Limonene Derivative of Spherosilicate as a Polylactide Modifier for Applications in 3D Printing Technology.

The first report of using limonene derivative of a spherosilicate as a modifier of polylactide used for 3D printing and injection moulding is presented. The paper presents the use of limonene-functionalized spherosilicate derivative as a functional additive. The study compared the material characteristics of polylactide modified with SS-Limonene (0.25-5.0% w/w) processed with traditional injection moulding and 3D printing (FFF, FDM). A significant improvement in the processing properties concerning rheology, inter-layer adhesion, and mechanical properties was achieved, which translated into the quality of the print and reduction of waste production. Moreover, the paper describes the elementary stages of thermal transformations of the obtained hybrid systems.

Functional Silsesquioxanes-Tailoring Hydrophobicity and Anti-Ice Properties of Polylactide in 3D Printing Applications.

To explore the tailoring of hydrophobicity in 3D-printed polylactide (PLA) composites for advanced applications using additive manufacturing (AM), this study focuses on the use of Fused Deposition Modeling (FDM) 3D printing. PLA, a material derived from renewable sources, is favored for its eco-friendliness and user accessibility. Nonetheless, PLA's inherent hydrophilic properties result in moisture absorption, negatively affecting its performance. This research aims to modify PLA with organosilicon compounds to enhance its hydrophobic and anti-icing properties. Incorporating fluorinated siloxane derivatives led to significant increases in water contact angles by up to 39%, signifying successful hydrophobic modification. Mechanical testing demonstrated that the addition of organosilicon additives did not compromise the tensile strength of PLA and, in some instances, improved impact resistance, especially with the use of OSS-4OFP:2HEX:2TMOS, which resulted in an increase in the tensile strength value of 25% and increased impact strength by 20% compared to neat PLA. Differential scanning calorimetry (DSC) analysis indicated that the modified PLA exhibited reduced cold crystallization temperatures without altering the glass transition or melting temperatures. These results suggest that organosilicon-modified PLA has the potential to expand the material's application in producing moisture and ice-resistant 3D-printed prototypes for various industrial uses, thereby facilitating the creation of more durable and versatile 3D-printed components.

Introduction of SWCNTs as a Method of Improvement of Electrical and Mechanical Properties of CFRPs Based on Thermoplastic Acrylic Resin.

The aim of this research was to improve the electrical and mechanical properties of carbon-fibre-reinforced polymers (CFRP) based on thermoplastic acrylic resin ELIUM®, by introducing single-walled carbon nanotubes (SWCNTs) into their structure. The laminates were fabricated using the infusion technique of infiltrating the carbon fabric with the mixture of acrylic resin and SWCNTs. The addition of SWCNTs improved the electrical conductivity through the thickness of the laminate by several times compared to the laminate without modification. No defects or voids were observed in the structure of the fabricated nanocomposites. The introduction of SWCNTs into the CFRP structure increased the Young's modulus, interlaminar shear strength and impact resistance. DMA analysis showed almost no change in the glass transition temperature of the fabricated SWCNT/CFRP nanocomposites compared to the reference laminate.

The Antifungal Fibers of Polyamide 12 Containing Silver and Metal Oxides.

The textile market is a vast industry that utilizes antimicrobial polymeric materials, including various types of fabrics, for medical and personal protection applications. Therefore, this study focused on examining four types of antimicrobial fillers, namely, metal oxides (zinc, titanium, copper) and nanosilver, as fillers in Polyamide 12 fibers. These fillers can be applied in the knitting or weaving processes to obtain woven polymeric fabrics for medical applications. The production of the fibers in this study involved a two-step approach: twin-screw extrusion and melt spinning. The resulting fibers were then characterized for their thermal properties (TGA, DSC), mechanical performance (tensile test, DMA), and antifungal activity. The findings of the study indicated that all of the fibers modified with fillers kill Candida albicans. However, the fibers containing a combination of metal oxides and silver showed significantly higher antifungal activity (reduction rate % R = 86) compared to the fibers with only a mixture of metal oxides (% R = 21). Furthermore, the inclusion of metal oxides and nanosilver in the Polyamide 12 matrix hindered the formation of the crystal phase and decreased slightly the thermal stability and mechanical properties, especially for the composites with nanosilver. It was attributed to their worse dispersion and the presence of agglomerates.

Hydro- and Icephobic Properties and Durability of Epoxy Gelcoat Modified with Double-Functionalized Polysiloxanes.

Anti-icing coatings have provided a very good alternative to current, uneconomic, active deicing methods, and their use would bring a number of significant benefits to many industries, such as aviation and energy. Some of the most promising icephobic surfaces are those with hydrophobic properties. However, the relationship between hydrophobicity and low ice adhesion is not yet clearly defined. In this work, chemical modification of an epoxy gelcoat with chemical modifiers from the group of double organofunctionalized polysiloxanes (generally called multifunctionalized organosilicon compounds (MFSCs)) was applied. The anti-icing properties of manufactured coatings were determined by means of measurements of shear strength between the ice layer and the modified surface, conducted using a tensile machine. In the work, tests were also performed on the roughness, wettability, and durability of the properties in an aging chamber. It was found that the performed modifications of the coating's chemical composition by the addition of polysiloxanes enabled us to reduce ice adhesion by 51% and to increase the water contact angle by 14% in comparison to the neat gelcoat. A reduction in ice adhesion was also observed with the increasing water contact angle and with decreasing surface roughness. In addition, only one modification recorded an increase in ice adhesion after exposure in the aging chamber.

Silsesquioxane-Doped Electrospun Nanofibrillar Membranes for Separation Systems.

In this study, a series of cage siloxanes (CS), e.g., three polyhedral oligomeric silsesquioxanes (SSQs) and one spherosilicate (SS) derivative, were applied as functional additives for the preparation of poly(lactic acid)-based (PLA) nanofibrillar membranes with an electrospinning technique utilizing an efficient spinning wire electrode setup. The impact of the additives' structure, chemistry, and electrospinning parameters on the obtained materials' morphology (scanning electron microscopy) and physicochemical (thermogravimetry, differential scanning calorimetry, contact angle analysis, air flow analysis) properties is discussed. It is presented that applying organosilicon additives may extend the already tuneable properties of the membranes produced by electrospinning performed under different conditions and that they enable to obtain nanofibres of smaller diameter, which in turn increases the membrane porosity. Furthermore, the solvent-assisted electrospinning method allowed for unparalleled mixing of the PLA matrix with the CS additives, as no traces of free additives were visible on the membranes by scanning electron microscopy (SEM) imaging. The resulting membranes can be utilized as filter materials.

Role of Surface Topography in the Superhydrophobic Effect-Experimental and Numerical Studies.

Within these studies, the effect of surface topography for hydrophobic coatings was studied both numerically and experimentally. Chemically modified polyurethane coating was patterned by application of a laser beam. A set of patterns with variously distant linear peaks and grooves was obtained. The cross section of the pattern showed that the edges of the peaks and grooves were not sharp, instead forming a rounded, rectangle-like shape. For such surfaces, experimental studies were performed, and in particular the static contact angle (SCA), contact angle hysteresis (CAH), and roll-off angle (ROA) were measured. Profilometry was used to create a numerical representation of the surface. Finite volume method was then applied to simulate the behavior of the water droplets. The model developed herewith enabled us to reproduce the experimental results with good accuracy. Based on the verified model, the calculation was extended to study the behavior of the water droplet on the simulated patterns, both spiked and rectangular. These two cases, despite a similar SCA of the water droplet, have shown extremely different ROA. Thus, more detailed studies were dedicated to other geometrical features of such topography, such as the size and distance of the surface elements. Based on the results obtained herewith, the future design of superhydrophobic and/or icephobic topography is discussed.

Biocomposites Based on Polyamide 11/Diatoms with Different Sized Frustules.

Amorphous diatomite was used as a filler for a thermoplastic polymer of polyamide 11 obtained from natural sources. The diatomite particles of different sizes were previously fractionated by sedimentation to obtain powders with varying particle size distribution, including powders with or without frustule particles, crushed, uncrushed or agglomerated. Biocomposites containing 2.5, 5, 10 and 20% filler were tested for their mechanical properties, including tensile strength, flexural strength and impact strength. In addition, a particle size analysis (by Dynamic Light Scattering, DLS) was performed and the dispersion of the filler in the polymer matrix (Scanning Electron Microscopy, SEM), thermal parameters (Differential Scanning Calorimetry, DSC, and Dynamic Mechanical Analysis, DMA) were determined. Testing showed that biocomposites modified with diatomaceous earth have a higher mechanical strength than the reference system, especially with larger amounts of the filler (10 and 20%), e.g., the tensile strength of pure PA11 is about 46 MPa, while 20OB and 20OF 47.5 and 47 MPa, respectively, while an increase in max. flexural strength and flexural modulus is also observed compared to pure PA11 by a maximum of 63 and 54%, respectively Diatomaceous earth can be obtained in various ways-it is commercially available or it is possible to breed diatoms in laboratory conditions, while the use of commercially available diatomite, which contains diatoms of different sizes, eliminates the possibility of controlling mechanical parameters by filling biocomposites with a filler with the desired particle size distribution, and diatom breeding is not possible on an industrial scale. Our proposed biocomposite based on fractionated diatomaceous earth using a sedimentation process addresses the current need to produce biocomposite materials from natural sources, and moreover, the nature of the process, due to its simplicity, can be successfully used on an industrial scale.

The Use of Carbon Fibers Recovered by Pyrolysis from End-of-Life Wind Turbine Blades in Epoxy-Based Composite Panels.

This work is devoted to evaluating the effectiveness of the recovery of carbon fibers from end-of-life wind turbine blades in the pyrolysis process, and the use of those fibers in the production of flat composite panels. The recovery of carbon fibers from wind turbine blades uses a pyrolysis process at 500-600 °C in a non-oxidizing atmosphere, in such a way that makes it possible to preserve the shape and dimensions of the fibers. Using recycled carbon fibers, flat CFRP sheets with epoxy resin matrix were produced by pressing. Seven different series of samples were tested, which differed in fiber length, fiber orientation, and pressure holding time. The results obtained on the recycled fibers were compared to the original carbon fibers, cut to corresponding lengths. Additionally, one of the series was reinforced with a biaxial fabric. The most favorable pressing parameters are empirically found to be pre-pressing 2 MPa (10 min), and further pressing at a pressure of 7 MPa until the resin completely cross-linked (about 120 min). A number of tests were carried out to demonstrate the usefulness of pyrolytic fibers, including tensile strength of carbon fibers, bending strength, SEM observations, FT-IR, and Raman spectroscopy. The tests carried out on the carbon fibers show that the pyrolysis process used leaves about 2% of the matrix on the surface of the fiber, and the tensile strength of the fibers drops by about 20% compared to the new carbon fibers. The research results show that the use of the recycled carbon fibers in the production of flat composite plates is reliable, and their mechanical properties do not differ significantly from plates made of corresponding original carbon fibers. Composite panels with the pyrolytic fibers (274 MPa) show up to a 35% higher flexural strength than similarly produced panels with the original new carbon fibers (203 MPa), which means that the panels can be used in the production of elements for footbridges, bridges, pipelines, or structural elements of buildings and roofing.

Effect of the Addition of Biobased Polyols on the Thermal Stability and Flame Retardancy of Polyurethane and Poly(urea)urethane Elastomers.

Due to the current trends in sustainable development and the reduction in the use of fossil fuels (Green Deal strategy and the circular economy), and thus, the increased interest of the polyurethane industry in polyols derived from renewable sources, it is important to study the impact of these polyols on the flammability of new bioelastomers. The goal of this study was to check the influence of biobased polyols, such as tall oil (TO)-based polyols, soybean oil (SO)-based polyol, and rapeseed oil (RO)-based polyol, on the reduction in the burning and fume emissions of polyurethane and poly(urea)urethane elastomers (EPURs and EPUURs). The thermal stability of these materials was tested using thermogravimetric analysis (TGA). In turn, the flame retardancy and smoke emissions were checked using a cone calorimetry test. The released gases were identified using TGA coupled with Fourier transform infrared (FT-IR) spectroscopy (TGA/FT-IR). Moreover, the morphological and structural characteristics of the char residues were characterized using FT-IR and scanning electron microscopy (SEM) with energy-dispersive spectroscopy (EDS). The obtained data were compared to the results received for elastomers produced with petroleum substrates. The addition of biobased polyols led to a reduction in the burning as a result of the formation of char, especially RO polyol. Moreover, the TO and RO polyols increased the thermal stability of the elastomers.

The Influence of the Microstructure of Ceramic-Elastomer Composites on Their Energy Absorption Capability.

The paper presents the experimental results of static and dynamic compressive tests conducted on ceramic-elastomer composites. The alumina ceramic preforms were fabricated by the four-step method: ceramic mixture preparation, consolidation under pressure, presintering, and sintering under pressure, respectively. To obtain ceramic preforms with a similar volume fraction of open pores, but with different pore sizes, alumina powder with different particle size and a ceramic binder were used, as well as pore-forming agents that were evenly distributed throughout the volume of the molding mass. The composites were obtained using vacuum pressure infiltration of porous alumina ceramic by urea-urethane elastomer in liquid form. As a result, the obtained composites were characterized by two phases that interpenetrated three-dimensionally and topologically throughout the microstructure. The microstructure of the ceramic preforms was revealed by X-ray tomography, which indicated that the alumina preforms had similar porosity of approximately 40% vol. but different pore diameter in the range of 6 to 34 µm. After composite fabrication, image analysis was carried out. Due to the microstructure of the ceramic preforms, the composites differed in the specific surface fraction of the interphase boundaries (Sv). The highest value of the Sv parameter was achieved for composite fabricated by infiltration method of using ceramic preform with the smallest pore size. Static and dynamic tests were carried out using different strain rate: 1.4·10-3, 7·10-2, 1.4·10-1, and 3·103 s-1. Compressive strength, stress at plateau zone, and absorbed energy were determined. It was found that the ceramic-elastomer composites' ability to absorb energy depended on the specific surface fraction of the interphase boundaries and achieved a value between 15.3 MJ/m3 in static test and 51.1 MJ/m3 for dynamic strain rate.

Effect of SWCNT-Tuball Paper on the Lightning Strike Protection of CFRPs and Their Selected Mechanical Properties.

The main aim of this work was the investigation of the possibility of replacing the heavy metallic meshes applied onto the composite structure in airplanes for lightning strike protection with a thin film of Tuball single-wall carbon nanotubes in the form of ultra-light, conductive paper. The Tuball paper studied contained 75 wt.% or 90 wt.% of carbon nanotubes and was applied on the top of carbon fibre reinforced polymer before fabrication of flat panels. First, the electrical conductivity, impact resistance and thermo-mechanical properties of modified laminates were measured and compared with the reference values. Then, flat panels with selected Tuball paper, expanded copper foil and reference panels were fabricated for lightning strike tests. The effectiveness of lightning strike protection was evaluated by using the ultrasonic phased-array technique. It was found that the introduction of Tuball paper on the laminates surface improved both the surface and the volume electrical conductivity by 8800% and 300%, respectively. The impact resistance was tested in two directions, perpendicular and parallel to the carbon fibres, and the values increased by 9.8% and 44%, respectively. The dynamic thermo-mechanical analysis showed higher stiffness and a slight increase in glass transition temperature of the modified laminates. Ultrasonic investigation after lightning strike tests showed that the effectiveness of Tuball paper is comparable to expanded copper foil.

Effect of Strain on Heating Characteristics of Silicone/CNT Composites.

In this work, silicone/carbon nanotube (CNT) composites were produced using a spread coating process, followed by morphological investigations and determination of their electrical properties and heating behaviour through the application of electric potential. Composites containing varying amounts of CNT (1-7%) were investigated for their thermal behaviour with the use of an IR camera. Subsequently, thermal behaviour and electrical properties were measured when the samples were stretched (up to 20%). With the 7% CNT composites, which had a conductivity of 106 S/m, it was possible to achieve a temperature of 155 °C at a relatively low voltage of 23 V. For high CNT contents, when the potential was controlled in such a way as to maintain the temperature well below 100 °C, the temperature remained almost constant at all levels of strain investigated. At higher potentials yielding temperatures around 100 °C and above, stretching had a drastic effect on temperature. These results are critical for designing composites for dynamic applications requiring a material whose properties remain stable under strain.

Push-Out Method for Micro Measurements of Interfacial Strength in Aluminium Alloy Matrix Composites.

The main goal of this work was the evaluation of the interfacial strength of the carbon fibres/aluminium matrix interface dependently on the utilised composite fabrication method, namely high pressure die casting and gas pressure infiltration. In addition, the influence of a Ni-P coating on the C-fibres was investigated. The proposed measurements of the interfacial strength were carried out by means of the "push-out" method. The interfacial strength of the samples fabricated using the high-pressure infiltration method average between 19.03 MPa and 45.34 MPa.

A Wind Tunnel Experimental Study of Icing on NACA0012 Aircraft Airfoil with Silicon Compounds Modified Polyurethane Coatings.

Ice formation on the aerodynamic surfaces of an aircraft is regarded as a major problem in the aerospace industry. Ice accumulation may damage parts, sensors and controllers and alter the aerodynamics of the airplane, leading to a range of undesired consequences, including flight delays, emergency landings, damaged parts and increased energy consumption. There are various approaches to reducing ice accretion, one of them being the application of icephobic coatings. In this work, commercially available polyurethane-based coatings were modified and deposited on NACA 0012 aircraft airfoils. A hybrid modification of polyurethane (PUR) topcoats was adopted by the addition of nanosilica and three-functional spherosilicates (a variety of silsesqioxane compound), which owe their unique properties to the presence of three different groups. The ice accretion on the manufactured nanocomposites was determined in an icing wind tunnel. The tests were performed under three different icing conditions: glaze ice, rime ice and mixed ice. Furthermore, the surface topography and wetting behavior (static contact angle and contact angle hysteresis) were investigated. It was found that the anti-icing properties of polyurethane nanocomposite coatings strongly depend on the icing conditions under which they are tested. Moreover, the addition of nanosilica and spherosilicates enabled the reduction of accreted ice by 65% in comparison to the neat topcoat.

Plasticized Poly(vinyl chloride) Modified with Developed Fire Retardant System Based on Nanoclay and L-histidinium Dihydrogen Phosphate-Phosphoric Acid.

The current work assessed the burning behavior of plasticized poly(vinyl chloride) (PVC-P) modified with a two-component composition, consisting of L-histidinium dihydrogen phosphate-phosphoric acid (LHP) and nanoclay (n). The thermal and thermodynamical properties of the PVC-P containing from 10 to 30 wt% of the fire retardant system (FRS) were determined by thermogravimetric analysis (TG) as well as by dynamic mechanical thermal analysis (DMTA). In contrast, fire behavior and smoke emission were studied with a cone calorimeter (CC) and smoke density chamber. The research was complemented by a microstructure analysis, using a scanning electron microscope, of the materials before and after burning CC tests. The effects were compared to those achieved for PVC-P, PVC-P with a commercially available fire retardant, the substrate used for the produced LHP, and the mixture of LHP and zinc borate, both of which contained the same share of nanoclay. Based on a notable improvement, especially in smoke suppression suggests that the n/LHP system may be a candidate fire retardant for decreasing the flammability of PVC-P.

Adhesive Joints with Laser Shaped Surface Microstructures.

One of the most commonly applied methods of joining dissimilar materials is gluing. This could be mainly attributed to the applicability of this technique in various industries. The article presents a method of material surface treatment, which increases the shear strength of adhesive joints for lightweight metals such as aluminum with plastics. For this purpose, laser surface microstructuring was performed on each of the selected construction materials. As a result of the performed treatment, the active surface of the glued area was increased, which increased the adhesive strength. The picosecond laser with UV radiation used in the research is TruMicro 5325c with which material can be removed as a result of the cold ablation phenomenon. The applied parameters of the laser device did not cause thermal damage to the surface of the microstructured materials, which was confirmed by microscopic examination. Laser micromachining did not deteriorate the degree of wetting of the tested materials, either, as was confirmed by the contact angle and surface energy measurements with the use of water as the measuring liquid. In investigated cases of microstructure types, the presented method significantly increased the shear strength of the joints formed, as demonstrated by the presented strength test results. Research has shown that created joints with microstructure made according to the described method, are characterized by a significant increase in strength, up to 376%, compared to materials without microstructure. The presented results are part of a series of tests aimed at selecting the operating laser parameters for the implementation of geometric shapes of microstructures which will increase the strength of adhesive joints in selected materials.

Relationship between Viscosity, Microstructure and Electrical Conductivity in Copolyamide Hot Melt Adhesives Containing Carbon Nanotubes.

The polymeric adhesive used for the bonding of thermoplastic and thermoset composites forms an insulating layer which causes a real problem for lightning strike protection. In order to make that interlayer electrically conductive, we studied a new group of electrically conductive adhesives based on hot melt copolyamides and multi-walled carbon nanotubes fabricated by the extrusion method. The purpose of this work was to test four types of hot melts to determine the effect of their viscosity on the dispersion of 7 wt % multi-walled carbon nanotubes and electrical conductivity. It was found that the dispersion of multi-walled carbon nanotubes, understood as the amount of the agglomerates in the copolyamide matrix, is not dependent on the level of the viscosity of the polymer. However, the electrical conductivity, analyzed by four-probe method and dielectric spectroscopy, increases when the number of carbon nanotube agglomerates decreases, with the highest value achieved being 0.67 S/m. The inclusion of 7 wt % multi-walled carbon nanotubes into each copolyamide improved their thermal stability and changed their melting points by only a few degrees. The addition of carbon nanotubes makes the adhesive's surface more hydrophilic or hydrophobic depending on the type of copolyamide used.