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 [...].

Cross-Linking Characteristics, Morphology, Dynamics, and Mechanical and Thermal Properties of Polychloroprene/Polybutadiene/Nano-Zinc (CR/BR/nZn) Compositions with Reduced Fire Hazard.

The properties of unconventional blends of crystallizable and thermo-cross-linkable polychloroprene (CR) with polybutadiene (BR) were investigated in this study. The compositions were prepared using the method of reactive processing and cross-linking in the presence of nano-sized zinc (nZn). The purpose of the research was to assess the efficacy of nano-zinc as a curing agent of polychloroprene and polybutadiene (CR/BR) composites and to obtain rubber goods characterized by increased flame resistance. The blends were filled with nano-silica (aerosil) and fillers of natural origin (chalcedonite or silitin). The cross-linking process was characterized by determining the kinetics curves, the equilibrium swelling, and the Mooney-Rivlin elasticity constants. The morphology of the vulcanizate surface was specified by scanning electron microscopy (SEM). The dynamic and mechanical properties, flammability, and toxicity of gaseous substances involved in thermal decomposition were determined. Mass changes and thermal effects were studied using simultaneous thermal analysis (STA). It was confirmed that nano-zinc is an efficient curing agent for the polychloroprene and polybutadiene compositions, with a satisfactory degree of cross-linking (αc = 0.10, CRI = 4.11 min-1), good mechanical strength (TSb = 5 MPa), satisfactory tear resistance (Ts = 2.9 N/mm), and very high flame resistance (OI = 30%, HRRmax = 283 kW/m2). Filled products could be used as non-combustible materials, confirming the low fire hazard (1/tflashover = 3.5-6.4 kW/m2∙s). The most effective filler of the tested composites was nano-sized silica.

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 Morphology, Mechanical and Dynamic Properties, Fire Hazard and Toxicity of Chloroprene and Butadiene Rubber Composites Cross-Linked with Zinc.

This paper presents the influence of zinc on the cross-linking process, mechanical and dynamic properties, morphologies and balance of thermal degradation of blends containing chloroprene rubber (CR) and butadiene rubber (BR). The novel aspect of this research is a comprehensive approach presenting a new curing agent for the CR/BR blends to increase their cross-linking density and final properties, including non-flammability and low fire hazard. This is due to the need to find an alternative to zinc oxide, which is the standard curing agent for chloroprene rubber. The regulations of the European Union enforce a significant limitation on the use of this compound in elastomer technology, due to its harmful effect on aquatic organisms. In this paper, the CR/BR composites were cured with zinc and filled with natural silica fillers (sillitin or chalcedonite) or synthetic silica filler (aerosil). The investigation focused on the morphology characterization of the obtained compounds, their cross-linking degree, swelling, mechanical and dynamic properties, fire hazard and toxicity. The structure of cured CR/BR blends was characterized via scanning electron microscopy (SEM). The fire resistance studies were performed using cone calorimetry or oxygen index methods, whereas toxicity tests were performed with the use of the FB-FTIR (fluidized bed reactor coupled with FTIR analyzer) method. The results showed that obtained CR/BR products were characterized by satisfactory final properties. The properties determined by the oxygen index and cone calorimetry methods, including the behaviors of the tested CR/BR vulcanizates in fire conditions, showed that the produced compounds were characterized by a low fire hazard and can be classified as non-combustible rubber products. However, the toxicity of the decomposition products, determined at 450, 550 and 750 °C, was very high.

The Use of Iron(II,III) Oxide (Fe3O4) as a Cross-Linking Agent for Unfilled and Filled Chlorosulfonated Polyethylene (CSM) and Study of the Vulcanizates Properties.

This paper discusses the cross-linking behaviors, mechanical and dynamical properties, and flammability of elastomeric composites containing unconventionally cured chlorosulfonated polyethylene (CSM). The purpose of this work was to verify the CSM ability to cross-link with iron(II,III) oxide (Fe3O4) and to produce flame retardant materials. During the first series of tests, three types of CSM were used, differing in the content of bound chlorine (29-43%). The results showed that the CSM with 43% bound chlorine (Hypalon 30, CSM43) was the most advantageous type of chlorosulfonated polyethylene in terms of its properties. It exhibited a short vulcanization time, a high degree of cross-linking, and very good mechanical properties. In the next stage, the CSM composites with various fillers (talc, arsil, kaolin, chalcedonite, or carbon black) were prepared, because filled rubber materials are of the greatest practical importance. The cross-linking kinetics, equilibrium swelling, mechanical and dynamic properties as well as flammability were studied. It was found that the addition of fillers led to a decrease in the degree of cross-linking, an increase in the vulcanization time (in the case of talc, arsil, or kaolin), an increase in the overall mechanical strength (in the case of carbon black, arsil or talc). All filled vulcanizates proved to be non-flammable, as the specific oxygen index value exceeded 37.5%.

Enhanced Hydrophobicity of Polymers for Protective Gloves Achieved by Geometric, Chemical and Plasma-Surface Modification.

Gloves are one of the most important elements of personal protective equipment (PPE). To improve gloves properties, a lot of different methods of surface modifications are used. In this work, the application of geometric, chemical, and plasma surface modifications to improve the hydrophobicity of butyl (IIR) and silicone (MVQ) rubber are described. To characterise surface properties contact angle measurements, FT-IR spectroscopy and scanning electron microscopy were used. This study showed that when the chemical modification applied, the contact angle value increases compared to non-modified samples. In addition, plasma modification raised the contact angle value and smoothed the surface morphology. An increase in the polymer surfaces hydrophobicity was the observed effect of the three modifications of rubber.

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.

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.

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.

Enhanced Hydrofobicity of Polymers for Personal Protective Equipment Achieved by Chemical and Physical Modification.

The article presents significant results in research on creating superhydrophobic properties of materials which can be used as an interesting material for use in self-cleaning polymer protective gloves and similar applications where the superhydrophobicity plays a significant role. In this work the influence of laser surface modification of MVQ silicone rubber was investigated. The research was conducted using a nanosecond-pulsed laser at 1060 nm wavelength. After a process of laser ablation, the surface condition was examined using a SEM microscope and infrared spectroscopy. During the tests, the contact angle was checked both before and after the laser modification of samples pre-geometrised in the process of their production. The test results presented in the paper indicate that the chemical and physical modifications contribute to the change in the MVQ silicone rubber contact angle. A significant increase (by more than 30°) in the contact angle to 138° was observed. It was confirmed that surface geometrisation is not the only factor contributing to an increase in the contact angle of the analyzed material; other factors include a change in laser texturing parameters, such as mean beam power, pulse duration, scanning speed and pulse repetition frequency.

Study on the Effect of Zinc on the Rheological, Mechanical and Thermal Properties and Fire Hazard of Unfilled and Filled CR/BR Vulcanizates.

This paper discusses the cross-linking and functional properties of elastomer composites containing chloroprene rubber (CR) and butadiene rubber (BR) cured in the presence of zinc (Zn) and reinforced with mineral fillers. The research aimed to evaluate the effectiveness of zinc as a new cross-linking substance with the simultaneous production of elastomer materials with good mechanical properties and a reduced fire hazard. The article concerns the study and explanation of the dependencies influencing the processing and functional properties of unfilled or filled elastomer blends containing different elastomers ratio or different zinc's amount. The following fillers were used: silica, kaolin, chalk and montmorillonite. The results revealed that the cross-linking degree of CR/BR blends decreased with the increasing amount of butadiene rubber in the blends. The mechanical properties of the cured blends depended on the proportion of elastomers in the composites, the zinc amount, and the presence and type of filler. The flammability of CR/BR/Zn vulcanizates has been investigated before and after the filling. The parameters assessed by the oxygen index method and cone calorimetry, characterizing the behavior of the tested CR/BR/Zn vulcanizates under fire conditions, have shown that they constitute a low fire hazard and can be considered as non-flammable materials.