Polycaprolactone composite films infused with hyperbranched polyester/reduced graphene oxide: influence on biodegradability, gas/water transport and antimicrobial properties for sustainable packaging.

Biodegradable polymers have gained great interest as ecofriendly packaging materials. However, addition of suitable fillers to the polymer matrix enhances their barrier and mechanical properties besides gaining new features such as bactericidal activity. This work deals with investigation of mechanical, gas/water transport properties and biodegradability performance of films based on polycaprolactone (PCL) reinforced by 1wt% of reduced graphene oxide (RGO) or modified graphene (mRG). To achieve this goal, nanosheets of RGO were firstly prepared then their surfaces were modified through in situ polymerization of hyperbranched polyester (PES) to obtain mRG. Then PCL was loaded with both fillers, and the nanocomposite films were prepared by a casting technique. Studying of the thermal properties of the films showed that the addition of RGO or mRG had no influence on the crystallinity of the PCL matrix. Although the mechanical characteristics of the PCL did not change when either filler was added, there was an increase in permeability and diffusivity in the presence of the fillers regardless of their composition. Nevertheless, the nanocomposites demonstrated antimicrobial properties against S. aureus and E. coli as models for Gram-positive and Gram-negative bacteria, respectively. The biodegradability test performed on the prepared film PCL, and those containing 1% of the filler, PCL/RGO, and PCL/mRG, emphasized that the film degradation became pronounced after three months for all samples.

Effect of Amino-Functionalized Polyhedral Oligomeric Silsesquioxanes on Structure-Property Relationships of Thermostable Hybrid Cyanate Ester Resin Based Nanocomposites.

Nanocomposites of cyanate ester resin (CER) filled with three different reactive amino-functionalized polyhedral oligomeric silsesquioxane (POSS) were synthesized and characterized. The addition of a small quantity (0.1 wt.%) of amino-POSS chemically grafted to the CER network led to the increasing thermal stability of the CER matrix by 12-15 °C, depending on the type of amino-POSS. A significant increase of the glass transition temperature, Tg (DSC data), and the temperature of α relaxation, Tα (DMTA data), by 45-55 °C of the CER matrix with loading of nanofillers was evidenced. CER/POSS films exhibited a higher storage modulus than that of neat CER in the temperature range investigated. It was evidenced that CER/aminopropylisobutyl (APIB)-POSS, CER/N-phenylaminopropyl (NPAP)-POSS, and CER/aminoethyl aminopropylisobutyl (AEAPIB)-POSS nanocomposites induced a more homogenous α relaxation phenomenon with higher Tα values and an enhanced nanocomposite elastic behavior. The value of the storage modulus, E', at 25 °C increased from 2.72 GPa for the pure CER matrix to 2.99-3.24 GPa for the nanocomposites with amino-functionalized POSS nanoparticles. Furthermore, CER/amino-POSS nanocomposites possessed a higher specific surface area, gas permeability (CO2, He), and diffusion coefficients (CO2) values than those for neat CER, due to an increasing free volume of the nanocomposites studied that is very important for their gas transport properties. Permeability grew by about 2 (He) and 3.5-4 times (CO2), respectively, and the diffusion coefficient of CO2 increased approximately twice for CER/amino-POSS nanocomposites in comparison with the neat CER network. The efficiency of amino-functionalized POSS in improving the thermal and transport properties of the CER/amino-POSS nanocomposites increased in a raw of reactive POSS containing one primary (APIB-POSS) < eight secondary (NPAP-POSS) < one secondary and one primary (AEAPIB-POSS) amino groups. APIB-POSS had the least strongly pronounced effect, since it could form covalent bonds with the CER network only by a reaction of one -NH2 group, while AEAPIB-POSS displayed the most highly marked effect, since it could easily be incorporated into the CER network via a reaction of -NH2 and -NH- groups with -O-C≡N groups from CER.

Mixed-Matrix Membranes Based on Polyetherimide, Metal-Organic Framework and Ionic Liquid: Influence of the Composition and Morphology on Gas Transport Properties.

In this work, membranes based on polyetherimide (PEI), a ZIF-8 metal-organic framework and 1-ethyl-methylimidazolium tetrafluoroborate ionic liquid (IL) were prepared. IL and ZIF-8 contents amounting to 7 wt% and 25 wt%, respectively, were investigated. CO2, He and H2 transport properties of PEI/IL/ZIF-8 membranes were compared to those obtained for the respective PEI/ZIF-8 and PEI/IL systems. Membranes' gas permeability and selectivity are discussed as a function of the membrane composition and morphology, and they were assessed in relation to existing experimental and theoretical data from the literature. Promising gas transport properties were obtained using the appropriate combination of ZIF-8 and IL amounts in the PEI matrix. Indeed, an increase in the CO2 permeability coefficient by a factor of around 7.5 and the He and H2 permeability coefficients by a factor of around 4 was achieved by adding 7 wt% IL and 10 wt% ZIF-8 to the PEI matrix. Moreover, diffusion was evidenced as a governing factor in the studied membrane series.

Tuning Polymer/TiO2 Nanocomposites Morphology by In Situ Non-Hydrolytic Sol-Gel Syntheses in Viscous Polymer Medium: Influence of the Polymer Nature and Oxygen Donor.

Herein, we reported the synthesis of TiO2 through different non-hydrolytic sol-gel (NHSG) routes in viscous polymer media. For the first time, the influence of the polymer nature (Polystyrene (PS) or Polypropylene (PP)) on the morphology of synthesized inorganic domains was investigated. The non-hydrolytic sol-gel reactions between titanium isopropoxide Ti(OiPr)4 and acetic anhydride in molten polypropylene lead to the formation of microfillers with a mean diameter of about 1 µm, while the same synthesis carried out in viscous polystyrene lead to the formation of nanofillers with diameter lower than 10 nm forming aggregates of approximately 200 nm. We have also investigated the influence of the oxygen donor nature on the morphology of synthesized fillers using aromatic oxygen donors in a polystyrene matrix. The use of benzoic anhydride or acetophenone as oxygen donors with Ti(OiPr)4 in viscous polystyrene lead to respectively platelet-like morphology or aggregated nanofillers. We demonstrated that the affinity between polymer, reactants, and/or by-products had an influence on the morphology and the size of in situ synthesized TiO2 fillers. These results evidenced for the first time the possibility to control and to tune the morphology of in situ grown inorganic objects through the NHSG process by the appropriate choice of solvent, here a viscous polymer medium, and reactants.

Influence of the Graphene Filler Nature on the Morphology and Properties of Melt Blended EVOH Based Nanocomposites.

In this study, ethylene vinyl alcohol (EVOH) nanocomposites elaborated by melt blending with four different fillers were investigated. Two graphene and two graphite fillers displaying various shapes were selected. The morphology, microstructure, thermal, mechanical, and barrier properties of the nanocomposite films prepared for 2 wt% fillers were analyzed with the aim to establish structure-function properties relationships. The nanocomposites properties significantly depended on the nature of the incorporated filler. The nanocomposite film prepared with the expanded graphite filler exhibited the highest Young modulus value (E = 1430 MPa) and the best barrier properties. Indeed, barrier properties, rarely studied at high water activities, evidenced a significant improvement with a decrease of the water vapor permeability by a factor 1.8 and of the oxygen permeabilities by a factor close to 2, for a critical water activity higher than 0.95. An increase of the thermal stability was also evidenced for this nanocomposite. It was shown that for all studied nanocomposites, the properties could be related to the dispersion state of the fillers and the simultaneous increase of the crystallinity of the matrix. A specific equation was proposed to take into account these both parameters to accurately predict the nanocomposite barrier properties.

Development of Breathable Pebax®/PEG Films for Optimization of the Shelf-Life of Fresh Agri-Food Products.

In this work, thin transparent breathable films were prepared for food packaging applications. The films were obtained by the solvent casting method from both the binary blends Pebax® MH1657 copolymer/ hydroxyl-terminated polyethylene glycol (PEGOH) and Pebax® MH1657/polyethylene glycol dimethyl ether (PEGDME) as well as the ternary blend Pebax® MH1657/PEGOH/PEGDME with a 50/50 and 37.5/62.5 PEGOH/PEGDME weight ratio for additive amounts comprised between 0 and 50 wt.%. The microstructure of these materials was investigated by differential scanning calorimetry (DSC) and wide-angle X-ray scattering (WAXS) analyses. Regardless of the PEG's nature, for a PEG amount inferior to 30 wt.%, the Pebax® and PEG phases were totally miscible. For higher amounts, a phase separation was obtained. In the presence of PEG, a decrease in crystallinity was obtained. The effects of the nature and amount of PEG on the thermo-mechanical, hydration, and gas (CO2, O2) transport properties were investigated. A study of the film's stability in terms of composition over time was also performed. From this work, a wide range of films could be proposed with a stable composition over time and adjustable mechanical and gas transport properties for the prolongation of the shelf-life of highly breathable fresh products.

Finite Element Analysis of Gas Diffusion in Polymer Nanocomposite Systems Containing Rod-like Nanofillers.

Polymer-based films with improved gas barrier properties are of great interest for a large range of applications, including packaging and coatings. The barrier effect is generally obtained via the addition of a sufficient amount of impermeable nanofillers within the polymer matrix. Due to their low environmental footprint, bio-based nanocomposites such as poly(lactic acid)-cellulose nanocrystal (PLA-CNC) nanocomposites seem to be an interesting alternative to synthetic-polymer-based nanocomposites. The morphology of such systems consists of the dispersion of impermeable rod-like fillers of finite length in a more permeable matrix. The aim of this work is to analyze, through finite element modeling (FEM), the diffusion behavior of 3D systems representative of PLA-CNC nanocomposites, allowing the determination of the nanocomposites' effective diffusivity. Parametric studies are carried out to evaluate the effects of various parameters, such as the filler volume fraction, aspect ratio, polydispersity, and agglomeration, on the improvement of the barrier properties. The role of the filler-matrix interfacial area (or interphase) is also investigated and is shown to be particularly critical to the overall barrier effect for highly diffusive interphases.

Multifunctional Pd-Based Nanocomposites with Designed Structure from In Situ Growth of Pd Nanoparticles and Polyether Block Amide Copolymer.

Nanocomposites containing palladium nanoparticles were synthesized by in situ generation route from palladium acetate and a polyether block amide matrix with the aim to obtain materials with specific nanoparticle location and function properties. The chosen Pebax matrix was composed of a continuous soft phase containing dispersed semi-crystalline rigid domains. Nanocomposite films with Pd amount up to 30 wt% (corresponding to 3.5 vol%) were directly prepared from the palladium precursor and the copolymer matrix through a solvent cast process. The microstructure of the films was investigated by microcalorimetry, X-ray diffraction analyses and transmission electron microscopy. The nanocomposites' function properties in terms of electrical conductivity and interaction towards hydrogen were studied as a function of the palladium content. It was shown that the spherical crystalline Pd nanoparticles that were in situ formed were located in the continuous soft phase of the copolymer matrix. They did not induce modification of Pebax microstructure and chain mobility. The specific location of the metal nanoparticles within the copolymer matrix associated with their low size allowed obtaining conductive materials for Pd amount equal to 3.5 vol%. Moreover, the affinity towards hydrogen evidenced from hydrogen permeation experiments made this nanocomposite series promising for further development in sensing applications.

Superabsorbent and Fully Biobased Protein Foams with a Natural Cross-Linker and Cellulose Nanofibers.

The development of fully natural wheat gluten foams showing rapid and high uptake of water, sheep blood, and saline solution, while maintaining high mechanical stability in the swollen state, is presented. Genipin was added as a natural and polar cross-linker to increase the polarity of the protein chains, whereas cellulose nanofibers (CNFs) were added as a reinforcement/stiffener of the foams, alone or in combination with the genipin. The presence of only genipin resulted in a foam that absorbed up to 25 g of water per gram of foam and a more than 15 g uptake in only 8 min. In contrast, with CNF alone, it was not possible to maintain the mechanical stability of the foam during the water uptake and the protein foam disintegrated. The combination of CNF and genipin yielded a material with the best mechanical stability of the tested samples. In the latter case, the foam could be compressed repeatedly more than 80% without displaying any structural damage. The results revealed that a strong network had formed between the wheat gluten matrix, genipin, and cellulose in the foam structure. A unique feature of the absorbent/foam, in contrast to commercial superabsorbents, was that it was able to rapidly absorb nonpolar liquids (here, n-heptane) due to the open-cell structure. The capillary-driven absorption due to the open-cell structure, the high liquid absorption in the cell walls, and the mechanical properties (both in dry and swollen states) of these natural foams make them interesting as a sustainable replacement for a range of petroleum-based foam materials, including absorbent hygiene products such as sanitary pads.

A Protein-Based Material from a New Approach Using Whole Defatted Larvae, and Its Interaction with Moisture.

A protein-based material created from a new approach using whole defatted larvae of the Black Soldier fly is presented. The larvae turn organic waste into their own biomass with high content of protein and lipids, which can be used as animal feed or for material production. After removing the larva lipid and adding a plasticizer, the ground material was compression molded into plates/films. The lipid, rich in saturated fatty acids, can be used in applications such as lubricants. The amino acids present in the greatest amounts were the essential amino acids aspartic acid/asparagine and glutamic acid/glutamine. Infrared spectroscopy revealed that the protein material had a high amount of strongly hydrogen-bonded ß-sheets, indicative of a highly aggregated protein. To assess the moisture⁻protein material interactions, the moisture uptake was investigated. The moisture uptake followed a BET type III moisture sorption isotherm, which could be fitted to the Guggenheim, Anderson and de Boer (GAB) equation. GAB, in combination with cluster size analysis, revealed that the water clustered in the material already at a low moisture content and the cluster increased in size with increasing relative humidity. The clustering also led to a peak in moisture diffusivity at an intermediate moisture uptake.

Nanoporous Cyanate Ester Resins: Structure-Gas Transport Property Relationships.

This contribution addresses the relationships between the structure and gas transport properties of nanoporous thermostable cyanate ester resins (CERs) derived from polycyclotrimerization of 1,1'-bis(4-cyanatophenyl)ethane in the presence of 30 or 50 wt% of inert high-boiling temperature porogens (i.e., dimethyl- or dibutyl phthalates), followed by their quantitative removal. The nanopores in the films obtained were generated via a chemically induced phase separation route with further porogen extraction from the densely crosslinked CERs. To ensure a total desorption of the porogen moieties from the networks, an additional short-term thermal annealing at 250 °C was performed. The structure and morphology of such nanoporous CER-based films were investigated by FTIR and SEM techniques, respectively. Further, the gas transport properties of CER films were analyzed after the different processing steps, and relationships between the material structure and the main gas transport parameters were established.

Polymer Nanocomposite Film with Metal Rich Surface Prepared by In Situ Single-Step Formation of Palladium Nanoparticles: An Interesting Way to Combine Specific Functional Properties.

This paper presents a continuous single-step route that permits preparation of a thermostable polymer/metal nanocomposite film and to combine different functional properties in a unique material. More precisely, palladium nanoparticles are in situ generated in a polyimide matrix thanks to a designed curing cycle which is applied to a polyamic acid/metal precursor solution cast on a glass plate. A metal-rich surface layer which is strongly bonded to the bulk film is formed in addition to homogeneously dispersed metal nanoparticles. This specific morphology leads to obtaining an optically reflective film. The metal nanoparticles act as gas diffusion barriers for helium, oxygen, and carbon dioxide; they induce a tortuosity effect which allows dividing the gas permeation coefficients by a factor near to 2 with respect to the neat polyimide matrix. Moreover, the ability of the in situ synthesized palladium nanoparticles to entrap hydrogen is evidenced. The nanocomposite film properties can be modulated as a function of the location of the film metal-rich surface with respect to the hydrogen feed. The synthesized nanocomposite could represent a major interest for a wide variety of applications, from specific coatings for aerospace or automotive industry, to catalysis applications or sensors.

Starch/silver nanocomposite: Effect of thermal treatment temperature on the morphology, oxygen and water transport properties.

The present work reports a strategy involving the preparation of nanostructured starch based film containing silver nanoparticles (AgNPs) using a completely green chemistry process. The nanocomposite films were prepared by solution cast process. The AgNPs were in situ generated inside the polymer film by thermal treatment at different temperatures (25, 40 and 85 °C). The influence of the presence and the amount of reducing agent (glucose) were also investigated. For all nanocomposite films, the AgNPs were spherical with a diameter less than 15 nm. Contrary to the presence of glucose, thermal treatment condition was a key factor for the AgNPs structure. Crystalline AgNPs were obtained only after thermal treatment at 85 °C. Improvements of water and oxygen barrier properties near to one decade were observed in this last case and were explained by the formation of crystalline AgNPs associated to the establishment of strong interactions between AgNPs and starch polymer matrix.

Effects of Block Length and Membrane Processing Conditions on the Morphology and Properties of Perfluorosulfonated Poly(arylene ether sulfone) Multiblock Copolymer Membranes for PEMFC.

Perfluorosulfonated poly(arylene ether sulfone) multiblock copolymers have been shown to be promising as proton exchange membranes. The commonly used approach for preparation of the membrane is solvent casting; the properties of the resulting membranes are very dependent on the membrane processing conditions. In this paper, we study the effects of block length, selectivity of the solvent, and thermal treatment on the membrane properties such as morphology, water uptake, and ionic conductivity. DiMethylSulfOxide (DMSO), and DiMethylAcetamide (DMAc) were selected as casting solvents based on the Flory-Huggins parameter calculated by inversion gas chromatography (IGC). It was found that the solvent selectivity has a mild impact on the mean size of the ionic domains and the expansion upon swelling, while it dramatically affects the supramolecular ordering of the blocks. The membranes cast from DMSO exhibit more interconnected ionic clusters yielding higher conductivities and water uptake as compared to membranes cast from DMAc. A 10-fold increase in proton conductivity was achieved after thermal annealing of membranes at 150 °C, and the ionomers with longer block lengths show conductivities similar to Nafion at 80 °C and low relative humidity (30%).

Green synthesis of colloid silver nanoparticles and resulting biodegradable starch/silver nanocomposites.

Environmentally friendly silver nanocomposite films were prepared by an ex situ method consisting firstly in the preparation of colloidal silver dispersions and secondly in the dispersion of the as-prepared nanoparticles in a potato starch/glycerol matrix, keeping a green chemistry process all along the synthesis steps. In the first step concerned with the preparation of the colloidal silver dispersions, water, glucose and soluble starch were used as solvent, reducing agent and stabilizing agent, respectively. The influences of the glucose amount and reaction time were investigated on the size and size distribution of the silver nanoparticles. Two distinct silver nanoparticle populations in size (diameter around 5 nm size for the first one and from 20 to 50 nm for the second one) were distinguished and still highlighted in the potato starch/glycerol based nanocomposite films. It was remarkable that lower nanoparticle mean sizes were evidenced by both TEM and UV-vis analyses in the nanocomposites in comparison to the respective colloidal silver dispersions. A dispersion mechanism based on the potential interactions developed between the nanoparticles and the polymer matrix and on the polymer chain lengths was proposed to explain this morphology. These nanocomposite film series can be viewed as a promising candidate for many applications in antimicrobial packaging, biomedicines and sensors.

Influence of chemical structure on hydration and gas transport mechanisms of sulfonated poly(aryl ether ketone) membranes.

This work reports the influence of the chemical structure of two sulfonated poly(aryl ether ketone)s (SPAEK) on the hydration and gas transport mechanism of thin membranes made thereupon. For this purpose, two sulfonated poly(aryl ether ketone)s having the same ionic exchange capacity (IEC) but bearing a different repartition of the sulfonic acid groups along the polymer backbone were prepared. These polymers were synthesized by direct copolymerization of two specific sulfonated precursors, bisphenol AF and 4,4'-difluorobenzophenone. The morphology of the membranes was studied by transmission electron microscopy, and the thermal properties of the ionomers were determined from differential scanning calorimetry and thermogravimetric analyses. A detailed analysis of the water sorption isotherms and kinetics was performed. The gas transport properties were also determined for He, H(2), and CO(2) in the full range of water activity. From the detailed analysis of the water sorption isotherm and of the relative contributions of the Fickian diffusion and relaxation phenomena, a water sorption mechanism was proposed in relation with the SPAEK architectures and polymers' chain mobility. This mechanism allowed explaining the different evolution of the gas transport properties observed as a function of the gas nature and hydration rate.