The viscoelastic behavior of concentrated polyacrylonitrile/1‐butyl‐3‐methylimidazolium chloride from solution to gel

The viscoelastic behavior of concentrated polyacrylonitrile (PAN) /1‐butyl‐3‐methylimidazolium chloride ([BMIM]Cl) solutions at different concentrations and temperatures has been investigated by rheology. For concentrated polymer solutions at low temperature (40°C), the shear viscosity was found to show a raid decrease from the ending of Newtonian plateau. At relatively high shear rate or frequency for the concentrated PAN/[BMIM]Cl solutions, the deviation from the empirical Cox–Merz rule was quite evident, which suggested the formation of heterogeneous structures within these solutions. However, the dependence of G′ and G″ on angular frequency presented approximate linearity with similar slope at some temperatures between 100°C and 20°C. All the results lead us to the fact that the gelation has occurred within the concentrated solutions during cooling and the process was found to be thermoreversible. The gelation temperatures of the solutions have exhibited strong concentration dependence. It may be suggested that the microphase separation may be the major reason for the gelation of the concentrated PAN/[BMIM]Cl solutions during cooling process. POLYM. ENG. SCI., 54:598–606, 2014. © 2013 Society of Plastics Engineers     

Diffusion dynamics of ionic liquids during the coagulation of solution spinning for acrylic fibers

The coagulation dynamics of acrylic polymer (PAN) with 1‐butyl‐3‐methylimidazolium chloride [BMIM]Cl as solvent for PAN and H₂O as nonsolvent was investigated in detail. On the basis of Fick's second law of diffusion, a mass‐transfer model of [BMIM]Cl from concentrated PAN/[BMIM]Cl solution was established as verified with the experimental data. The established model has a good fit with the experimental data and the diffusion coefficient D of [BMIM]Cl was calculated according to the model. The diffusion coefficient D decreased a little when the concentration of solution increased. As increasing the coagulation bath concentration, the diffusion coefficient D initially increased and then decreased, reaching a maximum of 5 wt% in the coagulation bath. The diffusion coefficient D decreased with the coagulation bath temperature. From the diffusion coefficient and the structure of the coagulated filament, it can be concluded that the diffusion rate of [BMIM]Cl from PAN concentrate solutions is relatively slow, which is prospective to prepare uniform‐structure fibers. POLYM. ENG. SCI., 48:184–190, 2008. © 2007 Society of Plastics Engineers     

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.     

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。     

MWCNTs含量对纤维素/[BMIM]Cl溶液及其纤维性能和形态结构的影响

分析了经表面功能化的MWCNTs(多壁碳纳米管)在纤维素/[BMIM]Cl(1-丁基-3-甲基咪唑氯盐)体系中的分散稳定性,探讨了MWCNTs/纤维素/[BMIM]Cl溶液的流变行为,并通过干湿法制备了不同MWCNTs含量的离子液体法纤维素纤维,对其力学性能和表面形态结构进行了研究。结果表明:MWCNTs/纤维素/[BMIM]Cl溶液为切力变稀流体。随着溶液中MWCNTs添加量的增加,溶液表观黏度先增大后减小;适量的MWCNTs可以均匀分散在纤维素/[BMIM]Cl溶液体系中并具有良好的可纺性,所制得的MWCNTs/纤维素纤维表面较光滑且力学性能明显改善。其中,含1%MWCNTs的纤维素纤维的初始模量和断裂强度较高,分别比未添加MWCNTs的纤维提高66.7%和22.7%。     

Characteristics of polyacrylonitrile solutions and fibers varied with the dissolution process in ionic liquid

The concentrated polyacrylonitrile (PAN) solutions were prepared with 1‐butyl‐3‐methylimidazolium chloride ([BMIM]Cl) as solvent by static state, stirring, and kneading. The steady and oscillatory shear tests were carried out to investigate the viscoelastic behaviors of the PAN/[BMIM]Cl solutions by rotational rheometer. It was found that the zero shear‐rate viscosity and relaxation time of the solution prepared by kneading were lowest and the non‐Newtonian index was largest among the solution. During kneading, the gelation temperature of the viscous and homogenous solution was at the lowest temperature 22.7°C among the all three solutions. Only the solutions prepared by stirring and kneading could be spun by dry‐jet wet spinning technology. The fiber processed with the solution prepared by kneading could be drawn with a higher draw ratio, showing the larger draw ability. The supramolecular structure and properties of the fibers were studied by synchrotron wide‐angle X‐ray diffraction (WAXD) technologies, dynamic mechanical analysis (DMA), and mechanical tests. All the results showed that the kneading is an efficient method for PAN fiber spinning with [BMIM]Cl as solvent. It lead to the investigation of the methods of preparation of PAN solution in [BMIM]Cl, which affect the homogeneity of the solutions and hence the resulting characteristics of PAN fibers. POLYM. ENG. SCI., 55:558–564, 2015. © 2014 Society of Plastics Engineers     

Solution behavior of two novel anionic polyacrylamide copolymers hydrophobically modified with n‐benzyl‐n‐octylacrylamide

Two novel hydrophobically modified anionic polyacrylamides (HM‐PAMs), p(AM/NaA/NaAMC₁₂S/BOAM) and p(AM/NaA/OP‐10‐AC/BOAM) have been prepared by an aqueous micellar copolymerization technique from acrylamide, sodium acrylate (NaA), sodium 2‐(acrylamido)dodecane‐1‐sulfonate (NaAMC₁₂S), octylphenol polyoxyethylene acrylate (OP‐10‐AC), and small amounts of N‐benzyl‐N‐octylacrylamide, respectively, with the objective of investigating the copolymers' rheological behaviors and surface activities under various conditions such as polymer concentration, shear rate, temperature, and salinity. As expected, the copolymers exhibit improved thickening properties due to intermolecular hydrophobic associations as the solution viscosity of the copolymers increases sharply with increasing polymer concentration. A decrease in viscosity is observed with increasing temperature, and the solution viscosity of the copolymers decreases with increasing NaCl concentration. Furthermore, the block copolymers exhibit high air–liquid surface activities as the surface tensions (STs) decrease with increasing polymer concentration. This behavior is yet another evidence of polymolecular micelles formation of the copolymers in aqueous solution, and thus the high tendency to adsorb at an interface. The ST exhibited by the copolymers was found to be relatively insensitive to the concentration of salt (NaCl). Scanning electron micrographs showed large aggregates in solutions, which is formed by the association from the hydrophobic groups of the polymers. POLYM. ENG. SCI., 2012. © 2012 Society of Plastics Engineers     

两种咪唑型离子液体对纤维素的溶解及纺丝性能的比较

以1-乙基-3-甲基咪唑醋酸盐（[EMIM]Ac）和1-丁基-3-甲基咪唑氯盐（[BMIM]CI）两种咪唑型离子液体为溶剂,研究比较了它们对纤维素的溶解性能及其溶液的纺丝加工性能。结果发现：两种离子液体均能在一定条件下溶解纤维素,但[EMIM]Ac较[BMIM]Cl对纤维素具有更低的溶解温度和更快的溶解速率。从流变分析还发现：纤维素/[EMIM]Ac溶液与纤维素/[BMIMCl溶液均为切力变稀流体,相同条件下纤维素/[EMIM]Ac溶液的黏度远低于纤维素/[BMIM]Cl溶液,使其可在相对低的温度下纺丝。此外,GPC分析结果表明：纤维素在用[EMIM]Ac溶解及纺丝过程中降解程度较小,而用[BMIM]Cl进行溶解纺丝时,降解作用则较明显。对纤维结构与力学性能的分析结果进一步表明：与相同喷头拉伸比下制得的[EMIM]Ac法再生纤维素纤维相比,[BMIM]Cl法再生纤维素纤维的聚集态结构相对较完善,结晶度与取向度更高些,从而使其力学性能也相对较好。     

溶解方式对聚丙烯腈-离子液体溶液和纤维的影响

通过静置、搅拌和捏合3种不同的溶解方式制备了聚丙烯腈(PAN)质量分数为13%的PAN-[BMIM]Cl(1-丁基-3-甲基咪唑氯盐)溶液。采用旋转流变仪研究了这3种溶液的流变特性,发现捏合溶解得到的溶液的零切黏度与松弛时间最小,非牛顿指数最大,溶液性质均一稳定。利用制备的纺丝溶液进行干喷湿纺试验,发现静置溶解的纺丝溶液无法纺丝,而捏合溶解的纺丝溶液可实现较高倍数的喷头拉伸和水浴拉伸。结合广角X射线衍射(WAXD)、力学性能测试、动态力学分析(DMA)等测试方法,对比分析了两种溶解方法制备的PAN纤维的超分子结构和性能,发现捏合溶解纺丝得到的纤维结构更为均匀,力学性能更好。     

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。     

Rheological Behavior of Poly(m-phenyleneisophthalamide) in Ionic Liquid

Summary The rheological behavior of poly(m-phenyleneisophthalamide) (PMIA) in 1-n-butyl-3-methylimidazolium chloride ([Bmim]Cl, ionic liquid) has been investigated. The polymer in the concentration range investigated exhibits very different behavior between [Bmim]Cl and DMAc/LiCl solvent. Unlike in DMAc/LiCl solvent, PMIA/[Bmim]Cl solution exhibits maxima in apparent viscosity-concentration plots in the range studied. The complex viscosity-frequency behavior of the PMIA/[Bmim]Cl solutions is similar to that steady-state rheological behavior. The different rheological behavior shows the interaction between macromolecule and IL which leading the supermolecular aggregates in PMIA/[Bmim]Cl solution.     

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     

Rheological study on thermal-induced gelation behavior of polyacrylonitrile solution

Thermal-induced gelation process of different polyacrylonitrile (PAN) solutions was investigated through dynamic rheological measurements. The rheological material parameters characterizing the gelation behavior of the PAN solutions were measured and the effects of such factors as water content, solvent type and concentration on the gelation process were analyzed. It is found that the gel point T _gel of PAN/DMSO (dimethyl sulfoxide)–water solution increases with increased water content in the solution. Also, T _gel becomes higher when the solvent has a lower solvency for PAN. A linear relationship between logG′ and logω, logG″ and logω indicates the beginning of gelation. The PAN concentration of the solution affects T _gel in a way similar to that of the water content. The relaxation exponent n is found to relate to the fractal dimension of the polymer gel. For PAN/DMSO–water solution, this exponent n remains almost constant when the water content differs. The solvent type and concentration respectively influences n value in their own way. The PAN/DMSO–water solution systems in our work exhibit similar characteristics of gel structure, concluded from the n and d _f values of these systems. A logarithmic plot between G′ and G″ can be used to evaluate the structural evolution of the solution, and a comparatively steep slope of the curve is an indication of gelation.     

Determination of physical properties for the mixtures of [BMIM]Cl with different organic solvents

Physical properties including refractive index, density, viscosity and conductivity for binary mixtures of 1-butyl-3-methyl imidazolium chloride ([BMIM]Cl) and different organic solvents at 298.15 K have been investigated. Ex-cess molar volumes have been calculated and obtained data has been fitted by the Redlich–Kister equation. The density and refractive index were found to increase with increasing concentration of [BMIM]Cl, however, excep-tions do exist as in the case of dimethyl sulfoxide (DMSO)/[BMIM]Cl. For DMSO/[BMIM]Cl, the density decreases with increasing concentration. The addition of different organic solvents was able to disrupt the interactions within mixtures, leading to free mobility of ions. The free mobility of ions has been found to enhance conductivity and decrease viscosity to varying extents in al mixtures studied. It has been observed that solubility parameters, dielectric constants and composition of the solvents used play a vital role in determining the resultant properties. The data obtained wil play an important role in understanding the effect of the addition of organic solvents in ILs to enhance their applicability.     

Viscoelasticity of concentrated polyacrylonitrile solutions: effects of solution composition and temperature

The effects of solution composition and temperature on the viscoelasticity of concentrated polyacrylonitrile (PAN) solutions were studied using a variety of rheological measurements, such as steady‐state shearing, dynamic stress sweep and transient rheological tests. The first normal stress difference N₁ and the shear stress τ were found to increase with decreasing temperature and increasing PAN concentration and water content in the solutions. The crossover point of N₁ and τ, denoting the equal contribution of viscosity and elasticity to the viscoelasticity of the solutions, moved to lower shear rates at lower temperature, higher PAN concentration and higher water content. The values of the relaxation time (λ) were larger at 70 °C than at 40 °C. In addition, the changes of λ with PAN concentration and water content were different at the two temperatures, ascribed to the different states of the solutions. The PAN solutions were in the linear viscoelastic regime in the temperature range 40–70 °C when the shear stress was below 300 Pa. The creep compliance recovery rate decreased with increasing temperature, but increased with increasing PAN concentration and water content. Thixotropic tests showed that the thixotropy of the solutions was also affected by the solution composition and temperature. Gelation was found to influence the way the solution composition and temperature affected the viscoelastic properties of the PAN solutions. Copyright © 2011 Society of Chemical Industry     

Preparation and characterization of imidazolyl ionic liquid-based shear thickening dispersion system

Shear thickening liquid (STF) is a new nonNewtonian fluid widely used in industrial production. In this paper, a novel shear thickening and dispersing system, namely poly methyl methacrylate (PMMA)/1-butyl-3-methylimidazole hexa-fluorophosphate ([BMIM]PF₆), was prepared using ultrasonic with PMMA as the dispersing phase and [BMIM]PF₆ as the dispersing medium. The stability, thixotropic, reversibility, rheology, and viscoelasticity of the dispersion system was studied, respectively. The dispersed system has good stability. The dispersed system shows high response sensitivity to shear rate, as well as good reversibility to shear thickening. Compared with traditional silicon dioxide/polyethylene glycol dispersion system, PMMA/[BMIM]PF₆ dispersion system displays a significantly enhanced shear thickening effect. Nonionic surfactant triton X-100 of 4 wt% can greatly improve PMMA/[BMIM]PF₆ dispersion system's shear thickening behavior. This paper provides a new idea for the further development of protective materials by using STF.     

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.     

The effect of shear rate on the molecular weight determination of acrylamide polymers from intrinsic viscosity measurements

The rheological response of dilute solutions of high molecular weight polyacrylamides at low shear rates has been measured using a capillary viscometer that provided for a fivefold variation in shear rate at each concentration. The non-Newtonian effects were found to be significant for polyacrylamides with number-average molecular weights exceeding 10⁶. The molecular weight average–intrinsic viscosity relationship most widely used in the literature, [η] = 6.80 × 10^?4M , was found to be valid when [η] was measured at high shear rates where the polymer solutions approached Newtonian behavior. A new relationship was developed relating M _n to the intrinsic viscosity extrapolated to zero shear rate.     

Solution and interfacial behavior of hydrophobically modified water-soluble block copolymers of acrylamide and N-phenethylacrylamide

Hydrophobically modified water-soluble block copolymers were prepared by aqueous micellar copolymerization of acrylamide and small amounts (2 and 3 mol %) of a hydrophobe (N-phenethylacrylamide) that is characterized by a long spacer that places the aromatic ring far away from the backbone, with the objective of investigating the copolymers' rheological behavior and surface and interfacial activities under various conditions such as polymer concentration, shear rate, temperature, and salinity. As expected, the block copolymers exhibit improved thickening properties attributed to intermolecular hydrophobic associations as the solution viscosity of the copolymers increases sharply with increasing polymer concentration. Additional evidence for intermolecular association is provided by the effect of NaCl, the presence of which substantially enhances the viscosity. An almost shear rate–independent viscosity (Newtonian plateau) is also exhibited at high shear rate and a typical non-Newtonian shear thinning behavior appears at low shear rates and high temperatures. Furthermore, the block copolymers exhibit high air–liquid surface and liquid–liquid interfacial activities as the surface and interfacial tensions decrease with increasing polymer concentration, indicating strong adsorption of the copolymer at the interface. The surface and interfacial tensions exhibited by the copolymers were found to be relatively insensitive to the concentration of salt (NaCl). © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 467–476, 2001     

Influence of surfactants on rheological behaviors of polyacrylonitrile/dimethyl sulfoxide/silicon blending polymer solutions

KH550, KH560, CTAB, and F127 were adopted to modify silicon (Si) to improve the dispersity and stability of Si in the polyacrylonitrile/dimethyl sulfoxide (PAN/DMSO) polymer solutions. The influence of surfactants on rheological behaviors of PAN/DMSO/Si blending polymer solutions was investigated by an advanced solution and melt rotation rheometer. The homogeneity and stability were also studied. The results showed that the surfactants could change the viscosity dependence of blending polymer solutions on shear rate, temperature and storage time by increase the steric hindrance of Si. Among the four solutions, PAN/DMSO/Si blending polymer solution with F127 exhibited the lowest viscosity, activation energy and the smallest structural viscosity index and exhibited the trend close to the Newtonian fluids. Moreover, PAN/DMSO/Si blending polymer solution with F127 exhibited the best dispersity and stability, indicating its best physical properties and machinability.