Search Results (353)

Divinylisoprene rubber, a copolymer of butadiene and isoprene, is used as raw material for rubber technical products, combining isoprene rubber’s elasticity and butadiene rubber’s wear resistance. These properties depend quantitatively on the copolymer composition, which depends on the kinetics of its synthesis. This work aims to theoretically describe how the monomer mixture composition in the butadiene–isoprene copolymerization affects the activity of the TiCl₄-Al(i-C₄H₉)₃ catalytic system (expressed by active sites concentration) via kinetic modeling. This enables development of a reliable kinetic model for divinylisoprene rubber synthesis, predicting reaction rate, molecular weight, and composition, applicable to reactor design and process intensification. Active sites concentrations were calculated from experimental copolymerization rates and known chain propagation constants for various monomer compositions. Kinetic equations for active sites formation were based on mass-action law and Langmuir monomolecular adsorption theory. An analytical equation relating active sites concentration to monomer composition was derived, analyzed, and optimized with experimental data. The results show that monomer composition’s influence on active sites concentration is well described by a two-step kinetic model (physical adsorption followed by Ti–C bond formation), accounting for competitive adsorption: isoprene adsorbs more readily, while butadiene forms more stable active sites. Full article

To obtain waterborne polymer-modified emulsified asphalt materials with better comprehensive performance, waterborne polymer modifiers including waterborne epoxy resin (WER)-reinforced styrene–butadiene–styrene block copolymer (SBS), waterborne acrylate (WA) or styrene butadiene rubber (SBR) emulsion were prepared. The mechanical strength, toughness, adhesion and impact resistance of these waterborne polymers were evaluated. Furthermore, the correlation between the performance indicators of the waterborne polymers was analyzed. Based on Fourier transform infrared (FTIR) spectroscopy and thermogravimetric (TG) analysis, the mechanism of WER-modified SBS and WA was characterized. The results show that adding 10%–15% WER can significantly improve the mechanical properties of the waterborne polymer. The performances of modified SBS and WA are better than that of modified SBR. When the content of WER is 10%, the tensile strength, elongation at break and pull-off strength of WER-modified SBS and WA are 4.80–6.38 MPa, 476.3%–579.6% and 1.62–1.70 MPa, respectively. The mechanical strength and breaking energy of the waterborne polymers show a significant linear correlation with their application properties such as adhesion, bonding and impact resistance. FTIR and TG analyses indicate that WER-modified SBS or WA prepared via emulsion blending undergo primarily physical modifications, enhancing thermal stability while promoting crosslinking and curing. Full article

The development of high-impact denture base formulations that are suitable for digital light processing (DLP) 3D printing is demanding. Indeed, a combination of high flexural strength/modulus and high fracture toughness is required. In this contribution, eight urethane macromonomers (UMs1-8) were synthesized in a one-pot, two-step procedure. Several rigid diols were first reacted with two equivalents of trimethylhexamethylene diisocyanate. The resulting diisocyanates were subsequently end-capped with a free-radically polymerizable monomer bearing a hydroxy group. UMs1-8 were combined with the monofunctional monomer (octahydro-4,7-methano-1H-indenyl)methyl acrylate and a poly(ε-caprolactone)-polydimethylsiloxane-poly(ε-caprolactone) (PCL-PDMS-PCL) triblock copolymer (BCP1) as a toughening agent. The double-bond conversion, glass transition temperature (T_g), and mechanical properties (flexural strength/modulus, fracture toughness) of corresponding light-cured materials were measured (cured in a mold using a light-curing unit). The results showed that the incorporation of BCP1 was highly efficient at significantly increasing the fracture toughness, as long as the obtained networks exhibited a low crosslink density. The structure of the urethane macromonomer (nature of the rigid group in the spacer; nature and number of polymerizable groups) was demonstrated to be crucial to reach the desired properties (balance between flexural strength/modulus and fracture toughness). Amongst the evaluated macromonomers, UM1 and UM2 were particularly promising. By correctly adjusting the BCP1 content, light-cured formulations based on those two urethane dimethacrylates were able to fulfill ISO20795-1:2013 standard requirements regarding high-impact materials. These formulations are therefore suitable for the development of 3D printable high-impact denture bases. Full article

To improve solid-state lithium batteries, solution casting has been employed to create lithium ion-conducting copolymer electrolytes involving poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP)/polyvinylpyrrolidone (PVP) blend polymers with various compositions. Following X-ray diffraction and Fourier transformation (FTIR), the structural characterisation and identification of molecular bonding in polymer electrolytes were confirmed. Through AC impedance analysis, the electrical characteristics of the solid-state polymer films were investigated. The dielectric conductivity of the sample was found to obey the modified Arrhenius relationship, while in the case of a sample with higher conductivity, it followed Arrhenius behaviour. The relaxation parameters and dielectric behaviour of the samples are demonstrated and discussed. Full article

In this study, a poly [ε-caprolactam-co-bis(2-hydroxyethyl) terephthalate] copolymer (P (CL-co-BHET)) was synthesized from para-terephthalic acid (PTA), ethylene glycol (EG), and caprolactam (CL). The crystallization behavior and thermal stability of the copolymer were thoroughly investigated. With the aid of molecular simulation, this study investigated the variation in interchain hydrogen bonding in the copolymer, focusing on the direction and the number of hydrogen bonds. The results revealed a close relationship between the copolymer chain structure, the variation in interchain hydrogen bonding, and the crystallization behavior and thermal stability of the copolymer. The introduction of BHET segments disrupted the regularity of the PA6 backbone and hydrogen bonding, leading to a decrease in the melting point, crystallization temperature, and crystallinity of the copolymer. The thermal stability of the copolymers also decreased, and the crystallization form gradually shifted from the α-crystalline to the γ-crystalline phase. The findings of this study are significant for evaluating the crystallization behavior of polyester amides and for predicting and regulating the properties of polyesteramide polymers. Full article

Poly(3,3-bis(azidomethyl)oxetane(BAMO)-tetrahydrofuran(THF)) copolymer (PBT) and ammonium perchlorate (AP) are critical components of solid rocket propellants, where their interfacial bonding mechanisms and temperature-dependent mechanical properties are pivotal to propellant reliability. In this study, density functional theory (DFT) calculations were employed to evaluate the adsorption energies between common AP crystal surfaces and PBT units, identifying the most energetically favorable adsorption configurations. The atomic configurations and charge transfer characteristics at the PBT-AP interface were systematically analyzed. Molecular dynamics (MD) simulations were further conducted to determine the thermally stable operating range of the PBT-AP system. The results reveal a strong temperature dependence of mechanical performance, with viscous failure mechanisms and damage thresholds during static tensile processes investigated across varying temperatures. Notably, mechanical properties remain stable below 60 °C but deteriorate significantly above this temperature. This study elucidates the influence of a PBT-AP interfacial microstructure and temperature on mechanical performance and tensile fracture damage boundaries, providing crucial insights for the design, formulation, and safe application of PBT-based solid rocket propellants. Full article

Unsaturated macrolactones (UMs) have long attracted researchers’ attention due to a combination of a reactive ester fragment and C=C bond in their structures. UMs of natural origin are comparatively few in number, and the task of developing synthetic approaches to new UMs is relevant. Recent advances in the synthesis of UMs cannot be dissociated from the progress in design of metathesis catalysts, since this catalytic approach is an atom-economy alternative to conventional organochemical methods. In the present review, we summarized and discussed the use of ring-closing metathesis, catalyzed by Ru and Group 6 metal complexes, in the synthesis of Ums and the advantages and shortcomings of the catalytic approach to UMs in comparison with organochemical methods. In a separate section, the use of UMs in the synthesis of unsaturated polyesters, the functionalization of these (co)polymers, and the prospects for practical use of the material obtained are also presented. It is essential that the actual approaches to UMs are often based on the use of renewable feedstocks, thereby meeting Green Chemistry principles. Full article

Poly(lactic acid) (PLA) is a widely used biobased polyester which can be derived from renewable resources. Due to its excellent properties, it has already been adopted in various industrial sectors. While PLA is compostable, its degradation to the environment is very slow, necessitating the development of efficient recycling methods. This study focuses on the chemical recycling via microwave-assisted alkaline hydrolysis of PLA and its copolymers with poly(ethylene azelate) (PEAz), aiming to recover both carboxylic acid monomers: lactic acid and azelaic acid. Moreover, our method tunes the degradation of PLA via the synthesis of the novel aliphatic PLA-based copolyesters, targeting engineering-like applications, specifically in the field of printed electronics. Various process parameters were analyzed, including the temperature and the duration of the experiments as well as different phase transfer catalysts. Complete degradation was achieved at low temperatures (110–125 °C) and short times (12–15 min) for the PLA-based copolyesters, offering significant environmental benefits, as considerably less energy is consumed compared to chemical conventional methods. So, by changing the composition of the copolyesters through the incorporation of PEAz blocky segments, the ester bonds became more susceptible to hydrolysis under alkaline conditions assisted with microwave irradiation. Additionally, enzymatic hydrolysis was also studied in parallel for comparative purposes, revealing low degradation rates, thus establishing the microwave-assisted alkaline hydrolysis as a solid and reliable method for tuning the degradation of PLA-based materials. Full article

In this review work, the different routes and methods for preparing hybrid materials based on nanostructured block copolymers (BCPs) and magnetic nanoparticles (MNPs) are analyzed, as they can be potentially employed in different sectors like biomedicine, electronic or optoelectronic devices, data storing devices, etc. The first procedure for their preparation consists of the nanostructuring of BCPs in the presence of previously synthesized NPs by modifying their surface for increasing compatibility with the matrix or employing magnetic fields for NP orientation, which can also promote the orientation of nanodomains. Surface modification with surfactants led to the selective confinement of NPs depending on the interaction (mainly hydrogen bonding) degree and their intensity. Surface modification with brushes can be performed by three methods, including grafting from, grafting to, or grafting through. Those methods are compared in terms of success for the positioning and confinement of NPs in the desired domains, showing the crucial importance of brush length and grafting density, as well as of NP amount and modification degree in the self-assembled morphology. Regarding the use of external magnetic fields, the importance of relative amounts of MNPs and BCPs employed and that of the magnetic field intensity for the orientation of the NPs and the nearby BCP domains is shown. The second procedure, consisting of the in situ synthesis of NPs inside the nanodomains by a reduction in the respective metallic ions or employing metal-containing BCPs for the generation of MNP patterns or arrays, is also shown. In all cases, the transference of magnetic properties to the nanocomposite was successful. Finally, a brief summary of some aspects about the use of BCPs for the synthesis, encapsulation, and release of MNPs is shown, as they present potential biomedical applications such as cancer treatment, among others. Full article

Precision micromilling is currently widely used for the fabrication of injection mold inserts for the mass production of microfluidic devices. However, for complex devices with micrometer-scale and high density of structures, micromilling results in high production times and costs for production runs of hundreds or thousands of units. Femtosecond laser (fs-laser) technology has emerged as a promising solution for high-precision micromachining. This study analyzes the potential of fs-laser micromachining for the fabrication of injection mold inserts for the large-scale production of thermoplastic microfluidic devices. For the evaluation of technology, a reference design was defined. The parameters of the fs-laser process were optimized to achieve high resolution of the structures and optimal surface quality, aiming to minimize production times and costs while ensuring the quality of the final part. The microstructures were replicated in two different grades of COC (Cyclic Olefin Copolymer) by injection molding. The dimensional tolerance of the structures and the surface finish achieved both in the insert and the polymer parts were characterized by scanning electron microscopy (SEM) and confocal microscopy. The surface quality of the final parts and its suitability for microfluidic fabrication were also assessed performing chemical bonding tests. The fs-laser machining process has shown great potential for the mass production of microfluidic devices. The developed process has enabled for a reduction of up to 90% in the fabrication times of the insert compared to micromilling. The parts exhibited very smooth surfaces, with roughness values (Sa) of 64.6 nm for the metallic insert and 71.8 nm and 72.9 nm for the COC E-140 and 8007S-04 replicas, respectively. The dimensional tolerance and the surface quality need to be improved to be competitive with the finishes achieved with precision micromilling. Nonetheless, there is still room for improvement considering the significant reduction in the production times through new laser processing strategies. Full article

This research presents the results of a combined numerical and experimental study of the thermal decomposition behavior of copolymers based on polypropylene glycol fumarate phthalate. The thermal decomposition of polymers plays a key role in various fields, such as waste recycling and energy recovery, and in the development of new materials. The objective of this study is to model the degradation kinetics using thermogravimetric data, matrix-based numerical methods, and quantum chemical calculations. To solve the resulting systems of linear algebraic equations (SLAEs), matrix decomposition algorithms (QR, SVD, and Cholesky) were employed, which enabled the determination of activation energy values for the process. Comparison of the activation energy (E_a) results obtained using the decomposition method of Cholesky (207.21 kJ/mol), normal equations (205.22 kJ/mol), singular value decomposition (206.23 kJ/mol), and QR decomposition (206.23 kJ/mol) showed minor changes that were associated with the features of each method. Quantum chemical calculations based on density functional theory (DFT) at the B3LYP/6-31G(d) level were performed to analyze the molecular structure and interpret the IR spectra. This study establishes that the content of functional groups (ether and ester) and the type of chemical bonds exert critical influences on the decomposition mechanism and associated thermal parameters. The results confirm that the polymer’s structural architecture governs its thermal stability. The scientific novelty of this work lies in the integration of numerical approximation methods and quantum chemical analysis for investigating the thermal behavior of polymers. This approach is applied for the first time to copolymers of this composition and may be employed in the design of heat-resistant materials for agricultural and environmental applications. Full article

The properties of compatibilized blends of polyethylene (PE) and polypropylene (PP), having reduced macromolecular entanglements, were studied. The density of PP macromolecular entanglements was controlled by prior disentangling in solution. The polymer ratio in the blend was 4:1 or 1:4. An ethylene–octene copolymer was used as a compatibilizer. The melt blending process resulted in good dispersion of the minority component, with slightly larger inclusions when more disentangled PP was used. Rheological studies confirmed the achievement of different entanglement densities of PP macromolecules in the blends. The partial disentanglement did not affect the thermal stability of the blends. During the isothermal crystallization studies, faster growth of PP spherulites was observed in the blend with reduced entanglements, which also influenced the entire crystallization process. The recovery time of equilibrium entanglement was investigated and it turned out to be 45 min if the blend was annealed at 190 °C, which was shorter than in the analogous homopolymer. Studies of tensile properties showed that in blends with a majority share of polyethylene, the elongation at break increased with the disentanglement of the minority component, due to better bonding of the blend components and thus the reduction in microcavitation. Full article

This study investigates the correlation between the cross-linked network structure and the macroscopic mechanical properties of 3,3-bis(azidomethyl)oxetane-tetrahydrofuran copolymer (PBT)-based solid propellants through molecular dynamics (MD) simulations. A multi-component system comprising PBT molecular chains, toluene diisocyanate (TDI), trimethylolpropane (TMP), tetraethylene glycol (TEG), and sodium perchlorate (AP) was constructed. Perl script programming was utilized to precisely control the dynamic cross-linking reaction. Molecular models with cross-linking densities of 0%, 50%, 60%, 70%, 80%, and 90% were established, and their mechanical properties were analyzed under varying cross-link densities and strain rates through uniaxial tensile simulations. The results indicate that the formation of the cross-linked network significantly alters the energy distribution and microstructural characteristics of the system. As the cross-linking density increases from 50% to 90%, the total energy of the system decreases by approximately 40%, primarily due to reductions in non-bonded energy. The radial distribution function (RDF) and root mean square displacement (MSD) curves reveal that the cross-linking reaction enhances covalent bond formation between molecular chains, reduces their degrees of freedom, and increases the glass transition temperature (Tg). Under identical strain conditions, the models with higher cross-link densities exhibit greater stress resistance. Specifically, the stress growth rate of the 90% cross-link density system increases by 42.1% as the stretching rate rises from 1.0 × 10¹¹ s⁻¹ to 2.0 × 10¹¹ s⁻¹, compared to an 18.7% increase for the 50% cross-link density system. These findings have significant implications for optimizing processing parameters and predicting the mechanical properties of propellants. Full article

The rapid advancement of 3D packaging technology has emerged as a key solution to overcome the scaling-down limitation of advanced memory and logic devices. Redistribution layer (RDL) fabrication, a critical process in 3D packaging, requires the use of polyimide (PI) films with thicknesses in the micrometer range. However, these polyimide films present surface topography variations in the range of hundreds of nanometers, necessitating chemical–mechanical planarization (CMP) to achieve nanometer-level surface flatness. Polyimide films, composed of copolymers of pyromellitimide and diphenyl ether, possess strong covalent bonds such as C–C, C–O, C=O, and C–N, leading to inherently low polishing rates during CMP. To address this challenge, the introduction of Fe(NO₃)₃ into CMP slurries has been proposed as a polishing rate accelerator. During CMP, this Fe(NO₃)₃ deformed the surface of a polyimide film into strongly positively charged 1,2,4,5-benzenetetracarbonyliron and weakly negatively charged 4,4′-oxydianiline (ODA). The chemically dominant polishing rate enhanced with the concentration of the Fe(NO₃)₃ due to accelerated surface interactions. However, higher Fe(NO₃)₃ concentrations reduce the attractive electrostatic force between the positively charged wet ceria abrasives and the negatively charged deformed surface of the polyimide film, thereby decreasing the mechanically dominant polishing rate. A comprehensive investigation of the chemical and mechanical polishing rate dynamics revealed that the optimal Fe(NO₃)₃ concentration to achieve the maximum polyimide film removal rate was 0.05 wt%. Full article

This study focuses on using constant and ramp cyclic processes to evaluate the performance of acrylonitrile–butadiene–styrene (ABS) copolymer with electron beam irradiation cross-linking. The main objective of this study is to compare the effects of both constant and ramp cyclic thermal processes on ABS where the results demonstrated degradation effects on ABS and its irradiated products. Under constant thermal ageing at 100 °C, the impact strength of the samples decreased drastically with increasing irradiation dosage, reaching a minimum value of 54 J/m² at 250 kGy. Tensile strength also showed a significant reduction, with values dropping from 49 MPa to 43 MPa for samples aged for 2 and 8 days, respectively, when dosages exceeded 100 kGy. This degradation is attributed to the chain scission process induced by prolonged thermal ageing and heating effects. In the ramp cyclic thermal ageing condition (Ramp-100), the impact strength followed a trend similar to the constant 100 °C thermal effect but exhibited less severe degradation. The impact strength decreased from 72 J/m² to 58 J/m² for the ramp cyclic effect compared to the greater reduction in the constant 100 °C condition (73 J/m² to 54 J/m²). This difference is likely due to the less harsh, intermittent heating ramp cyclic process compared to the continuous heating, suggesting that intermittent heating mitigated thermal degradation and chain scission mechanisms. Differential Scanning Calorimetry (DSC) analysis verified the effects of irradiation and thermal ageing on thermal properties. For unaged samples, the melting temperature remained low at 106.24 °C. With irradiation dosages of 100 and 200 kGy, the melting temperature increased to 107.76 °C and 111.43 °C, respectively, likely due to enhanced intermolecular bonding from increased cross-linking. Overall, cyclic thermal ageing caused less significant degradation of ABS products compared to constant thermal ageing. This suggests that ABS products have a longer service life in environments with ramp cyclic temperature variations compared to constant temperature conditions, which accelerate degradation. Full article