Nanostructured Fluids Research Articles

Wettability of Graffiti Coatings by Green Nanostructured Fluids.

Green nanostructured fluids (GNFs), specifically water-in-oil nanoemulsions (w/o NEs), were investigated as professional "brush on, wipe off" nanodetergents for the effective removal of various challenging graffiti coatings. The efficacy of the advanced nanodetergents in eradicating resilient graffiti coatings was evaluated using various methods to assess the surface properties of forming graffiti coatings. The surface properties of these coatings were examined by assessing their wettability by water, surface free energy, and topography to obtain information on the intermolecular interactions with the nanodetergent during the wetting and graffiti removal process. Our findings revealed significant variations in the coating removal rate and efficacy of green nanostructured fluids, which are stabilized using surfactants derived from saccharides or amino acids. A water-in-oil nanoemulsion, stabilized by caprylyl/capryl glucoside, demonstrated exceptional efficiency at cleaning graffiti paints based on alkyd resin and containing various additives such as nitrocellulose or bitumen, from any hard surface within a short time period. However, a w/o NE, stabilized by sodium cocoyl glycinate, also showed effective removal of graffiti paints containing durable bitumen, albeit at a slower rate on. These green nanostructured fluids can be used as specific nanodetergents for the comprehensive removal of various graffiti coatings, but require a specified action time to prevent damage to the original substrate beneath the paint coating.

Benefits of using nonionic saccharide surfactant‐based detergents for nanostructured fluids as stubborn graffiti paint remover

AbstractExamples of nanostructured fluids (NSFs) used as highly specialized “brush‐on, wipe‐off” detergents for the removal of graffiti coatings resistant to removal are water‐in‐oil nanoemulsions that have been stabilized with nonionic saccharide surfactants. Nanodetergents with safe, ecofriendly ingredients were produced using high‐pressure homogenization (HPH). These ingredients included D‐limonene or 3‐methoxy‐3‐methyl‐1‐butanol, esterified vegetable oils, and alkyl polyglucosides (APG). Responsive surface methodology (RSM) optimization was used to identify the most efficient detergents for removing stubborn graffiti coatings. Two different types of black paint containing nitrocellulose or bitumen as components to strengthen the paint properties were used to create a stubborn graffiti coating on a marble surface. The effectiveness of the nanodetergents in removing the stubborn graffiti coatings was evaluated, and the results revealed a considerable variation in the pace at which the coatings could be removed by the nanodetergents, despite the fact that both paints strengthened with different additives showed similar surface properties. It was found that alkyl polyglucosides are highly efficient in stabilizing water‐in‐oil nanoemulsion systems, including diverse solvent types. These nanoemulsions can be used as specialized “brush‐on, wipe‐off” detergents for the precise removal of different graffiti coatings, which require a specified action period to prevent destroying the underlying original substrate.

Surface Properties of Graffiti Coatings on Sensitive Surfaces Concerning Their Removal with Formulations Based on the Amino-Acid-Type Surfactants.

Water-in-oil (w/o) nanoemulsions stabilized with amino acid surfactants (AAS) are one example of nanotechnology detergents of the "brush on, wipe off"-type for removing graffiti coatings from different sensitive surfaces. The high-pressure homogenization (HPH) process was used to obtain the nanostructured fluids (NSFs), including the non-toxic and eco-friendly components such as AAS, esterified vegetable oils, and ethyl lactate. The most effective NSF detergent was determined by response surface methodology (RSM) optimization. Afterwards, several surface properties, i.e., topography, wettability, surface free energy, and the work of water adhesion to surfaces before and after their coverage with the black graffiti paint, as well as after the removal of the paint layers by the eco-remover, were determined. It was found that the removal of graffiti with the use of the NSF detergent is more dependent on the energetic properties and microporous structure of the paint coatings than on the properties of the substrates on which the layers were deposited. The use of NSFs and knowledge of the surface properties could enable the development of versatile detergents that would remove unwanted contamination from various surfaces easily and in a controlled way.

Cryogels loaded with nanostructured fluids studied by ultra-small-angle X-ray scattering

The combination of nanostructured fluids (NSFs), such as micellar solutions or microemulsions and highly-retentive hydrogels, such as PVA-based cryogels, represents nowadays a promising and innovative approach in the field of conservation of cultural heritage, as it enables the highest control available during cleaning interventions. However, at present, little is known about the confinement of NSFs into PVA-based cryogels. In the present work, small-angle X-ray scattering (SAXS) and ultra-small-angle X-ray scattering (USAXS), combined with fluorescence correlation spectroscopy (FCS), were used to address this issue. Two significantly different NSFs were selected for this purpose, based on anionic or nonionic surfactants, and they were confined into four different gels: two single PVA and two PVA/PVA “twin-chain polymer networks” (TC-PNs). The analysis of the experimental results shows that surfactant nature is crucial in determining the interaction of NSFs with the gels’ polymer network. Moreover it was demonstrated that loading NSFs on PVA-based cryogels does not significantly affect the short-range nanostructure of neither the NSFs nor the gels, preserving the cleaning performances of the combined system.

Graffiti coating eco-remover developed for sensitive surfaces by using an optimized high-pressure homogenization process

Nanostructured fluids (NSFs), such as water-in-oil (w/o) nanoemulsions (NEs), comprise one of the best examples of new, ecological products dedicated to removing various graffiti coatings (so-called eco-removers) from sensitive surfaces without causing damage underneath. These contemporary acceptable formulations are intended to be more efficient in removing undesirable graffiti coatings than traditional organic solvent-based preparations. In this paper, systematic studies were performed on the selective and controlled removal of paint and ink coatings from substrates that were sensitive to mechanical cleaning by using innovative graffiti coating removers in the form of “brush on, wipe off” detergents. The w/o NEs were fabricated by using a high-pressure homogenization process (HPH) from the following ingredients from sustainable sources of raw materials: esterified used cooking oils (Oil-PEG-8-ester), ethyl lactate (EL), water and saccharide-derived surfactants, such as alkyl polyglucosides (APGs), which have excellent wetting and detergent activities. The most efficient formulations achieved during the HPH process were determined by optimization through response surface methodology (RSM). The optimized w/o nanoemulsions were tested for the selective removal and wetting ability of graffiti coatings from selected sensitive surfaces, such as plastics, ceramics, or painted metal surfaces. Additionally, in studies of interaction with graffiti coatings, evaluating their surface properties (topography, wettability) on a real paint coating allowed for the assessment of the mechanism of graffiti paint removal by the proposed ecological remover. Using the "brush on, wipe off" cleaning procedure based on the developed w/o nanoemulsion systems has the potential to remove safely rough and heterogeneous graffiti coatings. Therefore, nanotechnological detergents are an outstanding environmentally friendly alternative to conventional graffiti coating removers.

Advances in the application of nanomaterials for natural stone conservation

The unpredictable effects of climate change impose the safeguarding of Cultural Heritage (CH) with effective and durable materials as a vital solution in the invaluable socioeconomic resource of CH. Conservation products and methodologies are addressed under recent advancements in colloidal science providing multi-functional solutions for cleaning, consolidation, protection, and monitoring of the architectural surfaces. Nanoscience significantly contributes to enrich the palette of materials and tools that can guarantee an effective response to aggressive environmental agents. Nanostructured multi-functional nanoparticles, nanostructured fluids, and gels for stone conservation are reviewed and future perspectives are also commented. The stability and high flexibility in designing tailored made nanoparticles according to the specific characteristics of the substrate enable their use in a variety of applications. Stemming from the well-performed in lab applications with nanomaterials, the testing onsite and the monitoring of their effectiveness are of crucial importance, considering also the constructive feedback from conservators and heritage stakeholders that can unquestionably contribute to the improvement and optimisation of the nanomaterials for CH protection.

The use of nanostructured fluids for the removal of polymer coatings from a Nuxalk monumental carving – exploring the cleaning mechanism

• Nuxalk painted carving conserved at AMNH was darkened by aged organic coatings • The stubborn coating was identified via FTIR and NMR as aged poly(vinyl acetal) • Poly(vinyl acetal) could not be removed using conventional methodologies • Nanofluids-loaded PVA-based hydrogels were used to successfully clean the carving • Lab experiments were performed to unveil the physico-chemical cleaning mechanism While undertaking treatment of a monumental Northwest Coast wooden carving at the American Museum of Natural History, conservators encountered a difficult cleaning challenge. The 19 th century painted red cedar carving served as a house entry pole in the Nuxalk village of Bella Coola in the province of British Columbia, Canada. The painted surface was weathered by years out of doors in front of the house of Chief Pootlass and obscured by darkened museum-applied coatings and grime acquired during more than 100 years of open display at the museum. The methods used to reduce the grime and cellulose nitrate coating found on the surface overall were not successful when applied to the green painted areas on the bottom of the pole, as it was covered with an additional coating of poly(vinyl acetal) resin. The present work reports on the testing and use of aqueous nanostructured fluids (NSFs) and hydrogels for succesfully cleaning these areas, where other methods could not be used safely. There have only been a few published examples of these recently developed cleaning fluids and gels being used on art objects and this is the first known use on this type of material. Further analyses were performed following the cleaning. Micro-reflectance FTIR, optical microscopy, SEM-EDX, and NMR were used to characterize paint and coating samples taken from the carving. In addition, laboratory tests were performed to evaluate the response of poly(vinyl acetal) to a selection of NSFs, providing an understanding of the mechanisms underlying the successful cleaning performed on the pole by the conservators.

Ionic liquids: "normal" solvents or nanostructured fluids?

Ionic liquids (ILs) are a class of non-conventional solvents, which, for almost two decades, have continued to generate burgeoning interest in different fields of present-day chemical research with few similar precedents. Among the various aspects related to ILs, a topic worthy of in-depth analysis is their influence on organic reactivity and reaction rates. In light of this, the present short review aims to provide an overview of the literature from 2010 to the present day that addresses this issue. In particular, we herein present two main different viewpoints by which the solvent effect of ILs is explained: the first is mainly based on considering the bulk polarity of ILs and linear solvation energy relationships, while the other treats ILs as nanostructured fluids. In both cases, studies dealing with IL mixtures are also covered. Finally, literature addressing the area of supramolecular catalysis "by" or "in" ILs is also reported. This is one of the few reviews covering these specific aspects, aiming to provide a useful framework to guide future research into the effects of ILs on organic reactivity.

Twin-chain polymer networks loaded with nanostructured fluids for the selective removal of a non-original varnish from Picasso\u2019s \u201cL\u2019Atelier\u201d at the Peggy Guggenheim Collection, Venice

This paper reports on the evaluation of a polyvinyl alcohol (PVA) “twin-chain” polymer network (TC-PN) combined with an oil-in-water nanostructured fluid (NSF) for the removal of a polyvinyl acetate (PVAc) varnish. Small Angle X-ray Scattering, Confocal Laser Scanning Microscopy, and Fluorescence Correlation Spectroscopy showed that the structure of the gel and the NSF are only minimally altered by loading the fluid into the gel. The NSF is partially free to diffuse through the network, but also interacts with the gel walls. During the cleaning, the dynamics of the fluid at the gel-substrate interface are controlled by the osmotic balance taking place among the interconnected pores. These features grant effective and controlled cleaning performances. The case study identified for this research is Pablo Picasso’s The Studio (L’Atelier, 1928), one of the masterpieces in the Peggy Guggenheim Collection, Venice (PGC). In 1969 the oil painting, originally unprotected, was wax-lined and then varnished using a PVAc varnish. Over the years, the white shades of the painting have been compromised by the yellowing of the varnish and soiling of deposits. On painting mock-ups, the NSF-loaded hydrogels allowed the swelling and softening of PVAc varnish and wax layers, which were then removed with gentle mechanical action. Effective varnish and wax removal at the micron scale, and the absence of residues from the cleaning system (gel and NSF), were confirmed by Fourier Transform Infrared Spectroscopy (FTIR) 2D imaging. The effective and safe removal of the aged PVAc varnish and wax layer from the surface of the painting was then carried out using the same cleaning protocol successfully tested on the mock-ups, setting the NSF-loaded PVA TC-PNs as robust and reliable tools for the cleaning of sensitive works of art.

Nonionic Surfactants for the Cleaning of Works of Art: Insights on Acrylic Polymer Films Dewetting and Artificial Soil Removal

The use of nanostructured fluids (NSFs), that is, micellar solutions and microemulsions, in art conservation is often associated with cleaning purposes as the removal of polymeric coatings and/or soil from artistic surfaces. In both cases, the use of NSFs grants significant improvements over the use of traditional cleaning techniques that employ neat unconfined organic solvents, water, or aqueous solutions. The study of the nature and properties of surfactants present in NSF formulations is important to boost the effectiveness of these systems in applicative contexts and in the search of innovative and highly performing amphiphiles. This work reports on the methoxy-pentadeca(oxyethylene) dodecanoate (MPD) surfactant in two different NSFs, whose utilization in conservation of cultural heritage is new. Its effectiveness is compared to the conventional nonionic amphiphiles used in conservation practice, as pentadeca(oxyethylene) dodecyl ether, for the cleaning of poly(ethyl methacrylate/methyl acrylate) 70:30, p(EMA/MA), and artificially soiled surfaces. The mechanism, through which NSFs interact with polymeric coatings or soiled surfaces, was investigated by confocal laser scanning microscopy, fluorescence correlation spectroscopy, photographic observation, contact angle, surface tension measurements, and small-angle X-ray scattering. The results highlighted the superior MPD’s performance, both in inducing polymer removal and in detaching the soil from coated surfaces. At the microscale, the cleaning involves dewetting-like processes, where the polymer or the soil oily phase is detached from the surface and coalesce into separated droplets. This can be accounted by considering the different surface tensions and the different adsorption mechanisms of MPD with respect to ordinary nonionic surfactants (likely due to the methyl capping of the polar head chain and to the presence of the ester group between the hydrophilic and hydrophobic parts of the MPD surfactant molecule), showing how a tiny change in the surfactant architecture can lead to important differences in the cleaning capacity. Overall, this paper provides a detailed description of the mechanism and the kinetics involved in the NSFs cleaning process, opening new perspectives on simple formulations that are able to target at a specific substance to be removed. This is of utmost importance in the conservation of irreplaceable works of art.

Removing Polymeric Coatings With Nanostructured Fluids: Influence of Substrate, Nature of the Film, and Application Methodology

Cleaning is one of the most important and delicate operations in the conservation of cultural heritage, and, if not correctly performed, may irreversibly damage works of art. The removal of aged or detrimental polymeric coatings from works of art is a common operation in conservation, and nanostructured fluids (NSFs), such as aqueous swollen micelles and oil-in-water (o/w) microemulsions, are used as an alternative to non-confined organic solvents that pose a series of non-negligible drawbacks. NSFs effectiveness in removing polymeric coatings has been thoroughly demonstrated in the last decades, while their cleaning mechanism is still under investigation. The present work deepens the knowledge on the removal mechanisms of NSFs, studying the interaction of a four-component NSF with four different types of acrylic and vinyl polymer films cast from solutions or aqueous polymer latexes on three substrates (glass, marble and polystyrene) with different hydrophilicity and wettability. NSFs were applied either as non-confined or confined in cellulose poultices (traditionally employed by conservators), or in highly retentive chemical gels, observing the influence of the confining matrix on the removal process. It was found that the NSF/polymer film interaction is greatly dependent on the film structure and composition. Films formed from solvent solutions can be swollen by water/organic solvents mixtures or dewetted when a surfactant is added to the cleaning fluid; films formed from polymer latexes, on the other hand, are generally swollen even just by water alone, but poorly dewet. The substrate also plays an important role in the removal of polymer films formed from solutions, for instance the removal of an acrylic polymer from polystyrene could be achieved only through highly selective cleaning using NSF-loaded chemical hydrogels. These results can be key for conservators, providing innovative solutions to face new challenges in art preservation.

Surfactants Mediate the Dewetting of Acrylic Polymer Films Commonly Applied to Works of Art.

The removal of hydrophobic polymer coatings from artistic surfaces is a ubiquitous challenge in art restoration. Over the years, nanostructured fluids (NSFs), aqueous surfactant solutions containing a good solvent for the polymer, have been successfully applied in polymer removal interventions; however, the precise role of the surfactant in promoting polymer film dewetting is not fully understood. This contribution addresses the interaction of a NSF of water/propylene carbonate containing a nonionic surfactant with an acrylic polymer film commonly used in art conservation. Combining confocal microscopy and fluorescence correlation spectroscopy, we monitored the penetration of the fluid into thepolymer film, defining its compositional changes and following the polymer swelling. The ensemble of results highlights that the surfactant role is twofold: (i) at the polymer-support interface, it promotes the detachment of the polymer film from the underlying support; (ii) inside the polymer film, it accelerates polymer swelling by increasing the chains' mobility.

Evaluation of polyvinyl alcohol\u2013borax/agarose (PVA\u2013B/AG) blend hydrogels for removal of deteriorated consolidants from ancient Egyptian wall paintings

This study concerns the assessment of a new polyvinyl alcohol–borax/agarose blend hydrogel (PVA–B/AG) tailored for the conservation of ancient Egyptian wall paintings. The increasing problems of deteriorated consolidants affecting ancient wall paintings have attracted the interest of conservation scientists in the last 20 years. The ability of a new blend for removing aged Paraloid® B-72 layers from painted stone and plaster samples has been evaluated. The hydrogel blend was used to expose the aged Paraloid in a controlled manner to six different cleaning system (CS). CS1–CS4 consist of solvents or solvent mixtures; CS5 and CS6 are nanostructured fluids (NSFs). The evaluation of the removal process was carried out by quantitative and qualitative methods, namely, visual examination, 3D microscopy, contact angle and colorimetric measurements and by Fourier transform infra-red spectrometry in reflectance mode. The results showed that the PVA–B/AG blend hydrogel, loaded with specific cleaning systems, was able to remove deteriorated B-72 and allowed to restore the painted surface to a state close to the original one. The PVA–B/AG blend showed good workability, permitting it to be easily cut, shaped, applied and removed. It could also be verified by means of different investigation methods that the blend left no detectable residues. As a final realistic check of the method, the PVA–B/AG hydrogel loaded with the best functioning cleaning system (CS3) was used to remove an aged consolidant layer from an ancient Egyptian wall painting.

CO2-controllable smart nanostructured fluids in a pseudo Gemini surfactant system

A novel CO2 responsive anionic smart wormlike micelles (SWLMs) was constructed by simply mixing sodium oleate (NaOA) and the small organic counterion 2, 6, 10-trimethyl-2, 6, 10-triazaundecane (TMTAD) in a 3:1 M ratio without complex organic synthesis. After bubbling CO2, TMTAD and NaOA molecules in aqueous solution, a pseudo Gemini surfactant is formed in situ due to electrostatic interactions. This system shows two obvious performance transitions when CO2 is continuously introduced, from a water-like solution to a viscoelastic fluid and then a milky solution. Such transitions reflect the continuous transformation of the self-assembled structure from spherical micelles to wormlike micelles and then vesicle or spherical micelles. Additionally, this system can exhibit two similar sequential transformations when the pH changes in the reverse process.

A Triton X-100-Based Microemulsion for the Removal of Hydrophobic Materials from Works of Art: SAXS Characterization and Application.

The removal of hydrophobic materials from a porous support, such as wax stains on wall paintings, is particularly challenging. In this context, traditional methods display several drawbacks. The limitations of these methods can be overcome by amphiphile-based aqueous nanostructured fluids, such as micellar solutions and microemulsions. In this study, a microemulsion for the removal of wax spots from artistic surfaces was formulated. The nanostructured fluid includes a non-ionic surfactant, i.e., Triton X-100, and two apolar solvents, namely p-xylene and n-nonane. The solvents were selected on the basis of solubility tests of three waxes in several organic solvents. The nanostructured fluid was characterized by means of small-angle X-rays scattering (SAXS) and the information about micelle structure was used to understand the interaction between the microemulsion and the selected waxes. The microemulsion was then tested during the restoration of the frescoes in the Major Chapel of the Santa Croce Basilica in Florence, Italy. After some preliminary tests on fresco mockups reproduced in the laboratory, the nanostructured fluid was successfully used to clean some wax deposits from the real paintings, hardly removable with traditional physico-mechanical methods.

Restoring artwork with nanostructured fluids

Restoring artwork with nanostructured fluids

Nanostructured fluids for the removal of graffiti – A survey on 17 commercial spray-can paints

Abstract Graffiti removal from monuments, such as statues or architecture, is becoming a priority for conservators and restorers. This operation is further complicated when the vandalism is carried out on surfaces that should be preserved, as in the case of writings or tags on historical wall paintings, or even on modern or contemporary pieces of street art. Several methods exist for graffiti removal, which include chemical, physical or biological approaches. However, traditional methodologies, such as the use of neat organic solvents, are often unsuitable. Moreover, due to the great variability of brands and formulation of commercial paints, a thorough study of materials used for graffiti and a deep knowledge of their behavior when exposed to cleaning media is currently lacking. In this contribution, we report a systematic laboratory survey on 17 different spray-can paints available on the market and commonly used for graffiti and vandalism in the Mexican area. These paints were analyzed by means of ATR FT–IR spectroscopy to characterize their composition. Several solvents, having different nature and polarity, were then used to remove the paints from glass slides. On the basis of these results, two different amphiphile-based nanostructured fluids, which present several advantages with respect to traditional cleaning methodologies, were formulated and tested on the same paint samples. Finally, the two nanostructured cleaning systems were used for the removal of vandalistic graffiti from stones decorated with red pre-Hispanic paintings in the archeological site of Ba’ Cuana, Asuncion Ixtalpetec, Oaxaca, Mexico.

Restoring artwork with nanostructured fluids

Restoring artwork with nanostructured fluids

Polymer Film Dewetting by Water/Surfactant/Good-Solvent Mixtures: A Mechanistic Insight and Its Implications for the Conservation of Cultural Heritage.

Aqueous nanostructured fluids (NSFs) have been proposed to remove polymer coatings from the surface of works of art; this process usually involves film dewetting. The NSF cleaning mechanism was studied using several techniques that were employed to obtain mechanistic insight on the interaction of a methacrylic/acrylic copolymer (Paraloid B72) film laid on glass surfaces and several NSFs, based on two solvents and two surfactants. The experimental results provide a detailed picture of the dewetting process. The gyration radius and the reduction of the Tg of Paraloid B72 fully swollen in the two solvents is larger for propylene carbonate than for methyl ethyl ketone, suggesting higher mobility of polymer chains for the former, while a nonionic alcohol ethoxylate surfactant was more effective than sodium dodecylsulfate in favoring the dewetting process. FTIR 2D imaging showed that the dewetting patterns observed on model samples are also present on polymer-coated mortar tiles when exposed to NSFs.

Polymer Film Dewetting by Water/Surfactant/Good‐Solvent Mixtures: A Mechanistic Insight and Its Implications for the Conservation of Cultural Heritage

AbstractAqueous nanostructured fluids (NSFs) have been proposed to remove polymer coatings from the surface of works of art; this process usually involves film dewetting. The NSF cleaning mechanism was studied using several techniques that were employed to obtain mechanistic insight on the interaction of a methacrylic/acrylic copolymer (Paraloid B72) film laid on glass surfaces and several NSFs, based on two solvents and two surfactants. The experimental results provide a detailed picture of the dewetting process. The gyration radius and the reduction of the Tg of Paraloid B72 fully swollen in the two solvents is larger for propylene carbonate than for methyl ethyl ketone, suggesting higher mobility of polymer chains for the former, while a nonionic alcohol ethoxylate surfactant was more effective than sodium dodecylsulfate in favoring the dewetting process. FTIR 2D imaging showed that the dewetting patterns observed on model samples are also present on polymer‐coated mortar tiles when exposed to NSFs.