Relationship between the Microstructure and Performance of Graphene/Polyethylene Composites Investigated by Positron Annihilation Lifetime Spectroscopy

The quantitative characterization of microstructure is most desirable for the establishment of structure-property relationships in polymer nanocomposites. In this work, the effects of graphene on the microstructure, mechanical, electrical, and thermal properties of the obtained graphene/polyethylene (PE) composites were investigated. In order to reveal the structure-performance relationship of graphene/PE composites, especially for the effects of the relative free volume fraction (fr) and interfacial interaction intensity (β), positron annihilation lifetime spectroscopy (PALS) was employed for its quantitative description. The relative free volume fraction fr gives a good explanation of the variation for surface resistivity, melting temperature, and thermal stability, and the variation of tensile strength and thermal conductivity agree well with the results of interfacial interaction intensity β. The results showed that fr and β have a significant effect on the properties of the obtained graphene/PE composites, and the effect on the properties was revealed.

Effect of Free Volume on Curcumin Release from Various Polymer-Based Composite Films Analyzed Using Positron Annihilation Lifetime Spectroscopy

This work reports the effects of free volume on curcumin release in various polymer-based composite films. Curcumin-reinforced biocomposite films were fabricated with natural biopolymers (carrageenan and chitosan) and bioplastics (poly(lactide) (PLA) and poly (butylene adipate-co-terephthalate) (PBAT)) via the solvent casting method. The curcumin release test was performed using an aqueous medium, and it was found that it was released the fastest in the carrageenan film, followed by the chitosan, PLA, and PBAT films, presumably owing to the dissimilarity of the polymer matrix. The free volume of the polymer films was determined using positron annihilation lifetime spectroscopy (PALS) to understand the release phenomena of curcumin. The free volume fraction was varied and reliant on the type of polymer, with the highest in the PBAT-based film followed by the PLA-, chitosan-, and carrageenan-based films. The free volume method helps analyze the release of bioactive compounds in a polymer matrix and may help to achieve a better understanding of the release of bioactive compounds.

Viscoelastic Behavior of Drug-Loaded Polyurethane

Drug-eluting stents are desirable platforms for local medicine delivery. However, the incorporation of drugs into polymers can influence the mechanical and physicochemical properties of said matrix, which is a topic that is still poorly understood. In fact, this is more noticeable since the apposition is most often accompanied by mechanical stresses on the polymer coating, which can induce therapeutic failure that can result in death. It is therefore necessary to better understand their behavior by examining their properties in conditions such as those in living beings. We studied polyurethane drug carriers made in-house. Diclofenac epolamine was chosen as a model hydrophilic medicine. We used thermal measurements (DMTA) and tensile tests. The aim was to establish the influence of the loading and release of the drug on the physicochemical properties of this polymer in the presence of a stagnant or circulating fluid medium, phosphate-buffered saline (PBS). For the two PU/drug loadings studied, the effect of the initial drug load was more marked. The free volume fraction and the number of pores in the samples increased with the increasing percent of the drug and with release time. The kinetic profiles were accelerated with the loading ratio and with the presence of flow. Young′s modulus and ultimate stress were not significantly influenced by the release time. A relevant relationship between the tensile properties and the viscoelastic behavior of the samples was developed. Our results have implications for optimizing the performance of drug coatings for stents.

Effect of Terminal Groups on Thermomechanical and Dielectric Properties of Silica–Epoxy Composite Modified by Hyperbranched Polyester

To study the effect of hyperbranched polyester with different kinds of terminal groups on the thermomechanical and dielectric properties of silica–epoxy resin composite, a molecular dynamics simulation method was utilized. Pure epoxy resin and four groups of silica–epoxy resin composites were established, where the silica surface was hydrogenated, grafted with silane coupling agents, and grafted with hyperbranched polyester with terminal carboxyl and terminal hydroxyl, respectively. Then the thermal conductivity, glass transition temperature, elastic modulus, dielectric constant, free volume fraction, mean square displacement, hydrogen bonds, and binding energy of the five models were calculated. The results showed that the hyperbranched polyester significantly improved the thermomechanical and dielectric properties of the silica–epoxy composites compared with other surface treatments, and the terminal groups had an obvious effect on the enhancement effect. Among them, epoxy composite modified by the hyperbranched polyester with terminal carboxy exhibited the best thermomechanical properties and lowest dielectric constant. Our analysis of the microstructure found that the two systems grafted with hyperbranched polyester had a smaller free volume fraction (FFV) and mean square displacement (MSD), and the larger number of hydrogen bonds and greater binding energy, indicating that weaker strength of molecular segments motion and stronger interfacial bonding between silica and epoxy resin matrix were the reasons for the enhancement of the thermomechanical and dielectric properties.

Shape and Temperature Expansion of Free Volume Holes in Some Cured Polybutadiene-Polyisoprene Rubber Blends

The free volume fraction of a macromolecular structure can be assessed theoretically by using a suitable model; however, it can also be evaluated from experimental data obtained from dilatometry and positron annihilation lifetime spectra. In this second case, a regular geometry of the sub-nanometric cavities forming the free volume has to be assumed, although in fact they are irregularly shaped. The most popular approach is to guess spherical holes, which implies an isotropic growth of these last with temperature. In this work, we compared the free volume fraction, as obtained from experiments in a set of polybutadiene and polyisoprene cured rubbers and their blends, with the analogous quantity expected by using the lattice-hole model. The results allowed us to obtain insights on the approximate shape of the holes. Indeed, a cylindrical flattened geometry of the cavities produced a better agreement with the theory than the spherical shape. Furthermore, the best fit was obtained for holes that expanded preferentially in the radial direction, with a consequent decrease of the aspect ratio with temperature.

Free volume, thermal and morphological properties of photo-crosslinked thiol-Ene/ nanodiamond hybrid network

Purpose The purpose of this research paper is to investigate the changes in free volume by adding acrylate modified nanodiamond particles. In this study, a cross-linked thiol-ene (T) network was obtained under ultraviole light. The changes in free volume were analyzed when acrylate-modified nanodiamond (M-ND) particles were added to the nanocomposites obtained. Positron annihilation lifetime spectroscopy (PALS), a well-established method, was used for this analysis. In addition, the effect of nanocomposites containing different ratios of acrylate M-ND particles (1, 2, 3 and 5 Wt. %) on the surface and the thermal properties were also examined. Design/methodology/approach The impact of different quantities of acrylate M-ND on the free volume and surface morphological properties of thiol-ene polymer networks were studied by using scanning electron microscopy, differential scanning calorimetry, attenuated total reflection, Fourier transform infrared spectroscopy, PALS and thermogravimetric analysis measurements. Findings The thermal properties of T/M-ND were found to depend on the weight percentages of the M-ND content. For increasing weight percentages of M-ND added to thio-lene polymer networks, the glass transition temperature (Tg) increased from 103°C to 154°C. The ortho-positronium (o-Ps) lifetime (free volume) and free volume fraction characterization of T/M-ND nanocomposites were investigated using PALS. Increasing temperature caused both the o-Ps lifetime (free volume) to change with increasing saturation and to linearly increase the intensity; however, an increasing weight percentage of M-ND caused no change at all for the o-Ps lifetime (free volume) and the free volume fraction. Originality/value According to published literature, and to the best of the authors’ knowledge, this is the first time a study examining the free volume properties in a thiol-ene system has been carried out.

Effect of introduction of fluoromonomer copolymerization on properties of polyimide hollow fibers

The novel copolymerization polyimide (PI) hollow fibers (HFs) of 4,4′-(hexafluoroisopropylidene) diphthalic anhydride (6FDA) containing –CF3 groups were prepared and investigated through both simulation and experiment. To demonstrate the alteration attributable to the introduction of fluoromonomers, the condensed states of pyromellitic dianhydride (PMDA)/4,4′-oxybisbenzenamine (ODA), PMDA/6FDA/ODA, and 6FDA/ODA PI were constructed by Material Studio, and we simulated the mobility of molecular chain, free volume fraction, and O2/N2 dissolution–diffusion process. The molecular dynamics simulation results demonstrated that the properties of the copolymerized PI system with 6FDA were significantly improved, while the selectivity remained almost unchanged. Then, the films of copolymerized PI and HFs were prepared by the two-step method, and O2/N2 permeability of the PI copolymer films was characterized, indicating that although the gas permeation performance was greatly improved, the selectivity was not so satisfactory. However, the selection factor increased heavily after polydimethylsiloxane coating.

BEYOND THE SPHERICAL APPROXIMATION: ELONGATED FREE VOLUME HOLES IN RUBBERS: A POSITRON ANNIHILATION STUDY

ABSTRACT The free volume fraction, a key parameter for the understanding of mechanical and transport properties of polymers, has been evaluated in a fluoroelastomer and a cis-polyisoprene rubber by means of positron annihilation lifetime spectroscopy and dilatometry. The evaluation showed that the assumption of elongated holes allows one to get a very good agreement between the free volume fraction experimentally determined and the theoretical expectation based on the lattice-hole model. On the other hand, systematic discrepancies are found using the spherical approximation. Moreover, the average hole size is found to be correlated to the effective bond length leff, a parameter connected to reptation motions and largely independent of the polymer structure. The result sheds some light on conformational statistics for the most flexible linear polymers that approach Gaussian chain behavior.

Synthesis and properties of highly processable asymmetric polyimides with bulky phenoxy groups

A series of new aromatic polyimides (PIs) and co-PIs containing bulky tert-butyl phenoxy group was synthesized by one-step high-temperature polycondensation of 1,3-diamino-4-(4′- tert-butylphenoxy)benzene ( tBuPDAB) with different commercially available aromatic dianhydrides. The polymers were obtained in quantitative yields with inherent viscosities of 0.40–0.70 dL g−1. They exhibited high thermal stability with 10% weight loss above 480°C and were cast in films with good mechanical properties capable to be tested as gas separation membranes. These PIs were compared with analogs bearing phenoxy group (PDAB). The incorporation of tBu improved the solubility of the PIs, their free volume fraction, d-spacing, and gas permeability coefficients in comparison with their analogs obtained from PDAB. The permeability enhancement was from 2.5 to 8 times depended on the gas tested. The PI, based on tBuPDAB and 4,4’-(hexafluoroisopropylidene)diphtalic anhydride and, thus, containing two different bulky pendant groups, showed the highest gas permeability coefficient for CO2 (58.3 Barrer) and moderate ideal selectivity to the gas pair CO2/CH4 ( α = 18.0).

Anchor Effect in Polymerization Kinetics: Case of Monofunctionalized POSS

The effect of the anchoring group on the detailed polymerization kinetics was investigated using monomethacryloxy-heptaisobutyl POSS (1M-POSS). This compound was copolymerized with lauryl methacrylate (LM) as the base monomer, at various molar ratios. The process was initiated photochemically. The polymerization kinetics were followed by photo-DSC and photorheology while the polymers were characterized by nuclear magnetic resonance (NMR), gel permeation chromatography (GPC), transmission electron microscopy (TEM), and differential scanning calorimetry (DSC). For comparison, a methacrylate containing the branched siloxy-silane group (TSM) was also studied. It was found that the modifiers with a bulky substituent have a dual effect on the termination process: (i) At low concentrations, they increase the molecular mobility by increasing the free volume fraction, which leads to an acceleration of the termination and slows the polymerization; while (ii) at higher concentrations, they retard molecular motions due to the “anchor effect” that suppresses the termination, leading to acceleration of the polymerization. The anchor effect can also be considered from a different point of view: The possibility of anchoring a monomer with a long substituent (LM) around the POSS cage, which can further enhance propagation. These conclusions were derived based on kinetic results, determination of polymerization rate coefficients, and copolymer analysis.