Search

This study investigated a blend of poly (lactic acid) (PLA) and Saqqez gum, with a weight ratio of 70:30, respectively, along with two plasticizers, acetyl tributyl citrate (ATBC) and polyethylene glycol (PEG), at three different concentrations (14%, 16% and 18% by weight of the PLA). The blend was analyzed using differential scanning calorimetry (DSC), scanning electron microscopy (SEM), tensile tests, water-absorption behavior (coefficients of water absorption, sorption, diffusion and permeability of the samples during 240 h) and chemical resistance (exposure to 1 mol/L HCl and 1 mol/L NaOH for 240 h). The desired elastomer blend was then used to prepare natural chewing gum, which was subsequently subjected to texture profile analyzer (TPA) tests and sensory evaluation. The results showed that the addition of both plasticizers increased the tensile properties of the blend. Compared to neat PLA, all the blends exhibited an increase in elongation at break and a decrease in yield strength, with the maximum elongation at break (130.6%) and the minimum yield strength (12.2 MPa) observed in the blend containing 16% ATBC. Additionally, all the thermal attributes studied, including Tg, Tc and Tm, were lower than those of neat PLA, and the Tg values deviated from the values predicted via Fox's equation. SEM images of the blends confirmed that plasticization improved the homogeneity and distribution of the components in the blend structure. PEG 18% and ATBC 16% exhibit the highest and lowest water-absorption behavior, respectively. Regarding chemical resistance, all blends showed weight gain when exposed to HCl, while no weight loss was observed for resistance to NaOH. The chewing gum sample obtained similar values for the mentioned tests compared to the commercial control sample. Overall, the results indicate that plasticization enhances the structure and performance of the PLA/Saqqez gum blend and further investigation is warranted. [ABSTRACT FROM AUTHOR]

Although several force application concepts are known that can be used to deform shape memory polymers (SMPs) within the scope of programming, controlled deformation is challenging in the case of samples with a cylinder-like shape, which need to be homogeneously compressed starting from the lateral surface. To solve this problem, this contribution follows a material approach that takes advantage of four-dimensional (4D) printing. Fused filament fabrication (FFF) was used as an additive manufacturing (AM) technique to produce a thermoresponsive tool in a cylindrical shape from a polyether urethane (PEU) having a glass transition temperature (Tg) close to 55 °C, as determined by differential scanning calorimetry (DSC). Once it was 4D-printed, a sample of laser cut polyester urethane urea (PEUU) foam with a cylindrical wall was placed inside of it. Subsequent heating to 75 °C and keeping that temperature constant for 15 min resulted in the compression of the foam, because the internal stresses of the PEU were transferred to the PEUU, whose soft segments were completely molten at 65 °C as verified by DSC. Upon cooling to −15 °C and thus below the offset temperature of the soft segment crystallization transition of the PEUU, the foam was fixed in its new shape. After 900 days of storage at temperatures close to 23 °C, the foam recovered its original shape upon reheating to 75 °C. In another experiment, a 4D-printed cylinder was put into hibernation for 900 days before its thermoresponsiveness was investigated. In the future, 4D-printed tools may be produced in many geometries, which fit well to the shapes of the SMPs to be programmed. Beyond programming SMP foams, transferring the forces released by 4D-printed tools to other programmable materials can further expand technical possibilities. [ABSTRACT FROM AUTHOR]

Although the mesomorphic phase as an intermediate state has been introduced to understand polymer crystallization, the understanding of the mesomorphic phase is far from complete. Here, the effect of chain mobility on the mesophase structuring in melt-quenched poly(ʟ-lactide) (PLLA) treated in low-pressure CO2 at 1.6–2.0 MPa and 0 °C was investigated using infrared (IR) spectroscopy, differential scanning calorimetry (DSC), and atomic force microscopy (AFM). The IR and AFM results demonstrated that the final degree of order and the kinetics of structural evolution during the CO2-induced mesophase formation were critically dependent on the CO2 pressure. This was attributed to the distinct dynamics of conformational evolution (gg to gt conformer transition) due to the different CO2 pressures. The thermal behavior from the DSC results showed that CO2 pressure dominated both the scale and dynamics of the chain motion of PLLA. At a lower CO2 pressure of 1.6 MPa, smaller-scale segmental motion was not replaced by the larger-scale cooperative motion that occurred at a relatively higher CO2 pressure of 2 MPa, which was favorable for faster mesophase formation. Consequently, by inhibiting direct crystallization under limited mobility conditions, it was demonstrated that different chain mobility controlled by CO2 pressure and thus CO2 solubility impacted the dynamics of the mesophase formation of PLLA. The present results have implications for understanding the role of chain mobility in determining the intermediate structural phases in semicrystalline polymers. [ABSTRACT FROM AUTHOR]

Nosocomial infections represent a major threat within healthcare systems worldwide, underscoring the critical need for materials with antimicrobial properties. This study presents the development of polyurethane foam embedded with silver nanoparticles (PUF/AgNPs) using a rapid, eco-friendly, in situ radiochemical synthesis method. The nanocomposites were characterized by UV–vis and FTIR spectroscopy, scanning electron microscopy coupled with energy dispersive X-ray technique (SEM/EDX), differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), tensile and compression strengths, antimicrobial activity, and foam toxicity tests. The resulting PUF/AgNPs demonstrated prolonged stability (over 12 months) and good dispersion of AgNPs. Also, the samples presented higher levels of hardness compared to samples without AgNPs (deformation of 1682 µm for V1 vs. 4307 µm for V0, under a 5 N force), tensile and compression strength of 1.80 MPa and 0.34 Mpa, respectively. Importantly, they exhibited potent antimicrobial activity against a broad range of bacteria (including Pseudomonas aeruginosa, Staphylococcus aureus, Escherichia coli, and Enterococcus faecalis) and a fungal mixture (no fungal growth on the sample surface was observed after 28 days of exposure). Furthermore, these materials were non-toxic to human keratinocytes, which kept their specific morphology after 24 h of incubation, highlighting their potential for safe use in biomedical applications. We envision promising applications for PUF/AgNPs in hospital bed mattresses and antimicrobial mats, offering a practical strategy to reduce nosocomial infections and enhance patient safety within healthcare facilities. [ABSTRACT FROM AUTHOR]

In this study, the objective was to optimize energy consumption in the fused deposition modeling (FDM) 3D printing process via a detailed analysis of printing parameters. By utilizing thermal analysis techniques, this research aimed to identify lower printing temperatures that could lead to reduced energy usage. Experimental analysis was conducted using a three-level L9 Taguchi orthogonal array, which involved a systematic combination of different extruder temperatures and cooling fan capacities. Furthermore, the research incorporated differential scanning calorimetry (DSC) and X-ray diffraction (XRD) methods to analyze the thermal properties and crystallinity of the 3D-printed specimens. The results indicated that temperature was a key factor affecting crystallinity, with samples printed at 190 °C and 60% fan capacity showing the highest mean values. By conducting a multi-objective desirability analysis, the optimal conditions for maximizing ultimate tensile strength (UTS), tensile modulus, and elongation at break while minimizing energy consumption for PLA 3D-printed samples were determined to be a temperature of 180 °C and a fan speed of 80%. [ABSTRACT FROM AUTHOR]

A plantain pseudostem was harvested and processed on the same day. The process began with manually separating the sheaths (80.85%) and the core (19.14%). The sheaths were subjected to a mechanical shredding process using paddles, extracting 2.20% of lignocellulosic fibers and 2.12% of sap, compared to the fresh weight of the sheaths. The fibers were washed, dried, combed, and spun in their native state and subjected to a steam explosion treatment, while the sap was subjected to filtration and evaporation. In the case of the core, it was subjected to manual cutting, drying, grinding, and sieving to separate 12.81% of the starch and 6.39% of the short lignocellulosic fibers, compared to the fresh weight of the core. The surface modification method using steam explosion succeeded in removing a low proportion of hemicellulose and lignin in the fibers coming from the shims, according to what was shown by Fourier Transform Infrared Spectroscopy (FT-IR), Thermogravimetric Analysis (TGA), and Differential Scanning Calorimetry (DSC), achieving increased σmax and ε from the tensile test and greater thermal stability compared to its native state. The sap presented hygroscopic behavior by FT-IR and the highest thermal stability from TGA, while the starch from the core presented the lowest hygroscopic character and thermal stability. Although the pseudostem supplied two types of fibers, lower lignin content was identified in those from the core. Finally, the yarns were elaborated by using the fibers of the sheaths in their native and steam-exploded states, identifying differences in the processing and their respective physical and mechanical properties. [ABSTRACT FROM AUTHOR]

Sodium hyaluronate (HA) is a natural polysaccharide. This biopolymer occurs in many tissues of living organisms. The regenerating, nourishing, and moisturizing properties as well as the rheological properties of HA enable its application in the pharmaceutical industry as a carrier of medicinal substances. The aim of this work was to assess the release of naproxen sodium (Nap) in the presence of lidocaine hydrochloride (Lid) from the biopolymer-based hydrogels and to determine the respective kinetic parameters of this process. The possible interaction between the HA polysaccharide carrier and the selected drugs was also investigated. Three hydrogels containing Nap and Lid with different concentrations of the biopolymer were prepared. The release of Nap was studied by employing USP apparatus 5. The infrared study and differential scanning calorimetry analysis of physical mixtures and dried formulations were performed. The highest amount of Nap was released from the formulation with the lowest concentration of the biopolymer. The most representative kinetic model that described the dissolution of Nap was obtained through the Korsmeyer–Peppas equation. The release rate constants were in the range of 1.0 ± 0.1 × 10−2 min−n–1.7 ± 0.1 × 10−2 min−n. Lid did not influence the dissolution of Nap from the formulations tested; however, in the desiccated samples of assessed formulations, the interaction between the polysaccharide and both drugs was observed. [ABSTRACT FROM AUTHOR]

The polar sulfonate groups in cationic dyeable polyester (CDP) lead to complex crystallization behavior, affecting CDP production's stability. In this study, cationic dyeable polyesters (CDP) with different sulfonate group contents were prepared via one-step feeding of sodium isophthalic acid-5-sulfonate (SIPA), terephthalic acid (PTA), and ethylene glycol (EG). The non-isothermal crystallization behavior of these copolyesters was analyzed by differential scanning calorimetry (DSC). Results show that the crystallization temperature of the sample shifts to lower values with the increase in SIPA content. The relaxation behavior of the molecular chain is enhanced due to the ionic aggregation effect of sulfonate groups in CDP. Therefore, at low cooling rates (2.5 °C/min and 5 °C/min), some molecular chain segments in CDP are still too late to orderly stack into the lattice, forming metastable crystals, and melting double peaks appear on the melting curve after crystallization. When the cooling rate increases (10–20 °C/min), the limited region of sulfonate aggregation in CDP increases, resulting in more random chain segments, and a cold crystallization peak appears on the melting curve after crystallization. The non-isothermal crystallization behavior of all samples was fitted and analyzed by the Jeziorny equation, Ozawa equation, and Mo equation. The results indicate that the nucleation density and nucleation growth rate of CDP decrease with the increase in SIPA content. Meanwhile, analysis of the Kissinger equation reveals that the activation energy of non-isothermal crystallization decreases gradually with the increase in SIPA content, and the addition of SIPA makes CDP crystallization more difficult. [ABSTRACT FROM AUTHOR]

The biaxially-oriented PA56/512 has excellent mechanical strength, extensibility and water–oxygen barrier properties and has broad application prospects in green packaging, lithium battery diaphragm and medical equipment materials. The correlation between the aggregation structure evolution and macroscopic comprehensive properties of copolymer PA56/512 under biaxial stretching has been demonstrated in this work. The structure of the random copolymerization sequence was characterized by 13C Nuclear magnetic resonance (NMR). The typical isodimorphism behavior of the co-crystallization system of PA56/512 and its BOPA-56/512 films was revealed by differential scanning calorimetry (DSC) and X-ray diffraction (XRD) tests. And the aggregation structure, including the hydrogen bond arrangement, crystal structure and crystal morphology of PA56/512 before and after biaxial stretching, was investigated by XRD, Fourier-transform infrared spectroscopy (FTIR) and polarized optical microscopy (POM) tests. Furthermore, the effect of the biaxially-oriented stretching process on the mechanical properties of PA56/512 has been demonstrated. In addition, a deep insight into the influence of the structure on the crystallization process and physical–mechanical performance has been presented. The lowest melting point at a 512 content of 60 mol% is regarded as a "eutectic" point of the isodimorphism system. Due to the high disorder of the structural units in the polymer chain, the transition degree of the folded chain (gauche conformation) is relatively lowest when it is straightened to form an extended chain (trans conformation) during biaxially-oriented stretching, and part of the folded chain can be retained. This explains why biaxially stretched PA56/512 has high strength, outstanding toughness and excellent barrier properties at the pseudo-eutectic point. In this study, using the unique multi-scale aggregation structure characteristics of a heterohomodymite polyamide at the pseudo-eutectic point, combined with the new material design scheme and the idea of biaxial-stretching processing, a new idea for customized design of high-performance multifunctional polyamide synthetic materials is provided. [ABSTRACT FROM AUTHOR]

Based on a novel phenylacetylene capped polyimide (PI) with unique high-temperature resistance, its curing kinetics and thermal decomposition behavior were investigated. The curing mechanism and kinetics were studied by differential scanning calorimetry (DSC), and the activation energy (Ea) and pre-exponential factor (A) of the curing reaction were calculated based on the Kissinger equation, Ozawa equation, and Crane equation. According to the curve of conversion rate changing with temperature, the relationship between the dynamic reaction Ea and conversion rate (α) was calculated by the Friedman equation, Starink equation, and Ozawa–Flynn–Wall (O-F-W) equation, and the reaction Ea in different stages was compared with the results of molecular dynamics. Thermogravimetric analysis (TGA) and a scanning electron microscope (SEM) were used to analyze the thermal decomposition behavior of PI resins before and after curing. Temperatures at 5% and 20% mass loss (T5%, T20%), peak decomposition temperature (Tmax), residual carbon rate (RW), and integral process decomposition temperature (IPDT) were used to compare the thermal stability of PI resins and cured PI resins. The results display that the cured PI has excellent thermal stability. The Ea of the thermal decomposition reaction was calculated by the Coats–Redfern method, and the thermal decomposition behavior was analyzed. The thermal decomposition reaction of PI resins at different temperatures was simulated by molecular dynamics, the initial thermal decomposition reaction was studied, and the pyrolysis mechanism was analyzed more comprehensively and intuitively. [ABSTRACT FROM AUTHOR]

An epoxy compound's polymer structure can be characterized by the glass transition temperature (Tg) which is often seen as the primary morphological characteristic. Determining the Tg after manufacturing thermoset-molded parts is an important objective in material characterization. To characterize quantitatively the dependence of Tg on the degree of cure, the DiBenedetto equation is usually used. Monitoring polymer network formation during molding processes is therefore one of the most challenging tasks in polymer processing and can be achieved using dielectric analysis (DEA). In this study, the morphological properties of an epoxy resin-based molding compounds (EMC) were optimized for the molding process using response surface analysis. Processing parameters such as curing temperature, curing time, and injection rate were investigated according to a DoE strategy and analyzed as the main factors affecting Tg as well as the degree of cure. A new method to measure the Tg at a certain degree of cure was developed based on warpage analysis. The degree of cure was determined inline via dielectric analysis (DEA) and offline using differential scanning calorimetry (DSC). The results were used as the response in the DoE models. The use of the DiBenedetto equation to refine the response characteristics for a wide range of process parameters has significantly improved the quality of response surface models based on the DoE approach. [ABSTRACT FROM AUTHOR]

This study addresses the challenge of enhancing the transverse mechanical properties of oriented polyacrylonitrile (PAN) nanofibers, which are known for their excellent longitudinal tensile strength, without significantly compromising their inherent porosity, which is essential for effective filtration. This study explores the effects of doping PAN nanofiber composites with varying concentrations of polyvinyl alcohol (PVA) (0.5%, 1%, and 2%), introduced into the PAN matrix via a dip-coating method. This approach ensured a random distribution of PVA within the nanofiber mat, aiming to leverage the synergistic interactions between PAN fibers and PVA to improve the composite's overall performance. This synergy is primarily manifested in the structural and functional augmentation of the PAN nanofiber mats through localized PVA agglomerations, thin films between fibers, and coatings on the fibers themselves. Comprehensive evaluation techniques were employed, including scanning electron microscopy (SEM) for morphological insights; transverse and longitudinal mechanical testing; a thermogravimetric analysis (TGA) for thermal stability; and differential scanning calorimetry (DSC) for thermal behavior analyses. Additionally, a finite element method (FEM) analysis was conducted on a numerical simulation of the composite. Using our novel method, the results demonstrated that a minimal concentration of the PVA solution effectively preserved the porosity of the PAN matrix while significantly enhancing its mechanical strength. Moreover, the numerical simulations showed strong agreement with the experimental results, validating the effectiveness of PVA doping in enhancing the mechanical properties of PAN nanofiber mats without sacrificing their functional porosity. [ABSTRACT FROM AUTHOR]

In our study, we investigated the accelerated aging process of PLA under 253.7 nm UV-C irradiation with the use of the GPC, NMR, FTIR, and DSC methods and formal kinetic analysis. The results of GPC and DSC indicated a significant degree of destructive changes in the PLA macromolecules, while spectroscopic methods NMR and FTIR showed maintenance of the PLA main structural elements even after a long time of UV exposure. In addition to that, the GPC method displayed the formation of a high molecular weight fraction starting from 24 h of irradiation, and an increase in its content after 144 h of irradiation. It has been shown for the first time that a distinctive feature of prolonged UV exposure is the occurrence of intra- and intermolecular radical recombination reactions, leading to the formation of a high molecular weight fraction of PLA decomposition products. This causes the observed slowdown of the photolysis process. It was concluded that photolysis of PLA is a complex physicochemical process, the mechanism of which depends on morphological changes in the solid phase of the polymer under UV radiation. [ABSTRACT FROM AUTHOR]

This study investigates the use of low molecular weight poly(ethylene glycol) (PEG) as a plasticizer for poly(lactic acid) (PLA). PLA/PEG blend films were prepared using the solvent casting method with varying mixing ratios. The films were analyzed using differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), and dynamic rheological analysis. The results indicate that the addition of PEG as a plasticizer affects the thermal and mechanical properties of the PLA/PEG blend films. The study found that the glass transition and cold crystallization temperatures decreased with increasing PEG content up to 20 wt%, while the crystallinity and crystallization rate increased. The blends with up to 20 wt% PEG were miscible, but phase separation occurred when the plasticizer content was increased to 30 wt%. Subsequently, amorphous samples of neat PLA and PLA plasticized with 10 wt% of PEG underwent annealing at various temperatures (Ta = 80–120 °C) for durations ta of 1 and 24 h. The samples were then analyzed using DSC and DMA. The addition of PEG to PLA altered the content of α′ and α crystalline forms compared to neat PLA at a given (Ta; ta) and favored the formation of a mixture of α′ and α crystals. The crystallinity achieved upon annealing increased with increasing Ta or ta and with the incorporation of PEG. [ABSTRACT FROM AUTHOR]

Two polyurethanes (PUs) were similarly synthesized by reacting a cycloaliphatic isocyanate with 1,4-butanediol and two polyols of different nature (polyester, polycarbonate diol) with molecular weights of 1000 Da. Only the PU synthesized with polycarbonate diol polyol (YCD) showed intrinsic self-healing at 20 °C. For assessing the mechanism of intrinsic self-healing of YCD, a structural characterization by molecular weights determination, infrared and X-ray photoelectronic spectroscopies, differential scanning calorimetry, X-ray diffraction, thermal gravimetric analysis, and dynamic mechanical thermal analysis was carried out. The experimental evidence concluded that the self-healing at 20 °C of YCD was due to dynamic non-covalent exchange interactions among the polycarbonate soft segments. Therefore, the chemical nature of the polyol played a key role in developing PUs with intrinsic self-healing at 20 °C. [ABSTRACT FROM AUTHOR]

The replacement of synthetic and petroleum-based ingredients with greener alternatives of natural origin is an imperative issue in rubber technology for the tire industry. In this study, a glycerin-esterified maleated rosin resin, derived from natural resources, is examined as a potential tackifier in styrene–butadiene rubber (SBR) formulations. A comparison is made with two synthetic resins commonly used as tackifiers in tire manufacturing: a petroleum-derived aromatic resin and a phenolic resin. Specifically, this research investigates how these resins affect the structure, dynamics, and curing characteristics of SBR compounds, which are strictly related to the mechanical and technological properties of the final products. Moving die rheometer and equilibrium swelling experiments are employed to analyze vulcanization kinetics and crosslink density, which are differently influenced by the different resins. Information on the polymer–resin compatibility is gained by differential scanning calorimetry and dynamo-mechanical analysis, while solid-state NMR methods offer insights into the structure and dynamics of both cured and uncured SBR compounds at the molecular level. Overall, our analysis shows that the resin of vegetal origin has a comparable impact on the SBR compound to that observed for the synthetic resins and could be further tested for industrial applications. [ABSTRACT FROM AUTHOR]

The crystal morphology and conformational changes during crystallization of a polypropylene random copolymer (PPR) are the basis for understanding its crystallization process. In this work, novel rare-earth β-nucleating agent WBN-28 was directly added into PPR to induce β-crystallization. The results of differential scanning calorimetry (DSC) showed that it has an excellent β-crystal-induced effect. The β-crystal content could surpass 85%, calculated from wide-angle X-ray diffraction (WAXD) data. The morphology of the β-crystal and α-crystal was intuitively observed via a polarizing optical microscope (POM). The β-crystallites were interconnected to naturally develop plate-like crystalline regions possessing a certain size, and the α-crystallites with sufficient thicknesses possessed a cross-hatched phenomenon. The bundle-like supramolecular structure of the β-crystal induced by WBN-28 was further observed via a scanning electron microscope (SEM). The conformational changes in the crystallization process of PPR were resolved via high-resolution infrared spectroscopy to understand its β-crystallization in depth. The conformational changes during the crystallization of PPR were found to be different from those of the isotactic polypropylene homopolymer (PPH); they had their own characteristics. This will provide guidance for understanding the β-crystallization of PPR in depth. [ABSTRACT FROM AUTHOR]

The application of mesoporous carriers in formulations of amorphous solid dispersions (ASDs) has been suggested to enhance the stability of amorphous drugs. However, mesoporous carriers do not demonstrate satisfactory inhibitory effects on the precipitation of active pharmaceutical ingredients (APIs), and the inclusion of an appropriate polymer within ASDs becomes imperative to maintaining drug supersaturation. The aim of this study was to evaluate ternary olanzapine (OLN) ASDs with Syloid 244FP and to find an appropriate polymeric carrier. The polymer's selection criteria were based on the physical stability of the ASDs and the release rate of the drug from the systems. The polymers investigated were hydroxypropylmethyl cellulose (HPMC) and copovidone (coPVP). The formation of ASDs was achievable in all investigated cases, as demonstrated by the complete lack of crystallinity confirmed through both powder X-ray diffraction (pXRD) analysis and differential scanning calorimetry (DSC) for all developed formulations. The solvent shift method was employed to evaluate the ability of the studied carriers to inhibit the precipitation of supersaturated OLN. coPVP emerged as a more suitable precipitation inhibitor compared with HPMC and Syloid 244 FP. Subsequently, in vitro dissolution studies under non-sink conditions revealed a higher degree of supersaturation in ternary systems where coPVP was used as a polymeric carrier, as these systems exhibited, under the examined conditions, up to a 2-fold increase in the released OLN compared with the pure crystalline drug. Moreover, stability studies conducted utilizing pXRD demonstrated that ternary formulations incorporating coPVP and Syloid 244 FP maintained stability for an extended period of 8 months. In contrast, binary systems exhibited a comparatively shorter stability duration, indicating the synergistic effect of coPVP and Syloid 244 FP on the physical stability of the amorphous API. Attenuated total reflectance–Fourier transform infrared (ATR-FTIR) studies showed that the development of stronger molecular interactions can be provided as an explanation for this synergistic effect, as the formation of robust H-bonds may be considered responsible for inhibiting the precipitation of the supersaturated API. Therefore, the incorporation of coPVP into OLN ASDs with Syloid 244 FP is considered a highly promising technique for increasing the degree of OLN supersaturation in in vitro dissolution studies and improving the stability of systems. [ABSTRACT FROM AUTHOR]

Several researchers have examined the interest in using a thermoplastic to increase thermoset polymers' shock resistance. However, fewer studies have examined the nature of the mechanisms involved between both kinds of polymers. This was the objective of our work, which was carried out using a gradual approach. First, we describe the synthesis of a poly(ether ether ketone) oligomer (oPEEK) with hydroxyl terminations from the reaction of hydroquinone and 4,4′-difluorobenzophenone in N-methyl-2-pyrrolidone. Then, the main physicochemical properties of this oligomer were determined using different thermal analyses (i.e., differential scanning calorimetry (DSC), thermogravimetric (ATG), and thermomechanical analyses) to isolate its response alone. The chemical characterisation of this compound using conventional analytical chemistry techniques was more complex due to its insolubility. To this end, it was sulfonated, according to a well-known process, to make it soluble and enable nuclear magnetic resonance (NMR) and size exclusion chromatography (SEC) experiments. Additional information about the structural and chemical characteristics of the oligomer and its average molecular weight could thus be obtained. The synthesis of an oligoPEEK with α,ω-hydroxyl end-groups and a molecular weight of around 5070 g/mol was thus confirmed by NMR. This value was in accordance with that determined by SEC analysis. Next, the reaction of oPEEK with an epoxy prepolymer was demonstrated using DSC and dynamic rheometry. To this end, uncured mixtures of epoxy prepolymer (DGEBA) with different proportions of oPEEK (3, 5, 10 and 25%) were prepared and characterised by both techniques. Ultimately, the epoxy-oPEEK mixture was cured with isophorone diamine. Finally, topological analyses were performed by atomic force microscopy (AFM) in tapping mode to investigate the interface quality between the epoxy matrix and the oPEEK particles indirectly. No defects, such as decohesion areas, microvoids, or cracks, were observed between both systems. [ABSTRACT FROM AUTHOR]

Biocomposite films based on PLA reinforced with different β-TCP contents (10%, 20%, and 25%wt.) were fabricated via solvent casting and immersed in SBF for 7, 14, and 21 days. The bioactivity, morphological, and thermal behavior of composites with immersion were studied using scanning electron microscopy (SEM), energy-dispersive X-ray (EDX) microanalysis, weight loss (WL), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), and gel permeation chromatography (GPC). This broad analysis leads to a deeper understanding of the evolution of the polymer–filler interaction with the degradation of the biocomposites. The results showed that β-TCP gradually evolved into carbonated hydroxyapatite as the immersion time increased. This evolution affected the interaction of β-TCP with PLA. PLA and β-TCP interactions differed from PLA and carbonated hydroxyapatite interactions. It was observed that β-TCP inhibited PLA hydrolysis but accelerated the thermal degradation of the polymer. β-TCP retarded the cold crystallization of PLA and hindered its crystallinity. However, after immersion in SBF, particles accelerated the cold crystallization of PLA. Therefore, considering the evolution of β-TCP with immersion in SBF is crucial for an accurate analysis of the biocomposites' degradation. These findings enhance the comprehension of the degradation mechanism in PLA/β-TCP, which is valuable for predicting the degradation performance of PLA/β-TCP in medical applications. [ABSTRACT FROM AUTHOR]

Background: Theophylline (THN), a bronchodilator with potential applications in emerging conditions like COVID-19, requires a controlled-release delivery system due to its narrow therapeutic range and short half-life. This need is particularly crucial as some existing formulations demonstrate impaired functionality. This study aims to develop a new 12-h controlled-release matrix system (CRMS) in the form of a capsule to optimize dosing intervals. Methods: CRMSs were developed using varying proportions of poloxamer 407 (P-407), stearyl alcohol (STA), and hydroxypropyl methylcellulose (HPMC) through the fusion technique. Their in vitro dissolution profiles were then compared with an FDA-approved THN drug across different pH media. The candidate formulation underwent characterization using X-ray diffraction, scanning electron microscopy, Fourier transform infrared spectroscopy, differential scanning calorimetry, and thermogravimetric analysis. Additionally, a comprehensive stability study was conducted. Results: In vitro studies showed that adjusting the concentrations of excipients effectively controlled drug release. Notably, the CRMS formulation 15 (CRMS-F15), which was composed of 30% P-407, 30% STA, and 10% HPMC, closely matched the 12 h controlled-release profile of an FDA-approved drug across various pH media. Characterization techniques verified the successful dispersion of the drug within the matrix. Furthermore, CRMS-F15 maintained a consistent controlled drug release and demonstrated stability under a range of storage conditions. Conclusions: The newly developed CRMS-F15 achieved a 12 h controlled release, comparable to its FDA-approved counterpart. [ABSTRACT FROM AUTHOR]

Lactide is one of the most popular and promising monomers for the synthesis of biocompatible and biodegradable polylactide and its copolymers. The goal of this work was to carry out a full cycle of polylactide production from lactic acid. Process conditions and ratios of reagents were optimized, and the key properties of the synthesized polymers were investigated. The influence of synthesis conditions and the molecular weight of lactic acid oligomers on the yield of lactide was studied. Lactide polymerization was first carried out in a 500 mL flask and then scaled up and carried out in a 2000 mL laboratory reactor setup with a combined extruder. Initially, the lactic acid solution was concentrated to remove free water; then, the oligomerization and synthesis of lactide were carried out in one flask in the presence of various concentrations of tin octoate catalyst at temperatures from 150 to 210 °C. The yield of lactide was 67–69%. The resulting raw lactide was purified by recrystallization in solvents. The yield of lactide after recrystallization in butyl acetate (selected as the optimal solvent for laboratory purification) was 41.4%. Further, the polymerization of lactide was carried out in a reactor unit at a tin octoate catalyst concentration of 500 ppm. Conversion was 95%; Mw = 228 kDa; and PDI = 1.94. The resulting products were studied by differential scanning calorimetry, NMR spectroscopy and gel permeation chromatography. The resulting polylactide in the form of pellets was obtained using an extruder and a pelletizer. [ABSTRACT FROM AUTHOR]

The food, pharmaceutical, and supply transport storage chain is seeking coolants that come with plastic-free packaging, are nontoxic, environmentally friendly, robust, reusable, and reduce water waste. To meet this demand, a new food coolant based on cornstarch hydrogel was developed and tested using the regeneration method. This study investigated the reusability, water retention, rehydration, and surface cleanliness of the hydrogel, along with its application in freshness retention for fruits. The results of the gel strength and differential scanning calorimetry (DSC) analysis showed that the ideal concentration of cornstarch hydrogel was 8%. Freezing and thawing experiments demonstrated that the hydrogel had the potential to be used as a cooling medium for refrigerated fresh foods. Moreover, the gel strength, scanning electron microscopy images (SEM), DSC, and thermogravimetric analysis (TG) revealed that the freeze–thaw reuse only slightly affected its freezable water content and that its gel strength gradually increased during reuse. Water retention and rehydration tests showed that the hydrogels could be better preserved at −20 °C compared to 4 °C, and the water lost during reuse could be replenished through rehydration. The flexibility in terms of shape and size also allows the hydrogel ice to be used as a customized coolant for various food shapes, as demonstrated by preservation experiments. Additionally, washing the hydrogel after each use can result in a significant reduction in Escherichia coli, Salmonella, and Staphylococcus aureus concentrations by 3.03, 3.47, and 2.77 log CFU/hydrogel, respectively. Overall, the new cornstarch hydrogel coolant is a promising alternative to conventional ice, with the potential to serve as a food coolant. [ABSTRACT FROM AUTHOR]

Aluminum butylmethylphosphinate AiBMP as a flame retardant and phenolphthalein as a synergistic agent were applied in a thermoplastic polyester elastomer (TPEE)) in the current study. The thermal properties, flame retardancy, crystallization and mechanical properties of TPEE/AiMBP with or without phenolphthalein were investigated using various characterizations, including the limiting oxygen index (LOI), vertical burning test (UL 94), thermogravimetric analysis TG, differential scanning calorimetry, microcombustion calorimeter (MCC), scanning electron microscopy (SEM), and mechanical tests. The results revealed that AiBMP alone is an efficient flame retardant of TPEE. Adding 15 wt.% AiBMP increases the LOI value of TPEE from 20% to 36%. The formula TPEE-15 AiBMP passed the UL 94 V-0 rating with no dripping occurring. The MCC test shows that AiBMP depresses the heat release of TPEE. In comparison with pure TPEE, the heat release rate at peak temperature and the heat release capacity of TPEE-15AiBMP are reduced by 46.1% and 55.5%, respectively. With the phenolphthalein added, the formula TPEE/13AiBMP/2Ph shows a higher char yield at high temperatures (>600 °C), and the char layer is stronger and more condensed than TPEE-15AiBMP.The tensile strength and elongation at break values of TPEE-13AiBMP-2Ph are increased by 29.63% and 4.8% in comparison with TPEE-15AiBMP. The SEM morphology of the fracture surface of the sample shows that phenolphthalein acts as a plasticizer to improve the dispersion of AiBMP within the matrix. The good char charming ability of phenolphthalein itself and improved dispersion of AiBMP make the TPEE composites achieve both satisfying flame retardancy and high mechanical properties. [ABSTRACT FROM AUTHOR]

A new family of polyester-based copolymers—poly(sorbitol adipate-co-ethylene glycol adipate) (PSAEG), poly(sorbitol adipate-co-1,4 butane diol adipate) (PSABD), and poly (sorbitol adipate-co-1,6 hexane diol adipate) (PSAHD)—was obtained with a catalyst-free melt polycondensation procedure using the multifunctional non-toxic monomer sorbitol, adipic acid, and diol, which are acceptable to the human metabolism. Synthesized polyesters were characterized by FTIR and 1H NMR spectroscopy. The molecular weight and thermal properties of the polymers were determined by MALDI mass spectroscopy, differential scanning calorimetry (DSC), and thermogravimetric analysis. The degradation rate was investigated, at 37 °C, in 0.1M NaOH (pH 13) and in phosphate-buffered solution (PBS) at pH 7.4. It was found that the polymers degraded faster in NaOH (i.e., in a day) compared to their degradation in PBS, which was much slower (in a week). The highest degradation rate was noticed for the PSAEG sample in both media, whereas PSAHD was the most stable polymer at pH 7.4 and 13. A reduced hydrophilicity of the polymers with diol length was indicated by low swelling percentage and sol content in water and DMSO. Mechanical studies prove that all the polymers are elastomers whose flexibility increases with diol length, shown by the increase in percentage of elongation at break and the decrease in tensile stress and Young's modulus. These biodegradable copolymers with adaptable physicochemical characteristics might be useful for a broad variety of biological applications by merely varying the length of the diol. [ABSTRACT FROM AUTHOR]

Recent focus on cellulose nanomaterials, particularly biodegradable and biocompatible cellulose nanocrystals (CNCs), has prompted their use as emulsion stabilizers. CNCs, when combined with salt, demonstrate enhanced emulsion stabilization. This study explored three emulsion stabilizers: Tween 80, soybean CNCs with salt (salted CNCs), and a combination of salted CNCs with Tween 80. Soybean CNCs, derived from soybean stover, were characterized by Fourier-transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). Antifungal testing against Aspergillus flavus revealed increased bioactivity in all lemongrass essential oil (EO)-loaded emulsions compared to pure essential oil. In addition, all three emulsions exhibited a slight reduction in antifungal activity after 30 days of room temperature storage. The release experiment revealed that the EO-loaded nanoemulsion exhibited a slow-release profile. The nanoemulsion stabilized by salted CNCs and Tween 80 exhibited significantly lower release rates when compared to the nanoemulsion stabilized solely by Tween 80, attributed to the gel network formed by salted CNCs. The findings of this study highlight the efficacy of cellulose nanocrystals procured from soybean byproducts in conjunction with synthetic surfactants to create nanoencapsulated essential oils, resulting in improved antimicrobial efficacy and the achievement of sustained release properties. [ABSTRACT FROM AUTHOR]

To enhance the degradability of poly(butylene adipate-co-terephthalate) (PBAT), reed fiber (RF) was blended with PBAT to create composite materials. In this study, a fifteen day degradation experiment was conducted using four different enzyme solutions containing lipase, cellulase, Proteinase K, and esterase, respectively. The degradation process of the sample films was analyzed using an analytical balance, Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), and differential scanning calorimetry (DSC). The PBAT/RF composites exhibited an increased surface hydrophilicity, which enhanced their degradation capacity. Among all the enzymes tested, lipase had the most significant impact on the degradation rate. The weight loss of PBAT and PBAT/RF, caused by lipase, was approximately 5.63% and 8.17%, respectively. DSC analysis revealed an increase in the melting temperature and crystallinity over time, especially in the film containing reed fibers. FTIR results indicated a significant weakening of the ester bond peak in the samples. Moreover, this article describes a biodegradation study conducted for three months under controlled composting conditions of PBAT and PBAT/RF samples. The results showed that PBAT/RF degraded more easily in compost as compared to PBAT. The lag phase of PBAT/RF was observed to decrease by 23.8%, while the biodegradation rate exhibited an increase of 11.8% over a period of 91 days. SEM analysis demonstrated the formation of more cracks and pores on the surface of PBAT/RF composites during the degradation process. This leads to an increased contact area between the composites and microorganisms, thereby accelerating the degradation of PBAT/RF. This research is significant for preparing highly degradable PBAT composites and improving the application prospects of biodegradable green materials. PBAT/RF composites are devoted to replacing petroleum-based polymer materials with sustainable, natural materials in advanced applications such as constructional design, biomedical application, and eco-environmental packaging. [ABSTRACT FROM AUTHOR]

An analysis of the influence of common modifiers on the kinetics of the curing process of epoxy-anhydride vitrimers was carried out. As common modifiers to enhance the "vitrimeric" nature of the material, zinc acetylacetonate as a transesterification catalyst and glycerol as a modifier of hydroxyl group content were chosen. The curing process of all obtained compositions was studied by differential scanning calorimetry (DSC) followed by the application of the isoconversional approach. It was shown that additives significantly affect the curing process. The resulting cured polymers were shown to be chemically recyclable by dissolution in the mixture of ethylene glycol and N-methylpirrolidone in a volume ratio of nine to one. The introduction of both zinc acethylacetonate and glycerol to the neat formulation led to a decrease in the dissolution time by 85.7% (from 35 h for the neat epoxy-anhydride formulation to 5 h for the modified formulation). In order to show the opportunity of the secondary use of recyclates, the mixtures based on the basic composition containing 10 wt. % of secondary polymers were also studied. The introduction of a recycled material to neat composition led to the same curing behavior as glycerol-containing systems. [ABSTRACT FROM AUTHOR]

A polyurethane series (PHEI-PU) was prepared via a one-shot bulk polymerization method using hexamethylene diisocyanate (HDI), polycarbonate diol (PCD), and isosorbide derivatives (ISBD) as chain extenders. The mechanical properties were evaluated using a universal testing machine (UTM), and the thermal properties were evaluated using thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). The PHEI-PU series exhibited excellent mechanical properties with an average tensile strength of 44.71 MPa and an elongation at break of 190%. To verify the applicability of different proportions of PU as an electrode binder, PU and Ag flakes were mixed (30/70 wt%) and coated on PCT substrates, the electrodes were evaluated by four-point probe before and after 50% elongation, and the dispersion was evaluated by scanning electron microscopy (SEM). The electrical resistance change rate of PHEI-PU series was less than 20%, and a coating layer with well-dispersed silver flakes was confirmed even after stretching. Therefore, it exhibited excellent physical properties, heat resistance, and electrical resistance change rate, confirming its applicability as an electrode binder for in-mold coating. [ABSTRACT FROM AUTHOR]

The long-term durability of polymer components produced by additive manufacturing (AM) in marine conditions is poorly understood. Here, fused filament fabrication (FFF) of Ultem 9085 was conducted and accelerated aging was performed. Two printing orientations (−45/45° and 0/90°) and two sample types (ASTM D638 Type 1 and Type 4) were produced and subjected to accelerated aging in either seawater or air. Results from tensile tests showed that the elastic modulus, yield strength and ultimate tensile strength increased after seawater aging, whereas the elongation to failure decreased. Results of thermogravimetric analysis (TGA) and derivative–TGA curves indicated that hydrolysis occurred after seawater exposure to the polycarbonate (PC) component and changes in structure or hydrogen bonds formed in the polyetherimide (PEI) component. Differential scanning calorimetry showed that physical aging occurred after short exposure periods and low temperature. Longer exposures and higher temperatures resulted in increasing plasticization by water and scission of the PC molecules. Results from Raman suggest that hydrolysis of the PC occurred, with a reduction in free volume produced by physical aging or hydrogen bonding with water molecules. These results highlight that Ultem 9085 is susceptible to degradation in marine environments, and there are two primary mechanisms, including physical and chemical aging. Their specific contribution is highly sensitive to the aging temperature and require careful selection in accelerated aging evaluations. [ABSTRACT FROM AUTHOR]

Colorless and transparent polyimide (CPI) films with good atomic oxygen (AO) resistance and high thermal endurance are highly required in low earth orbit (LEO) space exploration. Conventional CPI films based on fluoro-containing 4,4′-(hexafluoroisopropylidene)diphthalic anhydride (6FDA) have been widely used in space applications. However, the AO erosion yields and glass transition temperatures (Tg) of the 6FDA-based CPI films have to be modified in order to meet the severe serving environments. In the current work, novel CPI films based on a multi-ring fluoro-containing 9,9-bis(trifluoromethyl)xanthene-2,3,6,7-tetracarboxylicdianhydride (6FCDA) monomer were developed. In order to enhance the AO resistance of the derived CPI film, a phosphorus-containing aromatic diamine, 2,5-bis[(4-aminophenoxy)phenyl]diphenylphosphine oxide (BADPO) was used to polymerize with the dianhydride to create the organo-soluble resin. Then, two phosphorus-containing CPI films (PPI), including PPI-1 (6FDA-BADPO) and PPI-2 (6FCDA-BADPO) were prepared by thermally curing of the PPI solutions at elevated temperatures. The PPI films maintained good optical transparency with transmittance values over 80% at a wavelength of 450 nm. PPI-2 exhibited a Tg value of 311.0 °C by differential scanning calorimetry (DSC) measurement, which was 46.7 °C higher than that of the PPI-1 counterpart (Tg = 264.3 °C). In addition, the PPI-2 film showed a coefficient of linear thermal expansion (CTE) value of 41.7 × 10−6/K in the range of 50~250 °C, which was apparently lower than that of the PPI-1 sample (CTE = 49.2 × 10−6/K). Lastly, both of the two PPI films exhibited good AO resistance with the erosion yields (Ey) of 6.99 × 10−25 cm3/atom for PPI-1 and 7.23 × 10−25 cm3/atom for PPI-2 at an exposure flux of 5.0 × 1020 atoms/cm2. The Ey values of the current PPI films were obviously lower than that of the standard polyimide (PI) film based on pyromellitic dianhydride (PMDA) and 4,4′-oxydianiline (ODA) (Ey = 3.0 × 10−24 cm3/atom). [ABSTRACT FROM AUTHOR]

Polylactic acid (PLA) is a versatile and sustainable polymer used in various applications. This research explores the use of orotic acid (OA) and ethylene bis-stearamide (EBS) as nucleating agents to enhance the quiescent crystallization of PLA within the temperature range of 80 °C to 140 °C. Different blends were produced via melt processing before analyzing via DSC, XRD, and SEM. Our results show that both nucleating agents significantly accelerated the crystallization process and reduced the incubation time and the crystallization half-time. The most promising results were obtained with 1% EBS at 110 °C, achieving the fastest crystallization. The XRD analysis showed that at 80 °C, the disordered α'phase predominated, while more stable α phases formed at 110 °C and 140 °C. Combining the 1% nucleating agent and 110 °C promotes densely packed crystalline lamellae. The nucleated PLA exhibited a well-organized spherulitic morphology in agreement with the Avrami modeling of DSC data. Higher nucleating agent concentrations yielded smaller, more evenly distributed crystalline domains. Utilizing OA or EBS in PLA processing could offer enhanced properties, improved processability, and cost-efficiency, making PLA more competitive in various applications. [ABSTRACT FROM AUTHOR]

While dental poly methyl methacrylate(PMMA) possesses distinctive qualities such as ease of fabrication, cost-effectiveness, and favorable physical and mechanical properties, these attributes alone are inadequate to impart the necessary impact strength and hardness. Consequently, pure PMMA is less suitable for dental applications. This research focused on the incorporation of Strontium titanate (SrTiO3-STO) and hybrid filler STO/Manganese oxide (MnO2) to improve impact resistance and hardness. The potential of STO in reinforcing PMMA is poorly investigated, while hybrid filler STO/MnO2 has not been presented yet. Differential scanning calorimetry is conducted in order to investigate the agglomeration influence on the PMMA glass transition temperature (Tg), as well as the leaching of residual monomer and volatile additives that could pose a threat to human health. It has been determined that agglomeration with 1 wt% loading had no influence on Tg, while the first scan revealed differences in evaporation of small molecules, in favor of composite PMMA-STO/MnO2, which showed the trapping potential of volatiles. Investigations of mechanical properties have revealed the significant influence of hybrid STO/MnO2 filler on microhardness and total absorbed impact energy, which were increased by 89.9% and 145.4%, respectively. Results presented in this study revealed the reinforcing potential of hybrid nanoparticles that could find application in other polymers as well. [ABSTRACT FROM AUTHOR]

Alkaline sodium hydroxide/sodium silicate-activating high-purity metakaolin geopolymerization is described in terms of metakaolin deconstruction in tetrahedral hydrate silicate [O[Si(OH)3]]− and aluminate [Al(OH)4]− ionic precursors followed by their reassembling in linear and branched sialates monomers that randomly copolymerize into an irregular crosslinked aluminosilicate network. The novelty of the approach resides in the concurrent thermo-calorimetric (differential scanning calorimetry, DSC) and rheological (dynamic mechanical analysis, DMA) characterizations of the liquid slurry during the transformation into a gel and a structural glassy solid. Tests were run either in temperature scan (1 °C/min) or isothermal (20 °C, 30 °C, 40 °C) cure conditions. A Gaussian functions deconvolution method has been applied to the DSC multi-peak thermograms to separate the kinetic contributions of the oligomer's concurrent reactions. DSC thermograms of all tested materials are well-fitted by a combination of three overlapping Gaussian curves that are associated with the initial linear low-molecular-weight (Mw) oligomers (P1) formation, oligomers branching into alumina-rich and silica-rich gels (P2), and inter- and intra-molecular crosslinking (P3). The loss factor has been used to define viscoelastic behavioral zones for each DMA rheo-thermogram operated in the same DSC thermal conditions. Macromolecular evolution and viscoelastic properties have been obtained by pairing the deconvoluted DSC thermograms with the viscoelastic behavioral zones of the DMA rheo-thermograms. Two main chemorheological behaviors have been identified relative to pre- and post-gelation separation of the viscoelastic liquid from the viscoelastic solid. Each comprises three behavioral zones, accounting for the concurrently occurring linear and branching oligomerization, aluminate-rich and silica-rich gel nucleations, crosslinking, and vitrification. A "rubbery plateau" in the loss factor path, observed for all the testing conditions, identifies a large behavioral transition zone dividing the incipient gelling liquid slurry from the material hard setting and vitrification. [ABSTRACT FROM AUTHOR]

This paper presents the methodology for synthesizing and characterizing two carboxymethyl EOR-grade Scleroglucans (CMS-A and CMS-B). An O-Alkylation reaction was used to insert a hydrophilic group (monochloroacetic acid—MCAA) into the biopolymer's anhydroglucose subunits (AGUs). The effect of the degree of the carboxymethyl substitution on the rheology and thermal stability of the Scleroglucan (SG) was also evaluated. Simultaneous thermal analysis (STA/TGA-DSC), differential scanning calorimetry (DSC), X-ray Diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy, Scanning Electron Microscopy, and Energy Dispersive Spectroscopy (SEM/EDS) were employed to characterize both CMS products. FTIR analysis revealed characteristic peaks corresponding to the carboxymethyl functional groups, confirming the modification. Also, SEM analysis provided insights into the structural changes in the polysaccharide after the O-Alkylation reaction. TGA results showed that the carboxymethylation of SG lowered its dehydroxylation temperature but increased its thermal stability above 300 °C. The CMS products and SG exhibited a pseudoplastic behavior; however, lower shear viscosities and relaxation times were observed for the CMS products due to the breakage of the SG triple helix for the chemical modification. Despite the viscosity results, the modified Scleroglucans are promising candidates for developing new engineering materials for EOR processes. [ABSTRACT FROM AUTHOR]

In situ polymerization has proven to be an effective route through which to introduce function materials into polyamide materials. In this work, a nano-heterojunction material was evenly dispersed in PA66 via in situ polymerization methods to yield the antimicrobial PA66. The composites showed excellent antibacterial activity against Staphylococcus aureus and Escherichia coli, with strong mechanical properties. Fourier transform infrared spectroscopy (FTIR) showed that metal ions reacted with oxygen-containing functional groups. In addition, the shift of oxygen peaks in XPS spectra confirmed the occurrence of a complexation reaction. X-ray diffraction (XRD) and differential scanning calorimetry (DSC) confirmed the effect of nano-heterojunction, which induced crystallization. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) showed uniform dispersion of heterojunctions in PA66. Tensile testing revealed decreased toughness with higher loadings. The nanocomposite polyamide material has good processing properties which can be processed into thin films, molds, and wires without changing the morphology, and can be widely used in a variety of fields. [ABSTRACT FROM AUTHOR]

In this study, the effects of three diamine curing agents (aromatic, cycloaliphatic, aliphatic) on the photochemical behavior of bisphenol A diglycidyl ether networks were comparatively examined. In order to monitor structural changes and study the curing agents' action mode, the cured epoxy resins were characterized before and after photoirradiation by means of Fourier-transform infrared spectroscopy, contact angle, differential scanning calorimetry, scanning electron microscopy, and energy-dispersive X-ray analysis, mass loss, and color modification measurements. Water absorption tests were also conducted. The cured epoxy resins are to be used in different multicomponent polymer materials for outdoor protection. The presence of the cycloaliphatic hardener led to reduced water absorption, and after UV irradiation, an increase in the glass transition temperature and lowest mass loss of the corresponding cured epoxy resin compared to the ones cured with aromatic and aliphatic hardener. [ABSTRACT FROM AUTHOR]

A detailed investigation of the liquid-state polymerization of diacetylenes by calorimetric (DSC) and spectroscopic (in situ EPR) thermal analysis techniques is performed. Isoconversional kinetic analysis of the calorimetric data reveals that liquid-state polymerization is governed by a well-defined rate-limiting step as evidenced by a nearly constant isoconversional activation energy. By comparison, solid-state polymerization demonstrates isoconversional activation energy that varies widely, signifying multistep kinetics behavior. Unlike the solid-state reaction that demonstrates an autocatalytic behavior, liquid-state polymerization follows a rather unusual zero-order reaction model as established by both DSC and EPR data. Both techniques have also determined strikingly similar Arrhenius parameters for liquid-state polymerization. Relative to the solid-state process, liquid-state polymerization results in quantitative elimination of the p-toluenesulfonate group and the formation of p-toluenesulfonic acid and a polymeric product of markedly different chemical and phase composition. [ABSTRACT FROM AUTHOR]

Covalent adaptable networks (CANs) represent a pioneering advance in polymer science, offering unprecedented versatility in materials design. Unlike conventional adhesives with irreversible bonds, CAN-based polyurethane adhesives have the unique ability to undergo chemical restructuring through reversible bonds. One of the strategies for incorporating these types of reactions in polyurethanes is by functionalisation with Diels–Alder (DA) adducts. By taking advantage of the reversible nature of the DA chemistry, the adhesive undergoes controlled crosslinking and decrosslinking processes, allowing for precise modulation of bond strength. This adaptability is critical in applications requiring reworkability or recyclability, as it allows for easy disassembly and reassembly of bonded components without compromising the integrity of the material. This study focuses on the sustainable synthesis and characterisation of a solvent-based polyurethane adhesive, obtained by functionalising a polyurethane prepolymer with DA diene and dienophiles. The characterisation of the adhesives was carried out using different experimental techniques: nuclear magnetic resonance spectroscopy (NMR), Brookfield viscosity, differential scanning calorimetry (DSC), thermogravimetric analysis (TGA) and T-peel strength testing of leather/adhesive/rubber joints to determine the adhesive properties, both before and after the application of external stimuli. The conversion of both the DA and retro-Diels–Alder (r-DA) reactions was confirmed by 1H-NMR. The adhesive properties were not altered by the functionalisation of the adhesive prepolymer, showing similar thermal resistance and good rheological and adhesive properties, even exceeding the most demanding technical requirements for upper-to-sole joints in footwear. After the application of an external thermal stimuli, the bonded materials separated without difficulty and without damage, thus facilitating their separation, recovery and recycling. [ABSTRACT FROM AUTHOR]

In this work, a novel α-nucleating agent (NA) for polypropylene (PP) termed APAl-3C-12Li was prepared and evaluated compared with the commercially available type NA-21. For the synthesis of the organophosphate-type NA (APAl-3C), the -OH group of the acid part of NA-21 was substituted by the isopropoxy group. The structure of APAl-3C was analyzed by spectroscopy and element analysis, the results of which were consistent with the theoretical molecular formula. APAl-3C's thermal stability was studied by differential scanning calorimetry (DSC) and thermogravimetry (TG), which showed only weak mass loss below 230 °C, meaning that it would not decompose during the processing of PP. The APAl-3C-12Li was used as a novel nucleating agent, studying its effects on crystallization, microstructure, mechanical and optical properties. Tests were performed in a PP random copolymer at different contents, in comparison to the commercial NA-21. The composite with 0.5 wt% APAl-3C-12Li has a similar crystallization temperature of 118.8 °C as with the addition of 0.5 wt% NA-21. An advantage is that the composite with the APAl-3C-12Li has a lower haze value of 9.3% than the counterpart with NA-21. This is due to the weaker polarity of APAl-3C-12Li after the introduction of methyl and better uniform dispersion in the PP matrix, resulting in stronger improvement of optical and mechanical properties. [ABSTRACT FROM AUTHOR]

High-density polyethylene polymer (HDPE) and carbon black (CB) were utilized to create HDPE/CB composites with different filler concentrations (0.0, 2.0, 4.0, 6.0, 8.0, 10.0, 16.0, 20.0, and 24.0 wt.%). The composites were extruded into filaments, which were then utilized to fabricate 3D-printed specimens with the material extrusion (MEX) method, suitable for a variety of standard mechanical tests. The electrical conductivity was investigated. Furthermore, thermogravimetric analysis and differential scanning calorimetry were carried out for all the HDPE/CB composites and pure HDPE. Scanning electron microscopy in different magnifications was performed on the specimens' fracture and side surfaces to investigate the morphological characteristics. Rheological tests and Raman spectroscopy were also performed. Eleven different tests in total were performed to fully characterize the composites and reveal connections between their various properties. HDPE/CB 20.0 wt.% showed the greatest reinforcement results in relation to pure HDPE. Such composites are novel in the MEX 3D printing method. The addition of the CB filler greatly enhanced the performance of the popular HDPE polymer, expanding its applications. [ABSTRACT FROM AUTHOR]

Polyethylene (PE)-based elastomers are the ideal choice for enhancing the compatibility of polypropylene/polyethylene (PP/PE) blends and improving the mechanical properties of PP-based materials. However, the issue of blend systems lies in the interplay between the crystallization processes. Therefore, we investigated the crystallization behavior during the cooling process of a new generation of PP/PE block copolymers (PP-b-PE) and random polypropylene (PPR, a copolymer of propylene and a small amount of ethylene or an alpha-olefin) blends using in-situ X-ray diffraction/scattering and differential scanning calorimetry (DSC) techniques. We also conducted mechanical performance tests on PPR/PP-b-PE blends at room temperature and low temperature (−5 °C). The results indicate that during the cooling process, the PP phase of PP-b-PE will follow the PPR to crystallize in advance and form a eutectic mixture, thereby enhancing the compatibility of PP/PE. Moreover, the PPR/PP-b-PE blend will form stable β-(300) crystals with excellent mechanical properties. Due to the improved compatibility of PP/PE with PP-b-PE, PE crystals are dispersed within PP crystals, providing bonding that improves the toughness of PPR under the low stiffness failure conditions of PPR/PP-b-PE blends, thereby enhancing their impact performance at low and room temperatures. This research has great significance for both recycling waste plastics and enhancing the low-temperature toughness of PPR. [ABSTRACT FROM AUTHOR]

Due to the fact that impregnation with fire retardant usually reduces the strength of the produced particleboards, this research was carried out to investigate whether it is possible to use phenol–formaldehyde (PF) resin modified using various amounts (0%, 5%, 10%, 15%, and 20%) of polymeric 4,4′-methylene diphenyl diisocyanate (pMDI) for this purpose. The need to optimize the addition of pMDI is particularly important due to health and environmental aspects and high price. Furthermore, the curing process of hybrid resins is still not fully explained, especially in the case of small loadings. Manufactured particleboards differed in the share of impregnated particles (50% and 100%). The mixture of potassium carbonate and urea was used as the impregnating solution. Based on the outcomes of hybrid resins properties, it was found that the addition of pMDI leads to the increase in solid content, pH, and viscosity of the mixtures, to the improvement in resin reactivity determined using differential scanning calorimetry and to the decrease in thermal stability in the cured state evaluated using thermogravimetric analysis. Moreover, particleboard property results have shown that using impregnated particles (both 50% and 100%) decreased the strength of manufactured boards bonded using neat PF resin. However, the introduction of pMDI allowed us to compensate for the negative impact of fire-retardant-treated wood and it was found that the optimal loading of pMDI for the board containing 50% of impregnated particles is 5% and for board made entirely of treated wood it is 10%. [ABSTRACT FROM AUTHOR]

When navigating the environmental exigencies precipitated by global pandemics, the escalation of mask waste presents a multifaceted dilemma. In this avant-garde research, we unveil a novel approach: harnessing the sterilized shredded mask residues (SMRs), predominantly composed of 100 wt. % polypropylene, as pioneering modifiers for asphalt. Distinct proportions of SMR (e.g., 3, 6, and 9 wt. %) were judiciously integrated with fresh–virgin base AP-5 asphalt and subjected to an extensive suite of state-of-the-art examinations, encompassing thin-layer chromatography-flame ionization detection (TLC-FID), Fourier-transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), and specific rheological metrics. The TLC-FID diagnostic trajectories highlighted the nuanced rejuvenating influence of SMR on the binder, a facet reinforced by a pronounced elevation in the thermodynamic stability index (IC). The FT-IR spectra elucidated SMR's preeminent role as a filler, negating notions of chemical reactivity. The TGA analyses unveiled an elevated thermal onset of degradation, signposting enhanced thermal resilience, whereas the DSC readings illuminated a superior thermal comportment at lower extremities. The SEM evaluations rendered a clearer panorama: there was heightened textural perturbation at escalated SMR incorporations, yet the 3 wt. % concoction showcased an optimal, coherent microtexture symbiosis with asphalt. The rheological scrutinies revealed a systematic trajectory: a diminishing penetration and ductility countered by ascending softening points and viscosity metrics. The coup de maître stemmed from the DSR analyses, unequivocally validating SMR's unparalleled prowess in curtailing rutting distress. This seminal inquiry not only posits a blueprint for refined pavement longevity but also champions a sustainable countermeasure to pandemic-propelled waste, epitomizing the confluence of environmental prudence an d infrastructural fortitude. [ABSTRACT FROM AUTHOR]

Fibers made from biopolymers are one solution for conserving both resources and the environment. However, these fibers currently have limited strengths, which limit their use for textile applications. In this paper, a biopolymer stereocomplex poly(-lactide) (scPLA) formation on a technical scale of high-molecular-weight poly(D-lactide) (PDLA) and poly(L-lactide) (PLLA) is presented. This scPLA material is the basis for further research to develop scPLA yarns in melt spinning with technical strengths for technical application. scPLA is compared with standard and commercially available semi-crystalline PLA for the production of fibers in melt spinning (msPLA) with textile strengths. Differential scanning calorimetry (DSC) gives a degree of crystallization of 59.7% for scPLA and 47.0% for msPLA. X-ray diffraction (XRD) confirms the pure stereocomplex crystal structure for scPLA and semi-crystallinity for msPLA. scPLA and msPLA are also compared regarding their processing properties (rheology) in melt spinning. While complex viscosity of scPLA is much lower compared to msPLA, both materials show similar viscoelastic behavior. Thermal gravimetric analysis (TGA) shows the influence of the molecular weight on the thermal stability, whereas essentially the crystallinity influences the biodegradability of the PLA materials. [ABSTRACT FROM AUTHOR]

There are no previous studies on the interactions between polyols of different nature as a model for understanding the interactions between soft segments in PUs. In this study, different blends of two polyols of different natures (polyester—PE, and polycarbonate diol—CD) and similar molecular weights were prepared and their structural, thermal, surface, viscoelastic, and self-adhesion properties were assessed. Different experimental techniques were used: infrared spectroscopy (ATR-IR), differential scanning calorimetry (DSC), X-ray diffraction, thermal gravimetric analysis (TGA), and plate–plate rheology. PE showed a larger number of structural repeating units and a higher number of polar groups than CD, but the carbonate–carbonate interactions in CD were stronger than the ester–ester interactions in PE. The blending of CD and PE imparted synergic structural properties, particularly in the blends containing less than 50 wt.% PE, they were associated with the disrupt of the carbonate–carbonate interactions in CD and the formation of new ester–carbonate and hydroxyl–carbonate interactions. CD + PE blends with less than 50 wt.% PE exhibited higher glass transition temperatures, a new diffraction peak at 2θ = 24°, one additional thermal degradation at 426–436 °C, and a less-steep decline of the storage moduli. Furthermore, the different interactions between the polyol chains in the blends were also evidenced on their surface properties, and all CD + PE blends showed self-adhesion properties which seemed related to the existence of ester–carbonate and carbonate–carbonate interactions. [ABSTRACT FROM AUTHOR]

The UN 2030 Agenda for Sustainable Development established the goal of cutting the use of pesticides in the EU by 50% by 2030. However, a ban on pesticides could seriously affect the productivity of agriculture, resulting in severe issues due to global hunger and food deficiency. Controlled release (CR) of bioactive chemicals could play a valid alternative in this context. To this aim, two biodegradable polymers, namely sodium alginate (AL) and sodium carboxymethylcellulose (CMC), were employed to obtain crosslinked hydrogel beads for the encapsulation and CR of glycoalkaloids extracted from tomato and potato leaves to be used as biocompatible disinfectants for agricultural soils. The physico-chemical characterization of the controlled-release systems was carried out by means of Attenuated Total Reflectance–Fourier Transform Infrared (ATR-FTIR) spectroscopy, Scanning Electron Microscopy (SEM), thermogravimetry (TGA), differential scanning calorimetry (DSC) (FWI > 80%) and drying kinetics. The plant extracts and the encapsulation efficiency (~84%) were, respectively, characterized and evaluated by High-performance Liquid Chromatography–Mass Spectrometry (HPLC-MS). Finally, preliminary microbiological tests were conducted to test the efficacy of the most promising systems as biocidal formulations both in the lab and on a model soil, and interesting results were obtained in the reduction of bacterial and fungal load, which could lead to sustainable perspectives in the field. [ABSTRACT FROM AUTHOR]

A twin-screw extruder was used to fabricate poly(butylene succinate) (PBS)/high-density polyethylene (HDPE) blends (7:3 weight ratio) and blend-based nanocomposites. Carbon nanotubes (CNTs), graphene nanoplatelets (GNPs), and organoclays (15A and 30B) served as the nanofiller, while maleated HDPE (PEgMA) acted as an efficient compatibilizer for the blend. In the composites, individual nanofillers were mostly localized in HDPE domains, but some fillers were also observed at PBS–HDPE interfaces. The sea–island morphology of the compatibilized blend evolved into a pseudo-co-continuous morphology in the composites. Differential scanning calorimetry results confirmed that PEgMA with HDPE evidently accelerated the crystallization of PBS in the blend. The possible nucleation effect of added fillers on PBS crystallization was obscured by the formation of quasi-connected HDPE domains, causing fewer PBS nucleation sites. The presence of nanofillers improved the thermal stability and burning anti-dripping behavior of the parent blend. The anti-dripping efficiency of added fillers followed the sequence CNT > 15A > 30B > GNP. The rigidity of the blend was increased after the formation of nanocomposites. In particular, adding GNP resulted in 19% and 31% increases in the Young's modulus and flexural modulus, respectively. The development of a pseudo-network structure in the composites was confirmed by measurement of rheological properties. The electrical resistivity of the blend was reduced by more than six orders of magnitude at 3 phr CNT loading, demonstrating the achievement of double percolation morphology. [ABSTRACT FROM AUTHOR]

In the last decades, researchers have been developing bioresorbable stents (BRS) to overcome the long-term complications of drug-eluting stents (DES). However, BRS technology still presents challenging limitations in terms of manufacturing, materials, or mechanical properties. At this juncture, companies have developed ultrathin DES that may further improve the efficacy and safety profile of traditional DES by reducing the risk of target-lesion and target-vessel failures until BRS are developed. Nonetheless, the metallic platform of ultrathin DES still presents problems related to their cellular response. The use of polymers as a permanent platform in DES has not previously been studied due to the limitations of current manufacturing technologies. In this work, an innovative manufacturing method for polymeric stent production using tubular stereolithography (SLA) technology is proposed both for BRS and for ultrathin polymeric DES. The effects of manufacturing process parameters were studied by modelling the outcomes (stent thickness and strut width) with the key manufacturing variables (exposure, resin volume, and number of layers). Two different laser setups were used to compare the results. Microscopy results proved the merit of this novel tubular SLA process, which was able to obtain stents with 70 μm strut width and thickness in barely 4 min using only 0.2 mL of resin. Differential Scanning Calorimetry (DSC) results showed the stability of the manufacturing method. The results obtained with this innovative technology are promising and overcome the limitations of other previously used and available technologies. [ABSTRACT FROM AUTHOR]

Polymeric materials show great promise for use in a variety of dental applications. Manufacturers generally provide flexural strength information based on standardized (ISO and ASTM) specimen dimensions and loading conditions. It is not clear, however, if flexural strength data are predictive of the clinical performance of dental crowns. The objectives of this study were, therefore, to determine whether flexural strengths, as measured via three-point bending (3PB), would be predictive of failure loads assessed via crunch-the-crown (CTC) tests. Three brands of polymers (Trilor, Juvora, and Pekkton) were fabricated into rectangular bars and fully contoured crowns (10 specimens of each polymer brand, 30 specimens of each shape). Differential scanning calorimetry (DSC), Fourier transform infrared spectroscopy (FTIR), and burn off tests were used to characterize/confirm the materials. Bars were tested blindly in 3PB to determine flexural strength, and crowns were CTC-tested to determine failure load after luting to resin abutments. The statistical significance of the test results was evaluated via one-way ANOVA (α = 0.05) and Pearson's correlation coefficient, while regression analysis was used to test for a correlation between 3PB and CTC results. The fracture mechanisms and failure surface characteristics were characterized using scanning electron microscopy (SEM). There were significant differences (p < 0.05) in the mean crown failure loads (Trilor (7033 N) > Juvora (5217 N) > Pekkton (3023 N)) and mean flexural strengths of the bars (Trilor (468 MPa) > Juvora (197 MPa) = Pekkton (192 MPa)). The mode of crown fracture was different between the materials and included deformation (Juvora), ductile-to-brittle fracture (Pekkton), and a combination of cracks and deformation (Trilor). Flexural strengths did not correlate with the corresponding crown failure loads for any of the materials tested. These results suggest that dental practitioners should not rely on the flexural strengths reported from three-point bending tests, as advertised by the manufacturer, to predict the performance of polymeric crowns. [ABSTRACT FROM AUTHOR]