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Thermal Imidization Peculiarities of Electrospun BPDA-PDA/ODA Copolyamic Acid Nanofibers

机译:电纺BPDA-PDA / ODA共聚酰胺酸纳米纤维的热亚胺化特性

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摘要

Copolyamic acid (coPAA) based on 4,4'-oxydianiline (ODA), p-phenylenediamine (PDA) and 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA) was synthesized in N-dimethylformamide (DMF). The preparation of continuous defect-free nanofibers from BPDA-PDA/ODA coPAA was achieved by electrospinning of its DMF solution. The average fiber diameter significantly increased from 385 to 590 nm on increasing the total polymer concentration of the spinning solutions from 5 to 7 wt%. The addition of dodecylethyldimethylammonium bromide (DEDAB) salt to the spinning solution resulted in the procurement of coPAA nanofibers with a much smaller (more than 3 times) average diameter. The coPAA imidization process was investigated through FTIR spectroscopy. The chemical composition and morphology of coPI nanofibers were assessed by X-ray photoelectron spectroscopy and scanning electron microscopy. Imidization under isothermal conditions proceeded faster in the first stage. Activation energies in the first and second imidization stages were similar when DEDAB had been added into the electrospinning solution. Cylindrical or crimped defect-free nanofibers of BPDA-PDA/ODA copolyimide (coPI) were obtained by the stepped thermal imidization of coPAA. The morphology of coPI nanofibers depends on the curing temperature. The crimped coPI nanofibers were most probably due to the relief of residual stress when the curing temperature was higher than the polymer glass transition temperature.
机译:在N-二甲基甲酰胺(DMF)中合成了基于4,4'-氧二苯胺(ODA),对苯二胺(PDA)和3,3',4,4'-联苯四甲酸二酐(BPDA)的共聚酰胺酸(coPAA)。由BPDA-PDA / ODA coPAA制备连续无缺陷的纳米纤维是通过对其DMF溶液进行电纺丝来实现的。当纺丝溶液的总聚合物浓度从5wt%增加到7wt%时,平均纤维直径从385nm显着增加。向纺丝溶液中添加十二烷基乙基二甲基溴化铵(DEDAB)盐导致获得了平均直径小得多(大于3倍)的coPAA纳米纤维。通过FTIR光谱研究了coPAA的酰亚胺化过程。通过X射线光电子能谱和扫描电子显微镜对coPI纳米纤维的化学组成和形态进行了评估。在第一阶段,等温条件下的亚胺化进行得更快。当将DEDAB添加到电纺丝溶液中时,第一和第二酰亚胺化阶段的活化能相似。 BPDA-PDA / ODA共聚酰亚胺(coPI)的圆柱形或卷曲无缺陷纳米纤维是通过coPAA的逐步热酰亚胺化获得的。 coPI纳米纤维的形态取决于固化温度。当固化温度高于聚合物玻璃化转变温度时,卷曲的coPI纳米纤维最有可能是由于残余应力的减轻。

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