超高分子量聚苯乙烯的流变性能

以毛细管流变仪和Hakke转矩流变仪对稀土催化合成的超高分子量聚苯乙烯 (UHMWPS)的流变与加工性能进行了研究 .结果表明 ,UHMWPS最显著的流变特征为超高的熔体粘度和低剪切速率下出现不稳定流动 .不稳定流动与超高分子量聚合物长的松弛时间有关 ,并提出了临界剪切速率与分子量和温度的定量关系式 .较低的分子量和较高的温度有利于提高临界剪切速率 ,改善挤出物外观质量和降低熔体粘度 .分子链极度缠结不仅导致超高的熔体粘度 ,也使UHMWPS链解缠加快 ,导致更高的剪切速率敏感性 .UHMWPS塑化时熔体粘度高 ,转矩大 ,加工性能劣于通用聚苯乙烯 (GPPS)     

Investigation of the rheological and mechanical behavior of Polypropylene/ultra-high molecular weight polyethylene compounds related to new online process control

Ultra-high molecular weight polyethylene (UHMWPE) is a high performance material that has excellent wear and impact strength compared to other polymers. Due to its chemical structure and molecular mass, UHMWPE is difficult to handle on standard extrusion systems. In this paper, the compounding, rheological, and mechanical behavior of different Polypropylene (PP)/UHMWPE blends were investigated. Raw materials were blended on a co-rotating twin screw extruder. The shear and extensional viscosity of polymer blends were investigated using an inline rheometer. Mechanical and rheological properties were presented for various UHMWPE loadings, and correlations between mechanical and rheological data were examined.     

聚合物分散剂对氟铃脲水悬浮剂流变性质的影响

采用控制应力流变仪研究了聚合物分散剂苯乙烯丙烯酸无规共聚物（MOTAS）用量、分子量及氟铃脲质量分数等对氟铃脲水悬浮剂流变性质的影响。 结果表明,以聚合物MOTAS为分散剂制备的氟铃脲水悬浮剂的流变行为符合Herschel-Bulkley模型。 在固定氟铃脲质量分数为20%时,当分散剂质量分数≤3.0%时,流动行为指数n≤1.0,悬浮体系表现为假塑性流体,当分散剂质量分数≥3.5%时,流动行为指数n≥1.0,悬浮体系具有胀塑性流体特征。 氟铃脲水悬浮剂的流变参数屈服值τH与分散剂MOTAS和氟铃脲的加入量有关。 分散剂MOTAS质量分数≤2.5%时,分散剂在氟铃脲颗粒界面吸附很少,裸露的氟铃脲颗粒界面间相互搭接,具有较大的屈服值τH;当分散剂加入质量分数为3.0%时,分散剂可在氟铃脲颗粒界面形成饱和吸附,若再增加分散剂用量,多余分散剂在悬浮的氟铃脲颗粒间形成搭接,使其屈服值τH增大。 在MOTAS分散剂的分子量在10 000~30 000范围内时,MOTAS分子量愈大,所制得的氟铃脲水悬浮剂的表观粘度和屈服值τH愈小,流变行为指数n虽略有增加,但均小于1,没有改变“剪切变稀”的假塑性特征。     

Effect of cationic polymethacrylates on the rheology and flocculation of microfibrillated cellulose

Using two cationic methacrylate polymers: poly([2-(methacryloyloxy)ethyl] trimethyl ammonium iodide) (PDMQ) and poly[(stearyl methacrylate)-stat-([2-(methacryloyloxy)ethyl] trimethyl ammonium iodide)] (PSMA13Q), we modified microfibrillated cellulose (MFC) water suspensions. The aim was to affect the flocculation and rheological behavior of the MFC suspension. PDMQ is a strongly cationic polymer while PSMA13Q, also a cationic polymer, contains hydrophobic segments. We studied the MFC/polymer suspension rheological properties with a rotational rheometer in oscillatory and flow measurements. To observe structural changes in suspensions at different shear rates, we measured flow curves with transparent outer geometry and photographed the sample with a digital camera. The oscillatory measurements showed that a small amount of the cationic PDMQ in the MFC suspension strengthened the gel, whereas a small amount of amphiphilic PSMA13Q weakened it. Increased amounts of either polymer increased the gel strength. PSMA13Q also changed the rheological character of the MFC suspension turning it more fluid-like. When we photographed the flow curve measurement, we saw a clear change in the floc structure. This floc structure rupture coincided with a transient region in the flow curve.     

Rheological behavior of POM polymer melt flowing through micro-channels

Determination of the rheological behavior of the polymer melt within micro-structured geometry is vital for accurate simulation modeling of micro-molding. The lack of commercial equipment is one of main hurdles in the investigation of micro-melt rheology. In this study, a melt viscosity measurement system for POM melt flowing through micro-channels was established. For measured pressure drop and volumetric flow rate, both capillary and slit flow models were used for the calculation of viscosity. The calculated results were also compared with those of PS resin to discuss the effect of morphology structure on the viscosity characteristics of polymer within micro-channels. It was found that the measured POM viscosity values in the test ranges are significantly lower (about 29-35% for a channel size of 150 μm) than those obtained with a traditional capillary rheometer. Meanwhile, the percentage reduction in the viscosity value and the ratio of slip velocity relative to mean velocity all increase with decreasing micro-channel size, but less significantly when compared with PS resin. In the present study we emphasize that the rheological behavior of the POM resin in microscopic scale is also different from that of macroscopic scale as PS resin but displays a less significant lower. It also revealed that the wall slip occurs more easily for the PS resin within micro-channels than POM resin due to enlarge the effect of molecular weight.     

Model filled rubber. II. Particle composition dependence of suspension rheology

Monodisperse size colloidal particles varying in chemical composition were synthesized by emulsifier‐free emulsion polymerization. Using a stress‐controlled rheometer, the rheological behavior of colloidal suspensions in a low molecular weight liquid polysulfide was investigated. All suspensions exhibited shear thinning behavior. The shear viscosity, dynamic moduli, and yield stress increased as interactions between particles and matrix increased. The rheological properties associated with network buildup in the suspensions were sensitively monitored by a kinetic recovery experiment. We propose that interfacial interactions by polar and hydrogen bonding between particles and matrix strongly promote affinity of matrix polymer to the filler particles, resulting in adsorption or entanglement of polymer chains on the filler surface. A network structure was formed consisting of particles with an immobilized polymer layer on the particle surface with each particle floc acting as a temporary physical crosslinking site. As the interfacial interaction increases, the adsorbed layer thickness on the filler particles, hence, the effective particle volume fraction, increases. As a result, the rheological properties were enhanced in the order PS < PMMA < PSVP. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 815–824, 1999     

Melt‐compounded nanocomposites of titanium dioxide atomic‐layer‐deposition‐coated polyamide and polystyrene powders

Polyamide and polystyrene particles were coated with titanium dioxide films by atomic layer deposition (ALD) and then melt‐compounded to form polymer nanocomposites. The rheological properties of the ALD‐created nanocomposite materials were characterized with a melt flow indexer, a melt flow spiral mould, and a rotational rheometer. The results suggest that the melt flow properties of polyamide nanocomposites were markedly better than those of pure polyamide and polystyrene nanocomposites. Such behavior was shown to originate in an uncontrollable decrease in the polyamide molecular weight, likely affected by a high thin‐film impurity content, as shown in gel permeation chromatography (GPC) and scanning electron microscope (SEM) equipped with an energy‐dispersive spectrometer. Transmission electron microscope image showed that a thin film grew on both studied polymer particles, and that subsequent melt‐compounding was successful, producing well dispersed ribbon‐like titanium dioxide with the titanium dioxide filler content ranging from 0.06 to 1.12 wt%. Even though we used nanofillers with a high aspect ratio, they had only a minor effect on the tensile and flexural properties of the polystyrene nanocomposites. The mechanical behavior of polyamide nanocomposites was more complex because of the molecular weight degradation. Our approach here to form polymeric nanocomposites is one way to tailor ceramic nanofillers and form homogenous polymer nanocomposites with minimal work‐related risks in handling powder form nanofillers. However, further research is needed to gauge the commercial potential of ALD‐created nanocomposite materials. Copyright © 2011 John Wiley & Sons, Ltd.     

可控交联聚醚醚酮动态流变学行为的研究

聚芳醚酮类材料因其优异的综合性能在许多领域得到广泛应用 [1,2 ] .许多研究者通过提高聚芳醚酮分子链的刚性度来实现进一步提高其使用温度 ,但由于其在高温时流动性下降 ,熔体粘度增大 ,给加工及应用带来很大困难[3] .基于此 ,我们将可在高温或辐照条件下发生交联反应的硫醚结构作为交联点引入到聚醚醚酮主链中 ,合成了可控交联的聚醚醚酮[4 ,5] .聚合物的分子结构及其熔体中分子的内部作用可以用流变学进行研究 .因此 ,我们用动态流变学实验监测跟踪聚合物的交联反应过程 ,研究可控交联聚醚醚酮的交联反应动力学 ,为设计改造分子结构以满…     

熔体中转变对四氟乙烯-六氟丙烯共聚物熔体流变性能的影响

用差示扫描量热仪与扭辨分析检出了四氟乙烯-六氟丙烯共聚物熔体中的转变。为了阐明转变的性质,用毛细管流变仪和微型平板粘度计研究了其熔体粘度的温度依赖性。发现,当温度上升到转变温度附近,熔体粘度先升高,然后下降,其粘度行为与热致型小分子液晶相似。但用偏光显微镜观察FEP共聚物熔体,未发现双折射现象。根据实验结果对转变的机制提出了解释。     

动态流变法在聚合物/聚合物界面分子链扩散研究中的应用

聚合物/聚合物界面的分子链扩散问题在塑料注塑、焊接、共混等领域普遍存在.动态流变法是研究聚合物/聚合物界面分子链扩散的一种有力手段,这种方法对于界面间分子链扩散的监测非常灵敏.本文简述了用动态流变法研究聚合物/聚合物界面扩散的原理、实验方法以及优点,着重讨论了采用该方法研究初始界面分子链末端分布对扩散机理的影响、对称聚合物/聚合物界面分子链扩散的量化,非对称聚合物/聚合物界面的相互扩散,分子量多分散性对聚合物/聚合物界面扩散的影响,聚合物/聚合物界面间的流动和扩散耦合以及近年来动态流变法在化学反应型聚合物/聚合物界面的应用进展.     

4种低密度聚乙烯树脂的链结构及其性能

选用4种商品化的具有不同熔体流动速率的低密度聚乙烯(LDPE),利用高温凝胶渗透色谱仪(HT-GPC)、碳核磁共振谱仪(¹³C NMR)、差示扫描量热仪(DSC)和流变仪研究其链结构特点及其流变性能。 按照相对分子质量的差异分成两组,D-1和Q-1,D-3和Y-1,每组的两个样品具有相近的平均相对分子质量。 ¹³C NMR的结果表明,4种LDPE都既含有短链支化又含有长链支化,且短链支化含量均高于长链支化含量;而短链支化中丁基含量最多。 连续自成核退火热分级(SSA)结果表明,树脂中均含有不同长度的可结晶的亚甲基序列,即每种树脂分子链内的短链支化分布不均匀。 探讨了相对分子质量及其分布、亚甲基序列长度及其分布、支化含量、结晶度等因素对树脂熔融行为、流变行为和薄膜力学性能的影响,发现Q-1的低相对分子质量尾端和Y-1的长链支化含量均影响熔体流动速率,平均亚甲基序列长度决定熔融峰的位置,结晶度直接影响薄膜的力学性能。 基于上述结果,建立结构与性能的关联。     

Experimental methods in polymer melt rheology

Experimental developments in different areas of polymer melt rheology and recent results are reviewed: Shear oscillations were performed with mixtures of polyisobutylenes (PIB) of relatively small molecular mass distributions and with blends of polystyrene (PS) and polymethylmethacrylate (PMMA). For the latter, the interfacial tension between the melts of PS and PMMA can be derived from the results. - In constant shear rate flow, the measurement of the first normal stress difference N₁ in a commercial cone-and-plate rotational rheometer is simple if the test temperature is kept extremely constant. By a further modification a partial integral of the pressure distribution is measured from which the second normal stress difference N₂ can be determined. - The molecular orientation in shear flow results in a rheological anisotropy that can be studied in a parallel-plate shear rheometer in which the polymer melt sample can arbitrarily be sheared in two perpendicular directions. - For melt elongation by rotary clamps constant, arbitrary ratios of the strain rate components can be applied. Planar elongations of the PIB samples indicate an influence of the width of the molecular mass distribution. More general elongations with a change of the strain rate ratio during the test are of especial interest as is documented by the comparison of the resulting stresses with predictions from different network theories. - In a rheometer for simple elongation at 170°C, recovery after melt extension of the PS/PMMA blends reveals a value of the interfacial tension equal to the one obtained from shear oscillations.     

Rheology of polymer brush under oscillatory shear flow studied by nonequilibrium Monte Carlo simulation

The rheological behaviors of polymer brush under oscillatory shear flow were investigated by nonequilibrium Monte Carlo simulation. The grafted chain under oscillatory shear flow exhibited a waggling behavior like a flower, and the segments were found to have different oscillatory phases along the chain contour. Stress tensor was further obtained based on the statistics of sampled configuration distribution functions. The simulation reproduced the abrupt increase of the first normal stress difference N(1) with the flow velocity over a critical value, as observed in the experiment of Klein et al. [Nature (London) 352, 143 (1991)]. However, our simulation did not reproduce the brush thickening with shear velocity increased, which was suggested to be responsible for the abrupt increase of N(1) in the above-mentioned paper. This simulation demonstrates that the increase of normal stress might be an inherent behavior of polymer brush due to chain deformation under flow.     

Phenomenological analysis of elongational flow birefringence in semidilute solutions of hydroxypropylcellulose

The relaxation time of a polymer chain in an elongational flow field was investigated for hydroxypropylcellulose (HPC) semidilute solution systems by two methods: phenomenological analysis of elongational flow-induced birefringence, and dynamic light scattering (DLS) and rheological measurements. To understand the relaxation time of an entangled semiflexible polymer solution in an elongational flow field, scaling analysis of the elongational flow-induced birefringence curve was performed. The results of both temperature and concentration scaling analyses showed that birefringence curves at different temperatures and at several HPC concentrations were described well by a universal birefringence–strain rate curve. This scaling behavior was compared with the "fuzzy cylinder" model. The critical strain rate corresponded to the correlation time of the slow relaxation mode determined by DLS measurement and the relaxation spectrum obtained by dynamic viscoelasticity measurement. The elongational flow-induced birefringence observed in an HPC semidilute solution was concluded to be attributed to the orientation of the HPC segment in the entangled molecular system, because the dominant relaxation mode is found to be the concentration fluctuation of an entangled molecular cluster in a quiescent state.     

Effect of thermal degradation on rheological properties for poly(3-hydroxybutyrate)

Thermal degradation at processing temperature and the effect on the rheological properties for poly(3-hydroxybutyrate) have been studied by means of oscillatory shear modulus and capillary extrusion properties, with the aid of molecular weight measurements. Thermal history at processing temperature depresses the viscosity because of random chain scission. As a result, gross melt fracture hardly takes place with increasing the residence time in a capillary rheometer. Moreover, it was also found that the molecular weight distribution is independent of the residence time, whereas the inverse of the average molecular weight is proportional to the residence time. Prediction of average molecular weight with a constant molecular weight distribution makes it possible to calculate the flow curve following generalized Newtonian fluid equation proposed by Carreau as a function of temperature as well as the residence time.     

Flow-induced crystallization of poly(ethylene terephthalate) melts in a capillary die: Formation and properties of the crystalline toroid

An unusual crystalline aggregate, which is toroidal in shape, has been formed at the entrance region to capillary dies during the high-pressure extrusion of poly(ethylene terephthalate) melts in an Instron capillary rheometer. The toroidal remnant was discovered in capillary dies removed from the rheometer after the occurrence of oscillating flow. Detailed observations of the rheological factors involved in the formation of the crystalline toroid were made. Examination of recovered entrance plugs disclosed that the crystalline toroid was a hard, stagnant zone which throttled the bulk flow of polymer melt into the capillary during the extrusion experiments. Hot-stage optical microscopy, differential scanning calorimetry, and wide-angle x-ray techniques were used to initiate a structural study of the crystalline toroid. The toroid contained clusters of fibrous crystals which persisted to high temperatures. The fibrous clusters were randomly oriented in a matrix polymer which melted normally. Based upon the rheological and structural evidence, a mechanism of crystalline toroid formation is proposed.     

Towards online,continuous monitoring for rheometry of complex fluids

This paper presents an overview of the developments that have been made towards the design of an inline rheometer that has the capabilities for monitoring in real time the viscous constitutive parameters of non-Newtonian fluids in a pipe flow. This has potential applications for a wide range of fluids, including hydrocolloid solutions and polymer solutions. This is of relevance to many industries, for example the pharmaceutical, lubrication, food and printing industries. The use of mathematical algorithms for inferring rheological parameters from properties of flow field statistics is explored. Particular focus is given to the development of a flow cell rheometer containing a T-junction geometry with the capacity to induce a range of shear rates in the vicinity of the bend, and a distribution of elongational viscosities along the back-wall. Such features create an information-rich flow field that is beneficial for the development of a rheometer with a fast response time that is suitable for commercial purposes.     

热致性液晶共聚酯的拉伸流动行为

采用入口收缩流动的实验方法研究了改性PET/ 80PHB液晶共聚酯LCP80的拉伸流动行为 ,考察了拉伸速率、温度等对其拉伸粘度、Trouton比的影响 .实验结果表明 ,LCP80的入口压降值很大 ,其中由拉伸引起的入口压降是主要的 .在该文实验条件下LCP80均表现出拉伸稀化现象 ,并且Trouton比值都远大于 3 .根据流动中液晶织态结构的变化解释了实验现象 ,并对入口收缩流动的实验数据处理方法作了改进 ,比Beery的方法更为合理 ,也具有更广的适用性 .     

Rheology of polymers that are initially in the disentangled state

An attempt was made to measure the effects of molecular entanglements on the rheological properties of polymer melts. Two classes of polymers were studied; glassy atactic polystyrene polymers covering a 60-fold range in molecular weight, and semicrystalline high-density polyethylene from two sources covering about a twofold range in molecular weight. The entanglements initially present were removed or greatly reduced in number by freeze drying the polystyrene polymers from dilute solutions below and above C*, the critical overlap concentration, and by slowly crystallizing the polyethylene from very dilute solutions. Since only minor rheological changes were observed with polystyrene, it would appear that the initially isolated coils interpenetrate more rapidly than is indicated by the results of Liu and Morawetz, or that the rheological behavior is rather insensitive to whether the flow obstacles are intermolecular or intramolecular. The enhancement of the viscosity and elasticity observed with polyethylene polymers indicate the importance of the crystallization step on the local melt topology of the polymer chains.