Polymer最新文献

{"title":"Polymer stress relaxation in biaxially stretching-induced crystallization","authors":"Rongsheng Sun,&nbsp;Ruiqi Mi,&nbsp;Wen Luo,&nbsp;Wenbing Hu","doi":"10.1016/j.polymer.2025.128446","DOIUrl":"10.1016/j.polymer.2025.128446","url":null,"abstract":"<div><div>Biaxially stretching-induced polymer crystallization is a common yet fundamental process in the industrial processing for plastic thinfilms, bottles and foams, in which polymer stress relaxation plays an important role. By means of dynamic Monte Carlo simulations, we have previously investigated the role of polymer stress relaxation in uniaxial stretching-induced crystallization under various strain rates and temperatures. Hereby we extended our parallel study to biaxially stretching-induced crystallization and compared the results also to the cases without stress relaxation. At high temperatures, we observed a significant retardation of onset strains for biaxial crystallization, which could be attributed to the retardation of intermolecular crystal nucleation due to an enhanced stress relaxation among cross-stretching polymers. In consequence, fewer crystallites are generated to yield larger crystallites with a higher content of chain-folding. The more chain-folding favors a continuous biaxial stretching towards ultrathin polyethylene films with thickness down to 12 nm.</div></div>","PeriodicalId":405,"journal":{"name":"Polymer","volume":"328 ","pages":"Article 128446"},"PeriodicalIF":4.1,"publicationDate":"2025-04-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143872415","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Comprehensive Experimental Study of Mechanical Properties, Stress Relaxation, Shape Memory Performance, Thermal Analysis and Morphology of 3D/4D Printed HDPE-PETG","authors":"Tiejun Liu, Ke Chen","doi":"10.1016/j.polymer.2025.128431","DOIUrl":"https://doi.org/10.1016/j.polymer.2025.128431","url":null,"abstract":"This study addresses the critical limitations of 3D printing with high-density polyethylene (HDPE), such as poor printability and lack of smart functionality, by developing novel HDPE-PETG blends that simultaneously enhance printing performance and introduce 4D shape memory capabilities to HDPE. Through systematic characterization of blends containing 15, 30, and 45 wt% PETG, it was demonstrated that 30% PETG content optimally balances mechanical properties, achieving 24.5 MPa tensile strength and 87.2% elongation, and printability, with a reduction in interlayer gaps compared to 15% PETG. Meanwhile, higher PETG content (45%) achieves exceptional shape memory performance with 89.0% fixity and 75.7% recovery. Dynamic mechanical analysis reveals PETG's glass transition (80°C) as the shape memory switching temperature, with SEM confirming an immiscible two-phase morphology that synergistically combines HDPE's structural integrity with PETG's thermal responsiveness. Stress relaxation also increased with increasing PETG and the HDPE with a semi-crystalline structure improves stress relaxation resistance. These results establish HDPE-PETG as a novel material system that transforms conventional HDPE into a versatile, sustainable feedstock for advanced 3D/4D printing applications, overcoming processing challenges while adding smart functionality for the first time. Also, the results indicate excellent synergy in the blends due to the use of stress relaxation resistance, recyclability, low cost due to HDPE and excellent 3D printability, shape memory effect and mechanical properties due to PETG.","PeriodicalId":405,"journal":{"name":"Polymer","volume":"42 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-04-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143872419","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Degradation behavior and aging mechanisms of silicone rubber under Ultraviolet–Thermal–Humidity Coupling in simulated tropical marine atmospheric environment","authors":"Rui-Yuan Wang ,&nbsp;Zhao-Feng Dou ,&nbsp;Hao-Shan Li ,&nbsp;Ning Li ,&nbsp;Xue-Rong Liu ,&nbsp;Wei-Fang Zhang","doi":"10.1016/j.polymer.2025.128398","DOIUrl":"10.1016/j.polymer.2025.128398","url":null,"abstract":"<div><div>As a high-performance sealing material widely used in equipment, the degradation behavior and aging mechanism of silicone rubber have garnered significant attention under complex service environments. This study systematically investigates the degradation behavior and aging mechanisms of silicone rubber under simulated Ultraviolet(UV)–Thermal–Humidity (UTH) Coupling conditions in a tropical marine atmospheric environment. By establishing a conversion relationship between laboratory indoor radiation and outdoor UV radiation in the South China Sea, an accelerated aging test was designed. Comprehensive analyses of macroscopic physical properties, mechanical performance, and microstructural evolution reveal distinct phase characteristics of silicone rubber aging under coupling conditions. The early stage is dominated by surface cross-linking and initial oxidation induced by the synergistic effects of UV radiation and humidity. The intermediate stage is characterized by degradation reactions, leading to intensified crack propagation and structural reorganization. The late stage is governed by cross-linking reactions, resulting in densified internal structures. Compared to single-factor UV aging, degradation under coupling conditions penetrates deeper into the material, although the failure modes in both environments similarly transition from early-stage ductile fracture to late-stage brittle fracture. This study elucidates the dynamic relationship between the aging process and environmental factors, providing a theoretical foundation for aging analysis and residual life prediction of silicone rubber under complex coupling conditions. These findings may serve as a useful reference for optimizing the service performance of silicone rubber in marine atmospheric environments.</div></div>","PeriodicalId":405,"journal":{"name":"Polymer","volume":"328 ","pages":"Article 128398"},"PeriodicalIF":4.1,"publicationDate":"2025-04-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143876285","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"An Alkynyl-Based Olefin-linked Covalent Organic Framework as an Anode Material for Potassium-ion Batteries","authors":"Bertha Lotsi, Luke Schkeryantz, Chenhao Dang, Abigail M. Houser, Edgar Lopez-Torres, Yiying Wu, Shiyu Zhang, Psaras L. McGrier","doi":"10.1016/j.polymer.2025.128453","DOIUrl":"https://doi.org/10.1016/j.polymer.2025.128453","url":null,"abstract":"Rechargeable batteries, particularly lithium-ion batteries (LIBs), have become the preferred choice for high-performance energy storage systems powering portable electronics. However, potassium-ion batteries (KIBs) are emerging as a viable alternative due to lithium's limited availability and high cost. Covalent organic frameworks (COFs), an advanced class of crystalline porous polymers, have become attractive electrodes for KIBs thanks to their great chemical stabilities and tunable electrochemical properties. In this study, an olefin-linked alkynyl-based COF containing 1,3,5-tri(arylethynyl)benzene (TAEB) and 2,4,6-trimethyl-1,3,5-triazine (TMT) units was utilized as a bulk anode material for KIBs. The TAEB-TMT-COF demonstrated a reversible capacity of 124 mAh g^-1 after 300 cycles with an efficiency of ∼ 99 %. TAEB-TMT-COF also exhibited a reversible capacity of 105 mAh g^-1 after 300 cycles at a high current density of 500 mA g^-1 with ∼ 99 % efficiency. The excellent performance is attributed to the chemical stability of olefin-linkage and the presence of the alkynyl groups, which aid in enhancing the binding of K-ions.","PeriodicalId":405,"journal":{"name":"Polymer","volume":"70 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-04-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143876286","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Intrinsic thermal conductive ultra-high molecular weight polyethylene via cyclic pulsating pressure","authors":"Guang-Ming Huang,&nbsp;Lan-Wei Li,&nbsp;Kang-Wei Xia,&nbsp;Wen-Xu Rao,&nbsp;Jia-Chun Zheng,&nbsp;Chen-Hu Yuan,&nbsp;Jin-Ping Qu,&nbsp;Zhao-Xia Huang","doi":"10.1016/j.polymer.2025.128449","DOIUrl":"10.1016/j.polymer.2025.128449","url":null,"abstract":"<div><div>The miniaturization, integration, and performance enhancement of electronic devices have driven an urgent demand for efficient thermal management. Among which, ultra-high molecular weight polyethylene (UHMWPE) could be considered as a promising candidate due to its inherent high specific strength and theoretically ultra-high intrinsic thermal conductivity, once its chain structure been tailored. However, current methods for preparing intrinsic thermally conductive UHMWPE requires complex post-treatment for the extreme-stretching along machine direction, and can only employed as film and fibers. In this work, we introduce cyclic pulsating pressure (CPP) during the compression molding of UHMWPE, and for the first time, proposed a single-step method for fabricating intrinsic thermally conductive UHMWPE sheet. The evolutions in crystalline structure and molecular chains with different CPP conditions have been comprehensively investigated, and the results suggest that its structural changes with proper selection of the pressure-off period (T_off) in CPP process. Consequently, the as-prepared UHMWPE shows obviously enhancement in its thermal conductivity from 0.619 W/mK for conventional sheet to 3.91 W/mK for the one under CPP with optimized T_off, which is then considered due to the in-plane alignment of crystals. Ultimately, our novel intrinsic thermally conductive UHMWPE sheet was employed to transfer the heat from LED to show its ability as thermal conductive materials. We believe that this work can not only provide a highly thermal conductive polymer sheet with its fabrication protocol, but also supply fundamental insight around the dynamic pressure induced structural evolutions of UHMWPE.</div></div>","PeriodicalId":405,"journal":{"name":"Polymer","volume":"328 ","pages":"Article 128449"},"PeriodicalIF":4.1,"publicationDate":"2025-04-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143876256","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Research on performances and retarded recovery process of disentangled long chain branched polypropylene prepared by solution method","authors":"Jiangtao Li,&nbsp;Mingjin Liu,&nbsp;Yanjiang Li,&nbsp;Jie Min,&nbsp;Zheng Yan,&nbsp;Jie Zhang","doi":"10.1016/j.polymer.2025.128424","DOIUrl":"10.1016/j.polymer.2025.128424","url":null,"abstract":"<div><div>Freeze-drying of dilute polymer solution is a widely accepted method to yield disentangled polymer. Many researches have pointed out that reduction of entanglement density has a big impact on rheology and crystallization behavior of polymer, but the re-entangling would take place in the case of reheating, which is unfavorable to the secondary processing of disentangled polymer. The branched structure of polymer could slow down the relaxation process of the molecular chain, which may delay the recovery of entanglement. In this work, the disentangled long chain branched polypropylene (LCB-PP) was prepared by solution method. The rheological behavior, crystallization behavior, entanglement recovery and mechanical performance of disentangled LCB-PP were investigated. The results showed that the moduli and complex viscosity of LCB-PP decreases with entanglement density decreasing. The disentanglement of LCB-PP has significantly positive effect on crystallization kinetics, while slightly affects the yield strength, elastic modulus and elongation at break. The entanglement recovery time of LCB-PP is much longer than that of i-PP which indicates the retardation effect of LCB structure on entanglement recovery.</div></div>","PeriodicalId":405,"journal":{"name":"Polymer","volume":"328 ","pages":"Article 128424"},"PeriodicalIF":4.1,"publicationDate":"2025-04-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143872420","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Mathematical modeling of swelling and shrinking dynamics in pH-sensitive hydrogels composed of alginate, anionic cellulose, and chitosan","authors":"Aleš Ručigaj,&nbsp;Tilen Kopač","doi":"10.1016/j.polymer.2025.128452","DOIUrl":"10.1016/j.polymer.2025.128452","url":null,"abstract":"<div><div>This study develops a mathematical model to predict the swelling and shrinkage dynamics of pH-sensitive hydrogels composed of alginate, TEMPO-oxidized cellulose nanofibers (TOCNF), or chitosan. We investigated the effects of biopolymer type, cross-linking density, and/or pH conditions on hydrogel behavior. Swelling and shrinkage experiments revealed that cross-link density primarily governs the final equilibrium state but may also modulate the swelling and shrinkage rate under specific environmental conditions. To quantify this behavior, we introduce a novel parameter, the swelling/shrinkage affinity (<em>a</em>_sw, <em>a</em>_sh), which enables predictive evaluation of hydrogel responsiveness. The model integrates experimental data with rheological measurements, linking cross-link density to mechanical properties such as shear modulus. Rheological measurements validated the findings, correlating mechanical properties with cross-link density and aligning with swelling and shrinkage data. This work enhances the fundamental understanding of hydrogel behavior and offers a predictive tool for optimizing formulations in biomedical, environmental, and industrial applications. This framework may be extended in future work to incorporate external stimuli such as temperature or electromagnetic fields, potentially broadening the application of smart hydrogel systems.</div></div>","PeriodicalId":405,"journal":{"name":"Polymer","volume":"328 ","pages":"Article 128452"},"PeriodicalIF":4.1,"publicationDate":"2025-04-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143872418","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"The unique dynamics of water and polymer in polyethylene imine–water mixtures across the glass transition","authors":"K.P Safna Hussan ,&nbsp;Shiori Inoue ,&nbsp;Yuka Arai ,&nbsp;Kaito Sasaki ,&nbsp;Rio Kita ,&nbsp;Takeru Ito ,&nbsp;Shin Yagihara ,&nbsp;Naoki Shinyashiki","doi":"10.1016/j.polymer.2025.128447","DOIUrl":"10.1016/j.polymer.2025.128447","url":null,"abstract":"<div><div>This study investigates the molecular dynamics of polyethyleneimine (PEI)-water mixtures (100–50 wt% PEI) at subzero temperatures without ice formation, leveraging broadband dielectric spectroscopy. PEI's electrolytic nature and hydrogen bonding capabilities influence relaxation times (<em>τ</em>), strength (<em>Δε</em>), glass transition temperature (<em>T</em>_g), and fragility (m). Pure PEI exhibits slower α-relaxation from cooperative polymer segment motion and faster Johari-Goldstein (JG)-β-relaxation. In addition, <em>ν</em> process due to water molecules was observed from 95 wt% of PEI downwards. PEI-water mixtures exhibit unique relaxation dynamics compared to other polymer-water systems, such as polyvinyl pyrrolidone (PVP) and poly (vinyl methyl ether) (PVME), showing minimal plasticization by water down to a critical PEI concentration of 70 wt%. Strong hydrogen bonding between PEI and water increases <em>T</em>_g and ν-process relaxation times, preventing ice crystallization. These interactions yield concentration-independent relaxation dynamics (<em>τ</em>_α<em>,</em> <em>τ</em>_ν<em>,</em> <em>T</em>_gν and <em>T</em>_gα) in 95-70 wt % PEI-water mixtures compared to those in PVP and PVME-water mixtures. X-ray diffraction (XRD) patterns confirm these findings: amorphous PEI shows a broad peak at 2θ = 20°, which weakens and splits at 70 wt% PEI into peaks at 2θ = 15° and 24°, indicating amorphous ice. Molecular dynamics (MD) simulations reveal a cohesive energy density of 1.50 × 10⁹ J/m³, dominated by electrostatic interactions (1.40 × 10⁹ J/m³) with minor van der Waals contributions (9.9 × 10⁷ J/m³). FTIR spectroscopy highlights a broad, intense peak (3750–2500 cm⁻¹), confirming hydrogen bonding's role in PEI's structure and dynamics. These findings underscore PEI's unique capacity to prevent ice formation and maintain water at low temperatures despite its low <em>T</em>_g.</div></div>","PeriodicalId":405,"journal":{"name":"Polymer","volume":"328 ","pages":"Article 128447"},"PeriodicalIF":4.1,"publicationDate":"2025-04-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143866474","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"The effect of deformation temperature on microstructure and properties of die-drawn iPP/HDPE blends","authors":"Xuan Qin ,&nbsp;Ying Lu ,&nbsp;Dong Lyu ,&nbsp;Fin Caton-Rose ,&nbsp;Phil Coates ,&nbsp;Yongfeng Men","doi":"10.1016/j.polymer.2025.128448","DOIUrl":"10.1016/j.polymer.2025.128448","url":null,"abstract":"<div><div>It is urgent to recycle non-degradable waste plastics. Conventional mechanical recycling requires sorting different types of polymer materials which is quite expensive or even not practical. Hence it is crucial to develop a processing method for incompatible polymer blends. In this work, we successfully processed isotactic polypropylene (iPP) and high-density polyethylene (HDPE) blends via a die-drawing process at different temperatures. It turned out that changing the deformation temperature could influence the microstructure and properties of the die-drawn samples. For samples deformed at temperatures below the melting point of HDPE, the molecular chain orientation and long period increased markedly after die-drawing, while this increase was less significant for samples deformed at temperatures above the melting point of HDPE. Subsequently, the former samples exhibited better thermal stability and mechanical properties than both the latter samples and the undeformed samples. The Young's modulus is more than two times and the fracture stress is more than five times the values determined for the undeformed sample. As for the samples deformed at temperatures above the melting point of HDPE, their fracture stress doubled comparing to the one of undeformed sample, despite voids with dimensions of several hundreds of nanometers which were observed in these samples.</div></div>","PeriodicalId":405,"journal":{"name":"Polymer","volume":"328 ","pages":"Article 128448"},"PeriodicalIF":4.1,"publicationDate":"2025-04-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143866471","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Self-nucleation effect in crystallization of Poly(propylene-co-ethylene-co-1-butene) terpolymers","authors":"Pingjun Shao ,&nbsp;Xinyu Liu ,&nbsp;Youxu Chen ,&nbsp;Li Pan ,&nbsp;Yuesheng Li ,&nbsp;Zhe Ma","doi":"10.1016/j.polymer.2025.128436","DOIUrl":"10.1016/j.polymer.2025.128436","url":null,"abstract":"<div><div>The self-nucleation effect on crystallization kinetics and polymorphism in poly(propylene-co-ethylene-co-1-butene) terpolymer was investigated using differential scanning calorimetry and wide-angle X-ray diffraction. The incorporation of ethylene and 1-butene comonomers induces the occurrence of self-nucleation, which hardly appears in customary isotactic polypropylene homopolymer. Within the incorporation range of 5.5–12.7 mol%, self-nucleation effect could increase the crystallization peak temperature by around 17 °C with respect to the relaxed melt. However, the temperature window of self-nucleation Domain II decreased with increasing comonomer content, where Domain IIa was absent at 12.7 mol%. The successive self-nucleation and annealing (SSA) analysis revealed that the three terpolymers studied exhibited similar regular sequence lengths but various distributions, where the diminishing of the self-nucleation effect was correlated to the reduction in long regular sequences. Additionally, the incorporation of ethylene and 1-butene comonomers facilitated formation of the triclinic γ form, which could be tuned by self-nucleation temperature <em>T</em>_s. In Domain I, the amount of γ form with respect to α form was kept constant. Interestingly, enhancing self-nucleation by lowering <em>T</em>_s significantly increased the content of γ form, as self-nucleation accelerated crystallization kinetics and increased the cooling crystallization temperature. However, the further reduction of <em>T</em>_s within Domain III favored the formation of α form by preserving crystallites from partial melting and reducing regular sequences for the subsequent crystallization.</div></div>","PeriodicalId":405,"journal":{"name":"Polymer","volume":"328 ","pages":"Article 128436"},"PeriodicalIF":4.1,"publicationDate":"2025-04-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143866144","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}