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Nanocarrier strategies for deep tumour penetration 肿瘤深部渗透的纳米载体策略
Pub Date : 2025-08-12 DOI: 10.1039/D5LP00154D
Jinbo Zhang, Guanjiang Wu and Valentin A. Bobrin

Deep penetration of nanocarriers into solid tumours remains a major obstacle in cancer nanomedicine due to the complex tumour microenvironment (TME) and associated physiological barriers. This review provides a comprehensive analysis to guide the design of stimuli-responsive nanocarriers capable of overcoming these transport limitations and enhancing therapeutic efficacy. It begins by examining key nanocarrier classes, including lipid-based, polymeric, inorganic, biomacromolecular, and hydrogel systems, highlighting their structural features, advantages, and limitations. Special focus is given to charge-reversal nanoparticles, which leverage TME-specific triggers such as acidic pH, redox gradients, and enzymatic activity to enhance tumour infiltration and cellular uptake. The review also evaluates complementary strategies including size and shape transformation, surface ligand modification, propulsion-based delivery, and pharmacological modulation of the TME. Collectively, these approaches offer a promising framework for engineering nanocarrier systems capable of targeted delivery, enhanced tumour penetration, and precise spatiotemporal control of drug release.

由于复杂的肿瘤微环境(TME)和相关的生理障碍,纳米载体深度渗透到实体肿瘤中仍然是癌症纳米医学的主要障碍。这篇综述提供了一个全面的分析,以指导设计能够克服这些运输限制和提高治疗效果的刺激反应纳米载体。它首先检查了关键的纳米载体类别,包括脂基、聚合物、无机、生物大分子和水凝胶系统,突出了它们的结构特征、优势和局限性。特别关注的是电荷反转纳米颗粒,它利用tme特异性触发因素,如酸性pH值、氧化还原梯度和酶活性来增强肿瘤浸润和细胞摄取。该综述还评估了互补策略,包括大小和形状转化、表面配体修饰、基于推进的递送和TME的药理学调节。总的来说,这些方法为工程纳米载体系统提供了一个有希望的框架,该系统能够靶向递送,增强肿瘤穿透,并精确控制药物释放的时空。
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引用次数: 0
Synthesis of green-based carbon-doped nanosilica for enhanced mechanical properties of coconut oil-based rigid polyurethane foam 绿基碳掺杂纳米二氧化硅的合成及其增强椰子油基硬质聚氨酯泡沫材料力学性能的研究
Pub Date : 2025-08-12 DOI: 10.1039/D5LP00161G
Carlo Kurt F. Osorio, Christine Joy M. Omisol, Dan Michael A. Asequia, Blessy Joy M. Aguinid, Daisy Jane D. Erjeno, Kassandra Jayza Gift D. Tejas, Roger G. Dingcong, Tomas Ralph B. Tomon, Renzo Miguel R. Hisona, Andrei E. Etom, Ann Pearl G. Triana, Gerard G. Dumancas, Arnold C. Alguno, Joshua B. Zoleta, Roberto M. Malaluan and Arnold A. Lubguban

High-strength, bio-based rigid polyurethane foam (RPUF) was synthesized using coconut oil-based polyol reinforced with green silica nanoparticles (SNP) derived from rice husk ash (RHA). The SNPs were carbon-doped using κ-carrageenan to enhance their functional properties. Comprehensive characterization of the synthesized SNP and SNP-enhanced RPUF was conducted using Fourier-transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), dynamic light scattering (DLS), and scanning electron microscopy with energy dispersive X-ray spectroscopy (SEM-EDX). X-ray photoelectron spectroscopy (XPS) confirmed successful κ-carrageenan-mediated carbon doping, improving SNP reactivity. The incorporation of SNP (up to 0.3% by mass) significantly enhanced the compressive strength of RPUF by 92.42%, attributed to hydrogen bonding and induced crosslinking interactions between the SNP and amine groups in the bio-polyol, as evidenced by FTIR, SEM, and pycnometric analyses. Thermogravimetric analysis (TGA) demonstrated that SNP integration improved the thermal stability of RPUF without compromising its thermal conductivity, meeting industrial standards. This study highlights the potential of sustainably derived nanomaterials to improve the mechanical and thermal properties of bio-based composites. Furthermore, the SNP-reinforced RPUF offers promising applications in environmentally friendly materials for thermal insulation, structural components, and environmental remediation, contributing to the development of high-performance, sustainable materials for various industrial applications.

以稻壳灰(RHA)为原料,用绿色纳米二氧化硅(SNP)增强椰油多元醇,合成了高强度生物基硬质聚氨酯泡沫(RPUF)。利用κ-卡拉胶对snp进行碳掺杂以增强其功能特性。利用傅里叶变换红外光谱(FTIR)、x射线衍射(XRD)、动态光散射(DLS)和扫描电子显微镜(SEM-EDX)对合成的SNP和SNP增强的RPUF进行了综合表征。x射线光电子能谱(XPS)证实了κ-卡拉胶介导的碳掺杂成功,提高了SNP的反应性。FTIR、SEM和重量计量分析表明,SNP(质量为0.3%)的掺入显著提高了RPUF的抗压强度,提高了92.42%,这是由于生物多元醇中SNP和胺基之间的氢键和诱导交联相互作用。热重分析(TGA)表明,SNP集成提高了RPUF的热稳定性,而不影响其导热性,符合工业标准。这项研究强调了可持续衍生纳米材料在改善生物基复合材料的机械和热性能方面的潜力。此外,snp增强的RPUF在隔热、结构部件和环境修复等环保材料中提供了有前途的应用,有助于开发各种工业应用的高性能、可持续材料。
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引用次数: 0
Thermoplastic-like mechanical performance of heterogeneous photopolymers for additive manufacturing with tailored hyperbranched rubbers 用定制超支化橡胶增材制造的非均相光聚合物的热塑性类机械性能
Pub Date : 2025-08-06 DOI: 10.1039/D5LP00138B
Vojtěch Musil, Dominik Laa, Mojtaba Ahmadi, Jürgen Stampfl, Robert Liska, Jan Merna and Katharina Ehrmann

Conventional photopolymers used in light-based additive manufacturing are typically brittle materials with thermoset characteristics. Here we introduce a one-step synthesis of hyperbranched polyethylene rubbers functionalized with pendant methacrylic groups and their application as tougheners of a model brittle photopolymer based on non-volatile styrene and maleimide derivatives. The rubber tougheners can be tailored to tune their compatibility with the matrix, influencing the morphology and the thermomechanical properties of the final printed resins. The resulting polymer structures were analysed by atomic force microscopy, revealing various degrees of phase separation related to the rubber molar mass and methacrylate functionalization. Further, the analysis of the prepared toughened materials revealed the ability of functionalized hyperbranched polyethylene rubbers to improve the mechanical properties significantly (doubled stress at break and improvement of strain at break by a factor of 103 compared to the matrix), while glass transition temperatures around 100 °C could be maintained. Notably, even tensile behaviour mimicking typical thermoplastic yield strain comparable to ABS was observed in one of the prepared materials. This monomer/rubber system appeared to be the most promising and was therefore selected for in-depth analysis of the curing process using photo-rheology and photo-DSC. Finally, this material was used for hot lithography and several highly detailed objects were prepared, demonstrating the good printability of this toughened material.

用于光基增材制造的传统光聚合物通常是具有热固性特性的脆性材料。本文介绍了以甲基丙烯酸基团为官能团的超支化聚乙烯橡胶的一步法合成及其在非挥发性苯乙烯和马来酰亚胺衍生物为基础的模型脆性光聚合物增韧剂中的应用。橡胶增韧剂可以定制以调整其与基体的相容性,从而影响最终打印树脂的形态和热机械性能。通过原子力显微镜对聚合物结构进行了分析,揭示了不同程度的相分离与橡胶摩尔质量和甲基丙烯酸酯功能化有关。此外,对所制备的增韧材料的分析表明,功能化超支化聚乙烯橡胶能够显著改善机械性能(断裂应力加倍,断裂应变比基体提高103倍),而玻璃化转变温度可以保持在100℃左右。值得注意的是,在其中一种制备的材料中,甚至可以观察到类似ABS的典型热塑性屈服应变的拉伸行为。这种单体/橡胶体系似乎是最有前途的,因此被选中使用光流变学和光- dsc对固化过程进行深入分析。最后,将这种材料用于热光刻,并制备了一些非常详细的物体,证明了这种增韧材料的良好印刷性。
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引用次数: 0
Reversible B–O bond-based epoxy vitrimers with high thermomechanical and dynamic properties enhanced by intermolecular B–N coordination 分子间B-N配位增强了具有高热力学和动力学性能的可逆B-O键基环氧树脂
Pub Date : 2025-08-06 DOI: 10.1039/D5LP00144G
Qi Li, Dong Wang, Tianjiao Wang, Yang Zhang, Shiyang Liu, Shiwei Zhang, Zhufeng Hu, Liying Li, Guoyong Wang and Yingmin Zhao

The development of recyclable and self-repairable vitrimer materials featuring reversible B–O bonds has garnered increasing attention. However, their stability and thermomechanical properties remain insufficient for engineering applications in reusable carbon fiber-reinforced composites (CFRCs). Herein, we report a high-performance epoxy vitrimer containing boronic ester bond-based dynamic exchange networks, to which a small amount of N-donating imidazole has been added for introducing intermolecular N–B coordination interactions. The obtained vitrimer (E51-NBO-IMZ) possessed a high glass transition temperature (Tg) of 198 °C and tensile modulus of 3.71 GPa. Compared to the system without imidazole, it exhibited significantly improved solvent resistance due to the stabilization effect of N–B coordination on the B-center atoms. Moreover, stress relaxation tests also indicated a lower activation energy (Ea = 151.31 kJ mol−1) of the E51-NBO-IMZ vitrimer, suggesting better dynamic exchange activity. Despite the high stability and improved thermomechanical properties, the self-repairing, recycling and degradation of the vitrimer and its CFRCs were successfully achieved under heating, stress or chemical environmental conditions, showing outstanding potential for practical applications.

具有可逆B-O键的可回收自修复玻璃体材料的开发越来越受到人们的关注。然而,它们的稳定性和热机械性能仍然不足以用于可重复使用的碳纤维增强复合材料的工程应用。本文报道了一种含有硼酯键动态交换网络的高性能环氧玻璃聚合物,其中添加了少量供氮咪唑以引入分子间N-B配位相互作用。所得的玻璃相(E51-NBO-IMZ)玻璃化转变温度高达198℃,拉伸模量为3.71 GPa。与不含咪唑的体系相比,由于N-B配位对b中心原子的稳定作用,该体系的耐溶剂性显著提高。此外,应力松弛试验还表明,E51-NBO-IMZ的活化能较低(Ea = 151.31 kJ mol−1),表明其具有较好的动态交换活性。尽管具有较高的稳定性和较好的热机械性能,但已成功地在加热、应力或化学环境条件下实现了玻璃体及其CFRCs的自修复、回收和降解,具有突出的实际应用潜力。
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引用次数: 0
Short-side-chain composite membranes with polyaminobenzene sulfonic acid-enriched single-walled carbon nanotubes for polymer electrolyte fuel cells 富聚氨基苯磺酸单壁碳纳米管短侧链复合膜用于聚合物电解质燃料电池
Pub Date : 2025-08-06 DOI: 10.1039/D5LP00172B
Baskaran Mohan Dass, Ramya Padmanaban, Aparna Mahalingam, Neeshma Maniprakundil, Harshal Agarwal, Sreekuttan M. Unni, Vishal M. Dhavale and Santoshkumar D. Bhat

This study reports the fabrication of composite membranes based on short-side-chain perfluorosulfonic acid (SSC-PFSA) polymers reinforced with polyaminobenzene sulfonic acid-functionalized single-walled carbon nanotubes (PABS-f-SWCNTs) for enhanced polymer electrolyte membrane fuel cell (PEMFC) performance. The dual-functionalized SWCNTs, enriched with –SO3H and –NH2 groups, were uniformly dispersed within the SSC-PFSA matrix, promoting dipolar interactions and efficient proton conduction pathways. Comprehensive characterization confirmed improved ion exchange capacity, water uptake, thermal stability, and proton conductivity, with the 0.5 wt% PABS-f-SWCNT composite membrane exhibiting optimal performance. Under fuel cell operating conditions, this membrane demonstrated a peak power density of 1707 mW cm−2 at 100% RH and sustained high current density at reduced humidity, outperforming the pristine SSC-PFSA membrane. The findings highlight the synergistic role of zwitterionic functional groups and nanotube reinforcement in advancing next-generation PEMFC membrane technology.

本研究报道了基于短侧链全氟磺酸(SSC-PFSA)聚合物和聚氨基苯磺酸功能化单壁碳纳米管(PABS-f-SWCNTs)增强的复合膜的制备,用于增强聚合物电解质膜燃料电池(PEMFC)的性能。富含-SO3H和-NH2基团的双功能化SWCNTs均匀分散在SSC-PFSA基质中,促进了偶极相互作用和有效的质子传导途径。综合表征证实了离子交换能力、吸水性、热稳定性和质子电导率的提高,其中0.5 wt%的PABS-f-SWCNT复合膜表现出最佳性能。在燃料电池工作条件下,该膜在100%相对湿度下的峰值功率密度为1707 mW cm - 2,在降低湿度时保持高电流密度,优于原始SSC-PFSA膜。这些发现强调了两性离子官能团和纳米管增强在推进下一代PEMFC膜技术中的协同作用。
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引用次数: 0
Mussel-inspired biomimetic adhesive coatings for food preservation: a review 贻贝仿生粘接涂层用于食品保鲜的研究进展
Pub Date : 2025-08-04 DOI: 10.1039/D5LP00173K
Deepika Gupta, Dimpy Bhardwaj, Ruchir Priyadarshi, Saurav Kumar and Garima Agrawal

In recent years, taking inspiration from mussel, an underwater organism, various packaging alternatives including adhesive coatings have been developed for food preservation to ensure food availability for everyone. The extraordinary adhesion exhibited by mussel is mainly offered by mussel foot proteins containing catechol groups. This catechol-based chemistry not only improves adhesion but also helps in imparting antimicrobial, antioxidant, and UV-blocking properties to packaging materials for increasing the shelf-life of food items. Herein, we first present an overview of catechol-based chemistry followed by a discussion involving a combination of catechol and its derivatives with various biodegradable polymers and nanomaterials. Further, we summarize the recent efforts made for developing mussel-inspired catechol-based coatings for food preservation, keeping minimum environmental impact in mind. Finally, we discuss various challenges and opportunities existing in this area for the successful commercial utilization of such biomimetic coatings in the future.

近年来,从贻贝(一种水下生物)身上获得灵感,开发了各种用于食品保存的包装替代品,包括粘合剂涂层,以确保每个人都能获得食物。贻贝所表现出的非凡的粘附力主要是由含有儿茶酚基团的贻贝足蛋白提供的。这种以儿茶酚为基础的化学物质不仅可以改善附着力,还有助于赋予包装材料抗菌、抗氧化和阻挡紫外线的特性,从而延长食品的保质期。在本文中,我们首先概述了基于儿茶酚的化学,然后讨论了儿茶酚及其衍生物与各种可生物降解聚合物和纳米材料的组合。此外,我们总结了最近在开发以贻贝为灵感的儿茶酚基涂料用于食品保鲜方面所做的努力,同时将对环境的影响降到最低。最后,我们讨论了该领域存在的各种挑战和机遇,以便在未来成功地商业化利用这种仿生涂层。
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引用次数: 0
Hypercrosslinked polymers for oil adsorption: the influence of porosity and fluorine incorporation 高交联聚合物对油的吸附:孔隙度和含氟量的影响
Pub Date : 2025-08-04 DOI: 10.1039/D5LP00081E
Le Tang, Paul Schweng, Joseph J. Dale and Robert T. Woodward

The selective removal of oil and oil-based contaminants from water remains a critical challenge in environmental remediation. Here, we report a series of hypercrosslinked polymers with high surface areas and tuneable chemistries, achieving exceptional adsorption capacities for a variety of organic solvents, with a maximum capacity of >15 g g−1 for chlorinated solvents. We describe how the adsorption capacities of the materials in pure organic solvents are governed by porosity rather than sample fluorine content and its associated hydrophobicity, challenging conventional design strategies. Oil/water separation tests of the most promising networks demonstrated the effective removal of toluene from water, achieving separation efficiencies of >99%. The polymers also exhibit exceptional stability in organic solvents, allowing repeated use. This work establishes hypercrosslinked polymers as robust, scalable materials for efficient oil–water separation and advanced wastewater treatment.

选择性去除水中的油和油基污染物仍然是环境修复中的一个关键挑战。在这里,我们报道了一系列具有高表面积和可调化学性质的超交联聚合物,对各种有机溶剂具有优异的吸附能力,对氯化溶剂的最大吸附能力为15 g g−1。我们描述了材料在纯有机溶剂中的吸附能力是如何由孔隙率而不是样品氟含量及其相关的疏水性决定的,挑战了传统的设计策略。对最有前途的油水分离网络进行的测试表明,该网络可以有效地从水中去除甲苯,分离效率达到99%。该聚合物在有机溶剂中也表现出优异的稳定性,允许重复使用。这项工作确立了超交联聚合物作为高效油水分离和高级废水处理的坚固、可扩展材料。
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引用次数: 0
Structure–function correlation of branched and linear polyaramides for the removal of pollutants from water 支链和线型聚酰胺去除水中污染物的结构-功能相关性研究
Pub Date : 2025-08-01 DOI: 10.1039/D5LP00114E
Gomathi Mahadevan and Suresh Valiyaveettil

Plastic waste materials in the environment degrade and release smaller particles called microplastic and nanoplastic particles. In this study, a series of polyaramides (PAs) are prepared with different structural features and used to remove plastic nanoparticles and dissolved dyes. The prepared PAs showed good thermal stability, high surface area, and negative zeta surface potential, which were useful for the extraction of pollutants. Among the six PAs studied, PA3 showed the highest adsorption capacity of 342.54 mg g−1 towards cationic polyvinyl chloride nanoparticles (PVC NPs) and dissolved dyes such as neutral red (NR, 323.57 mg g−1) and methylene blue (MB, 312.23 mg g−1). The PA adsorbents were also able to remove multiple pollutants successively from water. The adsorption isotherms, kinetics, mechanism, and reusability were also thoroughly investigated. The anionic PVC NPs or dyes were not adsorbed on the surface of the PAs and showed poor adsorption efficiency. The cationic pollutants were removed from water due to strong electrostatic attraction with the negatively charged PA adsorbents. To understand the adsorption mechanism, the adsorption efficiencies of the branched PAs (1–3; A3B2) are compared with linear PAs (4, 5; A2B2) and a model triamide molecule (TA). PA3 showed high adsorption efficiencies compared to other polymers. After extraction of pollutants, all used adsorbents were regenerated using dilute acid washings and reused for pollutant removal from water with a minimum loss of efficiency. As a proof of concept, plastic particles from a commercial facial scrubber were removed efficiently using PA adsorbents. Synthetic functional polymers offer potential solutions for removing emerging pollutants such as plastic micro- and nanoparticles from water.

塑料废物在环境中降解并释放出更小的颗粒,称为微塑料和纳米塑料颗粒。在本研究中,制备了一系列具有不同结构特征的聚酰胺(PAs),并将其用于去除塑料纳米颗粒和溶解染料。制备的PAs具有良好的热稳定性、高的比表面积和负的zeta表面电位,有利于污染物的提取。在所研究的6种PAs中,PA3对阳离子聚氯乙烯纳米粒子(PVC NPs)和溶解染料如中性红(NR, 323.57 mg g - 1)和亚甲基蓝(MB, 312.23 mg g - 1)的吸附量最高,为342.54 mg g - 1。PA吸附剂还能连续去除水中的多种污染物。研究了吸附等温线、吸附动力学、吸附机理和可重复使用性。阴离子聚氯乙烯NPs或染料不吸附在PAs表面,吸附效率较差。由于带负电荷的PA吸附剂具有很强的静电吸引力,可以去除水中的阳离子污染物。为了了解吸附机理,将支链PAs (1-3; A3B2)与线性PAs (4,5; A2B2)和模型三酰胺分子(TA)的吸附效率进行了比较。与其他聚合物相比,PA3具有较高的吸附效率。在提取污染物后,所有使用过的吸附剂都使用稀酸洗涤再生,并以最小的效率损失重新用于水中的污染物去除。作为概念验证,使用PA吸附剂有效地去除了商用面部洗涤器中的塑料颗粒。合成功能聚合物为从水中去除塑料微粒和纳米颗粒等新出现的污染物提供了潜在的解决方案。
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引用次数: 0
Hydrogel-filled tubular scaffolds for directional tissue regeneration combining shape-memory polyester blends with hyaluronic acid click-hydrogels† 水凝胶填充管状支架的定向组织再生结合形状记忆聚酯混合物与透明质酸点击水凝胶†
Pub Date : 2025-07-28 DOI: 10.1039/D5LP00098J
Álvaro Hidalgo-Yerga, Leonor Resina, Jordi Casanovas, Hamidreza Enshaei, Francesc Estrany, José I. Iribarren, Maria M. Pérez-Madrigal and Carlos Alemán

A clinical need still exists for advanced therapeutics to improve the recovery of patients suffering from large-gap peripheral nerve injuries (PNI). In this study, tubular constructs of submicrometric thickness (<1 μm) are prepared using shape-memory 50 : 50, 70 : 30 and 90 : 10 poly(lactic acid) (PLA)/polycaprolactone (PCL) blends, which are filled with a hyaluronic acid (HA)-based hydrogel. The hydrogel is crosslinked in situ by click chemistry using a 3-arm alkyne-functionalized polyethylene glycol and thiol-modified HA. The Young's moduli of the hydrogels confined inside the different cylindrical constructs are similar to that of the free hydrogel, the tubular shell mainly affecting the tensile strength and deformability. On the other hand, cell adhesion and proliferation assays demonstrate that the cytocompatibility of the blends, the hydrogel and the filled tubular constructs is similar to or even higher than that of the tissue culture polystyrene used as the control. Furthermore, the scaffold derived from the 70 : 30 PLA/PCL blend provides a 3D cell-friendly mechanical environment that promotes the directional migration of cells towards the confined hydrogel. The engineered scaffolds may have important implications in the repairing of directional tissues.

临床仍然需要先进的治疗方法来改善大间隙周围神经损伤(PNI)患者的恢复。在本研究中,使用形状记忆50:50,70:30和90:10聚乳酸(PLA)/聚己内酯(PCL)共混物制备了亚微米厚度(<1 μm)的管状结构,并填充透明质酸(HA)基水凝胶。水凝胶通过点击化学使用3臂炔功能化聚乙二醇和巯基改性透明质酸原位交联。不同圆柱形结构中水凝胶的杨氏模量与自由水凝胶相似,管状壳主要影响其抗拉强度和变形能力。另一方面,细胞粘附和增殖实验表明,混合物、水凝胶和填充管结构的细胞相容性与用作对照的组织培养聚苯乙烯相似甚至更高。此外,由70:30 PLA/PCL混合物衍生的支架提供了一个3D细胞友好的机械环境,促进细胞向受限水凝胶的定向迁移。该工程支架在定向组织的修复中具有重要的应用价值。
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引用次数: 0
Concentric half-domain spacing morphologies and anomalous domain stretching in microwave annealed block copolymer thin films† 微波退火嵌段共聚物薄膜的同心半畴间距形貌和反常畴拉伸
Pub Date : 2025-07-22 DOI: 10.1039/D5LP00116A
Ugur Aslan, Maninderjeet Singh, Akhtar Gul, Jack F. Douglas and Alamgir Karim

Block copolymer (BCP) films hold significant promise for a wide array of technological applications, including nanopatterning, nanophotonics, polymer electrolytes, and optical waveguides. However, the practical realization of these applications is often hindered by the slow kinetics of the ordering of block copolymers, attributed to the inherently glassy dynamics of polymeric soft materials under standard processing conditions. The diverse range of BCP morphologies further highlights the unique self-assembly characteristics of polymeric materials. In this study, we employ a microwave annealing method that generates a high substrate heating rate (18 °C s−1) to rapidly order lamellar BCP thin films on a high-resistivity boron-doped silicon substrate. This substrate efficiently absorbs microwave energy, creating a rapid and substantial z-temperature gradient in the BCP film. The high-temperature annealing facilitated by microwave heating generates 1L0 surface terraces composed of unconventional rim-like morphologies with a 0.5L0 (half domain spacing) height, forming half-domain height island-on-island and hole-in-hole topographies. We hypothesize that these topographies are related to the highly dynamic through-film thickness temperature gradient. Notably, reducing the substrate heating rate to 13.5 °C s−1 only produces interesting 0.5L0 top surface structures. Additionally, the elevated high temperatures of microwave annealing significantly increase the vertical lamellar domain size, L0, of the BCP film surface topography, which we believe corresponds to an “intermediate segregation” regime of chain stretching. This domain size enhancement is due to the synergy of the reduced interaction parameter between blocks and improved interlayer diffusional dynamics resulting from the sharp temperature spike and rapid vitrification. These unique morphological effects, exclusive to microwave annealing, are not seen in conventional thermal or solvent annealing and open new avenues for microwave substrate-directed self-assembly (MS-DSA) to create unique surface and internal BCP morphologies for specialized applications.

嵌段共聚物(BCP)薄膜具有广泛的技术应用前景,包括纳米图案、纳米光子学、聚合物电解质和光波导。然而,这些应用的实际实现往往受到嵌段共聚物有序的缓慢动力学的阻碍,这归因于在标准加工条件下聚合物软材料固有的玻璃动力学。BCP形态的多样性进一步凸显了聚合物材料独特的自组装特性。在本研究中,我们采用微波退火方法,产生高衬底加热速率(18°C s−1),在高电阻率掺硼硅衬底上快速排列层状BCP薄膜。这种衬底有效地吸收微波能量,在BCP薄膜中产生快速而实质性的z-温度梯度。微波加热促进高温退火产生1L0的表面阶地,由高度为0.5L0(半畴间距)的非常规边缘状形貌组成,形成半畴高度的岛对岛和孔对孔形貌。我们假设这些地形与高度动态的薄膜厚度温度梯度有关。值得注意的是,将衬底加热速率降低到13.5°C s−1时,只产生有趣的0.5L0顶部表面结构。此外,微波退火的高温显著增加了BCP薄膜表面形貌的垂直层状畴尺寸L0,我们认为这对应于链拉伸的“中间偏析”状态。这种畴尺寸的增强是由于块间相互作用参数的减少和层间扩散动力学的改善的协同作用,这是由急剧的温度峰值和快速的玻璃化造成的。这些独特的形态效应,是微波退火所独有的,在传统的热退火或溶剂退火中是看不到的,为微波基板定向自组装(MS-DSA)开辟了新的途径,为专门应用创造独特的表面和内部BCP形态。
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引用次数: 0
期刊
RSC Applied Polymers
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