Search Results (24)

A set of eleven luxury glass archaeological objects dated to the 3rd century (Roman period) and excavated in Troia, Portugal, were treated in order to restore their shapes and decorative features. In this paper, the different stages of the treatment are presented and discussed. The treatment phases—cleaning, fragments’ assembly, and development of support structures for the objects in need—had to be adapted and the treatment outline had to be revised along the process because of the heavily weathered glass that showed extreme fragility. The treatment highlights the internal support structures—consisting of thin and light structures built with thin canes of glass—that were developed in borosilicate glass for three of the archaeological objects, ensuring their physical stability for handling and future exhibition. The structures were then attached to the archaeological glass with Paraloid B72 adhesive. The treatment of these outstanding artefacts and, in particular, the development of these structures heavily depended on interdisciplinary and teamwork that resulted in the completion of the treatment for all objects ensuring their future exhibition. Full article

The use of organic solvents, particularly those of a non-polar nature, is a common practice during cleaning operations in the restoration of polychrome artworks and metallic artifacts. However, these solvents pose significant risks to the health of operators and the environment. This study explores the formulation of innovative gels based on non-polar solvents and cellulose derivatives, proposing a safe and effective method for cleaning metallic artworks. The study is focused on a toxic apolar solvent, Ligroin, identified as one of the most widely used solvents in the cultural heritage treatments, and some “green” alternatives such as Methyl Myristate and Isopropyl Palmitate. The main challenge lies in overcoming the chemical incompatibility between non-polar solvents and polar thickening agents like cellulose ethers. To address this problem, the research was based on a hydrophilic–lipophilic balance (HLB) system and Hansen solubility parameters (HSPs) to select appropriate surfactants, ensuring the stability and effectiveness of the formulated gels. Stability, viscosity, and solvent release capacity of gels were analyzed using Static Light Multiple Scattering (Turbiscan), viscometry, and thermogravimetric analysis (TGA). The efficacy of cleaning in comparison with Ligroin liquid was evaluated on a metal specimen treated with various apolar protective coatings used commonly in the restoration of metallic artifacts, such as microcrystalline waxes (Reswax, Soter), acrylic resins (Paraloid B44), and protective varnishes (Incral, Regalrez). Multispectral analysis, digital optical microscopy, FTIR spectroscopy, and spectrocolorimetry allowed for the assessment of the gels’ ability to remove the different protective coatings, the degree of cleaning achieved, and the presence of any residues. The results obtained highlight the ability of the formulated gels to effectively remove protective coatings from metallic artifacts. Cetyl Alcohol proved to be the most versatile surfactant to realize a stable and efficient gel. The gels based on Methyl Myristate and Isopropyl Palmitate showed promising results as “green” alternatives to Ligroin, although in some cases, they exhibited less selectivity in the removal of protective coatings. Full article

Wood is a valuable material with incomparable advantages, though it is susceptible to biotic and abiotic factors action that affect it adversely and shorten its service life. In the current study, the surface modification of oak wood is carried out through brief immersion in a solution of acrylic polymer Paraloid B72, in which silica dioxide nanoparticles in the form of nanopowder were dissolved at different contents (1, 2, 3, and 4% w/v of the solution) aiming at the elimination of wood material hygroscopicity, and the protection and improvement of other properties. Specifically, the modified and unmodified wood specimens were characterized in terms of physical characteristics (density, equilibrium moisture content, colour, and surface roughness), hygroscopic properties (swelling and absorption percentage) and accelerated weathering performance using xenon light and cycles of moisturizing and drying. The results revealed the dimensional stability of the samples and a significant increase in the hydrophobicity of the modified wood, as well as a significant increase in the resistance to the ageing/weathering factors of oak wood, which was proportional to the increase in the presence of nanoparticles in the Paraloid B72 solution. The colour of the treated samples slightly changed towards darker shades, more reddish and yellowish (with L* to decrease, while a* and b* to slightly increase), though the treated wood revealed higher colour stability. The surface roughness parameters (Ra, Rq, and Rz) increased significantly, restricting the wide application of the treated wood in indoor or outdoor applications where surface roughness constitutes a critical factor. The findings of the current work contribute not only to the production of longer-lasting wood and timber structures, but also to the conservation of the existing weathered heritage timber structures. Full article

In the conservation of cultural relics, the application of Paraloid B72 in humid environments frequently results in the surface whitening of artifacts, which impairs their appearance and conceals important details. This study investigates the mechanisms underlying this phenomenon by examining the effect of ambient humidity, Paraloid B72 mass concentration, solution addition volume, and solvent type. To evaluate the microstructure, transmittance, and composition of the films, a range of analytical techniques were employed, including optical microscopy, scanning electron microscopy, a UV-Visible Spectrophotometer, and Fourier transform infrared spectroscopy. The findings indicate that higher ambient humidity, lower Paraloid B72 mass concentration, smaller solution addition volume, and solvents with higher volatility and water miscibility increase water content during curing, intensifying the whitening effect. These factors modify the interaction between water and solvent, altering the surface structure of Paraloid B72. The whitening mechanism is linked to the cooling effect of solvent volatility, which lowers the dew point temperature at the air–solution interface, causing moisture condensation. Moisture forms droplets that leave irregular pores upon volatility, resulting in surface roughness, optical heterogeneity, and a reduced refractive index, resulting in whitening. This study provides a theoretical basis for understanding and preventing the whitening of Paraloid B72. Full article

Paraloid B-72 (B72), as a transparent, colorless polymer material, has good film-forming ability when dissolved in acetone and is widely used as a sealing material for metal artifacts. In order to analyze and evaluate the preservation performance of B72 as a sealing material on the substrate of metal artifacts, a variety of electrochemical methods, mainly electrochemical noise (EN), and scanning electron microscopy (SEM) were applied to evaluate the B72 coating. The results showed that the B72 coating had a good preservation effect at the initial stage, and its poor water resistance led to the loss of its effectiveness after a few days of immersion. Compared with conventional electrochemical methods, electrochemical noise is non-destructive, which cannot cause new corrosion on the metal substrate and can well characterize the corrosion rate of the test system, and the results of its time domain and frequency domain analyses can correspond well with the polarization resistance and impedance spectra. Electrochemical noise is an effective method for evaluating the anti-corrosion performance of material preservation coatings. Full article

In this work, nanocellulose aqueous dispersions were studied as a bio-inspired consolidating agent for the recovery and conservation of ancient wood and compared with two of the most used traditional consolidants: the synthetic resins Paraloid B-72 and Regalrez 1126. The morphology of crystalline nanocellulose (CNC), determined using Scanning Electron Microscopy (SEM), presents with a rod-like shape, with a size ranging between 15 and 30 nm in width. Chemical characterization performed using the Fourier-Transform Infrared Spectroscopy (FT-IR) technique provides information on surface modifications, in this case, demonstrating the presence of only the characteristic peaks of nanocellulose. Moreover, conductometric, pH, and dry matter measurements were carried out, showing also in this case values perfectly conforming to what is found in the literature. The treated wood samples were observed under an optical microscope in reflected light and under a scanning electron microscope to determine, respectively, the damage caused by xylophages and the morphology of the treated surfaces. The images acquired show the greater similarity of the surfaces treated with nanocellulose to untreated wood, compared with other consolidating agents. Finally, a colorimetric analysis of these samples was also carried out before and after a first consolidation treatment, and after a second treatment carried out on the same samples three years later. The samples treated with CNC appeared very homogeneous and uniform, without alterations in their final color appearance, compared to other traditional synthetic products. Full article

Most of the artworks stored in museums are often kept in inappropriate climatic and environmental conditions that facilitate the formation and growth of microorganisms, such as fungi, which are responsible for many types of biodegradation phenomena. To mitigate and prevent these deteriorative processes, functionalized packaging materials can be used for the storage and handling of artworks. The aim of this study was to develop a potential anti-biodeterioration coating suitable for packaging purposes. TiO₂ and ZnO doped with different amounts of Ag (0.5 wt%, 1 wt%, and 3 wt%) were synthesized and dispersed in polyvinyl alcohol (PVA) and acrylic resin (Paraloid B72), then applied on different types of packaging materials (cellulose and the high-density spunbound polyethylene fiber Tyvek^®, materials that are frequently used as packaging in museums). Analytical investigations (SEM/EDS, Raman, FTIR, and XRD) were employed to assess dispersion on the packaging material. Furthermore, resistance against biodeteriogens was assessed using Cladosporium sp., a bioluminometer, to define the biocidal efficacy. Full article

Currently used organic coatings for the protection of bronze sculptures have a relatively short lifespan as a consequence of strict requirements of conservation ethics, which limit the selection of coatings. For that reason, enhancement of the corrosion protection level and durability of appropriate coatings is needed. The aim of this work was to examine if corrosion protection of bronze by selected acrylic and polyurethane coatings could be improved by using two phosphonic acids, 16-phosphonohexadecanoic acid (COOH-PA) and 12-aminododecylphosphonic acid (NH₂-PA). Electrochemical measurements (linear polarization and electrochemical impedance spectroscopy, EIS) were performed to gain an insight into the influence of these phosphonic acids on the performance of the coatings during a two-week exposure to artificial acid rain and a three-month outdoor exposure. Besides the influence on the corrosion protection level, the influence on the coating adhesion was examined as well. A pull-off test clearly confirmed that the studied phosphonic acids act as adhesion promoters of both polyurethane and acrylic coatings, while electrochemical studies revealed improvements in corrosion protection levels, especially in the case of the acrylic coating Paraloid B72. Full article

Acrylic polymers were extensively used in past restoration practices, usually as consolidants or protecting agents. Their removal is often required because polymer coatings can improve some decay processes of stone substrates and, after ageing, may generate undesirable materials on the surface of artifacts. Therefore, the removal of old polymer coating from the surface of artifacts has become a common operation in the conservation of cultural heritage. As with other cleaning operations, it is a delicate process that may irreversibly damage the artifacts if not correctly carried out. The main aim of this study was to determine the appropriate cleaning procedure for efficiently removing old acrylic polymers (e.g., Paraloid B-72) from the surface of historical buildings. For this purpose, a polymer was applied to two different porous stone substrates (bio-calcarenite and arenaria stone). The hydrogel cleaning approach was used for the present study, as preliminary results suggested that it is the most promising polymer-removing method. The considered hydrogel (based on a semi-interpenetrating polymer network involving poly(2-hydroxyethyl methacrylate) and polyvinylpyrrolidone) was prepared and characterized using different techniques in order to assess the gel’s properties, including the gel content, equilibrium water content, retention capability, hardness, Young’s modulus, and morphology. After that, the hydrogel was loaded with appropriate amounts of nano-structured emulsions (NSEs) containing a surfactant (EcoSuf^TM), organic solvents, and H₂O, then applied onto the coated surfaces. Moreover, plain EcoSurf^TM in a water emulsion (EcoSurf/H₂O) was also used to understand the polymer-removing behavior of the surfactant without any organic solvent. A comparative study was carried out on artificially aged and unaged polymer-coated samples to better understand the cleaning effectiveness of the considered emulsions for removing decayed polymer coatings. The experimental results showed that the NSE-loaded hydrogel cleaning method was more effective than other common cleaning procedures (e.g., cellulose pulp method). In fact, only one cleaning step was enough to remove the polymeric material from the stone surfaces without affecting their original properties. Full article

The entrance of the Madre de Dios convent in Seville was carved in stone by Juan de Oviedo y de la Bandera, an important sculptor who made great artistic productions, highlighting his carvings in wood and stone. Several studies have been carried out on the carvings in wood, but no interest has been paid by experts to the carving pieces in stone. In this work, this polychrome made on stone around 1590 was studied for the first time. Micro-samples were taken and studied using micro-analytical techniques (optical microscopy, SEM-EDX, colourimetry, XRD, FTIR, and Raman spectroscopy). The pigments (smalt, atacamite, malachite, copper resinate, cinnabar, red earth, yellow ochre, carbon, and bone black) and the consolidation product (acrylic resin, very possibly Paraloid B72) were characterized. The experimental study indicated that the polychrome was applied on a layer of white lead (cerussite and hydrocerussite) that was laid on the substrate stone, constituted by calcarenite. This study also includes a comprehensive discussion on the use of these materials and techniques in other artworks within Seville’s cultural heritage. Full article

Investigations of historical conservation materials on historical stained glass windows of the Naumburg Cathedral in Germany offered an opportunity for the study of polymers, naturally aged in a non-controlled environment. This allowed the conservation history of the cathedral to be traced and expanded by valuable insights. The historical materials were characterized through the use of spectroscopy (FTIR, Raman), thermal analysis, PY-GC/MS, and SEC on taken samples. The analyses show that acrylate resins were predominantly used for conservation. The lamination material from the 1940s is particularly noteworthy. Epoxy resins were also identified in isolated cases. Artificial aging was used to investigate the influence of environmental influences on the properties of the identified materials. Through a multi-stage aging program, influences of UV radiation, high temperatures and high humidity can be considered in isolation. Piaflex F20, Epilox, Paraloid B72 as a modern material and combinations of Paraloid B72/diisobutyl phthalate and PMA/diisobutyl phthalate were investigated. The parameters yellowing, FTIR spectra, Raman spectra, molecular mass and conformation, glass transition temperature, thermal behavior, and adhesive strength on glass were determined. The effects of the environmental parameters on the investigated materials are differentiated. UV and extreme temperatures tend to show a stronger influence than humidity. The comparison of the artificially aged samples with the naturally aged samples from the cathedral shows that the latter were less aged. Recommendations for the conservation of the historical stained glass windows were derived from the results of the investigation. Full article

Cleaning is one of the most important, essential, and delicate operation which has to be handled by conservators before applying new materials to any substrates. In past decades, nanotechnology introduced new concepts and materials in the conservation field, which have been providing many advantageous performances, especially higher than older materials. As a result, the conservators have already started to use nanomaterials in the cleaning processes of artifacts. Taking into consideration this new approach, our study has focused on using nano-structured emulsions (NSE) as smart cleaning materials for removing polymer coatings (e.g., acrylic polymers). For this purpose, Paraloid B-72 was applied on three different substrates (glass, Lecce stone, and Arenaria stone) and cleaning was performed by a specific nano-structured emulsion (NSE) based on an eco-friendly surfactant (EcoSurf) and two organic solvents in different proportions. In order to better understand the interaction of surfactant and organic solvents with polymer coating, plain EcoSurf in water was also used for comparison. In this study, the decay process of the considered polymer was also deeply studied, because it directly affects the cleaning effectiveness. Coated specimens of the different substrates were artificially aged and examined by different techniques: chromatic variations and contact angle measurements, optical microscopy, FTIR, and SEM-EDS. This material characterization process is important to understand the colour, morphology, and micro-structural difference, and the changes of hydrophobic behaviour as well as chemical composition of Paraloid B-72 polymer due to different ageing processes. After that, substrates coated with both unaged and aged polymer were cleaned by NSE according to the direct-contact procedure and cellulose pulp method. Preliminary analyses suggested that the direct-contact cleaning performed by nano-emulsion (i.e., NSE) induced a complete removal of the acrylic polymer, despite that this method is not recommended for the artifacts and can be hardly applicable in real cases. On the other hand, experimental results showed that satisfactory cleaning of stone substrates can be obtained by using NSE/the cellulose pulp system. Full article

This paper presents results on the protective properties of different coatings over metals representative of those found in scientific–technical heritage collections. An examination of several objects in the collection of the Spanish National Museum of Science and Technology have allowed the identification of brass and steel as the most representative metals, and the existence of coatings (mainly shellac and acrylic resins) applied for aesthetic and/or conservation purposes. Based on these findings, brass and steel coupons coated with Paraloid B-44, B-48, B-67, B-72, Incralac, Cosmolloid H80, B-72 + H80 double layer and shellac have been studied to carry out a first screening in order to select the most promising candidates and determine the most appropriate methodology and key factors for the study. Coatings have been aged up to 336 h using cycles of UV light and water condensation. The change in the aspect of the coupons has been assessed via visual examination, optical microscopy and colorimetric measurements, with B-44 and Incralac showing the least change. EIS has been used for a quantitative evaluation of the protective properties and FTIR to measure chemical changes experienced by some coatings, such as B-48 and B-67. These evaluations allowed us to follow, understand and compare the behaviour of the different coatings and substrates after artificial ageing. Full article

Bronze cultural heritage in urban areas is susceptible to decay due to the significant amount of pollutants present in the air. This causes the dissolution of bronze and the patina on its surface. The efficient protection of outdoor bronze cultural heritage is still an unresolved problem. The aim of this work is to investigate 16-phosphonohexadecanoic acid as an environmentally friendly and non-toxic corrosion inhibitor for patinated bronze. The corrosion protection of sulphide-patinated bronze by phosphonic acid alone and in combination with acrylic coating Paraloid B-72 is examined. In order to achieve efficient corrosion protection, various parameters of the phosphonic acid application were studied. The efficiency of protection is examined by electrochemical impedance spectroscopy (EIS) during the immersion in simulated acid rain solution and after exposure to a corrosion chamber. It was found that the studied phosphonic acid provides corrosion protection to patinated bronze and significantly improves the protective properties of Paraloid B72. This was also confirmed by scanning electron microscopy (SEM) examination of the coating surface after exposure to a corrosive environment. Full article

This work presents the formulation and characterization of a new product for the protection of outdoor frescoes from aggressive environmental agents. The formulation is designed as an innovative green coating, prepared through a zero-waste one-pot-synthetic method to form silver nanoparticles (AgNPs) directly in a chitosan-based medium. The AgNPs are seeded and grown in a mixed hydrogel of chitosan, azelaic, and lactic acid, by the reduction of silver nitrate, and using calcium hydroxide as precipitating agent. The rheological properties of this coating base are optimized by the addition of a solvent mixture of glycerol and ethanol with a 1:1 volume ratio. The new formulation and two commercial products (Paraloid^® B72 and Proconsol^®) are then applied by brush to ad hoc mock-ups to be evaluated for chemical stability, color and gloss variations, morphological variation, hydrophobicity, and water vapor permeability via Fourier-transform infrared spectroscopy (FT-IR) in attenuated total reflection (ATR) mode, spectrophotometer analysis, stereomicroscope observations, UNI EN 15802, and UNI EN 15803, respectively. The results show that the application of the hybrid chitosan-AgNPs coating is promising for the protection of outdoor frescoes and that it can underpin the development of new products that address the lack of conservation strategies specifically designed for wall painting. Full article