Polymer Composites with Carbon Fillers Based on Coal Pitch and Petroleum Pitch Cokes: Structure, Electrical, Thermal, and Mechanical Properties.

The effect of particle size and oxidation degree of new carbon microfillers, based on coal pitch (CP) and petroleum pitch (PET) cokes, on the structure as well as thermal, mechanical, and electrical properties of the composites based on ultrahigh molecular weight polyethylene (UHMWPE) was investigated. The composites studied have a segregated structure of filler particle distribution in the UHMWPE matrix. It was found that composite with smaller CP grain fraction has the highest Young's modulus and electrical conductivity compared to the other composites studied, which can be the result of a large contribution of flake-shaped particles. Additionally, conductivity of this composite turned out to be similar to composites with well-known carbon nanofillers, such as graphene, carbon black, and CNTs. Additionally, the relationship between electrical conductivity and Young's modulus values of composites studied was revealed, which indicates that electrical conductivity is very sensitive to the structure of the filler phase in the polymer matrix. In general, it was established that the properties, especially the electrical conductivity, of the composites studied strongly depends on the size, shape, and oxidative treatment of CP and PET filler particles, and that the CP coke of appropriately small particle sizes and flake shape has significant potential as a conductive filler for polymer composites.

Polymer Nanocomposites Based on Nanosized Substituted Ferrites (NiZn)1-xMnxFe2O4 on the Surface of Carbon Nanotubes for Effective Interaction with High-Frequency EM Radiation.

To create materials that interact effectively with electromagnetic (EM) radiation, new nanosized substituted ferrites (NiZn)1-xMnxFe2O4 (x = 0, 0.5, and 1) anchored on the surface of multi-walled carbon nanotubes (CNTs) have been synthesized. The concentration of CNTs in the (NiZn)1-xMnxFe2O4/CNT system was from 0.05 to 0.07 vol. fractions. The dielectric and magnetic characteristics of both pristine (NiZn)1-xMnxFe2O4 ferrites and (NiZn)1-xMnxFe2O4/CNT composite systems were studied. The introduction of (NiZn)1-xMnxFe2O4/CNT composites into the amorphous epoxy matrix allows to tailor absorbing properties at the high-frequency by effectively shifting the maximum peak values of the absorption and reflection coefficient to a region of lower frequencies (20-30 GHz). The microwave adsorption properties of (NiZn)1-xMnxFe2O4/0.07CNT-ER (x = 0.5) systems showed that the maximum absorption bandwidth with reflection loss below -10 dB is about 11 GHz.

Flexible Piezoresistive Polystyrene Composite Sensors Filled with Hollow 3D Graphitic Shells.

The objective of this research was to develop highly effective conductive polymer composite (CPC) materials for flexible piezoresistive sensors, utilizing hollow three-dimensional graphitic shells as a highly conductive particulate component. Polystyrene (PS), a cost-effective and robust polymer widely used in various applications such as household appliances, electronics, automotive parts, packaging, and thermal insulation materials, was chosen as the polymer matrix. The hollow spherical three-dimensional graphitic shells (GS) were synthesized through chemical vapor deposition (CVD) with magnesium oxide (MgO) nanoparticles serving as a support, which was removed post-synthesis and employed as the conductive filler. Commercial multi-walled carbon nanotubes (CNTs) were used as a reference one-dimensional graphene material. The main focus of this study was to investigate the impact of the GS on the piezoresistive response of carbon/polymer composite thin films. The distribution and arrangement of GS and CNTs in the polymer matrix were analyzed using techniques such as X-ray diffraction and scanning electron microscopy, while the electrical, thermal, and mechanical properties of the composites were also evaluated. The results revealed that the PS composite films filled with GS exhibited a more pronounced piezoresistive response as compared to the CNT-based composites, despite their lower mechanical and thermal performance.

Laminar Biomaterial Composite of PVA Cryogel with Amnion as Potential Wound Dressing.

Gel dressings, composed of polymers both natural and synthetic, are successfully used in the treatment of burn wounds. They protect the burn wound site against adverse external factors, ensure an adequate level of tissue hydration, have soothing and pain-relieving properties, and also support the healing process and reduce the risk of pathological scars. Another promising material that can be used in the wound-healing process is an amnion membrane. Due to its valuable properties such as protecting the body against bacterial infections and permeability to nutrition, it has found usage in different brands of medicine. In this work, we have combined the beneficial properties of hydrogels and amnion in order to make the laminar dressing that may serve for wound healing. For that purpose, the physically crosslinked cryogel of poly(vinyl alcohol) (PVA) was covered with an amnion membrane. Subsequently, gamma irradiation was performed, leading to the simultaneous internal crosslinking of the hydrogel, its permanent bonding with the amnion, and dressing sterilization. The physicochemical properties of the dressing including gel fraction, swelling, and hardness were studied. Biological tests such as the MTT assay, antimicrobial activity, and histopathological examination confirmed that the obtained material constituted a promising candidate for further, more in-depth studies aiming at wound dressing application.

Bioresorbable Nonwoven Patches as Taxane Delivery Systems for Prostate Cancer Treatment.

Prostate cancer is the second most common cancer in males. In the case of locally advanced prostate cancer radical prostatectomy is one of the first-line therapy. However, recurrence after resection of the tumor can appear. Drug-eluting bioresorbable implants acting locally in the area of the tumor or the resection margins, that reduce the risk of recurrence would be advantageous. Electrospinning offers many benefits in terms of local delivery so fiber-forming polyesters and polyestercarbonates which are suitable to be drug-loaded were used in the study to obtain CTX or DTX-loaded electrospun patches for local delivery. After a fast verification step, patches based on the blend of poly(glycolide-ε-caprolactone) and poly(lactide-glycolide) as well as patches obtained with poly(lactide-glycolide- ε-caprolactone) were chosen for long-term study. After three months, 60% of the drug was released from (PGCL/PLGA) + CTX and it was selected for final, anticancer activity analysis with the use of PC-3 and DU145 cells to establish its therapeutic potential. CTX-loaded patches reduced cell growth to 53% and 31% respectively, as compared to drug-free patches. Extracts from drug-free patches showed excellent biocompatibility with the PC-3 cell line. Cabazitaxel-loaded bioresorbable patches are a promising drug delivery system for prostate cancer therapy.

Surface Modification of PHBV Fibrous Scaffold via Lithium Borohydride Reduction.

In this study, lithium borohydride (LiBH4) reduction was used to modify the surface chemistry of poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) fibers. Although the most common reaction employed in the surface treatment of polyester materials is hydrolysis, it is not suitable for fiber modification of bacterial polyesters, which are highly resistant to this type of reaction. The use of LiBH4 allowed the formation of surface hydroxyl groups under very mild conditions, which was crucial for maintaining the fibers' integrity. The presence of these groups resulted in a noticeable improvement in the surface hydrophilicity of PHBV, as revealed by contact angle measurements. After the treatment with a LiBH4 solution, the electrospun PHBV fibrous mat had a significantly greater number of viable osteoblast-like cells (SaOS-2 cell line) than the untreated mat. Moreover, the results of the cell proliferation measurements correlated well with the observed cell morphology. The most flattened SaOS-2 cells were found on the surface that supported the best cell attachment. Most importantly, the results of our study indicated that the degree of surface modification could be controlled by changing the degradation time and concentration of the borohydride solution. This was of great importance since it allowed optimization of the surface properties to achieve the highest cell-proliferation capacity.

Poly(l-Lactide) Liquid Crystals with Tailor-Made Properties Toward a Specific Nematic Mesophase Texture.

This paper presents the liquid crystal (LC) properties of poly(l-lactide) (PLLA). Mesophase behavior is investigated using polarized optical microscopy, X-ray diffraction, and differential scanning calorimetry. The performed analyses confirm that pressed PLLA films exhibit the unique capability of self-assembling into a nematic mesophase under the influence of mechanical pressure, temperature, and time. It was originally demonstrated that the chiral nematic mesophase can be obtained by introducing fine powders into the polymer. Based on the research conducted, it was proved that the pressed PLLA films have a chiral nematic mesophase with a nematic-to-isotropic phase transition and a large mesophase stability range overlapping the temperature of the human body, which can persist for years at ambient temperature. The obtained films show tailor-made properties toward a nematic mesophase with a specific texture, including colored planar texture of the chiral nematic mesophase and blue-phase (BP) LC texture. The BP, described for the first time in plain PLLA, occurred over a wider than usual temperature range of stability between isotropic and chiral nematic thermotropic phases (ΔT ≈ 9 °C), which is an advantage of the obtained polymer material, in addition to ease of preparation. This opens up new prospects for advanced photonic green applications.

Comparison of PLA-Based Micelles and Microspheres as Carriers of Epothilone B and Rapamycin. The Effect of Delivery System and Polymer Composition on Drug Release and Cytotoxicity against MDA-MB-231 Breast Cancer Cells.

Co-delivery of epothilone B (EpoB) and rapamycin (Rap) increases cytotoxicity against various kinds of cancers. However, the current challenge is to develop a drug delivery system (DDS) for the simultaneous delivery and release of these two drugs. Additionally, it is important to understand the release mechanism, as well as the factors that affect drug release, in order to tailor this process. The aim of this study was to analyze PLA-PEG micelles along with several types of microspheres obtained from PLA or a mixture of PLA and PLA-PEG as carriers of EpoB and Rap for their drug release properties and cytotoxicity against breast cancer cells. The study showed that the release process of EpoB and Rap from a PLA-based injectable delivery systems depends on the type of DDS, morphology, and polymeric composition (PLA to PLA-PEG ratio). These factors also affect the biological activity of the DDS, because the cytotoxic effect of the drugs against MDA-MB-231 cells depends on the release rate. The release process from all kinds of DDS was well-characterized by the Peppas-Sahlin model and was mainly controlled by Fickian diffusion. The conducted analysis allowed also for the selection of PLA 50/PLA-PEG 50 microspheres and PLA-PEG micelles as a promising co-delivery system of EpoB and Rap.

Three-Dimensional Printed PLA and PLA/PHA Dumbbell-Shaped Specimens: Material Defects and Their Impact on Degradation Behavior.

The use of (bio)degradable polymers, especially in medical applications, requires a proper understanding of their properties and behavior in various environments. Structural elements made of such polymers may be exposed to changing environmental conditions, which may cause defects. That is why it is so important to determine the effect of processing conditions on polymer properties and also their subsequent behavior during degradation. This paper presents original research on a specimen's damage during 70 days of hydrolytic degradation. During a standard hydrolytic degradation study of polylactide and polylactide/polyhydroxyalkanoate dumbbell-shaped specimens obtained by 3D printing with two different processing build directions, exhibited unexpected shrinkage phenomena in the last degradation series, representing approximately 50% of the length of the specimens irrespective of the printing direction. Therefore, the continuation of previous ex-ante research of advanced polymer materials is presented to identify any possible defects before they arise and to minimize the potential failures of novel polymer products during their use and also during degradation. Studies on the impact of a specific processing method, i.e., processing parameters and conditions, on the properties expressed in molar mass and thermal properties changes of specimens obtained by three-dimensional printing from polyester-based filaments, and in particular on the occurrence of unexpected shrinkage phenomena after post-processing heat treatment, are presented.

Nanolayers of Poly(N,N'-Dimethylaminoethyl Methacrylate) with a Star Topology and Their Antibacterial Activity.

In this paper, we focus on the synthesis and characterization of novel stable nanolayers made of star methacrylate polymers. The effect of nanolayer modification on its antibacterial properties was also studied. A covalent immobilization of star poly(N,N'-dimethylaminoethyl methacrylate) (PDMAEMA) to benzophenone functionalized glass or silicon supports was carried out via a "grafting to" approach using UV irradiation. To date, star polymer UV immobilization has never been used for this purpose. The thickness of the resulting nanolayers increased from 30 to 120 nm with the molar mass of the immobilized stars. The successful bonding of star PDMAEMA to the supports was confirmed by surface sensitive quantitative spectroscopic methods. Next, amino groups in the polymer layer were quaternized with bromoethane, and the influence of this modification on the antibacterial properties of the obtained materials was analyzed using a selected reference strain of bacteria. The resulting star nanolayer surfaces exhibited higher antimicrobial activity against Bacillus subtilis ATCC 6633 compared to that of the linear PDMAEMA analogues grafted onto a support. These promising results and the knowledge about the influence of the topology and modification of PDMAEMA layers on their properties may help in searching for new materials for antimicrobial applications in medicine.

(Bio)degradable Polymeric Materials for Sustainable Future-Part 2: Degradation Studies of P(3HB-co-4HB)/Cork Composites in Different Environments.

The degree of degradation of pure poly(3-hydroxybutyrate-co-4-hydroxybutyrate) [P(3HB-co-4HB)] and its composites with cork incubated under industrial and laboratory composting conditions was investigated. The materials were parallelly incubated in distilled water at 70 °C as a reference experiment (abiotic condition). It was demonstrated that addition of the cork into polyester strongly affects the matrix crystallinity. It influences the composite degradation independently on the degradation environment. Moreover, the addition of the cork increases the thermal stability of the obtained composites; this was related to a smaller reduction in molar mass during processing. This phenomenon also had an influence on the composite degradation process. The obtained results suggest that the addition of cork as a natural filler in various mass ratios to the composites enables products with different life expectancies to be obtained.

The influence of chemical structure on thermal properties and surface morphology of polyurethane materials.

The surface morphology and thermal properties of polyurethanes can be correlated to their chemical composition. The hydrophilicity, surface morphology, and thermal properties of polyurethanes (differed in soft segments and in linear/cross-linked structure) were investigated. The influence of poly([R,S]-3-hydroxybutyrate) presence in soft segments and blending of polyurethane with polylactide on surface topography were also estimated. The linear polyurethanes (partially crystalline) had the granular surface, whereas the surface of cross-linked polyurethanes (almost amorphous) was smooth. Round aggregates of polylactide un-uniformly distributed in matrix of polyurethane were clearly visible. It was concluded that some modification of soft segment (by mixing of poly([R,S]-3-hydroxybutyrate) with different polydiols and polytriol) and blending of polyurethanes with small amount of polylactide influence on crystallinity and surface topography of obtained polyurethanes.

(Bio)degradable polymeric materials for a sustainable future - part 1. Organic recycling of PLA/PBAT blends in the form of prototype packages with long shelf-life.

Prediction studies of advanced (bio)degradable polymeric materials are crucial when their potential applications as compostable products with long shelf-life is considered for today's market. The aim of this study was to determine the effect of the polylactide (PLA) content in the blends of PLA and poly(butylene adipate-co-terephthalate) (PBAT); specifically how the material's thickness corresponded to changes that occurred in products during the degradation process. Additionally, the influence of talc on the degradation profile of all samples in all environments was investigated. It was found that, differences in the degradation rate of materials tested with a similar content of the PLA component could be caused by differences in their thickness, the presence of commercial additives used during processing or a combination of both. The obtained results indicated that the presence of talc may interfere with materials behavior towards water and consequently alter their degradation profile.