Search Results (28)

This work investigated the 3D printing of fully compounded thermoset elastomers using a custom-designed printer capable of processing both thermoplastics and elastomers containing fillers and specific cure packages. The adhesion strength between selected thermoset elastomers and thermoplastic combinations was studied, and the influence of key process parameters on adhesion was evaluated. The results showed that interfacial bonding was favored by the proximity of solubility parameters, the amorphous morphology of the thermoplastic, and increased chain mobility at the processing temperature. Rubber processing parameters significantly influenced adhesion, showing that curing at a lower temperature for a longer duration yielded better results than shorter, higher-temperature cures. Elemental analysis revealed the presence of rubber-specific components on the thermoplastic surface, suggesting interfacial migration. These findings contribute to advancing multi-material 3D printing by enabling the integration of rubber-like materials with thermoplastics, expanding opportunities for applications in high-temperature and chemically demanding environments. Full article

Copolymers of glycidyl azide polymer (GAP) and poly (caprolactone) (PCL) were obtained by introducing PCL molecular chains at both ends or side groups of GAP molecular chains, respectively. GAP/PCL elastomers were prepared via polyurethane curing reaction and compared with GAP/PCL elastomers prepared by physical blending, in order to clarify the relationship between microstructure and macroscopic properties. The results showed that no GAP and PCL phase separation was observed in the chemically bonded GAP/PCL elastomers. The elongation at break of the thermosetting GAP/PCL block copolymer elastomer increased significantly from 268% to 300% due to the increase in molecular weight between crosslinking points. The GAP/PCL graft copolymer, with its longer PCL segment length and higher segment mobility, formed microcrystalline domains within the elastomer, resulting in a significant improvement in tensile strength from 0.32 MPa to 1.07 MPa. In addition, differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA) revealed that the glass transition temperature of the GAP/PCL elastomer was 2.6 °C lower than that of the pure GAP elastomer, and the thermal stability was also enhanced. Full article

The paper presents an overview of conductive polymer composites based on thermosetting materials, thermoplastics, and elastomers modified with carbon nanotubes (CNTs). To impart conductive properties to polymers, metal, carbon-dispersed materials, or their combinations are used. The inclusion of dispersed materials in polymers is associated with their microstructural features, as well as with polymerization methods. Such polymerization methods as melt mixing, solution technology, and introduction of fillers into the liquid phase of the composite with subsequent polymerization due to the use of a catalyst are known. Polymer composites that are capable of conducting electric current and changing their properties under the influence of an electric field, i.e., having one or more functional purposes, are called “smart” or intelligent. One such application is electric heating elements with the function of adaptive energy consumption or the effect of self-regulation of temperature depending on the surrounding conditions. A wide variety of polymers and dispersed materials with conductive properties determines a wide range of functional capabilities of the composite, including a positive temperature coefficient of resistance (PTCR) required to control temperature properties. The most effective filler in a polymer for obtaining a composite with desired properties is carbon nanomaterials, in particular, CNT. This is due to the fact that CNTs are a nanosized material with a high bulk density at a low weight, which allows for high electrical conductivity. Calculation of model parameters of polymer composites containing carbon nanostructures can be carried out using neural networks and machine learning, which give a fundamentally new result. The article contains sections with an assessment of various types of polymer matrices based on thermosets, thermoplastics, and elastomers. To impart electrically conductive properties, various options for fillers based on Ag, Au, Cu, Ni, Fe, and CNTs are considered. Methods for introducing dispersed fillers into polymer matrices are presented. Functional composites with a positive temperature coefficient and methods for their regulation are considered. The mechanisms of various electrophysical processes in conductive composites are considered, taking into account the resulting electrical conductivity based on the tunnel effect and hopping conductivity. An analysis of electric heaters based on various polymer matrices and dispersed fillers is carried out, taking into account their operating modes. Thus, the conducted review of modern scientific and practical research in the field of obtaining electrically conductive composites based on various types of polymer matrices with nanosized additives allows us to assess the prospects for the formation of functional composites for electrical heating, taking into account the mechanisms of electrical conductivity and new technologies based on machine learning and neural networks. Full article

Polymer composites are engineered materials that combine polymers with diverse fillers to enhance their physicochemical properties. The electrical conductivity of polymer composites is a vital characteristic that significantly broadens their use, particularly in electronic applications. The addition of ionic liquids into polymer composites represents a new method to enhance their functional properties, particularly in terms of electrical conductivity. In this brief review, several polymer matrices, conductive fillers, and ionic liquids utilized in polymer composites are categorized. Additionally, the effect of ionic liquids on the electrical conductivity of polymer composites is concisely explained. This review gives brief information that increases the understanding of electrical conductivity in polymer composites containing ionic liquids. In summary, most studies show that adding ionic liquids enhances the electrical conductivity of polymer composites regardless of the polymer matrix or conductive filler type. This enhancement is due to ionic liquids improving filler dispersion and promoting the creation of effective three-dimensional conductive networks within the matrix, thus boosting electron transport and mobility throughout the structure. This review provides new insights into the behavior of ionic liquids in composite systems, highlighting their role in improving properties for advanced applications. It encourages innovation in next-generation conductive materials and assists future research and development of more efficient materials for electronics. Full article

Elastomers are made of chain-like molecules to form networks that can sustain large deformation. Rubbers are thermosetting elastomers that are obtained from irreversible curing reactions. Curing reactions create permanent bonds between the molecular chains. On the other hand, thermoplastic elastomers do not need curing reactions. Incorporation of appropriated filler particles, as has been practiced for decades, can significantly enhance mechanical properties of elastomers. However, there are fundamental questions about polymer matrix composites (PMCs) that still elude complete understanding. This is because the macroscopic properties of PMCs depend not only on the overall volume fraction ($\varphi$) of the filler particles, but also on their spatial distribution (i.e., primary, secondary, and tertiary structure). This work aims at reviewing how the mechanical properties of PMCs are related to the microstructure of filler particles and to the interaction between filler particles and polymer matrices. Overall, soft rubbery matrices dictate the elasticity/hyperelasticity of the PMCs while the reinforcement involves polymer–particle interactions that can significantly influence the mechanical properties of the polymer matrix interface. For $\varphi$ values higher than a threshold, percolation of the filler particles can lead to significant reinforcement. While viscoelastic behavior may be attributed to the soft rubbery component, inelastic behaviors like the Mullins and Payne effects are highly correlated to the microstructures of the polymer matrix and the filler particles, as well as that of the polymer–particle interface. Additionally, the incorporation of specific filler particles within intelligently designed polymer systems has been shown to yield a variety of functional and responsive materials, commonly termed smart materials. We review three types of smart PMCs, i.e., magnetoelastic (M-), shape-memory (SM-), and self-healing (SH-) PMCs, and discuss the constitutive models for these smart materials. Full article

This work investigated material extrusion additive manufacturing (MatEx AM) of specialized fluoroelastomer (FKM) compounds for applications in rubber seals and gaskets. The influence of a commercially available perfluoropolyether (PFPE) plasticizer on the printability of a control FKM rubber compound was studied using a custom-designed ram material extruder, Additive Ram Material Extruder (ARME), for printing fully compounded thermoset elastomers. The plasticizer’s effectiveness was assessed based on its ability to address challenges such as high compound viscosity and post-print shrinkage, as well as its impact on interlayer adhesion. The addition of the PFPE plasticizer significantly reduced the FKM compound’s viscosity (by 70%) and post-print shrinkage (by 65%). While the addition of the plasticizer decreased the tensile strength of the control compound, specimens printed with the plasticized FKM retained 34% of the tensile strength of compression-molded samples, compared to only 23% for the unplasticized compound. Finally, the feasibility of seals and gaskets manufacturing using both conventional and unconventional additive manufacturing (AM) approaches was explored. A hybrid method combining AM and soft tooling for compression molding emerged as the optimal method for seal and gasket fabrication. Full article

In this work, an additive manufacturing process for extruding fully compounded thermosetting elastomers based on fluorine-containing polymer compositions is reported. Additive manufacturing printers are designed with a dry ice container to precool filaments made from curable fluoroelastomer (FKM) and perfluoroelastomer (FFKM) compounds. A support tube guides the stiffened filament towards the printer nozzle. This support tube extends near the inlet to a printer nozzle. This approach allows low-modulus, uncured rubber filaments to be printed without buckling, a phenomenon common when 3D printing low-modulus elastomers via the fused deposition modeling (FDM) process. Modeling studies using thermal analyses data from a Dynamic Mechanical Analyzer (DMA) and a Differential Scanning Calorimeter (DSC) are used to calculate the Young’s modulus and buckling force, which helps us to select the appropriate applied pressure and the nozzle size for printing. Using this additive manufacturing (AM) method, the successful printing of FKM and FFKM compounds is demonstrated. This process can be used for the future manufacturing of seals or other parts from fluorine-containing polymers. Full article

Modern science and technology demand a low glass transition temperature, yet one tailored to specific thermoset needs and specific to individual hardener applications. Two novel, nonterminal liquid crystalline epoxy resins (LCER) were synthesised, with their structures characterized via nuclear magnetic resonance (NMR), mass spectrometry (MS), and elemental analysis. Their liquid crystalline nature and thermal properties were determined using polarized optical microscopy (POM), thermogravimetric analysis (TGA), and differential scanning calorimetry (DSC). A set of seven aromatic amines serving as curing agents was used to perform curing in fourteen different systems in order to assess the glass transition temperature (T_g) of the obtained polymer networks using DSC. The liquid crystalline elastomers were obtained with vitrification occurring in a low temperature range (−10–40 °C), with a more predictable outcome for amines with two aromatic rings in the structure than with one. Moreover, the resin with a core consisting of four aromatic rings produces networks with higher T_g than the three-aromatic resin. The use of nonterminal LCER allowed the lowering of the glass transition temperature of the polymers to more than 70 °C compared to a terminal analogue. This brings new possibilities of designing highly elastic yet cured polymers with potential for use in smart applications due to the LC nature of the resin. Full article

In 2021, global plastics production was 390.7 Mt; in 2022, it was 400.3 Mt, showing an increase of 2.4%, and this rising tendency will increase yearly. Of this data, less than 2% correspond to bio-based plastics. Currently, polymers, including elastomers, are non-recyclable and come from non-renewable sources. Additionally, most elastomers are thermosets, making them complex to recycle and reuse. It takes hundreds to thousands of years to decompose or biodegrade, contributing to plastic waste accumulation, nano and microplastic formation, and environmental pollution. Due to this, the synthesis of elastomers from natural and renewable resources has attracted the attention of researchers and industries. In this review paper, new methods and strategies are proposed for the preparation of bio-based elastomers. The main goals are the advances and improvements in the synthesis, properties, and applications of bio-based elastomers from natural and industrial rubbers, polyurethanes, polyesters, and polyethers, and an approach to their circular economy and sustainability. Olefin metathesis is proposed as a novel and sustainable method for the synthesis of bio-based elastomers, which allows for the depolymerization or degradation of rubbers with the use of essential oils, terpenes, fatty acids, and fatty alcohols from natural resources such as chain transfer agents (CTA) or donors of the terminal groups in the main chain, which allow for control of the molecular weights and functional groups, obtaining new compounds, oligomers, and bio-based elastomers with an added value for the application of new polymers and materials. This tendency contributes to the development of bio-based elastomers that can reduce carbon emissions, avoid cross-contamination from fossil fuels, and obtain a greener material with biodegradable and/or compostable behavior. Full article

Additive manufacturing (AM), commonly referred to as 3D printing, has revolutionized the manufacturing landscape by enabling the intricate layer-by-layer construction of three-dimensional objects. In contrast to traditional methods relying on molds and tools, AM provides the flexibility to fabricate diverse components directly from digital models without the need for physical alterations to machinery. Four-dimensional printing is a revolutionary extension of 3D printing that introduces the dimension of time, enabling dynamic transformations in printed structures over predetermined periods. This comprehensive review focuses on polymeric materials in 3D printing, exploring their versatile processing capabilities, environmental adaptability, and applications across thermoplastics, thermosetting materials, elastomers, polymer composites, shape memory polymers (SMPs), including liquid crystal elastomer (LCE), and self-healing polymers for 4D printing. This review also examines recent advancements in microvascular and encapsulation self-healing mechanisms, explores the potential of supramolecular polymers, and highlights the latest progress in hybrid printing using polymer–metal and polymer–ceramic composites. Finally, this paper offers insights into potential challenges faced in the additive manufacturing of polymer composites and suggests avenues for future research in this dynamic and rapidly evolving field. Full article

Today, plastic materials are mostly made from fossil resources, and they are characterized by their long lifetime and pronounced persistence in the open environment. These attributes of plastics are one cause of the ubiquitous pollution we see in our environment. When plastics end up in the environment, most of this pollution can be attributed to a lack of infrastructure for appropriately collecting and recycling plastic waste, mainly due to mismanagement. Because of the huge production volumes of plastics, their merits of being cheap to produce and process and their recalcitrance have turned into a huge disadvantage, since plastic waste has become the end point of our linear economic usage model, and massive amounts have started to accumulate in the environment, leading to microplastics pollution and other detrimental effects. A possible solution to this is offered by “bioplastics”, which are materials that are either (partly) biobased and/or degradable under defined conditions. With the rise of bioplastics in the marketplace, several standards and test protocols have been developed to assess, certify, and advertise their properties in this respect. This article summarizes and critically discusses different views on bioplastics, mainly related to the properties of biodegradability and biobased carbon content; this shall allow us to find a common ground for clearly addressing and categorizing bioplastic materials, which could become an essential building block in a circular economy. Today, bioplastics account for only 1–2% of all plastics, while technically, they could replace up to 90% of all fossil-based plastics, particularly in short-lived goods and packaging, the single most important area of use for conventional plastics. Their replacement potential not only applies to thermoplastics but also to thermosets and elastomers. Bioplastics can be recycled through different means, and they can be made from renewable sources, with (bio)degradability being an option for the mismanaged fraction and special applications with an intended end of life in nature (such as in seed coatings and bite protection for trees). Bioplastics can be used in composites and differ in their properties, similarly to conventional plastics. Clear definitions for “biobased” and “biodegradable” are needed to allow stakeholders of (bio)plastics to make fact-based decisions regarding material selection, application, and end-of-life options; the same level of clarity is needed for terms like “renewable carbon” and “bio-attributed” carbon, definitions of which are summarized and discussed in this paper. Full article

The temperature resistance of glued timber, which is crucial for glued wood construction, represents a significant assessment criterion. To gain insights into this aspect, this study utilized methods such as a shear strength test in accordance with EN 302-1:2013-06 under thermal loading (from 20 °C to 200 °C), and Differential Scanning Calorimetry (DSC) to determine the glass transition temperature (Tg). An increase in thermal load resulted in a decrease in shear strength and an increase in wood breakage. A hierarchy of adhesive groups was established based on strength performance and wood failure percentage (WFP) at 200 °C. Thermoset adhesives (MF: Melamine Formaldehyde, PRF: Phenol Resorcinol Formaldehyde) led the ranking, followed by elastomer adhesives (1C-PUR: One-Component Polyurethane, EPI: Emulsion Polymer Isocyanate), with thermoplastic adhesive (PVAc: Polyvinyl Acetate) last. Thermoset adhesives further cured under heat. PUR adhesives exhibited higher strength performance at 150 °C and lower temperatures. Full article

In this paper, four different kinds of diols were used for the alcoholysis of waste thermoplastic polyurethane elastomers. The recycled polyether polyols were used to prepare regenerated thermosetting polyurethane rigid foam through one-step foaming. We used four different kinds of alcoholysis agents, according to different proportions of the complex, and we combined them with an alkali metal catalyst (KOH) to trigger the catalytic cleavage of the carbamate bonds in the waste polyurethane elastomers. The effects of the different types and different chain lengths of the alcoholysis agents on the degradation of the waste polyurethane elastomers and the preparation of regenerated polyurethane rigid foam were studied. Based on the viscosity, GPC, FT-IR, foaming time and compression strength, water absorption, TG, apparent density, and thermal conductivity of the recycled polyurethane foam, eight groups of optimal components were selected and discussed. The results showed that the viscosity of the recovered biodegradable materials was between 485 and 1200 mPa·s. The hard foam of the regenerated polyurethane was prepared using biodegradable materials instead of commercially available polyether polyols, and its compressive strength was between 0.131 and 0.176 MPa. The water absorption rate ranged from 0.7265 to 1.9923%. The apparent density of the foam was between 0.0303 and 0.0403 kg/m³. The thermal conductivity ranged from 0.0151 to 0.0202 W/(m·K). A large number of experimental results showed that the degradation of the waste polyurethane elastomers by the alcoholysis agents was successful. The thermoplastic polyurethane elastomers can not only be reconstructed, but they can also be degraded by alcoholysis to produce regenerated polyurethane rigid foam. Full article

The increasing interest in stretchable conductive composite materials, that can be versatile and suitable for wide-ranging application, has sparked a growing demand for studies of scalable fabrication techniques and specifically tailored geometries. Thanks to the combination of the conductivity and robustness of carbon nanotube (CNT) materials with the viscoelastic properties of polymer films, in particular their stretchability, “surface composites” made of a CNT on polymeric films are a promising way to obtain a low-cost, conductive, elastic, moldable, and patternable material. The use of polymers selected for specific applications, however, requires targeted studies to deeply understand the interface interactions between a CNT and the surface of such polymer films, and in particular the stability and durability of a CNT grafting onto the polymer itself. Here, we present an investigation of the interface properties for a selected group of polymer film substrates with different viscoelastic properties by means of a series of different and complementary experimental techniques. Specifically, we studied the interaction of a single-wall carbon nanotube (SWCNT) deposited on two couples of different polymeric substrates, each one chosen as representative of thermoplastic polymers (i.e., low-density polyethylene (LDPE) and polypropylene (PP)) and thermosetting elastomers (i.e., polyisoprene (PI) and polydimethylsiloxane (PDMS)), respectively. Our results demonstrate that the characteristics of the interface significantly differ for the two classes of polymers with a deeper penetration (up to about 100 μm) into the polymer bulk for the thermosetting substrates. Consequently, the resistance per unit length varies in different ranges, from 1–10 kΩ/cm for typical thermoplastic composite devices (30 μm thick and 2 mm wide) to 0.5–3 MΩ/cm for typical thermosetting elastomer devices (150 μm thick and 2 mm wide). For these reasons, the composites show the different mechanical and electrical responses, therefore suggesting different areas of application of the devices based on such materials. Full article

Pseudo-semi interpenetrating polymer networks (pseudo-semi IPNs) are a special example of topological isomerism in macromolecules, which have attracted significant attention in recent years with a high potential in a variety of engineering applications of polymeric materials. In this article, pseudo-semi IPNs were synthetized by sequential polymerization of thermoplastic polymers (TPEs) in the presence of thermosetting elastomer (TSEs) with contents of 10, 20, 30, 40 and 50 wt.% in a vacuum oven at 60 °C for about 72 h. In addition, this article describes a method for researching the elastic modulus, effective crosslinking density and physical crosslinking density of TSEs and pseudo-semi IPNs. The inherent interactions and entanglements of pseudo-semi IPNs were discussed by analyzing the changes in elastic modulus and effective crosslinking density at different temperatures. The results show that after the TPE was added to the TSE matrix as a plastic-reinforced material, the ductility increased from 89.6% to 491%, the effective crosslinking density was increased by 100% at high temperatures and the strength of the material matrix was significantly improved. Two physical events take place in our pseudo-semi IPNs as result of energy dissipation and polymeric chains mobility. Full article