FENE珠-簧链聚合物分子模型流变性质Brown动力学模拟

通过布朗(Brown)动力学方法模拟了有限伸展非线性弹性(FENE)珠-簧链分子模型在稳态简单剪切流场和突始剪切流场中的运动,得到分子链的位形变化轨迹,同时对聚合物分子力场进行计算分析,模拟流变性质,研究温度、弹簧参数和剪切速率等对该模型定常与非定常流变性质的影响。结果表明,随温度升高,聚合物黏度下降,随剪切速率的升高伴随有假塑性剪切变稀现象发生,并且弹簧拉伸常数不同,聚合物黏度稳态值也不同。     

简单流场中聚合物稀溶液的分子构象

介绍了研究聚合物分子模拟流变性质的Brown动力学模拟方法,提出利用FENE珠-簧链分子模型来确定聚合物稀溶液分子链在简单剪切流场下不同时刻位形的变化,并对分子链与流动方向的取向角和分子链在速度梯度方向上的构象厚度进行了计算。     

支链长度及支化程度对聚苯乙烯流变行为的影响

将窄相对分子质量分布三臂星形聚苯乙烯与线型聚苯乙烯共混组成支化聚苯乙烯体系,通过共混比例调节支化程度,研究了支链长度及支化程度对支化聚苯乙烯流变行为的影响。研究表明,支化程度对支化PS流变行为的影响与支链长度有关。对于长支链体系(支链的珚Mw,branch大于PS临界链缠结相对分子质量(Me)的2倍),由于支链对链缠结具有促进作用,随支化程度增加,分子间作用力增大以及链缠结程度加重的共同作用,导致支化PS的零剪切黏度(η0)增大。对于短支链体系(支链的珚Mw,branch小于Me的2倍),由于短支链对于链缠结具有抑制作用,随支化程度增加,支化PS的η0呈先增加后降低的变化趋势。长支链PS体系的非牛顿指数随支化程度增加而下降,呈现更加偏离牛顿流体的流动行为,其粘流活化能则随支化程度增加略有增大。     

支化高分子熔体粘弹性本构行为的比较

首先给出表征XPP、DCPP和S-MDCPP 3种粘弹性本构模型流变特性的物料函数,比较了它们对稳态简单剪切和稳态单轴拉伸流动中熔体复杂流变行为的预测能力。结果表明,S-MDCPP本构模型能够较好地反映实际支化高分子熔体的复杂流变行为。最后,讨论了S-MDCPP本构模型中各参数(主链末端支链数q、取向和拉伸松弛时间之比r以及滑移系数ξ)对熔体流变行为的影响。分析表明,主链末端支链数q以及取向和拉伸松弛时间之比r均对熔体的拉伸黏度影响较大,随着q的增加或r的减小,熔体黏度均呈现增加的趋势;随着滑移系数ξ的增加,熔体的剪切黏度降低。     

支化程度和支链长度对支化聚苯乙烯粘弹行为的影响

将星形支化聚苯乙烯与线型聚苯乙烯共混组成支化体系,使用旋转流变仪测定样品的动态粘弹温度谱和频率谱,研究了支化结构对支化聚苯乙烯粘弹性能的影响。结果表明,支化程度对支化PS粘弹行为的影响与支链长度有关。长支链体系(支链的珨Mw,branch大于2 Me)中支链对链缠结具有促进作用,随支化程度增加,受相对分子质量和缠结的共同影响,支化PS在玻璃态与橡胶态的储能模量(G′)升高,玻璃化转变温度(Tg)、粘流转变温度(Tf)和主链特征松弛时间(τe)明显上升和延长,末端弹性效应增强,并在高频下观察到支链解缠结松弛。短支链体系(支链的珨Mw,branch小于2 Me)的支链对链缠结有抑制作用,随支化程度增加,支化PS的Tg,Tf和τe升速较慢,末端弹性效应表现不明显,高频下未观察到支链松弛。     

聚合物反应加工中的化学流变学模拟

综述了近年来热固,热塑性聚合物反应加工过程中的化学流变学模拟进展,反应过程对聚合物化学流变行为起着决定性作用,以Roller模型为基础的多参数模型,改进了WLF模型和包含结构变化信息的分子模型是3种应用广泛的化学流变模型,反应加工中剪切速率和填料的影响有时是不可忽略的,它们对化学流变行为的影响随聚合物体系不同而不同。     

退火对剪切改性的长链支化聚丙烯流变性能回复的影响

利用密炼机对长链支化聚丙烯(LCB-PP)施加一定的剪切历程,随后利用真空退火和高压二氧化碳(CO_2)饱和退火对剪切改性的样品作后处理。通过熔体流动速率(MFR)、挤出胀大比(SR)以及动态流变数据等表征方法,研究了退火工艺对剪切改性样品流变性能的回复作用。结果表明,退火使流变性能得到一定回复,包括MFR减小,SR增大,低频下的储能模量和复数黏度增大。MFR和SR的结果表明,CO_2的存在使得解缠结的支链能更快恢复缠结状态,因此高压CO_2饱和退火法加速了流变性能的回复。通过分析损耗角正切、Cole-Cole曲线,也证明了高压CO_2饱和退火法对剪切改性样品流变性能回复的作用比真空退火法更显著。     

三臂星形聚苯乙烯的链缠结及松弛行为

使用差示扫描量热仪和旋转流变仪测定了三臂星形聚苯乙烯(sPS)的玻璃化转变温度、稳态及动态流变性能,并与线型聚苯乙烯(lPS)进行对比分析,研究三臂星形支化结构对聚苯乙烯链缠结及松弛行为的影响。结果表明,当sPS双臂长度与lPS主链长度相当时,sPS的玻璃化转变温度(T_g)、储存模量(G')、零剪切黏度(η_0)、末端松弛时间均大于lPS,而非牛顿指数(n)更小;当sPS与lPS重均相对分子质量相当时,sPS的T_g、n更大,η_0更小,末端松弛时间更短。sPS长支链的存在对链缠结的促进作用小于sPS高线团密度对链缠结的抑制作用,单根支链的引入主要延缓了PS的链段松弛。     

聚对苯二甲酸乙二醇酯扩链产物的分子结构

采用不同含量的四官能团单体均苯四甲酸酐(PMDA)提高聚对苯二甲酸乙二醇酯(PET)的熔体强度,在增加PET分子量的同时,使PET发生支化反应。频率扫描结果表明,扩链反应显著提高了PET的弹性模量和复数黏度;运用傅立叶变换流变学方法对长支链进行表征,根据三次谐波与基频幅值比与应变的幂律关系,发现在中等应变幅值下,扩链产物的幂律指数n均小于2,表明生成了不同支化程度的支链结构。扩链产物的黏度随扩链剂的增加而增加,但是扩链产物的支化度对扩链剂浓度存在最大值。     

新型缔合聚合物P(AM/POEA)溶液的流变性质

应用黏度法和动态模量研究了新型缔合聚合物P(AM／POEA)的溶液流变性质。该聚合物由丙烯酰胺(AM)和少量2-苯氧乙基丙烯酸酯(POEA)(n(POEA)≤1．0％)组成。结果表明,共聚物的微结构对其溶液的流变性能有重要影响。嵌段共聚物(BP系列)具有显著的增黏能力,而无规共聚物(RP系列)则没有这种作用。这种由分子间的疏水缔合作用而产生的疏水缔合增黏能力与疏水嵌段的数量和长度密切相关．同时进一步研究了聚合物浓度、盐浓度、温度和剪切速率对溶液黏度的影响。动态模量测试表明,该聚合物缔合体系在实验浓度范围内黏性响应占有优势。     

Investigation of the flow behaviors of carbon nanotubes dispersed epoxy resin with modified bi-mode FENE dumbbell simulation

In this study, a modified bi-mode finitely extensible non-linear elastic (FENE) dumbbell model was introduced to investigate the concentration-dependent and shear-rate-dependent viscosity of carbon nanotubes (CNTs) dispersed polymer solutions. It is called bi-mode because the aggregated CNTs and free CNTs are considered as two different types of CNTs with different mobility. The diffusion coefficient was simulated by classical molecular dynamics (MD) simulation and input into the FENE models. For the steady shear flow, the coupled Fokker–Planck equations and the corresponding stress tensors were solved numerically. The influence of CNT diameter and CNT mass on the shear viscosity was discussed. In addition, the bi-mode FENE dumbbell simulation can be applied to investigate the shear viscosity under different shear rates and increase of shear viscosity with time evolution. With the model, the influence of the anisotropy parameter, finite extensibility parameter was investigated. The shear-rate-dependent viscosity profile of resin solutions with different CNT concentrations was also predicted and validated with experimental rheological behavior. The simulation model can provide qualitative prediction of rheological behavior of CNTs dispersed resin.     

平板Couette流场中聚合物流变性质及分子构象的数值模拟

通过耦合Brown构形场的有限体积法,对基于FENE(Finite Extension Non-linear Elastic)殊一簧链分子模型的平板Couette流动进行了模拟.不但得到了流动过程中的速度、应力等宏观信息,还得到了分子链的位形、分子链的取向角以及拉伸量等微观信息.另外,还研究了弹簧的最大拉伸长度b和we...     

支化高分子在收缩膨胀流道中的复杂流变行为

为了洞察支化高分子熔体在收缩膨胀流道内的复杂流变行为,文中采用S-MDCPP和DCPP模型分别描述支化高分子熔体的本构行为。针对黏弹性本构方程中的对流占优问题,采用离散的弹性-黏性应力分裂技术/迎风流线(DEVSS/SU)法解决。同时采用改进的有限增量微积分(FIC)法和等低阶单元插值求解变量。研究表明,2种模型预测的结果吻合较好,而且2种模型预测的等色条纹图与实验结果吻合较好。另外,还讨论了Weissenberg数对支化高分子流变行为的影响。     

In-process rheometry as a PAT tool for hot melt extrusion

Real time measurement of melt rheology has been investigated as a Process Analytical Technology (PAT) to monitor hot melt extrusion of an Active Pharmaceutical Ingredient (API) in a polymer matrix. A developmental API was melt mixed with a commercial copolymer using a heated twin screw extruder at different API loadings and set temperatures. The extruder was equipped with an instrumented rheological slit die which incorporated three pressure transducers flush mounted to the die surface. Pressure drop measurements within the die at a range of extrusion throughputs were used to calculate rheological parameters, such as shear viscosity and exit pressure, related to shear and elastic melt flow properties, respectively. Results showed that the melt exhibited shear thinning behavior whereby viscosity decreased with increasing flow rate. Increase in drug loading and set extrusion temperature resulted in a reduction in melt viscosity. Shear viscosity and exit pressure measurements were found to be sensitive to API loading. These findings suggest that this technique could be used as a simple tool to measure material attributes in-line, to build better overall process understanding for hot melt extrusion.     

Steady and oscillatory flows of silicon-polypropylene ceramic compounds

The rheological properties of a ceramic moulding compound, silicon powder with a polypropylene binder system, were studied using a Rheometrics mechanical spectrometer RMS-800 and an Instron capillary rheometer. The study included steady simple shear flow, transient start-up shear flow, stress relaxation upon cessation of steady shear flow, stress relaxation after a sudden shear displacement, and dynamic oscillatory shear flow. Yield behaviour was observed in both steady-shear and dynamic measurements. The empirical Cox-Merz rule which is usually applicable to polymer melts and solutions was found to be invalid for this material. The modified Cox-Merz rule, in which the apparent viscosity versus shear rate is equal to the complex viscosity versus the shear-rate amplitude in the highly nonlinear region, was found to be valid for this material system. A series of anomalous phenomena were also observed during the shear-flow experiments including work hardening in the very-low-shear-rate region, stress oscillation in the high-shear-rate region, and stress relaxation followed by substantial stress growth in the stress-relaxation measurements.     

水性室温交联聚丙烯酸酯乳液的流变性

以两种加料方法合成了含双丙酮丙烯酰胺(DAAM)功能单体的聚丙烯酸酯乳液,添加己二酰肼,获得单组分室温可固化乳液,并对两种乳液的流变性作了研究。研究发现,乳液的表观黏度(aη)、稠度系数(K)、零剪切黏度(0η)随DAAM含量的增加而增加,而流动指数(n)则减小;两段均预乳化法的aη、K、0η均大于仅一段预乳化法。     

PVDF、LCP及其共混物的流变行为

研究了ＰＶＤＦ、ＬＣＰ的表观粘度随温度,剪切速率的变化规律,并对液晶含量对共混物熔体度的影响进行了讨论。     

Time-Dependent and Flow Properties of Foams

Foams have been prepared from water added with a surfactant and a polymer. A controlled stress rheometer was used to study the changes of their rheological properties during ageing by the mean of different rheological tests: shear viscosity measurements, creep compliance tests at a constant low shear stress and dynamic experiments have been performed. It has been observed that apparent viscosity decreases with ageing. A thixotropic behaviour was also found, loading and unloading curves present an hysteresis. Then, the choice of the stress ascent time is of primary importance to study the time-dependent properties of the foam. The viscosity was found to decrease with the stress ascent time while the thixotropic area decreases. Creep flow and harmonic tests have shown important viscoelastic properties of the foams.The second part of this work is concerned with the study of the flow properties of the foams. Pressure drops were measured during flow in capillary tubes in laminar regime. Pronounced wall slip effects were found. While the Mooney method for slip correction is not applicable, the Oldroyd–Jastrzebski method leads to satisfactory results. The Metzner and Reed correlation method was found to be applicable in the case of the corrected data.