997)
6571.
[16] D. Benavente, M.A. Garca del Cura, J. Garca-Guinea, S. Sanchez-Moral,
S. Ordon ez, J. Crystal Growth 260 (2004) 532544.
[17] C. Cardell, F. Delalieux, K. Roumpopoulos, A. Moropoulou, F. Auger, R.
Van Grieken, Construct. Building Mater. 17 (2003) 165179.
[18] H.R. Sasse, R. Snethlage, in: N.S. Baer, R. Snethlage (Eds.), Saving Our
Cultural Heritage, Wiley, 1997, p. 223.