Effects of silica nanoparticle and GPTMS addition on TEOS-based stone consolidants

Consolidants based on tetraethoxysilane (TEOS) have been widely used for the consolidation of decaying stone heritages. These products polymerize within the porous structure of the decaying stone, significantly increasing the cohesion of the material. However, TEOS-based consolidants suffer from practical drawbacks, such as crack formation of the gel during the drying phase due to the developed capillary force, which is typical for TEOS-based consolidants. We have prepared new consolidants TEOS-based consolidants containing flexible (3-glycidoxypropyl) trimethoxysilane (GPTMS) and silica nanoparticles in order to reduce capillary force development during gel drying, and have characterized them for the application of stone consolidants. Different sizes of silica nanoparticles were used, which were smaller than the pore size of the tested stone. The properties of the TEOS/GPTMS/nanoparticle composite solution were compared with those of the commercial products Wacker OH and Unil sandsteinfestiger OH 1:1. The gelation time was similar to that of commercial consolidants, and the TEOS/GPTMS/nanoparticle solution was stable over a period of up to six months. The contact angle of the surface increased with the addition of the nanoparticle, as well as with the addition the GPTMS, which is higher than that of commercial Wacker OH. The addition of a nanoparticle, as well as GPTMS having flexible segment, provided a crack-free material, while the gels obtained from the commercial consolidants exhibited cracking.     

Water dispersed polymers for textile conservation: a molecular, thermal, structural, mechanical and optical characterisation

With the aim of identifying new water dispersed polymers for textile conservation, the structure and properties of three commercial polyacrylates and one commercial polyvinylacetate were analysed. The characteristics of these materials, not previously used in the conservation and restoration fields, were compared with that shown by Primal AC33 and Mowilith DMC2 and SDM5, widely used as consolidating or adhesive agents of ancient textiles. To achieve a thorough characterisation of each polymer, molecular, thermal, structural and mechanical investigation techniques were applied on film samples, obtained from polymer water dispersions through water casting at room temperature and/or compression moulding. The photo-oxidative resistance of these materials was also assessed by artificial weathering of water cast films and by measuring the Yellowing Index (YI) as a function of the exposure time under xenon-arc lamp. Collected data were used to appropriately compare the performances shown by these polymers when applied on artefacts consisting of natural fibres. In particular it was found that, among the products not previously used in the conservation and restoration fields, a high potential for carrying out treatments on textiles is shown by the samples commercialised with the trade names of Acrilem RP6005 and Acrilem 30WA. These products, in fact, exhibit properties that make them suitable as substitutes for Primal AC33 and Mowilith DMC2 and SDM5, respectively, depending upon conservation needs. It was very interesting to note that Acrilem 30WA, also after aging, shows YI values lower than that shown by Mowilith DMC2 and SDM5.     

Aging and yellowing of triterpenoid resin varnishes – Influence of aging conditions and resin composition

The aging of natural triterpenoid resins used as varnishes on paintings is still insufficiently understood. Although progress has been made, questions concerning the aging pathways in light vs. darkness, or the correlation of oxidation with yellowing, remain open. The influence of aging conditions, primarily the amount of light, but also resin composition, on the aging process were investigated. The aging reactions are followed using a variety of mass spectrometric and spectroscopic techniques. Aging processes in dammar and mastic varnishes are shown to be more dynamic and extensive than had generally been believed. In unaged bulk resins, large quantities of radicals develop within weeks after application as a varnish, due to the greatly increased surface-to-volume ratio. This is true for all aging conditions, including aging in darkness, and is accompanied by considerable oxidation as well. After a few months, most of the initial triterpenoids are oxidized. Natural aging in light and darkness leads to the same main aging products. All these findings point to the conclusion that aging largely proceeds by the same pathways in both light and darkness, mainly autoxidation. Without light, enough radicals are formed to maintain extensive autoxidation, although more slowly. Thus, differences between light and dark aging mechanisms are much smaller than often believed. In mastic, the absence of the polymeric constituents is found to enhance oxidation, but reduce yellowing. It appears that the polymer acts as a natural radical stabilizer, favoring the pronounced intrinsic yellowing tendency of mastic. The manipulation of resin composition might lead to improved aging properties of triterpenoid resin varnishes.     

Acrylic copolymer coatings for protection against UV rays

This paper summarizes the basic properties of new acrylic copolymers with UV-absorbing groups (derivates of benzotriazole) bonded in macromolecular chains. These polymers are highly suitable as a material for UV protective coating of artifacts sensitive to natural and/or artificial UV light. Diane type epoxy resin was used as a test organic material with very low resistance to UV radiation. The behavior of new copolymers was compared with the UV protecting ability of Paraloid B72. Based on obtained results, we have chosen the copolymer whose properties were most similar to those of Paraloid B72, but whose protective ability is superior. This copolymer is now commercially available.     

Methyl–modified hybrid organic-inorganic coatings for the conservation of copper

A simple sol-gel technique for the preparation of methyl–modified silica coatings for the protection of the external surface of copper has been used in this study. Tetraethylorthosilicate (TEOS) has been used as a precursor to prepare nanosilica coatings on the surface of copper. The methyl–modified silica sols were obtained by mixing of 3% SiO₂ sol solution with trimethylchlorosilane (TMCS) or hexamethyldisilozane (HMDS) as basic materials. For comparison, the copper substrates were also coated with commercial polymers (Paraloid B 72, Plexisol P 550-40 and polyvinyl butyral (PVB)). The surface morphology changes of uncoated and coated specimens were investigated by atomic force microscopy (AFM) and scanning electron microscopy (SEM). The hydrophobicity of surfaces and photochemical ageing effects were evaluated by contact angle measurements. Potentiodynamic measurements were obtained in order to compare corrosion parameters of the coatings.     

The case study of an Italian contemporary art object: Materials and state of conservation of the painting “Ragazzo seduto” by Remo Brindisi

This paper deals with the scientific survey of Remo Brindisi's painting “Ragazzo seduto” (Seated boy), made at the end of the 1950s, that is a symbolic figure of both his personal artistic solitude and the crisis of values determined by the economic boom in the post-war period. In a period of great changes and economic regrowth, the need to find a new style that could be the most authentic and personal as possible pressed the artist to experiment innovative products, including non-conventional support. Photographic and analytical techniques demonstrated the use of innovative products as an experimentation tendency, that pressed the artist to use non-conventional support, industrially treated with plasticized PVC and primed with acrylate polymers and to paint with traditional and industrial pigments mixed with an oil-modified alkyd resin. In the span of a few years, an unexpected and extended degradation on the whole surface of the painting took place, with the consequent formation of lifting and detachment of the paint film. The detected alteration is mainly due to the fast ageing of the employed polymeric materials, actually responsible of the impermanence of many contemporary works of arts. Clarifying the unknown aspects of the Remo Brindisi's stylistic choices together with the deterioration processes of the employed painting materials, this paper highlights the general problems related to the conservation of contemporary art, a neglected area of research in Italy, where more efforts are committed to the enormous and more ancient cultural heritage.     

In situ copolymerisation of ethylmethacrylate and methylacrylate for the restoration of stone artefacts

In this paper the consolidating and protective products used in the restoration of stone manufactured objects of artistic interest are discussed; advantages of the different products and the relevant properties of the polymeric materials are underlined. The penetration of polymeric consolidating materials is very small and the in situ polymerisation of the monomers is suggested as an alternative technique to using macromolecular solutions. Some experimental results are presented showing that the in situ polymerisation improves the consolidating and the protective properties of polymers.     

Epoxy monomers consolidant for lime plaster cured via a redox activated cationic polymerization

Epoxy resins, widely used in conservation, still remain controversial materials. Considering some of the drawbacks that currently limit the application of epoxy consolidants, we present the application of the cationic ring opening polymerization as a novel method to cure the epoxy monomer in the restoration field. The cationic polymerization was carried out through a redox system based on the reduction of the iodonium salt in the presence of ascorbic acid catalyzed by a copper salt. The use of this initiator system for carrying out a suitable consolidant for lime plaster is considered. First, the film properties of the cured films were investigated. Then, the formulation was applied on a sample of plaster and its compatibility was verified. Its effectiveness as a consolidant product is explored through the evaluation of chromatic changes, mechanical strength, morphology of the re-aggregated material, and changes of the surface properties.     

A new family of high viscosity polymeric dispersions for cleaning easel paintings

The procedures for making and applying a new family of high viscosity aqueous polymeric dispersions based on poly(vinyl alcohol)-borax (PVA-borax) matrices are presented. A specific system of this type has been used to remove an oxidized varnish coating from the surface of “Coronation of the Virgin with Saints”, a 15th century egg tempera painting on wood by Neri di Bicci (Florence, 1418–1492). FTIR spectra showed that the oxidized varnish was constituted of highly aged shellac resin. Good cleaning performance was attained when the liquid portion of the dispersion consisted of a mixture of water and acetone. Rheological investigations indicate that the acetone content does not affect the mechanical properties of the polymeric dispersion. Those mechanical properties permit easy removal of the cleaning agent simply by peeling it from the surface by means of a forceps or spatula once it has carried out its cleaning function. Optical microscopic and FTIR investigations show that the cleaning agent is able to remove the oxidized varnish coating from the surface of the Neri di Bicci painting without leaving detectable residues.     

Effect of the addition of hydroxyl-terminated polydimethylsiloxane to TEOS-based stone consolidants

Hybrid stone consolidants prepared from tetraethoxysilane (TEOS) and α,ω-hydroxyl-terminated polydimethylsiloxane (PDMS-OH) have been considered as one of the most promising approaches to improve the effectiveness of traditional alkoxysilane-based formulations. They have emerged as response to the negative reports commonly found in the literature: the resulting silica gel phase (SiO₂) tends to develop fractures and fissures inside the stone as the gel shrinks during the drying stage. In this work, we employed SEM, solid-state ²⁹Si NMR spectroscopy and compressive tests to characterize SiO₂-PDMS hybrid gels. We report the morphological characteristics exhibited by gels prepared in vitro and in situ. It was found an appreciable reduction of gel fracture for hybrids prepared from 5% w/w of PDMS. As TEOS polycondenses, PDMS-OH is chemically incorporated into the gel matrix via Si-O-Si bonds. The inclusion of these elastic chains provides the necessary flexibility to resist the stress imposed by capillary pressure. Additionally, an important hydrophobic character is imparted to the stone.     

Water-repellent and biocide treatments: Assessment of the potential combinations

It is a common practice to use several chemical products during restoration projects of monuments or sculptures. However, care must be taken when combining the products to avoid a misuse. For example, it is well-known that applying a biocide on stone before a water-repellent leads to a diminishment of the hydrophobic effect of the treatment. But the application of biocide after a water-repellent treatment has been poorly analysed, although studies have proven that the stone looses its hydrophobicity after the application of the biocide. Henceforth, this study investigates the effects of biocide application on a water-repellent film and focuses on the possibilities to restore the efficiency of the previous water-repellent treatment (after the application of the biocide). At first, the tests were performed on glass slides to understand the mechanisms, with the subsequent results revealing that the biocide product deposits on the water-repellent film. Then, the study focuses on determining methods to remove the remains of biocide on limestone samples, previously treated with a water-repellent. The water-repellent used in the study is an alkylpolysiloxane, Rhodorsil H224 from Rhodia.     

Critic power or star power? The influence of hallmarks of quality of motion pictures: an experimental approach

Most research into the film industry focuses on aggregate level market analysis of a range of devices used by the industry to ensure the success of its films. In contrast, in this paper, we experimentally test how individual cinema-goers are influenced by two variables that have aroused considerable interest in the literature: critical reviews and the role of box office stars. As regards the former, the results of our experiment indicate that negative reviews by film critics are cues that affect cinema-goers’ pre-film assessment of a film yet fail to exert any effect on post-film assessment. As regards the latter, a cast of box office stars is not seen to be an indication of quality per se for our experimental subjects. Nor do box office stars help to mitigate the potential effects of negative reviews.     

Definition of the procedure to determine the suitability and durability of an anti-graffiti product for application on cultural heritage porous materials

Anti-graffiti protection is becoming a common practice in many urban buildings, especially in areas of social decay. When Cultural Heritage objects are affected by graffiti, the application of anti-graffiti products can result not only in an unsatisfactory result but also in an irreversible damage of an invaluable cost. The materials commonly found in these constructions are very frequently porous and present different types of decay forms. For this reason, the protection of these materials should be carefully considered. This paper proposes a criterion to decide on the suitability and durability of an anti-graffiti product prior to its application in a porous surface of a protected building. Performance classifications are defined for a series of properties including colour and gloss, and hydric and durability properties, and minimum acceptable values or reductions in these properties are recommended.     

The varnished truth: The recipes and reality of tintype coatings

The most popular photographic technique in the USA between 1856 and 1900 was the tintype, with millions of these objects created by photographers in established studios, by itinerant artists in portable workshops, and by amateurs working from ‘how-to’ manuals and journal articles. Whereas the fundamentals for this photographic process (collodion binder on a japanned metal support) were largely invariant, historical documents recommended a wide variety of protective varnish materials. A collection of 221 tintypes was analyzed using pyrolysis gas chromatography-mass spectrometry (py-GC-MS) to compare the components of actual tintype varnishes with recipes from the historical literature. Several resins in published tintype varnish recipes, including mastic, copal, and amber, are entirely absent from this collection and only five constituents – shellac, Pinaceae resin (Canada balsam or colophony), dammar, sandarac, and camphor – are detected alone or in combination. Each detected resin appears in historical recipes, but just 24% of the samples have varnish layer constituents consistent with published tintype varnish recipes. Forty-four percent of the tintypes have varnish constituents consistent with formulations recommended for other collodion images, but the varnishes of the remaining samples have no direct literature equivalents. The preponderance of shellac- and Pinaceae-based varnishes suggests that these correspond to inexpensive commercial varnishes, but tintypists may have developed their own preferred mixtures or simply used what was at hand. This first in-depth technical analysis of tintype materials suggests that the cheapest and most readily available materials were employed in the varnishing process and that the artists were not bound by literature recommendations.     

Research on protection of the architectural glazed ceramics in the Palace Museum,Beijing

The main damage of architectural glazed ceramics in the Palace Museum was investigated and the photo resistance, thermal resistance of protective materials as well as the protected performance such as hydrophobicity, freeze-thaw resistance, bending and compressive strength of the polymer-applied ceramics was tested. The results showed the main damage of glazed ceramics was the shedding of glaze layer and the change of environmental water and temperature especially subzero was the main reason for the glaze shedding. The photo-resistant and thermal-resistant of protective materials fluorine resin and the compound materials composed mainly of the fluorine resin were better than Paraloid B72 and the compound materials composed mainly of Paraloid B72. The wrapping method was selected for the protection of glazed ceramics and the hydrophobicity, freeze-thaw resistance, bending and compressive strength of the polymer-applied ceramics were improved, especially protected by fluorine resin and the compound materials composed mainly of the fluorine resin. The optimum polymer could penetrate into the damaged seriously glazed ceramics and play a hydrophobic role in the protection. The report will be useful for the preservation of damaged seriously architectural glazed ceramics.     

Chinese archaeological artefacts: Microstructure and corrosion behaviour of high-leaded bronzes

Metallographic features of ancient bronze artefacts often hide peculiar micro-chemical processes and corrosion behaviours, which are worth to be studied as they can provide conservators and archaeologists with valuable tools and information. It is widely documented that Chinese bronzes were cast and the way to adjust their properties was to change the alloy composition. In particular, addition of lead, which is insoluble in the bronze matrix, results in the formation of inclusions or globules, which undergo oxidation processes leading to their conversion into corrosion products. The mechanisms through which this occurs were still poorly investigated. The present work was conducted to further study the corrosion behaviour of high-leaded bronze, especially focusing on the behaviour of lead globules. To this aim, a collection of Chinese archaeological bronzes, showing intermediate steps of degradation, were selected and investigated. The use of combined microscopy-based, molecular and elemental, analytical techniques allowed the characterization as well as the precise location of corrosion products, thus enabling us to propose a degradation pathway basing on thermodynamic data provided by Pourbaix diagram. The achieved results will be useful for researchers involved in these kinds of studies to better interpret data obtained.     

The performance of global film franchises: installment effects and extension decisions

An empirical exploration of global film franchises provides insights for managers of film franchises, investors in franchisable products, and scholars interested in motion picture performance. Performance tends to deteriorate as extensions are introduced: production budgets rise, advertising expenditures remain similar, and the number of opening-weekend theaters experiences a jump with the first sequel and then remains similar in subsequent installments. However, revenue, return-on-investment (ROI) and audience and critical reviews fall, and foreign performance becomes increasingly important. Offsetting deteriorating performance, risk falls: revenue and ROI become more predictable. An early change in the lead actor causes reduced performance, but changes in key product characteristics and inputs in later installments help prolong the franchise. ROI of the current installment is the most critical financial determinant of whether a further extension will occur, but high-budget films and those with higher domestic share of revenue are also more likely to yield further extensions.     

Determination of the impregnation depth of siloxanes and ethylsilicates in porous material by neutron radiography

For conservation of the built cultural heritage, the application of conservation products like consolidants or water repellents is often suggested. Their impregnation depth is a key factor for the assessment of the treatment efficiency. It will vary depending on the internal structure of the stone material and the properties of the conservation products. In this study a porous bioclastic limestone from Maastricht (the Netherlands) and a porous sandstone of Bray (Belgium) were selected for treatment with either ethylsilicate-based consolidant products or siloxane-based water repellents. We explore the potential of neutron radiography to visualize the conservation products after polymerization, since previous experiments already proved their detectability before polymerization. Additionally, water absorption by capillarity was monitored inside the samples. The experiments in this study illustrate that the ethylsilicate-based consolidants remained visible for neutrons even after the polymerization process, while the siloxane-based water repellents can only clearly be distinguished in the stone as long as they contain a certain amount of solvent. The study proves that neutron radiography can provide important additional information for the research in the built cultural heritage domain, especially as it allows to successfully visualize the impregnation depth of silicate-based consolidants inside natural building stones.     

Effect of thermal accelerated ageing on the properties of model canvas paintings

The aim of this study is to develop a laboratory technique to simulate a natural ageing of canvas paintings adopting artificial ageing methods in air (thermal oxidation), in the absence of light. Four models of canvas paintings aged up to 315 years are considered. Paintings are constituted of oil film on oil ground layer, oil film on tempera ground layer, tempera film on tempera ground layer or by tempera film on oil ground layer. Surface strength and the colour of the paintings and the degree of polymerization (DP) of linen canvas were evaluated at different steps of ageing. The degradative result was estimated as the DP of linen canvas after prefixed times of microbial attack.