Fractal Structure Evolution during Cement Hydration by Differential Scanning Calorimetry: Effect of Organic Additives

Low-temperature differential scanning calorimetry (LT-DSC) is used to investigate the microstructure of tricalcium silicate pastes, hydrating in pure water and in the presence of comb-shaped polycarboxylate ether superplasticizers. LT-DSC is shown to be a powerful technique, able to provide important information on the porosity and on the fractality of the porous evolving matrices by means of rapid and nondestructive measurements. In particular, LT-DSC gives a semiquantitative estimation of the evolving porosity (capillary, small gel, and large gel pores), the depercolation threshold of the capillary pores, and the fractal dimension associated with the probed porosity. The results are in good agreement with those obtained by small-angle scattering methods ensuring that this approach, based on the well-established and easily accessible DSC technique, can provide valuable information on the evolving porosity and the fractal nature of hydrating cement pastes

Nanostructured Surfactant-Based Systems for the Removal of Polymers from Wall Paintings: A Small-Angle Neutron Scattering Study

Nanostructured soft matter systems represent effective and long-lasting solutions with respect to traditional and often obsolete methodologies for the conservation of works of art. In particular, complex fluids such as micelles and microemulsions are the most performing media for the removal of organic materials from porous supports, like wall paintings or stones. In this Article, we report on the characterization of two systems, EAPC and XYL, which have shown good to optimal performances in the removal of organic polymers from wall paintings. EAPC is a five-components fluid composed of water, sodium dodecylsulfate (SDS), 1-pentanol (PeOH), propylene carbonate (PC), and ethyl acetate (EA), while XYL is a “classical” o/w microemulsion, where <i>p</i>-xylene droplets are stabilized in water by SDS and PeOH. Small-angle neutron scattering (SANS) with contrast variation is used to infer a detailed picture of the structure of these complex fluids, with a particular focus on the partition of the components between the bulk phase and the nanocompartments. We found that, differently from XYL, the EAPC system is neither a microemulsion nor a simple micellar solution, with the cosolvents partitioned between the dispersing phase and the disperse droplets. These different structural features play a key role in defining the cleaning effectiveness and specifically the kinetics of interaction between the nanofluid and the polymeric coating to be removed, which is of paramount importance for the application in the field. Both of these nanofluids are effective in polymer removal, but EAPC is considerably more efficient and versatile. The composition and the structure at the nanoscale determine the capability of removing a broad range of different polymer coatings from porous materials. A representative case study is here described, addressing a particularly challenging conservative issue, which is the removal of a multilayered aged coating that was irreversibly damaging the pictorial layer of the Annunciation Basilica in Nazareth

Multifunctional Magnetoliposomes for Sequential Controlled Release

The simultaneous or sequential delivery of multiple therapeutic active principles to a specific target is one of the main challenges of nanomedicine. This goal requires the construction of complex devices often extremely time and cost consuming. Supramolecular self-assemblies, with building blocks of different nature, each providing a specific function to the final construct, can combine a facile synthetic route with a high tunability and structural control. In this study we provide the proof-of-principle of a drug delivery system, DDS, constituted of (i) liposomes, providing a fully biocompatible lipid scaffold suitable to host both hydrophobic and hydrophilic drugs; (ii) a double-stranded DNA conjugated with a cholesteryl unit that spontaneously inserts into the lipid membrane; and (iii) hydrophobic and hydrophilic superparamagnetic iron oxide nanoparticles (SPIONs) embedded inside the lipid membrane of liposomes or connected to the DNA, respectively. Upon application of an alternating magnetic field, the SPIONs can trigger, through thermal activation, the release of a DNA strand or of the liposomal payload, depending on the frequency and the application time of the field, as proved by both steady-state and time-resolved fluorescence studies. This feature is due to the different localization of the two kinds of SPIONS within the construct and demonstrates the feasibility of a multifunctional DDS, built up from self-assembly of biocompatible building blocks

Tricalcium Silicate Hydration Reaction in the Presence of Comb-Shaped Superplasticizers: Boundary Nucleation and Growth Model Applied to Polymer-Modified Pastes

The Boundary Nucleation and Growth Model (BNGM), developed for the analysis of the hydration reaction of tricalcium silicate, has been applied to study the kinetic behavior of pastes containing chemical admixtures. Four comb-shaped polycarboxylate ether (PCE) superplasticizers with well-known molecular structures have been added to tricalcium silicate. The BNGM analysis performed on this series of additives allows insights into the effect of the molecular architecture of the PCEs on the induction time and rate constants. The results show that decreasing the length of the polyethylene oxide side chains of the PCE molecules increases the induction time. Also, the side chain density, which highly influences the adsorption of the polymer to the C₃S unreacted grains, is shown to significantly affect the duration of the induction period: in particular, molecules with low side chain density delay the setting of the paste to a greater extent than molecules with denser side chains. Moreover, the chemical admixtures influence the rate constants of the nucleation and growth processes, both reducing them and affecting their temperature dependence

Hofmeister Phenomena in Nonaqueous Media: The Solubility of Electrolytes in Ethylene Carbonate

The solubility of some potassium salts (KF, KCl, KBr, KI, KNO₃, KClO₄, KSCN, and KSeCN) in ethylene carbonate (EC) was determined at different temperatures with an inductively coupled plasma atomic emission spectrometer. From the solubility measurements, the thermodynamic parameters Δ<i>G</i>, Δ<i>H</i>, and Δ<i>S</i>, of solution and of solvation, were calculated. Measurements were carried out via XRD, ATR, and FTIR to determine the effect of each salt on the properties of the solvent. The open question of whether specific ion (Hofmeister) effects are restricted to hydration peculiar to water is resolved. As for water, the effects are due to solute (ion, dipolar) induced solvent structure not accounted for by electrostatic forces. Cooperative quantum mechanical forces are necessary to understand the phenomena

Magnetically Triggered Release From Giant Unilamellar Vesicles: Visualization By Means Of Confocal Microscopy

Magnetically triggered release from magnetic giant unilamellar vesicles (GUVs) loaded with Alexa fluorescent dye was studied by means of confocal laser scanning microscopy (CLSM) under a low-frequency alternating magnetic field (LF-AMF). Core/shell cobalt ferrite nanoparticles coated with rhodamine B isothiocyanate (MP@SiO₂(RITC)) were prepared and adsorbed on the GUV membrane. The MP@SiO₂(RITC) location and distribution on giant lipid vesicles were determined by 3D-CLSM projections, and their effect on the release properties and GUV permeability under a LF-AMF was investigated by CLSM time-resolved experiments. We show that the mechanism of release of the fluorescent dye during the LF-AMF exposure is induced by magnetic nanoparticle energy and mechanical vibration, which promote the perturbation of the GUV membrane without its collapse

State of Water in Hydrating Tricalcium Silicate Pastes: The Effect of a Cellulose Ether

Time-dependent quasi-elastic neutron scattering (QENS) and differential scanning calorimetry (DSC) were applied to study water dynamics and hydration kinetic of the hydration reaction of tricalcium silicate in the presence of a methyl hydroxyethyl cellulose (MHEC) additive. The translational dynamics of the water confined in the developing hydrated calcium silicate matrix was probed at the molecular scale by QENS during the first 4 days, while the evolution of the matrix porosity and the hydration kinetics were determined up to 28 days of hydration by differential scanning calorimetry. The application of the boundary nucleation and growth model consistently improved the hydration kinetics picture, usually obtained from the application of the classical Avrami-Erove’ev model, allowing the evaluation of the individual contributions of nucleation and growth over the entire hydration process. In the presence of the cellulose ether the nature of the nucleation process is strongly modified, approaching a “spatially random” hydration mechanism. The water contained in the nanometric porosity of the hydrated calcium silicate matrix, which is fundamental for the efficiency of the hydration process, results increased when MHEC is added, leading to a delay of the onset of the hydration process and the enhancement of the efficiency of the reaction

Pore Size Effect on Methane Adsorption in Mesoporous Silica Materials Studied by Small-Angle Neutron Scattering

Methane adsorption in model mesoporous silica materials with the size range characteristic of shale is studied by small-angle neutron scattering (SANS). Size effect on the temperature-dependent gas adsorption at methane pressure about 100 kPa is investigated by SANS using MCM-41 and SBA-15 as adsorbents. Above the gas–liquid condensation temperature, the thickness of the adsorption layer is found to be roughly constant as a function of the temperature. Moreover, the gas adsorption properties, such as the adsorbed layer thickness and the specific amount of adsorbed gas, have little dependence on the pore size being studied, i.e., pore radius of 16.5 and 34.1 Å, but are mainly affected by the roughness of the pore surfaces. Hence, the surface properties of the pore wall are more dominant than the pore size in determining the methane gas adsorption of pores at the nanometer size range. Not surprisingly, the gas–liquid condensation temperature is observed to be sensitive to pore size and shifts to higher temperature when the pore size is smaller. Below the gas–liquid condensation temperature, even though the majority of gas adsorption experiments/simulations have assumed the density of confined liquid to be the same as the bulk density, the measured methane mass density in our samples is found to be appreciably smaller than the bulk methane density regardless of the pore sizes studied here. The mass density of liquid/solid methane in pores with different sizes shows different temperature dependence below the condensation temperature. With decreasing temperature, the methane density in larger pores (SBA-15) abruptly increases at approximately 65 K and then plateaus. In contrast, the density in smaller pores (MCM-41) monotonically increases with decreasing temperature before reaching a plateau at approximately 30 K

Probing the Cleaning of Polymeric Coatings by Nanostructured Fluids: A QCM‑D Study

Complex fluids composed of water, an organic solvent, and a surfactant have been recently employed as cleaning systems to remove hydrophobic materials, such as polymeric coatings, from solid surfaces. The simultaneous presence of surfactants and an organic solvent with good affinity for the polymer was proven necessary for the polymer’s removal, but the comprehension of the cleaning mechanism is poorly understood. In this Article, we investigated the mechanism of removal, highlighting the specific role of each component in the interaction with the polymer film. In particular, the results from quartz crystal microbalance with dissipation monitoring (QCM-D) were compared with those obtained by using confocal microscopy to follow in situ the effect of a nanostructured fluid, i.e., a ternary formulation containing water, 2-butanone (MEK) as a good solvent for the polymer, and a nonionic surfactant (C_9–11 ethoxylated alcohol, BR) on acrylic copolymer films (Paraloid B72). The results indicate a two-step process: (i) the penetration of the good solvent across the film causes the swelling of the polymer, the weakening of polymer–polymer interactions, and an increase of molecular mobility, followed by (ii) the slow adsorption of amphiphilic aggregates promoting the film detachment from the solid substrate. A different behavior is observed in the presence of similar formulations containing an anionic surfactant (sodium dodecyl sulfate, SDS), where the adsorption of SDS micelles on the surface of the polymeric film hinders solvent access into the polymer layer, rather than promoting its detachment from the solid substrate

Complex Fluids Confined into Semi-interpenetrated Chemical Hydrogels for the Cleaning of Classic Art: A Rheological and SAXS Study

The removal of aged varnishes from the surface of easel paintings using the common conservation practice (i.e., by means of organic solvents) often causes pigment leaching, paint loss, and varnish redeposition. Recently, we proposed an innovative cleaning system based on semi-interpenetrated polymer networks (SIPNs), where a covalently cross-linked poly­(hydroxyethyl methacrylate), pHEMA, network is interpenetrated by linear chains of poly­(vinylpyrrolidone), PVP. This chemical gel, simply loaded with water, was designed to safely remove surface dirt from water-sensitive artifacts. Here, we modified the SIPN to confine complex cleaning fluids, able to remove aged varnishes. These complex fluids are 5-component water-based nanostructured systems, where organic solvents are partially dispersed as nanosized droplets in a continuous aqueous phase, using surfactants. The rheological behavior of the SIPN and the nanostructure of the fluids loaded into the gel were investigated, and the mechanical behavior of the gel was optimized by varying both the cross-linking density and the polymer concentration. Once loaded with the complex fluids, the hydrogels maintained their structural and mechanical features, while the complex fluids showed a decrease in the size of the dispersed solvent droplets. Two challenging case studies have been selected to evaluate the applicability of the SIPN hydrogels loaded with the complex fluids. The first case study concerns the removal of a surface layer composed by an aged brown resinous patina from a wood panel, the second case study concerns the removal of a homogeneous layer of yellowed varnish from a watercolor on paper. The results show that the confinement of complex fluids into gels allowed unprecedented removal of varnishes from artifacts overcoming the limitations of traditional cleaning methods