Effect of Modified and Unmodified Oak Bark (Quercus Cortex) on the Cross-Linking Process and Mechanical, Anti-Aging, and Hydrophobic Properties of Biocomposites Produced from Natural Rubber (NR).

The study explores the novel use of oak bark (Quercus cortex) as a bio-filler in elastomeric composites, aligning with the global trend of plant-based biocomposites. Both modified and unmodified oak bark were investigated for their impact on the physicochemical properties of natural rubber (NR) composites. The bio-filler modified with n-octadecyltrimethoxysilane exhibited enhanced dispersion and reduced aggregates in the elastomeric matrix. NR composites containing more than 20 phr of unmodified and modified oak bark demonstrated an increased degree of cross-linking (αc > 0.21). Mechanical properties were optimal at 10-15 phr of oak bark and the sample with modified bio-filler (10 phr) achieved the highest tensile strength (15.8 MPa). Silanization and the addition of the bio-filler increased the hardness of vulcanizates. The incorporation of oak bark improved aging resistance at least two-fold due to phenolic derivatives with antioxidant properties. Hydrophobicity decreased with added bark, but silanization reversed the trend, making samples with a high content of oak bark the most hydrophobic (contact angle: 129°). Overall, oak bark shows promise as an eco-friendly, anti-aging filler in elastomeric composites, with modification enhancing compatibility and hydrophobicity.

The New Elastomeric Compounds Made of Butyl Rubber Filled with Phyllosilicates, Characterized by Increased Barrier Properties and Hydrophobicity and Reduced Chemical Degradation.

The aim of the study was to produce new elastomeric materials containing butyl rubber (IIR) filled with silica and phyllosilicates (vermiculite, montmorillonite, perlite or halloysite tubes) with enhanced hydrophobicity and barrier properties and reduced chemical degradation. It was found that the filler type had a significant impact on the degree of cross-linking of butyl rubber and the properties of its vulcanizates. The highest degree of cross-linking and the highest mechanical strength were achieved for IIR composites filled with Arsil with perlite or halloysite tubes. The highest surface hydrophobicity (119°) was confirmed for the IIR vulcanizates with Arsil and montmorillonite. All tested samples showed high barrier properties because both the gas diffusion rate coefficient and the permeability coefficient reached low values. Both unfilled and filled IIR vulcanizates retained chemical resistance in contact with methanol for 480 min. Hour-long contact of a polar solvent (methanol) with each of the vulcanizates did not cause material degradation, while the presence of a non-polar solvent (n-heptane) worsened the mechanical parameters by up to 80%. However, the presence of fillers reduced the chemical degradation of vulcanizates (in the case of cured IIR filled with Arsil and halloysite tubes by 40% compared to the composite without fillers).

Correction: Smejda-Krzewicka et al. Interelastomer Reactions Occurring during the Cross-Linking of Hydrogenated Acrylonitrile-Butadiene (HNBR) and Chloroprene (CR) Rubbers Blends in the Presence of Silver(I) Oxide (Ag2O) and Mechanical Properties of Cured Products. Materials 2023, 16, 4573.

In the original publication [...].

Structure-activity relationship and cytotoxicity of the new thiosemicarbazide derivatives and their Cu(II) complexes against prostate and melanoma cancer cells.

In this study, eighteen new ligands (B1-B18) containing a thiosemicarbazide core were synthesized and characterized in terms of physicochemical properties, molecular docking and in vitro biological activity. The structures of eleven ligands were investigated using X-Ray diffraction and Hirschfeld Surface analysis. To study the structure-activity relationship, the organic ligands contained pyridin-2-ylmethyl, pyridin-3-ylmethyl or pyridin-4-ylmethyl moieties and various substituents. Their pharmakokinetic profiles and molecular docking results suggest high potential as new drug candidates. The complexing ability of the selected organic ligands was also evaluated, yielding five new Cu(II) complexes (Cu(B1)Cl2, Cu(B4)Cl2, Cu(B10)Cl2, Cu(B17)Cl2, Cu(B18)Cl2). The obtained results suggest the formation of the polymeric structures. All organic ligands and Cu(II) complexes were tested for anticancer activity against prostate and melanoma cancer cells (PC-3, DU-145, LNCaP, A375, G-361, SK-MEL-28) and normal fibroblasts (BJ), as well as antimicrobial activity against six selected bateria strains. Among B1-B18 compounds, B3, B5, B9, B10, B12 and B14 exhibited cytotoxic activity. The studied Cu(II) complexes were in general more active, with Cu(B1)Cl2 exhibiting antincancer activity agains all three prostate cancer cells and Cu(B10)Cl2 reaching the IC50 value equal to 88 µM against G-361 melanoma cells. Several compounds also exhibited antimicrobial activity against gram-positive and gram-negative bacteria. It was found that the type of specific substituents, especially the presence of -chloro and -dichloro substituents had a greated impact on the cytotoxicity than the position of the nitrogen atom in the pyridylacetyl moiety.

Effect of Liquid Glass-Modified Lignin Waste on the Flammability Properties of Biopolyurethane Foam Composites.

Water-blown biopolyurethane (bioPUR) foams are flammable and emit toxic gases during combustion. Herein, a novel approach suggested by the current study is to use different amounts of lignin waste (LigW), which increases the thermal stability and delays the flame spread and sodium silicate (LG), which has foaming ability at high temperatures and acts as a protective layer during a fire. However, there have been no studies carried out to investigate the synergy between these two materials. Therefore, two different ratios, namely 1/1 and 1/2 of LigW/LG, were used to prepare bioPUR foam composites. The obtained bioPUR foam composites with a 1/2 ratio of LigW/LG exhibited inhibition of flame propagation during the ignitability test by 7 s, increased thermal stability at higher temperatures by 40 °C, reduced total smoke production by 17%, reduced carbon monoxide release by 22%, and increased compressive strength by a maximum of 123% and 36% and tensile strength by a maximum of 49% and 30% at 100 °C and 200 °C, respectively, compared to bioPUR foam composites with unmodified LigW. Additionally, thanks to the sufficient compatibility between the polymeric matrix and LigW/LG particles, bioPUR foam composites were characterised by unchanged or even improved physical and mechanical properties, as well as increased glass transition temperature by 16% compared to bioPUR foam composites with unmodified LigW particles, making them suitable for application as a thermal insulating layer in building envelopes.

Interelastomer Reactions Occurring during the Cross-Linking of Hydrogenated Acrylonitrile-Butadiene (HNBR) and Chloroprene (CR) Rubbers Blends in the Presence of Silver(I) Oxide (Ag2O) and Mechanical Properties of Cured Products.

The purpose of this paper was to examine the possibility of producing new blends of hydrogenated acrylonitrile-butadiene and chloroprene rubbers (HNBR/CR) unconventionally cross-linked with silver(I) oxide (Ag2O), and to investigate the physicomechanical properties of the obtained materials. From the obtained results, it can be concluded that HNBR/CR composites were effectively cured with Ag2O, which led to interelastomer reactions, and the degree of binding of HNBR with CR was in the range of 14-59%. The rheometric and equilibrium swelling studies revealed that the cross-linking progress depended on the weight proportion of both elastomers, and the degree of cross-linking was greater with more content of chloroprene rubber in the tested blends. Interelastomer reactions occurring between HNBR and CR improved the homogeneity and miscibility of the tested compositions, which was confirmed by differential scanning calorimetry (DSC) and scanning electron microscopy (SEM) analyses. The tensile strength and hardness of the obtained HNBR/CR/Ag2O vulcanizates proportionally increased with the content of CR, while the tear strength showed an inverse relationship. The obtained new, unconventional materials were characterized by significant resistance to thermo-oxidative factors, which was confirmed by the high aging factor.

The Influence of Freeze-Dried Alcohol-Water Extracts from Common Yarrow (Achillea millefolium L.) and German Chamomile (Matricaria chamomilla L.) on the Properties of Elastomer Vulcanizates.

This research work aimed to investigate the properties of freeze-dried extracts from Matricaria chamomilla L. and Achillea millefolium L. and to perform a characterization of their impact on the natural rubber-based vulcanizates. First, extracts were prepared in three different solvents at selected volume ratios: water (100), water-methanol (50/50), and water-ethanol (50/50). Next, the freeze-drying of extracts was established and then obtained bio-additives were introduced to the rubber mixtures. Freeze-dried extracts were investigated by UV-VIS diffuse reflectance spectroscopy, Fourier Transform Infrared Spectroscopy (FTIR), Near-Infrared spectroscopy (NIR) and thermogravimetric analysis (TGA). Antioxidant activity and total phenolic content (TPC) were also defined. Rubber mixtures were examined in a rheometer and after vulcanization they were subjected to accelerated simulated aging by UV radiation and thermo-oxidative aging. To determine the resistance of vulcanizates to the degradation processes, the study of cross-linking density (equilibrium swelling method), mechanical properties (tensile strength, elongation at break) and color change were conducted. Performed studies proved the antioxidant activity of freeze-dried extracts caused by the high content of polyphenols and their beneficial influence on the properties of elastomer vulcanizates.

Antioxidant and Anti-Aging Activity of Freeze-Dried Alcohol-Water Extracts from Common Nettle (Urtica dioica L.) and Peppermint (Mentha piperita L.) in Elastomer Vulcanizates.

The research article aimed to examine the antioxidant nature of freeze-dried extracts from Urtica dioica L. and Mentha piperita L. and to present a deep characterization of their influence on the properties of natural rubber-based vulcanizates before and after simulated aging processes. Natural extracts were prepared in three solvent systems at selected volume ratios: water (100), methanol-water (50/50), ethanol-water (50/50), which were further lyophilized and used as additive to natural rubber mixtures. Freeze-dried materials were investigated by UV-VIS diffuse reflectance spectroscopy, Fourier Transform Infrared Spectroscopy (FTIR), thermal stability by thermogravimetric analysis (TGA). Antioxidant activity and total phenolic content (TPC) were also examined. Prepared samples were subjected to accelerated simulated degradation processes by using ultraviolet and thermo-oxidative aging. Vulcanizates resistance to degradation effects was determined by the study of cross-linking density (equilibrium swelling method), mechanical properties (tensile strength, elongation at break) and color change in comparison with the results of the reference samples. The research showed that analyzed extracts are characterized by a high content of polyphenols and antioxidant activity, thus have a protective influence on elastomer vulcanizates against damaging effects of aging processes, which consequently extends the lifetime of materials.

Cross-Link Density, Mechanical and Thermal Properties of Chloroprene Rubber Cross-Linked with Silver(I) Oxide.

The purpose of this work was to cross-link chloroprene rubber (CR) with silver(I) oxide (Ag2O) and to investigate the properties of the obtained vulcanizates. Silver(I) oxide was chosen as an alternative to zinc oxide (ZnO), which is part of the standard CR cross-linking system. The obtained results show that it is possible to cross-link chloroprene rubber with silver(I) oxide. This is evidenced by the determined vulcametric parameters, equilibrium swelling and elasticity constants. As the Ag2O content in the composition increases, the cross-link density of the vulcanizates also increases. However, the use of 1 phr of Ag2O is insufficient to obtain a suitably extensive network. Exclusively, the incorporation of 2 phr of Ag2O results in obtaining vulcanizates with great cross-link density. The obtained compositions are characterized by good mechanical properties, as evidenced by high tensile strength. The performed thermal analyses-differential scanning calorimetry (DSC) and thermogravimetry (TGA) allowed us to determine the course of composition cross-linking, but also to determine changes in their properties during heating. The results of the thermal analysis confirmed that CR can be cross-linked with Ag2O, and the increasing amount of oxide in the composition increases the degree of cross-linking of vulcanizates. However, the amount of Ag2O in the composition does not affect the processes occurring in the heated vulcanizate.

The Use of Copper Oxides as Cross-Linking Substances for Chloroprene Rubber and Study of the Vulcanizates Properties. Part II. The Effect of Filler Type on the Properties of CR Products.

The properties of rubber materials are dependent on the characteristics of the elastomer matrix, the filler type, the cross-linking agent, the number of ingredients, and their interactions. In the previous article, we showed that chloroprene rubber can be efficiently cross-linked with copper(I) oxide or copper(II) oxide. During the processing of rubber compounds, the incorporation of a filler and a curing substance are two substantial parameters, such as the homogeneity of mixing and cross-linking that significantly affect the properties of the vulcanizates. Therefore, this work aimed to evaluate the curing characteristics, mechanical and dynamical properties, morphology, and flammability of the composites containing chloroprene rubber cross-linked with Cu2O or CuO and filled with different fillers (silica, carbon black, montmorillonite, kaolin, chalk). It was found that the type of filler and curing agent had a significant impact on the degree of cross-linking of the chloroprene rubber and the properties of its vulcanizates. The degree and speed of the cross-linking of filled CR were higher when the CR was cured with copper(II) oxide. Among the fillers used, the presence of carbon black or silica ensured the highest degree of CR cross-linking and the most useful properties. The flammability tests indicated that all produced vulcanizates were characterized by a high oxygen index, which allows them to be classified as non-flammable materials.

Vermiculite Filler Modified with Casein, Chitosan, and Potato Protein as a Flame Retardant for Polyurethane Foams.

In this study, polyurethane (PU) composite foams were modified with 2 wt.% of vermiculite fillers, which were themselves modified with casein, chitosan, and potato protein. The impact of the fillers on selected properties of the obtained composites, including their rheological (foaming behavior, dynamic viscosity), thermal (temperature of thermal decomposition stages), flame-retardant (e.g., limiting oxygen index, ignition time, heat peak release), and mechanical properties (toughness, compressive strength (parallel and perpendicular), flexural strength) were investigated. Among all the modified polyurethane composites, the greatest improvement was noticed in the PU foams filled with vermiculite modified with casein and chitosan. For example, after the addition of modified vermiculite fillers, the foams' compressive strength was enhanced by ~6-18%, their flexural strength by ~2-10%, and their toughness by ~1-5%. Most importantly, the polyurethane composites filled with vermiculite filler and modified vermiculite fillers exhibited improved flame resistance characteristics (the value of total smoke release was reduced by ~34%, the value of peak heat release was reduced by ~25%).

The Use of Copper Oxides as Cross-Linking Substances for Chloroprene Rubber and Study of the Vulcanizates Properties. Part I.

The purpose of this work was to verify the ability to cross-link the chloroprene rubber (CR) by using copper oxides: copper(I) oxide or copper(II) oxide. The use of copper oxides arises from the need to limit the application of ZnO as a cross-linking agent of CR. The obtained results indicate that CR compositions cross-linked with copper oxides are characterized by good mechanical properties and a high cross-linking degree. The results show that the type and the amount of copper oxides influence the cross-linking of the CR and the properties of the vulcanizates. For compositions containing copper(II) oxide, the properties are linearly dependent on the amount of CuO. Such a relationship is difficult to notice in the case of the use of copper(I) oxide-when analyzing individual parameters, the best results are obtained for different samples. Infrared spectroscopy (IR) studies confirmed the possibility of cross-linking of chloroprene rubber with copper oxides. This is evidenced by the characteristic changes in the intensity of the bands. Structural changes in the material during heating were determined by the thermal analysis-differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). Regardless of the type and amount of copper oxide, all compositions exhibit similar characteristics, and there are no significant changes in the glass transition temperature of the material.

Bio-Based Rigid Polyurethane Foam Composites Reinforced with Bleached Curauá Fiber.

This study aims to evaluate the influence of using a bleached Curauá fiber (CF) as filler in a novel rigid polyurethane foam (RPUF) composite. The influence of 0.1, 0.5 and 1 wt.% of the reinforcements on the processing characteristics, cellular structure, mechanical, dynamic-mechanical, thermal, and flame behaviors were assessed and discussed for RPUF freely expanded. The results showed that the use of 0.5 wt.% of CF resulted in RPUF with smoother cell structure with low differences on the processing times and viscosity for the filled pre-polyol. These morphological features were responsible for the gains in mechanical properties, in both parallel and perpendicular rise directions, and better viscoelastic characteristics. Despite the gains, higher thermal conductivity and lower flammability were reported for the developed RPUF composites, related to the high content of cellulose and hemicellulose on the bleached CF chemical composition. This work shows the possibility of using a Brazilian vegetable fiber, with low exploration for the manufacturing of composite materials with improved properties. The developed RPUF presents high applicability as enhanced cores for the manufacturing of structural sandwich panels, mainly used in civil, aircraft, and marine industries.

Potential Application of Peppermint (Mentha piperita L.), German Chamomile (Matricaria chamomilla L.) and Yarrow (Achillea millefolium L.) as Active Fillers in Natural Rubber Biocomposites.

In this study, peppermint (Mentha piperita L.), German chamomile (Matricaria chamomilla L.) and yarrow (Achillea millefolium L.) were applied as natural fibrous fillers to create biocomposites containing substances of plant origin. The purpose of the work was to investigate the activity and effectiveness of selected plants as a material for the modification of natural rubber composites. This research was the first approach to examine the usefulness of peppermint, German chamomile and yarrow in the field of polymer technology. Dried and ground plant particles were subjected to Fourier transmission infrared spectroscopy (FTIR) and UV-Vis spectroscopy, thermogravimetric analysis (TGA), goniometric measurements (contact angle) and scanning electron microscopy (SEM). The characterization of natural rubber composites filled with bio-additives was performed including rheometric measurements, FTIR, TGA, cross-linking density, mechanical properties and colour change after simulated aging processes. Composites filled with natural fillers showed improved barrier properties and mechanical strength. Moreover, an increase in the cross-linking density of the materials before and after the simulated aging processes, compared to the reference sample, was observed.

Chlorine-Functional Silsesquioxanes (POSS-Cl) as Effective Flame Retardants and Reinforcing Additives for Rigid Polyurethane Foams.

The subject of the research was the production of silsesquioxane modified rigid polyurethane (PUR) foams (POSS-Cl) with chlorine functional groups (chlorobenzyl, chloropropyl, chlorobenzylethyl) characterized by reduced flammability. The foams were prepared in a one-step additive polymerization reaction of isocyanates with polyols, and the POSS modifier was added to the reaction system in an amount of 2 wt.% polyol. The influence of POSS was analyzed by performing a series of tests, such as determination of the kinetics of foam growth, determination of apparent density, and structure analysis. Compressive strength, three-point bending strength, hardness, and shape stability at reduced and elevated temperatures were tested, and the hydrophobicity of the surface was determined. The most important measurement was the determination of the thermal stability (TGA) and the flammability of the modified systems using a cone calorimeter. The obtained results, after comparing with the results for unmodified foam, showed a large influence of POSS modifiers on the functional properties, especially thermal and fire-retardant, of the obtained PUR-POSS-Cl systems.

Biobased Polyurethane Composite Foams Reinforced with Plum Stones and Silanized Plum Stones.

In the following study, ground plum stones and silanized ground plum stones were used as natural fillers for novel polyurethane (PUR) composite foams. The impact of 1, 2, and 5 wt.% of fillers on the cellular structure, foaming parameters, and mechanical, thermomechanical, and thermal properties of produced foams were assessed. The results showed that the silanization process leads to acquiring fillers with a smoother surface compared to unmodified filler. The results also showed that the morphology of the obtained materials is affected by the type and content of filler. Moreover, the modified PUR foams showed improved properties. For example, compared with the reference foam (PUR_REF), the foam with the addition of 1 wt.% of unmodified plum filler showed better mechanical properties, such as higher compressive strength (~8% improvement) and better flexural strength (~6% improvement). The addition of silanized plum filler improved the thermal stability and hydrophobic character of PUR foams. This work shows the relationship between the mechanical, thermal, and application properties of the obtained PUR composites depending on the modification of the filler used during synthesis.

Modified Nanoclays/Straw Fillers as Functional Additives of Natural Rubber Biocomposites.

Increasingly, raw materials of natural origin are used as fillers in polymer composites. Such biocomposites have satisfactory properties. To ensure above-average functional properties, modifications of biofillers with other materials are also used. The presented research work aimed to produce and characterize elastomeric materials with a straw-based filler and four different types of montmorillonite. The main research goal was to obtain improved functional parameters of vulcanizates based on natural rubber. A series of composites filled with straw and certain types of modified and unmodified nano-clays in various ratios and amounts were prepared. Then, they were subjected to a series of tests to assess the impact of the hybrids used on the final product. It has been shown that the addition of optimal amounts of biofillers can, inter alia, increase the tensile strength of the composite, improve damping properties, extend the burning time of the material and affect the course of vulcanization or cross-linking density.

Curing Behaviors, Mechanical and Dynamic Properties of Composites Containing Chloroprene and Butadiene Rubbers Crosslinked with Nano-Iron(III) Oxide.

This paper discusses the curing behaviors, mechanical and dynamical properties of composites containing chloroprene rubber (CR) and butadiene rubber (BR) reinforced with mineral fillers. The iron(III) oxide nanoparticles were used as a crosslinking agent of the CR/BR blends. The research aimed to evaluate the effectiveness of nano-iron(III) oxide (nano-Fe2O3) as a new crosslinking agent while producing elastomeric materials with good mechanical properties and reduced flammability. The CR/BR (chloroprene rubber/butadiene rubber) blends were filled with silicas from natural resources (chalcedony, Neuburg silica earth) or silicas used in elastomer technology in many fields (aerosil, ultrasil). The results revealed that all composites were characterized by satisfactory tensile strength, tear resistance, and high resistance to fire. The filler dispersion in the elastomer matrix was carried out by using scanning electron microscopy (SEM), while the possibility of the filler-filler or filler-rubber interaction in the designed compositions was determined using the Payne effect and the Mullins effect.

Common Nettle (Urtica dioica L.) as an Active Filler of Natural Rubber Biocomposites.

Common nettle (Urtíca Dióica L.), as a natural fibrous filler, may be part of the global trend of producing biocomposites with the addition of substances of plant origin. The aim of the work was to investigate and explain the effectiveness of common nettle as a source of active functional compounds for the modification of elastomer composites based on natural rubber. The conducted studies constitute a scientific novelty in the field of polymer technology, as there is no research on the physico-chemical characteristics of nettle bio-components and vulcanizates filled with them. Separation and mechanical modification of seeds, leaves, branches and roots of dried nettle were carried out. Characterization of the ground plant particles was performed using goniometric measurements (contact angle), Fourier transmission infrared spectroscopy (FTIR), themogravimetric analysis (TGA) and scanning electron microscopy (SEM). The obtained natural rubber composites with different bio-filler content were also tested in terms of rheological, static and dynamic mechanical properties, cross-linking density, color change and resistance to simulated aging processes. Composites with the addition of a filler obtained from nettle roots and stems showed the highest mechanical strength. For the sample containing leaves and branches, an increase in resistance to simulated ultraviolet and thermo-oxidative aging processes was observed. This phenomenon can be attributed to the activity of ingredients with high antioxidant potential contained in the plant.

Effects of Physical and Chemical Modification of Sunflower Cake on Polyurethane Composite Foam Properties.

Sunflower cake (SC), which is waste during the production of sunflower oil, was selected as a modifier of properties in polyurethane (PUR) foams. The SC was chemically modified with triphenylsilanol (SC_S) and physically modified with rapeseed oil (SC_O). The influence of SC on the rheological properties of the polyol and the kinetics of foam growth were investigated. PUR foams were characterized by morphological, mechanical, and thermal analysis. The results show that the physical and chemical modification of SC contributes to the changes in the properties of the foams in different ways. Too high hydrophobicity of SC_O affects the structure deterioration, and thus the mechanical properties, and in turn, reduces the affinity for water. In turn, chemical modification with silane allows for obtaining foams with the best mechanical properties.