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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

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 On the other hand, water repellents are intended to prevent

or reduce water penetration into stone and minimize the rate of
The use of strengthening agents for improving the physic- decay. Reduction in water absorption is desirable, since in most
ochemical and mechanical properties of deteriorated exposed cases deterioration is associated with the water. However, water
stone is an irreversible intervention. Therefore, particular atten- vapor transmission rates should not be reduced during treatment,
tion should be paid to the assessment of the possible strength- allowing moisture to evaporate from the stone.
ening agents. Stone consolidation is performed when serious Inorganic consolidants fail to achieve a strengthening effect
decay patterns and loose cohesion is encountered down to a cer- due to the formation of shallow hard surface layers [2], as
tain depth [1]. Stone strengtheners slow down the rate of surface a result of the insufficient penetration depth of the product.
loss by binding loosened grains. Consolidation should improve Another group of the organic compounds used for the stone con-
internal cohesion without altering other physical properties of solidation include alkoxysilanes [3]. Alkoxysilanes have been
the stone. The penetration depth of stone strengtheners through used worldwide for decades; their widespread application is
the deteriorated zone is critical for achieving a successful con- due to their abilitiy to penetrate deeply into porous stone, be
solidation. The penetration of the consolidant depends on the weather-resistant and slightly reduce the water vapor perme-
microstructural characteristics of the stone and especially the ability [3,4]. After hydrolysis and condensation alkoxysilanes
pore size, as well as the intrinsic properties of the consolidant deposit colloidal silica inside the porous structure. Although sil-
like viscosity and surface tension of the liquid. ica molecules show a great chemical affinity to the siliceous
sandstones, alkoxysilanes have been frequently used as consoli-
dants for carbonate materials. Important drawbacks of alkoxysi-
Corresponding author. Tel.: +30 28210 37661; fax: +30 28210 94487. lanes are the poor chemical bonding to calcite, and the tendency
E-mail address: (P. Maravelaki-Kalaitzaki). to crack during shrinkage and drying due to their brittleness.

0300-9440/$ see front matter 2006 Elsevier B.V. All rights reserved.
P. Maravelaki-Kalaitzaki et al. / Progress in Organic Coatings 57 (2006) 140148 141

The choice of alkoxysilanes for the consolidation of carbon- crystalline phases. Infrared spectroscopy (FTIR, Biorad FTS 40)
ate stones relies on the current absence of adequate products. In was used for gathering qualitative information on some of the
an attempt to improve the insufficient binding of the gel to the characteristic minerals contained in stone (calcium carbonates,
carbonic surface, some research groups have altered the min- quartz, clays, etc.) and for determining the presence of salts
erals surface by creating hydroxyl groups that can react with (nitrates, sulphates, oxalates, etc.) and consolidants. Chemical
alkoxysilanes [5]; this process consumes some calcite. Another analysis was also carried out using inductive-coupling plasma
approach is to employ alkoxysilanes coupling agents, in which with atomic emission spectrometry (ICP-AES).
the R group is compatible with the calcite substrate and the
silanol or silicate groups on the coupling agent are compatible 2.2. Products
with the alkoxysilanes-derived gels [6].
The second drawback of alkoxysilanes associated with their Composition, codename, characteristics and the way of appli-
tendency to crack with drying and shrinkage has been addressed cation of the four selected products are shown in Table 1.
by introducing segments of linear siloxanes that link up with the Keim-Silex OH (KS) is a tetraethylsilicate dissolved in
larger silicate networks of the gel [7]. In this way, thin elastic methylethylketone (butanol) and acetone, while ES (tetraethyl-
films (elastified silicic acid ethyl esters) develop on the surface silicate), HP (oligomeric siloxane) and PP (tetraethylsilicate and
of the macropores, and bind the components together by form- silane) are dissolved in isopropyl alcohol, which is considered
ing bridges of bigger gel flakes. Another research group noted less toxic and ecological solvent. Ludox HS30 (LD) is an aque-
that capillary pressure competes with the elastic modulus of the ous colloidal dispersion of very small silica particles (12 nm
gels shrinkage [8]; they proposed the addition of small parti- diameter). The product was used as a 20% per weight solution
cles (2 m) in silica sols in order to increase the moduli and of SiO2 . The LD has a high specific surface area. The parti-
therefore, the resulting gels experience reduced shrinkage. cles are dispersed in an alkaline medium (sodium hydroxide),
The aim of this work was to investigate the performance of which reacts with the silica surface to produce negative charges.
certain consolidants, such as tetraethoxysilanes, elastified silicic Because of the negative charges, the particles repel one another
acid ethyl esters, an aqueous colloidal dispersion of silica parti- resulting in stable products. During drying, the hydroxyl groups
cles, as well as an oligomeric siloxane water repellent applied on on the surface of the particles condense by splitting out water
bioclastic micritic porous limestones. The criteria for the selec- to form siloxane bonds (SiOSi), resulting in coalescence and
tion of the products for stone treatment were the frequency of interbonding.
their use and the suggestions of the recent literature. The eval- Consolidants were applied on the dry material under labora-
uation was based on measuring chromatic parameters, water tory conditions. After treatment, test specimens remained under
vapor permeability and water absorption by capillarity, porosity laboratory conditions until constant weight. Treatment with KS
and pore size distribution, and tensile strength. Special attention was applied by capillary absorption, while treatment with ES
was devoted to the determination of the penetration depth of the and HP was applied by brushing the consolidant solution on the
consolidants through the non-destructive analytical technique sample surface and after the surface drying the pure solvent was
energy dispersive X-ray fluorescence (EDXRF). This technique, applied to enhance the product penetration depth. The PP and
if combined with a micro-drilling process providing powder of LD were deposited on the sample surface with a pipette, alter-
the sample at different depths from the surface, can be also nately with the solvent. Specimens designed for measuring the
applied in situ. The product penetration depth determined by water vapor permeability, were treated by brushing the product
EDXRF was compared with Fourier transform infrared spec- on one face until total saturation.
troscopy (FTIR) and scanning electron microscopy with energy
dispersive X-ray analysis (SEM-EDS) analyses. An evaluation 2.3. Methods for evaluation of the applied products
of the mechanism of the treatment is suggested, in order to
improve the requirements for an efficient application. To evaluate color changes of the treated samples the chro-
matic parameters were obtained by reflectance using a colorime-
2. Experimental ter (Minolta, CR-200), calibrated to a white tile standard surface
(L* = 97.55, a* = 0.02, b* = 1.56) at channel 00. Random read-
2.1. Stones ings were taken from the treated and untreated area, at three
locations and the results were expressed as L* (lightness), a*
The examined porous stone of carbonate nature frequently (redness) and b* (yellowness) values [9].
occurs in the historic masonry of Crete, Greece. The studied The petrophysical characterization was carried out by deter-
samples originate from the archaeological area of Aptera, Hania, mining the capillarity coefficient [10], water vapor permeability
Crete, Greece. The examined lithotype (40 samples) is a bio- [11] and porosity with pore size distribution on the untreated and
clastic micritic limestone, which consists mostly of calcium treated stones. The water vapor permeability of the samples was
carbonate (approximately 95%) with small amounts of quartz evaluated by measuring the mass of water vapor passing though
and plagioclases. the unit surface in 24 h, at 30 C, under control conditions. Deter-
The mineralogical characterization of the stone was carried mination of porosity and pore size distribution were carried out,
out by X-ray diffraction analysis (XRD, Siemens D-500) of before and after application of the products, by means of mer-
finely pulverized samples for the identification of the mineral cury 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 (%, Viscosity Specific gravity
w/w) (25 C, cp) (15 C, g/cm3 )

KEIM-Silex OH (KS) Capillarity KEIM FARBEN Tetraethylsilicate 33 <2 0.940.97

Ethyl silicate PHASE (ES) Brushing PHASE Srl Tetraethylsilicate 40 3.3 0.70
PHASE PLUS 5035 (PP) Pipette PHASE Srl Tetraethylsilicate and silane 40 3.3 0.90
Hydrophase -Plus (HP) Brushing PHASE Srl Oligomeric siloxane 45 3.8 0.75
Ludox HS30 (LD) Pipette GRACE Colloidal silica (water solvent) 12 nm 30 6.4 1.201.22

EDXRF with 55 Fe and 109 Cd radioactive sources, Si(Li) far as porosity and pore size distribution are concerned, the stud-
semiconductor detector (resolution 150 eV at 5.9 keV) was also ied limestone has been differentiated into two categories (AM1
employed for the identification of the penetration depth of the and AM2) by the average pore radius, which is quadruple in
consolidants. The main advantages of the applied EDXRF tech- one category (AM1) as compared to the other (AM2). The other
nique are the capability of direct analysis of solid samples, the properties reported in Table 3, such as bulk density and spe-
simultaneous detection of almost all the elements with atomic cific surface area are in close relationship with the average pore
number higher than aluminium, and the short analytical time. radius. High specific surface is associated with low pore radius
EDXRF was performed both at the treated surface and in sev- and low bulk density. The building stones AM2 characterized
eral depths from the stone surface. In particular, about 15 mg of by a low average pore radius show good construction proper-
powder were extracted from several depths from the surface by ties as they register higher tensile strength and therefore behave
means of a dentists wheel and were subsequently analyzed by properly in the fortification walls against mechanical stress.
EDXRF. Therefore, a distribution of the silicon and a measure-
ment of the penetration depth of the consolidant were achieved. 3.2. Efciency of the applied consolidants
FTIR analysis of the EDXRF-analyzed powders was used to
compare the analytical results of both techniques. SEM analyses 3.2.1. Changes of the chromatic coordinates, water vapor
were performed in cross sections of treated samples for investi- permeability and capillarity coefcients
gating the penetration depth of the applied products by detecting Table 4 shows the changes of the chromatic coordinates for
the distribution of silicon inside the treated limestone. the treated stones originating from monuments (AM1 and AM2).
The mechanical properties of untreated and treated stones For the calculation of the chromatic variations the untreated
were evaluated using the indirect tension test (Brazil test) on stone was selected as reference area. L* refers to the bright-
cylindrical specimens prepared by wet coring. Specimen diam- ness, while a* and b* to the redgreen and yellowblue color,
eter was approximately 51 mm and specimen thickness was respectively. The L = Lt Lun value describes a change in
26 mm. Experiments were performed based on the International brightness, where positive values of L* correspond to treated
Society of Rock Mechanics (ISRM) guidelines where each spec- samples (index t), which reflect more light than untreated sam-
imen was mounted in curved jaws and loaded under a constant ples (index un). Positive values of a* and b* indicate that the
load rate of 200 N/s until failure. Testing was performed in an treated samples are more red and yellow, respectively, than the
MTS loadframe with closed loop servohydraulic control. untreated. The E* value, given in Eq. (1), represents the color
change between the treated and the untreated surface.

3. Results and discussion
E = (L )2 + (a )2 + (b )2 (1)
3.1. Characterization of the studied lithotypes The chromatic variations induced by the applied products
range in acceptable limits when the parameter E* is <2.5. The
The building material from the fortified wall of Aptera used most significant decrease in lightness was observed with the
for the tests is a bioclastic magnesium calcite (95.1%) with
quartz (4.9%). FTIR analysis reveals nitrates in almost all ana- Table 2
lyzed samples which are related to the presence of animals Chemical composition of bioclastic monument limestones by ICP-AES
in the archaeological area. Mirabilite, thenardite, gypsum and
SiO2 1.05
epsomite were formed in several samples, as a result of the sea Al2 O3 0.29
spray action. Table 2 shows the complete chemical analysis of Fe2 O3 0.06
the studied lithotype. The high sodium oxide content measured MgO 0.31
in the samples indicates the risk of salt crystallization and subse- CaO 52.44
quent decay. The main cause of decay of the studied lithotype is Na2 O 2.11
K2 O 0.75
the eroding effect of water and sea-salt spray inducing salt crys- IL 42.35
tallization, dissolution of the cementing material and grain loss.
Total 99.36
The results of the microstructural characteristics of the stone
as well as some mechanical properties are reported in Table 3. As IL: ignition loss.
P. Maravelaki-Kalaitzaki et al. / Progress in Organic Coatings 57 (2006) 140148 143

Table 3 Table 5
Petrophysical properties of monument limestones Variations (% reduction) of the water vapor permeability (WVP) and capillarity
absorption coefficients (CA) of treated limestones
Sample WVP (%) CA (%)
Bulk density (g/cm3 ) 2.10 (0.05) 2.06 (0.11)
Specific surface area (m2 /g) 1.3 (0.3) 2.2 (0.5) AM1
Average pore radius (m) 1.8 (0.3) 0.5 (0.1) KS 53.33 16.67
Total porosity (%) 22.9 (3.2) 21.1 (2.9) KS + PP 66.67 29.27
Capillarity coefficient (kg/m2 h1/2 ) 0.0036 (0.0001) 0.0032 (0.0002) ES + HP 78.57 51.87
Water vapor permeability 0.18 (0.01) 0.16 (0.01) ES + PP 62.55 33.12
coefficient (g/m2 24 h mmHg) PP + HP 52.63 69.70
Tensile strength (MPa) 2.8 (0.9) 4.5 (0.9) PP 22.82 38.46
LD 64.44 12.06
AM1 and AM2: bioclastic monument.
KS 58.67 11.11
application of LD. A decrease in lightness was also registered KS + PP 63.75 34.58
for the treatment with ES + HP for both monument limestones. KS + HP 73.83 63.09
Other chromatic variations include a slight increase in red (a* ) ES + HP 49.00 60.38
PP + HP 52.08 54.55
and yellow hues (b* ) for the case of the AM1 category treated
PP 24.33 32.31
limestones; the highest increase in yellow hues was induced by LD 75.76 15.25
LD on AM1 limestones.
AM1 and AM2: bioclastic monument.
AM2 limestones show an increase in yellow hues when apply-
ing LD, ES + HP and KS alone or in combination with PP and
HP. Concerning the chromatic variation, the best performing
idants, since low coefficients have also been recorded in the
products were: PP, PP + HP and KS, as well as KS + PP applied
untreated stones. Furthermore, it is desirable for a consolidant
to AM1 samples. The treatments responsible for the most signif-
to be capable of reducing the water absorption, but it is not a
icant changes in chromatic parameters were LD and ES applied
main requirement of the consolidation. The water absorption by
alone or in combination with PP or HP.
capillarity was significantly reduced when applying the water
The reduction induced by the applied products in the water
repellent HP, as it was expected [12].
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 3.2.2. Evaluation of the penetration depth of the
decrease was registered after application of KS + PP, LD and consolidants through EDXRF
HP. As far as water vapor transmission is concerned only PP The silicon K yield at 1.74 keV, was used for the identifi-
behaves properly, since it induces a reduction lower than 25% cation of the silicon-based products. This analysis revealed that
when applied alone. silicon was uniformly distributed on the treated surface and was
The capillarity coefficient measured on treated stones was detected up to a depth of 30 mm from the surface. In Fig. 1 the X-
lower than the untreated stones. However, this property was not ray yield of silicon and calcium is shown for the treated surface
considered when studying the efficiency of the applied consol- (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
Table 4
Variation of the chromatic parameters of treated limestones
EDXRF analysis of the treated surface, at various depths from

L* a* b* E*

KS 2.31 0.87 0.25 2.48
KS + PP 1.36 1.86 1.29 2.64
ES + HP 7.73 0.86 1.46 7.91
ES + PP 6.02 1.45 1.25 6.32
PP + HP 0.56 0.60 0.33 0.88
PP 1.02 1.53 0.24 1.85
LD 16.00 2.54 2.25 16.36
KS 1.11 0.14 3.07 3.27
KS + PP 1.49 0.97 3.84 4.23
KS + HP 0.99 0.70 2.97 3.21
ES + HP 5.89 0.93 3.17 6.75
PP + HP 0.76 0.38 0.82 1.18
PP 1.00 0.16 0.09 1.02
LD 15.98 0.79 4.14 16.53
Fig. 1. X-ray yield of silicon and calcium is shown for the treated surface (0 mm)
AM1 and AM2: bioclastic monument. 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) mea-
sured by EDXRF at depths from the surface of 0, 1, 10 and 30 mm. consequently the solvent, nevertheless, the product was accu-
mulated on the surface, as indicated by the corresponding SYs.
The SYs identified in samples treated with PP show the low-
the treated surface and the opposite untreated side, were used in est values at all depths, being proportional to the low quantity
order to estimate the penetration depth of the studied products. of the absorbed product. It is important to emphasize that the
The ratio of the EDXRF Si and Ca yields was introduced in all SYs identified on samples treated with PP at depths from the
calculations, in order to minimize errors involved in the quantifi- surface of 0, 1, 10 and 30 mm show similar trends, indicating
cation of these elements. Furthermore, the EDXRF Si/Ca ratio that the resin has been evenly distributed in the whole matrix of
of a treated sample divided by the same ratio of the untreated limestone.
material was defined as silicon yield (SY) at various depths from Conversely, high absorbed product amounts were registered
the surface. The division of treated to untreated material was for the samples treated with KS by capillary absorption, fol-
necessary, since the studied limestones also contain a quantity lowed by comparable SYs at all depths from the surface. Samples
of silicon-based minerals, which should be considered in the treated with KS, as well as KS + PP also show an even distribu-
overall calculation of the silicon. tion of the product in depth; the obtained SYs were higher than
Fig. 2 illustrates the mean values of SYs obtained for dif- the corresponding of the samples treated with PP, as a result of
ferent products and at different depths from the surface for the the higher absorbed amount. The AM2 limestones (with smaller
AM1 and AM2 treated limestones. In Fig. 2 the amount of the pores than AM1), absorbed less product and generally exhibited
applied product is also reported. The SY at 30 mm from the sur- lower SYs than AM1 limestones. Therefore, the resin quantity
face corresponds to the opposite of the treated side and usually which is spread deeply into the sample depends upon the resin
shows values higher than 1, implying that a part of resin has composition, the application mode and the microstructural char-
reached the untreated side. Limestones treated with PP (pipette) acteristics of the limestone.
and HP (brushing), as well as the AM2 limestones treated
with KS (capillarity) show a poorer penetration of the applied 3.2.3. Evaluation of the mechanical characteristics of
products. treated limestones
The obtained SYs of the treated samples were not always The absorbed amount of the products on the treated samples
proportional to the quantity of the applied resin. The lower was compared with the ratio of the tensile strength obtained
absorbed amounts of the applied products were recorded for between treated and untreated samples and the results are
PP, LD and ES applied either by a pipette or brushing. Even illustrated in Fig. 3. There is some correlation between these
though LD and ES were applied by depositing the solution and values, especially in cases treated with KS and PP in which
P. Maravelaki-Kalaitzaki et al. / Progress in Organic Coatings 57 (2006) 140148 145

Fig. 4. Porosity (% 0.1), specific surface area (m2 /g) and average pore radius Fig. 5. Percent relative volume as a function of pore radius (m) for the AM1
(m) for treated and untreated samples. and AM2 samples treated with KS + PP and the corresponding untreated ones.

the consumed product is proportional to the measured ten-

sile strength. The values of the tensile strength correspond- In the case of the high average pore radius AM1 limestones
ing to samples treated with PP are a bit lower or the same porosity, specific surface area and average pore radius were more
with the untreated ones, indicating that the applied consolidant reduced, while lower differences between treated and untreated
has not induced an over-strengthening. This is an important samples were observed for the AM2 limestones with small aver-
property of the elastic silicic acid ester, like the PP, which age pore radius.
does not modify the mechanical characteristics of the lime- The specific surface area was increased only in samples
stone. KS, however, produced over-strengthening, but this is treated with LD. The increase in the specific surface area induced
mostly related to the high consumed product by capillarity by LD can be explained by the nature of the product which pro-
absorption. duced 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 Par-
3.2.4. Mercury intrusion porosimetry aloid was increased.
After treatment, the AM1 and AM2 limestones show a The decrease in the specific surface area indicates that fine
decrease in porosity, specific surface area and average pore pores were reduced. The stone susceptibility to weathering, tak-
radius (Fig. 4). The decrease of the average pore radius is ing into consideration the salt crystallization pressure along with
due to deposition of the consolidants into the pores. These structural and mechanical parameters, is well documented in the
properties are desirable, since they contribute to a decrease of literature [1517]. Damage of stone due to mechanical actions
the decay susceptibility of the limestones, provided that the of crystallized salts into the pore network occurred, when crys-
pore size distribution has not been modified to a great extent tallization pressure exceeds the tensile strength. The smaller the
[13]. As an example, the percent relative volume distribution pore size, the higher the pressures caused by salt crystallization.
of the AM1 and AM2 treated with KS + PP and the corre- However, the results obtained in this work showed that the AM2
sponding untreated samples as a function of pore radius are limestones with small pore radii show better mechanical prop-
illustrated in Fig. 5. After treatment, the pore size distribution erties than the AM1 limestones, since in the AM2 limestones
shifts towards small radii without observing an occlusion of the pore system may have been built up by small isolated pores
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 surface of 1 and 30 mm, as well as the untreated limestone. The
Cardell et al. [17], where a micritic limestone with pores in the spectra indicate that SiOSi silicate linkages were developed,
range from 0.01 to 0.1 m resisted salt weathering better than as a result of the low quartz quantity of the limestones; quartz
stones with coarse pores. provides hydroxyl groups capable of creating linkages across the
interface between calcite and the alkoxysilanes-derived gels.
3.2.5. Comparison of the penetration depth of the Table 6 shows the calculated areas of the absorptions corre-
consolidants identied by EDXRF with FTIR and SEM-EDS sponding to CO3 2 bend at 877 cm1 and the SiOSi stretching
Two characteristic infrared absorptions were taken into con- vibration at 1100 cm1 , as well as the FTIR SiOSi/CO3 2
sideration (Fig. 6), which are related to the presence of both the ratio between treated and untreated stone and the corresponding
carbonatic matrix (877 cm1 corresponding to the CO3 2 bend) ratio of EDXRF Si/Ca X-ray yields. By dividing the FTIR to the
and the silica gel (peak at 1100 cm1 corresponding to the EDXRF ratios an almost stable value is obtained indicating that
SiOSi stretching vibration). Fig. 6 depicts the infrared spec- both techniques are in accordance concerning the measurement
tra of an AM1 limestone treated with KS + PP at depths from the of the product penetration depth.

Table 6
Comparison of the penetration depth of products evaluated with FTIR and EDXRF
Limestones Depth from the CO3 2 SiOSi FTIR SiOSi/CO3 2 t/un EDXRF Si/Ca t/un EDXRF/FTIR
and products surface (mm)

KS 1 23.60 51.65 10.94 4.89 0.45
KS 30 20.20 39.14 9.69 4.00 0.41
KS + PP 1 21.57 46.96 11.46 5.13 0.45
KS + PP 30 17.99 49.36 14.44 6.14 0.43
ES + HP 1 22.24 30.24 3.02 1.49 0.49
ES + HP 30 23.44 35.47 3.36 1.62 0.48
KS 1 20.77 20.34 1.46 0.62 0.42
KS 30 22.61 6.32 0.42 0.17 0.40
KS + PP 1 21.28 40.96 4.94 1.96 0.40
KS + PP 30 19.85 43.47 5.62 2.09 0.37
KS + HP 1 25.98 40.12 3.96 1.51 0.39
KS + HP 30 20.80 25.63 3.16 1.11 0.35

AM1 and AM2: bioclastic monument.

P. Maravelaki-Kalaitzaki et al. / Progress in Organic Coatings 57 (2006) 140148 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
EDXRF showed that the applied products reached a pene-
tration depth of 30 mm. KS and PP were evenly distributed
inside the limestone, while ES and LD accumulated on the
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
Fig. 7. Area analyzed by SEM, the corresponding SEM-EDS spectrum and the between calcite and the alkoxysilanes-derived gels, due to the
semi-quantitative analysis of an AM1 sample treated with KS. hydroxyl groups of the quartz included in the limestones.

Fig. 7 illustrates the area analyzed by SEM, the correspond- From the above studied products Ludox and ethyl silicate,
ing SEM-EDS spectrum and the semi-quantitative analysis of which remain on the surface and create an over-strengthening,
an AM1 sample treated with KS. The Si/Ca obtained SEM- are not recommended as consolidants for this kind of porous
EDS intensities (equal to 0.081) are in close relationship with limestones. The elastified silicic acid ethyl ester (PP) behaves
the corresponding EDXRF Si/Ca X-rays yields (equal to 0.093) properly and can be used for a consolidation treatment.
indicating that EDXRF can be used for evaluating the penetra-
tion depth of the consolidants. Acknowledgement

4. Conclusions The authors would like to acknowledge the valuable contri-

bution of Prof. A. Tsetsekou (Department of Mineral Resources
The selection of the most efficient consolidation treatment Engineering, Technical University of Crete) for the MIP mea-
takes into consideration the following criteria: least chromatic surements.
variation, lowest decrease in water vapor permeability, highest
liquid water-repellence, highest consolidant penetration depth References
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