Search

Additive manufacturing and 3D printing methods based on the extrusion of material have become very popular in recent years. There are many methods of printing ceramics, but the direct extrusion method gives the largest range of sizes of printed objects and enables scaling of processes also in large-scale applications. Additionally, the application of this method to ceramic materials is of particular importance due to its low cost, ease of use, and high material utilization. The paper presents the most important literature reports on ceramics printed by direct extrusion. The review includes articles written in English and published between 2017 and 2022. The aim of this literature review was to present the main groups of ceramic materials produced by extrusion-based 3D printing.

Al2O3-TiO2 systems with Ti:Al 0.1, 0.5 and 1.0 molar ratio obtained by the sol–gel method have been used as a platinum support. As a precursor of alumina gel, aluminum isopropoxide has been chosen. Titanium tert-butoxylate was applied to obtain titania gel and hexachloroplatinic acid was applied as a source of platinum. The systems have been characterized by the following methods: thermogravimetric analysis (TGA), Fourier transformation infrared spectroscopy (FTIR), X-ray powder diffraction (XRPD), low-temperature nitrogen adsorption–desorption isotherms (BET, BJH), temperature-programmed reduction with hydrogen (TPR-H2) and hydrogen chemisorption. Reactions of toluene to methylcyclohexane and selective o-chloronitrobenzene (o-CNB) to o-chloroaniline (o-CAN) hydrogenation were used as the tests of systems’ catalytic activity. The application of Al2O3-TiO2 as a support has enabled the obtaining of platinum catalysts showing high activities for hydrogenation of toluene and selective hydrogenation of o-chloronitrobenzene to o-chloroaniline in the liquid phase. The highest activity in both reactions has been found for Pt/Al2O3-0.5TiO2 catalyst and the highest selectivity for Pt/Al2O3-. The activity of Pt/Al2O3-TiO2 catalysts was higher than that of alumina-supported ones.

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

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.

Two series of binary xerogel systems of Sr/Al with molar ratios of 0.1, 0.25, 0.5, and 1.0 were synthesized by the sol-gel technique with metallic strontium component as a precursor. The influence of the metallic precursor on the properties of the final xerogel was determined. The properties of the gels were determined on the basis of X-ray powder diffraction (XRD), thermogravimetric analysis (TGA), low temperature nitrogen adsorption, transmission, and scanning electron microscopy with Energy Dispersive X-ray Spectroscopy (TEM, SEM, and SEM/EDS). The Al

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.

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.

In this study, the influence of TiO2 pigment filler modified with spherosilicate derivatives on the processes and thermomechanical properties of composites based on PLA was investigated. Rheological tests (MFR) were carried out, on the basis of which it was found that the addition of organosilicon compounds has a plasticizing effect on the polymer-filler systems. TGA and DSC analysis were performed. The analysis of the contact angle showed that 1.5% of the additives had an influence on the superhydrophobic properties of TiO2 (above 135°), and a slight improvement of this parameter was also observed for composites containing the modified pigment. Microscopic analysis and mechanical tests (tensile strength, impact strength and flexural strength tests) were carried out as well. It has been observed that the addition of certain derivatives adversely affects the dispersion of the filler, thus a slight improvement in mechanical properties is observed. For modifiers that do not affect filler agglomeration, a plasticizing effect on the composite is observed.

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.

Two series of binary xerogel systems of Sr/Al with molar ratios of 0.1, 0.25, 0.5, and 1.0 were synthesized by the sol–gel technique with metallic strontium component as a precursor. The influence of the metallic precursor on the properties of the final xerogel was determined. The properties of the gels were determined on the basis of X-ray powder diffraction (XRD), thermogravimetric analysis (TGA), low temperature nitrogen adsorption, transmission, and scanning electron microscopy with Energy Dispersive X-ray Spectroscopy (TEM, SEM, and SEM/EDS). The Al2O3/SrCO3 xerogels were tested as supports for platinum catalysts. Hydrogen chemisorption was used to determine the platinum dispersion of the Pt/Al2O3-SrCO3 systems. The original method of synthesis allows to obtain highly dispersed and stable strontium carbonate phases that allow for obtaining a high (42–50%) dispersion of platinum nanoparticles.

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 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.

The effect of the addition of octakis(tetramethylammonium)-t8-silsesquioxane (octaanion) on the modification of the porous structure of the silica gel obtained by the sol-gel method catalysed by acetic acid was studied. The obtained silica gel was characterised by the low-temperature nitrogen adsorption/desorption method (BET), powder diffraction (XRD), thermogravimetry (TG) and microscopic observations (TEM). The octaanion was found to act as a textural promoter, as evidenced by almost a 25% increase in the surface area of the obtained silica. As a result of the stabilisation in the porous structure of the silica gel, the tetramethylammonium groups of the octaanion show higher thermal stability than the groups present in the octaanion structure or those introduced in the form of tetramethylammonium hydroxide. Tetramethylammonium ions were proved to show increased thermal resistance, which is related to the porous properties of the SiO₂ matrix.

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.

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.

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.

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.

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.