PHB+aPHA Blends: From Polymer Bacterial Synthesis through Blend Preparation to Final Processing by Extrusion for Sustainable Materials Design.

The inherent brittleness of polyhydroxybutyrate (PHB), a well-studied polyhydroxyalkanoate (PHA), limits its applicability in flexible and impact-resistant applications. This study explores the potential of blending PHB with a different PHA to overcome brittleness. The synthesis of PHA polymers, including PHB and an amorphous medium-chain-length PHA (aPHA) consisting of various monomers, was achieved in previous works through canola oil fermentation. Detailed characterization of aPHA revealed its amorphous nature, as well as good thermal stability and shear thinning behavior. The blending process was carried out at different mass ratios of aPHA and PHB, and the resulting blends were studied by differential scanning calorimetry (DSC), X-ray diffraction (XRD), scanning electron microscopy (SEM), and thermogravimetric analysis (TGA). The blends exhibited complex DSC curves, indicating the presence of multiple crystalline forms of PHB. SEM images revealed the morphology of the blends, with PHB particles dispersed within the aPHA matrix. TGA showed similar thermal degradation patterns for the blends, with the residue content decreasing as the PHB content increased. The crystallinity of the blends was influenced by the PHB content, with higher PHB ratios resulting in an increased degree of crystallinity. XRD confirmed the presence of both α and ß crystals of PHB in the blends. Overall, the results demonstrate the potential of PHB+aPHA blends to enhance the mechanical properties of biopolymer materials, without com-promising the thermal stability, paving the way for sustainable material design and novel application areas.

Bio-Based Polymers for Environmentally Friendly Phase Change Materials.

Phase change materials (PCMs) have received increasing attention in recent years as they enable the storage of thermal energy in the form of sensible and latent heat, and they are used in advanced technical solutions for the conservation of sustainable and waste energy. Importantly, most of the currently applied PCMs are produced from non-renewable sources and their carbon footprint is associated with some environmental impact. However, novel PCMs can also be designed and fabricated using green materials without or with a slight impact on the environment. In this work, the current state of knowledge on the bio-based polymers in PCM applications is described. Bio-based polymers can be applied as phase-change materials, as well as for PCMs encapsulation and shape stabilization, such as cellulose and its derivatives, chitosan, lignin, gelatin, and starch. Vast attention has been paid to evaluation of properties of the final PCMs and their application potential in various sectors. Novel strategies for improving their thermal energy storage characteristics, as well as to impart multifunctional features, have been presented. It is also discussed how bio-based polymers can extend in future the potential of new environmentally-safe PCMs in various industrial fields.

Thermoplastic polyurethane/POSS nanohybrids: Synthesis, morphology, and biological properties.

Recent studies show good osteoinductive properties of polyurethanes modified with polyhedral oligomeric silsesquioxanes (POSS). In this work, three types of POSS; propanediolisobutyl-POSS (PHI-POSS), disilanolisobutyl-POSS (DSI-POSS), and octahydroxybutyl-POSS (OCTA-POSS) were chemically incorporated into linear polyurethane based on an aliphatic isocyanate, hexamethylene diisocyanate (HDI), to obtain new nanohybrid PU-POSS materials. The full conversion of POSS was confirmed by Fourier transform infrared spectroscopy (FTIR-ATR) spectra of the model reactions with pure HDI. The materials obtained were investigated by FTIR, SEM-EDS, and DSC. The DSC studies showed the thermoplasticity of the obtained materials and apparently good recovery. 30-day immersion in SBF (simulated body fluid) revealed an increase in the rate of deposition of hydroxyapatite (HAp) for the highest POSS loadings, resulting in thick layers of hydroxyapatite (~60-40 µm), and the Ca/P ratio 1.67 (even 1.785). The structure and properties of the inorganic layer depend on the type of POSS, the number of hard segments, and those containing POSS, which can be tailored by changing the HDI/poly(tetramethylene glycol) (PTMG) ratio. Furthermore, the obtained composites revealed good biocompatibility, as confirmed by cytotoxicity tests conducted on two cell lines; normal human dermal fibroblasts (NHDF) and primary human osteoblasts (HOB). Adherent cells seeded on the tested materials showed viability even after a 48-h incubation. After this time, the population of viable, and proliferating cells exceeded 90%. Bioimaging studies have shown the fibroblast and osteoblast cells were well attached to the surface of the tested materials.

Synthesis of Bis(cyclic carbonates) from Epoxy Resin under Microwave Irradiation: The Structural Analysis and Evaluation of Thermal Properties.

This article describes the use of microwave irradiation in the synthesis of bis(cyclo carbonate) compounds (BCCs) in bulk (without solvent) from carbon dioxide capture using an epoxidized compound-a commercial epoxy resin-and compares this process to the conventional method. CO2 cycloaddition to epoxides is an ecological and efficient method for the formation of bis(cyclic carbonates). Moreover, the introduction of gas into the reaction mixture was carried out at atmospheric pressure with a controlled flow rate, which is advantageous from an economic point of view. Progressive structural changes and the presence of characteristic chemical groups were monitored using attenuated total reflectance infrared spectroscopy with Fourier transform. The obtained crude products were purified to obtain three fractions, which were subjected to detailed structural analysis using FT-IR and 13CNMR. The formation of the main product with two cyclic carbonates was confirmed. The presence of monomers, dimers and trimers in individual fractions as well as their thermal stability were determined, and the molecular masses in individual fractions were determined using gel permeation chromatography (GPC).

Fabrication of Liquid Crystalline Polyurethane/Polyhedral Oligomeric Silsesquioxane Nanofibers via Electrospinning.

A series of fibrous meshes based on liquid crystalline polyurethane/POSS composites were prepared. Two types of polyhedral oligomeric silsesquioxanes (POSSs) of different structures were chosen to show their influence on electrospun fibers: aromatic-substituted Trisilanolphenyl POSS (TSP-POSS) and isobutyl-substituted Trisilanolisobutyl POSS (TSI-POSS) in amounts of 2 and 6 wt%. The process parameters were selected so that the obtained materials showed the highest possible fiber integrity. Moreover, 20 wt% solutions of LCPU/POSS composites in hexafluoroisopropanol (HFIP) were found to give the best processability. The morphology of the obtained meshes showed significant dependencies between the type and amount of silsesquioxane nanoparticles and fiber morphology, as well as thermal and mechanical properties. In total, 2 wt%. POSS was found to enhance the mechanical properties of produced mesh without disrupting the fiber morphology. Higher concentrations of silsesquioxanes significantly increased the fibers' diameters and their inhomogeneity, resulting in a lower mechanical response. A calorimetric study confirmed the existence of liquid crystalline phase formation.

Effects of Segment Length and Crosslinking via POSS on the Calorimetric and Dynamic Glass Transition of Polyurethanes with Aliphatic Hard Segments.

The glass transition in polyurethanes is a complicated phenomenon governed by a multitude of factors, including the microphase separation, which in turn depends strongly on the molar mass of the hard and soft segments, as well as the presence of additives. In this work, we study the effects of the segments' length on the microphase separation and consequently on the calorimetric and dynamic glass transition of a polyurethane with aliphatic, "flexible" hard segments. It is found that the dependence of the calorimetric glass transition follows the same principles as those in systems with aromatic hard segments. Strikingly, however, the dynamic glass transition, as studied by dielectric spectroscopy, shows a slowing down of its dynamics despite a decrease in Tg. This discrepancy is discussed in terms of the strong dielectric response of the flexible segments, especially those close to the interface between the hard domains and soft phase, as opposed to a weak thermal one. In addition, polyhedral oligomeric silsesquioxanes (POSS) are introduced in the soft phase of the three matrices as crosslinking centres. This modification has no visible effect on the calorimetric glass transition; nevertheless, it affects the microphase separation and the dielectric response in a non-monotonic manner.

Fire Retardant Phase Change Materials-Recent Developments and Future Perspectives.

The accumulation of thermal energy in the form of latent heat of phase transition using phase change materials (PCMs) is one of the most attractive and studied research areas with huge application potential in both passive and active technical systems. The largest and most important group of PCMs for low-temperature applications are organic PCMs, mainly paraffins, fatty acids, fatty alcohols, and polymers. One of the major disadvantages of organic PCMs is their flammability. In many applications such as building, battery thermal management, and protective insulations, the crucial task is to reduce the fire risk of flammable PCMs. In the last decade, numerous research works have been performed to reduce the flammability of organic PCMs, without losing their thermal performance. In this review, the main groups of flame retardants, PCMs flame retardation methods as well as examples of flame-retarded PCMs and their application areas were described.

POSS and SSQ Materials in Dental Applications: Recent Advances and Future Outlooks.

Recently, silsesquioxanes (SSQ) and polyhedral oligomeric silsesquioxanes (POSS) have gained much interest in the area of biomaterials, mainly due to their intrinsic properties such as biocompatibility, complete non-toxicity, the ability to self-assemble and to form a porous structure, facilitating cell proliferation, creating a superhydrophobic surface, osteoinductivity, and ability to bind hydroxyapatite. All the above has resulted in new developments in medicine. However, the application of POSS-containing materials in dentistry is still at initial stage and deserves a systematic description to ensure future development. Significant problems, such as reduction of polymerization shrinkage, water absorption, hydrolysis rate, poor adhesion and strength, unsatisfactory biocompatibility, and corrosion resistance of dental alloys, can be addressed by the design of multifunctional POSS-containing materials. Because of the presence of silsesquioxanes, it is possible to obtain smart materials that allow the stimulation of phosphates deposition and repairing of micro-cracks in dental fillings. Hybrid composites result in materials exhibiting shape memory, as well as antibacterial, self-cleaning, and self-healing properties. Moreover, introducing POSS into polymer matrix allows for materials for bone reconstruction, and wound healing. This review covers the recent developments in the field of POSS application in dental materials and gives the future perspectives within a promising field of biomedical material science and chemical engineering.

Examining the Water-Polymer Interactions in Non-Isocyanate Polyurethane/Polyhedral Oligomeric Silsesquioxane Hybrid Hydrogels.

Non-isocyanate polyurethane (NIPU) networks physically modified with octa(3-hydroxy-3-methylbutyldimethylsiloxy)POSS (8OHPOSS, 0-10 wt%) were conditioned in environments of different relative humidities (up to 97%) to study water-polymer interactions. The equilibrium sorption isotherms are of Brunauer type III in a water activity range of 0-0.97 and are discussed in terms of the Guggenheim (GAB) sorption model. The study shows that the introduction of 8OHPOSS, even in a large amount (10 wt%), does not hinder the water affinity of the NIPU network despite the hydrophobic nature of POSS; this is attributable to the homogenous dispersion of POSS in the polymer matrix. The shift in the urethane-derived carbonyl bands toward lower wavenumbers with a simultaneous shift in the urethane N-H bending bands toward higher wavenumbers exposes the breakage of polymer-polymer hydrogen bonds upon water uptake due to the formation of stronger water-polymer hydrogen bonds. Upon water absorption, a notable decrease in the glass transition temperature (Tg) is observed for all studied materials. The progressive reduction in Tg with water uptake is driven by plasticization and slaving mechanisms. POSS moieties are thought to impact slaving indirectly by slightly affecting water uptake at very high hydration levels.

Synthesis and Characterization of Thermally Stable Lignosulfonamides.

Lignin, a highly aromatic macromolecule building plant cells, and cellulose are two of the most commonly occurring natural polymers. Lignosulfonate is a grade of technical lignin, obtained as a by-product in the paper and wood pulping industries, a result of the used lignin isolation method, i.e., sulfite process. In this work, sodium lignosulfonate is used as a starting material to manufacture sulfonamide derivatives of lignin in a two-step modification procedure. Since this direction of the lignin modification is rather rarely investigated and discussed, it makes a good starting point to expand the state of knowledge and explore the properties of lignosulfonamides. Materials obtained after modification underwent characterization by FTIR, SS-NMR, WAXD, SEM, and TGA. Spectroscopic measurements confirmed the incorporation of dihexylamine into the lignin structure and the formation of lignosulfonamide. The crystalline structure of the material was not affected by the modification procedure, as evidenced by the WAXD, with only minute morphological changes of the surface visible on the SEM imaging. The obtained materials were characterized by improved parameters of thermal stability in relation to the raw material. As-prepared sulfonamide lignin derivatives with a potential application as a filler in biopolymeric composites may become a new class of functional, value-added, sustainable additives.

Flexible Polyurethane Foams Reinforced by Functionalized Polyhedral Oligomeric Silsesquioxanes: Structural Characteristics and Evaluation of Thermal/Flammability Properties.

In this work, we report on flexible toluene diisocyanate (TDI)-based polyurethane foams (FPUFs) chemically modified by POSS moieties, i.e., octa (3-hydroxy-3-methylbutyldimethylsiloxy) POSS (OCTA-POSS) and 1,2-propanediolizo-butyl POSS (PHI-POSS). The influence of silsesquioxane on the PU foaming process, structure, morphology, physicochemical, and mechanical properties, as well as flammability, was examined. FT-IR analysis provided evidence for the chemical incorporation of the nanofiller into the foam structure. It was found that the addition of POSS increases the apparent density of the foam and its compressive strength. The XRD and SEM-EDS techniques showed the uniform distribution of POSS in the FPUF with agglomeration depending on the kind and content of the introduced POSS moieties. The analysis of the thermogravimetric and microcalorimetry data revealed an improved resistance to the burning of FPUFs containing reactive POSS, as evidenced by the reduced rate of heat release (HRR). Importantly, the mechanical properties tests showed that the incorporation of silsesquioxane nanoparticles into the polyurethane structure via covalent bonds strengthens the foam integrity.

Alginate Hydrogels with Aloe vera: The Effects of Reaction Temperature on Morphology and Thermal Properties.

In this study, we investigated the impact of reaction temperature on the physicochemical, structural, morphological, and thermal properties of sodium alginate/poly (vinyl alcohol)-based hydrogels, both in the pure form and with the addition of 20% (v/v) Aloe vera solution. The materials were prepared by chemical crosslinking at temperatures in the range of 65-75 °C. Poly (ethylene glycol) diacrylate was used as a crosslinking agent. The extent to which the crosslinking reaction proceeded was studied as a function of the reaction temperature, along with the thermal properties and morphology of the final materials. A measurement of gel fraction, in agreement with differential scanning calorimetry and Fourier transform infrared spectroscopy, showed that a higher temperature of reaction promoted the crosslinking reaction. On the basis of the aforementioned techniques, as well as by energy dispersive X-ray analysis under an electron microscope, it was also shown that the bioadditive Aloe vera promoted the crosslinking reaction.

Chemical and Physical Modification of Lignin for Green Polymeric Composite Materials.

Lignin, a valuable polymer of natural origin, displays numerous desired intrinsic properties; however, modification processes leading to the value-added products suitable for composite materials' applications are in demand. Chemical modification routes involve mostly reactions with hydroxyl groups present in the structure of lignin, but other paths, such as copolymerization or grafting, are also utilized. On the other hand, physical techniques, such as irradiation, freeze-drying, and sorption, to enhance the surface properties of lignin and the resulting composite materials, are developed. Various kinds of chemically or physically modified lignin are discussed in this review and their effects on the properties of polymeric (bio)materials are presented. Lignin-induced enhancements in green polymer composites, such as better dimensional stability, improved hydrophobicity, and improved mechanical properties, along with biocompatibility and non-cytotoxicity, have been presented. This review addresses the challenges connected with the efficient modification of lignin, which depends on polymer origin and the modification conditions. Finally, future outlooks on modified lignins as useful materials on their own and as prospective biofillers for environmentally friendly polymeric materials are presented.

The Impact of the Preparation Method on the Properties of Orodispersible Films with Aripiprazole: Electrospinning vs. Casting and 3D Printing Methods.

Orodispersible films (ODFs) address the needs of pediatric and geriatric patients and people with swallowing difficulties due to fast disintegration in the mouth. Typically, they are obtained using the solvent casting method, but other techniques such as 3D printing and electrospinning have already been investigated. The decision on the manufacturing method is of crucial importance because it affects film properties. This study aimed to compare electrospun ODFs containing aripiprazole and polyvinyl alcohol with films prepared using casting and 3D printing methods. Characterization of films included DSC and XRD analysis, microscopic analysis, the assessment of mechanical parameters, disintegration, and dissolution tests. Simplified stability studies were performed after one month of storage. All prepared films met acceptance criteria for mechanical properties. Electrospun ODFs disintegrated in 1.0 s, which was much less than in the case of other films. Stability studies have shown the sensitivity of electrospun films to the storage condition resulting in partial recrystallization of ARP. These changes negatively affected the dissolution rate, but mechanical properties and disintegration time remained at a desirable level. The results demonstrated that electrospun fibers are promising solutions that can be used in the future for the treatment of patients with swallowing problems.

Recent Advances in Fabrication of Non-Isocyanate Polyurethane-Based Composite Materials.

Polyurethanes (PUs) are a significant group of polymeric materials that, due to their outstanding mechanical, chemical, and physical properties, are used in a wide range of applications. Conventionally, PUs are obtained in polyaddition reactions between diisocyanates and polyols. Due to the toxicity of isocyanate raw materials and their synthesis method utilizing phosgene, new cleaner synthetic routes for polyurethanes without using isocyanates have attracted increasing attention in recent years. Among different attempts to replace the conventional process, polyaddition of cyclic carbonates (CCs) and polyfunctional amines seems to be the most promising way to obtain non-isocyanate polyurethanes (NIPUs) or, more precisely, polyhydroxyurethanes (PHUs), while primary and secondary -OH groups are being formed alongside urethane linkages. Such an approach eliminates hazardous chemical compounds from the synthesis and leads to the fabrication of polymeric materials with unique and tunable properties. The main advantages include better chemical, mechanical, and thermal resistance, and the process itself is invulnerable to moisture, which is an essential technological feature. NIPUs can be modified via copolymerization or used as matrices to fabricate polymer composites with different additives, similar to their conventional counterparts. Hence, non-isocyanate polyurethanes are a new class of environmentally friendly polymeric materials. Many papers on the matter above have been published, including both original research and extensive reviews. However, they do not provide collected information on NIPU composites fabrication and processing. Hence, this review describes the latest progress in non-isocyanate polyurethane synthesis, modification, and finally processing. While focusing primarily on the carbonate/amine route, methods of obtaining NIPU are described, and their properties are presented. Ways of incorporating various compounds into NIPU matrices are characterized by the role of PHU materials in copolymeric materials or as an additive. Finally, diverse processing methods of non-isocyanate polyurethanes are presented, including electrospinning or 3D printing.

Characterization and Combustion Behavior of Single-Use Masks Used during COVID-19 Pandemic.

This work aims to study the thermal degradation and combustion behavior of single-use masks commonly used during the COVID-19 pandemic. The sudden increase in plastic waste underlines the crucial need for a proper disposal method. Therefore, to develop a suitable method of thermal disposal, it is first necessary to identify the primary waste materials and then study their thermal and flammability behaviors using thermal analysis methods. This research focuses on the characterization of individual parts of the masks, their thermal degradation, and pyrolysis processes via FTIR, TG, and MCC analyses. FTIR analysis indicated that all three masks were made out of polypropylene sheets, while two of the ear straps contained polyamide 6. One of the samples was composed mainly of poly (ethylene terephthalate) fiber and thin inner EPDM rubber. The EPDM ear strap left the highest residue and showed the lowest flammability among all samples. The analysis of heat of combustion and thermogravimetry shows that the most heat is generated above 450 °C. Therefore, for the disposal of single-use masks to be effective, it should be carried out in the temperature range from 450 to 750 °C.

Recent Advances in Polyurethane/POSS Hybrids for Biomedical Applications.

Advanced organic-inorganic materials-composites, nanocomposites, and hybrids with various compositions offer unique properties required for biomedical applications. One of the most promising inorganic (nano)additives are polyhedral oligomeric silsesquioxanes (POSS); their biocompatibility, non-toxicity, and phase separation ability that modifies the material porosity are fundamental properties required in modern biomedical applications. When incorporated, chemically or physically, into polyurethane matrices, they substantially change polymer properties, including mechanical properties, surface characteristics, and bioactivity. Hence, this review is dedicated to POSS-PU composites that have recently been developed for applications in the biomedical field. First, different modes of POSS incorporation into PU structure have been presented, then recent developments of PU/POSS hybrids as bio-active composites for scaffolds, cardiovascular stents, valves, and membranes, as well as in bio-imaging and cancer treatment, have been described. Finally, characterization and methods of modification routes of polyurethane-based materials with silsesquioxanes were presented.

PEG-POSS Star Molecules Blended in Polyurethane with Flexible Hard Segments: Morphology and Dynamics.

A star polymer with a polyhedral oligomeric silsesquioxanne (POSS) core and poly(ethylene glycol) (PEG) vertex groups is incorporated in a polyurethane with flexible hard segments in-situ during the polymerization process. The blends are studied in terms of morphology, molecular dynamics, and charge mobility. The methods utilized for this purpose are scanning electron and atomic force microscopies (SEM, AFM), X-ray diffraction (XRD), differential scanning calorimetry (DSC), and to a larger extent dielectric relaxation spectroscopy (DRS). It is found that POSS reduces the degree of crystallinity of the hard segments. Contrary to what was observed in a similar system with POSS pendent along the main chain, soft phase calorimetric glass transition temperature drops as a result of plasticization, and homogenization of the soft phase by the star molecules. The dynamic glass transition though, remains practically unaffected, and a hypothesis is formed to resolve the discrepancy, based on the assumption of different thermal and dielectric responses of slow and fast modes of the system. A relaxation α', slower than the bulky segmental α and common in polyurethanes, appears here too. A detailed analysis of dielectric spectra provides some evidence that this relaxation has cooperative character. An additional relaxation g, which is not commonly observed, accompanies the Maxwell Wagner Sillars interfacial polarization process, and has dynamics similar to it. POSS is found to introduce conductivity and possibly alter its mechanism. The study points out that different architectures of incorporation of POSS in polyurethane affect its physical properties by different mechanisms.

Physicochemical and Biological Characterisation of Diclofenac Oligomeric Poly(3-hydroxyoctanoate) Hybrids as ß-TCP Ceramics Modifiers for Bone Tissue Regeneration.

Nowadays, regenerative medicine faces a major challenge in providing new, functional materials that will meet the characteristics desired to replenish and grow new tissue. Therefore, this study presents new ceramic-polymer composites in which the matrix consists of tricalcium phosphates covered with blends containing a chemically bounded diclofenac with the biocompatible polymer-poly(3-hydroxyoctanoate), P(3HO). Modification of P(3HO) oligomers was confirmed by NMR, IR and XPS. Moreover, obtained oligomers and their blends were subjected to an in-depth characterisation using GPC, TGA, DSC and AFM. Furthermore, we demonstrate that the hydrophobicity and surface free energy values of blends decreased with the amount of diclofenac modified oligomers. Subsequently, the designed composites were used as a substrate for growth of the pre-osteoblast cell line (MC3T3-E1). An in vitro biocompatibility study showed that the composite with the lowest concentration of the proposed drug is within the range assumed to be non-toxic (viability above 70%). Cell proliferation was visualised using the SEM method, whereas the observation of cell penetration into the scaffold was carried out by confocal microscopy. Thus, it can be an ideal new functional bone tissue substitute, allowing not only the regeneration and restoration of the defect but also inhibiting the development of chronic inflammation.

Compression-Induced Phase Transitions of Bicalutamide.

The formation of solid dispersions with the amorphous drug dispersed in the polymeric matrix improves the dissolution characteristics of poorly soluble drugs. Although they provide an improved absorption after oral administration, the recrystallization, which can occur upon absorption of moisture or during solidification and other formulation stages, serves as a major challenge. This work aims at understanding the amorphization-recrystallization changes of bicalutamide. Amorphous solid dispersions with poly(vinylpyrrolidone-co-vinyl acetate) (PVP/VA) were obtained by either ball milling or spray drying. The applied processes led to drug amorphization as confirmed using X-ray diffraction and differential scanning calorimetry. Due to a high propensity towards mechanical activation, the changes of the crystal structure of physical blends of active pharmaceutical ingredient (API) and polymer upon pressure were also examined. The compression led to drug amorphization or transition from form I to form II polymorph, depending on the composition and applied force. The formation of hydrogen bonds confirmed using infrared spectroscopy and high miscibility of drug and polymer determined using non-isothermal dielectric measurements contributed to the high stability of amorphous solid dispersions. They exhibited improved wettability and dissolution enhanced by 2.5- to 11-fold in comparison with the crystalline drug. The drug remained amorphous upon compression when the content of PVP/VA in solid dispersions exceeded 20% or 33%, in the case of spray-dried and milled systems, respectively.