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Synthesis and characterization of a new polyimine-modified electrode for voltammetric determination of copper and cadmium ions using square wave voltammetry 方波伏安法测定铜和镉离子用聚酰亚胺修饰电极的合成与表征
IF 2.8 4区 化学 Q3 POLYMER SCIENCE Pub Date : 2026-01-09 DOI: 10.1007/s10965-025-04724-2
Sajida J. Kadhim, Mohammed Qasim Mohammed, Jasim M. Alshawi

Modified polymer electrodes are of particular importance in analytical and environmental applications. The goal of this paper is the modification of a polymer surface for sensing applications and the detection of trace- metal ions in aqueous solution. This study offers a novel electrochemical sensing device to detection copper and cadmium ions, created via modifying a glassy carbon electrode GC with a polyimine based pyrrole by using square wave voltammetry. Polyimine polymer film was characterized and examined via Fourier transform infrared (FTIR) spectroscopy, cyclic voltammetry (CV), and scanning electron microscopy (SEM). Spectroscopic devices were employed to identify the chemical structure of the prepared monomer, such as FTIR, 1H NMR, 13C NMR, and mass spectroscopy. Furthermore, rate of scan effects on the electrical performance of the polyimine film was also examined. Electro- experimental data were employed to calculate coverage of surface’s substance and their electrical stability in blank solutions. Polyimine film thickness and the effects of (pH) of the medium were also investigated. Linear responses to Cu(II) and Cd(II) ions in the range of concentration (5 to 100 µg L− 1) were acquired. Limit of detection (LOD) for the assay of Cu2+ and Cd2+ ions were 1.81 µg L− 1 and 2.68 µg L− 1, respectively. Encouraging results above indicated that modified polyimine films could potentially represent a viable candidate for electrochemical-sensor technologies.

改性聚合物电极在分析和环境应用中尤为重要。本文的目的是对聚合物表面进行改性,用于传感应用和水溶液中痕量金属离子的检测。本研究利用方波伏安法,将聚酰亚胺基吡咯修饰在玻碳电极GC上,建立了一种检测铜和镉离子的新型电化学传感装置。采用傅里叶变换红外光谱(FTIR)、循环伏安法(CV)和扫描电镜(SEM)对聚亚胺聚合物薄膜进行了表征和表征。采用FTIR、1H NMR、13C NMR、质谱等光谱设备对所制备单体的化学结构进行鉴定。此外,还研究了扫描速率对聚酰亚胺薄膜电性能的影响。利用电实验数据计算了表面物质的覆盖率及其在空白溶液中的电稳定性。考察了聚酰亚胺膜厚度和介质pH值的影响。对Cu(II)和Cd(II)离子在浓度范围(5 ~ 100µg L−1)内的线性响应。Cu2+和Cd2+的检出限分别为1.81µg L−1和2.68µg L−1。上述令人鼓舞的结果表明,改性聚酰亚胺薄膜可能成为电化学传感器技术的可行候选材料。
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引用次数: 0
Optimization of freeze–thawed humic acid/polyvinyl alcohol supramolecular hydrogels via Taguchi method: structural, mechanical, and biological evaluations 通过田口法优化冻融腐植酸/聚乙烯醇超分子水凝胶:结构、力学和生物学评价
IF 2.8 4区 化学 Q3 POLYMER SCIENCE Pub Date : 2026-01-08 DOI: 10.1007/s10965-025-04733-1
Yao-En Cai, Yu-Hsien Huang, Ke-Hung Tsui, Andrew E.-Y. Chuang, Shu-Fang Huang, Kuan-Ting Lee, Yi-Hsuan Lin

This study presents the development and optimization of humic acid/polyvinyl alcohol (HA/PVA) supramolecular hydrogels via the Taguchi method and cyclic freeze–thaw processing. Humic acid was extracted from spent coffee grounds and incorporated into a polyvinyl alcohol matrix to fabricate physically crosslinked hydrogels. The structural, mechanical, and biological properties of these hydrogels were systematically evaluated, focusing on key formulation parameters such as HDOM (humic dissolved organic matter) concentration, crosslinker dosage, and freeze–drying cycles. The results revealed that the number of freeze–thaw cycles was the most influential factor in enhancing mechanical strength, while optimal HA content significantly improved compressive stress by ~ 40%. Scanning electron microscopy confirmed the formation of a porous network favorable for nutrient diffusion and cellular attachment. In vitro assays confirmed excellent cytocompatibility, with extract dilutions (25–75%) significantly enhancing fibroblast proliferation and migration compared to control. The wound healing assay further demonstrated accelerated scratch closure most notably in the 75% group highlighting the hydrogel’s strong pro-migratory effect and its promising potential for soft tissue regeneration. The combination of structural integrity, biocompatibility, and tunable bioactivity positions these HA/PVA hydrogels as promising materials for wound healing and tissue engineering applications.

采用田口法和循环冻融工艺对腐植酸/聚乙烯醇(HA/PVA)超分子水凝胶进行了开发和优化。从废咖啡渣中提取腐植酸,并将其掺入聚乙烯醇基质中制备物理交联水凝胶。系统评价了这些水凝胶的结构、力学和生物学性能,重点评价了关键配方参数,如HDOM(腐殖质溶解有机物)浓度、交联剂用量和冷冻干燥周期。结果表明,冻融循环次数是提高混凝土机械强度的最重要因素,而最佳HA含量可显著提高约40%的压应力。扫描电镜证实形成有利于营养物质扩散和细胞附着的多孔网络。体外实验证实了出色的细胞相容性,与对照相比,提取物稀释度(25-75%)显著增强了成纤维细胞的增殖和迁移。伤口愈合实验进一步显示,75%浓度组的划痕愈合速度加快,突出了水凝胶强大的促迁移作用和软组织再生的潜力。结构完整性、生物相容性和可调节的生物活性使这些HA/PVA水凝胶成为伤口愈合和组织工程应用的有前途的材料。
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引用次数: 0
Epoxy resin-modified polysiloxane microspheres with dual-functionality: superhydrophobicity and high-haze light diffusion 具有双重功能的环氧树脂改性聚硅氧烷微球:超疏水性和高雾光扩散
IF 2.8 4区 化学 Q3 POLYMER SCIENCE Pub Date : 2026-01-08 DOI: 10.1007/s10965-025-04742-0
Haipeng Zou, Ting He, Xinmei Yan, Zichen Zhang, Guanghao Chen, Yan Jiang, Hongwen Zhang

In this paper, amino-terminated polymethylvinylsiloxane was synthesized via anionic ring-opening polymerization using Octamethylcyclotetrasiloxane (D4), 2, 4, 6, 8-tetramethyl-2, 4, 6, 8-tetravinyl cyclotetrasiloxane (D4V), 1, 3-Bis (3-aminopropyl) -1, 1, 3, 3 tetramethyldisiloxane (AT) as precursors, followed by modification with epoxy resin. Subsequently, a hydrosilylation reaction with hydrogen-containing silicone oil was conducted. This process produced microspheres where the epoxy modification and crosslinking induced the formation of a surface micro-nano rough structure. This specific topography, combined with the low surface energy of polysiloxane, resulted in superhydrophobicity. The optimal formulation was determined through orthogonal experimental design. Under the conditions of 20 wt% epoxy resin content, a vinyl-to-active hydrogen ratio of 1:2, and hydrosilylation reaction parameters of 85 °C for 4 h, the microspheres exhibited superior hydrophobicity and surface morphology, achieving a water contact angle of 154.2°. They were incorporated into a polydimethylsiloxane (PDMS) matrix to fabricate light diffusion materials. The composite with 5 wt% loading exhibited an excellent balance of optical properties, achieving a high light transmittance of 82.4% and a high haze of 90.8% (> 770% increase compared to pure PDMS). Additionally, the composite surface maintained a hydrophobic state (WCA of 128.9°). These findings demonstrate the potential of these bifunctional microspheres in self-cleaning LED lighting applications.

本文以八甲基环四硅氧烷(D4)、2,4,6,8 -四甲基- 2,4,6,8 -四甲基环四硅氧烷(D4V)、1,3 -二(3-氨基丙基)- 1,1,3,3四甲基二硅氧烷(AT)为前驱体,通过阴离子开环聚合法制备了氨基端聚甲基乙烯硅氧烷。随后,与含氢硅油进行了硅氢化反应。该工艺生产的微球,其中环氧改性和交联诱导表面微纳粗糙结构的形成。这种特殊的形貌,加上聚硅氧烷的低表面能,导致了超疏水性。通过正交试验设计确定最佳配方。在环氧树脂含量为20 wt%、乙烯基与活性氢比为1:2、硅氢化反应参数为85℃、反应时间为4 h的条件下,微球表现出优异的疏水性和表面形貌,水接触角达到154.2°。它们被掺入聚二甲基硅氧烷(PDMS)基质中以制造光扩散材料。负载为5 wt%的复合材料表现出良好的光学性能平衡,达到82.4%的高透光率和90.8%的高雾度(与纯PDMS相比增加了770%)。复合材料表面保持疏水状态(WCA为128.9°)。这些发现证明了这些双功能微球在自清洁LED照明应用中的潜力。
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引用次数: 0
The effect of the molecular weight of PEG and PCL on the physical, mechanical, and shape memory properties of polyurethane with dual-responsive behavior PEG和PCL分子量对双响应聚氨酯物理、力学和形状记忆性能的影响
IF 2.8 4区 化学 Q3 POLYMER SCIENCE Pub Date : 2026-01-08 DOI: 10.1007/s10965-025-04639-y
Pooria Hoseinzadeh, Zahra Telikani, Fatemeh Sajedi bejandi, Reza Lotfi Mayan Sofla

Shape memory polyurethanes are smart materials that give back their original shape once stimulated by heat or water, rendering them ideal for certain biomedical applications such as minimally invasive surgery or drug delivery. In this research, dual-responsive SMPUs were synthesized successfully through the use of polycaprolactone (PCL) (2000/4000 g/mol) and poly(ethylene glycol) (PEG) (400/4000 g/mol) in a 30/70 weight ratio. Microstructural analysis showed that among all the parameters, crystallinity of the soft segments dominated in governing the elastic modulus because the crystalline regions were much stiffer than the hard segment domains. These SMPUs showed excellent mechanical properties with tensile strengths ranging from 5.8 to 11.2 MPa and elongation at break ranging from 150 to 310%. The shape memory behavior of these SMPUs was extraordinary with shape fixity ratios of greater than 95% and recovery ratios of 98% at 65 °C. They also attained almost 92% recovery in water at 37 °C. Thermal analysis (DSC) revealed that the dual-responsiveness is due to a “phase-switching” mechanism where the crystalline soft segments (PCL/PEG) constitute the reversible switch that fixes the temporary shape and releases it, and the hard segments form the permanent netpoints which memorize the original shape. The improved water-driven recoveries are further correlated to the increase of the overall crystallinity (from 32% to 46%), with high polyol molecular weights that enhance the switching. Thus, these results prove the suitability of the synthesized SMPU materials for advanced biomedical applications.

形状记忆聚氨酯是一种智能材料,一旦受到热或水的刺激,就会恢复原来的形状,使其成为某些生物医学应用的理想选择,如微创手术或药物输送。本研究以聚己内酯(PCL) (2000/4000 g/mol)和聚乙二醇(PEG) (400/4000 g/mol)为原料,以30/70的质量比成功合成了双响应的smpu。显微组织分析表明,在所有参数中,软段的结晶度对弹性模量起主导作用,因为软段的结晶度比硬段的要硬得多。smpu具有优异的力学性能,抗拉强度为5.8 ~ 11.2 MPa,断裂伸长率为150 ~ 310%。这些smpu具有优异的形状记忆性能,在65°C下形状固着率大于95%,恢复率为98%。在37°C的水中,它们也达到了近92%的回收率。热分析(DSC)揭示了双响应性是由于“相位开关”机制,其中晶体软段(PCL/PEG)构成固定和释放临时形状的可逆开关,而硬段形成记忆原始形状的永久网络点。水驱动回收率的提高与整体结晶度的提高(从32%提高到46%)进一步相关,高多元醇分子量增强了转换。因此,这些结果证明了合成的SMPU材料在先进生物医学应用中的适用性。
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引用次数: 0
Developing dual-functional self-healing and anti-corrosion solvent-based epoxy coatings containing MXene-nanosheets decorated with benzotriazole-encapsulated bowl-shaped mesoporous polydopamine nanocontainers 用苯并三唑包封碗状介孔聚多巴胺纳米容器装饰mxene纳米片,制备双功能自愈防腐溶剂型环氧涂料
IF 2.8 4区 化学 Q3 POLYMER SCIENCE Pub Date : 2026-01-07 DOI: 10.1007/s10965-025-04737-x
Xiaohong Ji, Jingqiang Su, Zhen Wang, Quanqing Wu, Zixue Zhang, Yuefeng Tian, Liangliang Zhou, Guanghua Hu, Yunfei Yang, Sepideh Pourhashem, Huiwen Tian, Jizhou Duan, Baorong Hou

In this research, benzotriazole (BTA) is encapsulated as a corrosion inhibitor within bowl-shaped mesoporous polydopamine nanocontainers (MPDA), followed by decorating on the surface of the Ti3C2Tx MXene nanosheets and modifying with 3-aminopropyltriethoxysilane, and the synthesized Silane-MXene@MPDA-BTA is loaded in the weight percentages of 0.1 within solvent-based epoxy coating to apply on the carbon steel. The structure and morphology of the Silane-MXene@MPDA-BTA is considered using transmission electron microscopy, Fourier transform infrared spectroscopy, and thermogravimetric analysis. Besides, the corrosion resistance and self-healing performance of the nanofiller loaded epoxy coating are investigated by electrochemical impedance spectroscopy and salt spray tests. The results proved the barrier effect of the prepared MXene-based nanosheets through increasing the low-frequency impedance modulus to 9.76 × 109 Ω.cm2, compared to 9.35 × 105 Ω.cm2 for the blank sample after 60 days of immersion in the 3.5 wt% NaCl solution. Also, the self-healing efficiency of the scratched nanofiller system is about 94.5% (based on changes on charge transfer resistance) after 14 days of immersion.

本研究将苯并三唑(BTA)作为缓蚀剂包封在碗状介孔聚多巴胺纳米容器(MPDA)内,然后在Ti3C2Tx MXene纳米片表面进行修饰,再用3-氨基丙基三乙氧基硅烷进行改性,将合成的Silane-MXene@MPDA-BTA以0.1的质量百分比负载在溶剂型环氧涂层中,涂覆在碳钢表面。利用透射电子显微镜、傅里叶变换红外光谱和热重分析研究了Silane-MXene@MPDA-BTA的结构和形态。此外,通过电化学阻抗谱和盐雾试验研究了纳米填料负载环氧涂层的耐腐蚀性能和自愈性能。结果表明,制备的mxene基纳米片具有阻隔效应,其低频阻抗模量达到9.76 × 109 Ω.cm2,而空白样品在3.5 wt% NaCl溶液中浸泡60天后的低频阻抗模量为9.35 × 105 Ω.cm2。此外,在浸泡14天后,纳米填料系统的自修复效率约为94.5%(基于电荷转移电阻的变化)。
{"title":"Developing dual-functional self-healing and anti-corrosion solvent-based epoxy coatings containing MXene-nanosheets decorated with benzotriazole-encapsulated bowl-shaped mesoporous polydopamine nanocontainers","authors":"Xiaohong Ji,&nbsp;Jingqiang Su,&nbsp;Zhen Wang,&nbsp;Quanqing Wu,&nbsp;Zixue Zhang,&nbsp;Yuefeng Tian,&nbsp;Liangliang Zhou,&nbsp;Guanghua Hu,&nbsp;Yunfei Yang,&nbsp;Sepideh Pourhashem,&nbsp;Huiwen Tian,&nbsp;Jizhou Duan,&nbsp;Baorong Hou","doi":"10.1007/s10965-025-04737-x","DOIUrl":"10.1007/s10965-025-04737-x","url":null,"abstract":"<div><p>In this research, benzotriazole (BTA) is encapsulated as a corrosion inhibitor within bowl-shaped mesoporous polydopamine nanocontainers (MPDA), followed by decorating on the surface of the Ti<sub>3</sub>C<sub>2</sub>T<sub>x</sub> MXene nanosheets and modifying with 3-aminopropyltriethoxysilane, and the synthesized Silane-MXene@MPDA-BTA is loaded in the weight percentages of 0.1 within solvent-based epoxy coating to apply on the carbon steel. The structure and morphology of the Silane-MXene@MPDA-BTA is considered using transmission electron microscopy, Fourier transform infrared spectroscopy, and thermogravimetric analysis. Besides, the corrosion resistance and self-healing performance of the nanofiller loaded epoxy coating are investigated by electrochemical impedance spectroscopy and salt spray tests. The results proved the barrier effect of the prepared MXene-based nanosheets through increasing the low-frequency impedance modulus to 9.76 × 10<sup>9</sup> Ω.cm<sup>2</sup>, compared to 9.35 × 10<sup>5</sup> Ω.cm<sup>2</sup> for the blank sample after 60 days of immersion in the 3.5 wt% NaCl solution. Also, the self-healing efficiency of the scratched nanofiller system is about 94.5% (based on changes on charge transfer resistance) after 14 days of immersion.</p></div>","PeriodicalId":658,"journal":{"name":"Journal of Polymer Research","volume":"33 1","pages":""},"PeriodicalIF":2.8,"publicationDate":"2026-01-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145930601","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Enhancement of photoluminescence efficiency and optoelectronic/life cycle properties of poly (Thiophene) featured with zinc oxide quantum dots with silver electrode 银电极氧化锌量子点增强聚噻吩的光致发光效率和光电子/生命周期性能
IF 2.8 4区 化学 Q3 POLYMER SCIENCE Pub Date : 2026-01-07 DOI: 10.1007/s10965-025-04734-0
M. Aruna, Nagabhooshanam Nagarajan, Prahalad Singh Parihar, Nilesh Bhosle, S. Supriya, V. S. N. Kumar, Ramya Maranan, Thirugnanasambandham T, S. Sathiyamurthy

Poly (Thiophene) (PTh) is familiar for optoelectronic applications due to strong absorption, better conductivity, and high charge carrier mobility. However, it found low photoluminescence efficiency and variations in electron carrier mobility due to reduced photoluminescence. The motto of current research is to overcome the above drawback and enrich the optoelectronic behaviour of PTh featuring 30, 40, 50, and 60 nm of zinc oxide (ZnO) nanoparticles (20 nm) via the electrochemical deposition method. This structure consists of 100 nm indium tin oxide (ITO), ZnO electron transport layer (ETL), ZnO/PTh active emission layer, PTh hole transport layer (HTL), and 80 nm silver top electrode. The influences of ZnO quantum dot layer thickness and silver top electrode on optical, electrical, stability lifetime, and X-ray diffraction behaviour of PTh quantum dot are evaluated. The structural analyses confirmed improved structural integrity, and the stability evaluations showed enhanced operational lifetime. The 50 nm ZnO:PTh active layer found better functional characteristics like reduced wavelength, enhanced electron voltage, higher photoluminescence efficiency, superior electron mobility, higher current density, and superior lifespan (life cycle), which are 3%, 4.5%, 61.5%, more than 100%, 107%, and more than 100% better than the PTh quantum dot LED.

聚噻吩(PTh)具有强吸收、导电性好、载流子迁移率高等特点,在光电领域应用广泛。然而,它发现低光致发光效率和电子载流子迁移率的变化,由于光致发光减少。目前研究的重点是克服上述缺点,通过电化学沉积方法,以30、40、50和60 nm氧化锌纳米颗粒(20 nm)丰富PTh的光电行为。该结构由100 nm氧化铟锡(ITO)、ZnO电子传输层(ETL)、ZnO/PTh活性发射层、PTh空穴传输层(HTL)和80 nm银顶电极组成。考察了ZnO量子点层厚度和银顶电极对PTh量子点的光学、电学、稳定寿命和x射线衍射行为的影响。结构分析证实结构完整性得到改善,稳定性评估显示使用寿命延长。50nm ZnO:PTh活性层具有波长减小、电子电压增强、光致发光效率高、电子迁移率高、电流密度高、寿命(寿命周期)长等特点,分别比PTh量子点LED高3%、4.5%、61.5%、100%以上、107%和100%以上。
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引用次数: 0
Advanced ballistic protection: enhanced performance of p-aramid fabrics impregnated with novel gels and nanoparticles 先进的弹道防护:增强性能的对芳纶织物浸渍与新型凝胶和纳米颗粒
IF 2.8 4区 化学 Q3 POLYMER SCIENCE Pub Date : 2026-01-07 DOI: 10.1007/s10965-025-04708-2
Dayanne dos Santos Silva, Beatriz da Silva Fernandes, Maurício Ferrapontoff Lemos, André Ben Hur da Silva Figueiredo, Maria de Fátima Vieira Marques

This study reports advanced ballistic fabrics produced by impregnating p-aramid textiles with polyurethane-based gels and fluids derived from polyethylene glycol (PEG) and hydroxyl-terminated polybutadiene (HTPB), reinforced with silica (SiO₂), zinc oxide (ZnO), or boron carbide (B₄C) nanoparticles. The gels were synthesized via in situ crosslinking with 2,4-toluene diisocyanate (TDI), highlighting the potential of polyurethane-based systems for ballistic protection. Analyses revealed strong polymer–filler interactions and improvements in rheological, thermal, and mechanical properties. HTPB-based gels showed high hydrophobicity (contact angles > 110°) and superior ballistic performance compared to PEG-based systems. The HTPB–B₄C composite had the highest energy absorption, while ZnO-based gels achieved the highest projectile velocity limits. These results are comparable to values reported for STF-treated Kevlar® fabrics. To the best of our knowledge, this is among the first systematic comparisons between PEG- and HTPB-based gel systems reinforced with different nanoparticles, applied under identical ballistic testing conditions. Overall, nanoparticle-reinforced polymer gels emerge as promising, lightweight candidates for enhanced ballistic protection.

该研究报告了用聚乙二醇(PEG)和端羟基聚丁二烯(HTPB)衍生的聚氨酯凝胶和液体浸渍对芳纶纺织品,并用二氧化硅(SiO₂)、氧化锌(ZnO)或碳化硼(B₄C)纳米颗粒增强,从而生产出先进的弹道织物。凝胶是通过与2,4-甲苯二异氰酸酯(TDI)原位交联合成的,突出了聚氨酯基系统在弹道防护方面的潜力。分析表明,聚合物与填料之间有很强的相互作用,流变学、热学和机械性能都有所改善。与peg基凝胶相比,htpb基凝胶具有高疏水性(接触角>; 110°)和优越的弹道性能。HTPB-B₄C复合材料的吸能最高,而zno基凝胶的弹丸速度极限最高。这些结果与经stf处理的凯夫拉®织物的报告值相当。据我们所知,这是在相同的弹道测试条件下,首次对不同纳米颗粒增强的PEG-和htpb -凝胶体系进行系统比较。总的来说,纳米颗粒增强聚合物凝胶是增强弹道防护的有前途的轻量级候选材料。
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引用次数: 0
Effect of cross-linking degree on thermal-mechanical properties of vulcanized SBR 交联度对硫化SBR热力学性能的影响
IF 2.8 4区 化学 Q3 POLYMER SCIENCE Pub Date : 2026-01-06 DOI: 10.1007/s10965-025-04743-z
Tian Yan, Kejian Wang, Xiuying Zhao

The thermal-mechanical properties of vulcanized styrene-butadiene rubber (SBR) are fundamentally determined by its cross-linked network structure. However, a systematic understanding of how cross-linking degree influences molecular dynamics and thermal transport remains limited. In this work, we investigate the dual micro-mechanisms through which cross-linking degree (Dc) governs both viscoelastic and thermal properties: namely, the restriction of chain segment mobility and modulation of low-frequency phonon density. The molecular dynamics (MD) simulations coupled with experimental validation are employed to investigate the effect of Dc on shear viscosity(η), bulk viscosity(ηb), specific heat capacity (Cp, Cv), and thermal conductivity(κ). Results demonstrate that increasing Dc enhances intermolecular constraints, leading to a rise in η by 65.5–23.3% and an increase in ηb by 6.6–11.1% under fixed shear conditions. In contrast, increasing shear rate ((dot {gamma })) promotes molecular chain orientation, thereby decreasing η by 83.4–93.2%, while simultaneously strengthening intermolecular forces and constraining chain movement, which increases ηb by 88.6–100.9%. Thermally, κ increases by 48.4% at Dc = 8.0 compared to Dc = 1.0, due to enhanced low-frequency phonon excitation within the tightened network. Furthermore, suppressed chain mobility reduces specific heat capacity by 8.9% (Cp) and 8.6% (Cv) over the temperature range of 300–330 K. These findings establish a clear microstructure–property relationship that elucidates the competing roles of chain dynamics and phonon transport in cross-linking elastomers, providing a theoretical basis for the rational design of vulcanized rubber with tailored multifunctional performance.

硫化丁苯橡胶(SBR)的热力学性能从根本上取决于其交联的网络结构。然而,对交联度如何影响分子动力学和热传递的系统理解仍然有限。在这项工作中,我们研究了交联度(Dc)控制粘弹性和热性能的双重微观机制:即链段迁移率的限制和低频声子密度的调制。采用分子动力学(MD)模拟和实验验证相结合的方法,研究了直流对剪切粘度(η)、体积粘度(ηb)、比热容(Cp、Cv)和导热系数(κ)的影响。结果表明,增大Dc可增强分子间约束,η增大65.5 ~ 23.3% and an increase in ηb by 6.6–11.1% under fixed shear conditions. In contrast, increasing shear rate ((dot {gamma })) promotes molecular chain orientation, thereby decreasing η by 83.4–93.2%, while simultaneously strengthening intermolecular forces and constraining chain movement, which increases ηb by 88.6–100.9%. Thermally, κ increases by 48.4% at Dc = 8.0 compared to Dc = 1.0, due to enhanced low-frequency phonon excitation within the tightened network. Furthermore, suppressed chain mobility reduces specific heat capacity by 8.9% (Cp) and 8.6% (Cv) over the temperature range of 300–330 K. These findings establish a clear microstructure–property relationship that elucidates the competing roles of chain dynamics and phonon transport in cross-linking elastomers, providing a theoretical basis for the rational design of vulcanized rubber with tailored multifunctional performance.
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引用次数: 0
Synergistic functionalized polyethylene/attapulgite composites with maleic anhydride and silicone by reactive extrusion for enhanced metal-plastic interfacial adhesion 用反应挤出法制备马来酸酐和有机硅协同功能化聚乙烯/凹凸棒土复合材料以增强金属-塑料界面的附着力
IF 2.8 4区 化学 Q3 POLYMER SCIENCE Pub Date : 2026-01-04 DOI: 10.1007/s10965-025-04738-w
Minglei Hu, Wei Zhang, Bin Hu, Fuqiang Chu, Haicun Yang, Zheng Cao

To enhance both the adhesive strength and cohesion of the adhesive resin, attapulgite (ATP) was chemically modified by peroxy groups to parepared ATP with initiation function (ATP-CPO). Subsequently, a series of high density polyethylene/ATP composites (HDPE/ATP) functionalized with maleic anhydride and vinyl trimethoxysilane were prepared via surface-initiated graft copolymerization. The effects of ATP-CPO dosage on the mechanical, thermal, rheological, and morphological characteristics of the composites were evaluated in detail. It was found that the surface functionalization and reactive extrusion process contributed to the nano-scale dispersion of ATP in the HDPE matrix, forming well-compatibilized nanocomposites consisting of HDPE-g-(MAH-co-VTMS), ATP-g-(MAH-co-VTMS), and more complex MAH/VTMS synergistically functionalized ATP-g-HDPE. When the ATP-CPO content was 4%, the composite exhibited significantly enhanced tensile strength, 180° peel strength, and shear strength, which were 1.4, 26.3, and 21.7 times higher than those of pure HDPE, respectively. Concurrently, the composites displayed higher melting and crystallization temperatures. However, the crystallinity decreased slightly, while the thermal stability was significantly improved. The melt exhibited more pronounced non-Newtonian behavior. Compared to the loss modulus, the storage modulus increased more significantly in the low-frequency region, and a non-terminal effect was observed, which enhanced the structural stability of the system under low-frequency shear stress.

为了提高粘接树脂的粘接强度和内聚性,对凹凸棒土(ATP)进行过氧基化学修饰,制备了具有引发功能的ATP (ATP- cpo)。随后,采用表面引发接枝共聚法制备了一系列以马来酸酐和乙烯基三甲氧基硅烷为功能化的高密度聚乙烯/ATP复合材料(HDPE/ATP)。详细评价了ATP-CPO用量对复合材料力学、热、流变和形态特性的影响。研究发现,表面功能化和反应挤出过程有助于ATP在HDPE基体中的纳米级分散,形成由HDPE-g-(MAH-co-VTMS)、ATP-g-(MAH-co-VTMS)和更复杂的MAH/VTMS协同功能化的ATP-g-HDPE组成的相容性良好的纳米复合材料。当ATP-CPO含量为4%时,复合材料的抗拉强度、180°剥离强度和抗剪强度分别比纯HDPE提高1.4倍、26.3倍和21.7倍。同时,复合材料表现出较高的熔融和结晶温度。结晶度略有下降,热稳定性明显提高。熔体表现出更明显的非牛顿行为。与损耗模量相比,存储模量在低频区增加更为显著,存在非终端效应,增强了系统在低频剪切应力下的结构稳定性。
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引用次数: 0
Effect of PEG-Induced stereocomplexation on crystallization behavior of PLA/PVA blends 聚乙二醇诱导立体络合对聚乳酸/聚乙烯醇共混物结晶行为的影响
IF 2.8 4区 化学 Q3 POLYMER SCIENCE Pub Date : 2026-01-04 DOI: 10.1007/s10965-025-04744-y
Yottha Srithep, Jun Shen, Arissara Phosanam, Nutnicha Imnamkhao, Dutchanee Pholharn

This study investigates the effect of polyethylene glycol (PEG) on the crystallization behavior of polylactide (PLA) and polyvinyl alcohol (PVA) blends with stereocomplex (SC) formation. PLA was prepared using equimolar blends of PLLA and PDLA, with PVA and varying amounts of PEG (0–5 wt%) incorporated as a compatibilizer and crystallization modifier. Differential scanning calorimetry (DSC) was employed to analyze crystallization and melting behavior under various cooling rates. Results show that PEG significantly enhanced stereocomplex formation, as evidenced by a higher melting temperature (~ 230 °C) and increased SC crystallinity. At 5 wt% PEG, crystallization occurred faster and more completely, with the disappearance of homocrystal peaks. Non-isothermal kinetics were evaluated using the Avrami and Mo models, revealing that PEG and PVA accelerated primary crystallization while reducing activation energy. The Mo method provided better linear fits across different crystallization fractions. These findings demonstrate that PEG serves not only as a compatibilizer but also as an effective nucleating agent, enabling tunable crystallization behavior in PLLA/PDLA/PVA blends. The developed approach holds promise for controlling thermal and structural properties in biodegradable polymer systems.

Graphical abstract

研究了聚乙二醇(PEG)对立体络合物形成的聚乳酸(PLA)和聚乙烯醇(PVA)共混物结晶行为的影响。用PLLA和PDLA的等摩尔共混物制备PLA,加入PVA和不同量的PEG (0-5 wt%)作为相容剂和结晶改性剂。采用差示扫描量热法(DSC)分析了不同冷却速率下的结晶和熔化行为。结果表明,聚乙二醇显著促进了立体配合物的形成,表现为较高的熔融温度(~ 230℃)和SC结晶度的提高。在5 wt% PEG时,结晶发生得更快、更彻底,均晶峰消失。使用Avrami和Mo模型对非等温动力学进行了评估,结果表明PEG和PVA加速了一次结晶,同时降低了活化能。钼法在不同结晶组分间提供了较好的线性拟合。这些发现表明,PEG不仅可以作为相容剂,还可以作为有效的成核剂,在PLLA/PDLA/PVA共混物中实现可调的结晶行为。所开发的方法有望控制可生物降解聚合物系统的热性能和结构性能。图形抽象
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Journal of Polymer Research
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