Polyetheramine (PEA) is a swelling inhibitor used to address engineering challenges arising from the interaction between montmorillonite (Mt) and water. This study comprehensively investigates the adsorption characteristics of PEA on three representative expansive clay samples: Na-Mt, Ca-Mt, and engineered expansive soil. Additionally, the desorption of exchangeable ions is examined. The findings reveal that a two-stage adsorption kinetic model and a pseudo-second-order kinetic model can properly describe the adsorption kinetics of PEA on expansive clays. PEA exhibits a strong capacity for ion exchange with sodium ions, while the exchange capacity for calcium ions is limited. Both protonated and non-protonated PEA contribute to rapid adsorption processes. The adsorption isotherms are well-fitted by the Langmuir and Freundlich models, with the Langmuir model being reasonable. At lower equilibrium concentrations, a higher proportion of the adsorption amount is attributed to ion exchange compared to higher equilibrium concentrations. Ion exchange emerges as the primary factor contributing to the adsorption of PEA on Na-Mt, whereas the adsorption of PEA on Ca-Mt and expansive soil is primarily attributed to physical adsorption by non-protonated PEA. X-ray diffraction results reveal significant intercalation effects of PEA as they penetrate the interlayer space and hinder interlayer ion hydration. Fourier transform infrared spectrum results demonstrate that the adsorption of PEA minimally impacts the framework of Mt structural units but primarily reduces the adsorbed water content. Clay-PEA composites exhibit a decreased affinity for water. Zeta potential experiments indicate that the adsorption of PEA significantly diminishes the surface potential of clay-PEA composite particles, effectively inhibiting their hydration dispersion. Full article

Polylactide (PLA) is one of the most commonly used biomaterials nowadays, with many recognized benefits, particularly in the packaging and single-use products industries. However, little research has been conducted on its stretching behavior. This work investigates the optimal conditions of biaxial stretching of injection-molded PLA samples produced under different processing conditions (pressure, drying, and pre-processing by extrusion, to simulate a recycling step). The injection-molded samples were characterized to determine their mechanical, thermal and thermo-mechanical behavior, water absorption, thermal behavior, and crystallization kinetics. The extruded samples showed reduced thermal stability, lower viscosity, decreased mechanical properties, and higher crystallization rates due to thermal degradation. However, the stretched samples provided similar properties regardless of the materials pre-processing. Regarding the assessment of the biaxial stretching process, processing at lower temperatures provides the films with a higher yield and breaking strength, while the time and strain rates have little influence on such properties. It was then determined that 82 °C is the optimal temperature for stretching the PLA samples. An increase in the stretch ratio provided a higher elastic modulus and higher values of opacity due to an increased crystallinity induced by stress during the process. Films as thin as 50 μm can be obtained by biaxially stretching injection-molded preforms, producing a deformation over 150% and acquiring good mechanical properties: about 90 MPa for the yield and a breaking strength and elastic modulus of 4000 MPa. Full article

A novel synthetic procedure for the functionalisation of styrenic cross-linked polymers with perfluorinated acyl chains has been reported. The effective significant grafting of the fluorinated moieties is supported by {¹H}-¹³C and {¹⁹F}-¹³C NMR characterisations. This kind of polymer appears promising as catalytic support for a variety of reactions requiring a highly lipophilic catalyst. Indeed, the improved lipophilicity of the materials resulted in enhanced catalytic properties of the corresponding sulfonic materials in the reaction of esterification of a solution in a vegetable oil of stearic acid with methanol. Full article

Bisphosphonate drugs constitute the primary treatment for bone diseases such as Paget’s disease and osteoporosis. Despite their effectiveness, they also exhibit severe drawbacks, such as rapid excretion and limited oral bioavailability. High doses are usually administered to counterbalance these drawbacks. Subsequently, side effects are triggered, such as osteonecrosis of the lower jaw and esophageal cancer. Controlled drug release systems may be viable candidates to overcome those issues. Herein, we present novel functionalized silica-based hydrogels loaded with the osteoporosis drug etidronate (1,1-hydroxyethylidene-diphosphonate) used to control the release profile of the drug. Various methodologies were evaluated to control the initial release rate and the final released concentration of the drug. These included the gel density, by systematically increasing the initial concentration of silicate used to prepare the hydrogels, the presence of metal cations (Ca²⁺ and Cu²⁺), and the internal surface functionalization of the gel with silane-based grafting agents (with anionic, cationic, and neutral groups). This study also contributes to our continuous effort to develop new a priori programmable drug-loaded gels for the controlled release of osteoporosis drugs. Full article

In bio-nanocomposites with a poly(lactic acid) (PLA)/poly(ε-caprolactone) (PCL) matrix with neat and polydopamine (PDA)-coated cellulose nanocrystals (CNCd), the use of different mixing protocols with masterbatches prepared by solution casting led to marked variation of localization, as well as reinforcing and structure-directing effects, of cellulose nanocrystals (CNC). The most balanced mechanical properties were found with an 80/20 PLA/PCL ratio, and complex PCL/CNC structures were formed. In the nanocomposites with a bicontinuous structure (60/40 and 40/60 PLA/PCL ratios), pre-blending the CNC and CNCd/PLA caused a marked increase in the continuity of mechanically stronger PLA and an improvement in related parameters of the system. On the other hand, improved continuity of the PCL phase when using a PCL masterbatch may lead to the reduction in or elimination of reinforcing effects. The PDA coating of CNC significantly changed its behavior. In particular, a higher affinity to PCL and ordering of PLA led to dissimilar structures and interface transformations, while also having antagonistic effects on mechanical properties. The negligible differences in bulk crystallinity indicate that alteration of mechanical properties may have originated from differences in crystallinity at the interface, also influenced by presence of CNC in this area. The complex effect of CNC on bio-nanocomposites, including the potential of PDA coating to increase thermal stability, is worthy of further study. Full article

Nanocarriers (NCs) were designed from three polymer blends (B1, B2 and B3) and investigated as smart drug delivery systems (SDDS). The blends are composed of a “smart” copolymer, where methoxy poly(ethylene glycol) and poly(lactic acid) are connected via a redox-responsive disulfide bond (mPEG-SS-PLA), and of a “conventional” polymer, poly(lactic acid) (PLA). They differ by mPEG-SS-PLA/PLA ratio and PLA molecular weight. Nanoprecipitation was used to prepare NCs. Three concentrations were tested, and fluorescent dye Nile red (NR) was used as a model payload. The results show that the characteristics of the NCs, such as size and drug release kinetics, are influenced by the type of blend and the concentration used during the nanoprecipitation process. The more redox-responsive blend was B2 (ratio 1:3, PLA 5 kDa) at 16 mg/mL: the quantity of NR released was tripled upon 24 h of incubation in a reducing medium. This study reveals that the amount of disulfide bonds present in a NC is not the only parameter to be considered to design an SDDS. The stability of the SDDS in a presumably non-stimulating environment is also important to limit uncontrolled release during storage or in the body before the biological target is reached. Full article

A comprehensive study of the statistical distribution of the auto-adhesion lap-shear strength (σ) of amorphous polymer–polymer interfaces using various types of statistical tests and models is a useful approach aimed at a better understanding of the mechanisms of the self-healing interface. In the present work, this approach has been applied, for the first time, to a temperature (T) range below the bulk glass transition temperature (T_g^bulk). The interest of this T range consists in a very limited or even frozen translational segmental motion giving little or no chance for adhesion to occur. To clarify this issue, the two identical samples of entangled amorphous polystyrene (PS) with a molecular weight (M) of 10⁵ g/mol or 10⁶ g/mol were kept in contact at T = T_g^bulk − 33 °C for one day. The as-self-bonded PS–PS auto-adhesive joints (AJ) of PSs differing in M by an order of magnitude were fractured at ambient temperature, and their σ distributions were analyzed using the Weibull model, the quantile-quantile plots, the normality tests, and the Gaussian distribution. It has been shown that the Weibull model most correctly describes the σ statistical distributions of the two self-bonded PS–PS AJs with different M due to the joints’ brittleness. The values of the Weibull modulus (a statistical parameter) m = 2.40 and 1.89 calculated for PSs with M = 10⁵ and 10⁶ g/mol, respectively, were rather close, indicating that the chain length has a minor effect on the σ data scatter. The Gaussian distribution has been found to be less appropriate for this purpose, though all the normality tests performed have predicted the correctness of the normal distribution for these PS–PS interfaces. Full article

In recent years, there has been considerable research into functional materials inspired by living things. Much attention has been paid to the development of adhesive materials that mimic the adhesive proteins secreted by a mussel’s foot. These mussel-inspired materials have superior adhesiveness to various adherents owing to the non-covalent interactions of their polyphenolic moieties, e.g., hydrogen bonding, electrostatic interactions, and even hydrophobic interactions. Various factors significantly affect the adhesiveness of mussel-inspired polymers, such as the molecular weight, cross-linking density, and composition ratio of the components, as well as the chemical structure of the polyphenolic adhesive moieties, such as l-3,4-dihydroxyphenylalanine (l-Dopa). However, the contributions of the position and distribution of the adhesive moiety in mussel-inspired polymers are often underestimated. In the present study, we prepared a series of mussel-inspired alkyl methacrylate copolymers by controlling the position and distribution of the adhesive moiety, which are known as “forced gradient copolymers”. We used a newly designed gallic-acid-bearing methacrylate (GMA) as the polyphenolic adhesive moiety and copolymerized it with 2-ethylhexyl methacrylate (EHMA). The resulting forced gradient adhesive copolymer of GMA and EHMA (poly(GMA-co-EHMA), Poly1) was subjected to adhesion and dispersion tests with an aluminum substrate and a BaTiO₃ nanoparticle in organic solvents, respectively. In particular, this study aims to clarify how the monomer position and distribution of the adhesive moiety in the mussel-inspired polymer affect its adhesion and dispersion behavior on a flat metal oxide surface and spherical inorganic oxide surfaces of several tens of nanometers in diameter, respectively. Here, forced gradient copolymer Poly1 consisted of a homopolymer moiety of EHMA (Poly3) and a random copolymer moiety of EHMA and GMA (Poly4). The composition ratio of GMA and the molecular weight were kept constant among the Poly1 series. Simultaneous control of the molecular lengths of Poly3 and Poly4 allowed us to discuss the effects on the distribution of GMA in Poly1. Poly1 exhibited apparent distribution dependency with regard to the adhesiveness and the dispersibility of BaTiO₃. Poly1 showed the highest adhesion strength when the composition ratio of GMA was approximately 9 mol% in the portion of the Poly4 segment. In contrast, the block copolymer consisting of the Poly3 segment and Poly4 segment with only adhesive moiety 1 showed the lowest viscosity for dispersion of BaTiO₃ nanoparticles. These results indicate that copolymers with mussel-inspired adhesive motifs require the proper design of the monomer position and distribution in Poly1 according to the shape and characteristics of the adherend to maximize their functionality. This research will facilitate the rational design of bio-inspired adhesive materials derived from plants that outperform natural materials, and it will eventually contribute to a sustainable circular economy. Full article

In this work, we introduce lead-free organic ferroelectric perovskite N-methyl-N′-diazabicyclo[2.2.2]octonium)–ammonium triiodide (MDABCO-NH₄I₃) nanocrystals embedded in three different polymer fibers fabricated by the electrospinning technique, as mechanical energy harvesters. Molecular ferroelectrics offer the advantage of structural diversity and tunability, easy fabrication, and mechanical flexibility. Organic–inorganic hybrid materials are new low-symmetry emerging materials that may be used as energy harvesters because of their piezoelectric or ferroelectric properties. Among these, ferroelectric metal-free perovskites are a class of recently discovered multifunctional materials. The doped nanofibers, which are very flexible and have a high Young modulus, behave as active piezoelectric energy harvesting sources that produce a piezoelectric voltage coefficient up to g_eff = 3.6 VmN⁻¹ and show a blue intense luminescence band at 325 nm. In this work, the pyroelectric coefficient is reported for the MDABCO-NH₄I₃ perovskite inserted in electrospun fibers. At the ferroelectric–paraelectric phase transition, the embedded nanocrystals display a pyroelectric coefficient as high as 194 × 10⁻⁶ Cm⁻²k⁻¹, within the same order of magnitude as that reported for the state-of-the-art bulk ferroelectric triglycine sulfate (TGS). The perovskite nanocrystals embedded into the polymer fibers remain stable in their piezoelectric output response, and no degradation is caused by oxidation, making the piezoelectric perovskite nanofibers suitable to be used as flexible energy harvesters. Full article

A series of aromatic polyimides based on the asymmetrical diamine 3,4ʹ-oxydianiline and various tetracarboxylic acid dianhydrides, both “rigid” and “flexible” structure, have been synthesized using the original method of one-pot high-temperature catalytic polycondensation in molten benzoic acid. The synthesized polyimides were investigated using fourier-transform infrared (FTIR) and ¹H NMR spectroscopy, gel permeation chromatography (GPC), differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), thermomechanical analysis (TMA) and wide-angle X-ray scattering (WAXS). It was found that the synthesized polyimides, depending on the used dianhydride, are characterized by different solubility in organic solvent and molten benzoic acid, molecular weight, glass transition temperature (Tg) from 198 to 270 °C, an amorphous or semi crystalline structure with the degree of crystallinity from 41 to 52%. The influence of the method of synthesis on the formation of the crystalline phase of polyimides was studied, and the obtained results were compared with the literature data. The effect of dianhydride chemical structure on the performance of polyimide in pervaporation more specifically, dehydratation of azeotropic isopropanol solution was investigated and compared with the commercially available polyetherimide Ultem 1000™. Membrane structure was studied using scanning electron microscopy. It was found that polyimide PI-DA is the most effective for separation of 88 wt.% isopropanol/12 wt.% water mixture compared to the polyimide PI-6FDA and commercial polyetherimide Ultem 1000™ demonstrating normalized permeation flux of 2.77 kg µm m⁻² h⁻¹ and separation factor of 264 (water content in permeate 97 wt.%). Full article

For extensive radiation exposure, inventing a novel radiation shielding material is a burning issue at present for the purpose of life saving. Considering this thought, in this study, by adding sundry amounts of Bi₂O₃ into pure high-density polyethylene (HDPE), six HDPE systems were prepared to evaluate the radiation shielding efficiency. These HDPE systems were HDPEBi-0 (pure HDPE), HDPEBi-10 (10 wt% Bi₂O₃), HDPEBi-20 (20 wt% Bi₂O₃₋), HDPEBi-30 (30 wt% Bi₂O₃), HDPEBi-40 (40 wt% Bi₂O₃), and HDPEBi-50 (50 wt% Bi₂O₃). The values of the linear attenuation coefficients of the experimental results (calculated in the lab using HPGe) were compared with the theoretical results (obtained using Phy-X software) at 0.060, 0.662, 1.173, and 1.333 MeV energies. To ensure the accurateness of the experimental results, this comparison was made. It was crystal clear that for energy values from 0.06 MeV to 1.333 MeV, all the experimental values were in line with Phy-X software data, which demonstrated the research setup’s reliability. Here, the linear attenuation coefficient (LAC), and mean free path (MFP) shielding parameters were assessed. At the energy of 1.333 MeV, sample HDPEBi-0 showed an HVL value 1.7 times greater than that of HDPEBi-50, yet it was 23 times greater at 0.0595 MeV. That means that for proper radiation protection, very-low-energy HDPE systems containing 10–50% Bi₂O₃ could be used; however, the thickness of the HDPE system must be increased according to the energy of incident radiation. Full article

Silicone rubbers are a good choice for shielding materials because of having elastic and attenuating properties as well as cost-effectiveness. Thus, the aim of this study was to prepare ground-breaking silicone rubber samples by adding WO₃-nanoparticles and testing the performance of their radiation shielding ability against Cs-137, Co-60, and Am-241 gamma energy. Increasing the concentration of WO₃ nanoparticles in silicone rubber (SR) led to decreasing the half-value layer (HVL) and mean free path (MFP) values determined for the samples tested. Furthermore, the values of MFP and HVL upsurged according to the enhancement of the photon energy. It is noteworthy that the prepared silicone rubber (SR) systems with 50 and 60 wt% concentrations of WO₃-nanoparticles displayed lower HVL than the Bi₂O₃-containing silicone rubber (SR) systems. In the same way, studied silicone rubber SR-W60 represented the lowest HVL comprising iron ore containing silicone rubber. Full article

Polymers are of great interest in areas such as agriculture, medicine and pharmacy, the food and cosmetic industries, and the chemical and construction industries. However, many polymers are nonbiodegradable and are not environmentally friendly. They are highly resistant to degradation and therefore can lead to waste disposal problems. In recent years, the interest in the microbial degradation of polymeric materials has grown due to the desire for less waste pollution in the environment. In this study, the biodegradable polymer that was obtained by the ring-opening polymerization of ε-caprolactone (CL) using an aminopropyl-polydimethylsiloxane (APDMS) oligomer and the effects of the polymer towards the growth and development of tomato plants (Lypercosium esculentum) were investigated. The obtained product was characterized using FTIR spectroscopy, NMR spectroscopy, and energy dispersion spectroscopy (EDX) analysis, and the effects of this compound on the evolution of tomato plants (Lypercosium esculentum) were studied. We also studied the biological stability of the product by identifying some of the microorganisms that developed on the surface, given its susceptibility to biodegradation. Full article

In this study, the extremely important and difficult topic of flexographic printing on a heat-shrinkable substrate was taken up. Six commercially available, electrically conductive inks based on silver, copper and graphite nanoparticles were selected and tested upon their applicability for printing on the temperature-sensitive PET material. As a printing substrate, the one-direction heat-shrinkable PET film, with a maximum shrinkage of 78%, was selected. All of the examined inks were subjected to the printing process throughout three different anilox line screens. The tested inks, along with the electric paths printed with them, were subjected to various tests. The main parameters were evaluated, such as printability combined with the rheology tests and ink adhesion to the examined PET substrate together with the electrical conductivity before and after the shrinkage. Full article

Polyethylene terephthalate (PET) is a thermoplastic material that is widely used in many application fields, such as packaging, construction and household products. Due to the relevant contribution of PET to global yearly solid waste, the recycling of such material has become an important issue. Disposed PET does not maintain the mechanical properties of virgin material, as exposure to water and other substances can cause multiple chain scissions, with subsequent degradation of the viscoelastic properties. For this reason, chain extension is needed to improve the final properties of the recycled product. Chain extension is generally performed through reactive extrusion. As the latter involves structural modification and flow of PET molecules, rheology is a relevant asset for understanding the process and tailoring the mechanical properties of the final products. This paper briefly reviews relevant rheological studies associated with the recycling of polyethylene terephthalate through the reactive extrusion process. Full article

Efficient capture of CO₂ and its conversion into other high value-added compounds by electrochemical methods is an effective way to reduce excess CO₂ in the atmosphere. Porous polymeric materials hold great promise for selective adsorption and electrocatalytic reduction of CO₂ due to their high specific surface area, tunable porosity, structural diversity, and chemical stability. Here, we review recent research advances in this field, including design of porous organic polymers (POPs), porous coordination polymers (PCPs), covalent organic frameworks (COFs), and functional nitrogen-containing polymers for capture and electrocatalytic reduction of CO₂. In addition, key issues and prospects for the optimal design of porous polymers for future development are elucidated. This review is expected to shed new light on the development of advanced porous polymer electrocatalysts for efficient CO₂ reduction. Full article

The application of polymeric and composite materials in two-phase passive heat transfer devices is reviewed critically, with a focus on advantages and disadvantages of these materials in thermal management systems. Recent technology developments led to an increase of the power density in several applications including portable electronics, space and deployable systems, etc., which require high-performance and compact thermal management systems. In this context, passive two-phase systems are the most promising heat transfer devices to dissipate large heat fluxes without external power supply. Usually, heat transfer systems are built with metals due to their excellent thermal properties. However, there is an increasing interest in replacing metallic materials with polymers and composites that can offer cost-effectiveness, light weight and high mechanical flexibility. The present work reviews state-of the-art applications of polymers and composites in two-phase passive thermal management systems, with an analysis of their limitations and technical challenges. Full article