Thermogravimetric, Morphological and Infrared Analysis of Blends Involving Thermoplastic Starch and Poly(ethylene-co-methacrylic acid) and Its Ionomer Form.

This study focuses on the thermal properties and structural features of blends consisting of thermoplastic starch (TPS) and poly(ethylene-co-methacrylic acid) copolymer (EMAA) or its ionomer form (EMAA-54Na). The aim is to investigate how carboxylate functional groups of the ionomer form intervene in blends compatibility at the interface of the two materials and how this impacts their properties. Two series of blends (TPS/EMAA and TPS/EMAA-54Na) were produced with an internal mixer, with TPS compositions between 5 and 90 wt%. Thermogravimetry shows two main weight losses, indicating that TPS and the two copolymers are primarily immiscible. However, a small weight loss existing at intermediate degradation temperature between those of the two pristine components reveals specific interactions at the interface. At a mesoscale level, scanning electron microscopy confirmed thermogravimetry results and showed a two-phase domain morphology, with a phase inversion at around 80 wt% TPS, but also revealed a different surface appearance evolution between the two series. Fourier-transformed infrared spectroscopy analysis also revealed discrepancies in fingerprint between the two series of blends, analysed in terms of additional interactions in TPS/EMAA-54Na coming from the supplementary sodium neutralized carboxylate functions of the ionomer.

Influence of Surface Chemistry of Fiber and Lignocellulosic Materials on Adhesion Properties with Polybutylene Succinate at Nanoscale.

The production of bio-based composites with enhanced characteristics constitutes a strategic action to minimize the use of fossil fuel resources. The mechanical performances of these materials are related to the specific properties of their components, as well as to the quality of the interface between the matrix and the fibers. In a previous research study, it was shown that the polarity of the matrix played a key role in the mechanisms of fiber breakage during processing, as well as on the final properties of the composite. However, some key questions remained unanswered, and new investigations were necessary to improve the knowledge of the interactions between a lignocellulosic material and a polar matrix. In this work, for the first time, atomic force microscopy based on force spectroscopy measurements was carried out using functionalized tips to characterize the intermolecular interactions at the single molecule level, taking place between poly(butylene succinate) and four different plant fibers. The efficiency of the tip functionalization was checked out by scanning electron microscopy and energy-dispersive X-ray spectroscopy, whereas the fibers chemistry was characterized by Fourier-transform infrared spectroscopy. Larger interactions at the nanoscale level were found between the matrix and hypolignified fibers compared to lignified ones, as in control experiments on single lignocellulosic polymer films. These results could significantly aid in the design of the most appropriate composite composition depending on its final use.

Time/Molecular Weight Superposition to Describe the Behavior of Controlled-Rheology Polypropylenes.

Polypropylene resins issuing from polymerization reactors are degraded by peroxides in subsequent reactive extrusion processes to improve their processability. This operation reduces their molecular weight and, thus, their viscosity and elasticity. In a previous study, a series of homo- and copolymer polypropylenes of different molecular weight distributions were prepared by twin-screw extrusion and characterized by oscillatory rheometry. It was shown that their behavior could be described by Carreau-Yasuda equations, possibly with a yield stress, in which all parameters depended on the weight average molecular weight. By using these experimental data, it is show in the present study that a time/molecular weight superposition allowed for a drastic reduction in the number of parameters to be considered in order to precisely describe the viscous behavior of these materials. This concept was then validated by applying it to various experimental data from the bibliography.

Extrusion Simulation for the Design of Cereal and Legume Foods.

A 1D global twin-screw extrusion model, implemented in numerical software, Ludovic®, was applied to predict extrusion variables and, therefore, to design various starchy products with targeted structure and properties. An experimental database was built with seven starchy food formulations for manufacturing dense and expanded foods made from starches, starch blends, breakfast cereals, pulse crop ingredients such as pea flour, fava bean flour, and fava bean starch concentrated, and wheat flour enriched with wheat bran. This database includes the thermal and physical properties of the formulations at solid and molten states, melt viscosity model, extruder configurations and operating parameters, and extruded foods properties. Using extrusion and viscosity models, melt temperature (T) and specific mechanical energy (SME) were satisfactorily predicted. A sensitivity analysis of variables at die exit was performed on formulation, extruder configuration, and operating parameters, generating the extruder operating charts. Results allowed the establishment of relationships between predicted variables (T, SME, melt viscosity) and product features such as starch and protein structural change, density and cellular structure, and functional properties. The extrusion operating conditions leading to targeted food properties can be assessed from these relationships and also the relationship between extrusion operating parameters and variables provided by simulation.