Nanofluids confined in chemical hydrogels for the selective removal of graffiti from street art

The main challenge in the conservation of street art is the selective removal of graffiti (i.e. tags, writings and overpaintings) from the original artwork. Nowadays, the effective methods available for this intervention involve risking damage to the original. The novel combination of nanofluids with highly retentive pHEMA/PVP chemical hydrogels is proposed as a controllable cleaning method for selective removal of graffiti from street art. Nanofluid-loaded hydrogels were tested on laboratory models simulating street art paintings covered in graffiti. The outcome of cleaning tests was investigated by means of visual, photographic and microscopic observation, and micro-reflectance FTIR spectroscopy. It was shown that the proposed methodology is effective in removing acrylic-, nitrocellulose- and alkyd-based graffiti without damaging the underlying paint. This can be achieved by means of a gradual swelling action performed by the nanofluid, which is limited to the surface layers by the retentive power of the hydrogel.Nanofluid

Finding a reflexive voice : -- researching the problems of implementing new learning practices within a New Zealand manufacturing organisation : a 100pt thesis presented in partial fulfilment of the requirements for the degree of Master of Management in Human Resources Management at Massey University

This study explored the social forces mediating manager's participation in a new reflexive participative learning practice designed to improve profitability within a New Zealand manufacturing organisation. Despite a large theoretical and managerial body of literature on organisational learning there has been little empirical investigation of how people experience and engage their reflexivity towards challenging the status-quo to create high level learning and new knowledge. Power was identified as a potential moderator of the reflexive learning experience and the variable relations of power and learning were constructed from a review of literature and these relationships were explored and investigated within the case study. Two prevailing discourses were identified as powerful moderators of public reflexivity, the traditionalist discourse which constructed managers actions and conversations towards insularism and survivalist concerns and the productionist discourse in which institutionalised production practices encircled and mediated managers actions and what constituted legitimacy in conversations. This study used a critical action research method to place the reflexive experience of managers and the researcher at the centre of the study and provide data representative of the social discourses that constructed variable freedoms and constraints upon the reflexive voice

Halloysite nanotubes as nano-carriers of corrosion inhibitors in cement formulations

The ingress of water, as a vehicle for many harmful substances, is the main cause of all the major physical and chemical degradation processes affecting concrete buildings. To prevent damage and protect concrete surfaces, coatings are generally used. Cement-based coatings in particular can act as a physical barrier and reduce the permeability of surfaces. In case of chloride-induced corrosion, corrosion inhibitors are also generally used, and nano-carriers have been proven to provide a long-term protective effect. In this work, we designed a surface protection cementitious coating enhanced with nano-silica and halloysite nanotubes (HNTs). HNTs were loaded with a corrosion inhibitor, benzotriazole (BTA), and used as nano-reservoir, while nano-silica was used to improve the structure of the protective coating and to strengthen its adhesion to the surface of application. The cementitious coatings were characterized with a multi-technique approach including thermal and spectroscopic analysis, scanning electron microscopy, specific surface area and pore size distribution, and Vickers hardness test. The release of BTA was monitored through UV-vis analysis, and the transportation of BTA through coated mortars was studied in simulated rain conditions. We evidenced that the presence of silica densifies the porous structure and increases the interfacial bond strength between the protective coating and the surface of application. We report here, for the first time, that HNTs can be used as nano-carriers for the slow delivery of anti-corrosion molecules in cement mortars

pH-Controlled assembly of polyelectrolyte layers on silica nanoparticles in concentrated suspension

Hypothesis: Preparation of suspensions of nanoparticles (>1 wt%) coated with a polyelectrolyte multilayers is a challenging task because of the risk of flocculation when a polyelectrolyte is added to a suspension of oppositely charged nanoparticles. This situation can be avoided if the charge density of the polymers and particles is controlled during mixing so as to separate mixing and adsorption events. Experiments: The cationic polyethylenimine (PEI) and the anionic carboxymethylcellulose (CMC) were used as weak polyelectrolytes. Polyelectrolyte multilayers build-up was conducted by reducing the charge of one of the components during the addition of the next component. Charge density was controlled by tuning pH. Analysis of the suspension of coated nanoparticles was done by means of dynamic light scattering, electrophoresis and small angle x-ray scattering measurements, while quartz crystal microbalance was used to study the build-up process on flat silica surfaces. Findings: Charge density, controlled through pH, can be used as a tool to avoid flocculation during layerby-layer deposition of polyelectrolytes on 20 nm silica particles at high concentration (-40 wt%). When added to silica at pH 3, PEI did not induce flocculation. Adsorption was triggered by raising the pH to 11, pH at which CMC could be added. The pH was then lowered to 3. The process was repeated, and up to five polyelectrolyte layers were deposited on concentrated silica nanoparticles while inducing minimal aggregation

pH-Controlled assembly of polyelectrolyte layers on silica nanoparticles in concentrated suspension

Hypothesis: Preparation of suspensions of nanoparticles (>1 wt%) coated with a polyelectrolyte multilayers is a challenging task because of the risk of flocculation when a polyelectrolyte is added to a suspension of oppositely charged nanoparticles. This situation can be avoided if the charge density of the polymers and particles is controlled during mixing so as to separate mixing and adsorption events. Experiments: The cationic polyethylenimine (PEI) and the anionic carboxymethylcellulose (CMC) were used as weak polyelectrolytes. Polyelectrolyte multilayers build-up was conducted by reducing the charge of one of the components during the addition of the next component. Charge density was controlled by tuning pH. Analysis of the suspension of coated nanoparticles was done by means of dynamic light scattering, electrophoresis and small angle x-ray scattering measurements, while quartz crystal microbalance was used to study the build-up process on flat silica surfaces. Findings: Charge density, controlled through pH, can be used as a tool to avoid flocculation during layer-by-layer deposition of polyelectrolytes on 20 nm silica particles at high concentration (∼40 wt%). When added to silica at pH 3, PEI did not induce flocculation. Adsorption was triggered by raising the pH to 11, pH at which CMC could be added. The pH was then lowered to 3. The process was repeated, and up to five polyelectrolyte layers were deposited on concentrated silica nanoparticles while inducing minimal aggregation

[BMIm][BARF] imidazolium salt solutions in alkyl carbonate solvents: Structure and interactions

Solutions of weakly coordinating ionic liquids (ILs) in alkyl carbonates are gaining growing attention, as the latter are "green" solvents with high solvation power, but the phase behavior and structure of ILs in organic polar solvents are still poorly understood. Here, we study the interactions and nanoscale structure of 1-butyl-3-methylimidazolium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate, [BMIm][BARF], in three symmetrical alkyl carbonate solvents with increasing alkyl chain-length. Electrical conductivity and nuclear magnetic resonance measurements showed that [BMIm][BARF] was mostly undissociated in these solvents, especially at lower IL concentration. Small angle X-ray scattering patterns evidenced the presence of rod-like nanostructures in the IL/solvent mixtures. At higher IL concentration, [BMIm][BARF] is increasingly more dissociated in solvents with lower dielectric constant, as confirmed by analysis of the solvents' carbonyl stretching band via Fourier transform infrared spectroscopy. This trend is opposite to that exhibited by BMIm ILs with less bulky counterions. The bulky BARF(-) is weakly coordinating and has no ability to give strong H-bonding, thus short-range anisotropic van der Waals forces are likely key in the interaction of the ion pairs. The slower self-diffusion of the ions in alkyl carbonates with lower dielectric constants might partially hinder close contact needed for self-assembly into local nano-sized structures. Overall, our results shed light on interactions and self-organization in imidazolium salt-alkyl carbonate mixtures, with potential impact in applicative fields spanning from batteries, catalysis and extraction, up to bio-applications (antimicrobial and bioengineering)

Nanomaterials for the cleaning and pH adjustment of vegetable tanned leather

Leather artifacts in historical collections and archives are often contaminated by physical changes such as soiling, which alter their appearance and readability, and by chemical changes which occur on ageing and give rise to excessive proportion of acids that promote hydrolysis of collagen, eventually leading to gelatinization and loss of mechanical properties. However, both cleaning and pH adjustment of vegetable tanned leather pose a great challenge for conservators, owing to the sensitivity of these materials to the action of solvents, especially water-based formulations and alkaline chemicals. In this study the cleaning of historical leather samples was optimized by confining an oil-in-water (o/w) nanostructured fluid in a highly retentive chemical hydrogel, which allows the controlled release of the cleaning fluid on sensitive surfaces. The chemical gel exhibits optimal viscoelasticity, which facilitates its removal after the application without leaving residues on the object. Nanoparticles of calcium hydroxide and lactate, dispersed in 2-propanol, were used to adjust the pH up to the natural value of leather, preventing too high alkalinity which causes swelling of fibers and denaturation of the collagen. The treated samples were characterized using Scanning Electron Microscopy (FE SEM), controlled environment dynamic mechanical analysis (DMA-RH), and infrared spectroscopy (ATR-FTIR). The analytical assessment validated the use of tools derived from colloid and materials science for the preservation of collagen-based artifacts