The film formation of acrylic latex dispersions, containing different amounts of carboxylic acid functional groups by the incorporation of methacrylic acid (MAA), was studied with GARField 1H NMR at various relative humidities (RH). Polymer particles with glass-transition temperatures in the range from 26 to 50 °C formed films at room temperature because of hydroplasticization. It was found that with an increased drying rate due to lower RH, the evaporation flux of water was limited by the latex polymer. Only in the second stage of drying this phenomenon was more obvious with increasing MAA content. 1H NMR relaxometry was used to study the change of hydrogen mobilities during film formation and hardening of the films. This showed that the drying rate itself had no impact on the hydrogen mobility in the latex films as measured via the T2 relaxation time. Hydrogen mobilities of water and the mobile polymer phase only significantly decrease after most water has evaporated. This implies that the rigidity of the polymers increases with the evaporation of water that otherwise plasticizes the polymer through hydrogen bonding with the carboxylic acid groups. This hardening of the polymer phase is essential for applications in a coating. The hydrogen mobilities were affected by the MAA concentration. Densities of mobile hydrogens increase with increasing MAA content. This is expected if the mobile protons are contained in the MAA groups. The result thus confirms the role of carboxylic acid groups in hydrogen bonding and plasticization of the copolymers. Hydrogen mobilities, however, decrease with increasing MAA content, which is hypothesized to be caused by the formation of dimers of carboxylic acid groups that still hold water. They still enable short-range polymer hydrogen mobility due to hydroplasticization but limit long-range polymer mobility due to interaction between the carboxylic acid groups.
Young wines are supersaturated in potassium bitartrate, which induces rather uncontrolled crystallization processes. Delayed crystallization may occur even after bottling of the young wines, which is undesirable because it gives rise to a visual defect in the wine. Colloids such as mannoproteins, metatartaric acid, and carboxymethylcellulose are available on the market and may be added to delay crystallization. It has been a matter of debate whether such hydrocolloids prevent nucleation, growth of crystals, or both. It was the objective of this investigation to study the crystallization event by a new approach using dynamic light scattering and to clarify the mode of action of these hydrocolloids. To achieve this, model solutions and standardized wines were enriched with potassium bitartrate (KHT) to trigger crystallization. In this way, it was possible to distinguish between the influence of the hydrocolloids on nucleation and on crystal growth. It was found that the hydrocolloids do not prevent KHT nucleation. Instead, these compounds delay or even arrest the outgrowth of the crystals to a macroscopic, visual size.
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Moisture is a driving factor in the long-term mechanical deterioration of canvas paintings, as well as for a number of physico-chemical degradation processes. Since the 1990s a number of publications have addressed the equilibrium hygroscopic uptake and the hygro-mechanical deformation of linen canvas, oil paint, animal glue, and ground paint. In order to visualise and quantify the dynamic behaviour of these materials combined in a painting mock-up or reconstruction, we have performed custom-designed experiments with neutron radiography and nuclear magnetic resonance (NMR) imaging. This paper reports how both techniques were used to obtain spatially and temporally resolved information on moisture content, during alternate exposure to high and low relative humidity, or in contact with liquids of varying water activities. We observed how the canvas, which is the dominant component in terms of volumetric moisture uptake, absorbs and dries rapidly, and, due to its low vapour resistance, allows for vapour transfer towards the ground layer. Moisture desorption was generally found to be faster than absorption. The presence of sizing glue leads to a local increase of moisture content. It was observed that lining a painting with an extra canvas results in a damping effect: i.e. absorption and drying are significantly slowed-down. The results obtained by NMR are complementary to neutron radiography in that they allow accurate monitoring of water ingress in contact with a liquid reservoir. Quantitative results are in good agreement with adsorption isotherms. The findings can be used for risk analysis of paintings exposed to changing micro-climates or subjected to conservation treatments using water. Future studies addressing moisture-driven deformation of paintings can make use of the proposed experimental techniques.
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