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The toughening mechanism of β nucleated isotactic polypropylene β成核等规聚丙烯的增韧机理
IF 2.8 4区 化学 Q3 POLYMER SCIENCE Pub Date : 2025-12-15 DOI: 10.1007/s10965-025-04707-3
Conglong Lin, Enci Zhu, Ruiheng He, Shenghu Zhou, Shicheng Zhao

The incorporation of β nucleating agents has been demonstrated to improve the toughness of isotactic polypropylene (iPP), but the underlying mechanism remains ambiguous. This study presents a comprehensive investigation on the toughening mechanism in β nucleated iPP through systematic analysis of both macro-properties and micro-structures. The results show that with the addition of 0.1 wt%, three distinct β nucleating agents, BNA-01, zinc adipate (ZnAA) and zinc phthalate (ZnPA), significantly enhances the impact strength of iPP from 3.6 kJ/m² to 11.7 kJ/m², 6.1 kJ/m², and 8.7 kJ/m², respectively. To elucidate the toughening mechanism, the relative content of β form iPP (kβ) and crystallinity of nucleated iPP were characterized using wide-angle X-ray diffraction (WAXD) and differential scanning calorimetry (DSC). The results reveal a strong correlation between the β form iPP content and toughness, with higher β form iPP content leading to enhanced toughness. However, the results also indicate that when the content of β form iPP is the same, the toughness of nucleated iPP also differs. To address it, the distribution of β form iPP and spherulite size were examined using polarized optical microscopy (POM). The results indicate that, as the content of β form iPP increases, a continuous distribution of β form iPP will be formed, which can significantly improve the toughness of nucleated iPP. Moreover, under the condition of both continuous distributions, smaller spherulite size contributes to a larger fracture surface, consequently demanding more energy for fracture propagation and ultimately enhancing the toughness. Scanning electron microscopy (SEM) was applied to observe the fracture sections of samples to confirm the toughening mechanism. This study provides new insights into the role of β form iPP content, distribution and spherulite size in the toughening of nucleated iPP, offering a deeper understanding of its structure-property relationships.

β成核剂的掺入已被证明可以提高等规聚丙烯(iPP)的韧性,但其潜在的机制尚不清楚。本研究通过系统的宏观性能和微观结构分析,对β成核iPP的增韧机理进行了全面的研究。结果表明:当β成核剂BNA-01、己二酸锌(ZnAA)和邻苯二甲酸锌(ZnPA)的加入量为0.1 wt%时,iPP的冲击强度分别从3.6 kJ/m²、6.1 kJ/m²和8.7 kJ/m²显著提高。为了阐明增韧机理,采用广角x射线衍射(WAXD)和差示扫描量热法(DSC)对β型iPP的相对含量(kβ)和成核iPP的结晶度进行了表征。结果表明,β型iPP含量与韧性之间存在较强的相关性,β型iPP含量越高,韧性越强。然而,结果也表明,当β型iPP的含量相同时,成核iPP的韧性也不同。为了解决这一问题,利用偏光显微镜(POM)研究了β型iPP的分布和球晶尺寸。结果表明:随着β型iPP含量的增加,会形成连续分布的β型iPP,能显著提高成核iPP的韧性;而且,在两种连续分布的情况下,球晶尺寸越小,断口面积越大,因此需要更多的能量进行断裂扩展,最终提高韧性。采用扫描电镜(SEM)对试样断口进行观察,确定了增韧机理。该研究为β型iPP含量、分布和球晶尺寸在成核iPP增韧中的作用提供了新的见解,为其结构-性能关系提供了更深入的理解。
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引用次数: 0
Stimuli responsive polymeric micelles for combinational delivery and quantification of methotrexate and ciprofloxacin based on high performance liquid chromatography 基于高效液相色谱的甲氨蝶呤和环丙沙星复合递送和定量的刺激响应聚合物胶束
IF 2.8 4区 化学 Q3 POLYMER SCIENCE Pub Date : 2025-12-15 DOI: 10.1007/s10965-025-04714-4
Mahdi Abadi Gharehbaba, Majid Soleimani, Samira Jafari

A temperature and pH-sensitive biodegradable cationic amphiphilic copolymer, poly [2-hydroxyethyl methacrylate-caprolactone-dimethylamine ethyl methacrylate quaternary ammonium alkyl halide] [P(HEMA-PCL-MADQUAT)], was synthesized via ring-opening polymerization (ROP) and free radical polymerization methods. Structure confirmation was obtained by FT-IR and 1H-NMR spectroscopy. Nano-micelles derived from the copolymer were characterized by TEM (transmission electron microscopy), DLS (dynamic light scattering), zeta potential, and CMC (critical micelle concentration) analysis, revealing a uniform morphology with a surface charge of − 12.4 mV, an average diameter of 280 nm, and a CMC of 0.01 g/L. The micelles efficiently encapsulated methotrexate and ciprofloxacin, with loading efficiencies of 67.1% and 71.4%, respectively. MTT assays in MCF-7 cell lines demonstrated favorable biocompatibility and CIP@MTX micelles showed lower IC₅₀ than free CIP@MTX in MCF-7 cells (1.5 vs. 5.3 µg·mL⁻¹). These findings highlight P(HEMA-PCL-MADQUAT) micelles as a promising platform for breast cancer therapy, combining effective drug delivery with reduced side effects.

采用开环聚合(ROP)和自由基聚合的方法合成了对温度和ph敏感的可生物降解阳离子两亲性共聚物聚[2-甲基丙烯酸羟乙基-己内酯-二甲胺-甲基丙烯酸乙基-季烷基卤化铵][P(HEMA-PCL-MADQUAT)]。通过FT-IR和1H-NMR对结构进行了确证。通过TEM(透射电子显微镜)、DLS(动态光散射)、zeta电位和CMC(临界胶束浓度)分析对该共聚物的纳米胶束进行了表征,发现其表面电荷为- 12.4 mV,平均直径为280 nm, CMC为0.01 g/L。该胶束对甲氨蝶呤和环丙沙星的包封效率分别为67.1%和71.4%。MCF-7细胞系的MTT测定显示出良好的生物相容性,CIP@MTX胶束的IC₅₀比MCF-7细胞中的游离CIP@MTX低(1.5 vs. 5.3µg·mL⁻¹)。这些发现突出了P(HEMA-PCL-MADQUAT)胶束作为乳腺癌治疗的一个有希望的平台,结合了有效的药物传递和减少的副作用。
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引用次数: 0
Enhanced corrosion resistant, tribological properties and self-healing of epoxy-polyurethane coatings by dynamic Diels-Alder bond 通过动态Diels-Alder键增强环氧聚氨酯涂层的耐腐蚀性、摩擦学性能和自愈性
IF 2.8 4区 化学 Q3 POLYMER SCIENCE Pub Date : 2025-12-13 DOI: 10.1007/s10965-025-04718-0
Min Huang, Huan Ge, Changhong Lin, Zhengwei Zhang, Mu Lin, Minhua Mo, Laiming Yu, Vladimir Levchenko

Epoxy resin is a class of thermosetting polymer widely used in high performance protective coating due to its excellent physical and chemical properties. However, its inherent brittleness, along with difficulties in self-healing and recycling, limits its application. In this study, an epoxy resin coating was modified by the combination of Diels-Alder (DA) dynamic reversible bond and soft polyurethane segment. The DA bonds endowed the coating with the ability to repair damage and to be reprocessed, while the polyurethane chain segments, introduced through the DA reaction, can effectively enhance the toughness of the epoxy resin. The chemical structure and properties of the materials were characterized by FTIR, DSC, TGA and universal testing machine. The results showed that due to the presence of soft polyurethane segment, improve the corrosion resistance and wear resistance of coating. Additionally, the Diels-Alder bond endowed the material with excellent thermal self-healing and recycling properties. Therefore, this modified epoxy coating shows great potential in extending service life of metal materials and bringing considerable economic and social benefit.

环氧树脂是一类热固性聚合物,因其优异的物理化学性能而广泛应用于高性能防护涂料。然而,其固有的脆性,以及自修复和回收的困难,限制了其应用。本研究采用Diels-Alder (DA)动态可逆键与软聚氨酯段相结合的方法对环氧树脂涂层进行改性。DA键赋予涂层修复损伤和再加工的能力,而通过DA反应引入的聚氨酯链段可以有效增强环氧树脂的韧性。采用FTIR、DSC、TGA和万能试验机对材料的化学结构和性能进行了表征。结果表明,由于软质聚氨酯段的存在,提高了涂层的耐腐蚀性和耐磨性。此外,Diels-Alder键赋予材料优异的热自愈和回收性能。因此,该改性环氧涂料在延长金属材料使用寿命方面具有很大的潜力,具有可观的经济效益和社会效益。
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引用次数: 0
Rubber nanocomposites: a review of processing, thermo-mechanical properties, and industrial frontiers 橡胶纳米复合材料:加工、热机械性能和工业前沿的综述
IF 2.8 4区 化学 Q3 POLYMER SCIENCE Pub Date : 2025-12-13 DOI: 10.1007/s10965-025-04686-5
Soma A. El Mogy, Khaled Chawraba

Rubber nanocomposites offer unique advantages over conventional polymer nanocomposites due to their exceptional flexibility, resilience, and dynamic mechanical properties, making them ideal for applications that require elasticity, impact resistance, and energy dissipation. Unlike rigid thermoplastic-based nanocomposites, rubber matrices can deform significantly while maintaining strong interfacial interactions with nanofillers, leading to materials with enhanced thermal stability, mechanical strength, barrier properties, and multifunctionality. This review presents recent advancements in rubber nanocomposites, highlighting the synergistic effects between elastomeric matrices and various nanofillers including silica, nanoclay, carbon nanotubes, and bio-based materials. Key processing techniques, including direct mixing, solution mixing, and in-situ polymerization, are discussed in relation to their impact on filler dispersion and composite performance. Industrial applications in tire manufacturing, electronics, biomedical devices, separation membranes, sporting goods, and catalysis are explored to showcase the broad potential of these materials. Despite remarkable progress, challenges remain regarding nanofiller dispersion, cost-effective scalability, environmental concerns, and long-term durability. Future directions include using artificial intelligence for material design, circular economy approaches for sustainable sourcing, and developing hybrid nanofiller systems. This review highlights the critical role of rubber nanocomposites in creating high-performance, flexible, and multifunctional materials for next-generation industrial applications.

橡胶纳米复合材料比传统聚合物纳米复合材料具有独特的优势,因为它们具有卓越的柔韧性,弹性和动态机械性能,使其成为需要弹性,抗冲击性和能量耗散的应用的理想选择。与刚性热塑性纳米复合材料不同,橡胶基体可以在与纳米填料保持强界面相互作用的同时显著变形,从而使材料具有更高的热稳定性、机械强度、阻隔性能和多功能。本文综述了橡胶纳米复合材料的最新进展,重点介绍了弹性体基质与各种纳米填料(包括二氧化硅、纳米粘土、碳纳米管和生物基材料)之间的协同效应。讨论了直接混合、溶液混合和原位聚合等关键工艺技术对填料分散性和复合材料性能的影响。在轮胎制造、电子、生物医学设备、分离膜、体育用品和催化方面的工业应用被探索,以展示这些材料的广泛潜力。尽管取得了显著进展,但在纳米填料分散、成本效益可扩展性、环境问题和长期耐用性方面仍然存在挑战。未来的发展方向包括在材料设计中使用人工智能,在可持续采购中使用循环经济方法,以及开发混合纳米填料系统。本文综述了橡胶纳米复合材料在下一代工业应用中创造高性能、柔性和多功能材料的关键作用。
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引用次数: 0
Compressive mechanical properties of organic films 有机薄膜的压缩力学性能
IF 2.8 4区 化学 Q3 POLYMER SCIENCE Pub Date : 2025-12-12 DOI: 10.1007/s10965-025-04691-8
Gaoyu Zhong, Fei Ye, Baifan Qian, ShuaiShuai Du, Shuhui Li, Zhiyi Wei, Luchao Wu

We tested loading-unloading curves using nanoindentation and studied the mechanical properties of six polymer films, including polyethylene (PE), polypropylene (PP), polymethyl methacrylate (PMMA), Polytetrafluoroethylene (PTFE), polyethylene terephthalate (PET), and polyimide (PI). The loading-unloading curve is assumed to comprehensively reflect the relationship between intermolecular forces and intermolecular distances in polymer materials, and the force between organic molecules is usually the van der Waals force. We introduce the Lennard-Jones potential to describe the potential energy between the molecules of these materials and derive the intermolecular force as a function of the intermolecular distance. By fitting this relationship to the measured loading-unloading curves, it was found that they were consistent. Using the obtained fitting parameters, we calculated four mechanical parameters related to film compression: the binding energy between molecules on both sides of the cross-section per unit area (related to toughness); the binding force between molecules on both sides of the cross-section per unit area (related to strength); reduced Young’s modulus (related to stiffness); the total stretching distance between adjacent molecules stretched from the equilibrium position to the position where the binding force is maximum (related to the stretch performance of the material). The measured reduced modulus of PE, PP, PMMA, PTFE, PET, and PI films under zero stress/strain are 608.0, 42.8, 906.5, 36.1, 11.2, and 11.8 MPa, respectively. This research has the potential to develop an advanced and user-friendly universal testing tool for material mechanics, which can be utilized for sensing in robotics.

采用纳米压痕法测试了聚乙烯(PE)、聚丙烯(PP)、聚甲基丙烯酸甲酯(PMMA)、聚四氟乙烯(PTFE)、聚对苯二甲酸乙二醇酯(PET)和聚酰亚胺(PI)等六种聚合物薄膜的加载-卸载曲线,并对其力学性能进行了研究。假设加载-卸载曲线综合反映了高分子材料中分子间力与分子间距离的关系,有机分子间的力通常为范德华力。我们引入Lennard-Jones势来描述这些材料分子间的势能,并推导出分子间力作为分子间距离的函数。将这一关系拟合到实测的加载-卸载曲线上,发现两者是一致的。利用得到的拟合参数,我们计算了与薄膜压缩有关的四个力学参数:单位面积横截面两侧分子间的结合能(与韧性有关);单位面积横截面两侧分子间的结合力(与强度有关);降低的杨氏模量(与刚度相关);相邻分子之间从平衡位置拉伸到结合力最大位置的总拉伸距离(与材料的拉伸性能有关)。PE、PP、PMMA、PTFE、PET和PI薄膜在零应力/应变下的降低模量分别为608.0、42.8、906.5、36.1、11.2和11.8 MPa。该研究有潜力开发出一种先进且用户友好的材料力学通用测试工具,可用于机器人传感。
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引用次数: 0
Facile synthesis of tunable and processable shape-memory hemiamine thermoset by catalyst-free polycondensation 无催化剂缩聚法合成可调可加工形状记忆半胺热固性材料
IF 2.8 4区 化学 Q3 POLYMER SCIENCE Pub Date : 2025-12-12 DOI: 10.1007/s10965-025-04695-4
Mohsin Raza, Muhammad Imran Din, Zaib Hussain

Here, the report on a facile synthesis of hemiamine thermoset containing iron oxide nanodomains by polycondensation of formaldehyde, polyetheramine (Jeffamine) D-400 and (3-aminopropyl)triethoxysilane (APTES) functionalized iron oxide nanoparticles is accomplished. The synthesized material was molded to required shapes by using high pressure mold press machine. Hemiamine thermosets were prepared by varying the percentage of APTES functionalized iron oxide nanoparticles as 5%, 10%, 15%, 20% and 25%. The characterizations of hemiamine thermoset were carried out by Thermogravimetric analysis (TGA), Differential Scanning Calorimetry (DSC), Dynamic Light Scattering (DLS) and Transmission Electron Microscopy (TEM). The augmentation of hemiamine with Fe2O3-NH2 improved the thermomechanical characteristics in terms of glass transition temperatures (Tg,s) and tensile mechanical strength. The Young’s modulus and breaking strength was measured as 1.3 GPa and 72.5 MPa of the hemiamine thermoset containing 25% Fe2O3-NH2 nanoparticles. The shape memory and self-healing properties were investigated. The impregnation of Fe2O3-NH2 in hemiaminal dynamic covalent networks (HDCNs) was responsible of shape memory and self-healing properties due to improved thermal conductivity, reinforcement effect and interfacial interactions.

本文报道了用甲醛、聚醚胺(Jeffamine) D-400和(3-氨基丙基)三乙氧基硅烷(APTES)功能化氧化铁纳米颗粒缩聚制备含氧化铁纳米结构域的半胺热固性材料。利用高压模压机将合成材料模压成所需形状。通过改变APTES功能化氧化铁纳米颗粒的百分比为5%,10%,15%,20%和25%,制备了半胺热固性材料。采用热重分析(TGA)、差示扫描量热法(DSC)、动态光散射(DLS)和透射电镜(TEM)对半胺热固性材料进行了表征。Fe2O3-NH2的加入改善了半胺的玻璃化转变温度(Tg,s)和拉伸机械强度。结果表明,含25% Fe2O3-NH2纳米粒子的半胺热固性材料的杨氏模量为1.3 GPa,断裂强度为72.5 MPa。研究了材料的形状记忆和自愈性能。Fe2O3-NH2浸渍在半动态共价网络(HDCNs)中,由于提高了热传导率、增强效应和界面相互作用,具有形状记忆和自愈性能。
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引用次数: 0
Novel transparent poly(arylene ether nitrile) copolymers with pendant aliphatic rings: Synthesis and characterization 具有下垂脂肪环的新型透明聚(芳醚腈)共聚物:合成与表征
IF 2.8 4区 化学 Q3 POLYMER SCIENCE Pub Date : 2025-12-11 DOI: 10.1007/s10965-025-04700-w
Shajie Luo, Yuan Wang, Shuai Zhang, Jun Zhou, Jiale Wang, Xiaohan Wang, Lishi Jiang

Two kinds of novel poly(arylene ether nitrile) copolymers (P-HFD and P-PFD) containing pendant aliphatic rings and fluorene groups were synthesized by 4, 4’-cyclohexane-1, 1’-diyldiphenol (CHDP) or 4, 4’-cyclopentane-1, 1’-diyldiphenol (CPDP), 4, 4’-(9-fluorenylidene) diphenol and 2, 6-dichlorobenzonitrile (DCBN) in this work. The inherent viscosities of these two copolymers were 0.455 and 0.576 dL/g. The copolymers P-HFD and P-PFD exhibited good thermal property, the glass transition temperatures (Tg) were 202.2–214.9 °C, and the weight-loss temperatures (T5%) were 421.3–433.5 °C. The polymers’ films had good tensile strengths of 27.3–38.6 MPa. The result of dissolution experiment showed that the copolymers could be dissolved in some solutions at room temperature, such as NMP, DMF and CH2Cl2, implying they had good solubility, they can be processed by the solution method. Additionally, the optical transmittances of these two copolymers were 68.3–76.3% at 450 nm, indicating that they have the potential to be applied as the heat-resistant optical films.

以4,4′-环己烷- 1,1′-二基二酚(CHDP)、4,4′-环戊烷- 1,1′-二基二酚(CPDP)、4,4′-(9-芴基)二酚和2,6 -二氯苯腈(DCBN)为原料,合成了两种新型的含脂肪环和芴基团的聚(芳醚腈)共聚物(P-HFD和P-PFD)。这两种共聚物的固有粘度分别为0.455和0.576 dL/g。共聚物P-HFD和P-PFD表现出良好的热性能,玻璃化转变温度(Tg)为202.2 ~ 214.9℃,失重温度(T5%)为421.3 ~ 433.5℃。聚合物薄膜具有良好的抗拉强度(27.3 ~ 38.6 MPa)。溶解实验结果表明,共聚物在室温下可溶解于NMP、DMF和CH2Cl2等溶液中,具有良好的溶解性,可采用溶液法加工。另外,这两种共聚物在450 nm处的透过率为68.3 ~ 76.3%,表明它们具有作为耐热光学薄膜应用的潜力。
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引用次数: 0
Benzene-1,2,4,5-tetracarboxylic acid and graphene oxide-modified polyaniline composite for energy storage applications 苯-1,2,4,5-四羧酸和氧化石墨烯改性聚苯胺复合材料的储能应用
IF 2.8 4区 化学 Q3 POLYMER SCIENCE Pub Date : 2025-12-11 DOI: 10.1007/s10965-025-04701-9
Imran Hussain, Ashok Kumar Dasmahapatra

The development of advanced electrode materials with high specific energy and robust cycling stability is critical for next-generation energy storage systems, including hybrid electric vehicles, solar energy harvesting, and grid-scale energy management. This work reports the in-situ synthesis of a ternary nanocomposite comprising polyaniline (PANI), benzene-1,2,4,5-tetracarboxylic acid (BTCA), and graphene oxide (GO), engineered to enhance supercapacitive performance. BTCA serves both as a dopant and structure-directing agent, facilitating the formation of uniform PANI nanorods and optimized at molar ratios of BTCA:aniline (1:4) and aniline:ammonium persulfate (1:1). Morphological analysis confirms homogeneous GO distribution, while selected-area electron diffraction reveals polycrystalline features. The composite exhibits excellent thermal stability (91% weight retention at 800 °C) and a BET surface area of 36.53 m2/g with type IV isotherm characteristics. Enhanced π-π stacking reduces chain disorder, improving conjugation length and charge transport. Electrochemical studies demonstrate dominant capacitive behavior where Nyquist plot reveal ~ 2.9Ω equivalent series resistance, ~ 0.0001978 Ω charge transfer resistance and the vertical-like tail at low frequencies demonstrates EDLC, achieving a specific capacitance of 274.8 F/g, energy density of 38.17 Wh/kg, and power density of ~ 1000 W/kg. Long-term cycling performance confirms 88% and 98% retention after 10,000 GCD and CV cycles respectively (two-electrode). Despite minor ohmic losses, the BTCA/PANI/GO composite in a device configuration while charged for approximately 40 s can glow a red LED for more than 90 s, offering a promising platform for high-performance supercapacitor electrodes with superior thermal resilience and electrochemical durability.

具有高比能量和强大循环稳定性的先进电极材料的开发对于下一代储能系统至关重要,包括混合动力电动汽车,太阳能收集和电网规模的能源管理。本文报道了原位合成一种三元纳米复合材料,该材料由聚苯胺(PANI)、苯-1,2,4,5-四羧酸(BTCA)和氧化石墨烯(GO)组成,旨在增强超电容性能。BTCA作为掺杂剂和结构导向剂,有利于形成均匀的聚苯胺纳米棒,并在BTCA:苯胺(1:4)和苯胺:过硫酸铵(1:1)的摩尔比下进行了优化。形貌分析证实氧化石墨烯分布均匀,而选择区域电子衍射显示出多晶特征。该复合材料具有优异的热稳定性(800℃时重量保持率91%),BET表面积为36.53 m2/g,具有IV型等温线特性。增强的π-π堆叠减少了链的无序性,改善了共轭长度和电荷输运。电化学研究证实了主要的电容行为,Nyquist图显示~ 2.9Ω等效串联电阻,~ 0.0001978 Ω电荷转移电阻,低频垂尾显示EDLC,比电容为274.8 F/g,能量密度为38.17 Wh/kg,功率密度为~ 1000 W/kg。长期循环性能证实,在10,000次GCD和CV循环后,保留率分别为88%和98%(双电极)。尽管欧姆损耗很小,但在充电约40秒的情况下,器件配置中的BTCA/PANI/GO复合材料可以使红色LED发光超过90秒,为具有优异热弹性和电化学耐久性的高性能超级电容器电极提供了一个有前途的平台。
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引用次数: 0
Non-isothermal crystallization kinetics of modified polylactic acid/kenaf fiber biocomposites 改性聚乳酸/红麻纤维生物复合材料的非等温结晶动力学
IF 2.8 4区 化学 Q3 POLYMER SCIENCE Pub Date : 2025-12-11 DOI: 10.1007/s10965-025-04713-5
Adibah Borhan, Razaina Mat Taib

This study investigates the non-isothermal crystallization kinetics of polylactic acid (PLA), PLA/kenaf fiber (KF), and glycidyl methacrylate grafted polylactic acid (PLA-g-GMA)/KF biocomposites. Non-isothermal crystallization kinetics were analyzed with DSC, and crystallization morphologies were observed with POM. The Avrami, Ozawa, and Mo models described the non-isothermal crystallization kinetics. Determination of the half-time of crystallization (t1/2) and Avrami-Jeziorny crystallization rate constant (Zc) revealed that PLA/KF biocomposite reduced crystallization times across overall cooling rates and increased crystallization rates, indicating KF’s role as a nucleating agent. However, the crystallization rates of PLA/KF were hindered by the introduction of the PLA-g-GMA matrix. The Kissinger and Friedmann models agreed that activation energy (ΔE) for PLA/KF exhibited the lowest value, suggesting that KF accelerates the crystallization rate of PLA. Conversely, PLA-g-GMA/KF biocomposites exhibited the highest ΔE, providing direct kinetic evidence that the grafted GMA creates strong interfacial interactions with KF, which effectively restricts PLA chain mobility and dominates over the nucleating ability of the fiber. POM observations confirmed that KF promoted heterogeneous nucleation on PLA, while PLA-g-GMA inhibited crystallization by restricting PLA chain mobility.

研究了聚乳酸(PLA)、PLA/红麻纤维(KF)和甲基丙烯酸甘油酯接枝聚乳酸(PLA-g- gma)/KF生物复合材料的非等温结晶动力学。用DSC分析非等温结晶动力学,用POM观察结晶形貌。Avrami, Ozawa和Mo模型描述了非等温结晶动力学。结晶半衰期(t1/2)和Avrami-Jeziorny结晶速率常数(Zc)的测定表明,PLA/KF生物复合材料在整体冷却速率下减少了结晶次数,提高了结晶速率,表明KF作为成核剂的作用。然而,PLA/KF的结晶速率因PLA-g- gma基体的引入而受到阻碍。Kissinger和Friedmann模型一致认为PLA/KF的活化能(ΔE)最小,说明KF加速了PLA的结晶速率。相反,PLA-g-GMA/KF生物复合材料表现出最高的ΔE,这提供了直接的动力学证据,表明接枝的GMA与KF产生了强烈的界面相互作用,有效地限制了PLA链的迁移率,并主导了纤维的成核能力。POM观察证实KF促进PLA的非均相成核,而PLA-g- gma通过限制PLA链迁移率抑制结晶。
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引用次数: 0
Thermodynamic and kinetic study of oriented processes for the facilitated transport and extraction of lactic acid through a polymer inclusion membrane 乳酸通过聚合物包合膜的定向运输和萃取过程的热力学和动力学研究
IF 2.8 4区 化学 Q3 POLYMER SCIENCE Pub Date : 2025-12-10 DOI: 10.1007/s10965-025-04706-4
Rkia Louafy, Imane Touarssi, Rachid Ouchn, Saadia Es-sabbeur, Saad Oukkass, Khalifa Touaj, Miloudi Hlaibi

It is well-established that molecular recognition concerning carrier agents is key in transporting and diffusing biologically active molecules across cell membranes. In this context, synthetic facilitated transport membranes (FTMs) have been utilized to extract and transport lactic acid (LA), a valuable compound with various industrial applications. We applied a PVDF-based Polymeric Inclusion Membrane (PIM) incorporating Aliquat 336 as the carrier, prepared via the standard phase inversion method. The resulting PIMs were subsequently characterized using infrared spectroscopy (FTIR), scanning electron microscopy (SEM), and ATG-ATD thermal analysis. Macroscopic parameters, such as permeability (P) and initial flux (J0), were evaluated to characterize membrane performance, while microscopic parameters, including the association constant (Kass) and the apparent diffusion coefficient (D*), were determined to describe the transport mechanism of LA molecules through the membrane phase. These measurements were systematically performed by studying the effects of initial LA concentration (0.4, 0.5, 0.8, and 1 M), Aliquat 336 content in the membrane (20, 30, and 40 wt%), pH of the medium (2, 4, and 6), and temperature (298, 303, and 305 K). In addition, activation energy and thermodynamic parameters (Ea, ΔH, ΔS, and ΔHth) were determined to explain the kinetic and energetic aspects governing the mechanisms of the processes. Data demonstrate that PIM-Aliquat 336 (30 wt%) displayed high effectiveness and performance in the extraction and recovery of the value-added compound LA, particularly in a medium with a pH of 6 with permeability (P) of 35.926 × 10⁻⁷ cm²·s⁻¹ and initial flux (J0 ) of 16.750 × 10⁻⁵ mmol·cm⁻²·s⁻¹. These transport processes, generally directed by structural kinetic control within the PIM, remained efficient even at low temperatures, with activation energy (Ea) of 9.311 ∓ 0.199 kJ·mol⁻¹ and enthalpy of association ((:{varvec{varDelta:}varvec{H}}_{varvec{a}varvec{s}varvec{s}}^{ne:})) of 6.833 ∓ 0.199 kJ·mol⁻¹. Such characteristics make PIM- Aliquat 336 a promising membrane for the extraction and purification of temperature-sensitive biological compounds.

分子识别是生物活性分子跨细胞膜运输和扩散的关键。在这种情况下,合成促进转运膜(FTMs)已被用于提取和运输乳酸(LA),乳酸是一种有价值的化合物,具有各种工业应用。我们采用以Aliquat 336为载体的pvdf基聚合物包合膜(PIM),通过标准相转化法制备。随后使用红外光谱(FTIR)、扫描电镜(SEM)和ATG-ATD热分析对所得pim进行了表征。通过宏观参数,如渗透率(P)和初始通量(J0)来表征膜的性能,而微观参数,包括结合常数(Kass)和表观扩散系数(D*),来描述LA分子在膜相中的传输机制。通过研究初始LA浓度(0.4、0.5、0.8和1 M)、Aliquat 336在膜中的含量(20、30和40 wt)的影响,系统地进行了这些测量%), pH of the medium (2, 4, and 6), and temperature (298, 303, and 305 K). In addition, activation energy and thermodynamic parameters (Ea, ΔH≠, ΔS≠, and ΔHth) were determined to explain the kinetic and energetic aspects governing the mechanisms of the processes. Data demonstrate that PIM-Aliquat 336 (30 wt%) displayed high effectiveness and performance in the extraction and recovery of the value-added compound LA, particularly in a medium with a pH of 6 with permeability (P) of 35.926 × 10⁻⁷ cm²·s⁻¹ and initial flux (J0 ) of 16.750 × 10⁻⁵ mmol·cm⁻²·s⁻¹. These transport processes, generally directed by structural kinetic control within the PIM, remained efficient even at low temperatures, with activation energy (Ea) of 9.311 ∓ 0.199 kJ·mol⁻¹ and enthalpy of association ((:{varvec{varDelta:}varvec{H}}_{varvec{a}varvec{s}varvec{s}}^{ne:})) of 6.833 ∓ 0.199 kJ·mol⁻¹. Such characteristics make PIM- Aliquat 336 a promising membrane for the extraction and purification of temperature-sensitive biological compounds.
{"title":"Thermodynamic and kinetic study of oriented processes for the facilitated transport and extraction of lactic acid through a polymer inclusion membrane","authors":"Rkia Louafy,&nbsp;Imane Touarssi,&nbsp;Rachid Ouchn,&nbsp;Saadia Es-sabbeur,&nbsp;Saad Oukkass,&nbsp;Khalifa Touaj,&nbsp;Miloudi Hlaibi","doi":"10.1007/s10965-025-04706-4","DOIUrl":"10.1007/s10965-025-04706-4","url":null,"abstract":"<div><p>It is well-established that molecular recognition concerning carrier agents is key in transporting and diffusing biologically active molecules across cell membranes. In this context, synthetic facilitated transport membranes (<b>FTMs</b>) have been utilized to extract and transport lactic acid (LA), a valuable compound with various industrial applications. We applied a PVDF-based Polymeric Inclusion Membrane (PIM) incorporating Aliquat 336 as the carrier, prepared via the standard phase inversion method. The resulting PIMs were subsequently characterized using infrared spectroscopy (FTIR), scanning electron microscopy (SEM), and ATG-ATD thermal analysis. Macroscopic parameters, such as permeability (<b><i>P</i></b>) and initial flux (<b><i>J</i></b><sub><b><i>0</i></b></sub>), were evaluated to characterize membrane performance, while microscopic parameters, including the association constant (<b><i>K</i></b><sub><b><i>ass</i></b></sub>) and the apparent diffusion coefficient (<b><i>D*</i></b>), were determined to describe the transport mechanism of LA molecules through the membrane phase. These measurements were systematically performed by studying the effects of initial LA concentration (0.4, 0.5, 0.8, and 1 M), Aliquat 336 content in the membrane (20, 30, and 40 wt%), pH of the medium (2, 4, and 6), and temperature (298, 303, and 305 K). In addition, activation energy and thermodynamic parameters (<b><i>E</i></b><sub><b><i>a</i></b></sub>, <b><i>ΔH</i></b><sup><b><i>≠</i></b></sup>, <b><i>ΔS</i></b><sup><b><i>≠</i></b></sup>, and <b><i>ΔH</i></b><sub><b><i>th</i></b></sub>) were determined to explain the kinetic and energetic aspects governing the mechanisms of the processes. Data demonstrate that PIM-Aliquat 336 (30 wt%) displayed high effectiveness and performance in the extraction and recovery of the value-added compound LA, particularly in a medium with a pH of 6 with permeability (<b><i>P</i></b>) of 35.926 × 10⁻⁷ cm²·s⁻¹ and initial flux (<b><i>J</i></b><sub><b><i>0</i></b></sub> ) of 16.750 × 10⁻⁵ mmol·cm⁻²·s⁻¹. These transport processes, generally directed by structural kinetic control within the PIM, remained efficient even at low temperatures, with activation energy (<b>E</b><sub><b>a</b></sub>) of 9.311 ∓ 0.199 kJ·mol⁻¹ and enthalpy of association (<span>(:{varvec{varDelta:}varvec{H}}_{varvec{a}varvec{s}varvec{s}}^{ne:})</span>) of 6.833 ∓ 0.199 kJ·mol⁻¹. Such characteristics make PIM- Aliquat 336 a promising membrane for the extraction and purification of temperature-sensitive biological compounds.</p></div>","PeriodicalId":658,"journal":{"name":"Journal of Polymer Research","volume":"32 12","pages":""},"PeriodicalIF":2.8,"publicationDate":"2025-12-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145729640","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
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Journal of Polymer Research
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