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Mechanics manipulation in large-area organic solar modules achieving over 16.5 % efficiency 大面积有机太阳能电池组件中的机械操纵,实现超过 16.5% 的效率
IF 7 1区 化学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-05-11 DOI: 10.1016/j.giant.2024.100286
Hao Gu , Juan Zhu , Haiyang Chen , Guang Zeng , Xining Chen , Xiaohua Tang , Jinfeng Xia , Tianjiao Zhang , Ben Zhang , Jiandong Zhang , Junyuan Ding , Yaowen Li , Yongfang Li

High-efficiency organic solar cells (OSCs) are typically produced through spin-coating, restricting their application to small areas. Blade-coating, however, emerging as a promising method for large-scale production, yet faces challenges in film morphology optimization, which often leads to reduced power conversion efficiency (PCE). This study delves into the influence of both liquid and solid additives on the morphology of active layer in blade-coated OSCs, comparing them with spin-coated counterparts, using the high-efficiency PM6:D18:BTP-eC9 active layer. For the first time, we discovered the distinct impacts of solid versus liquid additives on the film uniformity, phase separation and crystalline regulation in blade-coating technique. Our findings reveal that liquid additives in blade-coating trigger outward Marangoni flow, causing undesirable material aggregation and phase separation, thereby impairing device performances. Conversely, switching to solid additives, like 1,4-Diiodobenzene (DIB), prevents these detrimental changes in fluid mechanics and preserves the desired additive effects. We demonstrate that solid additives can significantly change these inferior behaviors introduced by liquid additives in blade-coating, regulate phase separation, enhance π-π accumulation and delay crystallization, and ultimately boost OSC efficiency. Using DIB solid additive, we achieved a PCE of 18.81 % in blade-coated devices. Scaling up by 252 times, the PCE of large-area OSC module (15.64 cm²) sustained at 16.70 % (certified 16.66 %), ranking among the highest efficiency for OSC modules reported so far. These modules also exhibited exceptional storage stability, retaining 98 % efficiency after 5880 h in a nitrogen atmosphere. This research also provides a comprehensive understanding from various film characterizations and the perspective of fluid mechanics normally lack in the research. This research not only establishes a new framework for high-performance and large-area OSC modules but also extends its findings to other OSC systems with different additives, demonstrating a roll-to-roll compatible technique.

高效有机太阳能电池(OSCs)通常是通过旋涂法生产的,这限制了其在小面积领域的应用。然而,刀片涂层作为一种有前景的大规模生产方法,在薄膜形态优化方面面临挑战,这往往会导致功率转换效率(PCE)降低。本研究利用高效 PM6:D18:BTP-eC9 活性层,深入研究了液体和固体添加剂对叶片涂层 OSC 活性层形态的影响,并与旋涂 OSC 进行了比较。我们首次发现了固态添加剂和液态添加剂对刀片涂层技术中薄膜的均匀性、相分离和结晶调节的不同影响。我们的研究结果表明,刀片涂层中的液体添加剂会引发向外的马兰戈尼流,造成不良的材料聚集和相分离,从而影响器件性能。相反,改用固体添加剂(如 1,4-二碘苯 (DIB))则可防止流体力学发生这些有害变化,并保持所需的添加剂效果。我们证明,固体添加剂可以显著改变液体添加剂在叶片涂层中带来的这些不良行为,调节相分离,增强 π-π 积累和延迟结晶,并最终提高 OSC 效率。利用 DIB 固体添加剂,我们在叶片涂层器件中实现了 18.81 % 的 PCE。放大 252 倍后,大面积 OSC 模块(15.64 平方厘米)的 PCE 维持在 16.70 %(认证值为 16.66 %),是迄今为止报道的效率最高的 OSC 模块之一。这些模块还表现出卓越的储存稳定性,在氮气环境中储存 5880 小时后仍能保持 98% 的效率。这项研究还从各种薄膜特性和研究中通常缺乏的流体力学角度提供了一个全面的认识。这项研究不仅为高性能和大面积 OSC 模块建立了一个新的框架,而且还将其研究成果扩展到了使用不同添加剂的其他 OSC 系统,展示了一种卷对卷兼容技术。
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引用次数: 0
Monofilaments of isosorbide-based tetrapolyesters with enhanced (bio)degradability prepared by a solid-state drawing process: Synthesis and struture-property relations 通过固态拉丝工艺制备的具有更强(生物)降解性的异山梨醇基四聚酯单丝:合成与结构-性能关系
IF 7 1区 化学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-05-10 DOI: 10.1016/j.giant.2024.100281
Zhenguang Li , Yaning Wang , Jielin Xu , Jing Wu , Huaping Wang

To enhance the degradation rate of poly (butylene adipate-co-terephthalate) (PBAT) in the natural environment and to investigate the effect of modified monomers on the molding and structure of copolyester fibers, a series of isosorbide modified PBAT (PBIAT) tetrapolyesters were synthesized and monofilaments were prepared by solid-state drawing in this work. The experimental results revealed that the introduction of isosorbide formed a partial block structure in the molecular chain, and that a significant improvement in the properties of heat resistance and degradability of the copolyester was observed with the introduction of isosorbide. In the research of fiber forming and structure-property relationship by isosorbide, it was found that although the monofilament orientation process was affected by the V-shape structure of isosorbide, the change of the crystal structure under stress was similar to that of polybutylene terephthalate (PBT). The PBIAT monofilaments showed a decrease in the strength at break affected by the introduction of isosorbide but they still met the requirements for textile applications.

为了提高聚(己二酸丁二醇酯-对苯二甲酸丁二醇酯)(PBAT)在自然环境中的降解率,并研究改性单体对共聚酯纤维成型和结构的影响,本研究合成了一系列异山梨醇改性 PBAT(PBIAT)四元共聚酯,并通过固态拉伸制备了单丝。实验结果表明,异山梨醇的引入在分子链中形成了部分嵌段结构,并且随着异山梨醇的引入,共聚聚酯的耐热性和降解性得到了显著改善。在研究异山梨醇醚的纤维成型和结构-性能关系时发现,虽然单丝取向过程受到异山梨醇醚 V 型结构的影响,但晶体结构在应力作用下的变化与聚对苯二甲酸丁二醇酯(PBT)相似。PBIAT 单丝在引入异山梨醇后,断裂强度有所下降,但仍能满足纺织品应用的要求。
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引用次数: 0
Crystallization-driven tuneable lasing of perylene doped into the nematic liquid crystal 掺入向列液晶的珀烯的结晶驱动型可调激光
IF 7 1区 化学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-05-09 DOI: 10.1016/j.giant.2024.100279
Alina Szukalska , Andrzej Zak , Ewa Chrzumnicka , Anna Gibas , Agnieszka Baszczuk , Jaroslaw Mysliwiec

Versatile devices with tunable capabilities for controlling lasing wavelength and intensity are in high demand. Liquid crystals (LCs) exhibit immense potential for such applications, offering fine-tuning possibilities through external factors. On the other hand, laser technology is currently a research hotspot in optoelectronics, and also in practical applications. The recent market introduction of laser television marks a significant stride toward making such advanced technology accessible in every household. In synergy with laser pumping, the LCs unquestionably can be rediscovered. This study presents a comprehensive investigation into the crystallization phenomenon within a host-guest device, compact in size, free from moving parts, and integrating the liquid crystalline (LC) matrix doped with 3,4,9,10-tetra-(3-alcoxy-carbonyl)-perylene (THCP) dye. The focus lies in examining the influence of varying dye concentrations on multicolor fluorescence, lasing behavior, and device morphology. The systematic analysis of Random Lasing (RL) energy thresholds and the impact of DC voltage on light intensity modulation is demonstrated. Morphological changes were monitored in real-time using optical microscopy techniques, including crossed polarizer, and fluorescence imaging under 450 nm excitation. Utilizing advanced Transmission Electron Microscopy (TEM) techniques, we explore exceptional insights into our set of devices, providing novel information about the THCP crystallization process for the first time in the literature. To gain a comprehensive understanding of the crystal forming and molecular geometry we examined additionally the THCP dye, using X-ray diffraction and Raman spectroscopy. Furthermore, we showcase that varying the pumping energy enables multicolor tuning in the fabricated systems, presenting an attractive feature in the context of laser display technologies.

目前,市场对具有可调光波长和强度功能的多功能设备需求量很大。液晶(LC)在此类应用中展现出巨大的潜力,可通过外部因素进行微调。另一方面,激光技术是当前光电子学和实际应用的研究热点。最近市场上推出的激光电视标志着在实现家家户户都能使用这种先进技术方面迈出了一大步。在激光泵浦的协同作用下,低电平无疑可以被重新发现。本研究全面探究了在一个体积小巧、无活动部件、集成了掺杂 3,4,9,10-四(3-羰基-alcoxy-carbonyl)-perylene(THCP)染料的液晶(LC)基质的主客设备中的结晶现象。重点在于研究不同浓度的染料对多色荧光、激光行为和器件形态的影响。系统分析了随机激光(RL)能量阈值以及直流电压对光强调制的影响。利用光学显微镜技术,包括交叉偏振器和 450 纳米激发下的荧光成像,对形态变化进行了实时监测。利用先进的透射电子显微镜(TEM)技术,我们对这套器件进行了深入研究,首次在文献中提供了有关 THCP 结晶过程的新信息。为了全面了解晶体形成和分子几何形状,我们还使用 X 射线衍射和拉曼光谱对 THCP 染料进行了研究。此外,我们还展示了通过改变泵浦能量可以在制造的系统中实现多色调谐,这在激光显示技术方面是一个极具吸引力的特性。
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引用次数: 0
Machine learning assisted design and optimization of plate-lattice structures with superior specific recovery force 机器学习辅助设计和优化具有超强比恢复力的板格结构
IF 7 1区 化学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-05-09 DOI: 10.1016/j.giant.2024.100282
Amir Teimouri, Adithya Challapalli, John Konlan, Guoqiang Li

In load carrying structures and devices, there is a growing need for shape memory polymer (SMP) metamaterials that are lightweight and have superior strength, remarkable flexibility, and substantial specific recovery force (SFR). One of the challenges is to find optimum lightweight structures with high SFR. To address this challenge, we propose a novel inverse design framework to design plate-lattice structures (PLSs) with user-defined optimum specific maximum compression strength. Consisting of three sub-frameworks, the performance of the inverse design framework was validated before it was utilized to optimize PLSs. The optimum PLSs developed are fabricated with 3D printing using a novel SMP. In addition, we have printed a solid cylinder and Cubic+Octet (control) PLSs to compare their structural capacity with the predicted structures. The optimized PLSs display 30 ∼ 170 % greater SFR compared to the control PLS and solid cylinder. These findings suggest a promising strategy for enhancing the effectiveness of actuators based on SMP mechanical metamaterials. The inverse design framework has the potential to be utilized for generating structures with user-defined optimum mechanical properties.

在承载结构和设备中,对形状记忆聚合物(SMP)超材料的需求与日俱增,这些超材料重量轻、强度高、柔韧性好、比恢复力(SFR)大。其中一项挑战是找到具有高 SFR 的最佳轻质结构。为了应对这一挑战,我们提出了一种新颖的逆向设计框架,用于设计具有用户定义的最佳特定最大压缩强度的板格结构(PLS)。该反向设计框架由三个子框架组成,在用于优化 PLS 之前,对其性能进行了验证。开发出的最佳 PLS 使用新型 SMP 通过 3D 打印制造。此外,我们还打印了实心圆柱体和立方体+八面体(对照)PLS,以比较它们与预测结构的结构能力。与对照 PLS 和实心圆柱体相比,优化 PLS 的 SFR 高出 30 ∼ 170%。这些发现为提高基于 SMP 机械超材料的致动器的有效性提供了一种有前途的策略。反向设计框架可用于生成具有用户定义的最佳机械性能的结构。
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引用次数: 0
Fluorinated polymer-derived microporous carbon spheres for CFx cathodes with high energy density 用于高能量密度 CFx 阴极的氟化聚合物衍生微孔碳球
IF 7 1区 化学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-05-08 DOI: 10.1016/j.giant.2024.100273
Ziyue Zhao , Lingchen Kong , Jinxu Sun , Yu Li , Wei Feng

Fluorinated carbon (CFx) compounds have extensive applications in lithium primary battery cathodes owing to their high energy density. In this investigation, a novel CFx compound offering superior electrochemical properties was synthesized via a low-temperature fluorination process, utilizing Pluronic F127 as a template agent and microporous carbon spheres produced through soft template-assisted high-temperature carbonization and chemical activation as precursors, and by regulating the amount of soft template F127 added. The reduction in microsphere size, narrower particle size distribution, and introduction of defects contribute to augmenting the molar ratio of F to C (F/C) of CFx while preserving the electrochemical activity of C-F bonds. The specific capacity of fluorinated polymer-derived microporous carbon spheres (FPMCSs) with a high fluorination degree rivals that of commercial fluorinated graphite (FG). The microsphere morphology and microporous structure not only furnish abundant sites for fluorination reactions in electrode processes but also facilitate Li+ diffusion, ensuring ample rate capability. The synthesized FPMCSs exhibited a peak specific capacity of 1079 mAh g–1 and a maximum energy density of 2679 Wh kg–1 (substantially surpassing the 2180 Wh kg–1 of commercial FG). Hence, the prepared FPMCSs underscore the significance of selecting suitable carbonaceous materials and designing structures deliberately, showing promising potential for achieving high energy density in CFx cathodes in the future, employing readily available and cost-effective raw materials.

氟化碳(CFx)化合物因其能量密度高而在锂原电池阴极中有着广泛的应用。本研究以 Pluronic F127 为模板剂,以软模板辅助高温碳化和化学活化产生的微孔碳球为前驱体,通过调节软模板 F127 的添加量,采用低温氟化工艺合成了一种具有优异电化学性能的新型 CFx 化合物。微球尺寸的减小、粒度分布的缩小以及缺陷的引入有助于提高 CFx 的 F-C 摩尔比(F/C),同时保持 C-F 键的电化学活性。高氟化程度的氟化聚合物衍生微孔碳球(FPMCSs)的比容量可与商用氟化石墨(FG)媲美。微球形态和微孔结构不仅为电极过程中的氟化反应提供了丰富的场所,而且有利于 Li+ 扩散,从而确保了充足的速率能力。合成的 FPMCSs 的峰值比容量为 1079 mAh g-1,最大能量密度为 2679 Wh kg-1(大大超过商用 FG 的 2180 Wh kg-1)。因此,所制备的 FPMCSs 强调了选择合适的碳质材料和精心设计结构的重要性,显示了未来利用易于获得且具有成本效益的原材料实现 CFx 阴极高能量密度的巨大潜力。
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引用次数: 0
Highly stretchable alginate/methylcellulose hydrogels for 3D bio-printing: photopolymerization approach enhancing structural integrity 用于三维生物打印的高伸展性藻酸盐/甲基纤维素水凝胶:增强结构完整性的光聚合方法
IF 7 1区 化学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-05-07 DOI: 10.1016/j.giant.2024.100280
Sorour Sadeghzade , Jinrui Cao , Rui Yang , Yuanlong Li , Yanping Li , Dingcong Zhang , Jingyi Liu , Ziyue Yu , Liang Fang , Hongyan Yuan

In recent years, 3D hydrogels based on alginate (Alg) have undergone substantial advancements, holding transformative potential for biomedicine and regenerative medicine. Nevertheless, the viscosity of Alg needs to be further increased, in order to print complex 3D structures. Attempts to adjust printability often employ rheological modifiers like methylcellulose (MC), but these still lack mechanical integrity for broader biomedical applications. Our study sought to chemically modify Alg/MC to create a photopolymerizable hydrogel by incorporating acrylate-based monomers, which would enhance the curing ability of the base hydrogel, leading to better mechanical properties of Alg/MC, such as stretchability and stability with shape recovery. Comprehensive mechanical assessments unveiled remarkable tensile properties, achieving a notable specific strength benchmark of 44.72 kPa/(g.cm-3) before reaching the point of fracture. This represents a substantial 250 % improvement compared to samples lacking the acrylate monomer. Biomedical assessments confirmed the hydrogel's promising potential, especially with the MG-63 cell line, underscoring its suitability for advanced applications like tissue engineering.

近年来,基于藻酸盐(Alg)的三维水凝胶取得了长足的进步,为生物医学和再生医学带来了变革潜力。然而,为了打印复杂的三维结构,藻酸盐的粘度需要进一步提高。调整打印性能的尝试通常采用甲基纤维素(MC)等流变改性剂,但对于更广泛的生物医学应用而言,这些改性剂仍然缺乏机械完整性。我们的研究试图对 Alg/MC 进行化学改性,通过加入丙烯酸酯类单体来创建一种可光聚合的水凝胶,这将增强基础水凝胶的固化能力,从而提高 Alg/MC 的机械性能,如拉伸性和形状恢复稳定性。全面的机械评估揭示了其卓越的拉伸性能,在达到断裂点之前,比强度基准达到了 44.72 kPa/(g.cm-3)。与不含丙烯酸酯单体的样品相比,该性能大幅提高了 250%。生物医学评估证实了这种水凝胶的巨大潜力,尤其是在 MG-63 细胞系中的应用,突出了它在组织工程等高级应用中的适用性。
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引用次数: 0
Incorporation of self-heating effect into a thermo-mechanical coupled constitutive modelling for elastomeric polyurethane 将自热效应纳入弹性聚氨酯的热机械耦合构造模型中
IF 7 1区 化学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-05-06 DOI: 10.1016/j.giant.2024.100278
Jie Yang , Zisheng Liao , Deepak George , Mokarram Hossain , Xiaohu Yao

Elastomeric polyurethane (EPU) is characterised by distinctive mechanical properties, including high toughness, low glass transition temperature, and high impact resistance, that render it indispensable in diverse engineering applications from soft robotics to anti-collision devices. This study presents a thermo-mechanically coupled constitutive model for EPU, systematically incorporating hyperelasticity, viscoelasticity, thermal expansion, and self-heating effect in a thermodynamically consistent manner. Experimental data, obtained from previous studies, are then used for parameter identification and model validation, including iterative updates for temperature parameters considering the self-heating effect. Subsequently, the validated model is integrated into finite element codes, i.e., user subroutine to define a material’s mechanical behaviour (UMAT) based on the commercial finite element software ABAQUS, for the computation of three-dimensional stress-strain states, facilitating the analysis of the structural response to various mechanical loads and boundary conditions. The results obtained from simulations are compared with analytical solutions to confirm the precision of Finite Element Method (FEM) implementation. The self-heating effect is further analysed under different strain rates and temperatures. To validate the engineering significance of the FEM implementation, a plate with a hole structure is also simulated. In conclusion, this research provides a robust tool for engineers and researchers working with soft materials, enhancing their understanding and predictive capabilities, notably addressing the self-heating effect in thermo-mechanical behaviours.

弹性聚氨酯(EPU)具有独特的机械性能,包括高韧性、低玻璃化转变温度和高抗冲击性,使其在从软体机器人到防撞装置等各种工程应用中不可或缺。本研究提出了 EPU 的热机械耦合结构模型,以热力学一致的方式系统地纳入了超弹性、粘弹性、热膨胀和自热效应。然后,利用先前研究获得的实验数据进行参数识别和模型验证,包括考虑自热效应的温度参数迭代更新。随后,将验证后的模型集成到有限元代码中,即基于商业有限元软件 ABAQUS 的定义材料力学行为(UMAT)的用户子程序,用于计算三维应力-应变状态,便于分析各种力学载荷和边界条件下的结构响应。模拟结果与分析结果进行了比较,以确认有限元法(FEM)实施的精确性。在不同的应变率和温度条件下,进一步分析了自加热效应。为了验证有限元法实施的工程意义,还模拟了带孔结构的板。总之,这项研究为从事软材料研究的工程师和研究人员提供了一个强大的工具,增强了他们的理解和预测能力,特别是解决了热机械行为中的自热效应问题。
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引用次数: 0
Itaconic acid-based 3D printed nanocomposites: An in-depth study on the effect of nanoinclusions on the physicochemical properties and the printability of formulations based on polyester itaconates 基于衣康酸的 3D 打印纳米复合材料:深入研究纳米夹杂物对基于聚酯衣康酸酯的配方的理化性质和可打印性的影响
IF 7 1区 化学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-05-03 DOI: 10.1016/j.giant.2024.100275
Lazaros Papadopoulos , Lorenzo Pezzana , Natalia Malitowski , Nikolaos Kladovasilakis , Dimitrios Tzetzis , Marco Sangermano , Dimitrios N. Bikiaris , Tobias Robert

The demand for novel bio-based materials in UV-curing additive manufacturing has surged due to increasing environmental concerns and a growing emphasis on sustainable practices in the manufacturing industry. However, at the moment, their thermomechanical performance is not equal to that of their fossil-based counterparts and this impedes the acceptance of these materials within the industrial community. Therefore, in this study, a series of nanocomposite polyesters based on itaconic acid was synthesized for the first time with in-situ polymerization, in an attempt to leverage the unique properties of nanofillers and improve the overall performance of the material. A variety of reinforcing agents were utilized, namely cellulose nanocrystals (CNC), montmorillonite (MMT), graphene nanoplatelets (GNP) and titanium dioxide (TiO2), to understand the effect of each filler on the physicochemical properties of the polyester. Formulations of these polyesters were then prepared and processed on a digital light processing (DLP) 3D printer to prepare test specimens. Extensive thermomechanical characterization showed that the interference of the fillers with the UV curing process was the main parameter determining the mechanical performance of the 3D printed materials.

由于对环境的日益关注以及制造业对可持续发展的日益重视,紫外固化快速成型制造对新型生物基材料的需求激增。然而,目前生物基材料的热机械性能还无法与化石基材料相提并论,这阻碍了工业界对生物基材料的认可。因此,本研究首次采用原位聚合法合成了一系列基于衣康酸的纳米复合聚酯,试图利用纳米填料的独特性能来提高材料的整体性能。为了了解每种填料对聚酯理化性质的影响,我们使用了多种增强剂,即纤维素纳米晶体(CNC)、蒙脱石(MMT)、石墨烯纳米片(GNP)和二氧化钛(TiO2)。然后制备了这些聚酯的配方,并在数字光处理(DLP)3D 打印机上进行了处理,以制备测试试样。广泛的热力学特性分析表明,填料对紫外线固化过程的干扰是决定三维打印材料力学性能的主要参数。
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引用次数: 0
Advances in shape memory polymers and their composites: From theoretical modeling and MD simulations to additive manufacturing 形状记忆聚合物及其复合材料的研究进展:从理论建模和 MD 模拟到增材制造
IF 7 1区 化学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-04-30 DOI: 10.1016/j.giant.2024.100277
Yu Li, Denvid Lau

Shape memory polymers (SMPs) and their composites have broad application prospects in multiple fields due to their unique shape memory effects. However, they still face challenges in accurately controlling the shape recovery process, improving the stability of shape memory loops, and achieving the manufacturing of complex shapes and functions. At present, theoretical models, molecular dynamics (MD) simulations, and additive manufacturing technologies have been widely applied. Theoretical models and MD simulations provide theoretical foundations at both macro and micro levels, respectively. Meanwhile, by combining SMPs and their composites with additive manufacturing, some complex structures can be produced. This not only verifies the accuracy of the theoretical foundation, but also further expands its application. This review aims to review the application and intersection of theoretical models, MD simulations, and additive manufacturing in the research of SMPs and their composites, and analyze how they jointly promote the leap from theory to application, providing valuable insights for future development trends.

形状记忆聚合物(SMPs)及其复合材料因其独特的形状记忆效应而在多个领域具有广阔的应用前景。然而,它们在精确控制形状恢复过程、提高形状记忆回路的稳定性以及实现复杂形状和功能的制造等方面仍面临挑战。目前,理论模型、分子动力学(MD)模拟和增材制造技术已得到广泛应用。理论模型和分子动力学模拟分别从宏观和微观两个层面提供了理论基础。同时,通过将 SMP 及其复合材料与增材制造技术相结合,可以制造出一些复杂的结构。这不仅验证了理论基础的准确性,还进一步扩大了其应用范围。本综述旨在回顾理论模型、MD 模拟和增材制造在 SMPs 及其复合材料研究中的应用和交叉,分析它们如何共同促进从理论到应用的飞跃,为未来的发展趋势提供有价值的启示。
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引用次数: 0
Highly crystalline, heat resistant and biodegradable copolyesters from fully bio-based bis(pyrrolidone) monomer 由完全生物基双吡咯烷酮单体制成的高结晶性、耐热性和可生物降解的共聚聚酯
IF 7 1区 化学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-04-29 DOI: 10.1016/j.giant.2024.100276
Hanxu Zhu , Han Hu , Qingyang Luan , Chen Lin , Juanfang Xu , Jinggang Wang , Wu Bin Ying , Jin Zhu

Improving the heat resistance of bio-based and biodegradable polyesters is of great significance to extend their applications. Herein, N,N’-trans-1,4-cyclohexane-bis(pyrrolidone-4-methyl carboxylate) (T-CBPMC) was prepared through efficient Michael-addition reaction between dimethyl itaconate and trans-1,4-cyclohexanediamine. The obtained T-CBPMC was copolymerized into aliphatic poly(butylene succinate) (PBS), and a series of PBSPs copolymers with T-CBPMC (BP) molar percentages between 41−80 mol % and weight average molecular weight (Mw) values ranging between 5.77*104 and 6.67*104 g/mol were prepared. BP units efficiently facilitated the melting temperature (203-251 °C) and isothermal-crystallization rate (t1/2 < 20 s) of PBSPs, endowing the highest heat resistance among commercial biodegradable polyesters, which helps maintain stable in pasteurization, high-temperature disinfection, and microwave environments. Moreover, these copolymers displayed remarkable mechanical, gas barrier properties and degradability. PBSP40-PBSP60 obtained high elastic modulus (335–872 MPa) and tensile strength (24.7–31.5 MPa), and good toughness simultaneously. Multiple-ring structures and large steric hindrance of BP units resulted in superior O2 barrier performance than that of non-degradable PET films. Importantly, the PBSP copolyesters showed obvious degradation in water environments and relatively better enzymatic degradation. It was interesting to find that even with 70 % of the BP units, the PBSP copolyesters still retained hydrolysis ability. The resulting PBSP copolyesters open the way for alternative candidates of biodegradable packaging materials with rapid crystallization, high heat-resistance and gas barrier.

提高生物基和生物可降解聚酯的耐热性对扩大其应用范围具有重要意义。本文通过伊塔康酸二甲酯和反式-1,4-环己烷二胺之间的高效迈克尔加成反应,制备了N,N'-反式-1,4-环己烷-双(吡咯烷酮-4-甲基羧酸酯)(T-CBPMC)。将得到的 T-CBPMC 与脂肪族聚丁二酸丁二醇酯(PBS)共聚,制备出一系列 T-CBPMC 摩尔百分比(BP)介于 41-80 mol % 之间、重量平均分子量(Mw)介于 5.77*104 和 6.67*104 g/mol 之间的 PBSPs 共聚物。BP 单元有效地提高了 PBSP 的熔融温度(203-251 °C)和等温结晶速率(t1/2 < 20 s),在商用生物降解聚酯中具有最高的耐热性,有助于在巴氏杀菌、高温消毒和微波环境中保持稳定。此外,这些共聚物还具有显著的机械、气体阻隔性能和降解性。PBSP40-PBSP60 同时获得了较高的弹性模量(335-872 兆帕)和拉伸强度(24.7-31.5 兆帕)以及良好的韧性。与不可降解的 PET 薄膜相比,BP 单元的多环结构和较大的立体阻碍使其具有更优越的氧气阻隔性能。重要的是,PBSP 共聚多酯在水环境中降解明显,酶降解效果相对较好。有趣的是,即使添加了 70% 的 BP 单元,PBSP 共聚多酯仍能保持水解能力。由此产生的 PBSP 共聚多酯为替代具有快速结晶、高耐热性和气体阻隔性的可生物降解包装材料开辟了道路。
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