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MoS2 is an additive used to improve the tribological properties of plastics. In this work, it was decided to verify the use of MoS2 as a modifier of the properties of PLA filaments used in the additive FDM/FFF technique. For this purpose, MoS2 was introduced into the PLA matrix at concentrations of 0.025–1.0% by weight. Through extrusion, a fibre with a diameter of 1.75 mm was obtained. 3D printed samples with three different filling patterns were subjected to comprehensive thermal (TG, DSC and HDT), mechanical (impact, bending and strength tests), tribological and physicochemical characteristics. The mechanical properties were determined for two different types of fillings, and samples with the third type of filling were used for tribological tests. Tensile strength has been significantly increased for all samples with longitudinal filling with improvement up to 49%. In terms of tribological properties, higher values of the addition (0.5%) caused a significant increase of up to 457% of the wear indicator. A significant improvement in processing properties in terms of rheology was obtained (416% compared to pure PLA with the addition of 1.0%), which translated into more efficient processing, increased interlayer adhesion and mechanical strength. As a result, the quality of printed objects has been improved. Microscopic analysis was also carried out, which confirmed the good dispersion of the modifier in the polymer matrix (SEM-EDS). Microscopic techniques (MO, SEM) allowed for the characterization of the effect of the additive on changes in the printing process (improvement of interlayer remelting) and to assess impact fractures. In the tribological area, the introduced modification did not bring spectacular effects.

Titanium dioxide is a commonly used ingredient in cosmetics acting as a thickening agent and inorganic UV filter. However, TiO2 is difficult to disperse, which causes problems in spreading the formulations. The solution to this problem is to modify the titanium dioxide surface to change its properties by creation of the new type of hybrid inorganic–organic UV filter. Therefore, this study aimed to functionalize titanium dioxide with organosilicon compounds and determine how this modification will affect the dispersibility of TiO2 in the colloidal system and the stability of emulsions. First, the functionalized octaspherosilicates were obtained and characterized. Next, the synthesized compounds were applied as modifiers for titanium dioxide and were analyzed by FT-IR, UV-Vis, and laser diffraction. Furthermore, the hydrophilic–hydrophobic character was assessed by measuring the contact angle. The new materials were introduced into emulsions and the formulations were analyzed in terms of particle size distribution and stability by multiple light scattering. It was found that the modification of titanium dioxide with spherosilicates significantly improved both the stability of emulsion and the dispersibility of novel materials in the colloidal system compared to nonmodified TiO2. The covalent binding of the modifier with the titanium dioxide had an impact on the stability of the emulsion.

The work presents a comprehensive profile of the physicochemical characteristics of opoka sedimentary rock in the context of its use as a hybrid filler for thermoplastics. Determining the functional parameters of the studied filler was the main aim of this research. Thermal treatment leads to changes in its morphology and phase composition. A wide range of physicochemical techniques was used, such as low-temperature nitrogen adsorption, FT-IR, TGA, XRD, optical, and electron microscopy. The susceptibility of the material to micronisation was also tested (ball milling). Due to its widespread occurrence, opoka can be an attractive alternative to fillers such as silica or chalk. In order to verify this statement, polypropylene composites thereof were prepared by melt blending and injection molding, and studied by mechanical testing and microscopic imaging.

The presented work is a continuation of research on the reactivity of unsaturated borasilsesquioxanes under the conditions of common organometallic transformations. The catalytic hydrosilylation reaction with silanes, siloxanes and silsesquioxanes in presence of platinum catalyst was explored. The majority of the products were obtained in high yields (90 %) and their structures were confirmed and characterized by spectroscopy and spectrometry, i. e. NMR and MALDI-TOF-MS. The most significant segment of the work is research on the spontaneous redistribution reaction of the alkoxy group from silane to borane moiety occurring in the obtained products, not being limited to the heterosilsesquioxane chemistry, however. The products were confirmed using GC-MS, ESI-MS methods and B3LYP exchange-correlation, in order to ascertain formation of the silicon-boron hybrid molecule.

In this study, the influence of TiO

A series of binary oxide systems with Ca/Si molar ratios of 0.05, 0.1, 0.25, 0.5 and 1.0 have been synthesized by the sol-gel technique from tetraethyl orthosilicate (TEOS) and metallic calcium powder. Upon calcination, a side effect of wollastonite formation as a result of the reaction between the components of the material has been observed in the two calcium-richest systems. The increase in calcium content produces an effect of porosity promotion. At high calcium contents, the homogeneity of the systems is limited by the ability of silica to disperse the calcium component. The properties of these systems are determined by the silica surface coverage with a large amount of the scattered CaCO3 fine microcrystallites (calcite), resulting from the phase segregation. The gels were characterized by X-ray powder diffraction, low temperature nitrogen adsorption, transmission and scanning electron microscopy (TEM, SEM and SEM/EDS), thermogravimetric analysis (TGA), and FT-IR spectra, to describe the parameters important from the point of view of their application as a support for metal-based catalysts.

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.

In this work, silsesquioxane and spherosilicate compounds were assessed as novel organosilicon coupling agents for surface modification of TiO2 in a green process, and compared with their conventional silane counterparts. The surface-treated TiO2 particles were then applied in preparation of epoxy (EP) composites and the aspects of pigment dispersion, suspension stability, hiding power, as well as the composite mechanical and thermal properties were discussed. The studied compounds loading was between 0.005–0.015% (50–150 ppm) in respect to the bulk composite mass and resulted in increase of suspension stability and hiding power by over an order of magnitude. It was found that these compounds may be an effective alternative for silane coupling agents, yet due to their low cost and simplicity of production and manipulation, silanes and siloxanes are still the most straight-forward options available. Nonetheless, the obtained findings might encourage tuning of silsesquioxane compounds structure and probably process itself if implementation of these novel organosilicon compounds as surface treatment agents is sought for special applications, e.g., high performance coating systems.

This paper presents the impact of accelerated aging on selected mechanical and thermal properties of isotactic polypropylene (iPP) composites filled with sedimentary hybrid natural filler-Opoka rock. The filler was used in two forms: an industrial raw material originating as a subsieve fraction natural material, and a rock calcinated at 1000 °C for production of phosphorous sorbents. Fillers were incorporated with constant amount of 5 wt % of the resulting composite, and the material was subjected to accelerated weathering tests with different exposition times. The neat polypropylene and composites with calcium carbonate as a reference filler material were used for comparison. The aim of the research was to determine the possibility of using the Opoka rock as a new hybrid filler for polypropylene, which could be an alternative to the widely used calcium carbonate and silica. The thermal, mechanical, and structural properties were evaluated by means of differential scanning calorimetry (DSC), tensile tests, scanning electron microscopy (SEM), and Fourier-transform infrared spectroscopy with attenuated total reflectance (FTIR/ATR) prior to and after accelerated aging. As a result, it was found that the composites of polypropylene with Opoka were characterized by similar or higher functional properties and higher resistance to photodegradation compared to composites with conventional calcium carbonate. The results of measurements of mechanical properties, structural and surface changes, and the carbonyl index as a function of accelerated aging proved that Opoka was an effective ultraviolet (UV) stabilizer, significantly exceeding the reference calcium carbonate in this respect. The new hybrid filler of natural origin in the form of Opoka can therefore be used not only as a typical powder filler, but above all as a UV blocker/stabilizer, thus extending the life of polypropylene composites, especially for outdoor applications.

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.

The study aimed to investigate the effect of processing temperature and the content of multi-wall carbon nanotubes (MWCNTs) on the rheological, thermal, and electrical properties of polyphenylene sulfide (PPS)/MWCNT nanocomposites. It was observed that the increase in MWCNT content influenced the increase of the complex viscosity, storage modulus, and loss modulus. The microscopic observations showed that with an increase in the amount of MWCNTs, the areal ratio of their agglomerates decreases. Thermogravimetric analysis showed no effect of processing temperature and MWCNT content on thermal stability, however, an increase in stability was observed as compared to neat PPS. The differential scanning calorimetry was used to assess the influence of MWCNT addition on the crystallization phenomenon of PPS. The calorimetry showed that with increasing MWCNT content, the degree of crystallinity and crystallization temperature rises. Thermal diffusivity tests proved that with an increase in the processing temperature and the content of MWCNTs, the diffusivity also increases and declines at higher testing temperatures. The resistivity measurements showed that the conductivity of the PPS/MWCNT nanocomposite increases with the increase in MWCNT content. The processing temperature did not affect resistivity.

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.

We have developed a new effective route for obtaining (E)-vinyl-substituted silatranes via ruthenium-catalyzed silylative coupling of 1-allylsilatrane with olefins. Experimental research allowed us also to propose the mechanism of the process based on stoichiometric reactions.

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&ndash, 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.

New composites containing a natural filler made of diatom shells (frustules), permitting the modification of polylactide matrix, were produced by Fused Deposition Modelling (3D printing) and were thoroughly examined. Two mesh fractions of the filler were used, one of &lt, 40 &micro, m and the other of 40&minus, 63 &micro, m, in order to check the effect of the filler particle size on the composite properties. The composites obtained contained diatom shells in the concentrations from 0% to 5% wt. (0&minus, 27.5% vol.) and were subjected to rheological analysis. The composites obtained as filaments of 1.75 mm in diameter were used for 3D printing. The printed samples were characterized as to hydrophilic&ndash, hydrophobic, thermal and mechanical properties. The functional parameters of the printed objects, e.g., mechanical characteristics, stability on contact with water and water contact angle, were measured. The results revealed differences in the processing behavior of the samples as well as the effect of secondary granulation of the filler on the parameters of the printing and mechanical properties of the composites.

With the development of 3D printing technology, there is a need to produce printable materials with improved properties, e.g., sliding properties. In this paper, the authors present the possibilities of producing composites based on biodegradable PLA with the addition of graphite. The team created composites with the following graphite weight contents: 1%, 2.5%, 5%, 7.5%, and 10%. Neat material was also subjected to testing. Tribological, mechanical, and chemical properties of the mentioned materials were examined. Measurements were also made after keeping the samples in ageing and climatic ovens. Furthermore, SEM observations of samples before and after friction tests were carried out. It was demonstrated that increasing graphite content caused a significant decrease in wear (PLA + 10% graphite had a wear rate three times lower than for a neat material). The addition of graphite did not adversely affect most of the other properties, but it ought to be noted that mechanical properties changed significantly. After conditioning in a climatic oven PLA + 10% graphite has (in comparison with neat material) 11% lower fracture stress, 47% lower impact strength, and 21% higher Young&rsquo, s modulus. It can be certainly stated that the addition of graphite to PLA is a step towards obtaining a material that is low-cost and suitable for printing sliding spare parts.

A series of binary Al2O3–CaO and Al2O3–CaO–CaCO3 systems with Ca/Al molar ratios of 0.05, 0.1, 0.25, 0.5 and 1.0 have been synthesised by the sol–gel technique from aluminium isopropoxide and metallic calcium powder. The rate of the metal reaction is used as a limiting factor to control the binary gel formation. The proposed modification of the traditional sol–gel method was used to examine the influence the effect of the metallic form of the second component as an oxide precursor on the form of the final product. By applying acetic acid instead of mineral acid, calcium acetate is formed and then decomposed to calcium carbonate upon thermal processing. During the synthesis of the binary systems, metallic calcium acts both as a precursor of calcium acetate and as a secondary pH modifier of the gel system. Calcination in air at 600 °C did not produce systems containing only oxides and the calcium carbonate phase was still present. Due to particle size reduction, the CaCO3 to CaO decomposition temperature was lowered. The systems were characterised by X-ray powder diffraction, low-temperature nitrogen adsorption, transmission and scanning electron microscopy (TEM, SEM and SEM/EDS), thermogravimetric analysis (TGA) and FTIR spectra.

The rising demand for innovative and sophisticated personal care products is a driving factor for manufacturers to obtain new formulations that will fulfill the customers’ preferences. In recent years, silsesquioxanes have attracted the attention of the cosmetics industry. These compounds have been proposed to be used in novel cosmetic formulations as emollient, dispersant, and viscosity modifiers. Therefore, this publication aims to review the main important aspects of polyhedral oligosilsesquioxanes as ingredients of personal care formulations, taking into consideration different types of products. The methods of obtaining these compounds were also presented. Additionally, the detailed analysis of patents dedicated to the application of silsesquioxanes in cosmetic formulations was also performed.

A series of mixed oxide‑carbonate Al2O3-La2O2CO3 systems with the La/Al molar ratios of 0.05, 0.1, 0.25, 0.5 and 1.0 have been synthesized by the sol–gel technique from aluminum isopropoxide and metallic lanthanum powder. During the synthesis of Al2O3- La2O2CO3 system, metallic lanthanum acts both as a precursor of lanthanum oxide and as secondary pH modifier of the gel solution. The traditional sol-gel method was modified to provide a better control over the final product surface parameters and structure. The obtained systems were amorphous and highly homogenic. The rate of the metal reaction was used as a limiting factor to control the gel formation. The obtained oxide systems are intended as a support for metallic phase catalysts. Calcination in air at 600°C did not produce systems containing only oxides and the lanthanum (dioxy)carbonate phase was still present. This observation can be explained by the multi stage decomposition process of lanthanum acetate forming during the gel synthesis. The systems were characterized by X-ray powder diffraction, low temperature nitrogen adsorption, transmission and scanning electron microscopy (TEM, SEM and SEM/EDS), thermogravimetric analysis (TGA), and FTIR spectra.

This paper presents a new preparation method of SiO2 and Al2O3via a sol–gel route with CO2 as a pH regulator. The influence of carbon dioxide as a pH moderator on the textural parameters is demonstrated. The properties of the oxide xerogels were investigated using SEM, TEM, FT-IR, thermal analysis techniques, and low temperature nitrogen adsorption measurements to describe their structural evolution. The results illustrate differences in the final textural properties of the systems obtained depending on the pH regulator used in the synthesis. The method proposed is doubly beneficial as it eliminates the use of (organic or inorganic) acids and represents an interesting and new application of carbon dioxide.

Praca wykonana w ramach prac statutowych IMN O/Poznan CLAiO finansowanych przez Ministra Nauki i Szkolnictwa Wyzszego oraz we wspolpracy z Centrum Zaawansowanych Technologii Uniwersytetu im. Adama Mickiewicza w Poznaniu.

Ice accumulation on wind turbine blades due to the impact of supercooled water droplets can be reduced by the application of surfaces with anti-icing properties. Hydrophobic surfaces are considered as a promising solution because of their water repellent behavior. In recent years, short-pulsed laser technologies have been developed as an efficient technique to modify the surface properties of materials. However, the anti-icing properties of such surfaces have not yet been validated. In this work, a hybrid modification of polyester resin-based gelcoats was adopted. Laser patterning (LP) was used to produce periodic surface structures on modified unsaturated polyester resin (UPR) substrates. One of the innovations of this research is the utilization of novel purpose-made chemical modifiers for gelcoats. The implementation of linear polymethylhydrosiloxane (PMHS) as a building block is a key improvement in terms of durability and functionality of the coating, since there is an option of introducing not only groups bonding in the polyester into one molecule, but also groups that increase hydrophobicity. The other novelty is a successfully conducted experiment combining such chemical modification with laser texturization of the surface. The influence of the laser energy, pattern shape, and spatial periods on the topographical characteristics and hydrophobicity as well as the anti-icing properties of the produced surfaces were investigated. To characterize the surface topography of the produced structures, scanning electron microscopy (SEM) and profilometer were utilized. Measurements of the wettability parameters (static contact angle and contact angle hysteresis) on the treated surfaces allowed the identification of the influence of wetting behavior and laser parameters on the investigated materials. Anti-icing properties were characterized by ice adhesion (IA) and freezing delay time (FDT) tests. It was found that hybrid modification of unsaturated polyester resin by chemical modifiers and laser treatment increased the hydrophobic and anti-icing properties of polyester gelcoats., This research was funded by National Centre for Research and Development (NCBiR), grant number LIDER/16/0068/L-9/17/NCBR/2018.

The paper presents a comparison of two methods of manufacturing utility objects made of plastics, applied to the emerging immediate need in the field of quick provision of personal protective equipment for medical services. The traditional processing method, which is injection molding (IM), and a modern rapid prototyping method, which is fused filament fabrication (FFF) 3D printing, were compared in terms of unit costs and production possibilities at various timeframes. The paper presents the effects of launching two production processes of protective helmets (face shields) using the example of real cases implemented ad hoc during the epidemic development. The implementation of the protective helmet production project based on polyamide-6 processing showed the real possibilities of quickly launching the rapid production of protective equipment with the aid of mold injection technology.

A new route for the synthesis of functionalized alkenylsilatranes has been developed based on ruthenium-catalyzed trans-silylation with olefins. This transformation allowed for the synthesis of new (E)-alkenylsilatranes in good yields and excellent selectivity. Experimental studies concerning the reaction mechanism were carried out and the intermediate ruthenium-silatranyl complex was isolated and characterized. Moreover, detailed DFT calculations regarding the mechanism of the silylative coupling catalytic cycle of silatranes catalyzed by [Ru]-H complexes were also performed.

In this work, polyethylene (PE) composites were prepared with a series of completely condensed silsesquioxanes (SSQ), as well as with open-cage hepta(isobutyl)trisilanol silsesquioxane. The effect of the additives on the thermal, mechanical, rheological, and crystalline properties of the composites obtained was determined. The dispersion of trisilanol derivative within polymer matrix was slightly better than that of the other isobutyl compounds, suggesting condensation of the additive to less polar products of different structure, which was confirmed by thermogravimetry (TG) and matrix-assisted laser desorption-ionization time-of-flight (MALDI-TOF) mass spectrometry analysis. The additives improved the thermal stability of polyethylene and formed composites of higher rigidity than the neat polyolefin. The results were compared to the literature data, with aminopropylhepta(isobutyl)silsesquioxane and vinylhepta(isobutyl)silsesquioxane being used partially as references, as PE composites thereof were reported earlier, but lacked some analytical results and required further investigation. It was proven that the practical upper loading limit for such silsesquioxane compounds as processing and functional additives for polyethylene should be fixed at around 1%.

Protocols for the synthesis of cage-substituted 1-vinylsilatranes have been developed and updated. The 1-vinylsilatranes with organic substituents attached to silatrane cage were functionalized in ruthenium-catalyzed trans-silylation with olefins, leading to novel styrylsilatranes in high yields.

A series of SiO2-La2O2CO3 and SiO2-La2O3 mixed oxide/carbonate systems with La/Si molar ratios of 0.05, 0.1, 0.25, 0.5 and 1.0 have been obtained by the sol–gel technique from tetraethyl orthosilicate (TEOS) and metallic lanthanum powder. For the low lanthanum loading systems (La/Si 0.05 to 0.25) the lanthanum carboxy phase is easily transformed to oxide phase during thermal treatment in the presence of silica. The most important advantage of the proposed method is the possibility of obtaining a mixed oxide/carbonate phase and not directly an oxide phase as in the case of other methods. Depending on the calcination temperature and time, the proposed method can be used for obtaining compositions containing dioxycarbonate, oxide or mixed lanthanum phase. The systems were characterized by X-ray diffraction, low temperature nitrogen adsorption, transmission and scanning electron microscopy (TEM, SEM and SEM/EDS), thermogravimetric analysis (TGA), and FT-IR spectra.