Dynamics of Polymeric Fluids 1. The Molecular Theory of Die Swell： A Set of Equation on Swelling Ratio in Extrudates

The structural model of the multiple-transient networks and the mechanism of the multiple-reptation entangled chains due to the dynamic reorganization in the entangled sites were extensively applied on the die swell of polymeric liquids in the steady simple shear flow. The total (recoverable and unrecoverable) viscoelastic free energy of deformation and flow, the constitutive equation and the expression of the simple shear (tanψ)were deduced from the conformational probability distribution function of the entangled polymer chains. It found that: (1) the magnitudes of simple shear (tanψ) depended not only on the free recoil (or recoverable strain) but also on the viscous heating (or unrecoverable strain); (2) the total recoil may be resolved into the instantaneous and delayed recoil. Based on these facts, the functions of the partition and two experiential fractions of the recoverable (1(-W)γ) and the unrecoverable ((-W)γ) conformations for the recoil and viscous heating of polymeric liquids were defined correspondingly. Then the correlation of the instantaneously and ultimately (or total) recoverable strains to the (N1/τ12)w and the fraction of trans-form conformation was obtained. After introducing the condition of uniform two-dimensional extension (αx=αy=α, αz=α-2) and the swell ratio (B=α), two sets of equations on the instantaneous and ultimate swelling ratios (BE, BEVT) were obtained, and a method to determine the fraction of the recoverable transform conformation were proposed.The equations of BE and BE5 were verified by the experimental data of HDPE (high denisity polyethylene)at two different high temperatures. It shows that the molecular theory of die swell can be used to predict the correlation of the swelling to the (N1/τ12)w and the fraction of trans-form conformation.     

Melt-state shear flow and elasticity of a thermoplastic fluorosulphonated—PTFE copolymer

Some rheological properties of a perfluorosulphonated PTFE copolymer have been measured in order to characterise the melt-state viscous and elastic behaviour of a thermoplastic precursor of Nafion®, an ion-selective membrane used in the electrochemical industry. Steady-state shear viscosity measurements show conventional pseudoplastic flow behaviour over a wide temperature range, under high shear conditions. These data have been modelled to a high level of accuracy using polynomial simulations to obtain Carreau model coefficients and flow activation energies. Using an orifice die in a capillary rheometer, calculated extensional viscosity data are shown to decrease with stress and are more temperature-sensitive than shear viscosity. Although die swell increases with shear rate in a conventional manner, unusual and complex die swell data (at a fixed shear stress) have been obtained in response to an increase in process temperature. This behaviour is attributed to the breakdown of a small-scale network of domains and ordered crystalline material in the amorphous matrix of the precursor, as exemplified by a very broad melting endotherm. Different modes of deformation have been proposed to explain the rheological data observed across the process temperature range. The observed changes to the flow mechanism and elastic character of the melt carry practical implications for the extrusion processes and developed microstructure of film products manufactured from this precursor copolymer.     

Elastic behaviour of polyvinyl chloride melts

A study has been made of the elastic behaviour of Polyvinylchloride commercial samples at high shear stresses, under similar conditions to those used in the processing industry, by means of an extrusion capillary rheometer.The influence in the die swell of variables as molecular weight, temperature and shear rate has been studied. Results are in agreement with general literature data.Smooth extrudates are obtained only in the zone of intermediate shear rates. In this zone it is observed that the die swell increases with shear rate.     

动态硫化对TPU/EVM共混物加工流变行为的影响

采用过氧化二异丙苯(DCP)对热塑性聚氨酯弹性体(TPU)/乙烯-醋酸乙烯酯共聚物(EVM)共混物实施动态硫化后,TPU/EVM共混物的表观黏度增大,非牛顿性增强,挤出胀大比增大,挤出物表面粗糙。其中TPU/EVM=75/25时,黏度增加最大,并且随剪切速率的增加其非牛顿性由硫化前的减弱变为硫化后的增强。动态硫化后,纯TPU的表观黏度增大,说明过氧化物使其发生了一定程度的交联而又使其不失热塑性。     

聚合物熔体复合挤出胀大过程的数值模拟及可恢复弹性形变分析

建立了两种聚合物熔体流经矩形流道共挤出的三维数值计算模型,采用有限元方法数值模拟了共挤出成型过程及胀大过程,得到了速度场、压力场、应力场,并利用数值计算方法得到了共挤出流动过程的可恢复弹性形变场,分析了挤出胀大率以及可恢复弹性形变的变化过程。结果表明,在共挤出流动的胀大段,共挤出界面的形状和位置发生了改变;经矩形流道共挤出得到的挤出胀大末端截面形状为不对称的鼓形;在共挤出界面附近可恢复弹性形变值存在极值,运用数值方法计算可恢复弹性形变可以对流动过程中可能存在的缺陷进行预测。     

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.     

改性聚乙烯醇的流变行为及其吹塑加工研究

研究了改性PVA体系的流变性能及挤出胀大行为。结果表明,改性PVA熔体为假塑性流体,适合挤出吹塑成型。在相同加工条件下,Ac含量增加,改性PVA体系表观黏度和剪切敏感性下降,温度敏感性升高,且改性体系的挤出胀大比减少。通过优化改性PVA组分和挤吹工艺条件,初步实现了PVA吹塑成型。     

Study on viscosity of conventional and polymer modified asphalt binders in steady and dynamic shear domain

This study focuses on evaluating the flow behavior of conventional and polymer modified asphalt binders in steady- and dynamic-shear domain, for a temperature range of 20–70 °C, using a Dynamic Shear Rheometer (DSR). Steady-shear viscosity and frequency sweep tests were carried out on two conventional (VG 10 and VG 30) and two polymer (SBS and EVA) modified asphalt binders. Applicability of the Cox–Merz principle was evaluated and complex viscosity master curves were analyzed at five different reference temperatures. Cross model was used to simulate the complex viscosity master curves at different temperatures.It was found that asphalt binders exhibited shear-thinning behavior at all the test temperatures. The critical shear rate increased with increase in temperature and was found to be lowest for plastomeric modified asphalt binder. The Cox–Merz principle was found to be valid in the zero-shear viscosity (ZSV) domain and deviated at higher frequency/shear rate for all the binders. Results from the study indicated that the ratio of ZSV can be successfully used as shift factors for construction of master curves at different reference temperatures. Cross model was found to be suitable in simulating the complex viscosity master curves at all the test temperatures. Analysis of model parameters indicated that a strong relationship exists between ZSV and the critical shear rate. ZSV and critical shear rate varied exponentially with temperature. This relationship was used to propose a simple equation for assessing the shift factors for construction of master curves.     

聚碳硅烷的挤出胀大与Y型SiC纤维的异形度

研究了聚碳硅烷(PCS)熔体在Y型喷丝孔中的挤出胀大机理、膨胀模型以及膨胀比对Y型碳化硅纤维异形度的影响.结果表明:采用圆形喷丝孔时PCS的膨胀比为1.02～1.15,Y型喷丝孔时膨胀比为1.02～1.43,在与圆形喷丝孔成形条件相当的情况下,Y型喷丝孔的膨胀比比圆形孔的高出约15%,Y型口模周边的剪切应力分布不均、剪切应力内外差异和区域差异是造成其膨胀比增大的根本原因.PCS熔体温度降低或软化点提高,其出口挤出胀大效应增大.由于模口膨胀的影响,Y型PCS纤维的异形度比喷丝孔异形度下降10%～20%.     

聚合物气辅共挤成型中挤出胀大的数值模拟

以一矩形截面共挤型材为例,采用Giesekus本构方程和Navier滑移模型建立数值模型,使用EVSS、SU等有限元方法对气辅共挤和传统共挤时两种聚合物熔体在口模内外的等温粘弹流动做了三维数值模拟,得到了气辅共挤和传统共挤时的挤出胀大率、速度场、应力场及剪切速率分布。对模拟结果进行了分析和对比,结果表明,气辅共挤能消除挤出胀大和模外熔体偏转流动现象;气辅共挤时两相熔体的速度场均匀一致,熔体流动稳定,呈柱塞状挤出;熔体表面的切向和法向应力为零,因而可有效提高挤出速率,并防止制品表面"鲨鱼皮"现象的出现。     

Chemically etched open tubular and monolithic emitters for nanoelectrospray ionization mass spectrometry

We have developed a new procedure for fabricating fused-silica emitters for electrospray ionization-mass spectrometry (ESI-MS) in which the end of a bare fused-silica capillary is immersed into aqueous hydrofluoric acid, and water is pumped through the capillary to prevent etching of the interior. Surface tension causes the etchant to climb the capillary exterior, and the etch rate in the resulting meniscus decreases as a function of distance from the bulk solution. Etching continues until the silica touching the hydrofluoric acid reservoir is completely removed, essentially stopping the etch process. The resulting emitters have no internal taper, making them much less prone to clogging compared to, e.g., pulled emitters. The high aspect ratios and extremely thin walls at the orifice facilitate very low flow rate operation; stable ESI-MS signals were obtained for model analytes from 5-microm-diameter emitters at a flow rate of 5 nL/min with a high degree of interemitter reproducibility. In extensive evaluation, the etched emitters were found to enable approximately four times as many LC-MS analyses of proteomic samples before failing compared with conventional pulled emitters. The fabrication procedure was also employed to taper the ends of polymer monolith-containing silica capillaries for use as ESI emitters. In contrast to previous work, the monolithic material protrudes beyond the fused-silica capillaries, improving the monolith-assisted electrospray process.     

聚合物熔体的壁面滑移行为

用双筒毛细管流变仪和旋转流变仪研究了两种商用聚合物熔体——聚甲基乙烯基硅氧烷(PMVS)和线型低密度聚乙烯(LLDPE)的壁滑行为。通过剪切速率扫描的方法发现两种聚合物熔体均发生粘滑转变,而且发生粘滑转变的临界剪切应力随温度线性增加,这与Brochard和de Gennes提出壁滑的解缠机理一致。用壁滑外推长度表征壁滑程度,发现两种熔体在温度为60℃~210℃范围内的壁滑外推长度均为0.05 mm~0.06mm。结果表明,对于线形链高分子如PMVS,LLDPE和高密度聚乙烯(HDPE)等在剪切应力达到临界值时均发生同一类粘滑转变。     

Shifts in peptide and protein charge state distributions with varying spray tip orifice diameter in nanoelectrospray Fourier transform ion cyclotron resonance mass spectrometry

The influence of the diameter of the spray tip employed for nano-electrospray mass spectrometry (nano-ES-MS) upon mass spectral charge state distributions was investigated using angiotensin I (M(r) = 1296), insulin (M(r) = 5774), and ubiquitin (M(r) = 8560) as test analytes. Under a variety of experimental conditions, the charge state distributions of the test peptides and protein consistently shifted toward higher values as the tip orifice diameter decreased. This finding indicates that the use of narrow diameter capillaries can promote the formation of higher charge state ions that are more reactive precursors in tandem mass spectrometry experiments. A detailed comparison of charge state distributions obtained for nanospray capillaries of varying diameters was undertaken while systematically varying experimental parameters such as sample flow rate, analyte concentration, solvent composition, and electrospray current. The general tendency to obtain higher charge states from narrow diameter capillaries was conserved throughout, but tips with smaller orifices were more sensitive to sample flow rate (the average charge state was lowered significantly as flow was raised), whereas tips with bigger orifices were more sensitive to analyte concentration and pH of the solution (as each was lowered, the average charge state increased).     

Newtonian die swell evaluation for axisymmetric tube exits using a finite element method

Using a finite element method, a value of 13.2 per cent is obtained for the die swell of a highly-viscous Newtonian fluid flowing at very low Reynolds number from a circular tube of constant radius. The same method is then used to obtain die swell values for a variety of axisymmetric tube exits. It is found that, in general, conical constrictions at or near the tube exit result in a decrease in die swell, while conical expansions increase the die swell.     

Delamination and kink-band failure of pultruded GFRP laminates under elevated temperatures and compression

Compression experiments were conducted on slender glass fiber-reinforced polymer (GFRP) laminates at different temperatures in the elevated range. Experimental buckling loads, lateral second-order deformations, and shear strength decreased with increasing temperature until stable values were reached at a much lower level in the leathery material state. The resin-dominated bending stiffness decreased at a higher rate than the fiber-dominated compressive stiffness. Global buckling followed by a delamination failure during the post-buckling process was observed for temperatures below 180 °C, while pre-buckling kink-band failure occurred when the temperature increased to 220 °C. Recently proposed thermomechanical models were further validated and enabled the changing failure mode and associated Tresca and kink-band shear stress and strength conditions to be modeled.     

Physical anisotropy of solid-state extruded polyoxymethylene

Oriented polyoxymethylene extrudates of different draw ratios were prepared by solid-state extrusion. Various techniques were used to study their physical properties and to assess the observed physical anisotropy as a function of chain orientation by die swell, birefringence, elastic moduli, glass transition, thermal expansivity, melting point, heat of fusion, lamellar long period, crystallinity and radiation damage. WAXS, SAXS and SEM studies showed that a well defined lamellar and fibrillar structure can be developed by the solid-state extrusion process. Results of birefringence and elastic moduli showed that the extrudates possess optical and elastic anisotropy. Thermal expansivities measured parallel and perpendicular to the draw direction showed an opposite thermal anisotropy due to the difference between the force interactions along and normal to the molecular chains. It was seen that the orientation function and the thermal anisotropy parameter calculated from the aggregate model increase with the degree of the molecular orientation. The melting point measured from the DSC endotherms increased by only 2 °C and no shift in the glass transition temperature was observed from the DTMA peaks. X-ray diffraction data showed the measured crystallinity (~78% of the isotropic POM did not change with the extrusion ratio. Long period and crystal thickness decrease with the draw ratio and showed a breakup at draw ratio ~5.5. The observed increase in the long period at high draw ratio is attributed to annealing effect and interlamellar shear slip mechanism occurring during the extrusion process. It was observed in the scanning electron microscope that POM extrudates undergo rapid electron beam radiation damage which starts with narrow axial and transverse cracks and finishes with large voids and chain bundle rippling due to polymer contraction.     

An approach to controlled-release dosage form of propranolol hydrochloride

It is possible to release a drug with only limited diffusion from a membrane-coated system using osmotic pumping. In this study, a propranolol osmotic pump was produced by coating the core tablets with cellulose acetate. The effects of membrane thickness, pore size, and stirring rate on the release rate of propranolol hydrochloride were studied. It was found that the thickness of cellulose acetate membrane had a profound effect on the release rate of propranolol hydrochloride from the membrane-coated tablets. The results showed that, when the membrane thickness increased, the release rate of propranolol decreased. The drug release follows a zero-order release when the delivery orifice is between 200 and 800 μm, but when the delivery orifice size is increased to 1000μm, the release kinetic is abnormal. Fluid dynamics have an important effect on the delivery rate of propranolol from this device; the delivery rate increases as a function of the fluid flow. The drug release is higher under a turbulent condition with high rate of stirring.     

Dynamic and steady state viscoelastic behavior and morphology of MAPP treated PP/sisal composites

The present paper summarizes an experimental study on the molten viscoelastic behavior of PP/sisal composites under steady and dynamic state. Variations in melt viscosity and die swell of the composites with an increase in shear rate, fibre loading and coupling agent concentration have been investigated using capillary rheometer. It was observed that with the addition of sisal fibers and MAPP, the melt viscosity of the composites increased due to improved fiber–matrix interfacial adhesion. Further the dynamic viscoelastic behavior measured, employing parallel plate rheometer revealed an increase in the storage modulus (G′) indicating higher stiffness in case of fibre filled composites as compared with the virgin matrix. Time temperature superposition was applied to generate various viscoelastic master curves. The fiber–matrix morphology of the extrudates was also examined using scanning electron microscopy, which corroborated the findings of the rheological properties. The extrudate cross sections of the composites displayed uniform distribution of fibers within the PP matrix with lesser surface irregularities at high shear rates.     

Applying viscoplastic constitutive models to predict ratcheting behavior of sintered nanosilver lap-shear joint

A series of displacement-controlled tests were conducted for sintered nanosilver lap-shear joints at different loading rates and temperatures. The relationship between force and displacement was studied. It was found that higher loading rate or lower temperature caused higher stress–strain response of the sintered nanosilver joint. Force-controlled cyclic tests were also performed at different mean forces, force amplitudes, dwell time at peak force, and temperatures. The mean force, the force amplitude, and the temperature played key roles in the shear ratcheting strain accumulation. The ratcheting strain rate could be enhanced with increasing the dwell time at peak force as well. A viscoplastic constitutive model based on Ohno–Wang and Armstrong–Fedrick (OW–AF) non-linear kinematic hardening rule, and Anand model were separately embedded in ABAQUS to simulate the shear and the ratcheting behavior of the sintered nanosilver joint. It was concluded that OW–AF model could predict the ratcheting behavior of the sintered nanosilver joint better than Anand model, especially at high temperatures.     

线型聚乙烯熔体的剪切弹性行为表征

利用稳态剪切柔量，可回复剪切应变以及熔体挤出胀大比等参数，定量计算和定性表征了４种线型聚乙烯熔体的剪切弹性行为，研究了各表征参数之间及其与分子量，分子量分布等分子参数的关系，讨论了剪切弹性行为对加工性能的影响。