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Improvements in Injection Moulds Cooling and Manufacturing Efficiency Achieved by Wire Arc Additive Manufacturing Using Conformal Cooling Concept. 采用共形冷却概念的线弧快速成型技术提高了注塑模具的冷却和制造效率。
IF 4.7 3区 工程技术 Q1 POLYMER SCIENCE Pub Date : 2024-10-30 DOI: 10.3390/polym16213057
Alejandro Marqués, Jose Antonio Dieste, Iván Monzón, Alberto Laguía, Pascual Gracia, Carlos Javierre, Isabel Clavería, Daniel Elduque

The plastic injection moulding industry is a constantly developing industrial field. This industrial process requires the manufacturing of metal moulds using complex heating and cooling systems. The purpose of this research is to optimize both the plastic injection moulding process and the mould manufacturing process itself by combining practices in this industry with current additive manufacturing technologies, specifically Wire Arc Additive Manufacturing (WAAM) technology. A mould punch was manufactured by using both WAAM technology, whose internal cooling system has been designed under the concept of Conformal Cooling, and conventional cooling channel designs and manufacturing techniques in order to carry out a comparative analysis. Theoretical results obtained by CAE methods showed an improvement in heat extraction in the WAAM mould. In addition, the WAAM mould was able to achieve better temperature homogeneity in the final part, minimizing deformations in the final part after extraction. Finally, the WAAM manufacturing process was proven to be more efficient in terms of material consumption than the conventional mould, reducing the buy-to-fly ratio of the part by 5.11.

注塑成型工业是一个不断发展的工业领域。这一工业流程需要使用复杂的加热和冷却系统制造金属模具。本研究的目的是通过将注塑成型工艺与当前的快速成型技术(特别是线弧快速成型技术)相结合,优化注塑成型工艺和模具制造工艺本身。为了进行比较分析,采用 WAAM 技术(其内部冷却系统是根据共形冷却概念设计的)和传统的冷却通道设计和制造技术制造了一个模具冲头。通过 CAE 方法获得的理论结果表明,WAAM 模具的散热效果有所改善。此外,WAAM 模具还能在最终零件中实现更好的温度均匀性,最大限度地减少最终零件在萃取后的变形。最后,WAAM 制造工艺在材料消耗方面比传统模具更有效率,零件的买飞比降低了 5.11。
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引用次数: 0
The Impact of Chlorinated Water and Sun Exposure on the Durability and Performance of Swimwear Materials. 氯化水和日晒对泳装材料耐久性和性能的影响
IF 4.7 3区 工程技术 Q1 POLYMER SCIENCE Pub Date : 2024-10-30 DOI: 10.3390/polym16213050
Vesna Marija Potočić Matković, Ivana Salopek Čubrić, Katarina Krstović

Understanding the factors that affect how materials age is essential for creating a durable product with long-lasting properties. It is also important to prioritize defining aging parameters that reflect the real-world conditions the materials will encounter. For this study, a range of swimwear materials were selected consisting of a blend of polymer (polyamide/polyester) and elastane in varying ratios. In order to simulate aging conditions, materials were immersed in chlorinated outdoor pool water during the summer season, either in shade or the sun, for 200 and 300 h. The materials were tested for mass per unit area, thickness, tensile properties, and moisture management. A slight mass per unit area increase was observed, rising from 1.0% after 200 h of chlorine and sunlight exposure to 3.7% after 300 h. Thickness increased by 1.7% after 200 h and 3.2% after 300 h of chlorine exposure, with no significant effect of sunlight. Breaking force dropped by 12.4% after 200 h in chlorine and 8.2% in chlorine and sunlight, becoming more pronounced after 300 h (65.7% in chlorine and 65.1% in chlorine and sunlight). The overall moisture management capability declined from 0.4888 to 0.3457 after 200 h in chlorine and 0.3393 with sunlight, dropping further after 300 h to 0.3838 and 0.3253, respectively.

了解影响材料老化的因素对于制造具有持久特性的耐用产品至关重要。同样重要的是,要优先确定能反映材料实际使用条件的老化参数。在这项研究中,我们选择了一系列由不同比例的聚合物(聚酰胺/聚酯)和弹性纤维混合物组成的泳装材料。为了模拟老化条件,在夏季将材料浸泡在室外氯化池水中,在阴凉处或阳光下分别浸泡 200 小时和 300 小时。氯和阳光照射 200 小时后,单位面积的质量略有增加,从 1.0% 增加到 300 小时后的 3.7%;氯照射 200 小时后,厚度增加了 1.7%,300 小时后增加了 3.2%,阳光照射没有明显影响。在氯气中暴露 200 小时后,断裂力下降了 12.4%,在氯气和阳光下暴露 300 小时后,断裂力下降了 8.2%,在氯气中暴露 300 小时后,断裂力下降更为明显(在氯气中暴露 65.7%,在氯气和阳光下暴露 65.1%)。总体水分管理能力在氯气中 200 小时后从 0.4888 降至 0.3457,在阳光下为 0.3393,300 小时后进一步降至 0.3838 和 0.3253。
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引用次数: 0
Innovative Materials for High-Performance Tin-Based Perovskite Solar Cells: A Review. 用于高性能锡基包晶石太阳能电池的创新材料:综述。
IF 4.7 3区 工程技术 Q1 POLYMER SCIENCE Pub Date : 2024-10-30 DOI: 10.3390/polym16213053
Xiansheng Wang, Jianjun Yang, Jian Zhong, Junsheng Yu, Xinjian Pan

With the rapid development of lead-based perovskite solar cells, tin-based perovskite solar cells are emerging as a non-toxic alternative. Material engineering has been an effective approach for the fabrication of efficient perovskite solar cells. This paper summarizes the novel materials used in tin-based perovskite solar cells over the past few years and analyzes the roles of various materials in tin-based devices. It is found that self-assembling materials and fullerene derivatives have shown remarkable performance in tin-based perovskite solar cells. Finally, this article discusses design strategies for new materials, providing constructive suggestions for the development of innovative materials in the future.

随着铅基透辉石太阳能电池的迅速发展,锡基透辉石太阳能电池正成为一种无毒替代品。材料工程一直是制造高效光致发光太阳能电池的有效方法。本文总结了过去几年中用于锡基包晶石太阳能电池的新型材料,并分析了各种材料在锡基器件中的作用。研究发现,自组装材料和富勒烯衍生物在锡基磷灰石太阳能电池中表现出卓越的性能。最后,本文讨论了新材料的设计策略,为未来创新材料的开发提供了建设性建议。
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引用次数: 0
Characterization of Mixtures Based on High-Density Polyethylene and Plasticized Starch. 基于高密度聚乙烯和塑化淀粉的混合物的表征。
IF 4.7 3区 工程技术 Q1 POLYMER SCIENCE Pub Date : 2024-10-30 DOI: 10.3390/polym16213051
Maria Daniela Stelescu, Ovidiu-Cristian Oprea, Doina Constantinescu, Ludmila Motelica, Anton Ficai, Roxana-Doina Trusca, Maria Sonmez, Dana Florentina Gurau, Mihai Georgescu, Rodica Roxana Constantinescu, Bogdan-Stefan Vasile, Denisa Ficai

This paper presents the obtaining and characterization of blends based on high-density polyethylene (HDPE) and plasticized starch. In addition to plasticized starch (28.8% w/w), the compositions made also contained other ingredients, such as polyethylene-graft-maleic anhydride as a compatibilizer, ethylene propylene terpolymer elastomer, cross-linking agents, and nanoclay. Plasticized starch contains 68.6% w/w potato starch, 29.4% w/w glycerin, and 2% w/w anhydrous citric acid. Blends based on HDPE and plasticized starch were made in a Brabender Plasti-Corder internal mixer at 160 °C, and plates for testing were obtained using the compression method. Thermal analyses indicate an increase in the crystallization degree of the HDPE after the addition of plasticized starch. SEM micrographs indicate that blends are compatibilized, with the plasticized starch being well dispersed as droplets in the HDPE matrix. Samples show high hardness values (62-65° ShD), good tensile strength values (14.88-17.02 N/mm2), and Charpy impact strength values (1.08-2.27 kJ/m2 on notched samples, and 7.96-20.29 kJ/m2 on unnotched samples). After 72 h of water immersion at room temperature, mixtures containing a compatibilizer had a mass variation below 1% and water absorption values below 1.7%. Upon increasing the water immersion temperature to 80 °C, the sample without the compatibilizer showed a mass reduction of -2.23%, indicating the dissolution of the plasticized starch in the water. The samples containing the compatibilizer had a mass variation of max 8.33% and a water absorption of max 5.02%. After toluene immersion for 72 h at room temperature, mass variation was below 8%.

本文介绍了基于高密度聚乙烯(HDPE)和塑化淀粉的混合物的获得和特性分析。除塑化淀粉(28.8% w/w)外,所制得的混合物还含有其他成分,如作为相容剂的聚乙烯接枝马来酸酐、乙烯丙烯三元共聚弹性体、交联剂和纳米粘土。塑化淀粉含有 68.6% w/w 马铃薯淀粉、29.4% w/w 甘油和 2% w/w 无水柠檬酸。以高密度聚乙烯和塑化淀粉为基础的混合物是在 160 °C 下用 Brabender Plasti-Corder 内部混合器制成的,并使用压缩法获得了用于测试的板材。热分析表明,加入塑化淀粉后,高密度聚乙烯的结晶度增加。扫描电镜显微照片显示,混合物具有相容性,塑化淀粉以液滴形式很好地分散在高密度聚乙烯基体中。样品显示出较高的硬度值(62-65° ShD)、良好的拉伸强度值(14.88-17.02 N/mm2)和夏比冲击强度值(缺口样品为 1.08-2.27 kJ/m2,未缺口样品为 7.96-20.29 kJ/m2)。在室温下浸水 72 小时后,含有相容剂的混合物的质量变化低于 1%,吸水率低于 1.7%。当水浸温度升至 80 ℃ 时,未添加相容剂的样品质量减少了 -2.23%,表明塑化淀粉已溶解在水中。含有相容剂的样品质量变化最大为 8.33%,吸水率最大为 5.02%。在室温下用甲苯浸泡 72 小时后,质量变化低于 8%。
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引用次数: 0
On the Valorization of Olive Oil Pomace: A Sustainable Approach for Methylene Blue Removal from Aqueous Media. 橄榄油渣的价值化:从水介质中去除亚甲蓝的可持续方法。
IF 4.7 3区 工程技术 Q1 POLYMER SCIENCE Pub Date : 2024-10-30 DOI: 10.3390/polym16213055
El Mokhtar Saoudi Hassani, Hugo Duarte, João Brás, Abdeslam Taleb, Mustapha Taleb, Zakia Rais, Alireza Eivazi, Magnus Norgren, Anabela Romano, Bruno Medronho

Currently, industrial water pollution represents a significant global challenge, with the potential to adversely impact human health and the integrity of ecosystems. The continuous increase in global consumption has resulted in an exponential rise in the use of dyes, which have become one of the major water pollutants, causing significant environmental impacts. In order to address these concerns, a number of wastewater treatment methods have been developed, with a particular focus on physicochemical approaches, such as adsorption. The objective of this study is to investigate the potential of a bio-based material derived from olive oil pomace (OOP) as an environmentally friendly bio-adsorbent for the removal of methylene blue (MB), a cationic dye commonly found in textile effluents. The biobased material was initially characterized by determining the point of zero charge (pHpzc) and using scanning electron microscopy (SEM), X-ray diffraction (XRD), and Fourier transform infrared spectroscopy (FTIR). Subsequently, a comprehensive analysis was conducted, evaluating the impact of specific physicochemical parameters on MB adsorption, which included a thorough examination of the kinetic and thermodynamic aspects. The adsorption process was characterized using Langmuir, Freundlich, Brunauer-Emmett-Teller (BET), and Dubinin Radushkevich (D-R) isotherms. The results suggest that the equilibrium of adsorption is achieved within ca. 200 min, following pseudo-second-order kinetics. The optimal conditions, including adsorbent mass, temperature, bulk pH, and dye concentration, yielded a maximum adsorption capacity of ca. 93% (i.e., 428 mg g-1) for a pomace concentration of 450 mg L-1. The results suggest a monolayer adsorption process with preferential electrostatic interactions between the dye and the pomace adsorbent. This is supported by the application of Langmuir, BET, Freundlich, and D-R isotherm models. The thermodynamic analysis indicates that the adsorption process is spontaneous and exothermic. This work presents a sustainable solution for mitigating MB contamination in wastewater streams while simultaneously valorizing OOP, an agricultural by-product that presents risks to human health and the environment. In conclusion, this approach offers an innovative ecological alternative to synthetic adsorbents.

目前,工业水污染是一项重大的全球性挑战,有可能对人类健康和生态系统的完整性造成不利影响。全球消费量的持续增长导致染料使用量成倍增加,染料已成为主要的水污染物之一,对环境造成了重大影响。为了解决这些问题,人们开发了许多废水处理方法,尤其侧重于物理化学方法,如吸附法。本研究的目的是调查从橄榄油渣(OOP)中提取的生物基材料作为环保型生物吸附剂去除亚甲基蓝(MB)的潜力,亚甲基蓝是一种常见于纺织污水中的阳离子染料。通过测定零电荷点(pHpzc)以及使用扫描电子显微镜(SEM)、X 射线衍射(XRD)和傅立叶变换红外光谱(FTIR),对这种生物基材料进行了初步表征。随后进行了综合分析,评估了特定理化参数对甲基溴吸附的影响,其中包括对动力学和热力学方面的彻底检查。使用 Langmuir、Freundlich、Brunauer-Emmett-Teller(BET)和 Dubinin Radushkevich(D-R)等温线表征了吸附过程。结果表明,吸附平衡是在大约 200 分钟内达到的,遵循的是假秒阶动力学。最佳条件包括吸附剂质量、温度、体积 pH 值和染料浓度,当渣粕浓度为 450 mg L-1 时,最大吸附容量约为 93%(即 428 mg g-1)。结果表明,在染料和果渣吸附剂之间存在一种优先静电相互作用的单层吸附过程。Langmuir、BET、Freundlich 和 D-R 等温线模型的应用证实了这一点。热力学分析表明,吸附过程是自发和放热的。这项工作为减轻废水中的甲基溴污染提供了一种可持续的解决方案,同时也使对人类健康和环境造成危害的农副产品 OOP 增值。总之,这种方法为合成吸附剂提供了一种创新的生态替代品。
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引用次数: 0
Chitosan Nanoparticles Embedded in In Situ Gel for Nasal Delivery of Imipramine Hydrochloride: Short-Term Stage Development and Controlled Release Evaluation. 壳聚糖纳米颗粒嵌入原位凝胶用于盐酸丙咪嗪的鼻腔给药:短期阶段开发与控释评估》。
IF 4.7 3区 工程技术 Q1 POLYMER SCIENCE Pub Date : 2024-10-30 DOI: 10.3390/polym16213062
Samer Adwan, Teiba Obeidi, Faisal Al-Akayleh

Imipramine hydrochloride (IMP), a tricyclic antidepressant used for major depression, enuresis, and neuropathic pain, is limited by gastrointestinal complications, low oral bioavailability (44%), and complex dosing requirements. This study aimed to explore a novel non-invasive nasal delivery system using chitosan nanoparticles (Cs NPs) embedded in an in situ gel to address the limitations of oral IMP administration. Cs NPs loaded with IMP were synthesized via ionic gelation and assessed for precision in drug concentration using a validated HPLC method. The particles were integrated into a thermoresponsive polymer, Pluronic F127, to form an in situ gel suitable for nasal administration. The formulation was characterized for gelation temperature, duration, viscosity, mucoadhesive strength, and overall gel robustness. Drug release kinetics and the controlled release mechanism were studied using ex vivo permeation tests with Franz diffusion cells and nasal sheep mucosa. The optimized nanoparticle formulation (F4-50) exhibited a consistent PS of 141.7 ± 2.2 nm, a zeta potential (ZP) of 16.79 ± 2.1 mV, and a high encapsulation efficiency of 67.71 ± 1.9%. The selected in situ gel formulation, F4-50-P1, demonstrated a gelation temperature of 33.6 ± 0.94 °C and a rapid gelation time of 48.1 ± 0.7 s. Transform-attenuated total reflectance infrared spectroscopy (ATR-IR) confirmed the compatibility and effective encapsulation of IMP within the formulation. The release profile of F4-50 included an initial burst release followed by a sustained release phase, with F4-50-P1 showing improved control over the burst release. The flux rates were 0.50 ± 0.01 mg/cm2/h for F4-50 and 0.33 ± 0.06 mg/cm2/h for F4-50-P1, indicating effective permeation. The developed chitosan nanoparticle-based in situ gel formulation provides a promising approach for the controlled release of IMP, enhancing therapeutic efficacy and patient compliance while mitigating the disadvantages associated with oral delivery.

盐酸丙咪嗪(IMP)是一种三环类抗抑郁药,用于治疗重度抑郁症、遗尿症和神经性疼痛,但其胃肠道并发症、低口服生物利用度(44%)和复杂的剂量要求限制了该药物的应用。本研究旨在探索一种新型非侵入性鼻腔给药系统,该系统使用壳聚糖纳米颗粒(Cs NPs)嵌入原位凝胶,以解决口服 IMP 给药的局限性。通过离子凝胶法合成了负载 IMP 的 Cs NPs,并使用有效的 HPLC 方法评估了药物浓度的精确性。这些颗粒与热致伸缩性聚合物 Pluronic F127 结合,形成了一种适合鼻腔给药的原位凝胶。该制剂的凝胶化温度、持续时间、粘度、粘附强度和整体凝胶稳固性均符合标准。利用弗朗兹扩散细胞和绵羊鼻黏膜进行了体内外渗透试验,研究了药物释放动力学和控释机制。优化后的纳米颗粒配方(F4-50)显示出一致的 PS 值(141.7 ± 2.2 nm),zeta 电位(ZP)为 16.79 ± 2.1 mV,封装效率高达 67.71 ± 1.9%。所选的原位凝胶配方 F4-50-P1 的凝胶化温度为 33.6 ± 0.94 °C,快速凝胶化时间为 48.1 ± 0.7 秒。转化衰减全反射红外光谱(ATR-IR)证实了配方中 IMP 的相容性和有效封装。F4-50 的释放曲线包括最初的猝灭释放和随后的持续释放阶段,F4-50-P1 对猝灭释放的控制有所改善。F4-50 的通量为 0.50 ± 0.01 mg/cm2/h,F4-50-P1 的通量为 0.33 ± 0.06 mg/cm2/h,表明渗透效果良好。所开发的基于壳聚糖纳米粒子的原位凝胶制剂为 IMP 的控制释放提供了一种前景广阔的方法,在提高疗效和患者依从性的同时减轻了口服给药的相关缺点。
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引用次数: 0
Dynamic Mechanical Properties and Constitutive Modeling of Polyurethane Microporous Elastomers. 聚氨酯微孔弹性体的动态力学性能和构造模型。
IF 4.7 3区 工程技术 Q1 POLYMER SCIENCE Pub Date : 2024-10-30 DOI: 10.3390/polym16213056
Huiming Liu, Youcai Xiao, Yu Zou, Yong Han, Chenyang Fan, Yi Sun

The present study fabricated samples of polyurethane elastomers (PUEs) with three distinct densities and assessed their mechanical responses using split Hopkinson pressure bar (SHPB) tests. The findings reveal a significant increase in PUE stress with increasing strain rate and density. To further investigate the influence of strain rate sensitivity on PUEs, a strain rate sensitivity coefficient was employed to quantify the impact of strain rate on the mechanical properties of PUEs. Separate quantifications were performed for collapse stress, plateau stress, and densification strain as indicators of the strain rate sensitivity coefficient. The results demonstrate that the collapse stress sensitivity coefficient was notably affected by the applied strain rate. Additionally, both collapse and plateau stresses exhibited an increase with increasing density, which could be described by a power function relationship. Based on the theory of strain energy function, a constitutive model considering density and strain rate effects was developed to describe the stress-strain behavior of PUEs under various densities and strain rates. A comparison between this constitutive relationship and experimental results showed good agreement, highlighting its potential in describing dynamic mechanical behavior.

本研究制作了三种不同密度的聚氨酯弹性体(PUE)样品,并使用分体式霍普金森压力棒(SHPB)测试评估了它们的机械响应。研究结果表明,随着应变率和密度的增加,PUE 的应力也会明显增加。为了进一步研究应变速率敏感性对 PUE 的影响,采用了应变速率敏感性系数来量化应变速率对 PUE 机械性能的影响。作为应变速率敏感性系数的指标,分别对塌陷应力、高原应力和致密化应变进行了量化。结果表明,塌陷应力敏感系数受应用应变速率的影响明显。此外,塌陷应力和高原应力都随着密度的增加而增加,这可以用幂函数关系来描述。基于应变能函数理论,我们建立了一个考虑密度和应变率效应的构成模型,用于描述 PUE 在不同密度和应变率下的应力-应变行为。该构成关系与实验结果之间的比较显示两者之间具有良好的一致性,突出了其在描述动态机械行为方面的潜力。
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引用次数: 0
Low-Velocity Impact Resistance and Compression After Impact Strength of Thermoplastic Nanofiber Toughened Carbon/Epoxy Composites with Different Layups. 不同层叠结构的热塑性纳米纤维增韧碳/环氧树脂复合材料的低速抗冲击性和压缩后冲击强度
IF 4.7 3区 工程技术 Q1 POLYMER SCIENCE Pub Date : 2024-10-30 DOI: 10.3390/polym16213060
Timo Meireman, Erik Verboven, Mathias Kersemans, Wim Van Paepegem, Karen De Clerck, Lode Daelemans

This study investigates the effectiveness of polyether block amide (PEBA) thermoplastic elastomeric nanofibers in reducing low-velocity impact damage across three carbon fiber composite lay-up configurations: a cross-ply [0°/90°]2s (CP) and a quasi-isotropic [0°/45°/90°/-45°]s (QI) lay-up utilizing unidirectional plies, and a stacked woven [(0°,90°)]4s (W) lay-up using twill woven fabric plies. The flexural strength and interlaminar shear strength of the composites remained unaffected by the addition of nanofibers: around 750 MPa and 63 MPa for CP, 550 MPa and 58 MPa for QI, and 650 MPa and 50 MPa for W, respectively. The incorporation of nanofibers in the interlaminar regions resulted in a substantial reduction in projected damage area, ranging from 30% to 50% reduction over an impact energy range of 5-20 J. Microscopic analysis showed that especially the delamination damage decreased in toughened composites, while intralaminar damage remained similar for the cross-ply and quasi-isotropic lay-ups and decreased only in the woven lay-up. This agrees with the broad body of research that shows that interleaved nanofibers result in a higher delamination resistance due to toughening mechanisms related to nanofiber bridging of cracks. Despite their ability to mitigate delamination during impact, nanofibers showed limited positive effects on Compression After Impact (CAI) strength in quasi-isotropic and cross-ply composites. Interestingly, only the woven fabric composites demonstrated improved CAI strength, with a 12% improvement on average over the impact energy range, attributed to a reduction in both interlaminar and intralaminar damage. This study indicates the critical role of fiber integrity over delamination size in determining CAI performance, suggesting that the delaminations are not sufficiently large to induce buckling of sub-layers, thereby minimizing the effect of nanofiber toughening on the CAI strength.

本研究调查了聚醚嵌段酰胺(PEBA)热塑性弹性体纳米纤维在三种碳纤维复合材料铺层结构中减少低速冲击损伤的效果:利用单向层的交叉层 [0°/90°]2s (CP) 和准各向同性 [0°/45°/90°/-45°]s (QI) 铺层,以及利用斜纹编织层的叠层编织 [(0°,90°)]4s (W)铺层。复合材料的抗弯强度和层间剪切强度不受纳米纤维添加量的影响:CP 分别为 750 MPa 和 63 MPa,QI 分别为 550 MPa 和 58 MPa,W 分别为 650 MPa 和 50 MPa。显微分析表明,增韧复合材料中的分层损伤尤其减少,而层内损伤在交叉层叠和准各向同性层叠中保持相似,仅在编织层叠中有所减少。这与大量研究结果一致,这些研究结果表明,由于纳米纤维桥接裂缝的增韧机制,交错纳米纤维具有更高的抗分层能力。尽管纳米纤维能够减轻冲击过程中的分层,但对准各向同性和交叉层复合材料的冲击后压缩(CAI)强度的积极影响有限。有趣的是,只有编织物复合材料的 CAI 强度有所提高,在冲击能量范围内平均提高了 12%,这归因于层间和层内损伤的减少。这项研究表明,在决定 CAI 性能方面,纤维的完整性比分层大小起着关键作用,这表明分层的大小不足以引起子层的屈曲,从而最大限度地降低了纳米纤维增韧对 CAI 强度的影响。
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引用次数: 0
Crystallization-Controlled Structure and Thermal Properties of Biobased Poly(Ethylene2,5-Furandicarboxylate). 生物基聚(乙烯-2,5-呋喃二甲酸酯)的结晶控制结构和热性能。
IF 4.7 3区 工程技术 Q1 POLYMER SCIENCE Pub Date : 2024-10-30 DOI: 10.3390/polym16213052
Miroslaw Pluta, Joanna Bojda, Mariia Svyntkivska, Tomasz Makowski, Ele L de Boer, Ewa Piorkowska

Crystallization-controlled structure and thermal properties of biobased poly(ethylene 2,5-furandicarboxylate) (PEF) were studied. The cold-crystallization temperature controlled the structure and thermal properties of the biobased PEF. The melting was complex and evidenced the presence of a significant fraction of less-stable crystals with a low melting temperature that linearly increased with Tc, which formed already during the early stages of crystallization, together with those melting at a higher temperature. Low Tc resulted in the α'-phase formation, less crystallinity, and greater content of the rigid amorphous phase. At high Tc, the α-phase formed, higher crystallinity developed, the rigid amorphous phase content was lower, and the melting temperature of the less-stable crystals was higher; however, slight polymer degradation could have occurred. The applied thermal treatment altered the thermal behavior of PEF by shifting the melting of the less stable crystals to a significantly higher temperature. SEM examination revealed a spherulitic morphology. A lamellar order was evidenced with an average long period and small average lamella thickness, the latter about 3-3.5 nm, only slightly increasing with Tc.

研究了结晶控制生物基聚(2,5-呋喃二甲酸乙烯酯)(PEF)的结构和热性能。冷结晶温度控制着生物基 PEF 的结构和热性能。熔化过程十分复杂,表明存在相当一部分稳定性较差的晶体,其熔化温度较低,并随 Tc 的升高而线性增加,这些晶体在结晶的早期阶段就已形成,同时还存在在较高温度下熔化的晶体。低 Tc 导致α'相的形成,结晶度降低,刚性无定形相的含量增加。在高 Tc 下,α 相形成,结晶度提高,刚性无定形相含量降低,稳定性较差的晶体熔化温度升高;不过,可能会发生轻微的聚合物降解。热处理改变了 PEF 的热行为,使稳定性较差的晶体的熔化温度明显升高。扫描电子显微镜检查显示了球状形态。片层秩序明显,平均周期长,平均片层厚度小,后者约为 3-3.5 nm,仅随温度的升高而略有增加。
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引用次数: 0
Hydrogen Bond Donors in the Catalytic Pocket: The Case of the Ring-Opening Polymerization of Cyclic Esters Catalyzed by an Amino-Propoxide Aluminum Complex. 催化袋中的氢键供体:氨基丙氧基铝络合物催化环酯开环聚合反应的案例。
IF 4.7 3区 工程技术 Q1 POLYMER SCIENCE Pub Date : 2024-10-30 DOI: 10.3390/polym16213047
Salvatore Impemba, Antonella Viceconte, Irene Tozio, Shoaib Anwar, Gabriele Manca, Stefano Milione

A new aluminum complex (NSO)AlMe2 featuring a hydrogen bond donor on the ligand backbone has been synthesized via the reaction of AlMe3 with 1-((2-(isopropylamino)phenyl)thio)propan-2-ol (NSO-H) and spectroscopically characterized. In the complex, the aluminum atom is in a distorted tetrahedral coordination sphere determined by the anionic oxygen and neutral nitrogen atoms of the ligand and by the two carbon atoms of the alkyl groups. After proper activation, the complex (NSO)AlMe2 was able to promote the ring-opening polymerization of L-, rac-lactide, ε-caprolactone and rac-β-butyrolactone. The polymerization of rac-lactide was faster than that of L-lactide: in a toluene solution at 80 °C, the high monomer conversion of 100 equivalents was achieved in 1.5 h, reaching a turnover frequency of 63 molLA·molAl-1·h-1. The experimental molecular weights of the obtained polymers were close to those calculated, assuming the growth of one polymer chain for one added alcohol equivalent and the polydispersity indexes were monomodal and narrow. The kinetic investigation of the polymerization led to the determination of the apparent propagation constants and the Gibbs free energies of activation for the reaction; the terminal groups of the polymers were also identified. The complex (NSO)AlMe2 was active in harsh conditions such as at a very low concentration or in the melt using technical-grade rac-lactide. A relatively high level of activity was observed in the ring-opening polymerization of ε-caprolactone and rac-β-butyrolactone. DFT calculations were performed and revealed the central role of the NH function of the coordinated ligand. Acting as a hydrogen bond donor, it docks the monomer in the proximity of the metal center and activates it toward the nucleophilic attack of the growing polymer chain.

通过 AlMe3 与 1-((2-(异丙基氨基)苯基)硫)丙-2-醇 (NSO-H) 的反应,合成了一种新的铝络合物 (NSO)AlMe2,该络合物的配体骨架上有一个氢键供体,并对其进行了光谱表征。在该配合物中,铝原子位于一个扭曲的四面体配位圈中,该配位圈由配体的阴离子氧原子和中性氮原子以及烷基的两个碳原子决定。经过适当活化后,(NSO)AlMe2 复合物能够促进 L-、rac-内酯、ε-己内酯和 rac-β-丁内酯的开环聚合。rac-内酯的聚合速度比 L-内酯快:在 80 ℃ 的甲苯溶液中,1.5 小时就能实现 100 等量的高单体转化率,周转频率达到 63 molLA-molAl-1-h-1。所获得聚合物的实验分子量与假设每添加一个醇当量就增加一条聚合物链计算得出的分子量接近,且多分散指数为单模窄指数。通过对聚合反应的动力学研究,确定了反应的表观传播常量和活化吉布斯自由能;还确定了聚合物的末端基团。(NSO)AlMe2复合物在苛刻条件下具有活性,例如在极低浓度下或在使用工业级rac-内酰胺的熔体中。在ε-己内酯和 rac-β-butyrolactone 的开环聚合中观察到了相对较高的活性。DFT 计算揭示了配位配体 NH 功能的核心作用。作为氢键供体,它使单体靠近金属中心,并激活单体对不断增长的聚合物链进行亲核攻击。
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引用次数: 0
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Polymers
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