Design of biobased additives for tuning the properties of biopolymers

This work mainly arises from the necessity to support the rapid introduction of different biobased polymers that the industrial sector has been facing lately. Indeed, while considerable efforts are being made to find environmentally and economically sustainable materials, less attention is paid to their need to be properly compounded to fulfil increasingly rigorous technical and quality requirements. Therefore, there is a strong demand for the development of a novel generation of compatible additives able to improve the properties of biobased polymers while respecting sustainability. With this in mind, a new class of biobased plasticizers is herein proposed. Five different ketal-diesters were selectively synthesized starting from levulinic acid, a promising renewable chemical platform. These molecules were added to poly(vinyl chloride) as model polymer to test their plasticizing effectiveness. Complete morphological, thermal and viscoelastic characterizations showed a clear correlation between the structural features of the ketal-esters and the properties of the material. In addition, no significant leaching was found in both hydrophilic and lipophilic environments. Importantly, the proposed ketal-diesters performed comparably and, in some cases, even better than commercial plasticizers. The same molecules were then added to bacterial poly(3-hydroxybutyrate), a semicrystalline polyester characterized by poor thermal and mechanical properties. Morphology assessments showed no phase separation and the plasticizing effectiveness was confirmed by thermal and viscoelastic analyses, while leaching tests showed low extraction values. Readily usable fractions with controlled structure and tailored properties were obtained from highly heterogeneous industrial grade Kraft lignin. These fractions were then added to poly(vinyl alcohol). Promising preliminary results in terms of compatibility were achieved, with thermograms showing only one glass transition temperature. Finally, a fully biobased glycerol-trilevulinate was successfully synthesized by means of a mild and solvent-free route. Its plasticizing effectiveness was evaluated on poly(vinyl chloride), showing a significant decrease of the glass transition temperature of the material.

Exploring New Material and Analytical Method for Characterization and Conservation of Artifacts

In this dissertation, we focus on developing new green bio-based gel systems and evaluating both the cleaning efficiency and the release of residues on the treated surface, different micro or no destructive techniques, such as optical microscopy, TGA, FTIR spectroscopy, HS-SPME and micro-Spatially Offset Raman spectroscopy (micro-SORS) were tested, proposing advanced analytical protocols. In the first part, a ternary PHB-DMC/BD gel system composed by biodiesel, dimethyl carbonate and poly-3 hydroxybutyrate was developed for cleaning of wax-based coatings applied on indoor bronze. The evaluation of the cleaning efficacy of the gel was carried out on a standard bronze sample which covered a layer of beeswax by restores of Opificio delle Pietre Dure in Florence, and a real case precious indoor bronze sculpture Pulpito della Passione attributed to Donatello. Results obtained by FTIR analysis showed an efficient removal of the wax coating. In the second part, two new kinds of combined gels based on electrospun tissues (PVA and nylon) and PHB-GVL gel were developed for removal of dammar varnish from painting. The electrospun tissue combined gels exhibited good mechanical property, and showed good efficient in cleaning over normal gel. In the third part, green deep eutectic solvent which consists urea and choline chloride was proposed to produce the rigid gel with agar for the removal of proteinaceous coating from oil painting. Rabbit glue and whole egg decorated oil painting mock-ups were selected for evaluating its cleaning efficiency, results obtained by ATR analysis showed the DES-agar gel has good cleaning performance. Furthermore, we proposed micro-SORS as a valuable alternative non-destructive method to explore the DES diffusion on painting mock-up. As a result, the micro-SORS was successful applied for monitoring the liquid diffusion behavior in painting sub-layer, providing a great and useful instrument for noninvasive residues detection in the conservation field.