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Vip Cardiano2004
Vip Cardiano2004
Received 20 January 2004; received in revised form 18 May 2004; accepted 18 May 2004
Abstract
The ancient bricks of the monastery of Fragalà in Frazzanò, the first Basilian-Norman center in Sicily and symbol of 15 centuries of
cultural life, were studied and characterized by a combination of techniques (INAA, ICP, porosimetry, HPLC, TG-DTA and XRD). Chemical
analysis shows that the Byzantine samples were mainly manufactured by calcareous clay while medieval ones were made of limeless clay.
The combined results of TG-DTA and XRD analyses, based on the presence of high-T Ca silicate phases, suggest that the firing temperature
was not exceeding 900 ◦ C while HPLC investigations evidence that the building does not suffer from decay phenomena due to the presence
of soluble salts.
© 2004 Elsevier B.V. All rights reserved.
Keywords: Brick analysis; Thermal analysis; Mercury porosimetry; Major oxides; Rare-earth elements; Soluble salts; X-ray diffraction
0003-2670/$ – see front matter © 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.aca.2004.05.042
104 P. Cardiano et al. / Analytica Chimica Acta 519 (2004) 103–111
bearing on the conservation technology. Today in fact histor- tance from the kiln and some times excavated and fired on
ical buildings are restored using plasters, mortars and bricks the side of the building itself. The overall conservation state
made according to contemporary standards, neglecting that of the bricks was investigated through mercury intrusion
the preservation of the original appearance of an historical porosimetry, that provides data on the microstructure of the
building as well as the physico-chemical compatibility with samples, and by means of HPLC to determine the soluble
the old materials require individual solutions. The paper also salts content, that is related to the action of marine aerosol
remarks the central role played by the analytical chemists, and to the migration of salts solution from the ground.
among the other scientists, in the diagnosis of the conserva-
tion state of artworks as well as in the chemical characteri-
zation of artifacts of great historical and artistic value. 2. Experimental
We report here on the characterization and classification
of the bricks of Frazzanò Monastery according to their chem- The sampling was accomplished in conjunction with
ical (major and trace elements) and mineralogical features. archaeologists of “Soprintendenza ai Beni Culturali e
X-ray and TG-DTA analyses were also carried out to obtain Ambientali” of Messina and performed on the basis of his-
information about the raw materials used as well as qualita- torical and architectonic considerations. Information regard-
tive indications about firing temperatures. The characteriza- ing sampling location and historical periods are provided in
tion of the raw materials may be a source of information on Table 1 and Fig. 2. After removal of the external part in order
the technology of bricks production in Sicily, the identifica- to analyse only non-altered material, the samples, taken with
tion of the production centers and the periods in which they a chisel, were studied by a combination of techniques. Ma-
were manufactured. The raw materials to produce bricks in jor and rare-earth elements analyses were accomplished by
fact were usually outcropped within a relatively short dis- inductively coupled plasma atomic emission spectrometry
Table 1
Sampling
Samples Sampling area Height (m) Sampling point
BO1 NE corner, outside, Byzantine church 2.5 Central apse, arched lintel
BI2 NE corner, inside, Byzantine church 2 Left apse, inner arched lintel
BI3 NE corner, inside, Byzantine church 2 Central apse, left side, inner arched lintel
BI4 NE corner, inside, Byzantine church 2 Central apse, left side, superior arched lintel
BI5 NE corner, inside, Byzantine church 1 Right apse, arched lintel
NO1 NW corner, outside 0.3 Main portal, left side
NO2 NW corner, outside 2 Main portal, left side
NI3 Norman church, inside 1 Main arch, right pier
NI4 Norman church, inside 1 Main arch, right pier
NO5 E wall, outside, Norman church 1 Central apse, right pilaster strip
NO6 E wall, outside, Norman church 1 Central apse, left pilaster strip
MO1 N wall, outside 0.3 Under a balcony dated 1937
P. Cardiano et al. / Analytica Chimica Acta 519 (2004) 103–111 105
3.1. Bricks
Fig. 3. Major oxides (%): samples with low CaO content. Fig. 5. Major oxides (%): samples with high CaO content.
ticeable difference lies in the percentage of the voids corre- range 1–0.5 m), the pore size distribution of BI3 is mainly
sponding to the maxima. On the contrary MO1 appears very concentrated in the range 0.3–0.05 m.
different either in porosity as in the pore size distribution. Among the six middle age samples: NI3 and NI4 exhibit
The pore size distribution of MO1, the less porous (22.3%) comparable parameters while NO5 and NO6, expected to be
among all the analysed samples, is mainly concentrated in very similar as sampled in the two pilaster strips of the apse,
the range 0.3–0.003 m (85%), dramatically shifted towards according to analytical and thermogravimetric analyses (see
the micropore region. This means that MO1, the newest later) show significant differences above all in the pore size
sample, will show lower resistance to water and soluble salt distribution which for NO6 includes pores ranging from 1
migration. to 0.05 m while for NO5 it is mainly concentrated between
The samples taken from the Byzantine church BI2 (inter- 0.4 and 0.1 m.
nal part of the church) and BI3 (arched lintel of sacred arch)
are characterized by comparable values of porosity, while 3.4. Thermogravimetric analysis
BO1 (external part of the church) differs for the average
pore radius and the pore size distribution. It is to note that Thermogravimetric and thermal analyses are often used
sample BI4, taken from the arched lintel as well, is featured as a tool for the characterization and classification, in com-
by a very different texture. While BI3 shows a total poros- bination with other techniques, of historical mortars and
ity of 31.4%, with an average pore radius of 0.21 m, BI4 bricks [14]. Temperature range and weight loss allow identi-
is much more porous (42.6%) and exhibits an average pore fication and semiquantitative determination of calcite, lime,
radius of 0.64 m. They also considerably differ in the pore magnesite, hydromagnesite and gypsum, the detection of
size distribution: while the greatest percentage of pores of organic compounds and clay dehydroxylation phenomena
BI4 (70%) is detected in the range 1–0.4 m (58.91% in the [15]. Dehydroxylation–rehydroxylation of clay mineral is a
Table 2
Bricks porosimetric data
BO1 BI2 BI3 BI4 BI5 NO1 NO2 NI3 NI4 NO5 NO6 MO1
Total porosity (%) 32.9 32.5 31.4 42.6 39.4 35.5 37.9 35.3 35.4 35.4 32.2 22.3
Bulk density (g cm−3 ) 1.64 1.69 1.72 1.52 1.58 1.62 1.64 1.64 1.59 1.54 1.83 1.84
Average pore radius (m) 0.32 0.20 0.21 0.64 0.83 0.80 0.81 0.38 0.36 0.38 0.47 0.27
Relative volume (%)
reversible process. Clay fired at temperature below 800 ◦ C sponding to the four inflections observed at 78, 342, 432 and
may slowly rehydroxylate partially restoring the original 570 ◦ C. The partially superimposed weight losses falling in
material. Above this temperature the process becomes irre- the temperature range 342–500 and 500–650 ◦ C represent
versible [16,17] and the mineral clay undergoes structural the main processes and are ascribed to interlayer water loss
and/or compositional modifications. Suggestions on raw ma- and clay dehydroxylation, respectively [18]. A small peak
terial composition and provenance as well as information at 806 ◦ C and a not negligible amount of imbibition water
on the baking temperature may be also available based on was also observed. It is worth to remember that MO1, the
simultaneous TGA/DTA investigations. less porous brick sample, was taken in the northern side of
According to the porosimetric findings, the TG and DTA the monastery that has been restored in the 1930.
analysis of samples falling in set I, namely NO1, NO2, MO1 The curves of NO5 and NO6 are a little surprising. To
and BI5, allows to detect some differences that would lead confirm the differences found by ICP in the MgO and CaO
to a further grouping of the above bricks. Samples NO1 and content, despite their sampling points in the pilaster strips are
NO2 show similar featureless curves with less than 2% of very close, their thermogravimetric behaviour shows similar
total weight loss at 1000 ◦ C (Table 3). Most of the weight total weight loss but significant differences in the location
loss (1.2%) appears in the range 200–400 ◦ C, very likely of the inflections. The thermograms of NO6 are featured
due to loss of interlayer water. The total weight loss of by three processes, endothermic in nature: two partially su-
BI5, one of the oldest brick sampled, is quite low (ca. 2%) perimposed weight losses falling in the range 200–550 ◦ C,
in the whole range of temperature. Only two small inflec- very likely due to interlayer water escape and clay dehy-
tions centered at 217 and 299 ◦ C were detected. In contrast droxylation, and a small peak at 139 ◦ C (peak at 7.64 Å in
the derivative curve (DTG) of the scan of MO1 (total loss the X-ray diffractogram of NO6), assigned to gypsum dehy-
of 12.4%) shows four peaks, endothermic in nature, corre- dration. The paragenesis of CaSO4 may be due to residual
mortar joints traces or, alternatively, may be found in the sul-
phur oxide rich kiln environment. Burning of sulphureous
Table 3 coal or decomposition of sulphur compounds, such as pyrite,
Weight loss (%) present in the raw material, may generate a sulphur trioxide
<200 ◦ C 200–600 ◦ C 600–850 ◦ C 25–1000 ◦ C atmosphere which easily reacts with CaO leading to CaSO4 .
BO1 1.5 2.7 7.4 11.6
On the contrary sample NO5 shows, as a major process, a
BI2 1.4 2.2 5.0 8.6 weight loss (3.5%) at 659 ◦ C assigned to calcareous material
BI3 1.5 2.3 4.6 8.4 decomposition. These differences, also supported by XRD
BI4 0.4 0.9 2.7 4.0 investigations, suggest that the raw material used to manu-
BI5 0.2 1.7 – 1.9 facture NO5 and NO6, was recovered from different sources.
NO1 – 1.3 0.4 1.7
NO2 – 1.4 – 1.4
The DTG and DTA analysis of samples NI3, NI4 and
NI3 1.4 3.1 3.4 7.9 BO1–BI4, the latter set sampled in the Byzantine church,
NI4 2.0 3.1 3.9 9.0 show similar features: total weight loss in the whole range of
NO5 1.6 1.8 3.5 6.9 temperature lying between 12 and 4% and a main inflection
NO6 3.6 3.6 0.8 8.0 falling in the range 600–750 ◦ C, due to calcareous decom-
MO1 2.8 4.3 5.3 12.4
position. The decomposition temperature of calcitic mate-
P. Cardiano et al. / Analytica Chimica Acta 519 (2004) 103–111 109
Table 4
Soluble salts content (%)
Cl− NO2 − NO3 − SO4 2− PO4 3− Na+ NH4 + K+ Mg2+ Ca2+
(peaks at 10 and 4.499 Å) is present, with different abun- also out sulphatation phenomena. Furthermore, the low salt
dance, in all the samples except NO1, NO6, BI4. Inde- content detected can be referred to the original composition
pendently from age and composition, diffractometric data of the raw clay rather than a specific alteration. The only
suggest that the possible baking temperature for most of the notable data concern NI3, NI4 and MO1. Samples NI3 and
samples lies in the range of 800–900 ◦ C, except for MO1 NI4 show a nitrate content which approximates to 1%. They
and BI4 which appear baked at higher temperatures. have been sampled inside the Norman Church that has been
The low CaO-content samples NO1, NO2, MO1 and BI5 employed for a long time both as a stable and as a warehouse,
clearly show the peaks at 2.51 and 2.69 Å of hematite which, and then, the nitrates can be confidently explained by this
as before stated, starts to form at ca. 850 ◦ C. In addition kind of activities. Brick MO1, sampled at ca. 30 cm from
optical microscopy analysis (results not reported) shows the ground in the northern part of the building, exhibits a
extended vitrification for sample MO1 only, suggesting that chloride and nitrate content of ca. 1%. Taking into account
this sample was fired at higher temperature or baked for a the distance of the monument from the sea and the evidence
longer time. The Norman samples NI3, NI4, NO5, NO6 and of the low chloride content in all samples taken in the same
the eighth century sample BI2 exhibit, well detectable, the area, probably the presence of above ions can be ascribed to
peaks of the high-temperature Ca-silicate phases gehlenite capillary phenomena rather than marine aerosols transport
and anorthite that in NO5 and NO6 appear with differ- [20,21].
ent abundance. BO1 and BI3 besides, a large amount of
muscovite, shows only traces of gehlenite and hematite
suggesting they have been baked at lower temperature. BI4, 4. Conclusions
although sampled very close to BI3, is featured by a com-
paratively large amount of anorthite as well as evident traces Although the low number of bricks analysed does not al-
of diopside, indicative of a higher baking temperature. low a statistical treatment by hierarchical cluster analysis,
the outcomes of the investigations carried out on brick sam-
3.6. Soluble salts analysis ples taken from the monastery of San Filippo di Fragalà
allows us to draw some preliminary conclusions. Indepen-
The determination of soluble salts in building materials is dently from chemical composition, production technology
one of the tests recommended by the Normal Commission and conservation state, all the raw materials used in brick
in order to verify the degradation phenomena occurring on manufacturing originate from the same geological source.
lithic samples and to determine their state of conservation. Furthermore, the chemical analysis findings suggest that raw
In fact the amount of soluble salts can be related to specific clay was excavated from different local sources. In fact, dif-
decay phenomena such as atmospheric pollution, acid rain ferently from Norman samples, made of limeless clay, the
or effects concerning marine spray. They cause weakening oldest samples were mainly manufactured by using calcare-
and degradation of the materials with formation of crusts or ous raw material. Samples NO1, NO2, MO1 and BI5 (set
efflorescence as visible effects. I), although featured by a low percentage of CaO, can be
According to the low conductivity values (not reported), distinguished by means of porosimetric, thermogravimetric
a first sight analysis of the data reported in Table 4 clearly and mineralogical investigations. In fact the bricks NO1 and
shows that all the samples are featured by a low total salts NO2, both taken from the north-western side of the build-
content thus indicating that the building is not affected by ing near the main entrance (at different heights), show a
appreciable decay phenomena. The low sulphate content, unique weight loss (ca. 2%), mainly due to interlayer water
as confirmed by mineralogical-petrographic analysis, rules escape, while X-ray analysis suggests a firing temperature
P. Cardiano et al. / Analytica Chimica Acta 519 (2004) 103–111 111
reaching up at least 850 ◦ C. Furthermore, soluble salts in- laster strip which is decorative only. So this decorative motif
vestigations do not show differences between them, despite could be added later or alternatively it was restored later in
they have been taken, as already stated, at different heights time. The combined data concerning NO1–NO2, NI3–NI4,
(sample NO1 at about 30 cm from the ground, while NO2 and NO5–NO6 suggest that, although dated back to 12th
at ca. 3 m), meaning that in this part of the building there century, the Norman church and the main entrance of the
are not degradation phenomena caused by rising dump. monastery were built at different times or with different raw
Sample MO1, taken from the northern side in a zone that material.
was restored during the thirties, is characterized by the low- Finally, the low amount of soluble salts detected in all the
est CaO content and is very different from all the others. samples lead us to suggest that, independently from the lo-
It is the less porous (22.3%) with the pore size distribution cation, in contrast with the high porosity values, the building
considerably shifted towards the micropores region. TG ex- does not suffer from decay phenomena due to rising dump,
periments lead to a considerable weight loss mainly due to acid rain or marine spray.
phenomena typical of clay, namely interlayer water loss and All these findings must be considered as being of prelim-
clay dehydroxylation while the groundmass shows isotropic inary significance only since investigations on a large num-
feature, as if it has been fired at a relatively low tempera- ber of plasters and mortars are in due course.
ture for a long time. BI5 is doubtless the more mysterious
brick. Although, sampled in the arched lintel of the right
apse of the Byzantine church, a few meters from the main References
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