Emmanuelle Gastaldi

Controlling pesticide release via structuring agropolymer and nanoclays based materials

The potential use of nanoclays for modulating transfer properties of active agents in bio-sourced polymers was explored. For this purpose, new pesticide formulations were designed by combining wheat gluten, ethofumesate (model pesticide) and three montmorillonites (MMT) using a bi-vis extrusion process. Controlled release properties, evaluated through release experiments in water, were discussed in relation to the material formulations and their resulting structure. Partition coefficients were calculated from experimental data and diffusivity values were identified with a Ficks second law mechanistic model. The effect of temperature on release pattern was also evaluated and the activation energy of diffusion was determined. Ethofumesate release was slowed down for all wheat gluten based-formulations as compared to the commercial product. This slow release effect was increased in the presence of hydrophobic MMTs, due to a higher affinity for ethofumesate than for wheat gluten. Contrarily, hydrophilic MMT, displaying a greater affinity for wheat gluten than for ethofumesate seemed ineffective to slow down its release despite the tortuous pathway achieved through a well-exfoliated structure. To conclude, the release mechanisms would be rather governed by pesticide/MMT interactions than MMT/polymer matrix in the case of a hydrophobic pesticide such as ethofumesate and a hydrophilic matrix such as wheat gluten.

Control of aroma transfer by biopolymer based materials

Abstract Biopolymers such as proteins offer unique functional properties that can be used in the field of edible or biodegradable active packagings. Among the barrier properties of biopolymer based packaging, the knowledge of the aroma compound transfer is required (i) to control losses and sorption of aroma compounds which are important contributors to the sensory product quality (ii) or to emit desirable flavour from active packaging in a controlled way. Permeability of 2-heptanone in protein coated papers was investigated. It was demonstrated that coating by gluten or casein decreased the permeability of 2-heptanone and that coated papers had promising aroma barrier compared to other packaging materials such as sulphuric or paraffin papers or LDPE. The ability of biopolymer films to control aroma release was also demonstrated. An aroma compound (carvacrol) was incorporated in a gluten protein matrix, which showed adequate ability to maintain aroma compounds during film processing. The release of the aroma compound into the headspace was followed under accelerated conditions of temperature and relative humidity (30°C and 60% RH). It was shown that the release rate was not dependent on carvacrol amount. The gluten film delayed aroma compound emission into the headspace for more than a month.

Effect of nanoclay on the transfer properties of immanent additives in food packages

Polymer nanocomposites and specifically clay-based nanocomposites are emerging in the food packaging area and are promised to have a growing market. While the advantages of the nanoparticles on the gas barrier properties of the nanocomposites are already well-investigated and confirmed, the effect of these nanoparticles on the migration of other non-nano and potentially toxic components of the polymer packaging has still remained unclear. The present study addressed the effect of nanoclay on the migration of various additives from nanoclay/LLDPE nanocomposite packaging by determining the apparent diffusivity of these additives from the samples in contact with four different types of food simulants that distinctively exhibit hydrophilic and lipophilic characters. The results indicated that apart from the tortuosity effect that influence in a low extent the diffusivity of model migrants, the presence of nanoclays modifies the transport properties of materials as a result of their impact on other factors such as crystallinity and swelling capacity. PLS analysis on the influential geometrical and physical properties additionally revealed that the affinity between the food simulant and the polymer has the dominant effect on determining the order of apparent diffusivity as well as the effectiveness of barrier properties of nanoclays to reduce the diffusivity of additives through food packaging. Such statements suggest a benefit provided by nanoparticles incorporation in terms of the human exposure to plastic additives.

Biodegradable herbicide delivery systems with slow diffusion in soil and UV protection properties.

BACKGROUND New herbicidal formulations were designed by combining wheat gluten (WG), two montmorillonites (MMTs) (unmodified and organically modified) and a model pesticide (ethofumesate), and their performances were assessed through an integrative study conducted in soil using an experimental methodology with data modelling. RESULTS All the WG formulations tested were effective in decreasing the apparent diffusivity of ethofumesate in soil in comparison with the non-formulated active substance. The slow-release effect was significantly more pronounced in the presence of the organically modified MMT, confirming the importance of sorption mechanisms to reduce ethofumesate diffusion. The bioassays undertaken on watercress to evaluate herbicidal antigerminating performances showed that all the WG formulations (with or without MMT) were more effective than both the commercial formulation and the non-formulated ethofumesate, whatever the concentration tested. To explain such results, it was proposed that WG formulations would enable ethofumesate to be more available and thus more effective in inhibiting seed germination, as they would be less prone to be leached by water transport due to watering and also less subject to photodegradation. CONCLUSION The use of pesticide formulations based on wheat gluten and nanoclays appeared to be a promising strategy both to reduce the mobility of pesticides in soil and to protect UV-photosensitive pesticides from photodegradation.

A novel hybrid self-assembly process for synthesising stratified polyethylene–organoclay films

This study reports the first effort to synthesize a new type of PE–organoclay multilayer film by starting from an uncharged apolar polymer substrate and successively depositing apolar organoclay and uncharged apolar polyethylene (PE) layers with subsequent repeating depositions. The alternate variation of contact angle (85° average for organoclay and 107° for PE layers) confirmed the profilometry and the scanning electron microscopy results as well as the linear growth pattern, i.e. the successful highly stratified assembly of repetitive bilayers comprised of 450 nm organoclays and 2.25 μm PE layers. The self-assembly of organoclays on PE surfaces was driven by solvophobic molecular construction involving hydrophobic interactions between the organic parts of the organoclay tactoids dispersed in an organic solvent and the PE hydrophobic surface. The deposition of PE molecules on the organoclay layers was the result of a dip-coating process involving physical sorption of a highly viscous PE solution on the surface of the organoclay layers.

Lignocellulosic Fibres-Based Biocomposites Materials for Food Packaging

Current requests in the field of food packaging lead to the reasoned design of materials able to improve the global environmental balance of the food/packaging system by minimizing the negative environmental impact of the packaging material while improving its positive role in the food wastes and losses reduction that strongly impact our environment. This means to simultaneously control food degradation reactions while limiting undesirable migrations of additives from packaging towards in respect of our health and remaining economically competitive. The substitution of oil-based materials by ones issued from renewable and non-food resources (e.g. issued from bioconversion of agro-food wastes, for example) and furthermore, fully biodegradable in natural conditions is also a necessity and represents a significant breakthrough from the research in the field of food packaging. In this context, increasing attention is given to full-biocomposites, i.e. composite materials based on constituents all biosourced and biodegradable. Developing full-biocomposites for food packaging requires taken into account numerous factors, and this is even more important for complex biodegradable materials due to the gap in knowledge on their behaviour and potentialities in usage conditions. The objective of this chapter is to decipher the state of the art on full-biocomposites by considering the specific stakes relative to the food packaging application. After the first part of introduction, the second part will present the role of packaging to ensure food quality and safety and how it should be designed in such a way to reduce food waste and losses. The third part will present the window of mass transfer properties of full-biocomposites, which is the main functional property when considering the food packaging application. The fourth part will consider the economical competitiveness of full-biocomposites, the fifth part will treat the safety issues and the sixth of the different options of end of life and waste management.

How Performance and Fate of Biodegradable Mulch Films are Impacted by Field Ageing

Three black biodegradable films based on PBAT-blends (PBAT/PLA, PBAT/PPC and PBAT/Starch) were tested for vine mulching in real field conditions. The impact of field ageing on their morphology, mechanical performance and ultimate biodegradation was investigated on films exposed at the soil surface or buried into the soil in order to assess the respective contribution of the main related ageing factors i.e. UV radiations and microorganisms. The fact that the soil-facing surface of films exhibited holes 18 months after installation suggested that the biodegradation process could occur above-soil even without previous burying step. However, the early loss of integrity of the biodegradable materials was attributed to UV radiations since beyond a certain threshold the photochemical modifications undergone by the material were too high to sustain its integrity. Whatever the material tested the deterioration of mechanical properties was correlated with the crosslinking of polymer chains inducing the formation of a gel fraction. Considering that the major part of the three materials studied is made of PBAT, the nature of the other polymer constituting the blend would not have a significant impact on the ageing mechanism of the material. Biodegradation analyses conducted in compost medium indicated that field ageing had a low impact on the percentages of mineralization whether the materials had been previously aged or not.

Protein/Clay Nano-Biocomposites

In the current context, protein-based materials might be considered as an alternative to the petroleum-based plastics since fully biodegradable and characterized by remarkable functional properties that can be exploited in a wide range of non-food applications. To improve their performances that are often restricted by high water sensitivity and low mechanical properties, a relevant strategy consisted in the development of protein/clay nanocomposite. For this purpose, several examples of protein-based nano-biocomposites were presented with a special attention for the methods used for the incorporation of layered silicates (organically modified or not) into the matrices and the ultimate functional properties exhibited by the resulting materials. In terms of mechanical properties, the addition of nanoclays leads to a significant improvement of material performance with an increase of Young’s modulus and tensile strength ranging between 1.5 and 2 times. As regards as barrier properties, the improvement appeared quite moderate in spite of a rather good dispersion of layered silicates that would be expected to result in a tortuous pathway limiting diffusion of gases molecules. Thus, a two-fold reduction in water vapour permeability was obtained, and the same or no effect in the case of permeability toward O2 and CO2.