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.

The Influence of Urtica dioica and Vitis vinifera Fibers on the Thermal Properties and Flammability of Polylactide Composites.

This study focuses on examining the influence of bast fibers on the flammability and thermal properties of the polylactide matrix (PLA). For this purpose, Urtica dioica and Vitis vinifera fibers were subjected to two types of modifications: mercerization in NaOH solution (M1 route) and encapsulation in an organic PLA solution (M2 route). In a further step, PLA composites containing 5, 10, and 15 wt% of unmodified and chemically treated fibers were obtained. The results of the tests show that only biocomposites containing mercerized fibers had a nearly 20% reduced flammability compared to that of PLA. Moreover, the biofiller obtained in this way belongs to the group of flame retardants that generate char residue during combustion, which was also confirmed by TGA tests. The M2 modification route allowed to achieve higher mass viscosity than the addition of unmodified and M1-modified fibers. The reason is that fibers additionally encapsulated in a polymer layer impede the mobility of the chain segments. The inferior homogenization of the M2-modified fibers in the PLA matrix translated into a longer combustion time and only a 15% reduction in flammability.

Research on the Development of a Way to Modify Asphalt Mixtures with PET Recyclates.

Due to the growing need to recycle plastics, new possibilities for their reuse are intensively sought. In the Asian market, waste polymers are increasingly used to modify road bitumen. This solution is beneficial in many aspects, especially in economic and ecological terms. In this work, recycled poly(ethylene terephthalate) (RPET), obtained from storage points located in Lesser Poland, was subjected to material recycling, and its properties were examined using three analyses: differential scanning calorimetry (DSC), thermogravimetric analysis (TG), and Fourier transform infrared spectroscopy (FTIR). The most important point of this research was the selection of conditions for obtaining modified asphalt mixtures through the addition of RPET. Subsequently, the effect of the polymer on the properties of road bitumens was assessed on the basis of penetration tests, softening point, elastic recovery, and structure. In the last stage of our research work, asphalt mixtures with the addition of modified waste PET (PMA) containing mineral filler in the form of basalt dust were obtained. The properties of the obtained mineral-polymer-asphalt mixtures were compared in terms of frost resistance, structure, and abrasion resistance with the properties of mineral-asphalt mixtures that were taken from damaged road surfaces in four points in the city of Tarnów (Lesser Poland) in the winter of 2022. It has been shown that the modification of road bitumen with the use of recyclate and mineral filler has a significant impact on its performance properties.

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.

Preparation and Characterization of Novel Microgels Containing Nano-SiO2 and Copolymeric Hydrogel Based on Poly (Acrylamide) and Poly (Acrylic Acid): Morphological, Structural and Swelling Studies.

In this paper, novel microgels containing nano-SiO2 were prepared by in situ copolymerization using nano-SiO2 particles as a reinforcing agent, nanosilica functional monomer (silane-modified nano-SiO2) as a structure and morphology director, acrylamide (AAm) as a monomer, acrylic acid (AAc) as a comonomer, potassium persulfate (KPS) as a polymerization initiator, and N,N'-methylene bis (acrylamide) (MBA) as a crosslinker. In addition, a conventional copolymeric hydrogel based on poly (acrylamide/acrylic acid) was synthesized by solution polymerization. The microgel samples, hydrogel and nanoparticles were characterized by transmission electron microscopy (TEM), field emission scanning electron microscopy (FESEM), Fourier transform infrared (FTIR) spectroscopy, thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). A FESEM micrograph of copolymeric hydrogel showed the high porosity and 3D interconnected microstructure. Furthermore, FESEM results demonstrated that when nano-SiO2 particles were used in the AAm/AAc copolymerization process, the microstructure and morphology of product changed from porous hydrogel to a nanocomposite microgel with cauliflower-like morphology. According to FESEM images, the copolymerization of AAm and AAc monomers with a nanosilica functional monomer or polymerizable nanosilica particle as a seed led to a microgel with core-shell structure and morphology. These results demonstrated that the polymerizable vinyl group on nano-SiO2 particles have controlled the copolymerization and the product morphology. FTIR analysis showed that the copolymeric chains of polyacrylamide (PAAm) and poly (acrylic acid) (PAAc) were chemically bonded to the surfaces of the nano-SiO2 particles and silane-modified nano-SiO2. The particulate character of microgel samples and the existence of long distance among aggregations of particles led to rapid swelling and increasing of porosity and therefore increasing of degree of swelling.

Novel Synthesis, Characterization and Amoxicillin Release Study of pH-Sensitive Nanosilica/Poly(acrylic acid) Macroporous Hydrogel with High Swelling.

The effect of SiO2 nanoparticles on the formation of PAA (poly acrylic acid) gel structure was investigated with seeded emulsion polymerization method used to prepare SiO2/PAA nanoparticles. The morphologies of the nanocomposite nanoparticles were studied by transmission electron microscopy (TEM). Fourier-transform infrared (FTIR) spectroscopy results indicated that the PAA was chemically bonded to the surface of the SiO2 nanoparticles. Additionally, the resulting morphology of the nanocomposite nanoparticles confirmed the co-crosslinking role of the SiO2 nanoparticles in the formation of the 3D structure and hydrogel of PAA. SiO2/PAA nanocomposite hydrogels were synthesized by in situ solution polymerization with and without toluene. The morphology studies by field emission scanning electron microscopy (FESEM) showed that when the toluene was used as a pore forming agent in the polymerization process, a macroporous hydrogel structure was achieved. The pH-sensitive swelling behaviors of the nanocomposite hydrogels showed that the formation of pores in the gels structure was a dominant factor on the water absorption capacity. In the current research the absorption capacity was changed from about 500 to 4000 g water/g dry hydrogel. Finally, the macroporous nanocomposite hydrogel sample was tested as an amoxicillin release system in buffer solutions with pHs of 3, 7.2, and 9 at 37 °C. The results showed that the percentage cumulative release of amoxicillin from the hydrogels was higher in neutral and basic mediums than in the acidic medium and the amoxicillin release rate was decreased with increasing pH. Additionally, the release results were very similar to swelling results and hence amoxicillin release was a swelling controlled-release system.

Predicting the Mechanical Properties of RCA-Based Concrete Using Supervised Machine Learning Algorithms.

Environment-friendly concrete is gaining popularity these days because it consumes less energy and causes less damage to the environment. Rapid increases in the population and demand for construction throughout the world lead to a significant deterioration or reduction in natural resources. Meanwhile, construction waste continues to grow at a high rate as older buildings are destroyed and demolished. As a result, the use of recycled materials may contribute to improving the quality of life and preventing environmental damage. Additionally, the application of recycled coarse aggregate (RCA) in concrete is essential for minimizing environmental issues. The compressive strength (CS) and splitting tensile strength (STS) of concrete containing RCA are predicted in this article using decision tree (DT) and AdaBoost machine learning (ML) techniques. A total of 344 data points with nine input variables (water, cement, fine aggregate, natural coarse aggregate, RCA, superplasticizers, water absorption of RCA and maximum size of RCA, density of RCA) were used to run the models. The data was validated using k-fold cross-validation and the coefficient correlation coefficient (R2), mean square error (MSE), mean absolute error (MAE), and root mean square error values (RMSE). However, the model's performance was assessed using statistical checks. Additionally, sensitivity analysis was used to determine the impact of each variable on the forecasting of mechanical properties.

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.

Modeling of the Kinetics of Polyoxymethylene Decomposition under Oxidative and Non-Oxidative Conditions.

Research on the thermal and thermo-oxidative degradation of polyacetals allows for the development of effective methods of utilization of the waste of these polymers towards the recovery of monomers. For this purpose, in addition to qualitative analysis, it is necessary to understand the mechanisms of chemical reactions accompanying the decomposition process under the influence of temperature. Therefore, in this article, with the experimental results from the thermal analysis of the POM homopolymer of three various stages of life-POM-P-unprocessed sample; POM-R-recycled sample, and POM-O-sample waste-we took steps to determine the basic kinetic parameters using two well-known and commonly used kinetic models: Friedman and Ozawa-Flynn-Wall (OFW). Knowing the values of the course of changes in apparent activation energy as a function of partial mass loss, theoretical curves were fitted to the experimental data. The applied calculation models turned out to be consistent in terms of the nature of the curve changes and similar in terms of Ea in the entire range of mass loss. Both kinetic models showed a very similar course of the Ea curves. The samples that decompose under oxidative conditions obtained the best fit for the reaction of nth order with autocatalysis by product B model and the samples that decompose under inert conditions for the n-dimensional nucleation according to the Avrami-Erofeev model.

Dataset on flue gas composition during pyrolysis of polyoxymethylene in a fluidised bed with the possibility of incorporating CO2.

The dataset presented in this article is the supplementary data for the research article titled "The pyrolysis and combustion of polyoxymethylene in a fluidised bed with the possibility of incorporating CO2" [1], in which possible paths of polyoxymethylene conversion in the fluidised bed made from cenospheres and by means of various fluidising gases (air, N2, CO2) were tested. The use of CO2 as fluidising gas was particularly interesting because above 600°C its incorporation into process products (i.e. CO-rich flue gas) was observed. The gaseous products were detected using Fourier Transform Infrared Spectroscopy (FTIR, Gasmet DX-4000) at intervals of a few seconds. The data on the concentration changes over time will allow to evaluate and verificate of new kinetic models of polyoxymethylene degradation with the possibility of incorporating CO2.

Safety of the application of nanosilver and nanogold in topical cosmetic preparations.

The safety of the use of cosmetic preparations with silver or gold nanoparticles was assessed. This study describes the methodology and results of research involving the generation of suspensions of silver and gold nanoparticles and creams with added silver or gold at concentrations of 20, 65, 110, 155, and 200 mg/kg. The silver nanoparticles ranged from 8 to 140 nm, and the gold nanoparticles, measured 13-99 nm. The sizes were determined using dynamic light scattering. The presence of metallic nanoparticles in the obtained oil-in-water emulsions was confirmed with UV-vis spectroscopy and transmission electron microscopy with an X-ray scattering spectrometer (TEM-EDX). Additionally, based on the TEM-EDX results, it was possible to analyse the distributions of the silver nanoparticles in the tested cosmetic emulsions. Microbiological tests showed that both the silver and gold nanoparticle emulsion possessed satisfactory fungicidal properties. Based on viscosity curves, the lowest estimated yield limits were achieved by the reference cream and the creams with the gold and silver nanoparticles at concentrations of 20 and 65 mg/kg, respectively, which improved their consistencies and distributions on the skin. The best appraisals from the respondents in terms of consistency, absorption, oiling, colour, and smell were received for the emulsion containing 200 mg/kg gold nanoparticles. The worst assessment in terms of uniformity, colour, and smell were obtained for the emulsion with 200 mg/kg silver nanoparticles. However, the most important aspect of this study was the assessment of the permeabilities of the metallic nanoparticles through imitation skin in the form of dermal membranes. The highest permeabilities were confirmed for the creams with metallic nanoparticles present at 110--200 mg/kg. This permeability is an issue of concern given the toxic properties of metallic nanoparticles for living organisms.

Examining the Influence of Re-Used Nanofiller-Pyrolyzed Montmorillonite, on the Thermal Properties of Polypropylene-Based Engineering Nanocomposites.

Pyrolysis of the polypropylene/montmorillonite (PP/OMMT) nanocomposites allows for recovery of the filler that can be then re-used to produce PP/pyrolyzed MMT (PMMT) nanostructured composites. In this work, we discuss the thermal properties of PP/PMMT composites investigated by thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), and dynamic mechanical analysis (DMA). It has been found that effect of PMMT (5 wt. % and 10 wt. %) on matrix thermal stability occurs at temperatures above 300 °C. Addition of 5 wt. % and 10 wt. % of PMMT into polypropylene system gave good stabilization effect, as confirmed by the overall stabilization effect (OSE) values, which increased by 4% and 7%, respectively, compared to the control sample (PP). Interestingly, the presence of 1 wt. % and 3 wt. % of pyrolyzed clay stabilizes the system better than the same concentrations of organoclay added into polypropylene melt. DSC data revealed that pyrolyzed clay has still the same tendency as organoclay to enhance formation of the α and ß crystalline PP phases only. The pyrolyzed MMT causes an improvement of the modulus in the glassy as well as rubbery regions, as confirmed by DMA results.