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Enhancing the safety and thermal stability of polyurethane filling materials in the mining industry through expanded graphite-based hydrated salts 通过膨胀石墨水合盐提高采矿业聚氨酯填充材料的安全性和热稳定性
IF 4.1 2区 化学 Q2 POLYMER SCIENCE Pub Date : 2024-08-22 DOI: 10.1016/j.polymer.2024.127525

The utilization of Polyurethane foaming materials (PUF) to seal coal fissures presents a significant challenge due to the substantial heat generated during the reaction process, potentially accelerating fires. In order to study this issue, we propose a novel low-heat polymerization mechanism by incorporating a hydrated salt phase change composite that efficiently absorbs polymerization heat while encapsulating liquid water using expanded graphite (EG). Our findings demonstrate that integrating 10 % EG-6 leak-free phase change material effectively reduces the reaction temperature to a safer 91.4 °C, ensuring minimal impact on the inherent properties of the material. Thorough analyses via TGA and in-situ IR experiments reveal a noteworthy 17 °C elevation in the modified PUF's thermodynamic characteristic temperature point. Additionally, we developed a mixed combustion model of PUF and coal to investigate the gas generation pattern of polyurethane in the mine-filled state where fire occurs. Specifically, the introduction of PUF reduced O2 consumption and CO production while increasing CO2 and C2H4 production, which is consistent with the reality of increased carbon hydrocarbon gases being monitored downhole. These findings suggest a synergistic, mutually beneficial relationship between the two during the low-temperature oxidation stage. This research offers perspectives for the development of polymer materials for coal mines and the safe application of actual filling.

由于聚氨酯发泡材料(PUF)在反应过程中会产生大量热量,有可能加速火灾的发生,因此利用聚氨酯发泡材料封堵煤炭裂缝是一项重大挑战。为了研究这个问题,我们提出了一种新型低热聚合机制,即在使用膨胀石墨(EG)封装液态水的同时,加入一种水合盐相变复合材料,以有效吸收聚合热量。我们的研究结果表明,集成 10 % EG-6 无泄漏相变材料可有效地将反应温度降低到更安全的 91.4 °C,确保对材料固有特性的影响降到最低。通过热重分析和原位红外实验进行的彻底分析表明,改良聚氨酯泡沫的热力学特征温度点显著提高了 17 ℃。此外,我们还建立了聚氨酯和煤的混合燃烧模型,以研究聚氨酯在矿井充填状态下发生火灾时的气体生成模式。具体来说,聚氨酯泡沫的引入降低了 O 的消耗量和 CO 的产生量,同时增加了 CO 和 CH 的产生量,这与井下监测到的碳氢化合物气体增加的实际情况相符。这些研究结果表明,在低温氧化阶段,两者之间存在协同互利的关系。这项研究为煤矿聚合物材料的开发和实际充填的安全应用提供了前景。
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引用次数: 0
A non-destructive strategy to construct ZIF-8 interface layer of carbon fiber/hydroxyapatite-epoxy composites 构建碳纤维/羟基磷灰石-环氧树脂复合材料 ZIF-8 界面层的无损策略
IF 4.1 2区 化学 Q2 POLYMER SCIENCE Pub Date : 2024-08-22 DOI: 10.1016/j.polymer.2024.127533

The interface is the transition region between the fiber and the matrix, whose structure and characteristics determine the overall performance and sustained stability of carbon fiber/hydroxyapatite-epoxy (CHR) composites as bone implant materials. Similarly, carbon fibers, as reinforcement, also play an indispensable role in carrying external loads. Therefore, this work focuses on improving the fibers surface in a gentle and non-destructive way to ensure that the reinforcement of both the fibers and the interface is maximized, resulting in excellent mechanical and biotribological properties. In this work, a novel interface layer was designed by introducing zeolitic imidazolate framework-8 (ZIF-8) into CHR with a facile solvent method. The presence of ZIF-8 induces the formation of flower-cluster hydroxyapatite. The complex layer formed by the combination of the polyhedral shape ZIF-8 and the flower-cluster hydroxyapatite enhances the mechanical interlock and chemical interaction between the carbon fibers and the epoxy matrix. It also promotes the penetration and curing process of the epoxy matrix. The tensile strength of ZIF-8 reinforced CHR (ZIF-8@CHR) are 136.97 MPa, which is 38.43 % higher than that of the pristine CHR. And the wear rate (1.18 × 10−14 m3(N·m)−1) of ZIF-8@CHR is decreased by 81.65 %. ZIF-8@CHR with superior mechanical and biotribological properties provides new insights into the biological application of carbon fiber composites as an implant material for fracture fixation or reconstruction.

界面是纤维与基体之间的过渡区域,其结构和特性决定了碳纤维/羟基磷灰石-环氧树脂(CHR)复合材料作为骨植入材料的整体性能和持续稳定性。同样,碳纤维作为增强材料,在承受外部载荷方面也发挥着不可或缺的作用。因此,这项工作的重点是以温和、无损的方式改善纤维表面,以确保最大限度地增强纤维和界面的强度,从而获得优异的机械和生物分布特性。在这项工作中,我们采用简便的溶剂法在 CHR 中引入了沸石咪唑酸框架-8 (ZIF-8),从而设计出一种新型界面层。ZIF-8 的存在可诱导形成花簇状羟基磷灰石。多面体形状的 ZIF-8 和花簇状羟基磷灰石结合形成的复合层增强了碳纤维和环氧基质之间的机械互锁和化学作用。它还能促进环氧基质的渗透和固化过程。ZIF-8 增强 CHR(ZIF-8@CHR)的拉伸强度为 136.97 MPa,比原始 CHR 高 38.43 %。ZIF-8@CHR 的磨损率(1.18 × 10 m(N-m))降低了 81.65%。ZIF-8@CHR 具有优异的机械和生物ribological 性能,为碳纤维复合材料作为骨折固定或重建植入材料的生物应用提供了新的思路。
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引用次数: 0
Bromine-containing copolymer polycarbonate for simultaneous thermal stability, transparency, and thin-wall flame-retardant polycarbonate 同时具有热稳定性、透明度和薄壁阻燃性的含溴共聚聚碳酸酯
IF 4.1 2区 化学 Q2 POLYMER SCIENCE Pub Date : 2024-08-22 DOI: 10.1016/j.polymer.2024.127532

The incorporation of traditional low molecule bromine flame retardants can enhance the flame retardancy of polycarbonate (PC), yet their poor compatibility with PC impairs its transparency and mechanical properties. Here, brominated polycarbonate (B50PC) was synthesized by interfacial polycondensation method using bisphenol A, tetrabromobisphenol A, and triphosgene. The number average molecular weight (Mn) of B50PC reached 14,600, and compared to the low molecule bromine flame retardant tetrabromobisphenol A (TBBPA), its initial decomposition temperature increased by 38.7 % under air atmosphere. The PC composites containing 5 wt% B50PC achieved the V-0 rating in the UL-94 test, with LOI increased by 10.3 %. At the same time, the peak heat release rate (PHRR) was decreased by 28.6 % and the ignition time (TTI) was delayed by 21.3 %. Compared with that of samples with TBBPA, the composite with the same amount of B50PC maintained the original elongation at break of PC and the transmittance remained at 84.9 %. In summary, the composites with B50PC maintains outstanding transparency and mechanical properties while enhancing the flame retardancy. This work has developed a high molecular bromine flame retardant that combines flame retardancy and transparency, offering a strategy for expanding the application of PC in the electronics, construction, and aerospace sectors.

传统的低分子溴系阻燃剂可以提高聚碳酸酯(PC)的阻燃性,但它们与 PC 的相容性较差,会影响 PC 的透明度和机械性能。本文采用界面缩聚法,利用双酚 A、四溴双酚 A 和三光气合成了溴化聚碳酸酯(BPC)。BPC 的平均分子量()达到 14 600,与低分子溴系阻燃剂四溴双酚 A(TBBPA)相比,其在空气环境下的初始分解温度提高了 38.7%。含有 5 wt% BPC 的 PC 复合材料在 UL-94 测试中达到了 V-0 级,LOI 增加了 10.3%。同时,峰值热释放率(PHRR)降低了 28.6%,点火时间(TTI)延迟了 21.3%。与添加了 TBBPA 的样品相比,添加了等量 BPC 的复合材料保持了 PC 原有的断裂伸长率,透射率保持在 84.9%。总之,含有 BPC 的复合材料在提高阻燃性的同时,还保持了出色的透明度和机械性能。这项研究开发出了一种兼具阻燃性和透明度的高分子溴系阻燃剂,为扩大 PC 在电子、建筑和航空航天领域的应用提供了一种策略。
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引用次数: 0
Photo- and thermo-responsive poly(ionic liquid) hydrogel regulated by hierarchical host–guest interactions 由分层主客体相互作用调控的光和热响应聚(离子液体)水凝胶
IF 4.1 2区 化学 Q2 POLYMER SCIENCE Pub Date : 2024-08-22 DOI: 10.1016/j.polymer.2024.127505

Supramolecular hydrogels constructed through various host–guest interactions have attracted tremendous attention in view of their excellent dynamic and multi-stimuli responsive performances. Herein, benzyl (Bn) and azobenzene (Azo) grafted poly(ionic liquid)s (PILs) were prepared via a one-pot post-synthesis strategy. By virtue of the difference in binding affinity of Azo and Bn groups with the host compound cucurbituril [8] urea (CB[8]), the newly-developed supramolecular hydrogels exhibited distinctive photo- and thermo-responsive behaviors. Under UV light irradiation, PIL-Azo-Bn/CB[8] hydrogel got weaker, while a gel-to-sol transition was observed when treated by heating. Moreover, the above tunable behaviors were highly reversible. Variable-temperature measurements such as proton nuclear magnetic resonance and ultraviolet–visible spectroscopy illustrated that the photo- and thermo-regulated performances of PIL hydrogel were ascribed to the hierarchical host–guest interactions. As a prototype application in smart circuits, PIL hydrogel exhibited a photo- and thermo-tuned conductivity. Thus, our finding presented a novel and versatile platform to fabricate responsive functional hydrogels via host–guest interactions, which has great promising applications in smart materials and flexible sensors.

通过各种主客体相互作用构建的超分子水凝胶具有优异的动态和多刺激响应性能,因而备受关注。本文通过一锅后合成策略制备了苄基(Bn)和偶氮苯(Azo)接枝的聚(离子液体)(PILs)。由于偶氮基团和偶氮苯基团与宿主化合物葫芦脲(CB[8])的结合亲和力不同,新开发的超分子水凝胶表现出独特的光响应和热响应行为。在紫外线照射下,PIL-Azo-Bn/CB[8]水凝胶变弱,而在加热处理时则出现凝胶到溶胶的转变。此外,上述可调行为具有高度可逆性。质子核磁共振和紫外可见光谱等变温测量结果表明,PIL 水凝胶的光热调节性能归因于分层的主客体相互作用。作为智能电路的应用原型,PIL 水凝胶表现出了光调节和热调节的导电性。因此,我们的发现为通过主客体相互作用制造响应性功能水凝胶提供了一个新颖、多用途的平台,在智能材料和柔性传感器领域具有广阔的应用前景。
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引用次数: 0
Insight into the less β-phase induction by calcium pimelate in polypropylene random copolymer 聚丙烯无规共聚物中聚壬酸钙对β相诱导作用的深入研究
IF 4.1 2区 化学 Q2 POLYMER SCIENCE Pub Date : 2024-08-22 DOI: 10.1016/j.polymer.2024.127528

Although calcium pimelate (CaPim) is recognized as an efficient β-nucleating agent for polypropylene with nucleating ability solely for the β-phase, it was found to induce less β-phase in polypropylene random copolymer (PPR) compared to polypropylene homopolymer (PPH). Generally, this reduction is attributed to unfavorable β-growth. Besides growth, here, nucleation behavior was also investigated in detail. With nucleation barrier determined through fractionated crystallization, the relative β-nuclei proportion induced by CaPim was calculated to be 96.6 % for PPH and 79.1 % for PPR with 7.3 mol% ethylene inserted. This fewer β-nuclei induction may be linked to a decreased proportion of isometric sequences exceeding the critical length required for β-nucleation. As expected, the relative growth rate of the β- to α-phase (Gβ/Gα) is lower in PPR indicating unfavorable β-growth. These results indicate that diminished β-nuclei induction and subsequent unfavorable β-growth jointly result in less β-phase induction in PPR.

尽管聚丙烯酸钙(CaPim)被公认为是聚丙烯的高效 β 成核剂,其成核能力只针对 β 相,但研究发现,与聚丙烯均聚物(PPH)相比,它在聚丙烯无规共聚物(PPR)中诱导的 β 相较少。一般来说,这种减少归因于不利的 β 生长。除了生长之外,我们还对成核行为进行了详细研究。通过分馏结晶确定成核障碍后,计算出 CaPim 诱导的相对 β 核比例在 PPH 和 PPR 中分别为 96.6% 和 79.1%(其中乙烯插入量为 7.3 摩尔%)。β核诱导比例降低可能与超过β核形成所需的临界长度的等轴序列比例降低有关。正如预期的那样,PPR 中 β 相与 α 相的相对生长率(/)较低,这表明 β 生长不利。这些结果表明,β核诱导的减少和随后不利的β生长共同导致了 PPR 中β相诱导的减少。
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引用次数: 0
Low-energy micron dispersion of entangled polymers based on phase inversion composition of emulsion 基于乳液相位反转成分的纠缠聚合物低能微米分散技术
IF 4.1 2区 化学 Q2 POLYMER SCIENCE Pub Date : 2024-08-22 DOI: 10.1016/j.polymer.2024.127519

This article aims to propose a low-energy method for micron dispersion of entangled polymers. We chose Ethylene-Propylene-Diene Monomer (EPDM) as the entangled polymer and acrylic esters as the dispersants to prepare the organic dispersion of the entangled polymer based on the theory that in-situ polymerization of acrylic esters had the higher solubility parameter than the original monomer. The dispersion process of entangled polymer was similar to the phase inversion of emulsion due to the maximum viscosity and minimum interfacial tension at the point of dispersion. Specifically, the average diameter of the dispersed entangled polymer was 5–6 μm. The system could still maintain excellent dispersion stability without additional dispersants. Rheology characterized that the introduction of aliphatic isocyanate derivatives reacting with hydroxyl groups in the polyacrylate to form the cross-linked skeleton could enhance the stability of the system. Excitingly, this organic dispersion allowed flexible printed circuit to fold at any angle and direction when used as the coating, and the coating still maintained excellent dispersibility, flexibility, insulation, and adhesion after aging tests. This low-energy method for micron dispersion of entangled polymers could expand their applications in coatings and other fields while maintaining their own characteristics.

本文旨在提出一种低能耗的微米级分散缠结聚合物的方法。根据丙烯酸酯原位聚合的溶解度参数高于原始单体的理论,我们选择乙烯-丙烯-二烯单体(EPDM)作为缠结聚合物,丙烯酸酯作为分散剂来制备缠结聚合物的有机分散体。由于分散点具有最大粘度和最小界面张力,缠结聚合物的分散过程类似于乳液的相反转。具体来说,分散的缠结聚合物的平均直径为 5-6 μm。在不添加额外分散剂的情况下,该体系仍能保持良好的分散稳定性。流变学特征表明,引入脂肪族异氰酸酯衍生物与聚丙烯酸酯中的羟基反应形成交联骨架,可提高体系的稳定性。令人兴奋的是,当使用这种有机分散体作为涂层时,柔性印刷电路可以任意角度和方向折叠,而且涂层在老化测试后仍能保持良好的分散性、柔韧性、绝缘性和附着力。这种低能耗的微米分散缠结聚合物的方法可以在保持其自身特性的同时,扩大其在涂层和其他领域的应用。
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引用次数: 0
High-strength, impact-resistant PP/PTFE composite foam with enhanced surface appearance achieved through mold-opening microcellular injection molding 高强度、抗冲击的 PP/PTFE 复合泡沫,通过开模微孔注塑成型技术改善了表面外观
IF 4.1 2区 化学 Q2 POLYMER SCIENCE Pub Date : 2024-08-22 DOI: 10.1016/j.polymer.2024.127527

Poor surface appearance and decreased mechanical performance are critical factors limiting the broad application of Microcellular injection molding (MIM) in foamed polymer products. Herein, in-situ polytetrafluoroethylene (PTFE) nanofibrils reinforced polypropylene (PP) foams with high strength, impact resistance, and enhanced surface quality were prepared by mold opening microcellular injection molding (MOMIM). PTFE nanofibers with different diameters were introduced into the PP matrix via twin screw extrusion and significantly enhanced the crystallinity and viscoelasticity of the PP matrix with the enhancement being more pronounced for the finer PTFE fibers. High-density oriented cellular structures were formed in the MOMIM PP/PTFE foams owing to the heterogeneous nucleation of PTFE and the stretching effect of the mold opening process. The optimum MOMIM PP/PTFE foam fabricated possesses a high cell orientation angle close to 90° and a large cell aspect ratio of 5.3, which reached a 34.37 % increase in tensile strength and a 73.08 % increase in impact strength owing to the synergetic effects of the PTFE network and the highly oriented fine cell structure, which effectively dissipated the tensile stress and impact stress by cell wall twisting and folding deformation. Furthermore, the MOMIM PP/PTFE foam showed a significantly enhanced surface quality compared to the MIM foam due to the reduced dragging flow in MOMIM, which greatly hindered cell rupture on the foam surface. Therefore, this work provides insights into the MOMIM of polymer composites containing fibrous fillers and the enhancement of tensile properties, impact resistance, and surface quality of foam products.

表面外观不佳和机械性能下降是限制微孔注射成型(MIM)在发泡聚合物产品中广泛应用的关键因素。本文采用开模微孔注塑成型(MOMIM)技术制备了原位聚四氟乙烯(PTFE)纳米纤维增强聚丙烯(PP)泡沫,这种泡沫具有高强度、抗冲击性和更好的表面质量。通过双螺杆挤压将不同直径的 PTFE 纳米纤维引入聚丙烯基体,显著提高了聚丙烯基体的结晶度和粘弹性,其中较细的 PTFE 纤维的增强效果更为明显。由于聚四氟乙烯的异质成核和开模过程的拉伸效应,MOMIM PP/PTFE 泡沫中形成了高密度的定向蜂窝结构。由于聚四氟乙烯网络和高取向细胞结构的协同作用,拉伸强度提高了 34.37%,冲击强度提高了 73.08%。此外,与 MIM 泡沫相比,MOMIM PP/PTFE 泡沫的表面质量明显提高,这是因为 MOMIM 减少了拖流,大大阻碍了泡沫表面的细胞破裂。因此,这项研究为含纤维填料的聚合物复合材料的 MOMIM 以及提高泡沫产品的拉伸性能、抗冲击性和表面质量提供了深入的见解。
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引用次数: 0
Enhancing the dyeability of polyurethane fibers by introducing protonated tertiary amine groups 通过引入质子化叔胺基团提高聚氨酯纤维的染色性
IF 4.1 2区 化学 Q2 POLYMER SCIENCE Pub Date : 2024-08-22 DOI: 10.1016/j.polymer.2024.127524

Traditional polyurethane fibers (CPUF) are widely used in the preparation of blend clothing in order to improve the elasticity and comfort of fabrics. However, there has been a problem of low acid dye adsorption for CPUF, resulting in light hue of dyed CPUF. In this work, a poly (HMDI-BHOPA) was prepared with dicyclohexylmethane 4,4′-diisocyanate (HMDI) and 1,4-(2-hydroxyethyl) piperazine (BHOPA), and then added into the CPUF spinning solution for the preparation of modified polyurethane fibers (BPUFs) through dry-spinning technology. Tertiary amine groups were introduced after the addition of poly (HMDI-BHOPA), which could be protonated at acidic conditions to form binding sites for acid dyes, further enhancing the adsorption capacity of the fibers. Nuclear magnetic resonance spectroscopy (1H and 13C NMR) was used to confirm the structure of poly (HMDI-BHOPA). The results of differential scanning calorimetry (DSC) and thermogravimetry analysis (TGA) demonstrated that the addition of poly (HMDI-BHOPA) had little effect on the glass transition temperature and thermal stability of BPUFs. The addition of poly (HMDI-BHOPA) affected the ordered arrangement of hard segments and reduced crystallization enthalpy of hard and soft segments in polyurethane. Hence, the elastic recovery of BPUFs showed little change, and the elongation at break and break strength decreased compared to CPUF. Zeta potential testing results showed that BPUFs was protonated under acidic conditions. Dyeing results proved the enhancement of dyeability of BPUFs. The dyeing kinetics and thermodynamics of acid dyes on BPUFs were studied to investigate the dyeing mechanism. From the dyeing kinetics results, both CPUF and BPUFs fitted Elovich model. From dyeing thermodynamics results, Langmuir model showed a better applicability for BPUFs at a low pH and temperature condition, while Freundlich model fitted better for CPUF.

传统聚氨酯纤维(CPUF)被广泛应用于混纺服装的制作,以提高织物的弹性和舒适性。然而,CPUF 一直存在酸性染料吸附力低的问题,导致染色后的 CPUF 色调偏淡。本研究用 4,4′-二异氰酸酯二环己基甲烷(HMDI)和 1,4-(2-羟乙基)哌嗪(BHOPA)制备了聚(HMDI-BHOPA),并将其加入 CPUF 纺丝溶液中,通过干法纺丝技术制备改性聚氨酯纤维(BPUF)。加入聚(HMDI-BHOPA)后引入的叔胺基团可在酸性条件下质子化,形成酸性染料的结合位点,进一步提高纤维的吸附能力。核磁共振光谱(1H 和 13C NMR)用于确认聚(HMDI-BHOPA)的结构。差示扫描量热法(DSC)和热重分析法(TGA)的结果表明,添加聚(HMDI-BHOPA)对 BPUF 的玻璃化转变温度和热稳定性影响很小。聚(HMDI-BHOPA)的添加影响了硬段的有序排列,降低了聚氨酯中硬段和软段的结晶焓。因此,与 CPUF 相比,BPUF 的弹性恢复变化不大,断裂伸长率和断裂强度有所下降。Zeta 电位测试结果表明,BPUFs 在酸性条件下呈质子化状态。染色结果证明了 BPUFs 染色性的增强。研究了酸性染料在 BPUFs 上的染色动力学和热力学,以探究染色机理。从染色动力学结果来看,CPUF 和 BPUF 都符合 Elovich 模型。从染色热力学结果来看,在低 pH 值和低温条件下,Langmuir 模型对 BPUFs 更为适用,而 Freundlich 模型对 CPUF 更为适用。
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引用次数: 0
Impacts of viscosity on bending behavior of the electrospun jet: Simulation model and experiment 粘度对电纺射流弯曲行为的影响:模拟模型和实验
IF 4.1 2区 化学 Q2 POLYMER SCIENCE Pub Date : 2024-08-21 DOI: 10.1016/j.polymer.2024.127529

Numerous experimental data indicate that higher viscosity solutions make it easier to obtain coarser fibers. However, the influences of viscosity on the whipping behavior of the jet and their subsequent impacts on the formation of terminal fiber during electrospinning remain topics of ongoing research. Simulation model and experiment presented in this study aim to solve these problems. The simulation model alters the dimensionless parameter Fve to predict the impacts of different viscosities on the bending behavior of the electrospun jet, while the experiment observes this behavior under different viscosities by regulating the solution concentration. The consistency of the simulation and experimental data implies the accuracy of the conclusions in this paper. Furthermore, the simulation model and experiment have demonstrated that a higher viscosity jet results in a smaller radius of the jet trajectory and lower jet velocity, which in turn leads to the formation of coarser fiber.

大量实验数据表明,粘度较高的溶液更容易获得较粗的纤维。然而,粘度对射流鞭打行为的影响以及随后对电纺过程中末端纤维形成的影响仍是当前研究的主题。本研究中提出的仿真模型和实验旨在解决这些问题。仿真模型通过改变无量纲参数 Fve 来预测不同粘度对电纺射流弯曲行为的影响,而实验则通过调节溶液浓度来观察不同粘度下的电纺射流弯曲行为。模拟和实验数据的一致性意味着本文结论的准确性。此外,模拟模型和实验还证明,粘度越高,射流轨迹半径越小,射流速度越低,从而形成的纤维越粗。
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引用次数: 0
Corrigendum to “Phthalate-free plasticizer-based polyvinyl chloride gels for electrically focus-tunable microlens applications” [Polymer 308 (2024) 127338] 用于电聚焦可调微透镜应用的不含邻苯二甲酸酯增塑剂的聚氯乙烯凝胶"[聚合物 308 (2024) 127338] 更正
IF 4.1 2区 化学 Q2 POLYMER SCIENCE Pub Date : 2024-08-20 DOI: 10.1016/j.polymer.2024.127395
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引用次数: 0
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Polymer
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