DELL’ARCHITETTURA TRA BILANCI E - unive.it · s. gizzi ... diagnostici e interventi di...

Finito di stampare nel mese di giugno 2018presso Imoco Industrie Grafiche - Treviso - Italy

34° convegno internazionale Scienza e Beni CulturaliCollana Scienza e Beni CulturaliVolume.2018

ISSN 2039-9790ISBN 978-88-95409-22-1

INTERVENIRE SULLE SUPERFICIDELL’ARCHITETTURA TRA BILANCI EPROSPETTIVE.Bressanone, 3 - 6 luglio 2018

In questo volume vengono pubblicati i contributi estesi (Full-paper) chesono stati sottoposti a peer review da parte di referees qualificati.

ACTING ON ARCHITECTURAL SURFACE BETWEENBUDGETS AND PERSPECTIVES.Bressanone, 3 - 6 july 2018This volume includes extensive contributions (Full-paper) that have beensubject to peer review by qualified referees.

Tutti i diritti riservati 2018,EDIZIONE ARCADIA RICERCHE SrlParco Scientifico Tecnologico di VeneziaVia delle Industrie 25/11 – Marghera VeneziaTel.:041-5093048 E-mail: [email protected]

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SCIENZA E BENI CULTURALI

INTERVENIRE SULLE SUPERFICI

DELL’ARCHITETTURA

TRA BILANCI E PROSPETTIVE

34° convegno di studi internazionale Bressanone 3 – 6 luglio 2018

a cura di Guido Biscontin e Guido Driussi

INDICE

SUPERFICI ARCHITETTONICHE E PULITURE ECCESSIVE. S. Gizzi ....................................................................................................... 1

CONTRO IL COMUNE SENSO DEL DECORO: INTERVENTI SULLE

SUPERFICI DELL'EDILIZIA STORICA E MUTAMENTI FISICI E DI

IMMAGINE.

A. Squassina ................................................................................................ 13

LA CONSERVAZIONE DELLE FACCIATE NEI CENTRI STORICI: PERCHÈ,

COME E PER CHI.

R. Moioli ..................................................................................................... 23

CARATTERIZZAZIONE MECCANICA E TERMO-FISICA DI INTONACI

TRADIZIONALI VENEZIANI

I. Aldreghetti, G. Berto, P. Bison, G. Boscato, M. De Bei, L. Massaria, F. Peron, L. Scappin .................................................................... 33

LA TUTELA DELLA SUPERFICI ARCHITETTONICHE DEL PAESAGGIO

STORICO ITALIANO. OSSERVAZIONI SUL RUOLO DELLE NORMATIVE DI

SETTORE DOPO IL D.P.R. 31 DEL 2017

F. Trovò ....................................................................................................... 43

SURFACE PERCEPTION AND INTERPRETATION IN ARCHITECTURAL

CONSERVATION.

E. Macchioni ............................................................................................... 55

IL RESTAURO NELL’EPOCA DELL’APPARENZA: QUANDO INTERVENIRE

DIVENTA RINNOVARE.

C. Bartolomucci........................................................................................... 65

INTERVENIRE SULLE SUPERFICI TRA CONSERVAZIONE E LEGGIBILITÀ

DELL’IMMAGINE ARCHITETTONICA: IL CASO DELLE PROCURATIE

NUOVE A VENEZIA.

I. Cavaggioni, A. Turri................................................................................75

ORIENTAMENTI, TENDENZE, PROSPETTIVE. L’INTERVENTO SULLE

SUPERFICI DEL PATRIMONIO ARCHITETTONICO DEL NOVECENTO.

G. Favaretto, S. Massari, M. Pretelli, .......................................................... 85

FROM TRADITION TO TECHNOLOGICAL INNOVATION:

METHODOLOGIES, MORTAR DESIGN AND NANOTECHNOLOGIES IN THE

RESTORATION OF S. MARIA DI SPINERANO (TURIN)

L. Accurti, A. Giacomelli A.M. Gillio, S. Bocchio Vega, C.M. Tibaldeschi. ........................................................................................ 97

IL RESTAURO DELLE SUPERFICI DI PALAZZO MADAMA A TORINO:

METODI ED ESITI

F. Fratini, M. Mattone, S. Rescic ................................................................ 109

…CON LA CURA DOVUTA. IL NEGOZIO GAVINA DI CARLO SCARPA A

BOLOGNA: SUPERFICI, MATERIALI, RESTAURI.

A. Ugolini G.M. Costantini ........................................................................ 121 LEARNING FROM LOUIS KAHN’S SALK INSTITUTE PRESERVATION

PROGRAM? SPUNTI PER LA CONSERVAZIONE DELLE SUPERFICI

LIGNEE DEL XX SECOLO

S. Di Resta .................................................................................................. 133

LA MAPPA DEI GRAFFITI A MESSINA DISEGNATA DA GINO COPPEDÈ.

RESTAURI E DE-RESTAURI NEL RISPETTO DI UNA CIFRA PECULIARE

DELL’ARCHITETTO.

A. Cernaro, O. Fiandaca ............................................................................ 143

PRESERVATION AND RESTORATION. THE CONSTRUCTION SITE OF THE

CASTLE OF CASTELLALTO IN TELVE, TRENTINO.

G. Gentilini ................................................................................................. 153

LA CAVALLERIZZA DEL PALAZZO DUCALE DI MANTOVA: UN

BILANCIO DEGLI INTERVENTI SULLE SUPERFICI.

A. Adami, S. Della Torre, L. Fregonese, A. Mazzeri, B. Scala, ..................................................................................................... 165

SUSTAINABLE SILICA SOL-GEL BASED CLEANING SYSTEMS FOR

GRAFFITI REMOVAL.

M. Mussolino, F. Aricò, E. Griguol, P. Tundo ........................................... 183

STUDIO DELL’EFFICACIA DI CONSOLIDANTI A BASE DI DIAMMONIO

FOSFATO PER LA CONSERVAZIONE DI DECORAZIONI E FINITURE A

BASE DI LEGANTI IDRAULICI E CEMENTIZI.

L. Falchi, E. Balliana, L. Zecchin, E. Zendri .............................................. 193

NEW GREEN POLYMERS FOR APPLICATIONS IN CLEANING GRAFFITI

VANDALISM ON CULTURAL HERITAGE STONES.

L. Pietrobon, A. Vavasori, C. Tortato, L. Ronchin..................................... 203

LE SUPERFICI DELL'ARCHITETTURA: IL CASO DELLA BASILICA DI

SANTA CROCE DI LECCE E L’UTILIZZO DELL'OSSALATO E DEL

FOSFATO DI AMMONIO. CONFRONTI CON ALTRI ANALOGHI

MONUMENTI SIMILMENTE TRATTATI.

G. Cacudi, A. Di Marzo, M. Matteini, D. Melica, F. Vescera ................... 213

PHOSPHATE-BASED TREATEMENT FOR STONE CONSOLIDATION IN

TEMPERATE AND COOL CLIMATIC CONDITIONS. A CASE STUDY OF

RÖDBO GAMLA KYRKOGÅRD HISTORIC SITE IN SWEDEN.

S. Holickova, A. Defus ............................................................................... 225

TRATTAMENTI DE-SOLFATANTI UNA QUESTIONE SEMPRE APERTA. IL

CANTIERE PILOTA PER IL RECUPERO DEI DIPINTI DI GINO GRIMALDI.

D. Pittaluga,P. Bensi, M:L: Carlini, F: Fratini, D. Magrini, A. Mairani, M. Matteini, S. Vassallo, S: Vicini .......................................... 237

LE SUPERFICI ORIZZONTALI E L’ACCESSIBILITÀ DEI BENI CULTURALI.

MATERIALI E TECNICHE PER LA REALIZZAZIONE DI PERCORSI

INCLUSIVI IN CONTESTI STORICI.

C. Conti, L. Petriccione ............................................................................... 249 VALORIZZARE ATTRAVERSO LA SUPERFICIE TRA CREATIVITÀ E

CONSERVAZIONE S. Massari, E. Pozzi, L. Signorelli ............................................................... 259

MORTARS AND PLASTERS MIXES FOR ANCIENT BUILDINGS AND THEIR

MECHANICAL CHARACTERISTICS. FIRST RESULTS OF A RESEARCH

PROJECT (IN PROGRESS).

S. Fasana, A. Grazzini, M. Zerbinatti .......................................................... 271

MIGLIORAMENTO ANTISISMICO E SUPERFICI ARCHITETTONICHE: UN

COMPLESSO RAPPORTO FRA SICUREZZA E CONSERVAZIONE.

A. Donatelli ................................................................................................. 283

POST-SEISMIC RECONSTRUCTION AND PRESERVATION OF

ARCHITECTURAL SURFACES. THE GUIDELINES FOR BUILDING

FACADES AND EXTERNAL FINISHES IN THE RECONSTRUCTION PLAN OF

FOSSA (AQ).

M.R. Vitale .................................................................................................. 295

PROBLEMATICHE E INDIRIZZI OPERATIVI PER LA CONSERVAZIONE

DELLE FINITURE ANTICHE DEL CENTRO STORICO DELL’AQUILA.

A. Placidi ..................................................................................................... 307

LA BASILICA DI SANT’ANDREA APOSTOLO A MANTOVA: RESTAURO

DELLE SUPERFICI E MIGLIORAMENTO STRUTTURALE DELLA

FACCIATA PRINCIPALE E DEL PRONAO.

D. Lattanzi, E. Romoli, L. Sala, A. Moretti, E. Boglione ........................... 317

ORIZZONTI DI METODO PER L’INTEGRAZIONE DI SISTEMI

FOTOVOLTAICI SUL PATRIMONIO ARCHITETTONICO

A. Giuliani, M. Rossetti ............................................................................... 329

ENERGY CONSERVATION IN HISTORICAL BUILDINGS. A

METHODOLOGY FOCUSED ON BUILDING OPERATION AND USERS’

ENGAGEMENT.

G. Spigliantini, V. Fabi, M. Schweiker, C. Aghemo ................................... 339

LA TERMOGRAFIA COME STRUMENTO DI INDAGINE CONOSCITIVA

DELLE SUPERFICI ARCHITETTONICHE. INTERVENTI E PROSPETTIVE DI

RICERCA.

C. Crova F. Miraglia ................................................................................... 351

CONCRETE SURFACES CONSERVATION: REFLECTIONS ON THE MAIN

OPEN CHALLENGES AND PROPOSAL FOR A NEW ILLUSTRATED

GLOSSARY OF DETERIORATION PHENOMENA.

S. Landi ...................................................................................................... 361

VILLA MARINA A SORI: LA CONSERVAZIONE E IL RESTAURO DELLE

SUPERFICI TRA CONOSCENZA E INNOVAZIONE.DALLE INDAGINI

STRUMENTALI SUGLI INTONACI ALL’ANALISI CROMATICA.

G. Stagno, L. Blanc, L. Secondini, A. Tesfay, R. Forte, R. Morbiducci ............................................................................................ 371 SISTEMI DI MONITORAGGIO E CONTROLLO, APPROFONDIMENTI

DIAGNOSTICI E INTERVENTI DI MANUTENZIONE PER LA

CONSERVAZIONE PREVENTIVA DELLE SUPERFICI DECORATE DELLA

CAPPELLA DI S. UBERTO A VENARIA REALE.

L. Appolonia, M.C. Canepa, M.Cardinali, M.Girotto, A. Piccirillo, V.Scarano, V.Tasso, M. Volinia ........................................... 381

NUOVI DATABASE PER IL PIANO DEL COLORE DI SIENA: INTONACI

DECORATI E TROMPE L'OEIL DI PORTE E FINESTRE.

M. Gennari, E. Matteuzzi ........................................................................... 393

FORMAZIONE DI TERZO LIVELLO E OPERATORI LOCALI:

UN’ESPERIENZA SUGLI INTONACI DEL CENTRO STORICO DI SANREMO.

G. Franco, D. Pittaluga, P. Bensi, A. Rava, C. Terzi .................................. 405

CONSERVAZIONE DELLE SUPERFICI ARCHITETTONICHE DEL XX

SECOLO. INTERVENTI RECENTI DI ÁLVARO SIZA A PORTO.

T. Cunha Ferreira, E. Fantini ...................................................................... 415

IMMAGINE. IDENTITÀ. L’ESTETICA DELL’ARTE CONTEMPORANEA

NELLA CONSERVAZIONE DELLE SUPERFICI.

E. Sorbo, M. Chiuso ................................................................................... 425

LA SUPERFICIE ARCHITETTONICA NELL’ARTE CONTEMPORANEA:

ARCHITETTURE COME TELE.

G. Danesi .................................................................................................... 435

LE SUPERFICI STORICHE NELLA CITTÀ CONTEMPORANEA: IL CASO

DEL RESTAURO DELLE FACCIATE DEL PALAZZO DELLE SCINTILLE (EX

PADIGLIONE 3) NEL QUARTIERE STORICO FIERA DI MILANO.

N. Berlucchi, A. Artioli, F. Mainardi, F. Cogliati ...................................... 445

SUPERFICI VETRATE E LIMITI DELLA CONSERVAZIONE NELLE

ARCHITETTURE DEL MODERNO.

R. Maspoli ................................................................................................... 455 RESTAURI DEI DIPINTI MURALI IN VENETO DOPO LA SECONDA

GUERRA MONDIALE, DAGLI ANNI CINQUANTA AGLI ANNI OTTANTA.

P. Bensi, A. D’Ottavi, M. Serafini .............................................................. 467 SUPERFICI DIPINTE DI TRAVETTI E TAVOLE DA SOLAIO PROVENIENTI

DA PALAZZO GRILLO (GENOVA): UN’ESPERIENZA DIDATTICA TRA

INDAGINI CONOSCITIVE E PROVE DI INTERVENTO. A. Boato, G. Arena, M. Rocca, S. Vassallo ................................................ 479 SOFFITTI LIGNEI DIPINTI: UNA PRIMA RICOGNIZIONE SU SCALA

NAZIONALE. A. Boato, G. Arena, E. Ceccaroni, G. Colotto, L. Davite, F. Ferrari, G. Nani, S. Patrizi, M.S. Pirisino, L. Puglisi .............................. 487

I MURI DIPINTI DI DOZZA TRA STRATEGIE DI INTERVENTO E

PROGETTO GLOBALE DI MANUTENZIONE.

L. Vanghi, S. Penoni, A. Giuffredi .............................................................. 497

CENNI A (OVVIAMENTE CONGETTURALI) “PROSPETTIVE”,

PROFESSIONALI E PRODUTTIVE, PIÙ PROBABILI ANCHE PER I

PROGETTI DELLE VARIE SUPERFICIE DELL’ARCHITETTURA, IN UN

FUTURO NON PIÙ LONTANO, ANZI DIVENUTO ORMAI ATTUALE.

V. Borasi ...................................................................................................... 509

HYDRA R.O. CO2: UNA STRUMENTAZIONE INNOVATIVA PER LA

PULITURA CON ACQUA NEBULIZZATA.

S. Borghini, S. Di Silvestre ......................................................................... 509

NOTE PER LA CONSERVAZIONE E LA MANUTENZIONE DELLE

SUPERFICI STORICHE NELL’EDILIZIA CALABRESE. LA VIA PADOLISI

NEL CENTRO ANTICO DI COSENZA.

B. Canonaco ................................................................................................ 529

IN ASSENZA DI METODO: IL RESTAURO DELLA BASILICA DI SAN

GIOVANNI A FINALE LIGURE.

A. Canziani, A. Decri .................................................................................. 539

IL TRATTAMENTO DELLE SUPERFICI DELLE HEART WALLS DI

KYOTO: TECNOLOGIE COSTRUTTIVE, STILI E DECORAZIONI.

F. Ribera, P. Cucco ...................................................................................... 551

ACCORDARE LE SUPERFICI ARCHITETTONICHE RESTAURATE AL

CONTESTO: IL CASO DI PALAZZO CAMAJORI A CASTIGLIONE DELLA

PESCAIA (GR).

M. Eichberg ................................................................................................. 561

RESTORATION AND RE-USE OF COLONNA-BARBERINI PALACE IN

PALESTRINA, ROME.

R. Iacono, A. Fiasco, F. Pinci ..................................................................... 561

LA CHIESA DI SANTA MARIA ANNUNCIATA ALL’OSPEDALE SAN

CARLO BORROMEO A MILANO: INTERVENTI CONSERVATIVI SULLE

SUPERFICI DI UN’OPERA DI GIO PONTI E SULL’ANNUNCIAZIONE

DELLA FACCIATA SETTENTRIONALE..

R. Baratti Rava, M. Cappellina, M. Cecchin, D. Lattanzi, M. Mapelli .................................................................................................. 581

IL RECUPERO DELLA PAVIMENTAZIONE NELLA CONCATTEDRALE DI

TODI. RISOLUZIONE PROBLEMI DI CONDENSA.

A. Mannaioli, M. Pucci, P. Sammartino ..................................................... 591

LA BASILICA DEI SS. GIOVANNI E PAOLO A VENEZIA: INTERVENTI

OTTOCENTESCHI SULLE SUPERFICI ARCHITETTONICHE PER UNA

NUOVA IMMAGINE DEL MONUMENTO VENEZIANO.

V. Peron ...................................................................................................... 603

TECNICA ESECUTIVA E RESTAURO DI SUPERFICI “LUSTRE” ED AFFINI.

F. Amendolagine, L. Petriccione ................................................................ 613

CONTRO L’ADOZIONE DEL CAPPOTTO ESTERNO NEGLI INTERVENTI

SULL’ESISTENTE. IL POLICLINICO DI PADOVA DI GIULIO BRUNETTA

COME CASO DI STUDIO.

E. Pietrogrande, A. Dalla Caneva, C. Rampazzo ....................................... 623

LE FACCIATE DEL QUARTIERE DI PICCAPIETRA A GENOVA: TUTELA E

VALORIZZAZIONE DI UN PATRIMONIO DEL SECONDO NOVECENTO.

C. Repetti .................................................................................................... 633

LE SUPERFICI MURARIE A VISTA: RESTAURI A PALERMO E A RODI

(FINE SEC. XIX-PRIMA METÀ XX).

R. Scaduto................................................................................................... 645

LA CUPOLA DELLA CHIESA DI N. S. DELLA CONSOLAZIONE E S.

VINCENZO A GENOVA. METODOLOGIE SPERIMENTALI PER LA

CONOSCENZA E LA CONSERVAZIONE DELLE SUPERFICI DIPINTE.

G. Stagno, L. Secondini, A. Tesfay, G. Varese .......................................... 655

FAR VECCHIO IL NUOVO” E “NUOVO IL VECCHIO”: VERITÀ E

FINZIONE NEL 'COLORITO' DELLE SUPERFICI IN PIETRA.

A. Turri ....................................................................................................... 663

DOPO IL TERREMOTO. RISULTATI E QUESTIONI APERTE NEL

RESTAURO DELLE SUPERFICI ARCHITETTONICHE.

C. Verazzo, C. Varagnoli ........................................................................... 675

TREVISO URBS PICTA: UN PROGETTO INTEGRATO DI RICERCA E

CATALOGAZIONE PER LA CONOSCENZA DELLE FACCIATE DECORATE

PROPEDEUTICA ALLA VALORIZZAZIONE E SALVAGUARDIA.

R. Riscica, C. Voltarel, P. Boschiero .......................................................... 685

SCRITTE SUI MURI: I GRAFFITI ANTICHI TRA INDIFFERENZA E

CONSIDERAZIONE.

D. Oreni, G. Pertot, V. Pracchi, R. Valente ................................................. 697

BUNKER TEDESCHI DELLA SECONDA GUERRA MONDIALE. ESITI E

PROSPETTIVE PER LA CONSERVAZIONE DELLE SUPERFICI IN

CALCESTRUZZO ARMATO.

C. Mariotti, S. Pulga, A. Zampini................................................................ 709

NEW ON OLD: TO WHAT EXTENT SHOULD INTERVENTIONS BE DONE ON

SURFACES? MAINTENANCE WORKS AND RESTORATION ON AN

EXISTING PROJECT.

L. Serafini, S. Cecamore ............................................................................. 719

THE RESTORATION OF ARCHITECTURAL SURFACES IN JAPANESE

TEMPLES: REFLECTIONS.

F. Gotta ........................................................................................................ 729

A MEDITERRANEAN HISTORY: THE RESTORATION OF SHEIK

SOULEIMAN MESCIDE IN ISTANBUL.

A. Griletto, S.Vallese, O. Aydemir, M. Simsek .......................................... 743 COMPLESSITÀ E CONTRADDIZIONI NEL RESTAURO DELLE FACCIATE

IN "STILE" REALIZZATE FRA LA FINE DELL'OTTOCENTO E L'INIZIO

DEL NOVECENTO IN ROMA.

A. Pergoli Campanelli ................................................................................. 753

COLORE DELL’ARCHITETTURA STORICA E RESTAURO NEL MERIDIONE

D’ITALIA. IL CASO DI BISCEGLIE (PUGLIA).

A. La Notte .................................................................................................. 765

SANTA CHIARA DI BERNARDO ANTONIO VITTONE A TORINO: “BUONE

PRATICHE” IN UN SECOLO DI RESTAURI DELLE SUPERFICI.

F. Novelli ..................................................................................................... 777

GOOD PRACTICES FOR CONSERVATION HISTORICAL ARCHITECTURAL

FACADES:PIANO DI MANUTENZIONE DELLE SUPERFICI DI FACCIATA

DEL CENTRO STORICO DI SALUZZO.

S. Beltramo, P. Bovo. .................................................................................. 787

GRAFFITI E VANDALISMO GRAFICO: PULITURA E TRATTAMENTI

PROTETTIVI SU SUPERFICI LAPIDEE DELL’ARCHITETTURA

C. Ricci, F. Gambino, M. Nervo, A. Piccirillo, F. Zenucchini, A. Scarcella, A. De Stefanis, J. Santiago Pozo-Antonio, A. Borghi .. .................................................................................. 797 MATERIALS AND INTERVENTIONS FOR THE CLEANING AND

PROTECTION WORKS OF THE ARCHITECTURAL SURFACES OF THE

HISTORICAL RECTORSHIP BUILDING, IN THE HISTORICAL COMPLEX

OF NATIONAL TECHNICAL UNIVERSITY OF ATHENS, GREECE

E.T. Delegou, P. Moundoulas, M. Mertzani, A. Moropoulou.. ......................................................................................... 809 PAVIMENTAZIONI URBANE DI PIETRA: COME CONNETTERE

DUREVOLMENTE MATERIA E TRADIZIONE TENENDO CONTO DELLE

ESIGENZE DELLA MODERNITÀ? IL CASO VIRTUOSO DI PIAZZA DEL

MERCATO A SPOLETO (PG). G. Signori.. ................................................................................................. 819

Scienza e Beni Culturali

Intervenire sulle superfici dell’architettura

tra bilanci e prospettive

SCIENZA E BENI CULTURALI.2018

SUSTAINABLE SILICA SOL-GEL BASED CLEANING

SYSTEMS FOR GRAFFITI REMOVAL

MANUELE MUSOLINO,1 FABIO ARICÒ,1 ELENA GRIGUOL,1 PIETRO TUNDO*1,2

1 Ca’ Foscari University, Department of Environmental Science, Informatics and Statistics, Via Torino 155, 30172 Venezia, Italy. 2 GreeNovator, www.greenovator.eu.

ABSTRACT Graffiti – as an act of vandalism – represents a real economic, cultural and

social plague for community and administrations of urban areas. Despite the many efforts to contrast this phenomenon, no definitive, practical and cost-effective approach has been developed yet.

Herein we propose a sustainable methodology to prepare and screen libraries of new low-environmental impact products, suitable for removing graffiti and murals from stone materials belonging to Venice and its Lagoon UNESCO site. A first series of two-component systems has been accomplished by exploiting silicon and organic carbonate chemistry. Inorganic silica gels have been conceived as the solid matrixes, which were synthesised in acidic non-aqueous conditions by means of the well-known sol-gel chemistry. Dimethyl carbonate (DMC) has been selected as the green organic solvent to load into the gel. DMC belongs to the family of dialkyl carbonates (DACs), whose low toxicity and peculiar features render them valid alternatives to chlorine-based solvents.

Three new cleaning agents has been investigated on mock stained sample of Istrian stones provided by Fondazione Marghera by comparisons with a variety of silica gel systems loaded with polar protic, polar aprotic and non-polar aprotic solvents.

This preliminary evaluation of silica gel/DMC systems by visual inspection and FT-IR spectroscopy has provided promising results for their application as cleaning agents and paved the way to further improvements.

Key-words: Restoration, Silica sol-gel systems, Dialkyl carbonate, Graffiti

removal, Green chemistry.

184 SCIENZA E BENI CULTURALI.2018

INTRODUCTION

Chemistry for Restoration is a recognized discipline and Green Chemistry is gaining more and more authority in the design and development of innovative products and procedures for the diagnostics, restoration and maintenance of Cultural Heritage assets.

The increase of awareness campaigns promoted in the last few years in favor of the adoption of green materials and methodologies in the restoration and conservation fields, clearly testifies the urgent need to safeguard the operator health and the environment [1].

Green Chemistry is based upon the “benign by design” motto and in this scenario it can face up to new challenges arising in the context of ecological sustainability and product toxicity reduction, aiming at preventing any toxic or other harmful effects for human health and environment. The employment of hazardous chemicals in the interventions on Cultural Heritage artworks, such as solvents, biocides and other chemical substances exposes the restorers to the risk of developing serious diseases like carcinoma and endocrine dysfunctions. Moreover, there is the necessity to protect the environment through the sustainable design, manufacturing and use of eco-friendly products biocompatible at all life cycle stages. The correct disposal of hazardous chemical waste used in restoration is another critical issue, which should be conceived in order to create a more effective, cost-efficient and environmentally friendly waste management system.

Therefore, a multidisciplinary approach is needed to face the complexity posed by a restoration/conservation project, since it is necessary to focus on the operators’ health, environmental impact, waste disposal and on the economic implications of the interventions.

Some of the abovementioned issues have been addressed in our project “Product and process innovation for maintenance, conservation and sustainable restoration and programmed Cultural Heritage” funded by the Italian Ministry of Education, Universities and Research (see acknowledgement for more details).

This project aims to develop ad hoc researches relative to diagnostics, restoration and maintenance of Cultural Heritage assets, through the design and manufacture of innovative products and procedures for the restoration of architectural artworks and materials.

In this prospect, one of the major issues faced by our research team is graffiti vandalism in Venice, a real pervasive plague for historic centers and art cities (Figure 1) [2,3]. Figure 1.

Graffiti removal is always a critical, costly and time-expensive phase in a restoration project, due to the difficulty in defining the cleaning level and the possibility of damaging the artwork [4]. The spray, varnishes and the permanent felt tip markers used on the stone often damage the surfaces in irreversible way,

SCIENZA E BENI CULTURALI.2018 185

altering their appearance and preservation condition, often accelerating their decay with the consequent loss of materials.

The damages caused by this phenomenon are: 1) economical by involving extensive costs for the preventive and recovery interventions being faced by the community; 2) cultural by resulting in an inevitable negative impact to Cultural Heritage; 3) social by affecting citizens perception of the security of the area defaced by graffiti.

Possible solutions to the graffiti issue would be prevention strategies via public awareness and school education and simplification of administrative procedures dealing with graffiti clean-up operations, which may increase the number of cleaning interventions on buildings and monuments surfaces tagged by vandals.

In the Venetian context, the Superintendence of Archeology, Fine Arts and Landscape for the City of Venice and Lagoon must conform to national rules and comply with the specificity of the area [5]. In general, the recovery interventions imply [6]: • A preliminary study at microanalytical level of the varnishes/inks used, to

define their composition; often their specific chemical composition is unknown. • A preliminary study of the conditions of the stone surfaces and their state of

conservation. • Post factum cleaning interventions:

- physical-mechanical methods: pressure washing, air-powder abrasion, steam cleaning, laser technologies, sand blasting, brushes etc.

- chemical methods often using organic solvents. • Preventive intervention: the use of antigraffiti products to create a protection

layer on the surface to prevent the penetration of the inks and sprays in the porous network of the material and to make future graffiti removal faster and more cost-effective. There are different types of antigraffiti that range from the temporary to the permanent ones.

In this view, herein we report a preliminary investigation of a novel class of eco-sustainable and cost-effective cleaning agents, suitable for removing paint stains from stone masonries and artworks belonging to Venice and its Lagoon UNESCO site.

RESULTS AND DISCUSSION

The new products to be employed as cleaning agents have been conceived as two-component systems: dimethyl carbonate (DMC) as a solvent and silica gel as an adsorbent solid support in which the solvent is trapped. The general purpose was to exploit the properties of DMC as low volatile green solvent (b.p. 90 °C), which may dissolve the polymeric binder and additives included into a paint and thus detach the pigment from the surface of the treated stone. Then, the gel acting as a


sponge-like material may adsorb the dissolved polymer along with the additives and complete the pigment extraction from the stone. Once the DMC evaporates, the partially dried gel may be easily removed from the treated surface, without altering the stone composition/morphology.

DMC has been chosen as lead solvent, in as much it belongs to the family of dialkyl carbonates (DACs), which play a pivotal role, both as solvents and reagents, in synthetic procedure focused on developing compelling alternatives to chlorine derivatives [7-9]. In fact, since 2006, after the entry into force of Registration, Evaluation, Authorisation and restriction of Chemicals – REACH – regulation, many chemicals and processes extensively employed in industry have been banned and stricter safety standards adopted [10]. Therefore, as the Restoration and Conservation of Cultural Heritage are not exempted from this greener change, DACs may represent a valid low toxic and low impact replacement to those chlorine-based solvents (e.g. dichloromethane), routinely used by restores and art conservators.

DMC, diethyl carbonate (DEC) ethylene carbonate (EC) and propylene carbonate (PC) are already added in small amount to formulations, such as solvent mixtures and micro/nano emulsions, being used in cleaning procedure of paintings and stone artworks [11,12]. However, the potential role of DACs in art restoration and conservation has been barely investigated and thus it is still far to be unveiled.

Silica gels, selected as inorganic matrixes, can be easily achieved through well-known sol-gel chemistry methodologies. Silicon derivatives such as silica, silicates, silanols and siloxanes are commonly used in restoration as matting agents (e.g. micronized silica) and components of commercially available consolidating agents (tetraethylsilicate) [13,14] and hydrophobic coating agents [15,16].

The general mechanism of silica gels formation consists in the hydrolysis by basic or acidic aqueous conditions of a tetraalkylsilicate – generally tetramethoxysilicate (TMOS) and tetraethoxysilicate (TEOS) – followed by its condensation with at least another molecule of silicate (Scheme 1) [17]. An alcohol is usually added to the mixture as organic co-solvent to dissolve the hydrophobic tetralkylsilicate and to render the gel formation more uniform. Basic aqueous conditions provide highly branched oligomers/polymers as major components of the final colloid, while acidic aqueous conditions favour the formation of linear structures (Scheme 1). Scheme 1.

In our research, we have focused on the formation of silica gels in non-aqueous acidic conditions using formic acid (pKa = 3.75) as organic solvent and protons source [18]. In these conditions, the hydrolysis of a molecule of tetralkylsilicate produces the corresponding alcohol and/or alkylformate, which act as co-solvents and lead to the formation of a colloid with intermediate features relative to those of


gels formed in basic and acidic aqueous media (Scheme 1-3). Results of our preparations are reported in Table 1. Table 1.

Silica gels were obtained by mixing TMOS or TEOS (1 eq) with formic acid (4 eq.) and letting them react under stirring at r.t. until the gelation point (at 90 and 360 min respectively). Then, gels were left aging for 60 min prior to the solvent loading. G1 and G2 silica gel were prepared starting from TMOS and TEOS respectively and DMC was used for the solvent loading. DMC was replaced twice a day for three days to allow a complete solvent exchange, which was ascertained by measuring the acidity of the solution gels were placed in.

In order to evaluate and compare G1 and G2 efficiency as graffiti removal, different freshly prepared gels (from TMOS) were loaded with: protic polar solvents such as water (G3), MeOH (G4), EtOH (G5); aprotic polar solvents such as acetone (G6), ethyl acetate (G7); aprotic non- polar solvents such as toluene (G8), and xylene (G9), commonly used as solvents in aerosol paint spray cans. Finally, a nanofluid or microemulsion described by Baglioni et al. [12-19] to remove acrylic coatings from paintings and composed by water (73.3%), sodium lauryl sulfate (3.7%), pentanol (7%), ethyl acetate (8%) and propylene carbonate (8%) (G10) was also tested (Table 1).

In all the preparations, the solvent exchange step led usually to the formation of glassy gels, which had to be crushed finely before the application over the stained surface. Aiming to achieve easy to handle formulations, i.e. gelatin-like gels, three further gels were prepared by adding to the reaction mixture another polymeric material (w/w of TMSO): 0.5% of Agar (G11), 0.5% of polyacrilic acid or Carbopol (G12); 0.5% of Cellulose (G13) (Table 1). Gels were dried pre- and post- applications and analysed by FT-IR spectroscopy.

New gels systems efficiency in extracting polymer colours was investigated over samples of Istrian stone provided by Fondazione Forte Marghera. Istrian stone is the local stone of Venice its lagoon UNESCO site; it has been widely employed as architectural and decorative material in many historical buildings (e.g. Palazzo Ducale and Ponte di Rialto) for its peculiar composition and low porosity, which rendered it an ideal barrier to contrast the rising damp [20].

Istrian stone mock samples of different dimension were stained using commercially available red and blue aerosol paints, (Rubin Red, Enamel Acrylic Spray, Arexons). The aerosol paint was sprayed over samples from a distance of 20 cm and with an angle of approximatively 45°. Two layers of paint were applied over specimens that were stored in laboratory at 20 °C for one week prior to being used.

Si gel/solvent systems were applied over stained samples by following two different procedures: 1) by using a spatula and covering a surface of 10-20 cm2 protected with a PVC film to further limit the solvent evaporation; 2) by placing


over the sample surface a Pyrex glass blowing tube (l = 10 cm; dØ = 1 cm) filled with a gel (3 cm) that was pushed down through a glass piston, which worked also as a cap to limit the solvent evaporation. This latter was used to visually evaluate polymers colours extraction by gels (Figure 2). Figure 2.

After 10, 30, 60, 120 min the gels were brushed away from the stone. At end of the test, the collected gels were dried under vacuum and analysed via FT-IR spectroscopy by mixing samples with KBr.

In this preliminary investigation G1, G2, and G11 were identified as the most promising Si gel/DMC system of this series to extract polymer colours from stained stone samples within 60 min. Products optimisation and characterisation, as well as specific analysis of gel system-stone material and gel system-paint interactions are on-going.

Although further improvements and studies still need to be accomplished, this methodology represents a novel, green and cost-effective approach to easily develop and screen new cleaning agents based on the chemistry of silicon and dialkyl carbonates.

Moreover, a silica gel features, such as physical state (solid, solid-like or liquid-like), 3D-network, porosity, superficial tension, adhesive properties, thermal resistance etc, can be modulated by the synthetic procedure employed in its synthesis, the introduction of different functionalisation on its matrix [21,22], as well as the solvent or the mixture of solvents included into it. In turn, by tuning these features, a gel cleaning efficiency and suitability on various substrates can be properly tailored.

Ackonwledgement

The research presented in this article has been founded Italian Ministry of Education, Universities and Research programme “Smart cities and communities and social innovation - topic: Cultural Heritage”.

Project: Product and process innovation for maintenance, conservation and sustainable restoration and programmed cultural heritage: SCN_0052. The partners of the project are: the City of Venice, the Superintendence of Archeology, Fine Arts and Landscape for the City of Venice and Lagoon, ICAP LEATHER CHEM SPA, TAB CONSULTING SRL, the University Ca' Foscari of Venice, the University of Basilicata, the University of Aquila and the University Sapienza of Rome.


Figure 1. Examples of graffiti in Venice. Figure 2. Silica Gel/DMC systems application over stained samples of Istrian Stone.


Scheme 1. Simplified mechanisms of silica gel structures formation in basic (1), acidic (2) aqueous conditions and in acidic non-aqueous conditions (3).


Table 1. Silica gel systems G1-G13.a # Alkylsilicate

and additive

Solvent

loaded

Gel aspect Gel effciencyb

G1 TMOS DMC Clear glassy gel good G2 TEOS DMC Clear glassy gel good G3 TMOS water Faint white

glassy gel no colour extraction

G4 TMOS MeOH Clear glassy gel no colour extraction

G5 TMOS EtOH Clear glassy gel no colour extraction

G6 TMOS Acetone Orange glassy gel

not tested

G7 TMOS EtOAc Clear glassy gel good G8 TMOS Toluene Clear glassy gel partial colour

extraction G9 TMOS Xylene Clear glassy gel partial colour

extraction G10 TMOS Nanofluid Precipitate

formation no colour extraction

G11 TMOS 0.5% Agar

DMC Clear gelatin-like gel

good

G12 TMOS 0.5% Carbopol

DMC Glassy gel incorporating a

precipitate

partial colour extraction

G13 TMOS 0.5% Cellulose

DMC Glassy gel incorporating a

precipitate

partial colour extraction

a General synthetic procedure to obtain the final gels: i) TMSO or TEOS (1 eq), HCOOH (4 Eq), 1.5-4 h at r.t.; ii) 60 min aging; iii) Solvent loading 3 d. b Study carried out on painted samples of Istrian stone through visual inspection and FT-IR spectroscopy.


References

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TESTI DI

TESTI DI

Accurti L. 97 Adami A. 165 Aghemo C. 339 Aldreghetti I. 33 Amendolagine F. 613 Appolonia L. 381 Arena G. 479 Aricò F. 183 Artioli A. 445 Aydemir O. 743 Balliana E. 193 Baratti Rava R. 581 Bartolomucci C. 65 Beltramo S. 787 Bensi P. 237,405,467 Berlucchi N. 445 Berto G. 33 Bison P. 33 Blanc L. 371 Boato A. 479,487 Bocchio Vega S. 97 Boglione E. 317 Borasi V. 509 Borghi A. 797 Borghini S. 519 Boscato G. 33 Boschiero P. 685 Bovo P. 787 Cacudi G. 213 Canepa M.C. 381 Canonaco B. 529 Canziani A.. 539 Cappellina M. 581 Cardinali M. 381 Carlini M.L. 237 Cavaggioni I. 75 Cecamore S. 719 Ceccaroni E. 487,719 Cecchin M. 581 Cernaro A. 143 Chiuso M. 425 Cogliati F. 445

Colotto G. 487 Conti C. 249 Corgnati S. P. 339 Costantini G. M. 121 Crova C. 351 Cucco P. 551 Cunha Ferreira T. 415 Dalla Caneva A. 623 Danesi G. 435 Davite L. 487 De Bei M. 33 De Stefanis A. 797 Decri A. 539 Defus A. 225 Della Torre S. 165 Delegou E.T. 809 Di Marzo A. 213 Di Resta S. 133 Di Silvestre S. 519 Donatelli A. 283 D'Ottavi A. 467 Eichberg M. 561 Fabi V. 339 Falchi L. 193 Fantini E. 415 Fasana S. 271 Favaretto G. 85 Ferrari F. 487 Fiandaca O. 143 Fiasco A 571 Forte R. 371 Franco G. 405 Fratini F. 109,237 Fregonese L. 165 Gambino F. 797 Gennari M. 393 Gentilini G. 153 Giacomelli A. 97 Gillio A. M. 97 Girotto M. 381 Giuffredi A. 497 Giuliani A. 329

TESTI DI

Gizzi S. 1 Gotta F. 729 Grazzini A. 271 Griguol E. 183 Griletto A. 743 Holickova S.. 225 Iacono R. 571 La Notte A. 765 Landi S. 361 Lattanzi D. 317,581 Macchioni E. 55 Magrini D. 237 Mainardi F. 445 Mairani A. 237 Mannaioli A. 591 Mapelli M. 581 Mariotti C. 709 Maspoli R. 455 Massari S. 85,259 Massaria L. 33 Matteini M. 213,237 Matteuzzi E. 393 Mattone M. 109 Mazzeri A. 165 Melica D. 213 Mertzani M. 809 Miraglia F. 351 Moioli R. 23 Morbiducci R. 371 Moretti A. 317 Moropoulou A. 809 Moundoulas P. 809 Musolino M. 183 Nani G. 487 Nervo M. 797 Novelli F. 777 Oreni D. 697 Patrizi S. 487 Penoni S. 497 Pergoli Campanelli A. 753 Peron F. 33 Peron V. 603

Pertot G. 697 Petriccione L. 249,613 Piccirillo A. 381 Pietrobon L. 203 Pietrogrande E. 623 Pinci F. 571 Pirisino M. S. 487 Pittaluga D. 237,405 Placidi A. 307 Pozzi E. 259 Pracchi V. 695 Pretelli M. 85 Pucci M. 591 Puglisi L. 487 Pulga S. 709 Rampazzo C. 623 Rava A. 405 Repetti C. 633 Rescic S. 109 Ribera F. 551 Ricci C. 797 Riscica R. 685 Rocca M. 479 Romoli E. 317 Ronchin L. 203 Rossetti M. 329 Sala L. 317 Sammartino P. 591 Santiago PozoA. J. 797 Scaduto R. 645 Scala B. 165 Scappin L. 33 Scarano V. 381 Scarcella A. Schweiker M. 339 Secondini L. 371,655 Serafin M. 467 Serafini L. 719 Signorelli L. 259 Signori G. 819 Simsek M. 743 Sorbo E. 425

TESTI DI

Spigliantini G. 339 Squassina A. 13 Stagno G. 371,655 Tasso V. 381 Terzi C. 405 Tesfay A. 371,655 TibaldeschiC.M.A. 97 Tortato C. 203 Trovò F. 43 Tundo P. 183 Turri A. 75,663 Ugolini A. 121 Valente R. 697 Vallese S. 743 Vanghi L. 497 Varagnoli C. 675 Varese G. 655 Vassallo S. 237,479 Vavasori A. 203 Verazzo C. 675 Vescera F. 213 Vicini S. 237 Vitale M.R. 295 Volinia. M. 381 Voltarel C. 685 Zampini A. 709 Zecchini L. 193 Zendri E. 193 Zenucchini F. 797 Zerbinatti M. 271

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