Understanding of structure/mass transfer properties relationships in model biocomposite

L’objectif de ce travail de thèse est la formalisation des relations entre la structure et les propriétés de transfert de matière (sorption, diffusion, perméabilité) dans des matériaux biocomposites pour l’emballage alimentaire. Pour cela, la thèse se focalise sur deux questions scientifiques majeures : (i) comment évaluer les propriétés de transfert de vapeur d’eau et de gaz dans des particules végétales de taille micrométrique et (ii) comment formaliser l’influence de l’interphase sur les propriétés de transfert de matière en utilisant des approches expérimentales et de modélisation. Pour cela, a système composite modèle a été utilisé : un biocomposite polypropylène (PP) / particules de cellulose micrométrique produit par extrusion. La première partie de ces travaux est axée sur le développement d’une méthodologie fiable pour caractériser les propriétés de transfert dans des particules de taille micrométrique. Une nouvelle méthode ad hoc couplant microbalance à quartz et cellule d’absorption a été développée et comparée aux méthodes gravimétriques classiques telles que la DVS. La caractérisation fine de la taille / distribution en taille des particules est une étape essentielle pour garantir la fiabilité de l’estimation des paramètres de diffusion. Le deuxième objectif s’appuie sur une caractérisation quantitative fine de la structure 3D des matériaux composites (micro-tomographie X). En finalité, ces travaux de thèse permettent d’aller plus loin dans le développement de modèles prédictifs des relations entre structure et propriétés de transfert de matière, ce qui est l’étape nécessaire pour développer des matériaux biocomposites basés sur une approche d’ingénierie inverse.The objective of this thesis is to formalize the relationships between the structure and mass transfer properties (sorption, diffusion, permeability) in biocomposites for food packaging. It raises two main scientific questions: (i) how to evaluate the mass transfer properties in micrometric size vegetal particles and (ii) how to formalize the impact of the interphase on mass transfer properties by using experimental and modeling approaches. For this purpose, a model system has been considered, i.e. a biocomposite polypropylene (PP)/ micrometric cellulose particles, produced by melt extrusion. The first part of this work focuses on the development of reliable methodologies to characterize mass transfer properties in micrometer size particles. A new method based on the use of a quartz crystal microbalance coupled to an absorption system has been developed and critically compared to classical methods such as DVS. The accurate characterization of the particle morphology distribution is a key point for estimating diffusivity parameters. The second objective is dedicated to the quantitative characterization of the 3D microstructure using X-ray micro-tomography. Structural parameters are used in biphasic and triphasic (consideration of the interphase) models of mass transfer. This thesis brings new knowledge in the modeling of structure / mass transfer properties relations in biocomposites, which is the necessary step for developing biocomposites based on a reverse engineering approach

Formalisation des relations structure/propriétés de transfert de matière dans un biocomposite modèle

The objective of this thesis is to formalize the relationships between the structure and mass transfer properties (sorption, diffusion, permeability) in biocomposites for food packaging. It raises two main scientific questions: (i) how to evaluate the mass transfer properties in micrometric size vegetal particles and (ii) how to formalize the impact of the interphase on mass transfer properties by using experimental and modeling approaches. For this purpose, a model system has been considered, i.e. a biocomposite polypropylene (PP)/ micrometric cellulose particles, produced by melt extrusion. The first part of this work focuses on the development of reliable methodologies to characterize mass transfer properties in micrometer size particles. A new method based on the use of a quartz crystal microbalance coupled to an absorption system has been developed and critically compared to classical methods such as DVS. The accurate characterization of the particle morphology distribution is a key point for estimating diffusivity parameters. The second objective is dedicated to the quantitative characterization of the 3D microstructure using X-ray micro-tomography. Structural parameters are used in biphasic and triphasic (consideration of the interphase) models of mass transfer. This thesis brings new knowledge in the modeling of structure / mass transfer properties relations in biocomposites, which is the necessary step for developing biocomposites based on a reverse engineering approach.L’objectif de ce travail de thèse est la formalisation des relations entre la structure et les propriétés de transfert de matière (sorption, diffusion, perméabilité) dans des matériaux biocomposites pour l’emballage alimentaire. Pour cela, la thèse se focalise sur deux questions scientifiques majeures : (i) comment évaluer les propriétés de transfert de vapeur d’eau et de gaz dans des particules végétales de taille micrométrique et (ii) comment formaliser l’influence de l’interphase sur les propriétés de transfert de matière en utilisant des approches expérimentales et de modélisation. Pour cela, a système composite modèle a été utilisé : un biocomposite polypropylène (PP) / particules de cellulose micrométrique produit par extrusion. La première partie de ces travaux est axée sur le développement d’une méthodologie fiable pour caractériser les propriétés de transfert dans des particules de taille micrométrique. Une nouvelle méthode ad hoc couplant microbalance à quartz et cellule d’absorption a été développée et comparée aux méthodes gravimétriques classiques telles que la DVS. La caractérisation fine de la taille / distribution en taille des particules est une étape essentielle pour garantir la fiabilité de l’estimation des paramètres de diffusion. Le deuxième objectif s’appuie sur une caractérisation quantitative fine de la structure 3D des matériaux composites (micro-tomographie X). En finalité, ces travaux de thèse permettent d’aller plus loin dans le développement de modèles prédictifs des relations entre structure et propriétés de transfert de matière, ce qui est l’étape nécessaire pour développer des matériaux biocomposites basés sur une approche d’ingénierie inverse

Adapting gravimetric sorption analyzer to estimate water vapor diffusivity in micrometric size cellulose particles

This study aims at developing a reliable and simple-to-implement methodology for the estimation of apparent water vapor diffusivity at the scale of micrometric size cellulose particles based on gravimetric measurements. The water vapor apparent diffusivity value was evaluated by using a quartz crystal microbalance (QCM) on a cellulose sample of 1 µg was 4 × 10−12 m2 s−1. Water vapor sorption kinetics at successive relative humidity (RH) steps were measured using a dynamic vapor sorption (DVS) microbalance by testing two types of sample preparation, i.e. either a powder bed or a compressed tablet. Water vapor apparent diffusivity was identified at each RH step by employing an analytic solution corresponding to the sample type: plane sheet for both powder bed and tablet considered as porous media and finite cylinder for a population of particles. The impact of the initial cellulose sample mass was also investigated. Water vapor diffusivity values varied from 6 × 10−15 to 4 × 10−10 m2 s−1 depending on the sample mass, sample preparation mode, analytic solution and/or sample porosity. The DVS-based methodology was compared to the value obtained from QCM measurements

Impact of Two-Dimensional Particle Size Distribution on Estimation of Water Vapor Diffusivity in Micrometric Size Cellulose Particles

This work aims at assessing the impact of two-dimensional particle size distribution (2D-PSD) on the identification of water vapor diffusivity in micrometric size cellulose particles displaying a size aspect ratio lower than 2 and a cylindrical shape. First, different methodologies to obtain the two-dimensional (2D) particle size distribution (diameter versus length) were compared, based on image analysis. Then, experimental sorption kinetics were obtained by using a quartz crystal microbalance (QCM) coupled with a water vapor adsorption system. Diffusivity values were estimated when considering either the 2D-PSD or global descriptors, such as the mean or median diameter and length of particles. Results revealed that the use of an analytical approach when considering the 2D mean-PSD or the median-PSD was the most accurate way to get diffusivity values at the scale of particles in a polydisperse sample of cellulose particles. Following this approach, a water vapor apparent diffusivity of 3.1 × 10−12 ± 2.3 × 10−12 m2·s−1 was found for the considered cellulose sample. Neglecting PSD in diffusivity estimation led to an underestimation of a factor of 2. This procedure could be extended for all the polydisperse samples in order to have an accurate estimation of water vapor diffusivity at the scale of single particles

Cascading (3D) reconstruction procedure of composite structures from microtomography data

International audienceReconstruction of three-dimensional (3D) structure from experimental image acquisition (e.g., from micro computed tomography data) is very useful in composite material science. Composite considered are characterized by a dispersion of particles in a continuous phase. Many properties of the composite (e.g., mass transfer properties) depend on its structural assembly. A reliable prediction of these properties requires to well represent this structure and especially, the region at the vicinity of the dispersed phase. (3D) structure generation must thus permit to (1) simplify the real composite structure observed to make it compatible with further modelling tasks (e.g., meshing constraints in finite elements methods, computation time) and (2) keep enough representativeness of the structure of the specimen to produce reliable numerical predictions. This article describes an innovative, cascading (3D) reconstruction procedure of composite material from microtomography data. • First step of this pipeline is the extraction of relevant structural markers from microtomography images using image analysis. • Second step is the modelling of the distribution of the structural markers selected (statistical laws). • Third and final step is the reconstruction of the (3D) structures based on the pre-determined distribution laws in a RVE (representative volume element) of the composite

From 3D real structure to 3D modelled structure: Modelling water vapor permeability in polypropylene/cellulose composites

International audienceA 3D tri-phasic numerical model was developed to predict water vapor permeability in composite materials made of polypropylene (PP) as matrix and cellulose particles as fillers, with existence of an interphase around permeable inclusions. About 70 tri-phasic structures composed of ellipsoidal, heterogenous-size particles were generated to represent composites with four different filler contents () with interfacial region at the filler/matrix interface (either 1 or 2 μm thick) displaying its own permeability. The relative permeability (i.e., ratio between composite and neat matrix permeability) was calculated from Finite Element Method (FEM) simulations on these structures. A good prediction of experimental relative permeability for the whole filler content range investigated was observed. The presence of a percolating interphase observed in some structures explains the high permeabilization observed for high . The proposed 3D numerical model was confronted to five state-of-the art analytical models and was the only one able to describe the observed complex structures with identification of reliable characteristics for the interphase (thickness, permeability)

Assessing the potential of quartz crystal microbalance to estimate water vapor transfer in micrometric size cellulose particles

International audienceThis study aims at assessing the use of a quartz crystal microbalance (QCM) coupled with an adsorption system to measure water vapor transfer properties in micrometric size cellulose particles. This apparatus allows measuring successfully water vapor sorption kinetics at successive relative humidity (RH) steps on a dispersion of individual micrometric size cellulose particles (1 μg) with a total acquisition duration of the order of one hour. Apparent diffusivity and water uptake at equilibrium were estimated at each step of RH by considering two different particle geometries in mass transfer modeling, i.e. sphere or finite cylinder, based on the results obtained from image analysis. Water vapor diffusivity values varied from 2.4 × 10−14 m2.s−1 to 4.2 × 10−12 m2.s−1 over the tested RH range (0 to 80%) whatever the model used. A finite cylinder or spherical geometry could be used equally for diffusivity identification for a particle size aspect ratio lower than 2