Alain Guinault

• National Conservatory of Arts and Crafts

The surface properties of biomaterials interact directly with biological systems, influencing cellular responses, tissue integration, and biocompatibility. Surface topography plays a critical role in cardiac tissue engineering by affecting electrical conductivity, cardiomyocyte alignment, and contractile function. Current methods for controlling su...

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...

Three layers film shaped by thermocompression of acrylonitrile butadiene styrene copolymer and polycarbonate have been analyzed in dynamic mechanical thermal analysis in tensile mode. They present two peaks as the film is loaded perpendicularly to the layers and three peaks as the film is loaded in parallel to the layers. Numerical computations con...

Tissue engineering benefits from advances in 3D printing and multi‐material assembly to attain certain functional benefits over existing man‐made materials. Multilayered tissue engineering constructs might unlock a unique combination of properties, but their fabrication remains challenging. Herein, a facile process is reported to manufacture biomat...

The accelerated thermal ageing of ABS films has been investigated over a wide range of exposure temperatures in air, by FTIR, GPC, AFM and tensile testing in order to determine the origin of the ductile/brittle transition during exposure. Besides formation of oxidation products and decrease of unsaturated bonds in butadiene phase, molar mass change...

This paper reports the failure of bonded assemblies submitted to thermal ageing. Adhesives are either fully or incompletely cured. Despite comparable initial properties, depletion of mechanical properties (evaluated from single las shear tests) is faster in the case of incompletely cured polymer. A series of comprehensive experiments were conducted...

This work is a first attempt to study the crystallization behavior of ethylene-vinyl alcohol copolymer with 44 mol% of ethylene units (EVOH44) and to observe the supermolecular structures developed during its crystallization. Thermal analysis has evidenced a very fast crystallization and the formation of different crystal populations during isother...

For recycling purposes, the thermal degradation of post-consumed (pc) ABS/HIPS and PP/PE blends derived from waste electrical and electronic equipment (WEEE) was obtained by multiple extrusions. The evolution of molar mass (Mw), melt flow index (MFI), and ultimate elongation (εr) of reprocessed blends was evaluated as a function of extrusion cycles...

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...

Food packaging films must be reinvented in order to answer the new demanding ecological requirements. Biobased and/or biodegradable polymers appear as an interesting alternative to reduce petroleum dependence and carbon dioxide emissions. Poly(ethylene furanoate) (PEF) appears today as a new promising biopolymer thanks to its good gas barrier and m...

The barrier performance and structural lightening of organic materials are increasingly desired and constitute a major challenge for manufacturers, particularly for transport and packaging. A promising technique which tends to emerge in recent years is that of multinanolayer coextrusion. The advantage is that it can produce multilayers made of thou...

Biodegradable PLA/PBSA multinanolayer nanocomposites were obtained from semi-crystalline poly(butylene succinate-co-butylene adipate) (PBSA) nanolayers filled with nanoclays and confined against amorphous poly(lactic acid) (PLA) nanolayers in a continuous manner by applying an innovative coextrusion technology. The cloisite 30B (C30B) filler incorp...

Rheological behavior of nanolayered films of polyethylene/polyamide 6 (PE/PA6) compatibilized in situ during the coextrusion process has been studied at a temperature between the melting temperatures of PE and PA6. Thanks to the high number of interfaces, a drastic increase in dynamic moduli has been measured when increasing the interphase volume f...

Rheological behavior of nanolayered films of polyethylene/polyamide 6 (PE/PA6) compatibilized in situ during the coextrusion process has been studied at a temperature between the melting temperatures of PE and PA6. Thanks to the high number of interfaces, a drastic increase in dynamic moduli has been measured when increasing the interphase volume f...

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...

Chitosan (CS) layers are coated on a poly(ethylene terephthalate) (PET) film in order to decrease the oxygen permeability through the polymeric films for food packaging applications. Oxygen transmission rate (OTR) of the 130 μm PET films can be decreased from 11 to only 0.31 cm³/m².day with a coated layer of 2 μm of CS. Additional decrease is obtai...

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...

This paper reports a study of thermal oxidation induced embrittlement in several polyethylene grades differing mainly by the broadness of the molar mass distribution (ranging for lower than 3 to more than 30). Thermal oxidation was monitored at macromolecular scale (Gel Permeation Chromatography, Differential Scanning Calorimetry) and macroscopic s...

Multilayer films comprising polystyrene (PS)/polymethyl methalcrylate (PMMA) and PS/polycaprolatone (PCL) alternating nanolayers with varied layer thickness were fabricated by multilayer coextrusion. The nanolayers breakup phenomena of PMMA and PCL were characterized using atomic force microscopy (AFM), oxygen permeability, light transmission, wide...

Improving overall properties of poly(lactic acid) (PLA) by blending it with another biobased polymer has been a strong field of research over the last years. In this study we demonstrate the synergetic effect of a small amount (between 0.1 and 1 wt%) of oligomer-like PLA (oLA) on the thermal, mechanical and gas barrier properties of the widely stud...

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...

Multilayer coextrusion processing was applied to produce 2049-layer film of poly(butylene succinate-co-butylene adipate) (PBSA) confined against poly(lactic acid) (PLA) using forced assembly, where the PBSA layer thickness was about 60 nm. This unique technology allowed to process semi-crystalline PBSA as confined polymer and amorphous PLA as confi...

The in situ thermal oxidation of thin unstabilized polydicyclopentadiene was studied by TGA to monitor mass gain, and DSC to characterize hydroperoxides concentration. Results were discussed using kinetic analysis, which allowed the estimation of activation energies for key reactions of the oxidation process. Activation energy for termination was s...

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...

Films of PC and MXD6 were prepared via multilayer coextrusion. Films presenting stretched nodules/lamellas of MXD6 in the PC matrix, and films with quasi-continuous thin MXD6 layers alternating with PC layers were obtained. The transport properties were specifically investigated from water and gas permeation kinetics, and the corresponding permeati...

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...

We report the making of multilayered self-assembled films by coextrusion, composed of alternated layers of confining polycarbonate and confined poly(styrene-b -butadiene-b -methyl methacrylate), whose blocks are chemically different from the confining polymer, and presenting a self-assembled morphology directly after extrusion. The triblock copolym...

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...

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...

The kinetic model, established in a previous article (François-Heude et al., J. Appl. Polym. Sci., in press) to predict the homogeneous oxidation in iPP films typically thinner than 100 µm, is now extended to simulate the oxidation profiles in thicker plates by coupling the oxygen diffusion and its consumption by the chemical reactions. In this per...

A general kinetic model is proposed to describe the polypropylene thermal oxidation of thin polypropylene films in a wide range of temperatures (from 60 to 200°C) and oxygen partial pressures (from 0.02 to 5 MPa) using a single set of parameters. This model was calibrated with several series of experimental data including analyses of primary (hydro...

The PIMM (Processes and Engineering in Mechanics and Materials) laboratory has been involved in the development of architectured materials at multiple scales: at the nanoscale with nanostructured polymer blends and nanocomposites; at the microscale with laser-controlled microstructural tailoring of metals, including functionally graded materials, a...

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...

New dynamic materials, that can repair themselves after strong damage, have been designed by hybridization of polymers with structurally well-defined nanobuilding units. The controlled design of cross-linked poly(n-butyl acrylate) (pBuA) has been performed by introducing a very low amount of a specific tin oxo-cluster. Sacrificial domains with non-...

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...

The ability to achieve enhanced mechanical properties through in-plane orientation of platelet-like nanofillers is a challenge for nanocomposite fabrication and performance. Here we use forced assembly to orient graphene nanoplatelets in PMMA/PMMA-graphene films produced through multilayer coextrusion. Electron microscopy confirms the alternating l...

The influence of water vapour conditions on mass transport and barrier properties of chitosan based films and coatings were studied in relation to surface and structural properties. Water contact angles, material swelling, polymer degradation temperature, barrier properties (PO2, PCO2, WVP) and aroma diffusion coefficients were determined. The solv...

The thermo-oxidative degradation of polylactide (PLA) films was studied between 70 and 150 °C. It was shown that the oxidative degradation of PLA leads to a random chain scission responsible for a reduction of the molar mass. These molar mass changes affect Tg and the degree of crystallinity, and it was found that Tg decreases according to the Fox–...

Composition modifiant les propriétés mécaniques d'un polymère thermoplastique

Over the past few years, great attention has been paid to biodegradable and biocompatible polymers. Among them, Polylactide (PLA) gained worldwide consideration due to the fact that it is obtained from renewable ressources [1] and is recyclable and compostable. As a food packaging material, PLA is used for short shelf life products like containers,...

The use of renewable resources and biodegradable materials are appropriate solutions to reduce the environmental impact of plastics if only they have equal or superior performances to synthetic ones currently used at comparative prices. One of the most prominent polymers among these materials is polylactide (PLA), a thermoplastic aliphatic polyeste...

Surface modification of polypropylene (PP) sheets was carried out by radiation induced graft polymerization of hydrophilic functional molecules such as N,N-dimethylacrylamide (DMA) and [2-methacryloyloxy)ethyl] trimethylammonium chloride, which is a quaternary ammonium salt (QAS).Polypropylene sheets were activated prior to the grafting reaction by...

Thermo-oxidative degradation of polylactide (PLA) at low temperature: physical and mechanical aspects D. Rasselet1,2, A. Ruellan1,3, A. Guinault1,2, G. Miquelard-Garnier1,2, C. Sollogoub1,2 and B. Fayolle1 Damien.Rasselet@laposte.net, Alexandre.Ruellan@agroparistech.fr, Alain.Guinault@cnam.fr, Guillaume.Miquelard_Garnier@cnam.fr, Cyrille.Sollogo...

2 É cole de Technologie Sup erieure, Chaire des Mat eriaux et É quipements Utilis es en Sant e et S ecurit e du Travail, 1100 rue Notre-Dame Ouest, Montr eal QC, H3C 1K3, Canada 3 AgroParisTech, UMR 1145 Ing enierie Proc ed e Aliment, 1 avenue des Olympiades, ABSTRACT: The morphology and miscibility of commercial poly(lactide) (PLA)/poly(b-hydroxyb...

Due to their polyphenolic structure lignins bear a number of interesting functional properties, such as antioxidant activity. Natural antioxidants are very much looked for in the aim of protection of light or oxygen sensitive goods and are being used in active packaging. Poly(lactide) (PLA)-lignin films were prepared by twin screw extrusion followe...

Like parts or structures assembled from the common isotropic engineering materials, very fine particles reinforced epoxy resin matrix composite structures can be subjected to impact loading during their designed life. These composites have different interaction with the externally applied load. In fact, several damage mechanisms can be operative su...

Bien que prometteur pour l’emballage alimentaire, l’acide polylactique (PLA) présente des propriétés mécaniques et barrière modérées qui doivent être améliorées [1-3]. Deux voies ont été envisagées : i) la plastification par 20% d’acétyl citrate de tributyle (ATBC) [4], ii) la cristallisation, par l’ajout d’agent nucléant (talc) [5]. La formulation...

Bien que prometteur pour l’emballage alimentaire, l’acide polylactique (PLA) présente des propriétés mécaniques et barrière modérées qui doivent être améliorées [1-3]. Deux voies ont été envisagées : i) la plastification par 20% d’acétyl citrate de tributyle (ATBC) [4], ii) la cristallisation, par l’ajout d’agent nucléant (talc) [5]. La formulation...

Multilayer coextrusion was used to disperse Carbon Nanotubes (CNT) in polypropylene (PP). The dilution of commercially available masterbatches using a twin-screw extruder was first applied to produce several formulations, which were then mixed with PP using a multilayer coextrusion device to obtain films or pellets with CNT concentrations between 0...

Poly(lactic acid) (PLA) is a biodegradable thermoplastic polyester derived from renewable resources which may replace conventional polymers for some applications. To overcome some of its limitations such as poor gas barrier properties and low elongation at break, one method is to blend PLA with small amounts of other bio-based polymers. In this stu...

Blending poly(lactic acid) (PLA) with a small amount of poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV; 10 wt%) using a custom multilayer co-extrusion process increases both ductility and gas barrier properties of extruded films compared with neat PLA and classical blending methods. The co-extrusion process allows multiplication of the number o...

Thermal crystallization - Acceleration of gas diffusion upon crystallization might be correlated to occurrence of rigid amorphous phase - Crystallization in d-form with creation of RAF yields no gain in barrier properties - Crystallization in a-form without creation of RAF yields gain in barrier properties by a factor of 3 Compounding -Acceleration...

Thermoforming of PLA-PHBV films: effect on their morphology and gas barrier properties A. Ruellan, A. Guinault, S. Domenek, V. Ducruet, M. Boufarguine, G. Miquelard-Garnier and C. Sollogoub Key words: PLA, polylactic acid, thermoforming, morphology, gas barrier properties Introduction Driven by environmental concerns, new polymers based on renewa...

Poly(lactic acid) films have a great interest for food packaging. In order to improve the barrier properties of this biodegradable polymer, the influence of the structure must be investigated. Two methods were considered to modify the PLA morphology: (i) the process parameters modulation and (ii) the formulation. On the one hand, PLA films were ext...

Cette étude présente des résultats obtenus sur l’élaboration de composites à base de polypropylène recyclé renforcé par des fibres végétales (fibres de bambou), fabriqués à l’aide d’une extrudeuse double vis modulaire pour produire un composite sous forme de granulés transformables. L’effet de la teneur en fibres de bambou, du compatibilisant et de...

function of stereochemistry and crystallinity degree. Poly(L-lactide) and poly(D,L-lactide) films were obtained by extrusion and thermally cold crystallized in either a0- or a-crystalline form with increasing crystallinity degree. Annealing of the films at low temperatures yielded to a0-crystals as well as the creation of a rigid amorphous fraction...

Poly(lactic acid) (PLA) is a biodegradable, thermoplastic, aliphatic polyester derived from renewable resources, which is a potential candidate to replace conventional polymers in food packaging applications.. Other bio-based materials like polyhydroxyalkanoates (in our case PHBV) could be associated with PLA in order to improve its gas barrier pro...

Polylactide (PLA), a biodegradable polymer obtained from biomass, was formulated with a nucleating agent, talc, and a plasticizer, acetyl tributyl citrate, and cold crystallized in α and α� form. The barrier properties of crystallized PLA were investigated as a function of the formulation and the crystalline form, thanks to three molecules with inc...

Face to an ecologic problem because of the increase production of man-made polymers (polyamide, polyethylene, polypropylene, etc.), there is a great interest in developing “green materials” with a perspective of eco-design or sustainable development derived from renewable sources with enhance performances. Optimization of their properties has still...

Poly(lactic acid) is one of the most promising biobased and biodegradable polymers for food packaging, an application which requires good mechanical and barrier properties. In order to improve the mechanical properties, in particular the flexibility, PLA plasticization is required. However, plasticization induces generally a decrease in the barrier...

Polypropylene (PP) is among the most widely used thermoplastics in many industrial fields. However, like other recycled polymers, its properties usually decrease after recycling process and sometimes are degraded to poor properties level for direct re‐employment. The recycled products, in general, need to be reinforced to have competitive propertie...

ABS/PC blends have always presented a great interest both in industrial and academic contexts, since they combine the most desirable properties of both ABS and PC. Melt blends are classically prepared using a twin screw extruder. In this study, ABS/PC blends of two compositions were prepared with two blending techniques: coextrusion mixing method (...

The surface of polypropylene was modified by the post-irradiation grafting of acrylic acid (AAc), N,N-dimethylacrylamide (DMA) and mixtures of AAc (DMA) and a quaternary ammonium salt (QAS). The polypropylene sheets were activated by electron beam radiation before the grafting reaction. The degree of grafting was determined by weighing and the surf...

Driven by environmental concerns, new polymers based on renewable resources are arriving on the market to replace conventional polymers, obtained from petroleum, for different applications like food packaging. One of the most prominent polymers among these materials is poly(lactic acid) (PLA), a biodegradable, thermoplastic, aliphatic polyester der...

The application of a layer‐multiplying device to coextrusion has resulted in a process, called microlayer coextrusion, producing films with ten to thousands of layers of two different polymers. It was shown that this device is quite versatile and can be used to produce new layered systems with improved mechanical, optical, electrical and barrier pr...

Lignins are complex phenolic polymers. They are one of the main byproducts of mainly industries. The valorisation of lignin is therefore a key issue in the economic performance of these industries. One of the functional properties of lignin is an antioxidant action, the efficiency of which is closely linked to the lignin structure. Small phenolic c...

The miscibility and morphology of poly(lactic)acid (PLA)/polybeta-hydroxybutyrate (PHB) prepared by melt blending method were investigated by Fourier transform infrared (FTIR), Differential scanning calorimetry (DSC), melt rheology and scanning electron microscopy (SEM) observations. FTIR and DSC methods present some limits to examine the miscibili...

The present work should be considered in the context of the health safety and hygiene of materials.In several areas of application of plastic materials (agro-food industry, medical devices or even pharmaceuticals) it is necessary to understand how a surface reacts in contact with the surrounding environment (food, living beings, etc.) so that surfa...

This article reports the preparation of recycled polypropylene (RPP)/bamboo fiber (BF) composite via direct melt blends using a twin screw extruder. The effects of the chemical treatment of BF surface (alkaline and acetylation) on fiber structure and composite mechanical, thermal, rheological properties have been investigated. We showed that alkali...

Bien que prometteur pour l’emballage alimentaire, l’acide polylactique (PLA) présente des propriétés mécaniques et barrière modérées qui doivent être améliorées [1-3]. Deux voies ont été envisagées : i) la plastification par 20% d’acétyl citrate de tributyle (ATBC) [4], ii) la cristallisation, par l’ajout d’agent nucléant (talc) [5]. La formulation...

Lignins are complex phenolic polymers. They are one of the main byproducts of mainly industries. The valorisation of lignin is therefore a key issue in the economic performance of these industries. One of the functional properties of lignin is an antioxidant action, the efficiency of which is closely linked to the lignin structure. Small phenolic c...

PLA samples having different degree of crystallinity and plasticized with Acetyl Butyl Citrate were prepared by extrusion and thermo-moulding. In order to determine the solubility and diffusion coefficients of ethyl esters vapours into the polymer samples, two approaches were assessed, i) the first one by a microgravimetric method, ii) the second o...

The barrier properties of poly(lactic acid) (PLA) play a key role in food packaging applications. For their optimization, the influence of crystallinity on the barrier properties of PLA and the interaction of PLA with the aroma compound ethyl acetate were investigated. PLA film samples with various crystallinities were fabricated by flat die extrus...

Crystallinity is well-known to have major effects on the gas barrier properties. However, its effect on gas barrier properties is often dependant on the studied material and is difficult to anticipate because two aspects of crystallinity have to be considered: the crystallinity degree and the crystalline morphology. PLA is known to recrystallize wh...

The control of blend morphologies during process is of prime importance in order to predict the final properties of polymer blends. A coextrusion technique combined with static mixers was developed in order to smartly blend polymeric melts and to optimize the blend morphologies during the flow in static mixers [1]. The aim of this paper is to study...