Search Results (27)

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

To tackle the degradation of sealing performance in nitrile butadiene rubber (NBR) seals due to material aging during long-term service, this study integrates experimental and molecular simulation methods to elucidate the aging mechanism. Experimental results reveal that the contents of C=C and C=O functional groups significantly decrease during aging, accompanied by enhanced hydrophobicity and increased crosslink density of NBR, indicating that crosslinking reactions dominate the aging process with the participation of C=C and C=O groups. Quantum mechanics (QM) and molecular dynamics (MD) simulations further demonstrate that α-H, C=C, and C≡N groups are preferentially oxidized due to their low bond energies. The oxidation of NBR generates unstable epoxy intermediates, which undergo chain scission to form ketones, aldehydes, and ultimately crosslinked structures. Using a multi-dimensional evaluation system based on bond dissociation energy (BDE), solubility parameter (Δδ), and migration coefficient (MSD), four antioxidants (4010NA, 4010, MC, and BHT) were screened. BHT emerges as the optimal choice, exhibiting superior free radical scavenging ability (BDE = 346.3 kJ/mol), good matrix compatibility (Δδ = 2.95), and anti-migration properties. The MD-based screening method established herein provides a theoretical basis for designing antioxidant systems in high-performance rubber materials, facilitating the development of advanced rubber products. Full article

Asphalt modified with treated waste tires has good environmental protection and application value. However, the nano-interaction mechanism of crumb rubber (CR) and asphalt (especially its components) is unclear. In this study, molecular models of asphalt, asphalt components, CR, and CR-modified asphalt (CRMA) were constructed by molecular dynamics (MD) simulation. The validity of the model construction and parameter setting was verified by multiple indexes. The influence mechanism of CRMA density, asphalt-CR compatibility, mechanical indexes, and binding energy under the influence of temperature, CR dosage, and other factors was systematically analyzed. Results showed that the optimum temperature for preparing and storing to prevent segregation did not coincide. The solubility parameters (S_P) prediction model of the asphalt’s four components was obtained based on the multiple linear regression method. CR could enhance the mechanical properties of asphalt, but the improvement was limited to small dosages. Increasing the dosage can enhance the mechanical properties of asphalt; the mechanical properties can be significantly improved in medium- and high-temperature conditions. Bulk modulus and shear modulus were recommended for preferential analysis of the mechanical properties of CRMA. It is recommended that the optimal dosage be 20%. Full article

The equilibrium swelling test was employed to determine the swelling response of Nitrile Butadiene Rubber (NBR) with various acrylonitrile (ACN) contents, and the three-dimensional solubility parameter (HSP) and modified Flory–Huggins interaction parameter (χ_HSP) were used to establish the prediction model of the oil-resistant property. The results indicate that the energy difference (Ra) between NBR and solvents calculated by HSP values can be correlated with the swelling response qualitatively with an inversed “S-shape”, and high swelling response occurs at Ra < 8 MPa^1/2 for NBR. For the purpose of establishing the prediction model, the new modified χ_HSP value has been calculated and fitted with the swelling response using exponential and logarithmic fittings, respectively. Two prediction models considering all the possible influencing factors have been obtained to determine the swelling response and oil resistance of NBR-based rubber products in bio-fuels, represented by the bio-diesel and IRM 903 test oil in this work. The swelling response of NBR can be evaluated precisely, and high swelling regions can be predicted and avoided in the new emerging fuels through the prediction models. Thus, the oil resistance of NBR-based rubber products, such as seals, holes and gaskets can be well predicted now. Full article

This study investigated the synergistic effect of carbon black/multi-wall carbon nanotube (CB/MWCNT) hybrid fillers on the physical and mechanical properties of Ethylene propylene diene rubber (EPDM) composites after exposure to high-pressure hydrogen gas. The EPDM/CB/CNT hybrid composites were prepared by using the EPDM/MWCNT master batch (MB) with 10 phr CNTs to enhance the dispersion of CNTs in hybrid composites. The investigation included a detailed analysis of cure characteristics, crosslink density, Payne effect, mechanical properties, and hydrogen permeation properties. After exposure to 96.3 MPa hydrogen gas, the hydrogen uptake and the change in volume and mechanical properties of the composites were assessed. We found that as the MWCNT volume fraction in fillers increased, the crosslink density, filler–filler interaction, and modulus of hybrid composites increased. The hydrogen uptake and the solubility of the composites decreased with an increasing MWCNT volume fraction in fillers. Moreover, after exposure to hydrogen gas, the change in volume and mechanical properties exhibited a diminishing trend with a higher MWCNT volume fraction. We conclude that the hybridization of CB and CNTs formed strong filler–filler networks in hybrid composites, consequently reinforcing the EPDM composites and enhancing the barrier properties of hydrogen gas. Full article

In this study, we performed a detailed analysis of -sputtered-nylon 6,6 plasma polymer nanoparticles (NPs). Following a previous study using standard techniques such as X-ray photoelectron spectroscopy (XPS) and Fourier transform infrared (FTIR) spectroscopy, we employed unconventional approaches, specifically solid- and liquid-state high-resolution nuclear magnetic resonance (NMR) spectroscopy, supplemented by gel permeation chromatography (GPC). Scanning electron microscopy (SEM) was also used to examine changes in the size of the NPs after contact with solvents and after heating. Our investigations revealed suspected strong binding and networking of the NPs, and a soluble monomer/oligomer phase was identified and characterised. This fraction is removable using solvent or heat treatment without significantly affecting the size of the NPs. Additionally, we suggested the chemical structure of this soluble phase. Our findings support the proposed rubber-like character of plasma polymer NPs and explain their strong tendency to reflect from substrates upon high-speed impact. Full article

Gas emission and diffusion through polymeric materials play crucial roles in ensuring safety and monitoring gas concentrations in technology and industry. Especially, the gas permeation characteristics for O-ring material should be investigated for sealing application in a hydrogen infrastructure. To accommodate the requirements of different environments, we first developed four complementary effective methods for measuring the gas absorption uptake from polymers enriched by pure gas under high pressure and determining the gas diffusivity. The methods included the gravimetric method, the volumetric method, the manometric method, and gas chromatography, which are based on mass, volume, pressure, and volume measurements, respectively. The representative investigated results of the developed methods, such as gas uptake, solubility, and diffusivity are demonstrated. The measuring principles, measuring procedures, measured results, and the characteristics of the methods are compared. Finally, the developed methods can be utilized for testing transport properties, such as the leakage and sealing ability, of rubber and O-ring material under high pressure for hydrogen fueling stations and gas industry. Full article

Hydrogen uptake/diffusivity in nitrile butadiene rubber (NBR) blended with carbon black (CB) and silica fillers was measured with a volumetric analysis method in the 258–323 K temperature range. The temperature-dependent H₂ diffusivity was obtained by assuming constant solubility with temperature variations. The logarithmic diffusivity decreased linearly with increasing reciprocal temperature. The diffusion activation energies were calculated with the Arrhenius equation. The activation energies for NBR blended with high-abrasion furnace CB and silica fillers increased linearly with increasing filler content. For NBR blended with medium thermal CB filler, the activation energy decreased with increasing filler content. The activation energy filler dependency is similar to the glass transition temperature filler dependency, as determined with dynamic mechanical analysis. Additionally, the activation energy was compared with that obtained by the differential pressure method through permeability temperature dependence. The same activation energy between diffusion and permeation in the range of 33–39 kJ/mol was obtained, supporting the temperature-independent H₂ solubility and H₂ physisorption in polymer composites. Full article

Natural rubber (NR) latex derived from Hevea brasiliensis is a complex colloid comprising mainly rubber hydrocarbons (latex particles) and a multitude of minor non-rubber constituents such as non-rubber particles, proteins, lipids, carbohydrates, and soluble organic and inorganic substances. NR latex is susceptible to enzymatic attack after it leaves the trees. It is usually preserved with ammonia and, to a lesser extent, with other preservatives to enhance its colloidal stability during storage. Despite numerous studies in the literature on the influence of rubber proteins on NR latex stability, issues regarding the effect of protein hydrolysis in the presence of ammonia on latex stability during storage are still far from resolved. The present work aims to elucidate the interplay between protein hydrolysis and ammoniation in NR latex stability. Both high- and low-ammonia (with a secondary preservative) NR latexes were used to monitor the changes in their protein compositions during storage. High-ammonia (FNR-A) latex preserved with 0.6% (v/v) ammonia, a low 0.1% ammonia/TMTD/ZnO (FNR-TZ) latex, and a deproteinized NR (PDNR) latex were labeled with fluorescence agents and observed using confocal laser scanning microscopy to determine their protein composition. Protein hydrolysis was confirmed via sodium dodecyl sulfate–polyacrylamide gel electrophoresis (SDS-PAGE). The results revealed that protein hydrolysis increased with the storage duration. The change in protein composition accompanying hydrolysis also allows the spatial distribution of allergenic proteins to be estimated in the latex. Concurrently, the latex stability increased with the storage duration, as measured by the latex’s mechanical stability time (MST) and the zeta potential of the latex particles. As monitored by AFM, the surface roughness of the NR latex film increased markedly during extended storage compared with that of the DPNR latex, which remained smooth. These results underscore the pivotal role of ammonia in bolstering NR latex stability brought on by protein hydrolysis, which greatly impacts latex film’s formation behavior. NR latex stability underpins the quality of latex-dipped goods during manufacturing, particularly those for medical gloves. Full article

The photochemical degradation of natural rubber (NR) is a prevalent method used to modify its inherent properties. Natural rubber, predominantly derived from the Hevea Brasiliensis tree, exhibits an exceptionally high molecular weight (MW), often reaching a million daltons (Da). This high MW restricts its solubility in various solvents and its reactivity with polar compounds, thereby constraining its versatile applications. In our previous work, we employed TiO₂ in its powdered form as a photocatalyst for the functionalization of NR latex. However, the post-process separation and reuse of this powder present substantial challenges. In this present study, we aimed to functionalize deproteinized NR (DPNR) latex. We systematically reduced its MW via photochemical degradation under UVA irradiation facilitated by H₂O₂. To enhance the efficiency of the degradation process, we introduced TiO₂-coated hollow glass beads (TiO₂-HGBs) as photocatalysts. This approach offers the advantage of easy collection and repeated reuse. The modified DPNR showed a reduction in its number-average MW from 9.48 × 10⁵ to 0.28 × 10⁵ Da and incorporated functional groups, including hydroxyl, carbonyl, and epoxide. Remarkably, the TiO₂-HGBs maintained their performance over seven cycles of reuse. Due to their superior efficacy, TiO₂-HGBs stand out as promising photocatalysts for the advanced functionalization of NR across various practical applications. Full article

High-content waste-rubber-modified asphalt (HRMA) has high viscosity and poor storage stability. HRMA not only improves the properties of road asphalt, but also reduces the environmental pollution caused by waste tires. Enhancing the molecular interaction of waste rubber and asphalt is key to making full use of HRMA. In this paper, aromatic oil was used as the activator for waste rubber. The molecular interaction mechanism between aromatic oil and HRMA was investigated. The radial distribution function, diffusion coefficient, free volume, solubility parameter, and shear viscosity were calculated through molecular simulations. Storage stability, micromorphology, and adhesive force were measured via experiments. The adhesive force of HRMA−1 (4.9 nN) was lower than that of RMA (6.2 nN) and HRMA−2 (5.8 nN). The results show that aromatic oil can promote the dispersion of waste rubber, making the storage of asphalt systems stable. There exists a strong electrostatic force between rubber and asphaltenes and an intermolecular force between rubber and aromatic oil or aromatics, which makes the aromatic oil and aromatics of parcel rubber molecules and waste rubber highly soluble in asphalt. Molecular simulations confirmed the molecular interaction between rubber and aromatic oil, and aromatic oil was shown to reduce the viscosity of HRMA. Full article

Nanosized calcium carbonate (NCC) plays a vital role in the rubber and plastic fields as a filler, but it cannot resolve the electrostatic problem. Humic-acid-based NCC (HA-NCC) was accidentally discovered in the reaction between biogas slurry and calcium chloride (CaCl₂), based on nutrient recovery and gradient treatment technology to solve the biogas slurry problem. A preliminary study on the preparation of conductive nanosized calcium carbonate (CNCC) from the HA-NCC was implemented. Meanwhile, a synchronous double decomposition coating method was proposed to properly explain the formation of HA-NCC in the biogas slurry. The CNCC was further obtained through drying and carbonizing the HA-NCC sample. The morphology of CNCC was a square shape with aggregation, and its crystals were calcite. The C content of CNCC was 5% higher than that of the normal CaCO₃, implying a synchronous coating effect of soluble HA in biogas slurry on NCC. The weight loss of CNCC was about 2.5% at 630 °C, explaining why the HA-NCC remained black at 550 °C for 4 h. The CNCC was partly ordered and graphitized. The resistivity of the CNCC reached 2.62 × 10⁶ Ω·cm. It could be used as a conductive powder. In view of the favorable characteristics described above, CNCC would be expected to be a filler and antistatic agent for plastics and rubbers to enhance the tensile and bending resistance of polymer materials, while eliminating electrostatic hazards. The results are also of great significance for developing high-end products to realize resource utilization of biogas slurry. Full article

Waste tires can be ground as crumb rubber (CR) and incorporated into asphalt pavement for efficient resource utilization. However, due to its thermodynamic incompatibility with asphalt, CR cannot be uniformly dispersed in the asphalt mix. In order to address this issue, pretreating the CR with desulfurization is a common way to restore some of the properties of natural rubber. The main technique of desulfurization and degradation is dynamic desulfurization, requiring a high temperature that may lead to asphalt fires, aging, and the volatilization of light substances, generating toxic gases and resulting in environmental pollution. Therefore, a green and low-temperature controlled desulfurization technology is proposed in this study to exploit the maximum potential of CR desulfurization and obtain high-solubility “liquid waste rubber” (LWR) close to the ultimate regeneration level. In this work, LWR-modified asphalt (LRMA) with superior low-temperature performance and processability, stable storage, and less susceptibility to segregation was developed. Nevertheless, its rutting and deformation resistance deteriorated at high temperatures. The results showed that the proposed CR-desulfurization technology could produce LWR with 76.9% solubility at a low temperature of 160 °C, which is close to or even better than the finished products produced at the preparation temperature of TB technology, i.e., 220–280 °C. Full article

Fracture toughness is one of the main factors influencing the durability of light-cured composites used for dental restorations and fillings. One of the methods of increasing the fracture toughness is the modification of the matrix with liquid acrylonitrile-free liquid rubber. This study aimed to assess the miscibility of acrylonitrile-free liquid rubber with a blend of resins and their stability over time, and to determine the optimal amount of liquid rubber (LR) in the blend due to mechanical properties. Two blends of dimethacrylate resins were used: resin “F” composed of BisGMA (60 wt.%), TEGDMA (20 wt.%), BisEMA (10 wt.%) and UDMA (10 wt.%), and “C” resin containing BisGMA (40 wt.%), TEGDMA (40 wt.%), BisEMA (10 wt.%) and UDMA (10 wt.%). The modifier Hypro^® 2000X168LC VTB liquid rubber was used in at 1%, 2%, 3%, 4%, 5%, 10%, 15% and 20% by weight in the resin blend. The miscibility was assessed by microscopy. The fracture toughness, flexural strength and Young’s modulus were determined in the bending test. The results showed that the solubility of the liquid rubber depends on the ratio of BisGMA/TEGDMA in the resins. In resins with 40 wt.% TEGDMA, the LR solubility was as high as 5%, while resins with 20 wt.% TEGDMA, the liquid rubber did not dissolve. The LR-resin mixtures showed good time stability, and no changes in the size or morphology of the rubber domains were found after 24 h of mixing. The maximum fracture toughness (2.46 MPa m^1/2) was obtained for 5 wt.% LR in resin F and for 15 wt.% LR in resin C (2.53 MPa m^1/2). The modification with liquid rubber resulted in an exponential reduction in both flexural strength and Young’s modulus. The analysis of the results of the mechanical tests allowed us to determine the optimal amount of LR for both resins. For resin F it was 5.4 wt.%, and for resin C it was 8.3 wt.%. It can be stated that the optimal amount of liquid rubber increases with its solubility in the resin. Full article

This publication highlights the use of a high-speed thermokinetic mixer as an alternative to recycling ground tire rubber (GTR) using mechanochemical treatment. The GTR initially had a gelled fraction of 80% and presented a reduction of up to 50% of gel fraction in the most intensive condition (5145 rpm, n₂). The processing condition at the lowest speed (2564 rpm, n₁) resulted in greater selectivity in chain scission (K~1). However, in the most intense processing condition (10 min to n₂), more significant degradation was observed via random scission, reduction in the glass transition temperature, T_g (11 °C), increase in the soluble polymeric fraction, and a more significant reduction in the density of bonds occurs. The artificial neural network could describe and correlate the thermal degradation profile with the processing conditions and the physicochemical characteristics of the GTR. The n₂ velocity resulted in the formation of particles with a smoother and more continuous surface, which is related to the increase in the amount of soluble phase. The approach presented here represents an alternative to the mechanochemical treatment since it can reduce the crosslink density with selectivity and in short times (1–3 min). Full article