PVC/EVA-based polymer inclusion membranes with improved stability and Cr(VI) extraction capacity: Water plasticization effect.

Polymer inclusion membranes (PIMs) are far investigated for their ability to extract heavy metals and small organic compounds from aqueous media. Polyvinyl chloride (PVC) is one of the most widely used base polymers for the PIM elaboration. However, its use requires the incorporation of a relatively expensive liquid plasticizer. In the present work, poly(ethylene-co-vinyl acetate) (EVA) serves as a polymer plasticizer for the elaboration of PIMs based on PVC as a base polymer and Aliquat 336 as a carrier. The composition of PIMs was optimized in terms of the PVC/EVA ratio and the vinyl acetate (VA) groups content (x) of EVA (i.e. EVAx). Physical-chemical properties of the resulting membranes are analyzed and correlated with their structure. The results of SEM analysis revealed miscible PVC/EVA70 blends (i.e. with 70 wt% of VA groups) and partially miscible PVC/EVA40 blends. The plasticizing effect of the EVA copolymer was confirmed by the tensile test results. The results of transport measurements showed that PIMs containing EVA40 and PVC are more efficient for the Cr(VI) extraction than those with only PVC. Thus, EVA40 can effectively replace the conventional liquid plasticizers while improving the Cr(VI) permeability. Besides, it is stated that EVA40-based PIMs are more stable as compared with conventional PIMs due to the water plasticizing effect. After the membrane optimization, the highest Cr(VI) transport flux (54.7 µmol·m-2·s-1) was measured. Moreover, the addition of 10 wt% of tetradecanol causes the increase of the water plasticizing effect and allows obtaining a PIM with high stability (up to 24 cycles) required for the membrane long-term operation.

Enhanced water and oxygen barrier performance of flexible polyurethane membranes for biomedical application.

In order to improve water and oxygen barrier properties, the surface of two commercial medical grade polyurethane (PU) membranes (Chronoflex® AR-LT and Bionate® II) was modified by a spray deposited film of poly(ethylene-co-vinyl alcohol) (EVOH). The influence of the temperature, the deposited layer thickness and the EVOH ethylene group percentage (27%, 32%, and 44% for EVOH27, EVOH32, and EVOH44, respectively) on the barrier properties of the PU/EVOH multilayered membranes was investigated. The increase of the EVOH layer thickness leads to higher oxygen barrier properties (the highest barrier improvement factor of 412 was obtained). However, in case of the deposited layer thickness higher than 18 µm, microcracks appeared on the treated surface promote a significant loss of the barrier effect. Due to its higher crystallinity degree, EVOH27 provides a higher oxygen barrier effect compared to EVOH32 and EVOH44. On the contrary, an increase of the water barrier properties was observed with the increase of the percentage of ethylene groups. Moreover, the delamination of the EVOH layer was noted after water permeation, especially in case of EVOH44, which is the most hydrophobic layer. Nevertheless, significant decrease of the water and oxygen permeability of the modified PU membranes was achieved, thus showing the benefit of using the EVOH spray deposition for the biomedical application, which requires high performance material with flexible and barrier properties.

Novel Poly(Vinylidene Fluoride)/Montmorillonite Polymer Inclusion Membrane: Application to Cr(VI) Extraction from Polluted Water.

Novel hybrid polymer inclusion membranes (PIMs) based on poly(vinylidene fluoride) (PVDF) (polymer matrix) and Aliquat 336 (ion carrier) and containing native sodium (Cloisite Na+ (CNa)) and organo-modified (Cloisite 30B (C30B)) Montmorillonites were elaborated and tested for the removal of toxic Cr(VI) ions from the aqueous solution. The influence of the nanoclay incorporation on the physicochemical properties of PVDF-based PIMs was studied and the resulting membrane transport properties of the Cr(VI) ions were investigated in detail. The water contact angle measurements reveal that the incorporation of the CNa nanofiller affects the membrane wettability as less hydrophilic surface is obtained in this case-~47° in the presence of CNa as compared with ~15° for PIMs with C30B. The membrane rigidity is found to be dependent on the type and size of the used Montmorillonite. The increase of Young's modulus is higher when CNa is incorporated in comparison with C30B. The stiffness of the PIM is strongly increased with CNa amount (four times higher with 30 wt %) which is not the case for C30B (only 1.5 times). Higher Cr(VI) permeation flux is obtained for PIMs containing CNa (~2.7 µmol/(m2·s)) owing to their porous structure as compared with membranes loaded with C30B and those without filler (~2 µmol/(m2·s) in both cases). The PIM with 20 wt % of native sodium Montmorillonite revealed satisfactory stability during five cycles of the Cr(VI) transport due to the high membrane rigidity and hydrophobicity. Much lower macromolecular chain mobility in this case allows limiting the carrier loss, thus increasing the membrane stability. On the contrary, a deterioration of the transport performance is recorded for the membrane filled with C30B and that without filler. The obtained results showed the possibility to extend the PIM lifetime through the incorporation of nanoparticles that diminish the carrier loss (Aliquat 336) from the membrane into the aqueous phase by limiting its mobility within the membrane by tortuosity effect and membrane stiffening without losing its permselective properties.

Structural and Barrier Properties of Compatibilized PE/PA6 Multinanolayer Films.

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 thousands of very thin layers, leading to new properties due to crystalline morphology changes induced by confinement. This paper is focusing on the study of multinanolayered films with alternated polyethylene (PE), compatibilizer (PEgMA) and polyamide 6 (PA6) layers and made by a forced assembly coextrusion process equipped with layer multiplying elements (LME). PE/PA6 multilayer films consisting of 5 to 2049 layers (respectively 0 to 9 LME) were successfully obtained with well-organized multilayered structure. The evolution of the morphology and the microstructure of these two semi-crystalline polymers, when the thickness of each polymer layer decreases from micro-scale to nano-scale, was correlated to the water and gas transport properties of the PE/PA multilayers. The expected improvement of barrier properties was limited due to the on-edge orientation of crystals in very thin PE and PA6 layers. Despite this change of crystalline morphology, a slight improvement of the gas barrier properties was shown by comparing experimental results with permeabilities predicted on the basis of a serial model developed by considering a PE/PA6 interphase. This interphase observed by TEM images and the on-edge crystal orientation in multilayers were evidenced from mechanical properties showing an increase of the stiffness and the strength.

Novel Ionic Conducting Composite Membrane Based on Polymerizable Ionic Liquids.

In this work, the design and characterization of new supported ionic liquid membranes, as medium-temperature polymer electrolyte membranes for fuel-cell application, are described. These membranes were elaborated by the impregnation of porous polyimide Matrimid® with different synthesized protic ionic liquids containing polymerizable vinyl, allyl, or methacrylate groups. The ionic liquid polymerization was optimized in terms of the nature of the used (photo)initiator, its quantity, and reaction duration. The mechanical and thermal properties, as well as the proton conductivities of the supported ionic liquid membranes were analyzed in dynamic and static modes, as a function of the chemical structure of the protic ionic liquid. The obtained membranes were found to be flexible with Young's modulus and elongation at break values were equal to 1371 MPa and 271%, respectively. Besides, these membranes exhibited high thermal stability with initial decomposition temperatures > 300 °C. In addition, the resulting supported membranes possessed good proton conductivity over a wide temperature range (from 30 to 150 °C). For example, the three-component Matrimid®/vinylimidazolium/polyvinylimidazolium trifluoromethane sulfonate membrane showed the highest proton conductivity-~5 × 10-2 mS/cm and ~0.1 mS/cm at 100 °C and 150 °C, respectively. This result makes the obtained membranes attractive for medium-temperature fuel-cell application.

Polyimide/Ionic Liquid Composite Membranes for Middle and High Temperature Fuel Cell Application: Water Sorption Behavior and Proton Conductivity.

Four water insoluble room-temperature protic ionic liquids (PILs) based on the N-alkylimidazolium cation with the alkyl chain length from 1 to 4 and bis(trifluoromethylsulfonyl)imide anion were synthesized and their chemical structure was confirmed by the 1H NMR and 19F NMR analysis. PILs were revealed to be thermally stable up to 360 and 400 °C. At the same time, the proton conductivity of PILs was found to be dependent mostly on the temperature and, to a less extent, on the type of the cation, i.e., the increase of the conductivity from ~3 × 10-4 S/cm at 25 °C to 2 × 10-2 S/cm at 150 °C was observed. The water vapour sorption capacity of PILs was evaluated as a function of relative humidity and the influence of the alkyl chain length on the phase behaviour in the PIL-water system was discussed. The composite polyimide/PILs membranes were prepared by the PIL immobilization in the porous polymer (Matrimid® 5218) film. The composite membranes showed a high level of proton conductivity (~10-3 S/cm) at elevated temperatures (up to 160 °C). The obtained results reveal that the elaborated composite polyimide/PIL membranes are promising candidates for the application as proton exchange membrane at middle and high temperatures.

The Impact of Reactive Ionic Liquids Addition on the Physicochemical and Sorption Properties of Poly(Vinyl Alcohol)-Based Films.

A new type of hybrid polymeric-based film containing 1-(1,3-diethoxy-1,3-dioxopropan-2-ylo)-3-methylimidazolium bromide (RIL1_Br) and 1-(2-etoxy-2-oxoethyl)-3-methylimidazolium bromide (RIL2_Br) reactive ionic liquids was elaborated. Poly(vinyl alcohol) (PVA)-based films with 9-33 wt % of RILs were subsequently characterized using Fourier transform infrared spectroscopy with attenuated total reflectance (FTIR-ATR), scanning electron microscopy (SEM), atomic force microscopy (AFM), thermogravimetric analysis (TGA) and TGA-FTIR. PVA-RIL films were also studied in tensile tests, contact angle and sorption measurements. RIL incorporation enhanced thermal and mechanical stability of PVA membranes due to the hydrogen bonds between RILs and polymer chains. Membrane swelling behavior in water (H2O), ethanol (EtOH), and propan-2-ol (IPA) and the kinetics of water sorption process revealed that PVA-RILs membranes possess the highest affinity towards water. It was pointed out that both the RIL type and the RIL amount in the polymer matrix have significant influence on the membrane swelling behavior and the water sorption kinetics.

Biodegradable PLA/PBSA Multinanolayer Nanocomposites: Effect of Nanoclays Incorporation in Multinanolayered Structure on Mechanical and Water Barrier Properties.

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 incorporation in nanolayers was considered to be an improvement of barrier properties of the multilayer films additional to the confinement effect resulting to forced assembly during the multilayer coextrusion process. 2049-layer films of ~300 µm thick were processed containing loaded PBSA nanolayers of ~200 nm, which presented certain homogeneity and were mostly continuous for the 80/20 wt% PLA/PBSA composition. The nanocomposite PBSA films (monolayer) were also processed for comparison. The presence of exfoliated and intercalated clay structure and some aggregates were observed within the PBSA nanolayers depending on the C30B content. A greater reduction of macromolecular chain segment mobility was measured due to combined effects of confinement effect and clays constraints. The absence of both polymer and clays interdiffusions was highlighted since the PLA glass transition was unchanged. Besides, a larger increase in local chain rigidification was evidenced through RAF values due to geometrical constraints initiated by close nanoclay contact without changing the crystallinity of PBSA. Tortuosity effects into the filled PBSA layers adding to confinement effects induced by PLA layers have caused a significant improvement of water barrier properties through a reduction of water permeability, water vapor solubility and water vapor diffusivity. The obtaining barrier properties were successfully correlated to microstructure, thermal properties and mobility of PBSA amorphous phase.

Chronic wound healing: A specific antibiofilm protein-asymmetric release system.

Chronic infection is a major cause of delayed wound-healing. It is recognized to be associated with infectious bacterial communities called biofilms. Currently used conventional antibiotics alone often reveal themselves ineffective, since they do not specifically target the wound biofilm. Here, we report a new conceptual tool aimed at overcoming this drawback: an antibiofilm drug delivery system targeting the bacterial biofilm as a whole, by inhibiting its formation and/or disrupting it once it is formed. The system consists of a micro/nanostructured poly(butylene-succinate-co-adipate) (PBSA)-based asymmetric membrane (AM) with controlled porosity. By the incorporation of hydrophilic porogen agents, polyvinylpyrrolidone (PVP) and polyethylene glycol (PEG), we were able to obtain AMs with high levels of porosity, exhibiting interconnections between pores. The PBSA-PEG membrane presented a dense upper layer with pores small enough to block bacteria penetration. Upon using such porogen agents, under dry and wet conditions, membrane's integrity and mechanical properties were maintained. Using bovine serum albumin (BSA) as a model protein, we demonstrated that protein loading and release from PBSA membranes were affected by the membrane structure (porosity) and the presence of residual porogen. Furthermore, the release curve profile consisted of a fast initial slope followed by a second slow phase approaching a plateau within 24 h. This can be highly beneficial for the promotion of wound healing. Cross-sectional confocal laser scanning microscopy (CLSM) images revealed a heterogeneous distribution of fluorescein isothiocyanate (FITC) labeled BSA throughout the entire membrane. PBSA membranes were loaded with dispersin B (DB), a specific antibiofilm matrix enzyme. Studies using a Staphylococcus epidermidis model, indicate significant efficiency in both inhibiting or dispersing preformed biofilm (up to 80 % eradication). The asymmetric PBSA membrane prepared with the PVP porogen (PBSA-PVP) displayed highest antibiofilm activity. Moreover, in vitro cytotoxicity assays using HaCaT and reconstructed human epidermis (RHE) models revealed that unloaded and DB-loaded PBSA-PVP membranes had excellent biocompatibility suitable for wound dressing applications.

Permeation properties of poly(m-xylene adipamide) membranes.

The permeation properties of a semiaromatic polyamide, the poly(m-xylene adipamide) (MXD6), were investigated by water and carbon dioxide permeation experiments (pervaporation and gas permeation tests). Complementary microstructure informations were obtained from calorimetric measurements. Amorphous and semicrystalline MXD6 membranes were studied. The analysis of the water flux through amorphous MXD6 membranes showed a plasticization phenomenon followed by a water-induced crystallization. It resulted that the role played by water in these materials was complex because of the dependence of the water diffusivity on water concentration and time. Because of the presence of crystalline phase, a significant reduction of water and gas permeability of MXD6 and an increase in the delay of diffusion were observed. In terms of barrier properties for water and carbon dioxyde, MXD6 membrane crystallized at high temperature were more performant than water-induced crystallized ones. Correlations between microstructure and transport properties had been so established.

Chemically and Thermally Crosslinked PVA-Based Membranes: Effect on Swelling and Transport Behavior.

The novel poly(vinyl alcohol) (PVA)-based membranes were prepared using the two-step crosslinking approach: the chemical crosslinking of PVA using sulfosuccinic acid (SSA) (0-50 wt.%) and the thermal treatment (120-160 °C). The membrane composition and crosslinking temperature were optimized in terms of the mechanical and transport properties. The FTIR-ATR analysis revealed that the increase of the SSA concentration and crosslinking temperature resulted in the rise of the ester bond bands intensity due to the esterification reaction between PVA and SSA. As a consequence, the PVA-based membrane with 50 wt % SSA and crosslinked at 140 °C showed the reduced Young's modulus (from 1266.2 MPa to 1.4 MPa) and elongation at break (from 316% to 66%) in comparison with the pure PVA membrane. The studied swelling behavior of the obtained membranes revealed significantly higher water sorption than that in methanol and propal-2-ol whatever the crosslinking temperature. The performed studies provide a new way of tailoring the membrane physicochemical properties, in particular, the surface hydrophilicity. In addition, the obtained results are crucial for the design and elaboration of the polymer membranes for the pervaporative separation of the liquid-liquid mixtures, in particular, for the alcohol dehydration.

Polyepichlorhydrin membranes for alkaline fuel cells: sorption and conduction properties.

Polymer electrolytes, using a poly(epichlorhydrin-allyl glycidyl ether) copolymer as matrix, are shown to perform well in alkaline fuel cell electrolyte. An anion-conducting network is obtained by the incorporation of cyclic diamines, 1,4-diazabicyclo[2.2.2]octane (DABCO) and 1-azabicyclo[2.2.2]octane (quinuclidine). The physicochemical and electrochemical characteristics are evaluated. The best conductivity of 1.3.10 (-2) S/cm is obtained at 60 degrees C and a relative humidity of RH = 98%. Ionic conductivity is particularly sensitive to relative humidity. To gain insight into the OH (-) conduction mechanism and the role of water, sorption measurements versus water activity, differential scanning calorimetry, and NMR measurements are carried out.

Structure and Barrier Properties of Multinanolayered Biodegradable PLA/PBSA Films: Confinement Effect via Forced Assembly Coextrusion.

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 semicrystalline PBSA as confined polymer and amorphous PLA as confining polymer in a continuous manner. The continuity of PBSA layers within the 80/20 wt % PLA/PBSA layered films was clearly evidenced by atomic force microscopy (AFM). Similar thermal events to the reference films were revealed by thermal studies; indicating no diffusion of polymers during the melt-processing. Mechanical properties were measured for the multilayer film and the obtained results were those expected considering the fraction of each polymer, revealing the absence of delamination in the PLA/PBSA multinanolayer film. The confinement effect induced by PLA led to a slight orientation of the crystals, an increase of the rigid amorphous fraction (RAF) in PBSA with a densification of this fraction without changing film crystallinity. These structural changes allowed to strongly improve the water vapor and gas barrier properties of the PBSA layer into the multilayer film up to two decades in the case of CO2 gas. By confining the PBSA structure in very thin and continuous layers, it was then possible to improve the barrier performances of a biodegradable system and the resulting barrier properties were successfully correlated to the effect of confinement on the microstructure and the chain segment mobility of the amorphous phase. Such investigation on these multinanolayers of PLA/PBSA with the aim of evidencing relationships between microstructure implying RAF and barrier performances has never been performed yet. Besides, gas and water permeation results have shown that the barrier improvement obtained from the multilayer was mainly due to the reduction of solubility linked to the reduction of the free volume while the tortuosity effect, as usually expected, was not really observed. This work brings new insights in the field of physicochemical behaviors of new multilayer films made of biodegradable polyesters but also in interfacial processes due to the confinement effect induced in these multinanolayer structures obtained by the forced assembly coextrusion. This original coextrusion process was a very advantageous technique to produce eco-friendly materials with functional properties without the help of tie layer, additives, solvents, surface treatments, or inorganic fillers.

Designing Biodegradable PHA-Based 3D Scaffolds with Antibiofilm Properties for Wound Dressings: Optimization of the Microstructure/Nanostructure.

One major factor inhibiting natural wound-healing processes is infection through bacterial biofilms, particularly in the case of chronic wounds. In this study, the micro/nanostructure of a wound dressing was optimized in order to obtain a more efficient antibiofilm protein-release profile for biofilm inhibition and/or detachment. A 3D substrate was developed with asymmetric polyhydroxyalkanoate (PHA) membranes to entrap Dispersin B (DB), the antibiofilm protein. The membranes were prepared using wet-induced phase separation (WIPS). By modulating the concentration and the molecular weight of the porogen polymer, polyvinylpyrrolidone (PVP), asymmetric membranes with controlled porosity were obtained. PVP was added at 10, 30, and 50% w/w, relative to the total polymer concentration. The physical and kinetic properties of the quaternary nonsolvent/solvent/PHA/PVP systems were studied and correlated with the membrane structures obtained. The results show that at high molecular weight (Mw = 360 kDa) and high PVP content (above 30%), pore size decreased and the membrane became extremely brittle with serious loss of physical integrity. This brittle effect was not observed for low molecular weight PVP (Mw = 40 kDa) at comparable contents. Whatever the molecular weight, porogen content up to 30% increased membrane surface porosity and consequently protein uptake. Above 30% porogen content, the pore size and the physical integrity/mechanical robustness both decreased. The PHA membranes were loaded with DB and their antibiofilm activity was evaluated against Staphylococcus epidermidis biofilms. When the bacterial biofilms were exposed to the DB-loaded PHA membrane, up to 33% of the S. epidermidis biofilm formation was inhibited, while 26% of the biofilm already formed was destroyed. These promising results validate our approach based on the development of bioactive-protein-loaded asymmetric membranes for antibiofilm strategies in situations where traditional antibiotic therapies are ineffective.

Physicochemical properties and biological activities of novel blend films using oxidized pectin/chitosan.

Pectin has been widely used in a variety of biomedical applications. In this study, it was modified with sodium periodate as an oxidant and characterized by physicochemical methods Periodate oxidation increased the contents of dialdehyde units and carboxyl groups in pectin, and a decrease in pectin viscosity was measured. The oxidization reaction led to a significant decrease in all values of molecular weight and size (Mn, Mw, [η] and Rh) as determined by size exclusion chromatography (SEC), which allowed the selection of the oxidized pectin to be added to chitosan. Chitosan-based films were characterized by infra-red spectroscopy (FTIR), X-ray diffractometry (XRD), and differential scanning calorimetry (DSC) measurements. Thermal behaviour studies demonstrated that interactions existed between chitosan and oxidized pectin. The haemolysis percentages of films were found to be less than 5%, which indicated their good blood compatibility. Finally, the antibacterial activity was clearly improved. Cross-linking reactions between pectin and chitosan through ionic bonds and amide bonds and between chitosan and oxidized pectin through Schiff base formation were evidenced, which opens the way to extend applications of these polysaccharides; notably, the biocompatibility and biodegradability of these new networks is convenient for pharmaceutical, biomedical or cosmetic applications.

Elucidation of innovative antibiofilm materials.

It is known for roughly a decade that bacterial communities (called biofilms) are responsible for significant enhanced antibiotherapy resistance. Biofilms are involved in tissue persistent infection, causing direct or collateral damage leading to chronic wounds development and impairing natural wound healing. In this study, we are interested in the development of supported protein materials which consist of asymmetric membranes as reservoir supports for the incorporation and controlled release of biomolecules capable of dissolving biofilms (or preventing their formation) and their use as wound dressing for chronic wound treatment. In a first step, polyhydroxyalkanoates (PHAs) asymmetric membranes were prepared using wet phase inversion technique. Scanning microscopy (SEM) analysis has showed the influence of different processing parameters. In a second step, the porous side of the membranes were functionalized with a surface treatment and then loaded with the antibiofilm agent (dispersin B). In a third step, the properties and antibiofilm performance of the loaded-membranes were evaluated. Exposure of Staphylococcus epidermidis biofilms to such systems weakly inhibited biofilm formation (weak preventive effect) but caused their detachment and disaggregation (strong curative effect). These initial results are promising since they open the way to a new generation of effective tools in the struggle against persistent bacterial infections exhibiting enhanced antibiotherapy resistance, and in particular in the case of infected chronic wounds.

Effect of molecular structure of sulphonated polyimide membranes on water sorption.

Water sorption in sulphonated polyimides with or without ionic block structure was analysed with Feng's new dual mode model. The effect of their molecular structure that determines the chain organisation in the solid materials was analysed by using the model parameters. The model parameters Cp and A' correspond to the sorbed water molecules on the first layer close to the ionic groups and on the subsequent layers, respectively. Based on these fitted physical parameters, the water sorption on the membranes with different counterions was studied and the hydration energy was proved to have much influence on the Cp values. The effect of the structure of the block and the random copolymers on the Cp and A' values was discussed and compared with that for the well-known Nafion membranes. The large amount of sorbed water at high activities may induce a sufficiently large mobility of the polymer segments in the hydrophilic domains for material inflation, which leads to high A' values.

Thermal and mechanical properties of bio-nanocomposites reinforced by Luffa cylindrica cellulose nanocrystals.

Cellulose nanocrystals have been prepared by acid hydrolysis of Luffa cylindrica fibers. The acid-resistant residue consisted of rod-like nanoparticles with an average length an diameter around 242 and 5.2nm, respectively (aspect ratio around 46). These cellulose nanocrystals have been used as a reinforcing phase for the processing of bio-nanocomposites using polycaprolactone (PCL) as matrix. To promote interfacial filler/matrix interactions the surface of cellulose nanocrystals was chemically modified with n-octadecyl isocyanate (C(18)H(37)NCO). Evidence of the grafting was supported by infrared spectroscopy and elemental analysis. X-ray diffraction analysis was used to confirm the integrity of cellulose nanocrystals after chemical modification. Both unmodified and chemically modified nanocrystals were used to prepare nanocomposites. The thermal properties of these materials were determined from differential scanning calorimetry and their mechanical behavior was evaluated in both the linear and non-linear range.

Water barrier properties in biaxially drawn poly(lactic acid) films.

Crystallization is among the easiest ways to improve polymer barrier properties because of the tortuosity increase within the material and the strong coupling between amorphous and crystalline phases. In this work, poly(lactic acid) (PLA) films have undergone α' thermal crystallization or different drawing processes. Although no effect of α' thermal crystallization on water permeability is observed, the drawing processes lead to an enhancement of the PLA barrier properties. This work clearly shows that, in the case of PLA, the crystallinity degree is not the main parameter governing the barrier properties contrary to the crystalline and amorphous phase organizations which play a key role. X-ray analyses confirm that the macromolecular chain orientation in the amorphous phase is the main cause of the improvement of the drawn PLA water barrier property. This improvement is due to the orthotropic structure formation for sufficient draw ratios, particularly when using the Simultaneous Biaxial drawing mode. Moreover, independently of the draw conditions, the drawing process tends to reduce the plasticization coefficient. Consequently, the drawn material barrier properties are not much affected by the water passage.