Scuola di Dottorato in Scienze della Terra,
Dipartimento di Geoscienze, Università degli Studi di Padova – A.A. 2010-2011
CHARACTERIZATION STUDIES ON CEMENT CONGLOMERATES FROM HISTORIC
REINFORCED CONCRETE STRUCTURES
Ph.D. candidate: MICHELE SECCO
Tutors: Prof. GILBERTO ARTIOLI, Prof. CLAUDIO MAZZOLI
Cycle: XXIV
Abstract
One and a half century after its invention, the reinforced concrete is nowadays considered a cultural heritage material,
being the structural core of the 20th century contemporary architecture. The characterization of this heterogeneous artefact
has been for decades exclusive competence of structural engineers, but, over the last fifteen years, it has become one of the
main fields of study of material scientists, due to its mineralogical, textural and chemical complexity and high susceptibility to
the action of external chemical-physical degrading agents.
This research project is aimed at the multianalytical characterization of cement conglomerates from five historical
structures located in north-eastern Italy and built between the end of the 19th and the middle of the 20th century, paying
attention to the determination of the original mix designs, to the study of their conservation state and to the development of
novel medium invasive analytical techniques.
The materials were first of all characterized according to a multianalytical approach, starting from the petrographic
characterization of the conglomerates according to a custom-modified version of ASTM C856 standard and integrating the
petrographic data with mineralogical analyses by XRPD and microstructural-microchemical analyses by SEM-EDS. This
classic approach was only the starting point and the crosscheck for the quantitative reconstruction of concretes' mix designs,
performed through a newly-developed multiscale image analysis technique; the novel approach proved to be extremely
reliable to fully characterize these heterogeneous and poorly standardized materials. Finally, an accurate study of the
conservation state and degradation phenomena acting on the materials was performed by means of petrographic, XRPD and
SEM-EDS analyses, paying particular attention to the characterization of the newly described synergic sulphate-phosphate
attack, investigated also by synchrotron micro-diffraction, in situ XRPD studies using a diffractometer equipped with a hot
chamber, thermal analyses, ICP-OES, FT-IR spectroscopy and thermodynamic modelling.
1. The structures: historical background, architectural features and sampling strategies
The construction time of the five buildings spans over a wide chronological period, comprised
between the last decade of the 19th century and the 1960s. They all belong to the first era of reinforced
concrete production, characterized by the lack of plasticizers and water reducing admixtures in the mixes,
consistency of the pastes below S4, project of the mixes according to prescribed dosages and not to
performance criteria and prevalence of the in situ construction of the reinforced concrete structural
elements over the use of prefabricated modules. The studied buildings are described as follows:
 North wing of the Carraresi Castle (Padova). Originally built between the 13th and 14th century, the
building was heavily modified between the end of the 19th century and the middle of the 20th century
after its conversion to prison. Reinforced concrete elements were introduced in the original structure
in three distinct constructive phases: a first one at the end of the 19th century according to the
Hennebique construction method, a second one during the 1920s and the last one during the 1950s;
 Victory Monument (Bolzano). Designed by Marcello Piacentini in 1926 and built during the course of
1929, the Victory Monument is nowadays considered a masterpiece of fascist architecture. Inspired by
Roman triumphal arches, the structure stands on a concrete strip foundation. The substructure of the
podium is constituted by non-reinforced concrete walls, sustaining a series of reinforced concrete
slabs and beams forming the stairway and a non-reinforced concrete slab forming a central vault;
 Former Zweifel embroidery plant (San Giovanni Lupatoto, Verona). Originally built in 1926, the
structure was raised in 1964 with the construction of a great hall inspired to Pierluigi Nervi concrete
shells, made with both in situ produced and prefabricated elements. The building was interested in
2008 by a severe structural failure, which caused the collapse of a wide area of the great hall;
 “Ex Agrimont” area (Marghera, Venice). The industrial plant was founded in 1927 for the production
of fertilizers. During the 1950s a great reinforced concrete structure was built (C3 building),
constituted by in situ prefabricated structural arches. The complex is currently under restoration;
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Scuola di Dottorato in Scienze della Terra,
Dipartimento di Geoscienze, Università degli Studi di Padova – A.A. 2010-2011

“Ex Foro Boario” (Padova). Designed by Giuseppe Davanzo and characterized by an extremely
innovative design, the structure was built in 1968 and is made of prestressed and prefabricated
reinforced concrete slabs sustained by in situ-produced multiple concrete columns.
The study was focused only on the characterization of the in situ produced concrete elements, being
the most susceptible to problems correlated to non standardized production protocols. According to the
structural nature of the buildings, different elements were sampled (slabs, walls, columns, arches and
beams). Accurate surveys were performed prior to concrete sampling, to minimize the invasiveness of
sampling operations. When possible, concrete samples were taken from already detached portions or from
scarifications residuals. Micro-cores for petrographic examinations were also extracted by means of a
water-lubricated hollow tip drill. Large concrete cores, necessary both for the compression strength tests
and the mix designs reconstructions, were extracted by means of a water-lubricated concrete core drill.
Prior to perforation, the position of the structural elements with a low bending moment, shear and axial
force values was chosen and then a superficial scan by means of magnetic scanner was performed, to
avoid damage to the rebars.
2. The classic approach: multianalytical characterization of the concretes
The textural and minero-petrographic characteristics of the concretes were determined by integrating
the analytical results of the petrographic examination according to ASTM C856 standard with the
mineralogical profiles obtained by XRPD and the microstructural and microchemical features
investigated by SEM-EDS and chemical mapping.
The materials are characterized by heterogeneous volumetric proportions between inert fraction and
cement matrix, both between the various structures and the various structural elements of each structure.
High cement dosages are generally observable for structural elements built to withstand flexural stresses
(e.g. beams and arches), with the exception of the central arches of the former Zweifel Embroidery plant,
which show a marked cement underdosage.
The petrographic and morphological nature of the inert fractions indicates for all the studied structures
a local supply of the aggregate from adjacent alluvial deposits and river beds . The concretes of the North
Wing of the Carraresi Castle, the Ex Agrimont Area and the Ex Foro Boario are characterized by a coarse
fraction mainly constituted by carbonate rocks, with prevalence of dolostones over limestones, while it is
possible to observe an enrichment in siliceous clasts in the fine fraction. The concretes of the former
Zweifel embroidery plant differentiate from the previous ones, being constituted by an inert fraction
almost entirely composed of carbonate rocks as regards the coarse aggregate, with prevalence of micritic
and bioclastic limestones over dolostones. Finally, the concretes of the Victory Monument are made with
an inert fraction totally constituted by clasts of volcanic and metamorphic rocks, with prevalence of
ignimbrites and quartzites. The maximum dimensions of the aggregate are generally related to the
structural elements, being greater for beams and walls with respect to slabs and columns. As regards the
granulometric distribution of the inert fractions, it is possible to observe an absence of design of the
granulometric curves for the older concretes, both in terms of maximum packing (Fuller & Thompson
curve [1]) and maximum workability (Bolomey curve [1]), with frequent enrichment in medium and
coarse sand and coarse gravel. A good accordance with the ideal Bolomey curve is observable for the Ex
Agrimont Area and ex Foro Boario concretes only.
The density of the cement matrices varies according to each single structure and the type of structural
elements; generally, the most recent structures show a denser matrix, with lower capillary porosity,
indicating lower cement ratios of the fresh conglomerates. Moreover, beams and columns show a lower
degree of microcracking with respect to the other structural elements. The degree of hydration of the
cement paste is generally high with limited permanence of residual clinker grains. Still, it is possible to
observe the presence of C2S, C3S and C4AF in the finer fractions of the materials. The relict clinker
grains generally have dimensions of 30-50 µm, with rare particles of 80-100 µm in the older concretes
only. Microanalyses on the grains indicated a total reaction of C3S and an high degree of reaction of C2S
also, while the interstitial phase is frequently totally unreacted.
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Scuola di Dottorato in Scienze della Terra,
Dipartimento di Geoscienze, Università degli Studi di Padova – A.A. 2010-2011
The voids network is equally widely heterogeneous according to the different structures and elements.
A prevalence of millimetric entrapped air voids/water voids over submillimetric entrained air voids is
observable in the concretes of the second constructive phase of the North Wing of The Carraresi castle, as
well as in the concretes of the wall of the Victory Monument: these features indicate an inadequate degree
of compaction of the fresh conglomerate. The concretes of the arches of the former Zweifel embroidery
plant are characterized by an anomalous presence of large entrapped air voids, mainly due to the
inadequate volumetric proportions of the constituents. A prevalence of entrained air voids is observable in
the concretes of Ex Agrimont Area and Ex Foro Boario.
3. A novel approach: reconstruction of concretes mix designs through multiscale image analysis
The analytical results obtained with the previously described multianalytical protocol allowed an
accurate characterization of the analyzed materials, but still qualitative, in particular as regards the
determination of several parameters, fundamental for the reconstruction of the original mix designs (e.g.
water/cement ratio, cement/aggregate ratio, granulometric distribution curve of the inert fraction). At the
state of the art these characteristics are studied through manual point-count methodologies, such as those
explained in ASTM C 457 standard, with great limitations to the subjectivity of the analyses and to the
fact that they are highly time-consuming. In this respect, several studies [2] proved the efficacy of digital
image analysis to obtain an objective and unbiased volumetric and morphological estimation of concrete
pore network, without extending the technique to the characterization of all concrete constituents. One of
the main objectives of this research project is the development of a valid and multiscale protocol of
sample preparation, image acquisition, and analysis in order to fully and quantitatively reconstruct mix
designs of the studied historical concretes. The study was performed on the 26 structural elements from
which at least a large core for compression tests was extracted.
The macroscale image analysis was performed on several finely polished concrete slabs sawn from
the cores at a distance greater than 100 mm from the external surface, to avoid areas altered by external
degrading agents. To enhance the visibility of the macro-voids, a protocol of vacuum impregnation of the
porosity by a green dyed epoxy resin was developed. Moreover, micro-voids were enhanced by filling
them with a micronized powder of synthetic eskolaite, characterized by a green colour similar to the one
of the resin. The treated surfaces were scanned in 24-bit RGB color through an Epson V750 PRO flatbed
scanner at a 3600x3600 dpi (8x8 µm) optical resolution. Then, to enhance cement matrices, the surfaces
were subject to an acid attack with a solution of 3% tartaric acid-3% tannic acid [3], which selectively
stained the hardened paste only, and re-scanned at the same resolution with a fluid mount technique. After
an accurate registration, the six channels of the images were merged in a multi-channel composite image,
analyzed with a multispectral software (ENVI 4.7) to segment the three main volumetric components of
concretes (cement matrix, aggregate and voids). Excellent results were obtained by applying an algorithm
of maximum likelihood to defined classes, described by an adequate number of training pixels. The
volumetric estimations obtained by the segmentation procedure, calculated with ImageJ software, were
compared to the ones obtained performing a manual point count on the same samples: the data resulted to
be fully comparable, confirming the reliability of the image analysis procedure.
The macroscale data were extended at the microscale performing image analysis routines on several
images obtained by SEM imaging and EDS mapping on samples in thin section. The segmentation was
obtained with both a custom-formulated BSE-SE images merging technique and a multi-elemental image
analysis procedure, performed on multi-channel composite images created from the elemental maps and
analyzed with a multispectral software (ENVI 4.7). The latter technique allowed not only the
segmentation of the three main concrete constituents, but also a quantitative determination of the
mineralogical nature of the fine aggregate.
Considering the direct relation between capillary porosity and water/cement ratio [4], the latter was
determined on the studied concretes by means of automated image analysis on high magnification BSE
images of the cement matrices, using long-cured CEM I standard samples to extrapolate the regression
functions between the two parameters.
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Scuola di Dottorato in Scienze della Terra,
Dipartimento di Geoscienze, Università degli Studi di Padova – A.A. 2010-2011
The conversion of the volumetric percentages into absolute weight fractions was performed by
estimating the densities of the solid components of concretes. Sand densities were determined by the
quantitative determination of their mineralogical profiles obtained by multi-elemental image analysis,
while gravel densities were estimated considering their petrographic nature. Cement paste densities were
determined through the extrapolation of the regression function between their values and water/cement
ratios, using long-cured CEM I standard samples as reference, analyzed both by helium pycnometry and
thermogravimetry. The weight quantities of anhydrous cement on the original mixes were estimated
considering the amount of structural water on the hardened cement pastes, strictly related to water/cement
ratios, as determined by thermogravimetry on standard samples.
Finally, the granulometric distributions of the inert fractions were reconstructed by image analysis,
integrating the morphological data of the aggregate particles segmented at different scales, and the results
were compared with the corresponding Fuller & Thompson and Bolomey curves, to check the accuracy of
the initial aggregate proportioning.
The data obtained from the multiscale image analysis procedure resulted to be fully comparable with
the ones obtained from the multianalytical study, allowing the integration and quantitative confirmation
of the results. Generally, a lack of accurate mix design for the older concretes has been observed, in
accordance with the production of the conglomerates according to prescribed dosages and not to
performance criteria. The correspondence between experimental granulometric curves and reference
Bolomey curves is satisfied especially in the most recent structures, in particular on Ex Foro Boario
concretes, whereas in the older structures strong enrichments in coarse gravel and/or coarse and medium
sand are frequent (figure 1). Moreover, it was observed that high compression strength values were
obtained even in the oldest structures by using high cement dosages, whereas low compression strength
values are strictly correlated with anomalous porosities, due to both excessive water/cement ratios and
inadequate compaction procedures. In the most extreme cases, combinations of wrong constituents
proportioning, low cement dosages, excessive water/cement ratios and porosities and bad granulometric
distributions led to extremely poor mechanical properties, responsible for more or less accentuate
structural failures (e.g. former Zweifel embroidery plant).
4. The study of concrete degradation
The alteration phenomena acting on the concrete elements of the studied structures were studied
according to a multianalytical approach articulated in a preliminary petrographic study, integrated by
profile XRPD analyses on the finer fractions of the materials and SEM-EDS analyses both on massive
and thin section samples.
All the materials were interested by carbonation of the cement matrices. The degree of alteration
resulted to be strongly dependent to the textural characteristics of the materials and the environmental
conditions to which they were exposed. Generally, the carbonation is limited to the cortical portions of
the concretes, with maximum penetration of the front located in the concrete outer cover and permanence
of the alkaline environment in the core. The excessive porosity of some structural elements, the high
water percolation and relative humidity excursions, or a combination of both factors, caused anomalous
development of the degradation in some cases, with consequent oxidation of the rebars. As regards the
North Wing of the Carraresi Castle, the ground floor beams underwent total carbonation due to the high
porosity, while the third floor slab resulted to be totally carbonated due to both the anomalous porosity
and the exposition to massive water percolation due to the collapse of the roof. As regards the Victory
Monument, the massive water percolation and high relative humidity variations caused relevant
carbonation phenomena on the concrete samples of the walls only, characterized by high connected
macroporosity. The alteration was so intensive as to cause the formation of metastable calcium carbonate
(vaterite) in the matrices, often in framboidal aggregates, and to cause the formation of external concrete
stalactites. As regards the former Zweifel embroidery plant, the total carbonation was reached in the arch
concretes only, characterized by extremely high porosity values.
All the concretes underwent alteration due to external sulphate attack. The degradation resulted to be
in most cases limited to the cortical portions, and at an initial stage of secondary gypsum formation due to
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Scuola di Dottorato in Scienze della Terra,
Dipartimento di Geoscienze, Università degli Studi di Padova – A.A. 2010-2011
portlandite reaction with sulphates in pore solution, with limited formation of ettringite and thaumasite.
High carbonation rates resulted to be a limiting factor for the development of this form of alteration,
being a strong source of calcium hydroxide consumption. External sulphate attack resulted to be
extremely diffuse in the "ex Agrimont" area concretes, with precipitation of high amounts of gypsum,
ettringite and thaumasite even in the core of the materials: this is due to the high environmental pollution
related to the industrial area.
Chloride attack interested the "ex Agrimont" area concretes only, due to the proximity of the structure
to the coastline and the consequent exposure to saltwater capillary rise and saline aerosols. The effects are
formation of secondary Friedel's salts, due to the dissolution of hydrous calcium aluminates and reaction
with chloride-rich porewater, and pitting corrosion of the rebars, with precipitation of iron chlorides.
Alkali-silica reactions resulted to be widely diffused in the Victory Monument concretes, with
formation of hydrous alkali-silica gels due to the reaction between amorphous silica of the aggregate and
alkali ions in pore solution, leached from both the cement matrix and the volcanic glass of the ignimbrites
constituting the inert fraction. Microscopic observations show the widespread presence of stressed and
strongly corroded ignimbrite and microcrystalline quartz fragments with corrosion bends. Furthermore,
the samples show many micro-cracks, mostly oriented perpendicularly to the concrete’s external surface
and interconnected with each other by a network of random sub-micrometer cracks. The presence of
diffuse ASR gel products is confirmed by EDS mapping of the altered matrices, highly enriched in
potassium in comparison to standard unaltered concretes.
The Victory Monument concretes are also characterized by superficial scaling due to salt
crystallization pressure development related to the formation of sodium sulphates, both anhydrous
(thenardite) and hydrated (eugsterite and mirabilite). The development of these secondary phases, during
rapid and intense variations in relative humidity values and consequent wetting and drying cycles of the
pore water, is due to the reaction between alkalis and sulphate in pore solution.
The concrete samples of the "ex Foro Boario" are interested by a rare form of alkali carbonate
reaction which caused de-dolomitization phenomena on the dolostone clasts constituting the inert
fraction, that are characterized by the presence of reaction rims with precipitation of secondary magnesite
at the interface with the surrounding matrix.
Besides these common forms of concrete alteration, a novel type of degradation was for the first time
observed and described in the concrete samples of the "Ex Agrimont" area, the synergic sulphatephosphate attack. This form of alteration, related to the interaction between sulphate-rich atmospheric
multipollutants and phosphate-ammonia-rich solutions leached from the fertilizers production plant, was
studied through a profile multi-analytical approach consisting of a combination of optical microscopy,
synchrotron-based micro-XRPD (performed at the µ-spot beamline of BESSY II light source) and SEMEDS microanalysis. Moreover, the dehydration behaviour of the secondary phases was investigated on the
synthesized phases through in situ thermal XRPD and Rietveld refinement, thermal analyses, ICP-OES,
FT-IR spectroscopy and SEM-EDS analyses. Finally, a thermodynamic alteration model was elaborated
using PHREEQC2 software. The results suggest severe decalcification of the cement matrix and
formation of secondary sulphates and phosphates according to a marked mineralogical and textural
zoning: I) gypsum, bassanite, anhydrite and ardealite in the superficial efflorescence; II) monetite in the
superficial crusts; III) gypsum-brushite solid solution and ardealite in the external strata; IV) octacalcium
phosphate and struvite in the intermediate layers; V) apatite and struvite in the inner altered portions. The
heterogeneous microstructural development of secondary phases was interpreted taking into account the
different source of sulphate and phosphate pollutants. Moreover, the permanence of apatite acidic
precursors in the external strata suggests that these portions were exposed to high acidity conditions,
related to sulphuric acid formation in the pore water after reaction with sulphur dioxide, while the
presence of anhydrous calcium sulphates and phosphates suggest a progressive dehydration, possibly by
solar radiation warming of the solid solution end-members, i.e. gypsum and brushite-rich terms.
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Scuola di Dottorato in Scienze della Terra,
Dipartimento di Geoscienze, Università degli Studi di Padova – A.A. 2010-2011
Figure 1. Comparison between a low strength concrete (a, b, c: lateral wall of Victory Monument, Rck 10.05 MPa) and an high
strength concrete (d, e, f: column of "Ex Foro Boario", Rck 68.67 MPa). a, d) segmentation of cement matrix (cyan), aggregate
(magenta) and voids (yellow); cement dosages: 212.63 kg/m3 (lateral wall of Victory Monument), 330.31 kg/m3 (column of
"Ex Foro Boario". b, e) retained aggregate fractions at the ASTM standard sieves and comparison with reference Bolomey
values. c, f) cumulative passing granulometric curves, in comparison with reference Bolomey curves.
References
[1] COLLEPARDI, M., COLLEPARDI, S. & TROLI, R. 2008. Mix design del calcestruzzo. Enco S.r.l.,
Treviso.
[2] JAKOBSEN, U.H., PADE, C., THAULOW, N., BROWN, D., SAHU, S., MAGNUSSON, O., DE
BUCK, S. & DE SCHUTTER, G. 2006. Automated air void analysis of hardened concrete – a Round
Robin study. Cement and Concrete Research, 36, 1444-1452.
[3] LINARES, L., LOPEZ-ATALAJA, M. & CHINCHON, S. 2009. Cement content determination
through selective stain in hardened concrete. Cement and Concrete Research, 39, 1105-1109.
[4] INGHAM, J. 2011. Geomaterials under the microscope. Manson Publishing, London.
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Scuola di Dottorato in Scienze della Terra,
Dipartimento di Geoscienze, Università degli Studi di Padova – A.A. 2010-2011
SUMMARY OF LAST YEAR’S ACTIVITIES
Courses:
MAZZOTTI, C., SURICO, F., FERRARI, G. & MARINO, R.: "Tecnologia del calcestruzzo", Auditorium Mapei, Milano.
Schools, workshops and congresses
10th International Conference on non-destructive investigations and microanaysis for the diagnostics and conservation of
cultural and environmental heritage, ART'11 , Firenze, IT, 13th-15th April 2011.
13th International Congress on the Chemistry of Cement, ICCC 2011, Madrid, ES, 3rd-8th July 2011.
XCVII Congresso Nazionale della Società Italiana di Fisica, SIF 2011, L'Aquila, IT, 26th-30th September 2011.
SAIE Concrete 2011, Bologna, IT, 4th-9th October 2011.
Communications:
ARTIOLI, G., CASARIN, F., DALLA BENETTA, M., DA PORTO, F., SECCO, M., & VALLUZZI, M.R. 2011. Restoration of
historic masonry structures damaged by the 2009 Abruzzo earthquake through injection grouts. 9th Australasian Masonry
Conference. 15th-18th February 2011, Queenstown (NZ).
SECCO, M., STIEVANIN, E., DA PORTO, F., MODENA, C., ARTIOLI, G. & MAZZOLI, C. 2011. Non destructive and
medium destructive analyses on an early 20th century reinforced concrete structure: the case study of the Victory Monument in
Bolzano. 10th International Conference on non-destructive investigations and microanalysis for the diagnostics and
conservation of cultural and environmental heritage – ART ‘11, Firenze (IT).
SECCO, M., MARITAN, L., LAMPRONTI, G.I., ARTIOLI, G. & MAZZOLI, C. 2011. Degradation of reinforced concretes
from industrial buildings caused by combined sulphate-phosphate attack. 13th International Congress on the Chemistry of
Cement – ICCC 2011, Madrid (ES).
SECCO, M., ARTIOLI, G., DALLA BENETTA, M., DA PORTO, F., & COLETTI, C. 2011. Restoration of historic masonry
structures damaged by the 2009 Abruzzo earthquake: materials and methods. XCVII Congresso Nazionale della Società
Italiana di Fisica – SIF 2011, L'Aquila, IT.
Posters:
MARITAN, L., WAKSMAN, Y., SECCO, M., LAMPRONTI, G.I. & MAZZOLI, C. 2011. Alteration of lead-glazed ware and
amphorae from shipwrecks in the Black Sea (Ukraine). 11th European Meeting on Ancient Ceramics, EMAC 2011. 29th
September-1st October 2011, Natural History Museum, Vienna (AT).
MARITAN, L., SECCO, M. & MANTOVANI, V. 2011. The decorated Padan terra sigillata from Adria (north-eastern Italy):
provenance and production technology. 11th European Meeting on Ancient Ceramics, EMAC 2011. 29th September-1st October
2011, Natural History Museum, Vienna (AT).
Publications:
SECCO, M., MARITAN, L., MAZZOLI, C., LAMPRONTI, G.I., ZORZI, F., NODARI, L., RUSSO, U. & PESAVENTO
MATTIOLI, S. 2011. Alteration processes of pottery in lagoon-like environments. Archaeometry, 53, 809-829.
ARTIOLI, G., CASARIN, F., DALLA BENETTA, M., DA PORTO, F., SECCO, M., & VALLUZZI, M.R. 2011. Restoration of
historic masonry structures damaged by the 2009 Abruzzo earthquake through injection grouts. In: Proceedings of the 9th
Australasian Masonry Conference. 15th-18th February 2011, Queenstown (NZ).
7
Scuola di Dottorato in Scienze della Terra,
Dipartimento di Geoscienze, Università degli Studi di Padova – A.A. 2010-2011
SECCO, M., STIEVANIN, E., DA PORTO, F., MODENA, C., ARTIOLI, G. & MAZZOLI, C. 2011. Non destructive and
medium destructive analyses on an early 20th century reinforced concrete structure: the case study of the Victory Monument in
Bolzano. In: Proceedings of the 10th International Conference on non-destructive investigations and microanalysis for the
diagnostics and conservation of cultural and environmental heritage – ART ‘11, Firenze.
SECCO, M., MARITAN, L., LAMPRONTI, G.I., ARTIOLI, G. & MAZZOLI, C. 2011. Degradation of reinforced concretes
from industrial buildings caused by combined sulphate-phosphate attack. In: Proceedings of the 13th International Congress on
the Chemistry of Cement – ICCC, Madrid.
SECCO, M. 2011. Restoration of historic masonry structures damaged by the 2009 Abruzzo earthquake: materials and
methods. Il Nuovo Cimento C - Colloquia and communications in physics, in press.
STIEVANIN, E., DA PORTO, F., MODENA, C., SECCO, M. & ARTIOLI, G. 2011. Characterization studies on the reinforced
concrete dome of the former General Market of Verona, built in 1929. In: Proceedings of the "Domes in the World"
International Scientific Congress, Firenze.
Awards:
Award for the best communication at XCVII Congresso Nazionale della Società Italiana di Fisica, Sezione Vb "Fisica per i
Beni Culturali".
Teaching activities:
Co-supervisor of bachelor degree thesis in Science and Technology for Cultural Heritage. Student: Elena Squizzato; title of the
thesis: " Il degrado in ambiente di transizione: il caso delle ceramiche invetriate dall'affondamento di Novy Svet (Mar Nero) ".
Co-supervisor of bachelor degree thesis in Science and Technology for Cultural Heritage. Student: Vanessa Doulougeris; title
of the thesis: " Il degrado in ambiente di transizione: il caso delle anfore dall'affondamento di Novy Svet (Mar Nero) ".
Co-supervisor of bachelor degree thesis in Geological Science. Student: Federico Saporito; title of the thesis: "Studio
sull'influenza dei minerali argillosi sul fenomeno franoso in località Gamba (Monte di Malo, VI)".
Co-supervisor of master degree thesis in Science and Technology for Archaeological and Artistic Heritage. Student: Silvia
Madeddu; title of the thesis: "Caratterizzazione multi-analitica di conglomerati cementizi pertinenti a strutture storiche in
cemento armato".
Co-supervisor of bachelor degree thesis in Science and Technology for Cultural Heritage. Student: Alberto Zausa.
Co-supervisor of master degree thesis in Materials Science. Student: Riccardo Balzarin.
Field and experimental activities:
In situ non destructive and medium destructive analyses on reinforced concrete elements from late 19th – first 20th century
buildings located in the Veneto and Trentino-Alto Adige regions, together with adequate sampling by means of core-hole
drilling, local scarifications and superficial ablations. All analyses and sampling operations were performed in collaboration
with the Structural and Transportation Engineering Department of the University of Padova.
Petrographic, mineralogical, textural, microstructural and chemical analyses on the concrete samples taken during the field
activities by means of polarizing microscope and SEM observations, EDS microanalyses, XRPD analyses and image analysis.
All analyses were performed at the Geosciences Department, University of Padova.
Microstructural, microchemical and minero-petrographic analyses by means of polarizing microscope and SEM observations,
EDS microanalyses and XRPD analyses on samples of altered lead-glazed wares and amphorae from shipwrecks in the Black
Sea (Ukraine). All analyses were performed at the Geosciences Department, University of Padova.
Characterization studies through minero-petrographic and microchemical-microstructural analyses by means of polarizing
microscope and SEM observations, EDS microanalyses and XRPD analyses on historic mortars from San Pietro Apostolo
church (Onna, AQ). All analyses were performed at the Geosciences Department, University of Padova.
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Scuola di Dottorato in Scienze della Terra,
Dipartimento di Geoscienze, Università degli Studi di Padova – A.A. 2010-2011
Characterization studies through minero-petrographic and microchemical-microstructural analyses by means of polarizing
microscope observations and XRPD analyses on historic mortars from San Domenico church (L'Aquila). All analyses were
performed at the Geosciences Department, University of Padova.
Assessment of fire-damaged binders from Ex asilo Rossi (Schio, Vicenza) through microstructural, microchemical and mineropetrographic analyses by means of polarizing microscope and SEM observations, EDS microanalyses and XRPD analyses. All
analyses were performed at the Geosciences Department, University of Padova.
Study of the influence of mineral composition of soils on the activation and progression of Monte di Malo landslide (VI) by
means of XRPD analyses. All analyses were performed at the Geosciences Department, University of Padova.
Chemical-mineralogical and microstructural characterization of high-performance self-compacting reinforced concrete
modules by means of polarizing microscope and SEM observations, EDS microanalyses, XRPD analyses, XRF analyses and
mercury intrusion porosimetry. Optimization of mix designs for the improvement of the resistance to carbonatation
phenomena.
Mechanical and chemical-physical tests on prefabricated self-compacting concrete elements for sewage waters according to
standard UNI EN 1917. Study of the resistance of concretes to the action of highly aggressive wastewaters, through
mineralogical and chemical profiling by XRPD and SEM-EDS analyses. The analyses were performed at the Geosciences
Department and at the Structural and Transportation Engineering Department, University of Padova.
Characterization studies through minero-petrographic and microchemical-microstructural analyses by means of polarizing
microscope and SEM observations, EDS microanalyses and XRPD analyses on restoration plasters from a historic building in
Verona. All analyses were performed at the Geosciences Department, University of Padova.
Petrographic, mineralogical, textural and microstructural analyses on concrete samples from a hangar of Fiumicino airport
(Roma) by means of polarizing microscope and SEM observations, EDS microanalyses and XRPD analyses. The study was
aimed at determining the state of conservation of the structural materials. All analyses were performed at the Geosciences
Department, University of Padova.
Radiocarbon AMS dating on ancient mortars from three castle remains of different ages (Cuol di Ciastiel Castle, Late Roman
Empire, Pra di Got Castle, Early Middle Age, Sachuidic Castle, XII-XIII Century A.D.), located in the High Tagliamento river
Valley (Udine, Italy). All analyses were performed at the CIRCE AMS laboratory, Second University of Naples (Caserta).
SUMMARY OF SECOND YEAR’S ACTIVITIES
Courses:
BOURGARIT, D.: “Archaeometallurgy at the Louvre laboratory: from Bronze Age copper smelting to Renaissance bronze
statues casting”, Dipartimento di Geoscienze, Università degli Studi di Padova.
CALANDRUCCIO, E.: “Corso di Inglese parlato”, Dipartimento di Geoscienze, Università degli Studi di Padova.
DALCONI, M. C.: “Mineralogia applicata ai minerali industriali”, Dipartimento di Geoscienze, Università degli Studi di
Padova.
MAZZOLI, C.: “Laboratorio di Microscopia”, Dipartimento di Geoscienze, Università degli Studi di Padova.
NONAT, A.: “Generalities on cement and thermodynamics and kinetics of hydration”, Dipartimento di Geoscienze, Università
degli Studi di Padova.
SALMASO, L. & CORAIN, L.: "Statistica applicata alla sperimentazione scientifica", Centro studi per l’Ambiente Alpino,
San Vito di Cadore (BL).
SCRIVENER, K.: "Mapei symposium on the cement chemistry", Auditorium Mapei, Milano.
Schools, workshops and congresses
Second UNESCO World Heritage Workshop on “Disaster Risk Reduction to Cultural Heritage”. Acre, Israel, 14th-17th
November 2009.
38th International Symposium on Archaeometry, ISA 2010, Tampa, FL, U.S.A., 10th-14th May 2010.
9
Scuola di Dottorato in Scienze della Terra,
Dipartimento di Geoscienze, Università degli Studi di Padova – A.A. 2010-2011
The 20th General Meeting of the International Mineralogical Association, IMA 2010, Budapest, HU, 21st-27th August 2010.
SEM and Microanalysis in the Study of Historical Technology, Materials and Conservation, SEM 2010, London, GB, 9th-10th
September 2010.
2nd Historic Mortars Conference and RILEM TC 203-RHM “Repair Mortars for Historic Masonry” Final Workshop, Prague,
CZ, 22nd-24th September 2010.
Communications:
SECCO, M., MARITAN, L., LAMPRONTI, G.I., MAZZOLI, C., & ARTIOLI, G. 2010. Crystallization of secondary sulphate
and phosphate phases in cementitious conglomerates exposed to polluted environments. The 20th General Meeting of the
International Mineralogical Association, IMA 2010. 21st-27th August 2010, Danube Riverside Campus (Lágymányos) of the
Eötvös University, Budapest (HU).
Posters:
SECCO, M., ARTIOLI, G., MAZZOLI, C., GELICHI, S., CIANCIOSI, A. & PIUZZI, F. 2010. Archaeometrical studies on
mortars from the Sachuidic Castle (Forni di Sopra, North-eastern Italy): a tool for archaeological data interpretation. 38th
International Symposium on Archaeometry, ISA 2010. 10th-14th May 2010, University of South Florida, Tampa (FL, USA).
MARITAN, L., NODARI, L., THIELLA, V., SECCO, M., LAMPRONTI, G.I., RUSSO, U., MAZZOLI, C. & PESAVENTO
MATTIOLI, S. 2009. Transitional environments and alteration processes: the case study of pottery from the Roman river
harbour of Corte Cavanella (Rovigo, North-eastern Italy). 38th International Symposium on Archaeometry, ISA 2010. 10th-14th
May 2010, University of South Florida, Tampa (FL, USA).
MARITAN, L., SECCO, M., MAZZOLI, C. & , ARTIOLI, G. 2010. Secondary phases in historical materials: a microstructural
approach for interpreting correct sequences of crystallization. SEM and Microanalysis in the Study of Historical Technology,
Materials and Conservation, SEM 2010. 9th-10th September 2010, British Museum, London (UK).
ARTIOLI, G., SECCO, M., MAZZOLI, C., COLETTI, C., VALLUZZI, M.R. & DA PORTO, F. 2010. Characterization of
stone masonry panels consolidated by injection of grouts in buildings damaged by the 2009 Abruzzo earthquake. 2nd Historic
Mortars Conference and RILEM TC 203-RHM “Repair Mortars for Historic Masonry” Final Workshop. 22nd-24th September
2010, Hotel Diplomat, Prague (CZ).
Publications:
SECCO, M., MARITAN, L., LAMPRONTI, G.I., MAZZOLI, C., & ARTIOLI, G. 2010. Crystallization of secondary sulphate
and phosphate phases in cementitious conglomerates exposed to polluted environments. Acta Mineralogica-Petrographica,
Abstract Series, 6, 65.
ARTIOLI, G., SECCO, M., MAZZOLI, C., COLETTI, C., VALLUZZI, M.R. & DA PORTO, F. 2010. Characterization of
stone masonry panels consolidated by injection of grouts in buildings damaged by the 2009 Abruzzo earthquake. In: Valek, J.,
Groot, C. & Hughes, J.J. (ed.). Proceedings of the 2nd Historic Mortars Conference and RILEM TC 203-RHM “Repair Mortars
for Historic Masonry” Final Workshop, 871-881. RILEM Publications, Bagneux.
MARITAN, L., SECCO, M., MAZZOLI, C. & , ARTIOLI, G. 2010. Secondary phases in historical materials: a microstructural
approach for interpreting correct sequences of crystallization. In: Meeks, N. (ed.) Proceedings of the 1st conference “SEM and
Microanalysis in the Study of Historical Technology, Materials and Conservation, SEM 2010”. Archetype Publications,
London. In press.
Teaching activities:
Teaching assistant: 2 hours, “Petrografia applicata ai materiali ceramici”, Laurea di primo livello in Scienze e Tecnologie per i
Beni Culturali (2009/2010).
Teaching assistant: 4 hours, “Georisorse per i Beni Culturali”, Laurea specialistica in Scienze e Tecnologie per i Beni
Archeologici ed Artistici (2009/2010).
10
Scuola di Dottorato in Scienze della Terra,
Dipartimento di Geoscienze, Università degli Studi di Padova – A.A. 2010-2011
Co-supervisor of master degree thesis in Science and Technology for Archaeological and Artistic Heritage. Student: Chiara
Coletti; title of the thesis: "Iniezioni compatibili per il consolidamento di murature danneggiate dal sisma di Abruzzo 2009:
caratteristiche dei materiali strutturali e dei leganti".
Field and experimental activities:
In situ non destructive and medium destructive analyses on reinforced concrete elements from late 19th – first 20th century
buildings located in the Veneto and Trentino-Alto Adige regions, together with adequate sampling by means of core-hole
drilling, local scarifications and superficial ablations. All analyses and sampling operations were performed in collaboration
with the Structural and Transportation Engineering Department of the University of Padova.
Petrographic, mineralogical, textural, microstructural and chemical analyses on the concrete samples taken during the field
activities by means of polarizing microscope and SEM observations, EDS microanalyses, XRPD analyses and image analysis.
All analyses were performed at the Geosciences Department, University of Padova.
Petrographic, mineralogical, textural and microstructural analyses on a concrete pavement from an industrial building
(Villesse, Gorizia, Italy) by means of polarizing microscope observations and XRPD analyses. The study was aimed at
determining the state of conservation of the structural substrate and the superficial coating. All analyses were performed at the
Geosciences Department, University of Padova.
Study of the resistance of silica fume-additivated self compacting concretes to the action of highly aggressive wastewaters,
trough mineralogical and chemical profiling by XRPD and SEM-EDS analyses. All analyses were performed at the
Geosciences Department, University of Padova.
In situ samplings and archaeometrical studies by means of petrographic, microstructural, mineralogical and statistical analyses
on ancient mortars from three castle remains of different ages (Cuol di Ciastiel Castle, Late Roman Empire, Pra di Got Castle,
Early Middle Age, Sachuidic Castle, XII-XIII Century A.D.), located in the High Tagliamento river Valley (Udine, Italy). All
analyses were performed at the Geosciences Department, University of Padova.
Archaeometrical studies by means of petrographic, microstructural, mineralogical and statistical analyses on ancient mortars
from the Caporiacco Castle (XI Century A.D.), located in Colloredo di Monte Albano (Udine, Italy). All analyses were
performed at the Geosciences Department, University of Padova.
In situ samplings and characterization studies by means of petrographic, microstructural, mineralogical and microchemical
analyses on hardened restoration grouts injected inside multi-leaf medieval sea walls of the Citadel of Acre, Israel. All analyses
were performed at the Geosciences Department, University of Padova.
Participation to a pilot project for the restoration of masonry walls from the towns of Onna, Tempera and Sant’Eusanio
Forconese (L’Aquila, Italy), heavily damaged by the 2009 Abruzzo earthquake, by means of compatible injection grouts. The
project was done in collaboration with the Structural and Transportation Engineering Department of the University of Padova
and several industrial partners (Mapei, Kerakoll, Tassullo, Basf). Several portions of multi-leaf stone masonry walls were
selected for carrying out experimental injection tests, planned and verified by means of non-destructive and destructive
multiscale characterization studies. In particular, the original mortars were fully characterized from the mechanic,
petrographic, textural, mineralogical and chemical point of view, to choose the most suitable restoration products. The
characterization was carried out through compression strength tests, petrographic examinations, particle size distribution
studies, colorimetric measurements, XRPD analyses, microchemical and microstructural studies by SEM-EDS. The same
methodology was adopted to assess the compatibility of the chosen restoration products. The selected masonry portions were
characterized by means of non-destructive sonic tests. The shear strength and deformability of some of the masonry walls were
evaluated by means of diagonal tests, carried out in the original – non-reinforced – state. The remaining masonry walls were
injected with the selected grouts, and tested again by means of sonic and diagonal compression tests in the strengthened state,
to assess the effectiveness of the interventions. Finally, after the destructive tests, the effectiveness of the selected restoration
protocols and materials on the microstructures was checked through optical and electronic microscopy on the interfacial zones
between the grout and the original constituents.
Microstructural, microchemical and minero-petrographic analyses on samples of Roman Terra Sigillata potteries found in the
city of Adria (Rovigo, Italy). All analyses were performed at the Geosciences Department, University of Padova.
Microstructural, microchemical and mineralogical analyses by XRPD and SEM-EDS on samples of Roman potteries found in
the site of Corte Cavanella (Loreo, Rovigo, Italy). Analyses were performed both at the Geosciences Department, University of
Padova and at the Chemical Sciences Department, University of Padova, in collaboration with Dr. Valentina Thiella, Dr. Lara
Maritan, Dr. Luca Nodari and Prof. Umberto Russo, in order to understand the nature of various types of chromatic turnings.
11
Scuola di Dottorato in Scienze della Terra,
Dipartimento di Geoscienze, Università degli Studi di Padova – A.A. 2010-2011
SUMMARY OF FIRST YEAR’S ACTIVITIES
Courses:
BOESSO, S.: “Introduzione alla biblioteca”, Dipartimento di Geoscienze, Università degli Studi di Padova.
DALCONI, M. C.: “Mineralogia applicata ai minerali industriali”, Dipartimento di Geoscienze, Università degli Studi di
Padova.
FIORETTI, A., DI TORO, G. & ARTIOLI, G.: "Corso di comunicazione scientifica", Dipartimento di Geoscienze, Università
degli Studi di Padova.
GLASSER, F.: “The materials science of Portland cement”, Dipartimento di Geoscienze, Università degli Studi di Padova.
GULICK, L.: “Corso avanzato di Inglese”, Dipartimento di Geoscienze, Università degli Studi di Padova.
MAZZOLI, C.: “Laboratorio di Microscopia”, Dipartimento di Geoscienze, Università degli Studi di Padova.
PESARIN, F. & SALMASO, L.: "Statistica applicata alla sperimentaizone scientifica", Dipartimento di Ingegneria Meccanica,
Università degli Studi di Padova.
RASSU, A., VINANTE, C. & PRATICELLI, N.: “Introduzione a LinuX”, Dipartimento di Geoscienze, Università degli Studi
di Padova.
STUTZMAN, P. & BULLARD, J.: “Avanced course on cement characterization and modelling”, Dipartimento di Geoscienze,
Università degli Studi di Padova.
TEZA, G.: “Introduction to Matlab”, Dipartimento di Geoscienze, Università degli Studi di Padova.
Schools, workshops and congresses
X School on Synchrotron Radiation: Fundamentals, Methods and Applications. Duino (TS), Italy, 7th-18th September 2009.
Injection Grouts for the Conservation of Architectural Surfaces, Getty Conservation Institute, Los Angeles, CA, U.S.A., 2nd-3rd
November 2009.
Posters:
NODARI, L., MARITAN, L., SECCO, M., RUSSO, U., MAZZOLI, C. & PESAVENTO MATTIOLI, S. 2009. Alteration
processes in lagoon environments: the case study of the Roman pottery from Aquileia and Olbia (Italy). 10th European Meeting
on Ancient Ceramics, EMAC 2009. 10th-13th September 2009, British Museum, London (UK).
Publications:
MARITAN, L., SECCO, M., MAZZOLI, C., NODARI, L., RUSSO, U. & PESAVENTO MATTIOLI, S. (2009). Forme e fasi
di alterazione dei materiali ceramici di Canale Anfora: implicazione nella ricostruzione delle condizioni dell’ambiente di
seppellimento. In: Scotti Maselli, S., Pesavento Mattioli, S. (ed.). I materiali dal Canale Anfora di Aquileia. Editreg, Trieste.
In press.
MARITAN, L., MAZZOLI, C., SECCO, M. & PESAVENTO MATTIOLI, S. (2009). Analisi archeometriche sulle anforette
di Canale Anfora. In: Scotti Maselli, S., Pesavento Mattioli, S. (ed.). I materiali dal Canale Anfora di Aquileia. Editreg,
Trieste. In press.
Teaching activities:
Teaching assistant: 2 hours, “Petrografia applicata ai materiali ceramici”, Laurea di primo livello in Scienze e Tecnologie per i
Beni Culturali (2008/2009).
Teaching assistant: 4 hours, “Georisorse per i Beni Culturali”, Laurea specialistica in Scienze e Tecnologie per i Beni
Archeologici ed Artistici (2008/2009).
12
Scuola di Dottorato in Scienze della Terra,
Dipartimento di Geoscienze, Università degli Studi di Padova – A.A. 2010-2011
Field and experimental activities:
In situ non destructive and medium destructive analysis on reinforced concrete elements from late 19th – first 20th century
buildings located in the Veneto region, together with adequate sampling by means of core-hole drilling, local scarifications and
superficial ablations. All analyses and sampling operations were performed in collaboration with the Structural and
Transportation Engineering Department of the University of Padova.
Petrographic, mineralogical, microstructural and chemical analysis on the concrete samples taken during the field activities by
means of polarizing microscope and SEM observations, EDS microanalysis and XRPD and AAS analysis. All analyses were
performed at the Geosciences Department, University of Padova.
Analytical studies for the conservation state determination of the “Ex Tiro a Volo” complex entrance porch (Lido of Venice)
and formulation of an adequate restoration project,. The work, committed by the municipality of Venice (Public Buildings
Department) and done in collaboration with the Structural and Transportation Engineering Department of the University of
Padova, was aimed at the execution of an urgent restoration of the structure.
Archaeometrical studies by means of petrographic, microstructural and mineralogical analysis on ancient mortars from three
castle remains of different ages (Cuol di Ciastiel Castle, Late Roman Empire, Pra di Got Castle, Early Middle Age, Sachuidic
Castle, XII-XIII Century), located in the High Tagliamento river Valley (Udine, Italy). All analyses were performed at the
Geosciences Department, University of Padova.
XRPD analysis and compression tests on mortar samples used for the restoration of the Citadel of Acre, Israel. Analyses have
were performed at the Geosciences Department, University of Padova, and at the laboratory of the Structural and
Transportation Engineering, University of Padova.
Participation to the “Progetto Paganica”, organized by the RELUIS consortium in collaboration with the National Civil
Protection Department, in order to perform an urban survey of the city of Paganica, heavily damaged by the 2009 L’Aquila
earthquake. The field activities have been performed from the 27th to the 31st July 2009. During the survey activities a series of
mortar samples from various buildings of the town have been sampled and they will be studied from a petrographic and
mineralogical point of view, in order to correlate state of damage of the buildings and nature and quality of the building
materials.
Sampling of Roman Terra Sigillata potteries found in the city of Adria (Rovigo, Italy).
13