Rheology of polyacrylonitrile‐based precursor polymers produced from controlled (RAFT) and conventional polymerization: Its role in solution spinning

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.     

PAN链缠结的影响因素及其对PAN/DMSO溶液流变行为的影响

采用旋转流变仪对聚丙烯腈/二甲基亚砜（PAN/DMSO）溶液进行了流变学测试，探究了表观黏度（η_α）、储能模量、损耗模量、损耗正切角与温度、浓度以及剪切情况之间的关系，明确了PAN链缠结对PAN/DMSO溶液流变行为及其分子结构的影响，探究了PAN链缠结与浓度、温度及剪切速率之间的关系。结果表明，预剪切可以有效地拆除部分PAN链的缠结，使PAN/DMSO溶液η_α降低，且温度升高及浓度降低时剪切作用对η_α的影响作用减小，流变稳定性提高。     

Solubility parameter-based analysis of polyacrylonitrile solutions in N,N-dimethyl formamide and dimethyl sulfoxide

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 S_N2 reaction.     

碳添加剂对聚丙烯腈溶液流变性影响的研究

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。     

Constant rotational rheological behaviors of the PAN/DMSO/nonsolvent systems

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     

碳纳米管/聚丙烯腈复合纤维的制备及结构研究

通过原位聚合的方法制备了碳纳米管/聚丙烯腈(CNTs/PAN)聚合液,用湿法纺丝工艺制备了CNTs/PAN复合纤维,分析了复合纤维流变性能、热性能及截面形貌。结果表明:CNTs的加入使得聚合物溶液出现了假凝胶化,粘度和弹性均有所上升,纺丝时溶液细流的表层遇水迅速凝固成致密的皮层,影响了纤维芯部的二甲基亚砜(DMSO)和水的双扩散作用,凝固丝出现了很明显的皮芯结构,CNTs的加入还使得纤维预氧化放热过程得到了缓和。     

碳纳米管对聚丙烯腈溶液流变行为的影响

将混酸处理后的多壁碳纳米管(MWNT)超声分散于含5%水的二甲基亚砜(DMSO)中,然后将其与聚丙烯腈(PAN)/DMSO(含5%水)的纺丝溶液剪切共混,制备含碳纳米管的PAN纺丝溶液。采用椎板旋转流变仪研究了PAN纺丝溶液的流变行为。结果表明,添加碳纳米管后,PAN纺丝溶液的表观粘度变大,且其对剪切速率的敏感性增强。同时,随着MWNT含量的增加,PAN纺丝溶液的非牛顿指数降低,结构粘度指数和粘流活化能增大。     

聚丙烯腈/凹凸棒土纺丝溶液的流变行为

将纳米凹凸棒土(AT)加入聚丙烯腈(PAN)/二甲基亚砜(DMSO)纺丝溶液中,用平板流变仪研究了温度、AT含量对纺丝溶液流变性能的影响。结果表明:随着AT含量的提高,纺丝溶液的表观黏度及结构黏度指数降低,非牛顿指数和粘流活化能增大。     

纤维素原料/离子液体溶液体系流变性能的研究

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。     

UHMW-PAN中空纤维膜的研制及应用——Ⅲ.温度对UHMW-PAN/DMSO溶液流变性能的影响

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.     

PAN／DMSO溶液凝胶化行为的流变学研究

通过动态流变测试,研究PAN／DMSO溶液的热致变凝胶化过程和测定PAN／DMSO溶液的凝胶点温度。主要通过测量动态流变学参数（动态模量G′i和G″ii、损耗角正切tanδ、复数粘度η^＊）来表征PAN溶液的凝胶化行为,分析了含水量对溶液凝胶化行为和凝胶结构的影响。结果发现,虽然PAN溶液的凝胶点温度随着溶液中含水量的增加而升高,但是由松弛指数n和分形维数值df表征的凝胶结构几乎不受溶液中含水量的影响。     

PAN/PBA复合聚合物乳液性质的研究

用三种不同的加料方法和两种不同的加料顺序,制备了PAN/PBA复合聚合物乳液。测定了乳胶粒子的大小,分布,形态及胶体的表面张力,电导率,离心稳定性,电解质稳定性。发现单体全滴加法和AN先加入法的胶体表面张力大,电导率小,对电解质和离心稳定性较好。     

Investigation of Poly(vinyl alcohol)/Pluronic F127 Physical Gels

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.     

Rheological Behaviors of Polyacrylonitrile/1-Butyl-3-Methylimidazolium Chloride Concentrated Solutions

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.     

硅烷偶联剂对白炭黑填充溴化丁基橡胶/天然橡胶并用胶性能的影响

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。     

聚丙烯腈/离子液体溶液流变性能的研究

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。     

PAN/氧化石墨烯纳米复合材料的热性能研究

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。     

聚丙烯腈/多壁碳纳米管共混纤维的研制

碳纳米管经表面改性后与聚丙烯腈溶液共混制备了纺丝浆液,采用湿法纺丝技术制备了聚丙烯腈/多壁碳纳米管(PAN/MWNT)共混纤维。研究了碳纳米管对共混溶液动态流变性能的影响,探讨了共混纤维的物理机械性能和结晶特性。结果表明:MWNTs的加入降低了纺丝原液的黏度,明显提高了共混纤维的力学性能,降低了延伸率,并对纤维的结晶度有一定的影响。     

聚丙烯腈纺丝原液三元体系的流变行为

用流变测试方法研究了非溶剂水的含量对聚丙烯腈/二甲基亚砜/水三元纺丝原液溶胶-凝胶的转变过程的影响,并测定了不同组成的原液的凝胶点。结果表明:随着非溶剂含量的提高,原液的凝胶点提高。聚丙烯腈纺丝原液凝胶转变的行为与非溶剂的含量密切相关。     

落球法研究PAN/DMSO溶液的溶胶凝胶化转变

该研究测定不同温度下PAN/DMSO溶液落球粘度的变化,以活化能的转变为判据,确定了不同条件下PAN/DMSO溶液的溶胶凝胶化转变温度。将落球法的结果与动态流变法结果相比较,发现两者十分接近,所以改进的落球法是一种研究溶液凝胶化转变的简单、可信的方法。