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.

The Effect of Femtosecond Laser Irradiation and Plasmon Field on the Degree of Conversion of a UDMA-TEGDMA Copolymer Nanocomposite Doped with Gold Nanorods.

In this work, the effects of femtosecond laser irradiation and doping with plasmonic gold nanorods on the degree of conversion (DC) of a urethane dimethacrylate (UDMA)-triethylene glycol dimethacrylate (TEGDMA) nanocomposite were investigated. The UDMA-TEGDMA photopolymer was prepared in a 3:1 weight ratio and doped with dodecanethiol- (DDT) capped gold nanorods of 25 × 75 or 25 × 85 nm nominal diameter and length. It was found that the presence of the gold nanorods alone (without direct plasmonic excitation) can increase the DC of the photopolymer by 6-15%. This increase was found to be similar to what could be achieved with a control heat treatment of 30 min at 180 °C. It was also shown that femtosecond laser impulses (795 nm, 5 mJ pulse energy, 50 fs pulse length, 2.83 Jcm-2 fluence), applied after the photopolymerization under a standard dental curing lamp, can cause a 2-7% increase in the DC of undoped samples, even after thermal pre-treatment. The best DC values (12-15% increase) were obtained with combined nanorod doping and subsequent laser irradiation close to the plasmon resonance peak of the nanorods (760-800 nm), which proves that the excited plasmon field can directly facilitate double bond breakage (without thermoplasmonic effects due to the short pulse length) and increase the crosslink density independently from the initial photopolymerization process.

Incidence of the Brownian Relaxation Process on the Magnetic Properties of Ferrofluids.

Ferrofluids containing magnetic nanoparticles represent a special class of magnetic materials due to the added freedom of particle tumbling in the fluids. We studied this process, known as Brownian relaxation, and its effect on the magnetic properties of ferrofluids with controlled magnetite nanoparticle sizes. For small nanoparticles (below 10 nm diameter), the Néel process is expected to dominate the magnetic response, whereas for larger particles, Brownian relaxation becomes important. Temperature- and magnetic-field-dependent magnetization studies, differential scanning calorimetry, and AC susceptibility measurements were carried out for 6 and 13.5 nm diameter magnetite nanoparticles suspended in water. We identify clear fingerprints of Brownian relaxation for the sample of large-diameter nanoparticles as both magnetic and thermal hysteresis develop at the water freezing temperature, whereas the samples of small-diameter nanoparticles remain hysteresis-free down to the magnetic blocking temperature. This is supported by the temperature-dependent AC susceptibility measurements: above 273 K, the data show a low-frequency Debye peak, which is characteristic of Brownian relaxation. This peak vanishes below 273 K.

Decomposition Behavior of Stereocomplex PLA Melt-Blown Fine Fiber Mats in Water and in Compost.

This study introduces systematic and comparative investigations of various PLA fine fiber mats prepared by melt blowing. A series of PLLA and PDLA melt-blown fibers from various L and D enantiomers blends were produced. Their morphological, mechanical, and thermal properties were studied, and their decomposition in water and compost was investigated. It was found that the 1:1 ratio blend with stereocomplex crystals had an 80% lower average fiber diameter, 60% higher specific strength and better thermal stability than the PLLA and PDLA fiber mats. In the case of composting, the crystalline peak melting temperature, crystallinity, and thermogravimetric decomposition temperatures marginally decreased after 14 days. The high surface of the fine fiber mats played a crucial role in fast decomposition, as they entirely disintegrated in less than only 40 days. In the case of water, the homocrystalline domains were more susceptible to hydrolysis than the stereocomplex ones. All the PLA fiber mats underwent decomposition and extensive disintegration for 70 days in water. Hydrolysis reduced the amorphous and crystalline fraction of the fibers via surface and bulk erosion, while the decomposition of stereocomplex-crystalline-rich domains mainly exhibited surface erosion. Findings revealed that high porosity and the high surface area of PLA melt-blown fine fiber mats undergo fast decomposition in compost and in water. Supplementary Information: The online version contains supplementary material available at 10.1007/s10924-022-02694-w.

Photodegradation of polylactic acid: Characterisation of glassy and melt behaviour as a function of molecular weight.

During the COVID-19 pandemic, UV-C germicidal lamps became widely available, even for household applications. However, their long-term degradation effects on the mechanical and rheological properties of polylactic acid (PLA) are still not well established. The relationship between degradation and its effects on the molecular structure and macroscale properties are hardly known. In this study, we investigated the effects of long-term exposure to UV-C irradiation on the properties of PLA and interpreted the results at the molecular scale. We performed gel permeation chromatography, Fourier-transform infrared spectroscopy and UV-Vis spectroscopy to analyse changes in chemical structure induced by the UV-irradiation. Then, we carried out thermal, rheological and tensile tests to investigate mechanical and melting properties, and we investigated the applicability of these test results to estimate molecular weight loss. We have created a 3D irradiation map that can facilitate the design of disinfection devices. Based on our results, we propose a maximum number of sterilisation cycles (13 cycles) for the tested PLA films that do not result in significant changes in tensile strength and modulus.

Preparation and Characterization of Fibrous Alumina and Zirconia Toughened Alumina Ceramics with Gradient Porosity.

This paper investigated a synthesis process for highly porous Al2O3, Y-ZTA, and Ce-ZTA ceramic nanocomposites with gradient microstructure and improved mechanical properties. Ceramic nanofibres were synthesized as the starting material. The gradient microstructure was developed during spark plasma sintering using an asymmetric graphite arrangement that generated significant temperature differences (80-100 °C) between the opposite sides of the samples. Structural and mechanical properties of the fibrous ceramic composites were investigated. The effect of the temperature gradient on properties was also discussed. While the asymmetric configuration resulted in a gradient porosity, reference samples fabricated in standard graphite configuration were uniformly porous. The gradient structure and the ZrO2 addition led to improved hardness and compression strength of the sintered samples. However, the opposite sides of the samples exhibited considerable variations in both microstructure and in terms of properties. The upper part of the Ce-ZTA ceramic showed a highly porous structure with 18.2 GPa hardness, while the opposite side was highly densified with 23.0 GPa hardness. Compressive strength was 46.1 MPa and 52.1 MPa for Y-ZTA and Ce-ZTA sintered at 1300 °C, respectively, despite their high porosity. The research provided a promising approach to prepare highly porous ZTA composites with high strength for a wide range of applications.

3D Printed and Electrospun, Transparent, Hierarchical Polylactic Acid Mask Nanoporous Filter.

Face masks are becoming one of the most useful personal protective equipment with the outbreak of the coronavirus (CoV) pandemic. The entire world is experiencing shortage of disposable masks and melt-blown non-woven fabrics, which is the raw material of the mask filter. Recyclability of the discarded mask is also becoming a big challenge for the environment. Here, we introduce a facile method based on electrospinning and three-dimensional printing to make changeable and biodegradable mask filters. We printed polylactic acid (PLA) polymer struts on a PLA nanofiber web to fabricate a nanoporous filter with a hierarchical structure and transparent look. The transparent look overcomes the threatening appearance of the masks that can be a feasible way of reducing the social trauma caused by the current CoV disease-19 pandemic. In this study, we investigated the effects of nozzle temperature on the optical, mechanical, and morphological and filtration properties of the nanoporous filter.

The Effect of Multilevel Carbon Reinforcements on the Fire Performance, Conductivity, and Mechanical Properties of Epoxy Composites.

We studied the effect of a multilevel presence of carbon-based reinforcements-a combination of conventional load-bearing unidirectional carbon fiber (CF) with multiwalled carbon nanotubes (CNT) and conductive CNT-containing nonwoven carbon nanofabric (CNF(CNT))-on the fire performance, thermal conductivity, and mechanical properties of reference and flame-retarded epoxy resin (EP) composites. The inclusion of carbon fibers and flame retardant reduced the peak heat release rate (pHRR) of the epoxy resins. The extent to which the nanoreinforcements reduced the pHRR depended on their influence on thermal conductivity. Specifically, high thermal conductivity is advantageous at the early stages of degradation, but after ignition it may lead to more intensive degradation and a higher pHRR; especially in the reference samples without flame retardant. The lowest pHRR (130 kW/m²) and self-extinguishing V-0 UL-94 rating was achieved in the flame-retarded composite containing all three levels of carbon reinforcement (EP + CNF(CNT) + CNT + CF FR). The plasticizing effect of the liquid flame retardant impaired both the tensile and flexural properties; however, it significantly enhanced the impact resistance of the epoxy resin and its composites.

Corona alternating current electrospinning: A combined approach for increasing the productivity of electrospinning.

Corona alternating current electrospinning (C-ACES), a scaled-up productivity electrospinning method was developed by combining the intense forces of the alternating electrostatic field and a sharp-edged spinneret design with increased free surface. C-ACES reached two orders of magnitude higher productivity (up to 1200 mL/h) than the classical single needle direct current electrospinning (DCES) without any alteration of fiber properties. Polyvinylpyrrolidone K90 (PVPK90), a water soluble high molecular weight nonionic polymer was processed for the first time with single needle alternating current electrospinning (ACES) and C-ACES in order to prepare fast dissolving amorphous solid dispersions of spironolactone (SPIR), a poorly water-soluble antihypertensive model drug. The limited spinnability of PVPK90 with AC high voltage could only be resolved by optimizing the solution conductivity with organophilic salts such as sodium dodecyl sulfate (SDS) demonstrating the importance of conductivity during ACES. The effects of varied solution properties (composition and conductivity) and scaling-up were investigated by SEM imaging. Solid state analyses revealed that SPIR was dispersed in an amorphous form in the fibrous mats. In vitro dissolution tests showed ultrafast drug release in case of the amorphous formulations even when prepared with scaled-up C-ACES. Besides the enhancement of conductivity SDS also prevents SPIR from precipitation from the dissolution media due to its solubilization ability.

High speed electrospinning for scaled-up production of amorphous solid dispersion of itraconazole.

High speed electrospinning (HSES), compatible with pharmaceutical industry, was used to demonstrate the viability of the preparation of drug-loaded polymer nanofibers with radically higher productivity than the known single-needle electrospinning (SNES) setup. Poorly water-soluble itraconazole (ITRA) was formulated with PVPVA64 matrix polymer using four different solvent-based methods such as HSES, SNES, spray drying (SD) and film casting (FC). The formulations were assessed in terms of improvement in the dissolution rate of ITRA (using a "tapped basket" dissolution configuration) and analysed by SEM, DSC and XRPD. Despite the significantly increased productivity of HSES, the obtained morphology was very similar to the SNES nanofibrous material. ITRA transformed into an amorphous form, according to the DSC and XRPD results, in most cases except the FC samples. The limited dissolution of crystalline ITRA could be highly improved: fast dissolution occurred (>90% within 10min) in the cases of both (the scaled-up and the single-needle) types of electrospun fibers, while the improvement in the dissolution rate of the spray-dried microspheres was significantly lower. Production of amorphous solid dispersions (ASDs) with the HSES system proved to be flexibly scalable and easy to integrate into a continuous pharmaceutical manufacturing line, which opens new routes for the development of industrially relevant nanopharmaceuticals.

Epoxy/Polycaprolactone Systems with Triple-Shape Memory Effect: Electrospun Nanoweb with and without Graphene Versus Co-Continuous Morphology.

Triple-shape memory epoxy (EP)/polycaprolactone (PCL) systems (PCL content: 23 wt %) with different structures (PCL nanoweb embedded in EP matrix and EP/PCL with co-continuous phase structure) were produced. To set the two temporary shapes, the glass transition temperature (Tg) of the EP and the melting temperature (Tm) of PCL served during the shape memory cycle. An attempt was made to reinforce the PCL nanoweb by graphene nanoplatelets prior to infiltrating the nanoweb with EP through vacuum assisted resin transfer molding. Morphology was analyzed by scanning electron microscopy and Raman spectrometry. Triple-shape memory characteristics were determined by dynamic mechanical analysis in tension mode. Graphene was supposed to act also as spacer between the nanofibers, improving the quality of impregnation with EP. The EP phase related shape memory properties were similar for all systems, while those belonging to PCL phase depended on the structure. Shape fixity of PCL was better without than with graphene reinforcement. The best shape memory performance was shown by the EP/PCL with co-continuous structure. Based on Raman spectrometry results, the characteristic dimension of the related co-continuous network was below 900 nm.