Influence of hydrophilic block length on the aggregation properties of polyglycidol-polystyrene-polyglycidol copolymers.

Amphiphilic triblock copolymers, polyglycidol-polystyrene-polyglycidol (PGL-PS-PGL), were synthesised via anionic polymerization starting from the synthesis of a polystyrene macroinitiator with 60 styrene units in the block terminated by ethylene oxide. Poly(ethoxyethyl glycidyl ether) blocks of different lengths were created on both sides of the macroinitiator. By removing the ethoxyethyl blocking groups, PGL-PS-PGL copolymers containing polyglycidol blocks with DP 11, 23, 44 and 63 were received. Their structures were determined by NMR and FTIR. The hydrophilicity of PLG-PS-PGL films was studied upon exposure to water vapour. To perform the copolymers' aggregation in water, the samples were dialysed from DMF into water. The critical concentration of their micellisation (CMC) was determined by measuring the absorbance of the 1,6-diphenylhexa-1,3,5-triene (DPH) probe and the intensity of light scattered by the copolymers' solution as a function of concentration. CMC values increased with increasing the number of hydrophilic glycidol units in the copolymer chain. The sizes of aggregates formed slightly above the critical concentration were measured by dynamic light scattering (DLS), and particles were imaged by cryo-TEM. Cryo-TEM pictures showed the presence of regular micelles in copolymer dispersions. For copolymers with shorter PGL chains aggregated partices were detected. Moreover, cryo-TEM demonstrated that the copolymers with a polyglycidol block of DP = 63 formed regular spherical micelles that formed 2D ordered organisation on the surface. X-ray measurements showed the formation of a partially crystallised PS core in the micelle's interior. The aggregates of all copolymers were stable. Their sizes did not change after one year of storage. The particles did not disassociate even after diluting their dispersions to a concentration 10 times lower than the critical concentration.

Formation of Three-Dimensional Polysuccinimide Electrospun Fiber Meshes Induced by the Combination of CaCl2 and Humidity.

Even though electrospinning is getting more and more attention, the preparation of 3D nanofibrous meshes is still a big challenge that limits the application of electrospun materials, especially in tissue engineering. To overcome this problem, several solutions are introduced but most of them focus on the postprocessing of the electrospun meshes. This paper presents a straightforward novel method that utilizes the joint effect of the addition of CaCl2 and the relative environmental humidity (RH), which can induce the random 3D formation of polysuccinimide (PSI) electrospun fibers with different such as wrinkled or ribbon-like structures. Although the effect of humidity and inorganic salt additives on the micro and macrostructure of electrospun fibers is known, the connection between the two in this manner has never been presented. To investigate the effect, fibers with different PSI and CaCl2 concentrations at different humidity RH levels are prepared, and their microstructure is visualized with high-resolution scanning electron microscopy (SEM). To reveal the nature of the interaction between the polymer and the CaCl2, Fourier-transformed infrared (FTIR), X-ray diffraction (XRD), and thermogravimetry (TGA) measurements are carried out and 3D nanofibrous structures are obtained.

X-ray Diffraction and Piezoelectric Studies during Tensile Stress on Epoxy/SbSI Nanocomposite.

In this paper, the performance of epoxy/SbSI nanocomposite under tensile stress was investigated. X-ray diffraction studies show the main stress mode has shear nature in the case of elastic deformation, while a combination of shear and tensile stress during plastic deformation caused lattice deformation of SbSI and shift of sulfur atoms along the c axis of the unit cell. Apart from that, the piezoelectric signals were recorded during tensile tests. Epoxy/SbSI nanocomposite responded to the applied tensile stress by generating a piezoelectric current with a relatively high value. The measured piezoelectric peak-to-peak current is relatively high (Ip-p = 1 pA) in comparison to the current flowing through the sample (8.16 pA) under an applied voltage of 100 V. The current level is independent of the deformation speed rate in contradistinction to complex stress states. The signal comes from the whole volume of the sample between electrodes and is generated by shear stress.

Nematic-to-Isotropic Phase Transition in Poly(L-Lactide) with Addition of Cyclodextrin during Abiotic Degradation Study.

Poly(L-lactide) is capable of self-assembly into a nematic mesophase under the influence of temperature and mechanical stresses. Therefore, subsequent poly(L-lactide) films were obtained and characterized, showing nematic liquid crystal properties both before and after degradation. Herein, we present that, by introducing ß-cyclodextrin into the polymer matrix, it is possible to obtain a chiral nematic mesophase during pressing, regardless of temperature and time. The obtained poly(L-lactide) films exhibiting liquid crystal properties were subjected to degradation tests and the influence of degradation on these properties was determined. Thermotropic phase behavior was investigated using polarized optical microscopy, X-ray diffraction, and differential scanning calorimetry. The degradation process demonstrated an influence on the liquid crystal properties of pressed polymer films. The colored planar texture of the chiral nematic mesophase, which was not observed prior to degradation in films without the addition of ß-cyclodextrin, appeared after incubation in water as a result of the entrapment of degradation products in the polymer matrix. These unusual tailor-made properties, obtained in liquid crystals in (bio)degradable polymers using a simple method, demonstrate the potential for advanced photonic applications.

Hydroxyapatite Obtained via the Wet Precipitation Method and PVP/PVA Matrix as Components of Polymer-Ceramic Composites for Biomedical Applications.

The aspect of drug delivery is significant in many biomedical subareas including tissue engineering. Many studies are being performed to develop composites with application potential for bone tissue regeneration which at the same provide adequate conditions for osteointegration and deliver the active substance conducive to the healing process. Hydroxyapatite shows a great potential in this field due to its osteoinductive and osteoconductive properties. In the paper, hydroxyapatite synthesis via the wet precipitation method and its further use as a ceramic phase of polymer-ceramic composites based on PVP/PVA have been presented. Firstly, the sedimentation rate of hydroxyapatite in PVP solutions has been determined, which allowed us to select a 15% PVP solution (sedimentation rate was 0.0292 mm/min) as adequate for preparation of homogenous reaction mixture treated subsequently with UV radiation. Both FT-IR spectroscopy and EDS analysis allowed us to confirm the presence of both polymer and ceramic phase in composites. Materials containing hydroxyapatite showed corrugated and well-developed surface. Composites exhibited swelling properties (hydroxyapatite reduced this property by 25%) in simulated physiological fluids, which make them useful in drug delivery (swelling proceeds parallel to the drug release). The short synthesis time, possibility of preparation of composites with desired shapes and sizes and determined physicochemical properties make the composites very promising for biomedical purposes.

Specific Condis Crystal-like Mesophase of Poly(butylene succinate-co-butylene adipate).

Understanding the properties of polymers, such as their crystallinity, is crucial for their material performance and predicting their behavior during and after use, especially in the case of environmentally friendly (bio)degradable polymers, enabling optimized design. In this work, for the first time, a pressure-induced condis crystal-like mesophase of poly(butylene succinate-co-butylene adipate) (PBSA) is presented. The phase behavior of pressed films obtained from commercial PBSA with 25% butylene adipate units is investigated at various processing temperatures from room temperature to 100 °C, pressed at a pressure of the press jaws and at 2-5 t for 1-5 min. The characterization and quantification evaluation of the condis crystal-like mesophase of pressed PBSA formed at temperatures above the glass transition is investigated by X-ray diffraction, polarized optical microscopy (POM), and differential scanning calorimetry (DSC) methods. Our results demonstrate that pressed PBSA films at 60 °C show a condis crystal-like mesophase, characterized by the presence of reflections at wide angles, birefringence by POM, as well as a higher melting point (endotherm) by DSC. The resulting oriented mesomorphic green polymer can, in a sustainable manner, expand further technological applications of (bio)degradable polymers, especially in the medical field, and open up opportunities for further research that could provide such polymers with tailored persistence and degradation, thus changing the shelf life.

Tribological Properties of Composites Based on Single-Component Powdered Epoxy Matrix Filled with Graphite.

Composites based on powdered single-component epoxy matrix are an alternative technological solution for composites produced using liquid epoxy resins. This article describes in detail the process of producing graphite-reinforced composites for tribological applications. The advantages and disadvantages of technological processes where the matrix is a single-component epoxy powder were demonstrated, and the properties of the obtained materials were examined. A series of composite materials with the graphite filler with sizes below 10 µm and below 45 µm and weight additions of 5, 10, 20, 30% were produced. Mechanical tests and tribological tests conducted with the pin-on-block method were performed, and the mechanism of tribological wear was described. The conducted research allowed us to conclude that the incorporation of graphite, regardless of particle size, above 10% by weight results in a significant reduction in the friction coefficient (approximately 40-50% lower than in unfilled epoxy resin), which is beneficial in the production of cheap self-lubricating materials.

Heating and Strain Sensing Elements Based on Segregated Polyethylene/Carbon Black Composites in Polymer Welded Joints.

The development of easy and direct real-time monitoring of welded joint quality instead of surface damage analysis is crucial to improve the quality of industrial products. This work presents the results of high-density polyethylene (HDPE)-based composites with various carbon black (CB) content (from 20 to 30 vol.%) for use as a heating element and strain sensor in electrofusion-welded polymer joints. The pyroresistive heating process was used to determine the effect of generated Joule heat during welding on the structure and sensor properties of polymer-carbon composites. It is shown that the generation of Joule heat depends on the nanocarbon content and affects the crystallinity of the polymer matrix. The partial disruption of the conductive path of carbon black particles was observed and, as a result, a decrease in electrical conductivity for composites with lower CB content after welding was found. For the highest CB amount, conductivity increased, which is caused by smaller particle-to-particle distance for filler paths. Therefore, the best balance between pyroresistive and sensor properties was found.

The Influence of Graphite Filler on the Self-Lubricating Properties of Epoxy Composites.

In this work, epoxy composites filled with flake graphite of various size (less than 10 µm and less than 45 µm) were produced. The aim of the research was to develop a self-lubricating material with favorable tribological properties, i.e., reduced friction coefficient compared to unfilled epoxy resin and limited abrasive wear. The research material was produced using technical epoxy resins based on bisphenol A. The detailed process of composite production was described, and typical technological problems were considered. The addition of graphite led to an increase in dynamic viscosity, which positively limits the phenomenon of sedimentation, but an increase in the filler content also led to an increase in the porosity of the material. A series of tests have shown that the addition of graphite above 5% by weight allows for a reduction in the friction coefficient from 0.6 to 0.4 and significantly reduces the material's tendency to abrasive wear.

The influence of UV radiation on the properties of GFRP laminates in underwater conditions.

Degradation of polymer composites is a significant problem in many engineering aspects. Due to the interaction of various degradation factors during the exploitation of composites, a synergistic effect of destruction is observed. The article describes the phenomena occurring in glass fiber reinforced polyester laminates under the influence of ultraviolet radiation (UV) in an aquatic environment. The laminates were exposed to UV-A, UV-B and UV-C radiation for 1000 h in free-air and underwater conditions. During the test, the materials were immersed at stable depth of 1 mm and 10 mm, respectively. The three-point bending tests performed on the samples after being exposed to UV showed an increase in the flexural strength of the composites. Simultaneously, degradation of the outer surface layer was observed. The degradation removed the thin resin film from the surface which resulted in a direct exposure of the reinforcing fibers to the environment. The transformations taking place in the deeper layers of the composite increased the mechanical strength due to the additional cross-linking reactions excited by the energy arising from the radiation. Moreover, the formation of polymer structures from free styrene remaining after the technological process and the occurrence of free radical reactions as a result of the cage effect was also observed.

Comparison of PLLA-PEG and PDLLA-PEG micelles for co-encapsulation of docetaxel and resveratrol.

The interest in combining chemosensitizers with cytostatics in cancer therapy is growing, which causes also a need to develop their delivery systems. Example of the combination with beneficial therapeutic effects is docetaxel (Dtx) and resveratrol (Res). Although poly(lactide)-co-poly(ethylene glycol) (PLA-PEG) micelles have been considered as one of the most promising platforms for drug delivery, their properties may depend on the stereoisomeric form of hydrophobic block. Therefore, the aim of this study was evaluation of the effect of PLA block on co-encapsulation and release rate of Dtx and Res, which has not been studied so far. This article presents a comparison of single- (Dtx or Res) and dual-drug (Dtx and Res) loaded micelles obtained from poly(l,l-lactide)-co-poly(ethylene glycol) (PLLA-PEG) and poly(d,l-lactide)-co-poly(ethylene glycol) (PDLLA-PEG). The analyzes of the micelles have been conducted including morphology, drug(s) encapsulation efficiency, intermolecular interactions, in vitro drug release, and cytotoxicity. Differences in drug loading ability and release profile have been observed between Res and Dtx but also depending on the polymer and number of drugs in micelles (single vs. dual loaded). The PLLA-PEG micelles have a significantly higher Dtx encapsulation capacity than PDLLA-PEG micelles. The highest cytotoxicity was shown for Dtx and Res dual-loaded micelles, regardless of the polymer. The findings may be used for selection of PLA-based drug delivery systems containing Dtx and Res.

Properties of biodegradable polymer coatings with hydroxyapatite on a titanium alloy substrate.

Purpose: Titanium alloys are among the most widely used materials in medicine, especially in orthopedics. However, their use requires the application of an appropriate surface modification method to improve their properties. Such methods include anodic oxidation and the application of polymer coatings, which limit the release of alloying element ions. In addition, biodegradable polymer coatings can serve as a carrier for drugs and other substances. The paper presents the results of research on the physical properties of biodegradable polymer coatings containing nanoparticle hydroxyapatite on a titanium alloy substrate. Methods: A PLGA coating was used in the tests. The coatings on the substrate of the anodized Ti6Al7Nb alloy were applied by ultrasonic spray coating. The tests were carried out for coatings with various hydroxyapatite content (5, 10, 15, 20%) and thickness resulting from the number of layers applied (5, 10, 15 layers). The scope of the research included microscopic observations using scanning electron microscopy, topography tests with optical profilometry, structural studies using X-ray diffraction, as well as wettability and adhesion tests. Results: The results shows that with the use of ultrasonic spray coating system is possible to obtain the continuous coatings containing hydroxyapaptite. Conclusions: The properties of the coating can be controlled by changing the percentage of hydroxyapatite and the number of layers of which the coating is composed.

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.

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.

Development of Polyhydroxybutyrate-Based Packaging Films and Methods to Their Ultrasonic Welding.

This study developed a technical task associated with the formation of welded joints based on biodegradable polymers and their subsequent physicochemical characterization. The primary objective was to establish the effect of the welding process and modification of natural poly(3-hydroxybutyrate) (PHB) with N,N-dibutylundecenoylamide (DBUA) as a plasticizing agent on the structure and properties of PHB-based biopolymer materials as well as the process and structure of welded joints formation using ultrasonic welding technique. The weldability of biodegradable layers based on PHB and PHB/DBUA mixture was ultrasonically welded and optimized using a standard Branson press-type installation. The effect of the DBUA plasticizer and welding process on the structure of PHB-based biodegradable material was investigated using scanning electron microscopy, X-ray diffraction, FT-IR spectroscopy, differential scanning calorimetry, and thermomechanical analysis. The results confirmed that the DBUA acted as an effective plasticizer of PHB, contributing to lower crystallinity of the PHB/DBUA mixture (63%) in relation to the crystallinity degree of pure PHB film (69%). Ultrasonic welding resulted in an additional increase (approximately 8.5%) in the degree of crystallinity in the PHB/DBUA in relation to the initial PHB/DBUA mixture. The significant shift toward lower temperatures of the crystallization and melting peaks of PHB modified with DBUA were observed using DSC concerning pure PHB. The melt crystallization process of PHB was affected by welding treatment, and a shift toward higher temperature was observed compared with the unwelded PHB/DBUA sample. The butt-welded joints of biodegradable PHB/DBUA materials made using the ultrasonic method tested for tensile strength have damaged the area immediately outside the joining surface.

Glassy Carbon Open-Celled Foams as a Reinforcement in Polymer Matrix Composites Dedicated for Tribological Applications.

This work presents the results of a tribological examination of polymer matrix composites reinforced with carbon foams with different porosity. The application of open-celled carbon foams allows an easy infiltration process by liquid epoxy resin. At the same time, carbon reinforcement remains its initial structure, which prevents its segregation in polymer matrix. Dry friction tests, conducted under 0.7, 2.1, 3.5 and 5.0 MPa loads, show that higher friction load results in higher mass loss, but it strongly lowers the coefficient of friction (COF). The change in coefficient of friction is related to the size of the pores of the carbon foam. Open-celled foams with pores size below 0.6 mm (40 and 60 ppi), used as a reinforcement in epoxy matrix, allow to obtain COF twice lower than composite reinforced with 20 ppi open-celled foam. This phenomenon occurs due to a change of friction mechanisms. In composites reinforced with open-celled foams, general wear mechanism is related to destruction of carbon components, which results in solid tribofilm formation. The application of novel reinforcement, in the form of open-celled foams with stable distance between carbon components, allows the decrease of COF and the improvement of stability, even under a very high friction load.

Pyroresistive Properties of Composites Based on HDPE and Carbon Fillers.

Electrothermal processes were studied in pyroresistive composites based on high-density polyethylene (HDPE) containing 8 vol.% carbon black (CB), 8 vol.% carbon fibers (CF), and their mixture 4 vol.% CB + 4 vol.% CF. It is shown that the kinetic heating curves of composites are well described by an exponential dependence with a certain heating rate constant k for each type of composite. After a short heating time, the equilibrium temperature Te is reached in the sample. When the applied voltage exceeds a certain value, the Te value decreases due to the presence of the positive temperature coefficient of resistance (PTC) effect. Due to the PTC effect, the composites exhibit a self-regulating effect relative to the Te. Relations between the applied voltage, electric power, and equilibrium temperature are found, the Te value depends on the applied voltage according to the quadratic law whereas there is a linear relationship between the Te and electric power. A possible application of such pyroresistive composites is resistance welding of plastics using a heating element (HE) made of a pyroresistive material. The use of HDPE-CB composite to create HE for resistance welding is demonstrated and the welded joint of HDPE parts obtained using HE is shown.

Bismuth sulfoiodide (BiSI) nanorods: synthesis, characterization, and photodetector application.

The nanorods of bismuth sulfoiodide (BiSI) were synthesized at relatively low temperature (393 K) through a wet chemical method. The crystalline one-dimensional (1D) structure of the BiSI nanorods was confirmed using high resolution transmission microscopy (HRTEM). The morphology and chemical composition of the material were examined by applying scanning electron microscopy (SEM) and energy-dispersive X-ray spectroscopy (EDS), respectively. The average diameter of 126(3) nm and length of 1.9(1) µm of the BiSI nanorods were determined. X-ray diffraction (XRD) revealed that prepared material consists of a major orthorhombic BiSI phase (87%) and a minor amount of hexagonal Bi13S18I2 phase (13%) with no presence of other residual phases. The direct energy band gap of 1.67(1)  eV was determined for BiSI film using diffuse reflectance spectroscopy (DRS). Two types of photodetectors were constructed from BiSI nanorods. The first one was traditional photoconductive device based on BiSI film on stiff glass substrate equipped with Au electrodes. An influence of light intensity on photocurrent response to monochromatic light (λ = 488 nm) illumination was studied at a constant bias voltage. The novel flexible photo-chargeable device was the second type of prepared photodetectors. It consisted of BiSI film and gel electrolyte layer sandwiched between polyethylene terephthalate (PET) substrates coated with indium tin oxide (ITO) electrodes. The flexible self-powered BiSI photodetector exhibited open-circuit photovoltage of 68 mV and short-circuit photocurrent density of 0.11 nA/cm2 under light illumination with intensity of 0.127 W/cm2. These results confirmed high potential of BiSI nanorods for use in self-powered photodetectors and photo-chargeable capacitors.

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.