Biological gels (bio-gels) are hydrated polymer networks that serve diverse biological functions, which often lead to intentional or unintentional exposure to particulate matter. In this work, we derive a microscopically motivated framework that enables the investigation of penetration mechanisms into bio-gels. We distinguish between two types of mechanisms: spontaneous (unforced) penetration and forced penetration. Using experimental data available in literature, we exploit the proposed model to characterize and compare between the micro-structures of respiratory, intestinal, and cervicovaginal mucus and two types of biofilms. Next, we investigate the forced penetration process of spherical and ellipsoidal particles into a locally quadrilateral network. The proposed framework can be used to improve and complement the analysis of experimental findings in vitro, ex vivo, and in vivo. Additionally, the insights from this work pave the way towards enhanced designs of nano-medicines and allow to assess risk factors related to the nano-pollutants exposure.

This study explores the potential to reach a circular economy for post-consumer recycled polyethylene terephthalate (rPET) packaging and bottles by using it as a distributed recycling for additive manufacturing (DRAM) feedstock. Specifically, rPET is processed using only an open source toolchain with fused particle fabrication (FPF) or fused granular fabrication (FGF) processing. In this study, first the impact of granulation, sifting and heating (and their combination) is quantified on the shape and size distribution of the rPET flakes. Then feeding studies were performed to see if they could be printed through an external feeder or needed to be direct printed with a hopper using two Gigabot X machines, one with extended part cooling and one without. Print settings were optimized based on thermal characterization and for the latter which was shown to print rPET directly from shredded water bottles mechanical testing is performed. The results showed that geometry was important for extended feeding tubes and direct printed using a hopper. Further there is a wide disparity in the physical properties of rPET from water bottles depending on source and the history of the material. Future work is needed to enable water bottles to be used as a widespread DRAM feedstock.

The thermal properties of novel nanomaterials play a significant role in determining the performance of the material in technological applications. Herein, direct measurement of the temperature diffusivity of cellulose nanocomposite films was carried out by the micro-contact method. Polymer films containing up to 2%wt. of nanocellulose were synthesised by a simple chemical process. Films of a high optical transmittance T ≈ 80 % (for a 200- μ m-thick film), which were up to 44% crystalline, were characterised. Two different modalities of temperature diffusivity based on: 1) a resistance change and 2) micro-thermocouple detected modulation of a heat wave, were used for the polymer films with cross-sections of ∼ 100 μ m thickness. Twice different in-plane α ‖ and out-of-plane α ⊥ temperature diffusivities were directly determined with high fidelity: α ‖ = 2 . 12 × 10 − 7 m 2 /s and α ⊥ = 1 . 13 × 10 − 7 m 2 /s. An amorphous polyethylene terephthalate (PET) fiber was measured for comparison α ‖ = 1 . 15 × 10 − 7 m 2 /s. This work provides an example of a direct contact measurement of thermal properties of nanocellulose composite films. The thermal diffusivity, which is usually high in strongly interconnected networks and crystals, was investigated for the first time in this composite.

In a recent reformulation of the Marrucci-Ianniruberto constitutive equation for the rheology of entangled polymer melts in the context of non-equilibrium thermodynamics, rather large values of the convective constraint release parameter \beta_{ccr} had to be used in order not to violate the second law of thermodynamics. In this work, we present an appropriate modification of the model which avoids the splitting of the evolution equation for the conformation tensor into an orientation and a stretching part. Then, thermodynamic admissibility dictates simply that \beta_{ccr}≥ 0, thus allowing for more realistic values of \beta_{ccr} to be chosen. Moreover, and in view of recent experimental evidence for a transient stress undershoot (following the overshoot) at high shear rates whose origin may be traced back to molecular tumbling, we have incorporated in the model additional terms accounting, at least in an approximate way, for non-affine deformation through a slip parameter \xi. Use of the new model to describe available experimental data for the transient and steady-state shear and elongational rheology of entangled polystyrene melts and solutions shows close agreement. Overall, the modified model proposed here combines simplicity with accuracy, which renders it an excellent choice for managing complex viscoelastic fluid flows in large-scale numerical calculations.

A methodology is proposed for designing the stabilization process of polyacrylonitrile (PAN) fibers. In its core, this methodology is based on a model that describes the characteristic fiber length change during the treatment, through the de-convolution of the three main contributors (i.e. entropic shrinkage, creep, and chemical shrinkage). The model has the additional advantage of offering further insight into the physical and chemical phenomena taking place during the treatment. Validation of PAN-model prediction performance for different processing parameters was achieved as demonstrated by FTIR and DSC. Τensile testing revealed the effect of processing parameters on fiber quality, while model prediction demonstrated that ladder polymer formation is accelerated at temperatures over 200oC. Additionally, according the DSC and FTIR measurements predictions from the application of the model during stabilization seem to be more precise at high-temperature stabilization stages. It was shown that mechanical properties could be enhanced preferably by including a treatment step below 200oC, before the initiation of cyclization reactions. Further confirmation was provided via Raman spectroscopy, which demonstrated that graphitic like planes are formed upon stabilization above 200oC, and thus multistage stabilization is required to optimize synthesis of carbon fibers. Optical Microscopy proved that isothermal stabilization treatment did not severy alter the cross section geometry of PAN fiber monofilaments.

In this study, differences in the kinetics of thermal-supported hydrolytic degradation of poly(lactic acid) (PLA) sample wet spinning fibres due to material variance in the initial molecular and supramolecular structure were analysed. The investigation was carried out at the microstructural and molecular levels by using readily available methods such as scanning electron microscopy, mass erosion measurement and estimation of intrinsic viscosity. The results show a varying degree of influence of the initial structure on the degradation rate of studied PLA fibres. The experiment shows that hydrolytic degradation at a temperature close to the cold crystallization temperature on a macroscopic level is definitely more rapid for the amorphous material, while on a molecular scale it is similar to a semi-crystalline material. Further, for the adopted degradation temperature of 90 °C, a marginal influence of pH of the degradation medium on the degradation kinetics was also demonstrated

The interlaminar strength of mechanically interlocked polymer-metal-interfaces is strongly dependent on the surface structure of the metal component. Therefore, this contribution assesses the suitability of the fractal dimension for quantification of the surface structure as well as interlaminar strength prediction of aluminum/polyamide 6 polymer-metal-hybrids. Seven different surface structures, manufactured by blasting, combined blasting and etching, thermal spraying and laser ablation, are investigated. The experiments are carried out on a novel butt-bonded hollow cylinder testing method that allows shear and tensile strength determination with one specific specimen geometry. The fractal dimension of the metal surfaces is derived from cross-sectional images. For comparison, the surface roughness slope is determined and related to the interlaminar strength. Finally, a fracture analysis is conducted. For the investigated material combination, the experimental results indicate that the fractal dimension is an appropriate measure for predicting the interlaminar strength

Polypropylene (PP) is commonly used in the polymer processing industry. Its feature is a good chemical resistance, it is non-toxic and not harmful to people. Polypropylene is widely used in the manufacturing of food packages, laboratory and medical equipment, electric cables insulators, automotive parts, toys and furniture. The application of this material enables us to obtain complicated shapes of big surfaces. It is also highly recyclable. Polylactide (PLA) is a product of the so called “green chemistry” because it is obtained from the renewable raw materials (biomass). As its price is higher compared to the traditional polymers, its repeated use (recycling) is of high interest. Due to the same reason (cost) the mixtures of PLA with other polymers are applied. In this paper the results of testing the PP/PLA mixtures of various mass ratio of the components are presented. Technical terms of preparing and processing such mixtures have been practically tested. Also the mechanical strength was determined based on the static tensile tests. The results showed that those mixtures can be repeatedly processed. Even five-times reprocessing does not cause essential drop of mechanical properties

Static (SLS) and dynamic (DLS) light scattering techniques are assessed for their capacity to detect colloidal particles with diameters between d = 0.1 and 0.8 µm at very low concentrations in seawater. The detection limit of the apparatus was determined using model monodisperse spherical polystyrene latex particles with diameters 0.2 µm and 0.5 µm. It is shown that the concentration and size of colloids can be determined down to about 10^-6 g/L. Seawater obtained from different locations in western Europe was characterized using light scattering. It was found that seawater filtered through 0.45 µm pore size membrane filters was within the experimental error the same as that of ultrapure Milli-Q water containing the same amount of sea salt and no colloids could be detected with DLS. When the seawater was filtered through 0.8 µm pore size filters, colloidal particles were detected. The measurements show that the concentration of colloids in the seawater samples is not higher than 10^-6 g/L and that they have an average diameter of about 0.6 µm. We stress that these particles are not necessarily nanoplastics.

Atomic force microscopy (AFM) has been extensively used for the nanoscale characterization of polymeric materials. The coupling of AFM with infrared spectroscope (AFM-IR) provides another advantage to the chemical analyses and thus helps to shed light upon the study of polymers. In this perspective paper, we review recent progress in the use of AFM-IR in polymer science. We describe first the principle of AFM-IR and the recent improvements to enhance its resolution. We discuss then the last progress in the use of AFM-IR as a super-resolution correlated scanned-probe IR spectroscopy for chemical characterization of polymer materials dealing with polymer composites, polymer blends, multilayers and biopolymers. To highlight the advantages of AFM-IR, we report here several results in studying crystallization of both miscible and immiscible blends as well as polymer aging. Then, we demonstrate how this novel technique can be used to determine phase separation, spherulitic structure and crystallization mechanisms at the nanoscale, which have never been achieved before. The review also discusses future trends in the use of AFM-IR in polymer materials, especially in polymer thin film investigation.

The objective of this study was to assess the ability of producing laminated edible films manufactured using the following proteins; gelatin (G), whey protein isolate (WPI), and polysaccharide; sodium alginate (SA), and to evaluate their physical properties. Additionally, films’ preparation employing these ingredients was optimized through the addition of corn oil (O), Overall, 8-types of laminated films (G-SA, G-WPI, SA-WPI, SA-G-WPI, GO-SAO, GO-WPIO, SAO-WPIO, SAO-GO-WPIO were developed in this study. The properties of the prepared films were characterized through the measurement of; tensile strength (TS), elongation at break point (EB), puncture resistance (PR), tear strength (TT), water vapour permeability (WVP) and oxygen permeability (OP). The microstructure of cross-sections of laminated films was investigated by scanning electron microscopy (SEM). Mechanical properties of films were dramatically enhanced through the addition of film layers. GO-SAO laminate showed the best barrier properties to water vapour (22.6 ± 4.04 g mm/kPa d m2) and oxygen (18.2 ± 8.70 cm3 mm/kPa d m2). SAO-GO-WPIO laminate film was the strongest of all laminated films tested, having the highest TS of 55.77 MPa, PR of 41.36 N and TT of 27.32 N. SA-G-WPI film possessed the highest elasticity with an EB value of 17.4%.

The effect of the addition of maleated polyethylene (MAPE) to compounds of natural rubber (NR) and Teline monspessulana flour (TMF) previously mercerized was investigated. Two factors were analyzed: A. concentration of MAPE with five levels 2; 4; 6; 8; 10 phr (parts per hundred rubber), B. concentration of TMF with two levels 25 and 40 phr. The effect of MAPE on compatibility between NR and HTM was evaluated by tensile testing the compounds. The mixing was performed in a laboratory scale mill. The test tubes were obtained by cutting or die-cutting crosslinked peroxide sheets, these were obtained during the compression molding process. Analysis indicate that the MAPE coupling agent improved the compatibility between HTM and NR, this effect was evidenced by the values of tensile strength and elongation at break. However, the gel content determination indicates that the addition of 10 phr of MAPE crosslinking decreases due to competition with coupling reaction MAPE - HTM.

This paper addresses investigation of guided-wave excitation by angle-beam wedge piezoelectric transducers in multi-layered composite plate structure with orthotropic symmetry of the material. The aim of the present study is to determine the capability of such actuators to provide the controlled generation of an acoustic wave of a desirable type with the necessary wavelength, propagation distance and directivity. The studied CFRP panel is considered as homogenous with effective elastic moduli and anisotropic structural damping, whose parameters were determined experimentally. According to the results of dispersion analysis and taking into account the data of wave attenuation in a highly damping CFRP composite, the two types of propagating waves A0 and S0 were considered theoretically and experimentally in the frequency range 10 - 100 kHz. Using the results of a previous study, the structure of the wedge actuator was reconstructed to develop its finite element (FE) model, and a modal analysis was carried out, which revealed the most intense natural vibration modes and their eigenfrequencies within the used frequency range. Both experimental and numerical studies of the generation, propagation, directivity and attenuation of waves in the orthotropic composite panel under study revealed the influence of the angular orientation of the actuator on the formation of wave patterns and allowed to determine the capabilities of the wave's directivity control.

This paper considers a new approach to the modeling of the vacuum infusion process at the manufacturing three-dimensional composite parts of complex shape. The developed approach and numerical methods are focused on the reliable prediction with the needed accuracy and elimination the unrecoverable defect of composite structure such as the dry spots. The paper presents some experimental results, which demonstrate two cases of dry spots formation in large aircraft composite panels, and analyses the reasons of these defects arising. Our numerical technique is based on the vacuum infusion of the liquid resin into porous preform as the two phase flow, which is described by the phase field equation coupled with the Richards equation describing the fluid motion in unsaturated soils with spatially varied pressure dependant porosity and saturation. This problem statement allowed to correctly reconstruct the resin front motion and formation of inner and outer dry spots depending on its movement. For the rapid detection of preform zones that are suspicious for defect formation two indicators calculated during process simulation are proposed and tested at the numerical experiments. The auxiliary program tool has been developed in MATLAB environment to correctly detect the times of formation, localization and dimensions of the arising dry spots by using the results of the finite element model simulation.

Vulcanized Rubber, as elastomer, is difficult to recycle. Today, the main end of life routes of tyres and other rubber products are landfilling, incineration in e.g. cement plants, and grinding to a fine powder, with huge quantities lacking sustainable recycling of this valuable material. Devulcanization, i.e. the breaking up of sulfur bonds by chemical, thermo-physical or biological means, is a promising route that has been investigated for more than 50 years. This review article presents and update on the state-of-the art in rubber devulcanization. This review article addresses established devulcanization technologies and novel processes described in the scientific and patent literatures. It is expected that the public discussion of environmental impacts of thermoplastics will soon spill over to thermosets and elastomers. Therefore, the industry needs to develop and market solutions proactively. Tyre recycling through devulcanization has a huge lever, since approx. 30 million tons of tyres are discarded annually.

In this experimental report the biocompatibility of elastomeric scaffold structures made via stereolithography employing table-top 3D printer (Ember, Autodesk) and commercial resin FormLabs Flexible (FormLabs) was studied. The samples were manufactured using standard printing and development protocol, which is known to inherit cytotoxicity due to remaining non-polymerized remaining monomers, despite the polymerized material being fully biocompatible. Additional steps were taken to remedy this problem: the fabricated structures were soaked in isopropanol and methanol for different conditions (temperature, duration) in order to leach out the non-polymerized monomers. Also printed structures were UV exposed to assure maximum polymerization degree of the material. Post-processed structures were seeded with myogenic stem cells and the number of live cells was evaluated as an indicator for the material biocompatibility. The straightforward post-processing protocol enhances the biocompatibility by 7 times after 7 days soaking in isopropanol and methanol and is comparable to control (glass and polystyrene) samples. This proposes the approach as a novel and simple method to be widely applicable for dramatic cytotoxicity reduction of optically 3D printed micro-/nano-scaffolds for biomedical applications.

The interfacial polymerization (IP) of piperazine (PIP) and trimesoyl chloride (TMC) has been extensively utilized to synthesize nanofiltration (NF) membranes. However, it is still a huge challenge to monitor the IP reaction, because of the fast reaction rate and the formed ultra-thin film. Herein, two effective strategies were applied to reduce the IP reaction rate: (1) the introduction of hydrophilic interlayers between the porous substrate and the formed polyamide layer, and (2) the addition of macromolecular additives in the aqueous solution of PIP. As a result, in situ Fourier transform infrared (FT-IR) spectroscopy was firstly used to monitor the IP reaction of PIP/TMC with hydrophilic interlayers or macromolecular additives in the aqueous solution of PIP. Moreover, the formed polyamide layer growth on the substrate was studied in a real-time manner. The in situ FTIR experimental results confirmed that the IP reaction rates were effectively suppressed and that the formed polyamide thickness was reduced from 138 ± 24 nm to 46 ± 2 nm according to TEM observation. Furthermore, an optimized NF membrane with excellent performance was consequently obtained, which included boosted water permeation of about 141–238 (L/m²·h·MPa) and superior salt rejection of Na₂SO₄ > 98.4%.

This paper addresses investigation of guided-wave excitation by angle-beam wedge piezoelectric transducers in multi-layered composite plate structure with orthotropic symmetry of the material. The aim of present study is to determine the capability of such actuators to provide the controlled generation of acoustic wave of desirable type with the necessary wavelength, propagation distance and directivity. The studied CFRP panel is considered as homogenous with effective elastic moduli and anisotropic structural damping, whose parameters were determined experimentally. According to the results of dispersion analysis and taking into account the data of wave attenuation in a highly damping CFRP composite, two types of propagating waves A0 and S0 were considered theoretically and experimentally in the frequency range 10 - 100 kHz. Using the results of a previous study, the structure of the wedge actuator was reconstructed to develop its finite element (FE) model, and a modal analysis was carried out, which revealed the most intense natural vibration modes and their eigenfrequencies within the used frequency range. Both experimental and numerical studies of the generation, propagation, directivity and attenuation of waves in the orthotropic composite panel under study revealed the influence of the angular orientation of the actuator on the formation of wave patterns and allowed to determine the capabilities of the wave's directivity control.

Nowadays, the chemical industry is looking for sustainable chemicals to synthesize nanocomposite bio-based polyurethane foams, PUs, with the aim to replace the conventional petrochemical precursors. Some possibilities to increase the environmental sustainability in the synthesis of nanocomposite PUs include the use of chemicals and additives derived from renewable sources (such as vegetable oils or biomass wastes) which comprise an increasing wider base raw materials. Generally, sustainable PUs exhibit chemico-physical, mechanical and functional properties which are not comparable with those of PUs produced from petrochemical precursors. In order to enhance the performances as well as the bio-based aspect, the addition in the polyurethane formulation of renewable or natural fillers can be considered. Among these, walnut shells and cellulose are very popular wood-based waste and due to their chemical composition, carbohydrate, protein and/or fatty acid, can be used as reactive fillers in the synthesis of PUs, diatomite as natural inorganic nanoporous filler can be also evaluated to improve mechanical and thermal insulation properties of rigid PUs. In this respect, sustainable nanocomposite rigid PU foams are synthesized by using a cardanol-based Mannich polyol, MDI as isocyanate source, catalysts and surfactant to regulate the polymerization and blowing reactions, H2O as sustainable blowing agent and suitable amount (5wt%) of ultramilled walnut shell, cellulose and diatomite as filler. The effect of these fillers on the chemico-physical, morphological, mechanical and functional performances on PU foams has been analyzed.

Here we report highly efficient, indium tin oxide (ITO)-free polymer solar cells (PSCs) with an ultrathin copper (Cu) film(~10 nm) coated with a thin layer of poly[(9,9-bis(3‘-(N,N-dimethylamino)propyl)-2,7-fluorene)-alt-2,7-(9,9-dioctylfluorene)] (PFN) as transparent electrode. Despite of its lower far-field transmittance of the electrode, the obtained ITO-free device based on the ultrathin Cu film can delivery higher absorption efficiency than that of the device based on ITO substrate in the long wavelength region, which can be attributed to the formation of metal resonant microcavity between the opaque back metal mirror (MoO3/Al electrode) and the transparent Cu film with high reflectance. As a result, polymer solar cells based on poly[[2,6'-4,8-di(5-ethylhexylthienyl)benzo[1,2-b;3,3-b]dithiophene][3-fluoro-2[(2-ethylhexyl)carbonyl]thieno[3,4-b]thiophenediyl]] (PTB7-Th) and [6,6]-phenyl C71-butyric acid methyl ester (PC71BM) blend show a high power conversion efficiency (PCE) of 8.21 %, comparable to that of the control device based on ITO electrode (with a PCE of 9.60% ). The results demonstrate that thermally evaporated Cu thin film electrode can be promising candidate to replace ITO for highly efficient PSCs, thus may open up the possibility for massive production of PSCs with low cost.

The interfacial polymerization (IP) of piperazine (PIP) and trimesoyl chloride (TMC) has been extensively utilized to synthesize the nanofiltration (NF) membrane. However, it is still a huge challenge to monitor the IP reaction, because of the fast reaction rate and the formed ultra-thin film. Herein, two effective strategies are applied to reduce the IP reaction rate: (1) the introduction of hydrophilic interlayers between the porous substrate and the formed polyamide layer; (2) the addition of macromolecular additives in the aqueous solution of PIP. As a result, in-situ FT-IR spectroscopy was firstly used to monitor the IP reaction of PIP/TMC reaction system, with hydrophilic interlayers or macromolecular additives. Moreover, we study the formed polyamide layer growth on the substrate, in a real-time manner. The in-situ FT-IR experimental results confirm that the IP reaction rates are effectively suppressed and the formed polyamide thickness reduces from 138±24 nm to 46±2 nm. Furthermore, the optimized NF membrane with excellent performance are consequently obtained, which include the boosted water permeation flux about 141~238 (L·m2·h/MPa) and superior salt rejection of Na2SO4 > 98.4%.

The interfacial polymerization (IP) of piperazine (PIP) and trimesoyl chloride (TMC) has been extensively utilized to synthesize the nanofiltration (NF) membrane. However, it is still a huge challenge to monitor the IP reaction, because of the fast reaction rate and the formed ultra-thin film. Herein, two effective strategies are applied to reduce the IP reaction rate: (1) the introduction of hydrophilic interlayers between the porous substrate and the formed polyamide layer; (2) the addition of macromolecular additives in the aqueous solution of PIP. As a result, in-situ FT-IR spectroscopy was firstly used to monitor the IP reaction of PIP/TMC reaction system, with hydrophilic interlayers or macromolecular additives. Moreover, we study the formed polyamide layer growth on the substrate, in a real-time manner. The in-situ FT-IR experimental results confirm that the IP reaction rates are effectively suppressed and the formed polyamide thickness reduces from 138±24 nm to 46±2 nm. Furthermore, the optimized NF membrane with excellent performance are consequently obtained, which include the boosted water permeation flux about 141~238 (L·m2·h/MPa) and superior salt rejection of Na2SO4 > 98.4%.

The aim of this study is to provide a detailed strategy for Safe-by-Design (SbD) 3D printed lab-on-a-chip (LOC) device manufacturing, using Fused Filament Fabrication (FFF) technology. At first, the applicability of FFF in lab-on-a-chip device development is briefly discussed. Subsequently, a methodology to categorize, identify and implement SbD measures for FFF is suggested. Furthermore, the most crucial health risks involved in FFF processes are examined, placing the focus on the examination of ultrafine particle (UFP) and Volatile Organic Compound (VOC) emission hazards. Thus, a SbD scheme for lab-on-a-chip manufacturing is provided, while also taking into account process optimization for obtaining satisfactory printed LOC quality. This work can serve as a guideline for the effective application of FFF technology for lab-on-a-chip manufacturing through the safest applicable way, towards a continuous effort to support sustainable development of lab-on-a-chip devices through cost-effective means.

Clean use of photons from light to activate chemical reactions offer many possibilities in different fields, from chemistry and biology to materials science and medicine. This review article describes the advances carried out in last decades toward the phototriggered synthesis of single-chain polymer nanoparticles (SCNPs) as soft nanomaterials with promising applications in enzyme-mimicking catalysis and nanomedicine, among other different uses. First, we summarize different strategies developed to synthesize SCNPs based on photoactivated intrachain homocoupling, phototriggered intrachain heterocoupling and photogenerated collapse induced by external cross-linker. Next, we comprehensively review the emergent topic of photoactivated multifolding applied to SCNP construction. Finally, we conclude by summarizing recent strategies towards phototriggered disassembly of SCNPs.

This work addresses the role of charge regulation (CR) and the associated fluctuations in the conformational and mechanical properties of weak polyelectrolytes. Due to CR, changes in the pH-value modifies the average macromolecular charge and conformational equilibria. A second effect is that, for a given average charge per site, fluctuations can alter the intensity of the interactions by means of correlation between binding sites. We investigate both effects by means of Monte Carlo simulations at constant pH-value, so that the charge is a fluctuating quantity. Once the average charge per site is available, we turn off the fluctuations by assigning the same average charge to every site. A constant charge MC simulation is then performed. We make use of a model which accounts for the main fundamental aspects of a linear flexible polyelectrolyte i.e. proton binding, angle internal rotation, bond stretching and bending. Steric excluded volume and differentiated treatment for short-range and long-range interactions are also included in the model. It can be regarded as a kind of "minimal'' model in the sense that contains a minimum number of parameters but still preserving the atomistic detail. It is shown that, if fluctuations are activated, gauche state bond probabilities increase, and the persistence length decreases, so that the polymer becomes more folded. Macromolecular stretching is also analyzed in presence of CR (the charge depends on the applied force) and without CR (the charge is fixed to the value at zero force). The analysis of the low force scaling behavior concludes that Pincus exponent becomes pH-dependent. Both with and without CR, a transition from 1/2 at high pH-values (phantom chain) to 3/5 to low pH-values (Pincus regime), is observed. Finally, the intermediate force stretching regime is investigated. It is found that CR induces a moderate influence in the force-extension curves and persistence length (which in this force regime becomes force-dependent). It is thus concluded that the effect of CR on the stretching curves is mainly due to changes in the average charge at zero force. It is also found that, for the cases studied, the effect of steric excluded volume is almost irrelevant compared to electrostatic interactions.

Membranes based on sulfonated synditoactic polystyrene were thoroughly characterized by contrast variation SANS over a wide Q-range in dry and hydrated states. The film samples were prepared by solid-state sulfonation that allowed a uniform sulfonation of only the amorphous phase while preserving the crystallinity of the membrane. The samples were loaded with different guest molecules in either the amorphous (fullerenes) or the crystalline (toluene) regions, in order to vary the neutron contrast or to reproduce the conditions enabling an increased resistance of the membranes to chemical decomposition. The use of uni-axially deformed film samples and contrast variation with different H2O/D2O mixtures allowed for the identification and characterization of different structural levels with sizes between nm and μm, which form and evolve in the membrane morphology in dry and hydrated states and produce scattering features on different detection sectors and at different detection distances after the sample, depending on their size and orientation.

One-dimensional shape memory polymer fibers (SMPFs) have obvious advantages in mechanical properties, dispersion properties and weavability. In this work, a method for fabricating semi-crystallization ethylene-vinyl acetate copolymer (EVA) fiber with two-way shape memory effect by melt spinning and ultraviolet (UV) curing was developed. Here, the effect of crosslink density on its performance was systematically analyzed by gel fraction measurement, tensile tests, DSC and TMA analysis. The results showed that the crosslink density and shape memory properties of EVA fiber could be facilely adjusted by controlling UV curing time. The resulting EVA fiber with cylindrical structure had a diameter of 247.13 ± 10.07 μm, and its mechanical strength and elongation at break were 64.46 MPa and 114.33%, respectively. The critical impact of the crosslink density and applied constant stress on the two-way shape memory effect were analyzed. Moreover, the single EVA fiber could lift more than 143 times its own weight and achieve 9% reversible actuation strain. The reversible actuation capability was significantly enhanced by a simple winding design of the single EVA fiber, which provided great potential applications in smart textiles, flexible actuators and artificial muscles.

The paper is aimed to develop an improved acoustic-based Structural Health Monitoring (SHM) and Non-Destructive Evaluation (NDE) techniques, which provide the waves directivity emitting by the angle-beam wedge actuators in the thin-walled structures made of plastic materials and polymeric composites. Our investigation includes the dispersive analysis of the waves that can be excited in the studied plastic panel. Its results allowed to find two kinds of the generated acoustic waves - anti-symmetric Lamb waves A0 and shear horizontally polarized SH waves SS0. The bounds of the chosen frequency range for the experimental and numerical studies were accepted as a compromise between the desire to obtain high defects resolution by generating short waves, their adjustable directivity and maximum propagation length. The finite element model for the transducer was built by using the results of actuator structure experimental study. The frequency response functions for the actuator current and oscillation amplitude of the footprint surface demonstrated good agreement. The found eigenfrequencies of actuator's structure were used for the numerical and experimental study of the Lamb and SH wave generation and propagation in a thin-walled plastic panel. Our results convincingly demonstrated the satisfactory directivity of the actuated waves at their excitation on the frequencies that corresponded to the natural modes of the actuator oscillation. The authors assume that an efficient use of the proposed technique for other analyzed quasi-isotropic materials and applied actuators can be provided by a preliminary research using the similar approach and methods presented in this article.

Hierarchical honeycomb patterns were manufactured with the breath-figures self-assembly by drop-casting on the silicone-oil lubricated glass substrates. Silicone oil promoted spreading of the polymer solutions. The process was carried out with the industrial grade polystyrene and polystyrene with the molecular weight Mw=35.000. Both of polymers gave rise to the patterns, built from micro- and nano-scaled pores. Ordering of the pores was quantified with the Voronoi tessellations and calculating the Voronoi entropy. Measurement of the apparent contact angles evidenced the Cassie - Baxter wetting regime of the porous films.

Homogeneous water dispersions of MWCNTs were prepared by ultrasonication in the presence of an amphiphilic polystyrene-block-poly(acrylic acid) (PS-b-PAA) copolymer. The ability of PS-b-PAA to disperse and stabilize MWCTNs was investigated by UV-vis, SEM and zeta potential. It is shown that the copolymer can disperse nanotubes directly by sonication in water. The results show that the addition of a styrene block to PAA enhances the dispersion efficiency compared to pure PAA, possibly due to the nanotube affinity with the polystyrene moiety. Notably, the dispersions show an evident pH-responsive behavior, being MWCNTs reaggregation promoted in basic environment. Furthermore, composites obtained by drop casting display electrical conductivity responsive to pH variations, showing the potential of such materials for sensing applications.

As a special class of “green” elastomers, thermoplastic vulcanizates (TPVs) have been widely used in industries due to the combination of the excellent resilience of conventional elastomers and the easy recyclability of thermoplastics. Here, the morphology evolution of TPVs based on polyamide 6/ethylene-propylene-diene rubber (PA6/EPDM) blends was investigated by varying the content of the curing agent, phenolic resin (PF). With the incorporation of 6 wt% PF, the gel content of the EPDM phase reaches a high value of 49.6wt% and a typical sea-island structure is formed with EPDM domain in a micro-nano size. The dynamic rheology behaviors of TPVs showed that with the curing degree of EPDM phase increasing, a denser network of EPDM particles is formed in PA6 matrix. Also, a lower crystal degree and crystal peak temperature are observed, indicating that the presence of a growth restriction of PA6 crystal plate induced by a thinner plastic layer between the adjacent EPDM particles. However, the crystal form of PA6 is not changed with the increasing curing degree of the EPDM phase. This study provides an effective strategy to realize a new kind of TPVs, which can be easily introduced into industrial applications.

In this paper, we synthesized MC(BeA-co-MMA) copolymer microcapsules through suspension polymerization. The pendent n-behenyl group of BeA is highly crystalline, and it acts as the side-chain in the structure of BeA-co-MMA copolymer. The highly crystalline n-behenyl side-chain provides BeA-co-MMA copolymer thermal-energy-storage capacity. In order to investigate the correlation between thermal properties and crystal structure of BeA-co-MMA copolymer, the effects of monomer ratio, temperature changing and changing rate, as well as synthesis method were discussed. The monomer ratio influenced crystal transition behavior and thermal properties greatly. The DSC results proved that when the monomer ratio of BeA and MMA was 3:1, MC(BeA-co-MMA)3 showed the highest average phase change enthalpy ΔH (105.1 J·g–1). It indicated that the n-behenyl side-chain formed relatively perfect crystal region, which ensured a high energy storage capacity of copolymer. All the DSC and SAXS results proved that the amount of BeA had a strong effect on the thermal-energy-storage capacity of copolymer and the long spacing of crystals, but barely on the crystal lamella. It was found that MMA units worked like defects in the n-behenyl side-chain crystal structure of BeA-co-MMA copolymer. Therefore, a lower fraction of MMA, that is, a higher fraction of BeA contributed to a higher crystallinity of BeA-co-MMA copolymer for providing a better energy storage capacity and thermoregulation property. ST(BeA-co-MMA) copolymer sheets with the same ingredients as microcapsules were also prepared through light-induced polymerization aiming at clarifying the effect of synthesis method. The results proved that synthesis method mainly influenced the copolymer chemical component, but lightly on the crystal packing of n-behenyl side-chain.

The influence of lignin modification on drug release and pH-dependent releasing behaviour of oral solid dosage form was investigated using three different formulations. The first formulation contains microcrystalline cellulose (MCC101) as excipient and paracetamol as active pharmaceutical ingredient (API). The second formulation includes Alcell lignin and MCC 101 as excipient and paracetamol, and the third formulation consists of carboxylated Alcell lignin, MCC 101 and paracetamol. Direct compaction was carried out in order to prepare the tablets. Lignin can be readily chemically modified due to the existence of different functional groups in its structure. The focus of this investigation is on lignin carboxylation and its influence on paracetamol control release behaviour at varying pH. Results suggest that carboxylated lignin tablets had the highest drug release, which is linked to their faster disintegration and lower tablet hardness.

A multiscale modelling approach was developed in order to estimate the effect of defects on the strength of unidirectional carbon fiber composites. The work encompasses a micromechanics approach, where the known reinforcement and matrix properties are experimentally verified and a 3D finite element model is meshed directly from micrographs. Boundary conditions for loading the micromechanical model are derived from macroscale finite element simulations of the component in question. Using a microscale model based on the actual microstructure, material parameters and load case allows realistic estimation of the effect of a defect. The modelling approach was tested with a unidirectional carbon fiber composite beam, from which the micromechanical model was created and experimentally validated. The effect of porosity was simulated using a resin-rich area in the microstructure and the results were compared to experimental work on samples containing pores.

Current paper investigates the influence of hardware setup and parameters of a 3D printing process based on fused filament fabrication (FFF) technology on resulting sample strength. Three-point bending of samples printed with long side oriented along Z axis was used as a measure of the interlayer bonding strength. The same CAD model was converted into NC-programs through same slicing software to be run on four different desktop FFF 3D printers, out of filament of same brand and color. Within all the printers same ranges of layer thickness values from 0.1 to 0.3 mm and feed rates from 25 to 75 mm/s were planned to be varied. All the machines demonstrated statistically almost identical values of maximum flexural strength, however the different machines exhibited maximum sample strength with different combinations of varied parameters. Among all the hardware factors observed, the most important was proved to be extruder type, direct or Bowden. This feature fundamentally changes the nature of studied parameters influence onto the resulting strength of the FFF process. For the extruders of Bowden type the length of flexible guiding tube is of great importance.All the machines demonstrated statistically almost identical values of maximum flexural strength, however the different machines exhibited maximum sample strength with different combinations of varied parameters. Among all the hardware factors observed, the most important was proved to be extruder type, direct or Bowden. This feature fundamentally changes the nature of studied parameters influence onto the resulting strength of the FFF process. For the extruders of Bowden type the length of flexible guiding tube is of great importance.

Butyl rubber-based composite (BRC) is one of the most popular materials for the fabrication of protective glove against chemical and mechanical risks. However, in many working places such as metal manufacturing or automotive mechanical services, its mechanical hazards usually appear together with metalworking fluids (MWFs). The presence of these contaminants, particularly at high temperature, could modify its properties due to the scission, the plasticization, the crosslinking of polymer network and thus led to severe modification of mechanical and physicochemical properties of material. This work aims to determine the effect of temperature and a metalworking fluid on mechanical behavior of butyl rubber composite dealing with crosslinking density, cohesion forces and elastic constant of BRC on the based on Mooney-Rivlin’s theory. The effect of temperature with and without MWFs on thermo dynamical properties and morphology of butyl membranes is also investigated. The prediction of service lifetime is then evaluated from extrapolation of Arrhenius plot at different temperatures.

The way in which a perforated structure is formed has attracted much interest in the porous membrane research community. This novel structure gives materials an excellent antifouling property as well as a low operating pressure and other benefits. Unfortunately, the current membrane fabrication methods usually involve multi-step processes and the use of organic solvents or additives. Our study is the first to offer a way to prepare perforated membrane by using a physical foaming technique with CO₂ as the blowing agent. We selected thermoplastic polyurethane (TPU) as the base material because it is a biocompatible elastomer with excellent tensility, high abrasion resistance, and good elastic resilience. Various processing parameters, which included the saturation pressure, the foaming temperature, and the membrane thickness, were applied to adjust the TPU membrane’s perforated morphology. We proposed a possible formation mechanism of the perforated membrane. The as-prepared TPU membrane had good mechanical properties with a tensile strength of about 5 MPa and an elongation at break above 100%. Such mechanical properties make this novel membrane usable as a self-standing filter device. In addition, its straight-through channel structure can separate particles and meet different separation requirements.

Additive manufacturing (AM) is an attractive technology for manufacturing industry due to flexibility in design and functionality, but inconsistency in quality is one of the major limitations that does not allow utilizing this technology for production of end-use parts. Prediction of mechanical properties can be one of the possible ways to improve the repeatability of the results. The part placement, part orientation, and STL model properties (number of mesh triangles, surface, and volume) are used to predict tensile modulus, nominal stress and elongation at break for polyamide 2200 (also known as PA12). EOS P395 polymer powder bed fusion system was used to fabricate 217 specimens in two identical builds (434 specimens in total). Prediction is performed for XYZ, XZY, ZYX, and Angle orientations separately, and all orientations together. The different non-linear models based on machine learning methods have higher prediction accuracy compared with linear regression models. Linear regression models have prediction accuracy higher than 80% only for Tensile Modulus and Elongation at break in Angle orientation. Since orientation-based modeling has low prediction accuracy due to a small number of data points and lack of information about material properties, these models need to be improved in the future based on additional experimental work.

Polydimethylsiloxane with hydroxy groups was functionalized to form functionalized polydimethylsiloxane, which subsequently underwent an addition reaction with isophorone diisocyanate to form the prepolymer. Next, 3-aminopropyltriethoxysilane (APTS) reacted with 3-glycidoxypropyltrimethoxysilane (GPTS) to produce bridged polysilsesquioxanes, and the sol–gel technology was employed to form hyperbranched polysiloxane nanoparticles with hydroxy groups, which was used as the additive. The hyperbranched polysiloxane and the prepolymer containing NCO functional groups then underwent an addition reaction to produce the hybrid materials. Fourier-transform infrared spectroscopy and 29Si nuclear magnetic resonance were used to characterize the structure of the polyurethane hybrid. Regarding thermal stability, after the hyperbranched polysiloxane nanoparticles was introduced, the integral procedural decomposition temperature increased from 348 ºC for polyurethane matrix to 859 ºC for the hybrid material. The results revealed that the thermal stability of the hybrid material substantially increased by approximately 247%.

This study analyzed the structural changes of semicrystalline polylactide (PLA) in the form of spun-bonded mulching nonwoven, during outdoor composting. The investigation was carried out at the microstructural, supramolecular and molecular levels using scanning electron microscopy (SEM), wide-angle X-ray diffraction (WAXD) and the viscosity method, respectively. The results showed the varying degree of influence of the climatic condition, prepared compost mixtures and time on the molecular, supramolecular and micromorphological structure of PLA spun-bonded mulching nonwoven and its degradation rate. The obtained experimental results revealed how the popular outdoor composting method, realized under two different European climatic conditions (in Poland and in Bulgary), affects the degradation of PLA nonwoven, designed for agriculture use.

The effects of carbon fiber hybridisation on the thermal properties of woven kenaf reinforced epoxy composites kenaf fibre were studied. Woven kenaf hybrid composites at the different weave designs of plain and satin, and fabric count of 5 × 5 and 6 × 6 were manually prepared by vacuum infusion technique. Thermal properties of pure carbon fibre and hybrid composites were conducted by using thermogravimetric analyser (TGA) and differential scanning calorimeter (DSC). It was found that at high kenaf fibre content showed better thermal stability while the highest thermally stable was found in pure carbon fibre composite. The TG and DTG results showed that the amount of residue decreased in plain-designed hybrid composite compared to satin-designed hybrid composite. The DSC data revealed that the presence of woven kenaf increase decomposition temperature.

Vitrimers are covalent network materials, comparable in structure to classical thermosets. Unlike normal thermosets, they possess a chemical bond swap mechanism that makes their structure dynamic and suitable for activated welding and even autonomous self-healing. The central question in designing such materials is the trade-off between autonomy and material stability: The swap mechanism facilitates the healing but it also facilitates creep, which makes the perfectly stable self-healing solid a hard goal to reach. Here, we address this question for the case of self-healing vitrimers made from star polymers. Using coarse-grained molecular dynamics simulations, we study the adhesion of two vitrimer samples and find that they bond together on timescales that are much shorter than the stress relaxation time. We show that the swap mechanism allows the star polymers to diffuse through the material through coordinated swap events, but the healing process is much faster and does not depend on this mobility.

This review is focused on current state-of-the-art research on electroactive-based materials and their synthesis, as well as their physicochemical and biological properties. Special attention is paid to pristine intrinsically conducting polymers (ICPs) and their composites with other organic and inorganic components, well-defined micro- and nanostructures, and enhanced surface areas compared with those of conventionally prepared ICPs. Hydrogels, due to their defined porous structures and being filled with aqueous solution, offer the ability to increase the amount of immobilized chemical, biological or biochemical molecules. When other components are incorporated into ICPs, the materials form composites; in this particular case, they form conductive composites. The design and synthesis of conductive composites result in the inheritance of the advantages of each component and offer new features because of the synergistic effects between the components. The resulting structures of ICPs, conducting polymer hydrogels and their composites, as well as the unusual physicochemical properties, biocompatibility and multi-functionality of these materials, facilitate their bioapplications. The synergistic effects between constituents have made these materials particularly attractive as sensing elements for biological agents, and they also enable the immobilization of bioreceptors such as enzymes, antigen–antibodies, and nucleic acids onto their surfaces for the detection of an array of biological agents. Currently, these materials have unlimited applicability in biomedicine. In this review, we have limited discussion to three areas in which it seems that the use of ICPs and materials, including their different forms, are particularly interesting, namely, biosensors, delivery of drugs and tissue engineering.

The preparation and thermal properties of polypropylene foils, filled with ceramic microparticles, talc or boron nitride, are described. A slow, linear increase of thermal conductivity with volume percent of filler up to 30 vol % is detected. Reduction of the foil thickness bellow 200 micrometers leads to a significant increase of thermal conductivity. Specific thermal capacities of foils are temperature dependent, they decrease with filler incorporation.

Polypropylene (PP) foam has a great deal of application since it normally exhibits non-uniform cell size distribution, low cell density, and cracked cells. In this study, a small amount of fluoroelastomer (FKM) was used as a nucleating agent to prepare well-defined microporous PP foam by supercritical CO₂. It was observed that solid FKM was present as the nanoscale independent phase in PP matrix and the FKM could induce a mass of CO₂ aggregation, which significantly enhanced the diffusion rate of CO₂ in PP. The resultant PP/FKM foams exhibited much smaller cell size (～24 μm), and more than 16 times cell density (3.2×10⁸ cells/cm³) as well as a much more uniform cell size distribution than that of the neat PP foam. PP/FKM foams possessed major concurrent enhancement in their tensile stress and compressive stress compared to neat PP foam. We believed that the added FKM played a key role in enhancing the heterogeneous nucleation, combined with the local strain field variation in the multiple-phase system, which was responsible for the considerably improved cell morphology of PP foaming. This paper provides a deep understanding of the scCO₂ foaming behavior of PP in the presence of FKM.

Synergistic effect of different fillers is widely utilized in polymer technology. The combination of various types of fillers is used to improve various properties of polymer composites. In this paper a synergistic effect of flame retardants was tested for the improvement of ceramizable composites performance. The composites were based of styrene-butadiene rubber (SBR) used as polymer matrix. Three different types of flame retardants were tested for synergistic effect: Mica (phlogopite) high aspect-ratio platelets along with low softening point temperature glass frit (featuring ceramization effect) and melamine cyanurate, a commonly used flame retardant promoting carbonaceous char. In order to characterize the properties of the composites, combustibility, viscoelastic properties and mechanical properties before and after ceramization were tested. The results obtained show that the synergistic effect of ceramization promoting fillers and melamine cyanurate is especially visible with respect to the flame retardant properties resulting in a significant improvement of fire resistance of the composites.

Two region asymmetric polymers PR2F and PR1F with three repeat units of A-D-A, π-D-A, and π-D-π along the polymer backbone were attained by polymerizing different fluorinated benzothiadiazole-thiophene units, FBT-T and 2FBT-T units (A–π), with benzodithiophene unit (D), respectively. Here, the new region asymmetric polymers were in contrast to the traditional polymers featuring a D–A or D–π–A–π backbone. Both the region asymmetric polymers showed a low lying of HOMO energy level in relation to that of the PC61BM acceptor and then obtained the high open-circuit voltage of ~1 V in both PR2F and PR1F devices. Bulk-heterojunction devices based on PR2F with difluorinated BT exhibited an appreciable power conversion efficiency (PCE) of 4.73% due to the relatively high and balanced charge carrier mobilities, while the mono-fluorinated BT polymer PR1F-based devices gave a lower PCE of 2.92%. These results indicate that the region asymmetric conjugated polymer is a promising class of materials for polymer solar cell applications, and it is significant to further understand the influence of polymer structure on optoelectronic properties.

Dynamic mechanical analysis (DMA) is a versatile technique that complements the information given by the more traditional thermal analysis techniques such as differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), and thermal mechanical analysis (TMA). Dynamic constants such as storage modulus, loss modulus, and loss factor are temperature dependent and provide information about interfacial bonding between reinforced fibre and polymer matrix of composite material. To study the above mentioned properties at the glass transition region, for unidirectional fibrous composites reinforced with continuous fibers a reliable model was applied. In particular, the composite material was considered as composed of three phases with the intermediate phase between matrix and fibres, the interphase, to have variable properties depending on those of main phases and the mode of preparation of the overall material. The glass transition temperature is defined as the point at which the specific volume versus temperature curve changes abruptly slope marking the region between rubbery polymer and glassy polymer nature. Hence, the behaviour of unidirectional fibrous composites was investigated at this region. Examination of the glass transition temperature, which constitutes an upper limit for the structurally important glassy region through the loss factor, was performed by its consideration as a combination of glass transition temperature of matrix and interphase.

Polymers in highly confined geometries can display complex morphologies including ordered phases. A basic component of a theoretical analysis of their phase behavior in confined geometries is the knowledge of the number of possible single-chain conformations compatible with the geometrical restrictions and the established crystalline morphology. While the statistical properties of unrestricted self-avoiding random walks (SAWs) both on and off-lattice are very well known, the same is not true for SAWs in confined geometries. The purpose of this contribution is a) to enumerate the number of SAWs on the simple cubic (SC) and face-centered cubic (FCC) lattices under confinement for moderate SAW lengths, and b) to obtain an approximate expression for their behavior as a function of chain length, type of lattice, and degree of confinement. This information is an essential requirement for the understanding and prediction of entropy-driven phase transitions of model polymer chains under confinement. In addition, a simple geometric argument is presented that explains, to first order, the dependence of the number of restricted SAWs on the type of SAW origin.

We quantitatively investigated the statistical behaviors of semiflexible polymer chains, which are simultaneously subjected to force stretching and rectangular tube confinement. Based on the wormlike chain model and Odijk deflection theory, we derived a new deflection length, by which new compact formulas are obtained for the confinement free energy and force-confinement-extension relation. These newly derived formulas have been justified by numerical solutions of an eigenvalue problem associated with the Fokker-Planck governing equation and extensive Brownian dynamics simulations based on the so-called Generalized Bead-Rod (GBR) model. We found that, comparing to the classical deflection theory, these new formulas are valid for a much extended range of the confinement-size /persistence-length ratio, and have no adjustable fitting parameters for sufficient long semiflexible chains in the whole deflection regime.

Electrically conductive polymer composites are in high demand for modern technologies, however, the intrinsic brittleness of conducting conjugated polymers and the moderate electrical conductivity of engineering polymer/carbon composites have highly constrained their applications. In this work, super high electrical conductive polymer composites were produced by a novel hot embossing design. The polydimethylsiloxane (PDMS) composites containing short carbon fiber (SCF) exhibited an electrical percolation threshold at 0.45 wt%, and reached a saturated electrical conductivity of 49 S/m at 8 wt% of SCF. When reduced the sample thickness from 1.0 mm to 0.1 mm by the hot embossing process, a compression-induced percolation threshold occurred at 0.3 wt%, while the electrical conductivity was further enhanced to 378 S/m at 8 wt% SCF. Furthermore, the additional of a second nanofiller of 1 wt%, such as carbon nanotube or conducting carbon black further increased the electrical conductivity of the PDMS/SCF (8 wt%) composites to 909 S/m and 657 S/m, respectively. The synergy of the densified conducting filler network by the mechanical compression and the hierarchical micro-/nanoscale filler approach has realize super high electrical conductive yet mechanical flexible polymer composites for modern flexible electronics applications.

Three kinds of hydrophobic groups grafted starches of maleic anhydride grafted starch (MAH-g-starch), lactic acid grafted starch (LA-g-starch), and methyl acrylate grafted starch (MA-g-starch) were prepared by in-situ solid phase polymerization. The results of Fourier transform infrared spectroscopy (FT-IR) and X-ray photoelectron spectroscopy (XPS) were confirmed successful grafting. The grafting ratios of MAH-g-starch, LA-g-starch and MA-g-starch were 6.50%, 12.45%, and 0.57%, respectively. Influenced by the grafting ratio, LA-g-starch had the best hydrophobic properties and the largest molecular weight, and those for MA-g-starch was the worst. The surfaces of grafted starches were covered with graft polymer, with obvious surface roughness and bond degree of MAH-g-starch and LA-g-starch. The crystalline structure of grafted starches showed some damage, with LA-g-starch exhibiting the greatest decrease in crystallinity, and less of a change for MA-g-starch. Overall, the grafting reaction improved thermoplasticity, with LA-g-starch the most improved, followed by MAH-g-starch, and then MA-g-starch.

Evaluating new, promising organic molecules to make next-generation organic optoelectronic devices necessitates the evaluation of charge carrier transport performance through the semi-conducting medium. In this work, we utilize quantum chemical calculations (QCC) and kinetic Monte Carlo (KMC) simulations to predict the zero-field hole mobilities of ~100 morphologies of the benchmark polymer poly(3-hexylthiophene), with varying simulation volume, structural order, and chain-length polydispersity. Morphologies with monodisperse chains were generated previously using an optimized molecular dynamics force-field and represent a spectrum of nanostructured order. We discover that a combined consideration of backbone clustering and system-wide disorder arising from side-chain conformations are correlated with hole mobility. Furthermore, we show that strongly interconnected thiophene backbones are required for efficient charge transport. This definitively shows the role "tie-chains" play in enabling mobile charges in P3HT. By marrying QCC and KMC over multiple length- and time-scales, we demonstrate that it is now possible to routinely probe the relationship between molecular nanostructure and device performance.

In this work, nylon 6/ P(N-phenylmaleimide-alt-styrene) blends were prepared by melt blending, and the mechanical, heat-resistant, crystallographic and dynamical mechanical properties of nylon 6/ P(N-phenylmaleimide-alt-styrene) blends with different contents were investigated and analyzed. The results showed that the mechanical properties decreased with increasing PNS, while the heat deflection temperature (HDT), relative crystallinity (Xn), and storage modulus (G’) increased with increasing PNS. The results of differential Scanning Calorimetry (DSC) proved the PNS played the positive role of nucleating PA6. And the results of dynamic mechanical analysis (DMA) proved the PNS could improve the rigidity of PA6/PNS blends. From the SEM, these PNS domains were between 0.2 and 4 μm in diameter. The experimental results indicated that the addition of PNS improved the rigidity of PA6/PNS blends, and then improved the heat-resistant property.

High density polyethylene (HDPE) and poly(lactic) acid (PLA) blends with different ratios of both polymers, namely 30:70, 50:50 and 70:30, were produced. Polyethylene grafted maleic anhydride and a random copolymer of ethylene and glycidyl methacrylate, were also proposed as compatibilizers to modify HDPE-PLA optimal blends and were added in the amounts of 1, 3 and 5 wt.%. Blends properties have been evaluated through different aspects by performing tensile tests, scanning electron microscopy to analyze blend morphology and interfaces, and thermomechanical analysis through differential scanning calorimetry, thermo-gravimetric analyses and infrared spectroscopy. The second blend, the one with equal amounts of HDPE and PLA seems to represent a good balance between high amount of bio-derived charge and acceptable mechanical properties. This suggests a good potential of these blends, which would be a good starting point for the production of composites with lingo-cellulosic fillers.

The article describes the study of the properties of polytetrafluoroethylene, modified using natural layered silicates—serpentinite. It is shown that the introduction of a small amount of layered silicates significantly increases the tribological characteristics of the material. The additional introduction of magnesium nano-spinels facilitated the formation of an intercalated polymer-silicate nanocomposite.

Fibre-reinforced composite structures under complex loads exhibit gradual damage behaviour with a degradation of effective mechanical properties and change of their structural dynamic behaviour. Damage manifests itself as spatial increase of inter-fibre failure and delamination-growth, resulting in local changes of stiffness. These changes affect not only the residual strengths but more importantly the structural dynamic behaviour. In case of composite rotors, this can lead to catastrophic failure if an eigenfrequency coincides with the rotational speed. The description and analysis of the gradual damage behaviour of composite rotors therefore provides the fundamentals for a better understanding of unpredicted structural phenomena. The gradual damage behaviour on the example of composite rotors and the resulting damage-dependent dynamic behaviour is experimentally investigated under propagating damage for combined out-of-plane and in-plane loads. A novel observation is reported, where monotonic increase of damage results in non-monotonic frequency shift of significant amount of eigenfrequencies.

Structural vibration induced by dynamic load or natural vibration is a nonnegligible factor in failure analysis. Based on vibrating boundary condition, impact resistance of shape memory alloy reinforced composites is investigated. In this investigation, modified Hashin’s failure criterion, Brinson’s model and visco-hyperelastic model are implemented into the numerical model to charactering the mechanical behavior of glass fiber/epoxy resin laminates, SMAs and interphase, respectively. First, fixed boundary condition is maintained in simulation to verify the accuracy of material parameters and procedures by comparing with experimental data. Then, a series of vibrating boundaries with different frequencies and amplitudes are applied during the simulation process to reveals the effect on impact resistances. The statistics of absorbed energy and contact force indicate that impact resistance of the composite under high frequency and large amplitude is lower than that under low frequency and small amplitude, and summarized by a mathematical expression.

We develop an optimized force-field for poly(3-hexylthiophene) (P3HT) and demonstrate its utility for predicting thermodynamic self-assembly. In particular, we consider short oligomer chains, model electrostatics and solvent implicitly, and coarsely model solvent evaporation. We quantify the performance of our model to determine what the optimal system sizes are for exploring self-assembly at combinations of state variables. We perform molecular dynamics simulations to predict the self-assembly of P3HT at ~350 combinations of temperature and solvent quality. Our structural calculations predict that the highest degrees of order are obtained with good solvents just below the melting temperature. We find our model produces the most accurate structural predictions to date, as measured by agreement with grazing incident X-ray scattering experiments.

Hybrid woven kenaf-carbon composite were fabricated in this study using epoxy resin as matrix. Effects of different fabric material namely weave designs (plain and satin) and fabric counts (5×5 and 6×6) on the properties of laminated woven kenaf polymer composite were evaluated. This study evaluates the mechanical and morphological properties of hybrid fabric kenaf-carbon from kenaf yarn of 500tex. Kenaf and carbon fabrics were used in this work, where vacuum infusion technique was selected to prepare the composite and epoxy resin was used as a matrix. The fibre weight content is 30% and four specimens were prepared for each samples and tested for their tensile, flexural, and impact strengths. The morphological properties of composites were analysed through the scanning electron microscope (SEM). The results revealed that plain woven fabric is favourable in terms of tensile and impact strengths compared to satin woven fabric. Meanwhile, 5×5 of fabric count gives better flexural modulus than composite fabricated with 6×6 fabric count. The morphologies of the fractured surface investigated by SEM demonstrated better adhesion properties and less fibre pull-out on plain woven fabric.

Polymers in highly confined geometries can display complex morphologies including ordered phases. A basic component of a theoretical analysis of their phase behavior in confined geometries is the knowledge of the number of possible single-chain conformations compatible with the geometrical restrictions and the established crystalline morphology. While the statistical properties of unrestricted self-avoiding random walks (SAWs) both on and off-lattice are very well known, the same is not true for SAWs in confined geometries. The purpose of this contribution is a) to enumerate the number of SAWs on the simple cubic (SC) and face-centered cubic (FCC) lattices under confinement for moderate SAW lengths, and b) to obtain an approximate expression for their behavior as a function of chain length, type of lattice, and degree of confinement. This information is an essential requirement for the understanding and prediction of entropy-driven phase transitions of model polymer chains under confinement. In addition, a simple geometric argument is presented that explains, to first order, the dependence of the number of restricted SAWs on the type of SAW origin.

Fire behavior of natural rubber latex foam under different thickness conditions(d=1,2and 5cm)were explored though a little of experiments by using the self-built small scale experimental platform. It can be shown that the flame spread law of thermally thin and thermally thickness are different. Natural rubber latex foam with thickness of 2cm show higher fire risk, which value of flame spread rate, maximum flame height, maximum mass loss rate and maximum temperature is 0.00293m/s, 851.875mm, 1.83g/s, 948K,repectively.That may because the thickness of residue formed of thermally thick materials is larger than the thin one, obstructing the contact of the natural rubber latex foam with fresh air .In addition, a special phenomenon is noticed that during the second stage, the bottom unburned zone located in the four edges(thermally thin material) and middle player(thermally thick material).

Nanoparticles of graphene and carbon nanotubes are attractive materials for improvement of mechanical and barrier properties and functionality of biodegradable polymers for food packaging applications. However, the increase of the manufacture and consumption increases the probability of exposure of human and environment to such nanomaterials, this rising questions about the risks of nanomaterials since they can be toxic. For a risk assessment, it is crucial to know whether airborne nanoparticles of graphene and carbon nanotubes can be released from nanocomposites into the environment at their end-life, or they remain embedded in the matrix. In this work the release of graphene and carbon nanotubes from the poly(lactic) acid nanocomposite films were studied for the scenarios of: (i) biodegradation of matrix polymer at the disposal of wastes; and (ii) combustion and fire of nanocomposite wastes. Thermogravimetric analysis in air atmosphere, TEM, AFM and SEM were used to verify the release of nanoparticles from nanocomposite films. The three factors model was applied for the quantitative and qualitative risk assessment to the release of graphene and carbon nanotubes from nanocomposite wastes for these scenarios. Safety concern is discussed in respect to the existing regulations for nanowastes stream.

The recyclability of polystyrene, acrylonitrile butadiene styrene, polystyrene and polyvinylchloride waste and using them as a source for 3D printing were studied. Filaments of about 3 mm in diameter were extruded successfully with a small-size extruder. The processed filaments were tested on a broad range of parameters - glass transition temperature, tensile properties and a pyrolysis scenario were obtained. The measured parameters were compared with parameters of virgin counterparts presented in the literature. In order to estimate the toxicity of the recycled material, elemental analysis of the samples was done.

In this study is reported the optical, structural and dielectric properties of Poly (vinyl alcohol) thin films membranes with embedded ZnO nanoparticles (PVA/ZnO) obtained by solution casting method at low temperature of deposition. Fourier Transform Infrared spectra showed the characteristics peaks, which correspond to O-H and Zn-O bonds present in the hybrid material. The X-ray diffraction patterns indicated the presence of ZnO structure into the films. The composite material showed low absorbance and a wide band gap energy from 5.6 to 5.9 eV. The surface morphology for the thin films of PVA/ZnO was studied by Atomic Force Microscopy and Scanning Electron Microscopy. The dielectric properties of the nanocomposites were measured from low to high frequencies, the results showed a high dielectric constant (ε) in the order of 10⁴ at low frequency and values from ε ≈ 2000 to 100 in the range of 1KHz-1MHz respectively, the properties of PVA/ZnO such as the high permittivity and the low temperature of processing make it a suitable material for potential applications in the development of flexible electronic devices.

The possibility of using additive manufacturing (AM) in the medicine area has created a new opportunities in health care. This has contributed to a sharp increase in demand for 3D printers, their systems and materials that are adapted to strict medical requirements. We described herein a medical-grade thermoplastic polyurethane (S-TPU), which was developed and then formed into a filament for Fused Deposition Modeling (FDM) 3D printers during a melt-extrusion process. S-TPU consisting of aliphatic hexamethylene 1,6-diisocyanate (HDI), amorphous α,ω-dihydroxy(ethylene-butylene adipate) (PEBA) and 1,4 butandiol (BDO) as a chain extender, was synthesized without the use of a catalyst. The filament properties were characterized by rheological, mechanical, physico-chemical and in vitro biological properties. The tests showed biocompatibility of the obtained filament as well as revealed no significant effect of the filament formation process on its properties. This study may contribute to expanding the range of medical-grade flexible filaments for standard low-budget FDM printers.

Amine containing polymers are extensively studied as special carriers for short-chain RNA (13–25 nucleotides) which are applied as gene silencing agent in gene therapy of various diseases including cancer. Elaboration of the oligonucleotide carriers requires knowledge about peculiarities of oligonucleotide - polymeric amine interaction. Critical length of the interacting chains is the important parameter which allows to design sophisticated constructions containing oligonucleotide binding segments, solubilizing, protective and aiming parts. We studied interaction of (TCAG)n, n=1-6 DNA oligonucleotides with polyethylenimine and poly(N-(3-((3-(dimethyl­amino)propyl)(methyl)amino)propyl)-N-methylacrylamide). Critical length for oligonucleotides in interaction with polymeric amines is 8-12 units and complexation at these length can be accompanied by "all-or-nothing" effects. New dimethylacrylamide based polymers with grafted polyamine chains were obtained and studied in complexation with DNA and RNA oligonucleotides. The most effective interaction and transfection activity into A549 cancer cells was found for a sample with average number of nitrogens in polyamine chain equal to 27, i.e. for a sample in which all grafted chains are longer the critical length for polymeric amine - oligonucleotide complexation.

Novel multifunctional fluorescent chemosensors composed of electrospun (ES) nanofibers with high sensitivity toward pH, mercury ions (Hg²⁺), and temperature were prepared from poly(N-Isopropylacrylamide-co-N-methylolacrylamide-co-rhodamine derivative) (poly(NIPAAm-co-NMA-co-RhBN2AM)) by employing electrospinning process. NIPAAm and NMA moieties provide hydrophilic and thermo-responsive properties (absorption of Hg²⁺ in aqueous solutions), and chemical cross-linking sites (stabilization of the fibrous structure in aqueous solutions), respectively. The fluorescent probe, RhBN2AM is highly sensitive toward pH and Hg²⁺. Synthesis of poly(NIPAAm-co-NMA-co-RhBN2AM) with different compositions were carried on via free-radical polymerization. ES nanofibers prepared from sensory copolymers with a 71.1:28.4:0.5 NIPAAm: NMA: RhBN2AM ratio (P3 ES nanofibers) exhibited significant color change from nonfluorescent to red fluorescence while sensing pH or Hg²⁺, and high reversibility of on/off switchable fluorescence emission when Hg²⁺ and ethylenediaminetetraacetic acid (EDTA) were sequentially added. The P3 ES nanofibrous membranes had a higher surface-to-volume ratio to enhance their performance than did the corresponding thin films. In addition, the fluorescence emission of P3 ES nanofibrous membranes exhibited second enhancement above the lower critical solution temperature. Thus, the ES nanofibrous membranes prepared from P3 with on/off switchable capacity and thermo-responsive characteristics can be used as multifunctional sensory devise for specific heavy transition metal (HTM) in aqueous solutions.

Over the past decades, research has escalated on the use of polylactic acid (PLA) as replacement for petroleum-based polymers. This is due to its valuable properties, such as renewability, biodegradability, biocompatibility and good thermomechanical properties. Despite possessing good mechanical properties comparable to conventional petroleum-based polymers, PLA suffers from some shortcomings such as low thermal resistance, heat distortion temperature and rate of crystallization, thus different fillers have been used to overcome these limitations. In the frame work of environmentally friendly processes and products, there has been growing interest on the use of cellulose nanomaterials viz. cellulose nanocrystals (CNC) and nanofibers (CNF) as natural fillers for PLA towards advanced applications other than short-term packaging and biomedical. Cellulosic nanomaterials are renewable in nature, biodegradable, eco-friendless and they possess high strength and stiffness. In the case of eco-friendly processes, various conventional processing techniques, such as melt extrusion, melt-spinning, and compression moulding, have been used to produce PLA composites. This review addresses the critical factors in the manufacturing of PLA-cellulosic nanomaterials by using conventional techniques and recent advances needed to promote and improve the dispersion of the cellulosic nanomaterials. Different aspects, including morphology, mechanical behavior and thermal properties, as well as comparisons of CNC- and CNF reinforced PLA, are also discussed

Thermal and catalytic pyrolysis of virgin low-density polyethylene (LDPE), high-density polyethylene (HDPE), polypropylene (PP) and mixtures of LDPE/PP were carried out in a 200 ml laboratory scale batch reactor at 460 °C in a nitrogen atmosphere. Thermogravimetric analysis (TGA) was carried out to study the thermal and catalytic degradation of the polymers at a heating rate of 10 °C/min. The amount of PP was varied in the LDPE/PP mixture to explore its effect on the reaction. In thermal degradation (TGA) of LDPE/PP blends, a lower decomposition temperature was observed for LDPE/PP mixtures compared to pure LDPE, indicating interaction between the two polymer types. In the presence of a catalyst (CAT-2), the degradation temperatures for the pure polymers were reduced. The TGA results were validated in a batch reactor using PP and LDPE respectively. Thermal cracking results showed that the oil product contains a significant amount of gasoline (C7 − C12) and diesel (C13 − C20) hydrocarbon fractions. The catalyst enhanced cracking at lower temperatures and narrowed the hydrocarbon distribution in the oil towards the gasoline range fraction (C7 – C12). The result suggests that the oil produced from catalytic pyrolysis of waste plastics has a potential as an alternative fuel.

In this present study, 3-pentadecyl-phenol was selected as a modifier to prepare a foamable phenolic resin with excellent performance, which was successfully prepared by in-situ modification. Fourier transform infrared spectroscopy (FT-IR) and nuclear magnetic resonance (¹H NMR, ¹³C-NMR) were used to test and characterize the molecular structure of the modified resin. The results showed that 3-pentadecyl-phenol successfully modified the molecular structure of phenolic resin with a reduction in resin gel time. The effect of changing the added amount of 3-pentadecyl-phenol on the mechanical properties, microstructure and flame retardancy of the modified foam was investigated. The results showed that when the amount of added 3-pentadecyl-phenol was 15% of the total amount of phenol, this resulted in the best toughness of the modified foam, which could be increased to 300% compared to the bending deflection of the unmodified phenolic foam. The cell structure showed that the modified phenolic foam formed a more regular and dense network structure and the closed cell ratio was high. Furthermore, the compressive strength, bending strength, and limited oxygen index were improved, while the water absorption rate was lowered. However, the foam density could be kept below 40 mg/cm³, which does not affect the load.

In this paper, ground tire rubber (GTR) was mechano-chemically modified with road bitumen 160/220 and subsequently treated using a microwave radiation. The combined impact of bitumen 160/220 content and microwave treatment on short-term devulcanization of GTR were studied by thermal camera, wavelength dispersive X-ray fluorescence spectrometry (WD-XRF), static headspace and gas chromatography-mass spectrometry (SHS-GC-MS), thermogravimetric analysis combined with Fourier transform infrared spectroscopy (TGA-FTIR), oscillating disc rheometer and static mechanical properties measurements. The obtained results showed that bitumen plasticizer prevent oxidation of GTR during microwave treatment and simultaneously improves processing and thermal stability of obtained reclaimed rubber.

Simulation programs contain Computational Fluid Dynamics - CFD codes and are a useful tool used for gas flow through porous materials. Conducting numerical simulations allows for detailed analysis of hydrodynamic phenomena. The results of numerical modeling should always be verifiable based on experimental data. Only their compliance with the results of experimental tests is a determinant of the correctness of the applied method. As part of the work, experimental studies of hydrodynamics of gas flow through an isotropic porous material were carried out and numerical simulation for material of the same shape was used. In the CFD modeling Kolmogorov's hypothesis for the transport of kinetic energy of turbulence k and transport of dissipation rate of kinetic energy of turbulence ε was used.

The reinforcing ability of the fillers results in significant improvements in properties of polymer matrix at extremely low filler loadings compared to conventional fillers. In view of this, present review article describes the different methods used in preparation of different rubber nanocomposites reinforced with nanodimensional individual carbonaceous fillers, such as graphene, expanded graphite, single walled carbon nanotubes, multiwalled carbon nanotubes and graphite oxide, graphene oxide and hybrid fillers consisting combination of individual fillers. This is followed by review of mechanical properties (tensile strength, elongation at break, Young modulus, and fracture toughness) and dynamic mechanical properties (glass transition temperature, crystallization temperature, melting point) of these rubber nanocomposites. Finally, Payne and Mullin Effects have also been reviewed in rubber filled with different carbon based nanofillers.

Here, we present a series of novel block copolymers (BCP) from bio-derived monomers, poly(lactic acid)-block-poly(2,5-furandimethylene succinate) (PLA-b-PFS), in which the furan groups from PFS block can be crosslinked with bis(maleimido) triethylene glycol (M2) through a Diels-Alder reaction. This dynamic crosslinking reaction leads to a network structure for enhancing the mechanical properties compared to their linear BCP analogous. Decreasing the crosslinking density leads to a decrease of glass transition temperature of BCPs and a transition from glassy to rubbery-like behavior at room temperature. This allows a wide tunablity of both elastic moduli and yields of the materials. For the lowest crosslinking density. the material exhibits an over 50% self-healing efficiency at room temperature after five days, attributed to the low Tg (15.2 C) from the introduction of PFS block, allowing sufficient chain mobility for structure re-organization. Moreover, with the appropriate selection of crosslinking density (PLA-b-PFS/M2 (6/1)), it also shows an excellent shape memory property with a high recovery rate of 96.3% and a fixity rate of 97.3%. The permanent shape can be rewriteable due to the reversibility of Diels-Alder reaction. With these advanced functionalities and ease in large-scale fabrication, the PLA-b-PFS/M2 shows great promises for self-healing coatings or films with shape memory properties in a wide variety of applications such as packaging materials

Most of the phase change materials (PCMs) have been limited to use as functional additions or sealed in containers, and extra auxiliary equipment or supporting matrix is needed. The emergence of 3D printing technique has dramatically advanced the developments of materials and simplified production processes. This study focuses on a novel strategy to model thermal energy storage crystalline gels with three-dimensional architecture directly from liquid resin without supporting materials through light-induced polymerization 3D printing technique. A mask-projection stereolithography printer was used to measure the 3D printing test, and the printable characters of crystalline thermal energy storage P(SA-DMAA) gels with different molar ratios were evaluated. For the P(SA-DMMA) gels with small fraction of SA, the 3D fabrication was realized with higher printing precision both on mili- and micro-meter scales. As a comparison of 3D printed samples, P(SA-DMAA) gels made by other two methods, post-UV curing treatment after 3D printing and UV curing using conventional mold, were prepared. The 3D printed P(SA-DMAA) gels shown high crystallinity. Post–UV curing treatment was beneficial to full curing of 3D printed gels, but did not lead to the further improvement of crystal structure to get higher crystallinity. The P(SA-DMAA) crystalline gel having the highest energy storage enthalpy that reached 69.6 J·g⁻¹ was developed. Its good thermoregulation property in the temperature range from 25 to 40 °C was proved. The P(SA-DMAA) gels are feasible for practical applications as one kind of 3D printing material with thermal energy storage and thermoregulation functionality.

In this work we have investigated the role of various additives (emulsifier, anti-dripping agent) and formulation procedure (pre- dispersion of solid additives in polyol via milling) which influence the flame retardancy of 6,6′-[ethan-1,2-diylbis(azandiyl)]bis(6H-dibenzo[c,e][1,2]oxaphosphin-6-oxid) (EDA-DOPO) containing flexible polyurethane foams. For comparison, the flame retardancy of two additional structurally analogues bridged 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) based compounds i.e. ethanolamine-DOPO (ETA-DOPO) and ethylene glycol-DOPO (EG-DOPO) were also evaluated together with EDA-DOPO in flexible PU foams of various formulations. The flame retardancy of three bridged-DOPO compounds depends on the type of PU formulation. For certain PU formulation containing EDA-DOPO, lower fire performance was observed. Addition of emulsifier and polytetrafluoroethylene (PTFE) to these PU formulations influenced positively the flame retardancy of EDA-DOPO/PU foams. In addition, dispersion of EDA-DOPO and PTFE via milling in polyol improved the flame retardancy of the PU foams. Mechanistic studies performed using pyrolysis combustion flow calorimetry (PCFC) and its coupling to FTIR showed no difference in the combustion efficiency of the bridged-DOPO compounds in PU foams. From these PCFC experiments we can conclude that these bridged-DOPO compounds and their decomposition products may work primarily in the gas phase as flame inhibitors. Physiochemical behavior of additives in PU formulation responsible for the improvement in the flame retardancy of PU foams was further investigated by studying the dripping behavior of the PU foams in UL 94 HB test. A high-speed camera was used to study the dripping behavior in the UL 94 HB test and results indicate a considerable reduction of a total number of melt drips and flaming drips for the flame retardant formulations. This reduction in melt drips and flaming drips during the UL 94 HB tests help PU foams achieve higher fire classification.

Free volume is an extremely important intrinsic defect in polymers. Structurally, the free volume is the randomly distributed holes in the polymer molecular chain segments. From the perspective of molecular movement, it is also the space needed for the movement of molecular segments. In proton exchange membrane fuel cells, the free volume is also the space needed for the directional conduction of protons. Irradiation grafting sulfonated polyvinylidene fluoride (PVDF) is one of the methods to produce proton exchange membrane with good proton channel rate. Using the LYS-1 program, based on the linear absorption coefficient and backscatter coefficient models, the percentage of annihilated positrons in PVDF in the two-layer model and the three-layer model was studied, and comparing the two fitting results it is determined that the model closest to the positron annihilation percentage required by the PALS experiment is the two-layer model, which allows the percentage of positrons that are annihilated in PVDF films with a thickness of 100 μm to reach 46% using the high energy positron source ⁴⁴Ti without using the positron moderator. Using positron annihilation lifetime spectrum (PALS) analysis methods, based on Eldrup's classical model of free volume, the influence of absorbed doses of α particles on the free volume and crystallinity of PVDF was investigated, respectively. Based on the two test results the model of cross-linking and degradation of polyvinylidene fluoride irradiated by α particles was determined. Afterwards, X-ray diffraction (XRD) methods was used to study the change of PVDF crystal area before and after irradiation. The XRD results are consistent with the results measured by PALS.

Water pollution in developing countries affects the public health of humans and the environment. It is therefore essential to develop environmentally friendly biopolymer, sustainable and low-cost membranes. Biopolymer nanofiber membranes are made by an electrospinning process of polylactic acid (PLLA) with additives. The main objective of this study is to manufacture biodegradable nanofiber membranes for use in filtering the suspended elements in wastewater at the level of drinkable or in agricultural fields. It is known that PLLA is brittle and therefore it is difficult to apply in industry. To solve this problem and enhance its flexibility. Flexible biopolymer polypropylene carbonate (PPC) and plasticizer are the addition in PLLA to reduce its glass transition and enhance its crystallization by adding Poly(3-hydroxy butyrate) PHB. In this work, 20 wt% of PPC was added to PLLA matrix to improve its elasticity and elongation at break. DSC shows that the addition of PPC, PHB, and TEC did affect the thermal properties like T_g, T_cc and T_m of the PLLA blends. The position of the T_g, T_cc, and T_m is shifting, the consequence the chain mobility is increased, therefore the crystallinity is enhanced. Electrospun fibers of PLLA/PPC/PHB/TEC were successfully manufactured. Tensile tester showed the increase in elongation at break of PLLA blend films, the elongation at break increases by 285 times. It observed with the increasing the elongation at break, a decrease in stress strength. After improving the mechanical properties with the higher elongation at break values, this blend is optimal for filtrations process.

Lightning strike can cause a considerable damage in aircraft parts made from semiconducting materials such as Carbon Fiber Reinforced Plastics (CFRPs). Therefore, in recent years, the lightning strike phenomenon has attracted the interest of the academic community and the aircraft industry. Until now, the problem has been addressed mainly experimentally, while the reported numerical works are very limited. In the present work, a coupled electro-thermal FE model has been developed using the ANSYS commercial FE code to simulate the lightning strike damage in unidirectional CFRP laminates due to the Joule heat flux phenomenon. The model is based on the SOLID69 thermoelectric element and applies a non-linear, time-transient analysis. The main input to the model is the thermal-electrical properties of the composite material which vary with temperature. Using the model, a parametric study on the effect of mesh density and peak intensity on the thermal damage has been performed. Three electrical lightning strikes of low (10 kA), medium (30 kA) and high peak intensity (40 kA) have been applied according to the SAE ARP 5412 standard. The electro-thermal model has been validated against a numerical model from the literature. The numerical results reveal that the increase of peak intensity leads to the increase of the area and penetration depth of matrix thermal damage (pyrolysis) as well as to the increase of the area of fiber damage (deterioration and ablation). Through progressive damage modeling, the residual tensile strength of the CFRP plate after being subjected to lightning strike of different peak intensity has been predicted. Lightning strike initial damage has been simulated by translating the thermal field into degradation of elastic properties of the lamina. The results show an increase in the accumulated matrix damage and a decrease of tensile strength due to the initial lightning strike damage. For the maximum peak intensity of 40 kA, a decrease in tensile strength of 4.8% has been predicted

This article discusses the results of a series of experiments on pulse ultrasonic cure monitoring of carbon fiber reinforced plastics applied to the pultrusion process. The aim of this study is to validate the hypothesis that pulse ultrasonic cure monitoring can be applied a) for profiles having small cross sections such as 7x0.5 mm and b) within the environment of the pultrusion process. Ultrasonic transducers are adhesively bonded to the pultrusion tool as actuators and sensors. The time-of-flight and the amplitude of an ultrasonic wave are analyzed to deduce the current curing state of the epoxy matrix. The experimental results show that ultrasonic cure monitoring is indeed applicable even to very thin cross sections. However, significant challenges can be reported when the techniques are used during the pultrusion process.

Polyurethane (PU) foam adhesives were prepared from castor oil as a polyol with isocyanate poly (4,4′-methylene diphenyl isocyanate) (PMDI) using a solvent-free process. The NCO/OH molar ratio used for the preparation of PU foams was 1.5. Water, organosiloxane and dibutyltin dilaurate were blowing agent, surfactant and catalyst, respectively. Effects of the ratio of blowing agent and catalyst were adjusted to optimize the properties. The results show that 4 wt% of castor oil of catalyst and blowing agent minimizes water absorption and maximizes volume expansion in the PU foams. FT-IR analysis shows that urethane bond was formed by hydroxyl group of castor oil and –NCO group of isocyanate PMDI. More blowing agent and catalyst could improve the volume expansion ratio and reduce water retention of PU foams. It was found that Moso bamboo charcoal (Phyllostachys pubescens) or/and China fir wood particle (Cunninghamia lanceolate) composites with setting densities of 500 and 600 kg/m³ can be prepared from optimized castor oil-based PU foam adhesive at 100 °C for 5 min under a pressure of 1.5 MPa. Increasing the amount of bamboo charcoal decreases the equilibrium moisture content, water absorption and internal bonding strength of the composite. Notably, bamboo charcoal composite exhibits excellent dimensional stability. The optimized density and bamboo charcoal percentages of the composite were 500 kg/m³ and 50 to 100%. The castor oil-based PU composites containing bamboo charcoal fulfilled the CNS 2215 standards for particleboard. This dimensionally stable, low-density bamboo charcoal composite has high potential to replace current indoor building materials.

The effect of hybrid carbon fillers of multi-walled carbon nanotubes (CNT) and carbon black (CB) on the electrical and morphological properties of polystyrene (PS) nanocomposites were systematically investigated in microinjection molding (μIM). The polymer nanocomposites with three different filler concentrations (i.e. 3, 5 and 10 wt%) at various weight ratios of CNT/CB (100/0, 30/70, 50/50, 70/30, 0/100) were prepared by melt blending, then followed by μIM under a defined set of processing conditions. A rectangular mold insert which has three consecutive zones with decreasing thickness along the flow direction was adopted to study abrupt changes in mold geometry on the properties of resultant microparts. The distribution of carbon fillers within microparts was observed by scanning electron microscope, which was correlated with electrical conductivity measurements. Results indicated that there is a flow-induced orientation of incorporated carbon fillers and this orientation increased with increasing shearing effect along the flow direction. High structure CB is found to be more effective than CNT in terms of enhancing the electrical conductivity, which was attributed to the good dispersion of CB in PS and their ability to form conductive networks via self-assembly. Morphology observations indicated that there is a shear-induced depletion of CB particles in the shear layer, which is due to the marked difference of shear rates between the shear and core layers of the molded microparts. Moreover, an annealing treatment is beneficial to enhance the electrical conductivity of CNT-containing microparts.

Abstract: We have filled a 24 mm diameter glass sphere with a transparent polymer-gel that is radio-fluorogenic, i.e. it becomes (permanently) fluorescent when irradiated, with an intensity proportional to the local dose deposited. The gel consists of >99.9% tertiary-butyl acrylate (TBA) pre-polymerized to ~15% conversion, and ~100 ppm maleimido-pyrene (MPy). Its dimensions and physical properties are close to those of the vitreous body of the human eye. We have irradiated the gel with a 3 mm diameter, 200 kVp X-ray beam with a dose rate of ~1 Gy/min. A 3D (video) view of the beam within the gel has been constructed from tomographic images obtained by scanning the sample through a thin sheet of UV light. To minimize optical artifacts, the cell was immersed in a square tank containing a refractive-index-matching medium. The 20%-80% penumbra of the beam was determined to be ~0.4 mm. The research was a preparatory investigation of the possibility of using the method to monitor the millimetre diameter proton pencil beams used in ocular radiotherapy.

Bamboo plastic composites have become a hot research topic and a key focus of research. However, the many strong, polar, hydrophilic hydroxyl groups in bamboo flour (BF) results in poor interfacial compatibility between BF and hydrophobic polymers. Maleic anhydride-esterified (MAH-e-BF) and lactic acid-esterified bamboo flour (LA-e-BF) were prepared using an in situ solid-phase esterification method with BF as the raw material and maleic anhydride or lactic acid as the esterifying agent. Fourier transform infrared spectroscopy results confirmed that BF esterification with maleic anhydride and lactic acid was successful, with the esterification degrees of MAH-e-BF and LA-e-BF at 21.04 and 14.36%%, respectively. Esterified BF was characterized by scanning electron microscopy, contact angle testing, X-ray diffractometry, and thermogravimetric analysis. The results demonstrated that esterified BF surfaces were covered with graft polymer and the surface roughness and bonding degree of MAH-e-BF clearly larger than those of LA-e-BF. The hydrophobicity of esterified BF was significantly higher than BF and the hydrophobicity of MAH-e-BF better than LA-e-BF. The crystalline structure of esterified BF showed some damage, with MAH-e-BF exhibiting a greater decrease in crystallinity than LA-e-BF. Overall, the esterification reaction improved BF thermoplasticity, with the thermoplasticity of MAH-e-BF appearing better than LA-e-BF.

The capacity of 3D printing (3DP) technologies to initiate speedy polymerization of solvent free resins accounts for their utility in the manufacturing of medical devices. Nonetheless, independent biological evaluation of 3D printed materials is recommended due to the unique parameters of the manufacturing process, which can influence their physical, chemical, and biological properties. In this study, E-Shell 450 material indicated for 3DP of hearing aid shells and inner ear devices was examined for biological safety using zebrafish bioassays adapted to OECD fish embryo test. In addition, the proprietary material was characterized for composition using headspace gas-chromatography mass spectrometry (GC-MS). To initiate test, newly fertilized zebrafish eggs were cultured on non-treated and ethanol-treated materials in glass petri dishes with ultrapure water, incubated at 28.5°C and assessed for developmental endpoints of toxicity at 24h interval until 96h. Data confirmed non-treated material was extremely toxic in bioassays within 24h whereas ethanol-treated material showed a relative lower toxicity possibly due to ethanoic-aqueous interactions as observed by GC-MS. With the current influx of 3D printing materials, users are urged to exercise caution. Operators must also take cognizance of the potential toxicity of the chemicals used in 3DP and implement safety measures to limit their exposure.

In this work, nylon 6/ P(N-phenylmaleimide-alt-styrene) blends were prepared by melt blending, and the mechanical, heat-resistant, crystallographic and dynamical mechanical properties of nylon 6/ P(N-phenylmaleimide-alt-styrene) blends with different contents were investigated and analyzed. The results showed that the mechanical properties decreased with increasing PNS, while the heat deflection temperature (HDT), relative crystallinity (Xn), and storage modulus (G’) increased with increasing PNS. The results of differential Scanning Calorimetry (DSC) proved the PNS played the positive role of nucleating PA6. And the results of dynamic mechanical analysis (DMA) proved the PNS could improve the rigidity of PA6/PNS blends. From the SEM, these PNS domains were between 0.2 and 4 μm in diameter. The experimental results indicated that the addition of PNS improved the rigidity of PA6/PNS blends, and then improved the heat-resistant property.

The capacity of 3D printing (3DP) technologies to initiate speedy polymerization of solvent free resins accounts for their utility in the manufacturing of medical devices. Nonetheless, independent biological evaluation of 3D printed materials is recommended due to the unique parameters of the manufacturing process, which can influence their physical, chemical, and biological properties. In this study, E-Shell 450 material indicated for 3DP of hearing aid shells and inner ear devices was examined for biological safety using zebrafish bioassays adapted to OECD fish embryo test. In addition, the proprietary material was characterized for composition using headspace gas-chromatography mass spectrometry (GC-MS). To initiate test, newly fertilized zebrafish eggs were cultured on non-treated and ethanol-treated materials in glass petri dishes with ultrapure water, incubated at 28.5°C and assessed for developmental endpoints of toxicity at 24h interval until 96h. Data confirmed non-treated material was extremely toxic in bioassays within 24h whereas ethanol-treated material showed a relative lower toxicity possibly due to ethanoic-aqueous interactions as observed by GC-MS. With the current influx of 3D printing materials, users are urged to exercise caution. Operators must also take cognizance of the potential toxicity of the chemicals used in 3DP and implement safety measures to limit their exposure.

Herein, we present preparation of solid polymer electrolyte (SPE) comprising of PEO, NaPF₆ and varying fraction of Succinonitrile (SN) by standard solution cast technique. The morphological features and structural properties were studied by the FESEM, XRD, respectively. FTIR was performed to study the interactions between polymer host, salt, and SN. Impedance spectroscopy, Transference number measurements, LSV and CV were used to examine the electrochemical properties. The complex permittivity/conductivity & modulus were studied to understand the dielectric properties by evaluating the dielectric strength, relaxation time, hopping frequency and dc conductivity. Based on the experimental results an interaction mechanism is presented.

In this paper, an icosahedral non – body centered model to simulate the periodic structure of homogeneous particulate composites, by predicting the particle arrangement, is presented. This model has yielded three different variations which correspond at three different deterministic particle configurations. In addition, the concept of boundary interphase between matrix and inclusions was taken into account. Thus, the influence of particle vicinity was examined in parallel with the interphase concept on the thermomechanical properties of the overall material. Next, by the use of this model the authors derived a closed – form expression to estimate the thermal conductivity of this type of composites. To test the validity of the model, the theoretical values arising from the proposed formula were compared with other theoretical predictions obtained from several accurate formulae found in the literature and an adequate accordance was observed.

The separator membrane is an essential component of lithium-ion batteries, separating the anode and cathode and controlling the number and mobility of the lithium ions. Among the polymer matrices most investigated for battery separators are poly(vinylidene fluoride) (PVDF) and its copolymers poly(vinylidene fluoride-co-trifluoroethylene) (PVDF-TrFE), poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP), and poly(vinylidene fluoride-cochlorotrifluoroethylene) (PVDF-CTFE), due to their excellent properties such as high polarity and the possibility of controlling the porosity of the materials through binary and ternary polymer/solvent systems, among others. This review presents the recent advances on battery separators based on poly(vinylidene fluoride) (PVDF) and its copolymers for lithium-ion batteries. It is divided in the following sections: single polymer and co-polymers, surface modification, composites and polymer blends. Further, a critical comparison between those membranes and other separator membranes is presented, as well as the future trends on this area.

Decomposition of natural and synthetic polymeric materials (peat, humates, biochar, strongly swelling hydrogels and other soil conditioners) in a biologically- and chemically- active soil environment inevitably leads to their degradation and ability to improve the structure, water-retention, absorptive capacity and actual fertility of artificial soil constructions in urbanized ecosystems and agro landscapes (constructozems). Quantitative assessment of the biodegradation process using field and laboratory incubation experiments, as well as mathematical modeling, showed the possibility of significant (up to 30-50% per year) losses of organic matter of constructozems and a corresponding deterioration in their quality. Incubation experiments with the analysis of carbon dioxide emission for polymeric materials under given thermodynamic conditions allow to estimate the potential rates of their decomposition (half-life) and their dependence on the dose of inhibitors of microbial activity. Special nomographs provide an opportunity to determine the optimum depth of the arrangement of organic components in soil constructions to ensure their stable functioning during a fixed operating time in urban conditions. The results of the study are useful for geo-engineers and landscaping practitioners.

We investigated the structural evolution of the two-phase blends of polycarbonate (PC) and poly(methyl methacrylate) (PMMA) at various blend compositions by simultaneous biaxial stretching using optical microscopy and SEM observation. The spherical PMMA domains and PC matrix in 30/70 PC/PMMA were enlarged uniformly at all in-plane direction, while the anisotropic-shaped co-continuous structure in 50/50 PC/PMMA was deformed to crosshatched one by in-plane bimodal orientation. In 70/30 PC/PMMA, the phase inversion was found to occur by simultaneous biaxial stretching; i.e., the spherical PMMA domains were changed to crosshatched matrix by in-plane bimodal orientation due to coalescence of the PMMA domains during the stretching. Owing to the phase inversion, the surface hardness estimated by pencil hardness test became harder from 2B to 2H with increasing the strain from 1.0 to 2.0.

Abstract: We review the development and application of an organic polymer-gel capable of producing fixed, three-dimensional fluorescent images of complex radiation fields. The gel consists for more than 99% of γ-ray-polymerized (~15% conversion) tertiary-butyl acrylate (TBA) containing ~100 ppm of a fluorogenic compound, e.g. maleimido-pyrene (MPy). The radio-fluorogenic effect depends on copolymerization of the MPy into growing chains of TBA on radiation-induced polymerization. This converts the maleimido residue, which quenches the pyrene fluorescence, into a succinimido moeity (SPy), which doesn't. The intensity of the fluorescence is proportional to the yield of free-radicals formed and hence to the local dose deposited. Because the SPy moieties are built into the cross-linked polymer matrix the image is fixed. The method of preparing the gel and imaging the radiation-induced fluorescence are presented and discussed. The effect is illustrated with fluorescent images of the energy deposited in the gel by beams of X-rays, electrons and protons as well as a radioactive isotope.

The kinetics and optimal efficacy conditions of photoinitiated polymerization are theoretically presented. Analytic formulas are derived for the crosslink time, crosslink depth and efficacy function. The roles of photosensitizer (PS) concentration, diffusion depth and light intensity on the polymerization spatial and temporal profiles, for both uniform and non-uniform cases, are presented . For optimal efficacy, a strategy via controlled PS concentration is proposed, where re-supply of PS in high light intensity may achieve a combined-efficacy similar to low light intensity, but has a much faster procedure. A new criterion of efficacy based on the polymerization (crosslink) [strength] and [depth] is introduced.

Solvent-free, single-ion conducting electrolytes are sought after for use in electrochemical energy storage devices. Here, we investigate the ionic conductivity and how this property is influenced by segmental mobility and conducting ion number in crosslinked single-ion conducting polyether-based electrolytes with varying tethered anion and counter-cation types. Crosslinked electrolytes are prepared by the polymerization of poly(ethylene glycol) diacrylate (PEGDA), poly(ethylene glycol) methyl ether acrylate, and ionic monomers. The ionic conductivity of the electrolytes is measured and interpreted in the context of differential scanning calorimetry and Raman spectroscopy measurements. A lithiated crosslinked electrolyte prepared with PEG₃₁DA and STFSI monomers is found to have a lithium ion conductivity of 3.2 × 10^-6 and 1.8 × 10⁻⁵ S/cm at 55 and 100 °C, respectively. The percentage of unpaired anions for this electrolyte was estimated at about 23% via Raman spectroscopy. Despite the large variances in metal cation – STFSI binding energies as predicted via DFT and large variations in ionic conductivity, STFSI-based crosslinked electrolytes with the same charge density and varying cations (Li, Na, K, Mg, and Ca) were estimated to all have unpaired anion populations in the range of 19 to 29%.

Aiming to improve the flame retardancy performance of natural rubber (NR), we developed a novel flame retardant synergistic agent through grafting of MCM-41 to graphene oxide (GO)，named as GO-NH-MCM-41，as an assistant of intumescent flame retardants (IFR). The structure of GO-NH-MCM-41 was characterized by FTIR, TEM and SEM tests, which confirmed that a fine grafting had been applied between GO and MCM-41. The flame retardancy of NR/IFR/GO-NH-MCM-41 composites was evaluated by limited oxygen index (LOI), UL-94 and cone calorimeter test. The LOI value of NR/IFR/GO-NH-MCM-41 reached to 26.3%; the UL-94 ratings improved to V-0 rating. Moreover, the addition of GO-NH-MCM-41 obviously decreased the peak heat release rate (PHRR) and the total heat release (THR) of the natural rubber composites. And the addition of GO-NH-MCM-41 increased the thickness of char residue. The images of SEM indicated the char residue were more compact and continuous. The degradation of GO-NH-MCM-41 based NR composites completed with a mass loss of 35.57% at 600 ℃. The tensile strength and the elongation at break of NR/IFR/GO-NH-MCM-41 composites were 13.9 MPa and 496.7%, respectively. The results of rubber process analyzer (RPA) reached the maximum value, probably due to a better network of the fillers in the matrix.

An immiscible blend of poly(hydroxy ether of bisphenol-A) (phenoxy) and poly(1,4-butylene terephthalate) (PBT) with phase separation was observed in as-blended samples. However, compatibilization of the phenoxy/PBT blends can be promoted through chemical exchange reactions of phenoxy with PBT upon annealing. In contrast to the as-blended samples, the annealed phenoxy/PBT blends had a homogeneous phase with a single T_g that could be enhanced by annealing at 260°C. Infrared (IR) spectroscopy demonstrated that phase homogenization could be promoted by annealing of the phenoxy/PBT blend, where alcoholytic exchange occurred between the dangling hydroxyl group in phenoxy and the carbonyl group in PBT in the heated blends. The alcoholysis reaction changes the aromatic linkages to aliphatic linkages in carbonyl groups, which initially led to the formation of a graft copolymer of phenoxy and PBT with an aliphatic/aliphatic carbonyl link. The progressive alcoholysis reaction resulted in the transformation of the initial homopolymers into block copolymers and finally into random copolymers, which promoted phase compatibilization in blends of phenoxy with PBT. Due to the fact that the amount of copolymers increased upon annealing, crystallization of PBT was inhibited by alcoholytic exchange in the blends.

In this paper, an upper bound of the longitudinal elastic modulus of unidirectional fibrous composites is proposed according to strength of materials approach, on the premise that the fiber is much stiffer than the matrix. In the mathematical derivations, the concept of boundary interphase between fiber and matrix was also taken into account and the main objective of this work is the attainment of an upper bound for the interphase stiffness with respect to fiber concentration by volume. The novel element here is that the authors have not taken into consideration any specific variation law to approximate the interphase modulus. The theoretical results arising from the proposed formula were compared with those obtained from some reliable theoretical models as well as with experimental data found in the literature, and a satisfactory agreement was observed.

Resides derived from liquefaction of oil palm trunk in the presence of polyhydric alcohol with different liquefaction temperature and time were characterized to provide a new approach to understand some fundamental aspects of the liquefaction reaction. Higher temperature and longer reaction time resulted in lower residue content, indicating more decomposition of components of oil palm trunk. The amorphous polymer comprised of lignin, hemicellulose, starch, and cellulose with non-crystalline structure are firstly degraded at low liquefaction temperature, followed by the decomposition of crystalline region of cellulose. Although it was relatively difficult to destroy the ordered structure of cellulose, most of them could be liquefied via prolonging reaction time or enhancing reaction temperature. Nevertheless, it was found that re-condensation of liquefied products occurred during the liquefaction process when higher temperature of 180 oC was used after 60 min, leading to the gradual increase of residue content with increase of reaction time.