Sandra Domenek

• Dr.
• Professor at AgroParisTech

Molecular mobility and physical ageing of amorphous plasticized polylactide (PLA) with two different contents of mesolactide are studied with the help of thermal analysis. Used plasticizers are acetyl tributyl citrate (ATBC) and triacetin (TA), two molecules with established miscibility and plasticizing efficiency. Lower plasticizer permanence of T...

Semicrystalline polylactide (PLA) films with controlled morphology were produced by thermal crystallization to optimize the oxygen barrier properties. The crystalline morphology of PLA at the scales of the lamella and the spherulite was investigated and the mobile amorphous phase dynamics were studied. The crystalline morphology had a negligible im...

Nanocomposites are an opportunity to increase the performance of polymer membranes by fine-tuning their morphology. In particular, the understanding of the contribution of the polymer matrix/nanofiller interface to the overall transport properties is key to design membranes with tailored selective and adsorptive properties. In that aim, cellulose n...

The development of polylactide (PLA)/cellulose nanocrystals (CNC) nanocomposites in the aim to increase gas barrier properties has been widely studied, but gave rise to conflicting results. To better understand the underlying gas transport mechanisms, PLA/CNC nanocomposites were produced at concentrations between 5 and 50 wt%. The role of the PLA/C...

Assessing the contamination of paper and board (P&B) food packaging materials poses significant challenges due to the sensitivity limits of analytical methods and the low precision of sampling processes. This study aims to enhance the understanding of P&B food packaging contamination by investigating the distribution of contaminants at different sc...

The dataset reports the impact of incorporating commercial compostable plastics into a full-scale open-air windrow composting process using household-separated biowaste. Two batches were prepared from the same biowaste mixture: one as a control and the other with 1.28 wt% of certified compostable plastics. The degradation of the materials was monit...

Lignins are phenolic polymers that reinforce plant cell walls within the conductive and supporting tissues of higher plants. They are generated as by-products through chemical pulp processes and biorefinery pretreatments for bioethanol production. After a brief description of constitutive monomeric subunits, their inter-units linkages and functiona...

In recent years, synthetic polymers have become an integral part of our daily lives, with applications ranging from packaging and construction to automotive and electronics. However, this widespread use has led to significant environmental challenges, notably plastic pollution in oceans, rivers, and land. In response to this issue, there is ongoing...

Poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate) (PHBV) is a biodegradable polymer with significant potential for use in food packaging. However, its limited melt strength poses a challenge when employing film‐blowing techniques to produce flexible packaging. To overcome this obstacle, we developed blends consisting of 70 wt% PHBV and 30 wt% poly(butyl...

To enhance PLA gas barrier properties, multilayer designs with highly polar barrier layers, such as nanocelluloses, have shown promising results. However, the properties of these polar layers change with humidity. As a result, we investigated water transport phenomena in PLA films coated with nanometric layers of chitosan and nanocelluloses, utiliz...

While conventional plastics are practical and offer numerous advantages in our daily lives, their use has fostered a throwaway culture that highlights the negative aspects of these materials. Currently, the packaging sector alone contributes to about 50 % of the total annual plastic production (equivalent to 146 million tons). This results in more...

Environmental issues related to the use of plastic packaging have sparked a growing interest in the development of more sustainable solutions. Biopolymers, used alone or in combina-tion with other materials, have been considered a potential alternative to conventional fos-sil-based plastics. Hence, this study aimed at unraveling the potentiality of...

European and national environmental protection policies have programmed the forthcoming end of single-use plastics, including food packaging. Because plastic materials account for 50% of plastic waste, closed-loop recycling seems imperative. Still, plastics other than PET (Polyethylene terephthalate) are not widely recycled for food contact due to...

Poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) is a sustainable and biodegradable polymer that has potential for use in food packaging. However, its low melt strength makes it difficult to process using film-blowing techniques. To address this issue, 70% PHBV and 30% poly(butylene-co-succinate-co-adipate) (PBSA) were blended with dicumyl perox...

Nanocelluloses are promising high gas barrier materials for biobased food packaging, but they must be protected from water to preserve high performance. The respective O2 barrier properties of different types of nanocelluloses were compared (nanofibers (CNF), oxidized nanofibers (CNF TEMPO) and nanocrystals (CNC)). The oxygen barrier performance fo...

Melt blending of poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate) (PHBV) and poly(butylene‐co‐succinate‐co‐adipate) (PBSA) was investigated by means of batch mixing at different weight ratios (100:0, 70:30, 50:50, 30:70, and 0:100). PHBV and PBSA were immiscible. PBSA formed small nodules in PHBV, while PHBV formed large inclusions in PBSA. In 50/50 wt...

Polyethylene terephthalate (PET) is the plastic packaging material most widely used to produce bottles intended for contact with food and beverages. However, PET is not inert, and therefore, some chemical compounds present in PET could migrate to food or beverages in contact, leading to safety issues. To evaluate the safety of PET samples, the iden...

Nanocomposites of poly(lactide) (PLA) and cellulose nanocrystal (CNC) were fabricated using two different types of covalently grafted surface compatibilizers, namely fatty acids (lauric or stearic acid) and poly(glycidyl methacrylate) (PGMA) bearing reactive epoxy end-groups. Temperature-Modulated DSC analysis informed on weak attractive interactio...

The use of date palm fibres, which are an abundant by-product of agriculture, as natural reinforcement in polypropylene (PP) was studied. Because odour emissions are one of the major challenges for natural fibre-based composites, the emission of Volatile Organic Compounds (VOC) generated at different processing steps was analysed online. The severe...

Packaging materials are decisive to preserve the quality and nutritional value of food. Polylactide (PLA) is a biodegradable polymer with adequate mechanical properties for packaging applications, but its moderate oxygen barrier properties and high UV light transmission hamper its performance as packaging for oxygen‐ and light‐sensitive products. B...

The development of functional additives for packaging polymers starting from by-products of the agriculture and food industry is a very active research field. Different examples are discussed concerning the formulation of polylactides (PLA) with the aim to increase ductility and barrier properties or developing active packaging using by-products of...

Cellulose nanocrystals (CNCs) are used to design nanocomposites because of their high aspect ratio and their outstanding mechanical and barrier properties. However, the low compatibility of hydrophilic CNCs with hydrophobic polymers remains a barrier to their use in the nanocomposite field. To improve this compatibility, poly(glycidyl methacrylate)...

Plasticization of amorphous polylactide shifts the glass transition and extends its temperature range of crystallization to lower temperatures. In this work, we focus on how low−temperature crystallization impacts the mobility of the amorphous phase. Plasticizer accumulates in the amorphous phase because it is excluded from the growing crystal. The...

The barrier properties of poly(L-lactide) (PLLA) were investigated in multi-nanolayer systems, probing the effect of confining, the compatibility between the confining and the confined polymer, crystal orientation and amorphous phase properties. The multilayer co-extrusion process was used to confine PLLA between two amorphous polymers (polystyrene...

Mass transfer of penetrants is among the most important physical properties of polymer films to properly ensure function during service. In the case of interaction between penetrants and polymer, non-Fickian diffusion can be observed. This phenomenon is described by numerous reports and a few models have been proposed. Nevertheless, few of them qua...

One-hundred percent renewable triphenol—GTF—(glycerol trihydroferulate) and novel bisphenols—GDFx–(glycerol dihydroferulate) were prepared from lignocellulose-derived ferulic acid and vegetal oil components (fatty acids and glycerol) using highly selective lipase-catalyzed transesterifications. Estrogenic activity tests revealed no endocrine disrup...

In this work we study the effect of zinc oxide (ZnO) nanoparticle morphology and concentration on the resulting relaxation and transport properties of polylactide (PLA) nanocomposites. Films containing spherical and rod-shaped ZnO nanoparticles were incorporated into an amorphous polylactide (PLA) matrix through a solvent-precipitation and compress...

The kinetic fragility of a glass-forming liquid is an important parameter to describe its molecular mobility. In most polymers, the kinetic fragility index obtained from the glassy state by thermally stimulated depolarization current is lower than the one determined in the liquid-like state by dielectric relaxation spectroscopy, as shown in this wo...

Despite their great antioxidant activities, the use of natural phenols as antioxidant additives for polyolefins is limited owing to their weak thermal stability and hydrophilic character. Herein, we report a sustainable chemo-enzymatic synthesis of renewable lipophilic antioxidants specifically designed to overcome these restrictions using naturall...

Polylactide has been plasticized with acetyl tributyl citrate at several degrees (0 to 13%), leading to a modification of the Van der Waals interactions between the macromolecules without damaging the covalent bonding. The decrease of the dynamic glass transition temperature with plasticizer content has been recorded from calorimetric measurements...

The physical aging behavior of amorphous polylactide constrained against polystyrene in layers of 300 nm, thanks to the layer–multiplying co–extrusion process, was investigated by fast–scanning calorimetry (FSC). By cooling down the sample from the liquid state to the glassy one at very fast scanning rates, it was possible to investigate the struct...

En constante évolution socio-économique et technologique, le domaine de l’emballage confronte en permanence les industriels à de nouvelles contraintes d’adaptation, notamment en agroalimentaire, afin de garantir la qualité et la sécurité sanitaire des denrées et leur conservation.À l’interface de nombreuses disciplines (génie des procédés alimentai...

Multi-nanolayered polystyrene/poly(l,l-lactide) (PS/PLLA) films were obtained by the layer-multiplying coextrusion process, with an individual PLLA layer thickness as thin as 20 nm. The confinement of the amorphous PLLA induced a change in the molecular mobility, evidenced by a drop of the cooperative rearranging region (CRR) size at the glass tran...

Antioxidant norbornene-based monomers bearing biobased sterically hindered phenols (SHP)—NDF (norbornene dihydroferulate) and NDS (norbornene dihydrosinapate)—have been successfully prepared through biocatalysis from naturally occurring ferulic and sinapic acids, respectively, in presence of Candida antarctica Lipase B (Cal-B). The ring opening met...

This work investigated the impact of two homogenization treatments, High Shear (HS) and High Pressure (HP), on the structure and antioxidant activity of chitosan-lignin bio-composite films. Laser light scattering analysis revealed that smaller lignin particles were obtained after HP processing, around 0.6 µm, compared to HS treatment, between 2.5 a...

Polylactide (PLA), a bio-based polyester, has been used in wide applications including food packaging. Nevertheless, it is well known that mass transfer occurs between packaging polymer and foodstuff leading to safety and quality issues. In this sense, volatile organic compounds (VOCs) present in packaging materials can migrate to the food in conta...

Knowledge of the fundamental parameters of the poly(lactic acid) (PLA) molecular chain and resulting macroscopic properties is important for successful application of this polymer in different domains. Rheological data show that PLA has the typical properties of a linear and semi-stiff polymer chain. The stereochemical composition of the atactic po...

The surface grafting of cellulose nanocrystals (CNC) is a valuable tool to increase opportunities for their application. This work had several goals designed to improve CNC: reduction of hornification, increased re-dispersibility after CNC drying, and tuning of the surface graft to enhance the adsorption of particular molecules. To achieve this, th...

Green chemistry principles recommend the use of renewable feedstocks and biocatalysis to decrease environmental impact of chemicals manufacturing. In this scope, three ferulic acid based bisphenols and one trisphenol were synthesized using enzymatic catalysis. Their antioxidant activity at polymer processing and service temperature was investigated...

Composite films based on chitosan and lignin biopolymers were investigated for their mechanical, barrier, surface and antioxidant properties and linked to an extensive microscopic analysis of their external and internal structure. In particular, the fluorescence properties of lignins were exploited, using two-photon microscopy, to achieve a 3D repr...

Plastiques: quels enjeux pour demain? Pollution physico-chimique et impacts environnementaux et sanitaires

Polylactide (PLA) is the most used biodegradable and biobased food packaging polymer for rigid containers and films. However, its low ductility is a hurdle for increasing applications in flexible food packaging. A solution is the use of additives. Palm oil deodorization condensates (PODC) revealed to be an excellent additive promoting PLA ductility...

The synthesis, structural characterization and properties of new bio-based oligomers with bisguaiacol-type moieties esterified by diverse aliphatic linkers are described. These oligomers, produced by oxidative oligomerization of renewable dihydroferulic acid-based bisphenols with commercially available Trametes versicolor laccase, are proposed as p...

Compliance of plastic food contact materials (FCMs) with regulatory specifications in force, requires a better knowledge of their interaction phenomena with food or food simulants in contact. However these migration tests could be very complex, expensive and timeconsuming. Therefore, alternative procedures were introduced based on the determination...

Knowledge of the fundamental parameters of the poly(lactic acid) (PLA) molecular chain and resulting macroscopic properties is important for successful application of this polymer in different domains. Rheological data show that PLA has the typical properties of a linear and semi-stiff polymer chain. The stereochemical composition of the atactic po...

Chemo-enzymatic synthesis and screening of a library of renewable saturated and unsaturated bis- and trisphenols deriving from p-hydroxycinnamic acids (i.e., p-coumaric acid, ferulic acid, and sinapic acid) and biobased diols/triol (i.e., isosorbide, 1,4-butanediol, glycerol) showed that these compounds were potent antioxidants/antiradicals. To opt...

Conference Biopol2015, San Sebastian, Spain

Polylactide (PLA) which is already available in large commercial quantities shows a good potential as biobased and biodegradable polymer in several sectors. Nevertheless its low ductility narrows its usage potential needed to manufacture efficient thermoplastic films for food packaging. External plasticization is the main solution employed trying t...

The molecular dynamics in the amorphous phase of electrospun fibers of polylactide (PLA) has been investigated using the cooperative rearranging region concept. An unusual and significant increase of the cooperativity length at the glass transition induced by the electrospinning has been observed. This behavior is attributed to the singularity of t...

Cellulose nanocrystals (CNC) and starch nanocrystals (SNC) were grafted by ozone-initiated free-radical polymerisation of styrene in a heterogeneous medium. Surface functionalisation was confirmed by infrared spectroscopy, contact angle measurements, and thermogravimetric and elemental analysis. X-ray diffraction and scanning electron microscopy sh...

The use of industrial by-products of the vegetable oil industry as ductility agents of polylactide (PLA) was investigated. Vegetable oil deodorization condensates were melt-blended by twin-screw extrusion up to a maximum inclusion quantity of 20 wt% without preliminary purification. Sample films were obtained by single screw cast extrusion. Compoun...

Changes in the thermomechanical properties of polylactide (PLA) plasticized by two biodegradable and biobased molecules, Polysorb ID37 (PID37) and squalene, were compared to formulations with petroleum-based plasticizers, namely, acetyl tributyl citrate, poly(ethylene glycol) 400, and dioctyl adipate (DOA). The solubility parameters of the additive...

Environ 40 % des matières plastiques annuellement produites trouvent des débouchés dans des utilisations à courte durée de vie telles que l’emballage. L’utilisation de ressources renouvelables, ainsi que la production de matériaux biodégradables à durée de vie raisonnée, sont des solutions pertinentes afin de réduire l’impact écologique de la filiè...

Driven by environmental concerns, innovative, biodegradable packaging materials such as poly(lactic acid), PLA, and poly(hydroxybutyrate), PHB are emerging on the market. The capability of these novel polyesters to stabilise the aroma formulation of foodstuff during storage has been subject to only a few studies to date. The aim of this work is to...

Il existe une préoccupation croissante en matière d’environnement se traduisant par une demande citoyenne de produits « verts ». Néanmoins, ces derniers doivent posséder des performances égales ou supérieures aux matériaux synthétiques communément utilisés afin d’être concurrentiels. Actuellement, dans le secteur de l’emballage alimentaire, une des...

L'acide polylactique (PLA) est actuellement un des bioplastiques les plus utilisés dans le domaine de l'emballage alimentaire, malgré l'ample domination du marché mondial par les matières d'origine pétrochimique. Mais sa cristallisation, qui dicte ses propriétéss (mécaniques, barrière aux gaz, etc) est relativement complexe et induit des comporteme...

A new, simple and environmental-friendly method, named SolReact, has been developed for a solvent-free esterification of cellulose nanocrystals (CNC) surface by using two non-toxic carboxylic acids (CA), phenylacetic acid and hydrocinnamic acid. In this process, the carboxylic acids do not only act as grafting agent, but also as solvent media above...

External plasticization is a widely applied technique to improve PLA processability and toughness. Keys to successful plasticization of PLA are the miscibility of the plasticizer and its permanence in the polymer structure to ensure long-term stability of the material. To provide rules for successful plasticizing of PLA, a brief reminder of physico...

Influence of the plasticizer chemical structure on the plasticization behaviour of PLA A. Ruellan, A. Guinault, C. Sollogoub, V. Ducruet, S. Domenek poly(lactic acid), polylactide, plasticizer, ATBC, DOA, PEG, polysorb ID37, solubility parameters, free volume, lubrication, polar interactions. Abstract Changes in the mechanical and thermal properti...

Thermogravimetric analysis (TGA) coupled with gas chromatography mass spectrometry (GC-MS) provides a powerful tool to identify compounds evolving during a specific weight-loss event in a TGA analysis. In fact, heating a sample induces the release of volatile compounds initially present in the material or generated during the heating cycle. These v...

Thermogravimetric analysis (TGA) coupled with gas chromatography mass spectrometry (GC-MS) provides a powerful tool to identify compounds evolving during a specific weight-loss event in a TGA analysis. In fact, heating a sample induces the release of volatile compounds initially present in the material or generated during the heating cycle. These v...

Polylactide (PLA), a biobased polymer, might prove suitable as eco-friendly packaging, if it proves efficient at maintaining food quality. To assess interactions between PLA and food, an oïl in-water model emulsion was formulated containing aroma compounds representing different chemical structure classes (ethyl esters, 2-nonanone, benzaldehyde) at...

The objective of this work is to identify additives present in five commercial grades of PLA (GA, GB, GC, GD and F1) and to monitor their migrations into aqueous medium. Dissolution-precipitation was used to extract additives and was optimized using dichloromethane as solvent for PLA and ethanol as solvent for additives. Additives were identified b...