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 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.     

Liquid Guayule Natural Rubber,a Sustainable Processing Aid,Enhances the Processability,Durability and Dynamic Mechanical Properties of Rubber Composites

Petroleum-based oils are widely used as processing aids in rubber composites to improve processability but can adversely affect rubber composite performance and increase carbon footprint. In this research, liquid guayule natural rubber (LGNR), produced from guayule natural rubber, was used as a renewable processing aid to replace naphthenic oil (NO) in Hevea natural rubber, styrene-butadiene rubber (SBR) and guayule natural rubber (GNR) composites. The rheological properties, thermal stability, glass transition temperature, dynamic mechanical properties, aging, and ozone resistance of rubber composites with and without NO or LGNR were compared. Natural and synthetic rubber composites made with LGNR had similar processability to those made with NO, but had improved thermal stability, mechanical properties after aging, and ozone resistance. This was due to the strong LGNR–filler interaction and additional crosslinks formed between LGNR and the rubber matrices. The glass transition temperature of SBR composites was reduced by LGNR because of its increased molecular mobility. Thus, unlike NO, LGNR processing aid can simultaneously improve rubber composite durability, dynamic performance and renewability. The commercialization of LGNR has the potential to open a new sustainable processing-aid market.     

Casein/Apricot Filler in the Production of Flame-Retardant Polyurethane Composites

Polyurethane (PUR) composites reinforced with 1, 2, and 5 wt.% of apricot filler modified with casein were synthesized in the following study. The impact of 1, 2, and 5 wt.% of casein/apricot filler on the cellular structure and physico-mechanical performances of reinforced PUR composites were determined. It was found that the incorporation of 1 and 2 wt.% of casein/apricot filler resulted in the production of PUR composites with improved selected physical, thermal, and mechanical properties, while the addition of 5 wt.% of casein/apricot filler led to some deterioration of their physico-mechanical performance. The best results were obtained for PUR composites reinforced with 2 wt.% of casein/apricot filler. Those composites were characterized by a uniform structure and a high content of closed cells. Compared with the reference foam, the incorporation of 2 wt.% of casein/apricot filler resulted in improvement in compressive strength, flexural strength, impact strength, and dynamic mechanical properties—such as glass transition temperature and storage modulus. Most importantly, PUR composites showed better fire resistance and thermal stability due to the good thermal performance of casein. The main aim of this article is to determine the influence of the natural combination of the apricot filler and casein on the mechanical properties and flammability of the obtained composites.     

Synergistical Performance Modification of Epoxy Resin by Nanofillers and Carboxyl-Terminated Liquid Nitrile–Butadiene Rubber

Epoxy composite materials are widely used in power equipment. As the voltage level increases, the requirement of material properties, including electrical, thermal, and mechanical, has also increased. Introducing thermally conductive nanofiller to the epoxy/liquid rubber composites system is an effective approach to improve heat performance, but the effects of thermally conductive nanofillers on relaxation characteristics remain unclarified. In this paper, nano-alumina (nano-Al₂O₃) and nano-boron nitride (nano-BN) have been employed to modify the epoxy/carboxyl-terminated liquid nitrile–butadiene rubber (epoxy/CTBN) composites system. The thermal conductivity and glass transition temperature of different formula systems have been measured. The effect of the nanofillers on the relaxation behaviors of the resin matrix has been investigated. Results show that the different kinds of nanofillers will introduce different relaxation processes into the matrix and increase the conductivity at the same time. This study can provide a theoretical basis for the synergistic improvement of multiple properties of epoxy resin composites.     

Effectiveness of Se/ZnO NPs in Enhancing the Antibacterial Activity of Resin-Based Dental Composites

Biofilm formation in the resin-composite interface is a major challenge for resin-based dental composites. Using doped z nanoparticles (NPs) to enhance the antibacterial properties of resin composites can be an effective approach to prevent this. The present study focused on the effectiveness of Selenium-doped ZnO (Se/ZnO) NPs as an antibacterial nanofiller in resin composites and their impact on their mechanical properties. Pristine and Se/ZnO NPs were synthesized by the mechanochemical method and confirmed through UV-Vis Spectroscopy, FTIR (Fourier Transform Infrared) analysis, X-ray Diffraction (XRD) crystallography, Scanning Electron Microscopy (SEM), Energy Dispersive Spectroscopy (EDS), and Zeta analysis. The resin composites were then modified by varying concentrations of pristine and Se/ZnO NPs. A single species (S. mutans and E. faecalis) and a saliva microcosm model were utilized for antibacterial analysis. Hemolytic assay and compressive strength tests were also performed to test the modified composite resin’s cytotoxicity and mechanical strength. When incorporated into composite resin, 1% Se/ZnO NPs showed higher antibacterial activity, biocompatibility, and higher mechanical strength when compared to composites with 1% ZnO NPs. The Se/ZnO NPs has been explored for the first time as an efficient antibacterial nanofiller for resin composites and showed effectiveness at lower concentrations, and hence can be an effective candidate in preventing secondary caries by limiting biofilm formation.     

Fabrication of Millable Polyurethane Elastomer/Eucommia Ulmoides Rubber Composites with Superior Sound Absorption Performance

Sound absorbing materials combining millable polyurethane elastomer (MPU) and eucommia ulmoides rubber (EUG) were successfully fabricated via a physical blending process of EUG and MPU. The microstructure, crystallization performances, damping, mechanical and sound absorption properties of the prepared MPU/EUG composites were investigated systematically. The microstructure surface of various MPU/EUG composites became rough and cracked by the gradual incorporation of EUG, resulting in a deteriorated compatibility between EUG and MPU. With the increase of EUG content, the storage modulus (E’) of various MPU/EUG composites increased in a temperature range of −50 °C to 40 °C and their loss factor (tanδ) decreased significantly, including a reduction of the tanδ of MPU/EUG (70/30) composites from 0.79 to 0.64. Specifically, the addition of EUG sharply improved the sound absorption performances of various MPU/EUG composites in a frequency range of 4.5 kHz–8 kHz. Compared with that of pure MPU, the sound absorption coefficient of the MPU/EUG (70/30) composite increased 52.2% at a pressure of 0.1 MPa and 16.8% at a pressure of 4 MPa, indicating its outstanding sound absorption properties.     

The Influence of Sub-Zero Conditions on the Mechanical Properties of Polylactide-Based Composites

Polylactide-based composites filled with waste fillers due to their sustainability are a subject of many current papers, in which their structural, mechanical, and thermal properties are evaluated. However, few studies focus on their behavior in low temperatures. In this paper, dynamic and quasi-static mechanical properties of polylactide-based composites filled with 10 wt% of linseed cake (a by-product of mechanical oil extraction from linseed) were evaluated at room temperature and at −40 °C by means of dynamic mechanical analysis (DMA), Charpy’s impact strength test and uniaxial tensile test. It was found that the effect of plasticization provided by the oil contained in the filler at room temperature is significantly reduced in sub-zero conditions due to solidification of the oil around −18 °C, as it was shown by differential scanning calorimetry (DSC) and DMA, but the overall mechanical performance of the polylactide-based composites was sufficient to enable their use in low-temperature applications.     

Study of the Effect of Modified Aluminum Oxide Nanofibers on the Properties of PLA-Based Films

To find out whether Al₂O₃ nanofiller is effective in improving the characteristics of polymer composites, composite polymer films based on biodegradable polylactide and epoxidized aluminum oxide nanofibers were obtained by solution casting. Surface morphology, mechanical and thermal properties of composites were studied by SEM, IR-Fourier spectroscopy, DSC and DMA. It was shown that, below and above the percolation threshold, the properties of the films differ significantly. The inclusion of alumina nanoparticles up to 0.2% leads to a plasticizing effect, a decrease in the crystallization temperature and the melting enthalpy and an increase in the tensile stress. An increase in the content of alumina nanoparticles in films above the percolation threshold (0.5%) leads to a decrease in the crystallinity of the films, an increase in stiffness and a drop in elasticity. Finding the percolation threshold of alumina nanoparticles in PLA films makes it possible to control their properties and create materials for various applications. The results of this study may have major significance for the commercial use of aluminum oxide nanofibers and can broaden the research field of composites.     

Sustainable Epoxidized Guayule Natural Rubber,Blends and Composites with Improved Oil Resistance and Greater Stiffness

Production of petroleum-based synthetic rubbers (SRs) causes an enormous carbon footprint for the rubber industry. Carbon footprint would be reduced if natural rubber (NR) could take a larger market share and replace significant quantities of SR. However, some SRs have higher oil resistance than NRs, and, in applications where these properties are needed, chemically modified NR will be required. Epoxidation is a chemical modification of NR which partially converts unsaturated bonds on the backbone of NR to epoxy groups. In this research, epoxidized guayule natural rubber (EGNR)/guayule natural rubber (GNR) blends and GNR were used to make carbon black (CB) filled composites. The processability, mechanical properties, swelling behaviors and dynamic mechanical properties were characterized at various epoxide fractions. Composites made with EGNR/GNR had higher oil resistance, wet traction and stiffness than GNR composites, although tensile strength and elongation at break were reduced by epoxidation. EGNR is expected to lead to the development of new NR products with similar properties to SR, eroding SR markets and increasing the sustainability of the rubber industry.     

Effect of 3-Mercaptopropyltriethoxysilane Modified Illite on the Reinforcement of SBR

To achieve the sustainable development of the rubber industry, the substitute of carbon black, the most widely used but non-renewable filler produced from petroleum, has been considered one of the most effective ways. The naturally occurring illite with higher aspect ratio can be easily obtained in large amounts at lower cost and with lower energy consumption. Therefore, the expansion of its application in advanced materials is of great significance. To explore their potential use as an additive for reinforcing rubber, styrene butadiene rubber (SBR) composites with illites of different size with and without 3-mercaptopropyltriethoxysilane (KH580) modification were studied. It was found that the modification of illite by KH580 increases the K-illite/SBR interaction, and thus improves the dispersion of K-illite in the SBR matrix. The better dispersion of smaller size K-illite with stronger interfacial interaction improves the mechanical properties of SBR remarkably, by an increment of about nine times the tensile strength and more than ten times the modulus. These results demonstrate, except for the evident effect of particle size, the great importance of filler–rubber interaction on the performance of SBR composites. This may be of great significance for the potential wide use of the abundant naturally occurring illite as substitute filler for the rubber industry.     

Influence of Silica-Aerogel on Mechanical Characteristics of Polyurethane-Based Composites: Thermal Conductivity and Strength

Polyurethane foam (PUF) has generally been used in liquefied natural gas (LNG) carrier cargo containment systems (CCSs) owing to its excellent mechanical and thermal properties over a wide range of temperatures. An LNG CCS must be designed to withstand extreme environmental conditions. However, as the insulation material for LNGC CCSs, PUF has two major limitations: its strength and thermal conductivity. In the present study, PUFs were synthesized with various weight percentages of porous silica aerogel to reinforce the characteristics of PUF used in LNG carrier insulation systems. To evaluate the mechanical strength of the PUF-silica aerogel composites considering LNG loading/unloading environmental conditions, compressive tests were conducted at room temperature (20 °C) and a cryogenic temperature (−163 °C). In addition, the thermal insulation performance and cellular structure were identified to analyze the effects of silica aerogels on cell morphology. The cell morphology of PUF-silica aerogel composites was relatively homogeneous, and the cell shape remained closed at 1 wt.% in comparison to the other concentrations. As a result, the mechanical and thermal properties were significantly improved by the addition of 1 wt.% silica aerogel to the PUF. The mechanical properties were reduced by increasing the silica aerogel content to 3 wt.% and 5 wt.%, mainly because of the pores generated on the surface of the composites.     

Graphene Infused Ecological Polymer Composites for Electromagnetic Interference Shielding and Heat Management Applications

In the age of mobile electronics and increased aerospace interest, multifunctional materials such as the polymer composites reported here are interesting alternatives to conventional materials, offering reduced cost and size of an electrical device packaging. We report a detailed study of an ecological and dual-functional polymer composite for electromagnetic interference (EMI) shielding and heat management applications. We studied a series of polylactic acid/graphene nanoplatelet composites with six graphene nanoplatelet loadings, up to 15 wt%, and three different flake lateral sizes (0.2, 5 and 25 μm). The multifunctionality of the composites is realized via high EMI shielding efficiency exceeding 40 dB per 1 mm thick sample and thermal conductivity of 1.72 W/mK at 15 wt% nanofiller loading. The EMI shielding efficiency measurements were conducted in the microwave range between 0.2 to 12 GHz, consisting of the highly relevant X-band (8–12 GHz). Additionally, we investigate the influence of the nanofiller lateral size on the studied physical properties to optimize the studied functionalities per given nanofiller loading.     

Effect of the Topology of Carbon-Based Nanofillers on the Filler Networks and Gas Barrier Properties of Rubber Composites

The topology of nanofillers is one of the key factors affecting the gas barrier properties of rubber composites. In this research, three types of carbon-based nanofillers, including spherical carbon black (CB), fibrous carbon nanotubes (CNTs), and layered graphene (GE) were chosen to investigate the effect of the topological structures of nanofillers on the gas barrier properties of styrene-butadiene rubber (SBR) composites. Results showed that the structure and strength of the filler networks in SBR composites were closely associated with the topology of nanofillers. When filled with 35 phr CB, 8 phr CNTs, and 4 phr GE, the SBR composites had the same strength of the filler network, while the improvement in gas barrier properties were 39.2%, 12.7%, and 41.2%, respectively, compared with pure SBR composites. Among the three nanofillers, GE exhibited the most excellent enhancement with the smallest filler content, demonstrating the superiority of two-dimensional GE in improving the barrier properties of rubber composites.     

Modification of Laser Marking Ability and Properties of Polypropylene Using Silica Waste as a Filler

Polypropylene (PP) belongs to the group of polymers characterized by low susceptibility to absorption of electromagnetic radiation in the infrared range (λ = 1064 nm). This research consisted of assessing the possibility of using silica waste from the metallurgic industry as an additive for PP laser marking. The modifier was introduced into the polymer matrix in the range from 1 to 10 wt%. The effects of laser radiation were assessed based on colorimetric tests and microscopic surface analysis. The mechanical properties of the composites were determined during the static tensile tests. The thermal properties were investigated via differential scanning calorimetry. It was found that the introduction of silica waste into polypropylene allows for the effective marking of sample surfaces with the use of a laser beam. The greatest contrast between the graphic symbol and the background was obtained for silica contents of 3 and 5 wt%, with the use of a low-speed laser head and a strong concentration of the laser beam. The application of silica caused an increase in the modulus of elasticity and the tensile strength of the composite samples. Increases in the crystallization temperature and the degree of crystallinity of the polymer matrix were also observed. It was found that silica waste can act as multifunctional additive for polypropylene.     

Effect of Basalt Powder Surface Treatments on Mechanical and Processing Properties of Polylactide-Based Composites

Legislative restrictions and the needs of consumers have created a demand for sustainable materials. Polylactide (PLA) is a biodegradable polyester with advantageous mechanical properties, however, due to its low crystallization rate, it also has low thermomechanical stability. Its range of application temperatures can be widened using nucleating agents and fillers including basalt powder (BP), a waste product from the mining industry. This study analyzed the possibility of enhancing the properties of a PLA-BP composite by chemically treating the filler. Basalt powder was subjected to silanization with 3-aminopropyltriethoxysilane or γ-glycidoxypropyltrimethoxysilane and mixed with PLA at 5–20 wt%. The nucleating effect of a potassium salt of 3,5-bis(methoxycarbonyl) (LAK-301) in the silanized composite was also evaluated. The properties of the materials with silanized BP were compared with the unmodified basalt powder. The miscibility of the filler and the polymer was assessed by oscillatory rheometry. The structure of the composites was studied using scanning electron microscopy and their thermomechanical properties were analyzed using dynamic mechanical thermal analysis. Mechanical properties such as tensile strength, hardness and impact strength, and heat deflection temperature of the materials were also determined. It was concluded that BP-filled nucleated PLA composites presented satisfactory thermomechanical stability without silanization, but chemical treatment could improve the matrix–filler interactions.     

Preparation and Properties of Thermoplastic Polyurethane Composites Filled with Powdered Buckwheat Husks

Bio-based fillers for the polymer composites are still interesting from the scientific and industrial point of view, due to their low cost and renewable nature. In this work partially green composites were obtained by the mixing of thermoplastic poly(ester-urethane) with the unmodified and modified (by acetylation) grinded buckwheat husks. Obtained biocomposites were characterized in the terms of their chemical structure (FTIR), microstructure (SEM), thermal stability (TGA), thermomechanical properties (DMTA), and selected mechanical properties. The results showed that introduction of grinded buckwheat husks (even if the amount is 60 wt%) permit retaining high values of tensile strength (around 8–10 MPa), but the increasing amount of applied filler is connected with the decreasing of elongation at break. It can result from good interaction between the polymer matrix and the bio-based filler (confirmed by high values of polymer matrix-filler interaction parameter determined from Pukánszky’s model for the tensile strength of composites). The applied chemical treatment results in changing of mechanical properties of filler and composites. Obtained results confirmed the possibility of using powdered buckwheat husks as filler for thermoplastic polyurethane.     

Influence of the Size of the Fiber Filler of Corn Stalks in the Polylactide Matrix Composite on the Mechanical and Thermomechanical Properties

This paper presents results of a study on the effect of filler size in the form of 15 wt% corn stalk (CS) fibers on the mechanical and thermomechanical properties of polylactide (PLA) matrix composites. In the test, polylactidic acid (PLA) is filled with four types of length of corn stalk fibers with a diameter of 1 mm, 1.6 mm, 2 mm and 4 mm. The composites were composed by single screw extrusion and then samples were prepared by injection molding. The mechanical properties of the composites were determined by static tensile test, static bending test and Charpy impact test while the thermo-mechanical properties were determined by dynamic mechanical thermal analysis (DMTA). The composite structures were also observed using X-ray microcomputed tomography and scanning electron microscopy. In the PLA/CS composites, as the filler fiber diameter increased, the degradation of mechanical properties relative to the matrix was observed including tensile strength (decrease 22.9–51.1%), bending strength (decrease 18.9–36.6%) and impact energy absorption (decrease 58.8–69.8%). On the basis of 3D images of the composite structures for the filler particles larger than 2 mm a weak dispersion with the filler was observed, which is reflected in a significant deterioration of the mechanical and thermomechanical properties of the composite. The best mechanical and thermomechanical properties were found in the composite with filler fiber of 1 mm diameter. Processing resulted in a more than 6-fold decrease in filler fiber length from 719 ± 190 µm, 893 ± 291 µm, 1073 ± 219 µm, and 1698 ± 636 µm for CS1, CS1.6, CS2, and CS4 fractions, respectively, to 104 ± 43 µm, 123 ± 60 µm, 173 ± 60 µm, and 227 ± 89 µm. The fabricated green composites with 1 to 2 mm corn stalk fiber filler are an alternative to traditional plastic based materials in some applications.     

High-Performance Thermal Interface Materials with Magnetic Aligned Carbon Fibers

Thermal interface materials with high thermal conductivity and low hardness are crucial to the heat dissipation of high-power electronics. In this study, a high magnetic field was used to align the milled carbon fibers (CFs, 150 μm) in silicone rubber matrix to fabricate thermal interface materials with an ordered and discontinuous structure. The relationship among the magnetic field density, the alignment degree of CFs, and the properties of the resulting composites was explored by experimental study and theoretical analysis. The results showed higher alignment degree and enhanced thermal conductivity of composites under increased magnetic flux density within a certain curing time. When the magnetic flux density increased to 9 T, the CFs showed perfect alignment and the composite showed a high thermal conductivity of 11.76 W/(m·K) with only 20 vol% CF loading, owing to the ordered structure. Meanwhile, due to the low filler loading and discontinuous structure, a low hardness of 60~70 (shore 00) was also realized. Their thermal management performance was further confirmed in a test system, revealing promising applications for magnetic aligned CF–rubber composites in thermal interface materials.