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Rheology of polyacrylonitrile‐based precursor polymers produced from controlled (RAFT) and conventional polymerization: Its role in solution spinning 下载免费PDF全文
Polymer solutions in dimethyl sulfoxide (DMSO) as a solvent, made from reversible addition fragmentation chain transfer (RAFT)‐mediated polyacrylonitrile (RAFT¥ PAN) terpolymer with molecular weight (MW) of 260,000 g/mol and dispersity (Ð) of 1.29, behave differently under applied shear stress than polymer solutions made from conventional PAN (Control PAN) with similar MW (258,000 g/mol) but Ð of 2.05 in the same solvent. The unique rheology of RAFT PAN is because of the reduced amount of high MW polymer fractions. Specifically, a 25% (w/v) polymer solution of RAFT PAN had a viscosity of 198 Pas while the equivalent control PAN polymer solution had a viscosity of 968 Pas at a shear rate of 1 s?1. Also, RAFT PAN polymer solutions had a longer Newtonian plateau than control PAN polymer solutions. This exhibits more liquid character in RAFT PAN polymer solutions than control PAN polymer solutions at same temperature and concentration. In dynamic tests, RAFT PAN polymer solutions gelled slower than their equivalent control PAN polymer solutions because of their longer polymer chain relaxation times. Slow gelling and higher liquid character in RAFT PAN polymer solutions can result in obtaining stronger and finer precursor fibers during wet spinning. Since RAFT PAN polymer solutions exhibit low viscosity and higher liquid character when compared to its equivalent control PAN at same concentration and temperature, these can allow a wider working window for wet spinning and can also allow higher solid content in the polymer solutions that remain easy to wet spin. This is expected to lead to compact and finer fibers with less voids and higher strength. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44273. 相似文献
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The physical properties of the solutions of polyacrylonitrile (PAN) in N,N-dimethyl formamide (DMF) and dimethyl sulfoxide (DMSO) were characterized in terms of solubility parameter. The physical properties were largely determined by individual solubility parameters, particularly the polar term, rather than overall solubility parameter. With increasing temperature, the intrinsic viscosity and hydrodynamic diameter of dilute solutions were decreased but the dynamic viscosity (η′) of concentrated solutions was increased. Of the two solvents, these phenomena were more pronounced with DMF; DMF gave greater η′ and yield stress than DMSO. When the polymer solutions were dried at 25 °C DMSO generated a cocontinuous structure whereas DMF produced a dispersed morphology. In addition, DMF dissolved PAN faster than DMSO, and the dissolution process followed a mechanism analogous to SN2 reaction. 相似文献
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以碳纳米管(MCNT)和碳黑(CB)为添加剂,采用溶液共混的方法,讨论了添加剂浓度、放置时间、温度、剪切速率对聚丙烯腈溶液的表观黏度及黏流活化能(ΔΕη)的影响。结果表明:随着MCNT含量的增加,聚丙烯腈溶液的黏度先增大后减小,添加1.0%MCNT时,聚丙烯腈溶液的黏度最大,活化能也同时达到最大;随着碳黑含量的增加,黏度与活化能都随之增加,但增加幅度不大。两种PAN溶液都属于明显的切力变稀的非牛顿流体,随着剪切速率的增加,黏度下降;但在高切变速率(>800s-1)时,黏度几乎不变。 相似文献
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The constant rotational rheological behaviors of PAN/DMSO solutions with two kinds of nonsolvent (water and ethanol) have been investigated, respectively, using a cone‐plate rheometer. From viscosity measurements, the flow behavior was described within the shear rate range 0.1–1000 s?1. The PAN solutions show shear thinning at high shear rates. The viscosities of the solutions decreased with the rising of the temperature at low shear rate. H2O content has great influence on the viscosity of the solutions, depending on the hydration of H2O and PAN or desolvent effect, according to different H2O content. The role of ethanol compared with H2O was also researched and higher viscosity was found. Non‐Newtonian index, structural viscosity index Δη, and flow activation energy of the PAN/DMSO/H2O systems were also studied. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009 相似文献
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纤维素原料/离子液体溶液体系流变性能的研究 总被引:5,自引:0,他引:5
利用NDJ-1型旋转粘度计分别对木浆/离子液体氯化1-丁基-3-甲基咪唑([BMIM]Cl)溶液体系和水洗汽爆麦草/[BMIM]Cl溶液体系的流变性能进行了研究。考察了转子转速、温度、纤维素浓度及添加剂等对溶液粘度的影响。结果表明,两种溶液体系的流动活化能均较低,分别为42 kJ/mol和47 kJ/mol,其表观粘度随温度升高而降低;纤维素浓度和浆粕聚合度的增加都可使溶液的粘度增加。进一步研究了不同添加剂对粘度的影响,发现二甲基亚砜(DMSO)、N,N-二甲基乙酰胺(DMAC)和1,4-二氧六环的加入都能降低溶液的粘度,但以DMSO的效果最佳。 相似文献
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在前文的基础上,研究了温度对超高分子量聚丙烯腈/二甲基亚砜溶液的零切粘度、流动曲线、非牛顿指数、最大松弛时间、结构粘度指数的影响,探讨了它们与溶液流动性、可纺性和挤出过程稳定性的关系.发现与常规分子量聚丙烯腈/二甲基亚砜溶液相比,其非牛顿指数和粘流活化能较小;而最大松弛时间却高出约三个数量级,因此当原液温度低于130℃时,流动曲线上不出现第一牛顿区.确定了溶液流动性、可纺性和挤出过程稳定性均较好的温度应不低于130℃,为纺制高强UHMW-PAN纤维和中空纤维膜提供了依据. 相似文献
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Weiwei Liu Lingyan Cheng Hongyan Zhang Yumei Zhang Huaping Wang Mingfang Yu 《International journal of molecular sciences》2007,8(3):180-188
One of the room temperature ionic liquids (RTILs), 1-butyl-3-methylimidazolium chloride ([BMIM]Cl) was chosen to prepare the concentrated solutions of Polyacrylonitrile (PAN). The rheological behaviors of the solutions were measured with rotational rheometry under different conditions, including temperatures, concentration, and molecular weight of PAN. The solutions exhibited shear-thinning behaviors, similar to that of PAN/DMF solutions. The viscosities decreased with the increasing of shear rates. However, the viscosity decreased sharply at high shear rates when the concentration was up to 16wt%. The dependence of the viscosity on temperature was analyzed through the determination of the apparent activation energy. Unusually, the viscosity of solutions of higher concentration is lower than that of lower concentration. Similarly, the viscosity of low molecular weight PAN was higher than high molecular weight PAN at high shear rates. The dynamic rheological measurement indicates the loss modulus is much higher than storage modulus. The trend of complex viscosity is similar with the result of static rheological measurement. The interaction between PAN and ionic liquid [BMIM]Cl was discussed. 相似文献
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Maria Bercea Simona Morariu Loredana Elena Nita Raluca Nicoleta Darie 《Polymer-Plastics Technology and Engineering》2013,52(13):1354-1361
The application of Pluronic F127 as injectable gel-forming solution is limited by poor mechanical properties. The purpose of this study was to develop low viscosity formulations at ambient temperature that undergo a transition to gel under physiological conditions. Mixtures of Pluronic F127 and poly(vinyl alcohol) with different compositions were prepared in aqueous solutions and their in-situ gelation was investigated by dynamic light scattering and rheology. The results obtained for different formulations showed synergistic effects of polymer mixtures in aqueous media and their properties can be tuned by varying polymer concentration, system composition or changing temperature. 相似文献
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试验研究硅烷偶联剂Si69,Si75和KH560对白炭黑填充溴化丁基橡胶(BIIR)/天然橡胶(NR)并用胶性能的影响。结果表明:随着硅烷偶联剂Si75或KH560用量的增大,胶料的挤出膨胀率呈增大趋势,门尼粘度和F;减小,Payne效应减弱,定伸应力和拉伸强度呈增大趋势,拉断伸长率和撕裂强度呈减小趋势,加工性能和老化后耐屈挠性能改善;硅烷偶联剂Si75和KH560能够明显改善白炭黑填充BIIR/NR并用胶的加工性能和老化后的耐屈挠性能。 相似文献
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采用应力流变仪对聚丙烯腈/1-丁基-3-甲基咪唑氯化物(PAN/[BMIM]Cl)溶液体系的稳态和动态流变性能进行了研究,讨论了PAN相对分子质量(Mη)对溶液稳态和动态流变性能的影响。结果表明:PAN/[BMIM]Cl溶液在低剪切速率区表现出牛顿流体特征,在高剪切速率区随着剪切速率的增大粘度降低,表现为切力变稀流体;溶液的粘度大于常规溶剂体系,随着PAN的Mη增大,PAN/[BMIM]Cl溶液表观粘度明显增大,非牛顿指数减小,粘流活化能增大;溶液的损耗模量和储能模量越大,溶液更容易表现出弹性效应。 相似文献
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PAN/氧化石墨烯纳米复合材料的热性能研究 总被引:1,自引:0,他引:1
采用原位聚合的方法制备了聚丙烯腈(PAN)/氧化石墨烯(GO)纳米复合材料;利用红外光谱和紫外光谱表征了试样的组成及组分间的相互作用;使用扫描电镜和透射电镜对试样的微观形貌进行观察;从单体转化率和聚合液的黏度变化研究了GO对丙烯腈自由基聚合的影响;用热分析仪分析了GO对PAN热稳定化过程的影响。结果表明:复合体系聚合至13 h时,与空白试样(PAN)相比,聚合液的黏度和单体转化率分别降低了1.3%和2.9%,说明在聚合前期GO对自由基聚合起到一定的阻聚作用;GO的厚度由聚合前的3~4 nm剥离到聚合后的1 nm,表明GO在原位聚合过程中以单层形式分散在PAN基体中;PAN与GO之间存在较强的π-π相互作用,这种相互作用抑制了PAN在热稳定化过程中的环化反应。 相似文献
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Jong Hak Kim Byoung Ryul Min Hyun Chae Park Jongok Won Yong Soo Kang 《应用聚合物科学杂志》2001,81(14):3481-3488
The solubility gaps for poly(vinyl pyrrolidone) (PVP) in four polyimide solutions (NMP, DMF, GBL, DMSO) were determined by cloud point measurement and correlated with χPI/Solvent and ΔδPVP/Solvent. Membranes prepared with NMP and DMF systems showed a tendency of suppressing fingerlike structure with addition of PVP. On the other hand, membranes prepared with GBL and DMSO systems showed an inclination toward inducing macrovoid formation. These effects of PVP on the membrane morphology were explained by means of miscibility gap, viscosity of the polymer solution, polymer–polymer phase separation, and overall porosity. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 3481–3488, 2001 相似文献