Contribution à la compréhension de l'influence des paramètres de formulation et de procédé sur la structure et les propriétés fonctionnelle de films actifs à base de bio-polymères

Comprehensive study of the effects of formulation and processing parameters on structural and functional properties of active bio-based packaging films

Sveobuhvatno istraživanje utjecaja formulacije i procesnih parametara na strukturna i funkcionalna svojstva aktivnih ambalažnih biomaterijala

• Auteur / Autrice : Mia Kurek
• Direction : Frédéric Debeaufort, Kata Galić
• Type : Thèse de doctorat
• Discipline(s) : Sciences de l'alimentation
• Date : Soutenance le 24/10/2012
• Etablissement(s) : Dijon en cotutelle avec Sveučilište u Zagrebu (Hrvatska)
• Ecole(s) doctorale(s) : École doctorale Environnements, Santé (Dijon ; Besançon ; 2012-....)
• Partenaire(s) de recherche : Laboratoire : Procédés Alimentaires et Microbiologiques (PAM) (Dijon) - Procédés Alimentaires et Microbiologiques
• Jury : Président / Présidente : Damir Ježek
• Jury : Examinateurs / Examinatrices : Nadia Oulahal
• Jury : Rapporteurs / Rapporteuses : Stéphane Desobry, Srećko Valić

Mots clés

Mots clés contrôlés

Aliments -- Emballage

Polymères dans les industries agroalimentaires

Effet retard

Carvacrol

Composition chimique

Chitosane

Mots clés libres

Chitosane

Emballages actifs

Transfert de matière

Eau

Perméabilité

Libération contrôlée

Activité antimicrobienne

Phase vapeur

Chitosan

Active packaging

Mass transfer

Water vapour

Permeability

Release

Antimicrobial efficiency

Headspace

Kitozan

Aktivno pakiranje

Prijenos mase

Vodena para

Propusnost

Otpuštanje

Antimikrobna efikasnost

Plinovito stanje

Résumé

Cette étude porte sur l’analyse du mécanisme de transfert du carvacrol (molécule antimicrobienne volatile) au travers de films à base de chitosan. La composition, la structure, les paramètres de procédés et de séchage de la couche de chitosan ont été corrélés aux propriétés physico-chimiques et fonctionnelles des films. La compréhension de ces facteurs et de leurs influences est cruciale à l’optimisation de la production de films actifs à base de polyéthylène enduits de chitosan. En effet, composition, microstructure et condition environnementale (température, humidité) conditionnent la rétention puis la libération contrôlée du carvacrol. La présence d’humidité induit absorption, gonflement, et plastification du chitosan, et par conséquent influe sur la structure, ses propriétés thermiques et de surface. L’absorption d’humidité, due au changement de structure, entraîne une forte augmentation de la perméabilité aux gaz et à la vapeur d’eau, et favorise ainsi la libération du carvacrol, nécessaire à une efficacité antimicrobienne rapide. Cette dernière, ainsi que l’impact sensoriel sur l’aliment emballé, sont directement corrélés aux aspects cinétiques et de partage des vapeurs de carvacrol. Ces travaux ont ainsi mis en évidence l’importance le compréhension de mécanismes de transfert dans les emballages à base de bio-polymères sur leur production et application industrielles

The aim of this study is the analysis of structure and transfer mechanisms through chitosan based food packaging materials with incorporated carvacrol as a model of antimicrobial active substance. Integration of composition parameters, structure, processing and drying of chitosan systems is correlated to its physico chemical and functional properties. Understanding and detailed analyses of processing parameters is crucial in production of active chitosan coatings applied on conventional materials such as polyethylene. So, the knowledge of composition and microstructure in association to environmental conditions, control the retention and the release kinetics of carvacrol from chitosan film. Water vapour was crucial parameter that strongly influenced adsorption, swelling and plasticization of chitosan based films, as well as thermal, surface and mechanical properties. By changing the matrix structure, penetrating water molecules decreased gas barrier efficiency and increased release of carvacrol. Furthermore, release of carvacrol in the headspace was correlated to the antimicrobial efficiency and to the organoleptic impact on packed food products. Such investigation highlights the transfer mechanism within bio-based materials, prior to efficiency prediction for their industrial development.In dry conditions, all chitosan films were fairly good gas barriers (about 10 17 g/m∙s∙Pa). Chitosan coated polyethylene films were up to 10000 times less permeable than uncoated PE. Increase in the environmental humidity above 60% and up to 96% (that represents the conditions of a real fresh food packaging system), significantly increased gas permeability of all chitosan films. Mechanical tests confirmed that when relative humidity increased, structural changes were induced. Therefore, extensive water plasticization of chitosan matrix was observed.Diffusion coefficients of carvacrol from chitosan film increased up to 1000 times when humidity increased from 0% to 100%. Water vapour triggers the release of carvacrol in the vapour phase. This indicates the importance of controlling the environmental conditions in the packaging at the time of the application but also during the active film storage.Films with carvacrol concentrations in the vapour phase above 2x10-7 g/mLair were efficient against large spectrum of bacteria, including some Gram-positive bacteria, Gram-negative bacteria and fungi. In some instances the concentration that was required for carvacrol antimicrobial efficiency was not organoleptically acceptable to consumers.

Cilj ovog rada je analiza strukture i mehanizama prijenosa tvari kroz ambalažne materijale za pakiranje hrane na bazi kitozana s inkorporiranim karvakrolom kao modelnom aktivnom antimikrobnom tvari. Integrirani sastavni parametri, struktura, proizvodnja i sušenje kitozanskog sustava korelirani su sa njegovim fizikalno-kemijskim i funkcionalnim svojstvima. Razumijevanje i detaljna analiza procesnih parametara predstavlja ključan korak u proizvodnji aktivnih kitozanskih prevlaka na konvencionalnim materijaima kao što je polietilen. Dakle, poznavanje sastava i mikrostrukture u ovisnosti o okolnim uvjetima, osnovni je preduvjet za kontrolirano zadržavanje i otpuštanje karvakrola iz filmova na bazi kitozana. Vodena para predstavlja ključni parametar koji značajno utječe na adsorpciju, bubrenje i plastifikaciju kitozanskih filmova, kao i na njegova toplinska, površinska, i mehanička svojstva. Penetracijom (prodiranjem) molekula vode dolazi do promjene strukture matriksa, smanjuje se učinkovitost barijernih svojstava prema plinovima i povećava otpuštanje karvakrola. Otpuštanje karvakrola u zračnom prostoru u korelaciji je sa antimikrobnom učinkovitosti i organoleptičkim svojstvima upakiranih prehrambenih proizvoda. Ovo istraživanje prije svega naglašava značaj poznavanja mehanizma prijenosa tvari unutar biomaterijala koji je neophodan za predviđanje učinkovite primjene na industrijskoj razini