The Influence of Environmental Factors on the Degradation of PLA/Diatomaceous Earth Composites.

In the present study, tests were carried out on composite samples on a polylactide matrix containing 25% by weight of mineral filler in the form of diatomaceous earth, base, and silanized with GPTMOS (3-glycidoxypropyltrimethoxysilane), OTES (n-octyltriethoxysilane), and MTMOS (methyltrimethoxysilane) silanes. The addition of two types of waxes, synthetic polyamide wax and natural beeswax, were used as a factor to increase the rheological properties of the composites. The obtained samples were characterized in terms of the effect of filler silanization on the degradation rate of the composites. The tests were conducted under different conditioning conditions, i.e., after exposure to strong UV radiation for 250 and 500 h, and under natural sunlight for 21 days. The conditioning carried out under natural conditions showed that the modified samples exhibit up to twice the degradation rate of pure polylactide. The addition of synthetic wax to the composites increases the tendency to agglomerate diatomaceous earth, while natural wax has a positive effect on filler dispersion. For composites modified with GPTMOS and OTES silanes, it was noted that the addition of natural wax inhibited the degree of surface degradation, compared to the addition of synthetic wax, while the addition of MTMOS silane caused the opposite effect and samples with natural wax degraded more strongly. It was shown that, despite the high degree of surface degradation, the process does not occur significantly deep into the composite and stops at a certain depth.

Nanocomposites Based on Thermoplastic Acrylic Resin with the Addition of Chemically Modified Multi-Walled Carbon Nanotubes.

The main goal of this work was an improvement in the mechanical and electrical properties of acrylic resin-based nanocomposites filled with chemically modified carbon nanotubes. For this purpose, the surface functionalization of multi-walled carbon nanotubes (MWCNTs) was carried out by means of aryl groups grafting via the diazotization reaction with selected aniline derivatives, and then nanocomposites based on ELIUM® resin were fabricated. FT-IR analysis confirmed the effectiveness of the carried-out chemical surface modification of MWCNTs as new bands on FT-IR spectra appeared in the measurements. TEM observations showed that carbon nanotube fragmentation did not occur during the modifications. According to the results from Raman spectroscopy, the least defective carbon nanotube structure was obtained for aniline modification. Transmission light microscopy analysis showed that the neat MWCNTs agglomerate strongly, while the proposed modifications improved their dispersion significantly. Viscosity tests confirmed, that as the nanofiller concentration increases, the viscosity of the mixture increases. The mixture with the highest dispersion of nanoparticles exhibited the most viscous behaviour. Finally, an enhancement in impact resistance and electrical conductivity was obtained for nanocomposites containing modified MWCNTs.

Organosilicon Compounds in Hot-Melt Adhesive Technologies.

Hot-melt adhesives (HMAs) are thermoplastic materials that can bond various substrates by solidifying rapidly upon cooling from the molten state, and their modification with organosilicon compounds can result in crosslinking behavior, characteristic of gels. Organosilicon compounds are hybrid molecules that have both inorganic and organic components and can enhance the properties and performance of HMAs. The gel aspect of HMA with and without organosilicon modifiers can be considered in organosilicon-modified systems, the modifiers are often either sol-gel condensation products or their mechanism of action on the adherent surface can be considered of sol-gel type. The purpose of this manuscript is to present the current state of the art on the formulation, characterization, and application of HMAs and optimize their performance with organosilicon compounds for application in various industries such as automotive, construction, and photovoltaics. This review covers articles published within the period of 2018-2022. The article is divided into sections, in which information about hot-melt adhesives is described at the beginning. The following part of the presented review focuses on the composition of hot-melt adhesives, which takes into account the use of organosilicon compounds. The last part of this review outlines the future trends in hot-melt adhesives.

Trimming flow, plasticity, and mechanical properties by cubic silsesquioxane chemistry.

In this work, the possibility of managing the rheological and mechanical parameters of composites based on PLA with the use of cubic structures of organofunctional spherosilicates was verified. To accurately observe the effect of various organosilicon modifier substitutions on changes in composites' properties, we synthesized and used monofunctional octasubstituted derivatives as reference systems. The OSS/PLA systems were tested with concentrations of 0.1-2.5% (w/w) using extrusion to obtain a filament with a diameter of 1.75 mm. The printed samples underwent comprehensive tests including microscopic (SEM-EDS, optical microscope), rheological, thermal (TG, DSC, HDT), mechanical (impact and strength) as well as water contact angle tests. The work is interdisciplinary in nature and combines elements of organosilicon synthesis, materials engineering, and materials processing and characterization technology.

Feldspar-Modified Methacrylic Composite for Fabrication of Prosthetic Teeth.

This study was aimed at investigating poly(methyl methacrylate) (PMMA), modified with a silanized feldspar filler at 10 wt.% and 30 wt.%, as a dental material system for the production of prosthetic teeth. Samples of this composite were subjected to a compressive strength test, three-layer methacrylic teeth were fabricated with the said materials, and their connection to a denture plate was examined. The biocompatibility of the materials was assessed via cytotoxicity tests on human gingival fibroblasts (HGFs) and Chinese hamster ovarian cells (CHO-K1). The addition of feldspar significantly improved the material's compressive strength, with neat PMMA reaching 107 MPa, and the addition of 30% feldspar raising it up to 159 MPa. As observed, composite teeth (cervical part made of neat PMMA, dentin with 10 wt.%, and enamel with 30 wt.% of feldspar) had good adhesion to the denture plate. Neither of the tested materials revealed any cytotoxic effects. In the case of hamster fibroblasts, increased cell viability was observed, with only morphological changes being noticed. Samples containing 10% or 30% of inorganic filler were determined to be safe for treated cells. The use of silanized feldspar to fabricate composite teeth increased their hardness, which is of significant clinical importance for the duration of use of non-retained dentures.

Polyamide 11 Composites Reinforced with Diatomite Biofiller-Mechanical, Rheological and Crystallization Properties.

Amorphic diatomaceous earth is derived from natural sources, and polyamide 11 (PA11) is produced from materials of natural origin. Both of these materials show a low harmfulness to the environment and a reduced carbon footprint. This is why the combination of these two constituents is beneficial not only to improve the physicochemical and mechanical properties of polyamide 11 but also to produce a biocomposite. For the purpose of this paper, the test biocomposite was produced by combining polyamide 11, as well as basic and pre-fractionated diatomaceous earth, which had been subjected to silanization. The produced composites were used to carry out rheological (melt flow rate-MFR), mechanical (tensile strength, bending strength, impact strength), crystallographic (X-ray Diffraction-XRD), thermal and thermo-mechanical (differential scanning calorimetry-DSC, dynamic mechanical thermal analysis-DMTA) analyses, as well as a study of hydrophobic-hydrophilic properties of the material surface (wetting angle) and imaging of the surface of the composites and the fractured specimens. The tests showed that the additive 3-aminopropyltriethoxysilane (APTES) acted as an agent that improved the elasticity of composites and the melt flow rate. In addition, the produced composites showed a hydrophilic surface profile compared to pure polylactide and polyamide 11.

Silane-Bearing Borasilsesquioxanes: Synthetic Protocol and Unsuspected Redistribution Reactions.

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.

Beeswax as a natural alternative to synthetic waxes for fabrication of PLA/diatomaceous earth composites.

In this study, injection moulding was applied to produce biocomposites consisting of polylactide (PLA) and amorphous diatomaceous earth used as a filler at different concentrations. Natural wax and synthetic wax were added to improve processing properties, comparing the resulting biocomposites. The use of natural beeswax makes the composite environmentally friendly. The prepared composites contained 2.5, 5, 10 and 15% w/w filler. The test samples have been injection moulded. Rheological, mechanical, surface and other properties were assessed for the fabricated composites. The testing has shown that the use of wax additives has a significant influence on the mechanical properties (tensile strength, flexural strength, impact strength) and the hydrophilicity/hydrophobicity of composite surfaces. The addition of natural wax, especially at lower concentration, has a positive effect on the rheological properties of composites (melt flow rate, MFR), flexural modulus and impact strength. Different composite parameters are modified by different wax types so both natural and synthetic waxes, can be used interchangeably, depending on the required final material characteristics.

Effect of Wax Additives and Silanization of Diatom Surfaces on Thermomechanical Properties of Polylactide Composites.

In the present study, tests were conducted on high-filled composite samples on a polylactide matrix, modified with diatomaceous earth, three types of silanes, and natural and synthetic wax. The obtained samples were characterized in terms of the effect of modifications on mechanical properties (tensile strength, flexural strength, and impact resistance) or processing properties, e.g., melt flow rate (MFR). The study showed that the modification had a favorable effect on the processing properties of the composites, associated with up to an eight-fold increase in flow rate index compared with the reference sample, especially for samples treated with methyltrimethoxysilane (MTMOS), and up to a ten-fold increase under low shear-rate flow conditions. The effect of the addition of waxes of different origins (synthetic and natural) was also determined, and it was shown that beeswax tended to reduce the flow rate of the composites regardless of the silane used. The addition of synthetic wax to composites increased the tendency to agglomerate diatomaceous earth, while natural wax had a positive effect on filler dispersion.

Aspects and Principles of Material Connections in Restorative Dentistry-A Comprehensive Review.

The combination of two dissimilar materials has always been a serious problem in dentistry. In order to meet this challenge, it is necessary to combine both chemical methods (treatment with silanes, (meth)acrylic functional monomers) and the development of the surface of the joined material in a physical way, e.g., by sandblasting with alumina, alumina with silica, acid etching, the use of lasers and other means. The purpose of this literature review is to present all methods of joining dental composites with other materials such as ceramics, metal, another composite material. This review covers articles published within the period 2012-2022 in journals indexed in the PubMed database, written in English and describing joining different dental materials to each other. All the critical steps of new joint preparation have been addressed, including proper cleaning of the joint surface, the application of appropriate primers capable of forming a chemical bond between ceramics, zirconium oxide or metals and alloys, and finally, the application of new composite materials.

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.

Sulfur-Containing Silsesquioxane Derivatives Obtained by the Thiol-ene Reaction: Synthesis and Thermal Degradation.

This article presents the synthesis of new derivatives of octa(3-thiopropyl)silsesquioxane (SSQ-8SH) via thiol-ene reaction with simple olefins bearing alkyl groups as well as methoxysilyl, substituted aryl or fluoroalkyl groups. All products were characterized by 1 H NMR, 13 C NMR, 29 Si NMR, FTIR, GPC, MALDI-TOF-MS, as well as thermal analysis (TGA) to confirm their structures, purity and thermal stability, and finally give some insight into their thermal degradation pathway. In some of the structures obtained, the T5% values take place at high temperatures and are close to 230 °C. The thiol-ene reaction allowed to obtain 7 new compounds with high yield (>92 %), no by-products and in a relatively short time (24 h). All products are characterized by high conversion >99 %. New derivatives can find potential use as modifiers of plastics to improve their certain properties for example hydrophobicity or thermo-oxidative stability.

Novel Multifunctional Spherosilicate-Based Coupling Agents for Improved Bond Strength and Quality in Restorative Dentistry.

The aim of this study was to investigate the restorative connections of composite materials after fracture, under controlled conditions of treating the materials with novel, spherosilicate-based (SS) primers bearing both methacryl (MA) and trimethoxysilyl (TMOS) groups. The chemistry of methacrylate group insertion and reactive groups hydrolysis has been studied with the aid of 1H NMR (Nuclear Magnetic Resonance) spectroscopy. The light-cured resin composites were repaired by activating the connection site with the obtained primers and, for comparison, a silane (methacryloxypropyltrimethoxysilane, MATMOS) as a conventional coupling agent bearing the same reactive groups. The resistance of such a joint was tested in a three-point bending test after 24 h and 28 days period of sample conditioning. The effect of bond application was also studied, showing that spherosilicate-based primers may be used more effectively than MATMOS for two-step (primer-composite) restorative process, while for silane, the three-step process with bond application is crucial for satisfactory joint quality. The joint failure mode was determined by microscopic analysis and it was found that SS-4MA-4TMOS and SS-2MA-6TMOS application resulted in mostly composite, and not joint, failure. After 28 days of conditioning, the flexural strength of the joint repaired with SS-4MA-4TMOS was at 94% of the neat, solid material under the same procedure. However, the strength of the neat composite was observed to decline during the conditioning process by ~30%. The joint behavior was explained on the basis of the gradual hydrolysis effect (the greatest decrease being observed for silane).

Influence of Diatomaceous Earth Particle Size on Mechanical Properties of PLA/Diatomaceous Earth Composites.

The fractionation of diatomaceous earth (DE) using sedimentation made it possible to obtain separate unbroken diatom fractions from broken or agglomerated bodies with a range of particle sizes. The produced filler was used to prepare polylactide (PLA)/diatomaceous earth biocomposite samples containing different particle sizes, which were subjected to mechanical testing (tensile strength, flexural strength, impact strength), colloidal testing (contact angle, color change test, SEM/EDS), and thermal testing (TGA, DSC, DMA). Modification of the PLA containing the smallest particle size with diatomaceous earth (Fraction 5) resulted in a higher impact strength compared to both the pure PLA and the PLA/DE composite that contained base diatomaceous earth. Furthermore, the melt flow rate was improved by more than 80 and 60% for the composite modified with fractionated diatomaceous earth (Fraction 4) compared to pure PLA and base diatomaceous earth, respectively. The elasticity of the composite was also improved from 3.3 GPa for pure polylactide to 4.4 GPa for the system containing the smallest diatomaceous earth particles (Fraction 5).

Silsesquioxanes in the Cosmetics Industry-Applications and Perspectives.

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.

Where ppm Quantities of Silsesquioxanes Make a Difference-Silanes and Cage Siloxanes as TiO2 Dispersants and Stabilizers for Pigmented Epoxy Resins.

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.

The Accelerated Aging Impact on Mechanical and Thermal Properties of Polypropylene Composites with Sedimentary Rock Opoka-Hybrid Natural Filler.

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.

Methodological Aspects of Obtaining and Characterizing Composites Based on Biogenic Diatomaceous Silica and Epoxy Resins.

Diatomaceous earth are sediments of unicellular algal skeletons with a well-defined hierarchical structure. Despite many tests conducted on systems using diatomaceous earth and epoxy resins, we can find many differences in the methods of acquisition and characteristics of the composite, which may considerably affect the results. In our study, we have conducted tests to verify the impact of the method of obtaining samples and the degassing of the composite on its mechanical properties and standard deviation. The samples were cast in glass moulds and silicone moulds and then subjected to testing for their mechanical and functional properties, imaging with the use of an optical microscope and a scanning electron microscope. The tests have shown that, for samples cast in glass moulds, there is no heterogeneity within the area of the tested sample, as in the case of samples cast in silicone moulds. Silicone moulds allow for quite effective self-degassing of the resin due to the large area-to-mass ratio, and the small remaining air vesicles have a limited effect on the mechanical properties of the samples. The filler used also played a significant role. For systems containing base and rinsed diatomite, it is clear that the degassing of mixtures increases the tensile strength. For treated diatomite, the elongation at break grew along with increasing filler concentration, while for base diatomite, the improvement was observed for flexural strength and impact strength. A non-modified epoxy resin shows a tensile strength at 19.91 MPa (silicone mould cast). At the same time, the degassed, glass mould-cast systems containing 12% of base and rinsed diatoms showed a tensile strength of 27.4 MPa and 44.7 MPa, respectively. We have also observed that the higher the filler concentration, the higher were the tensile strength values, which for the rinsed diatoms reached over 55.1 MPa and for the base diatoms were maximum of 43.8 MPa. The tests, therefore, constitute a set of guidelines and recommendations for testing with the use of fillers showing an extended inner structure.

Novel Silsesquioxane-Derived Boronate Esters-Synthesis and Thermal Properties.

The functionalization of mono- and octahydrospherosilicate with vinylboranes and allylboranes via hydrosilylation reaction in the presence of a Karstedt's platinum (0) catalyst is presented. This is the catalytic route to obtain a new class of silsesquioxanes containing boron atoms in their structure in high yields (>90%) and with satisfactory selectivity. The obtained compounds were fully characterized by spectroscopic (1H, 13C, 29Si NMR) and spectrometric methods (MALDI-TOF-MS), as well as thermal analysis (TGA). The obtained compounds were subjected to thermal tests, characterizing the processes of melting, thermal evaporation, sublimation and thermal decomposition.

Why POSS-Type Compounds Should Be Considered Nanomodifiers, Not Nanofillers-A Polypropylene Blends Case Study.

In this work, a series of silsesquioxanes (SSQ) and spherosilicates (SS), comprising a group of cage siloxane (CS) compounds, was tested as functional additives for preparation of isotactic polypropylene (iPP)-based nanocomposites and discussed in the aspect of their rationale of applicability as such additives. For this purpose, the compounds were prepared by condensation and olefin hydrosilylation reactions. The effect of these cage siloxane products on properties of obtained CS/iPP nanocomposites was analyzed by means of mechanical, microscopic (scanning electron microscopy-energy dispersive spectroscopy), thermal (differential scanning calorimetry, thermogravimetry), thermomechanical (Vicat softening point) analyses. The results were compared with the previous findings on CS/polyolefin composites. The role of CS compounds was discussed in terms of plastic processing additives.